![CHAPTER 1
Introduction to nanomaterials and
nanomanufacturing for nanosensors
Tariq Mahbuba
, Md Enamul Hoqueb
a
Department of Mechanical Engineering, Military Institute of Science and Technology,
Dhaka, Bangladesh
b
Department of Biomedical Engineering, Military Institute of Science and Technology (MIST),
Dhaka, Bangladesh
1.1 Nanosensors
Sensors are devices used to detect the presence of a specific substance or to measure a physical
property such as temperature, mass, or electrical or optical characteristics and produce a
signal for recording or further postprocessing. The history of sensors is a long one. The first
thermostat came into existence in the 1880s, and the first infrared sensor was developed in
1940. Nanosensors are similar to macrolevel sensors but have at least one dimension in
nanoscale and can be used to measure signals available at that scale. Nanotechnology, with its
rapid developments in recent years, has shown great potential in almost all industries.
Various electronics industries have fueled these developments to satisfy their need for
miniaturization, and the nanosensor field has taken advantage of these advances for its own
development. A large volume of research has been conducted over the last two decades in
the area of nanomaterials for wider applications, including nanosensors [1–10]. Since
nanosensors can deal with signals produced at the nanoscale, the sample quantities needed are
quite small and detection is very rapid. All of these qualities have helped the applications
of various types of nanosensors in different fields, especially in the medical and homeland
security fields. Gaining a clearer understanding of the special properties offered at the
nanoscale by nanomaterials, evolution of the various techniques for nanomaterial production,
and exploitation of the special properties of nanomaterials have all advanced nanosensor
development.
Nanofabrication for Smart Nanosensor Applications. https://doi.org/10.1016/B978-0-12-820702-4.00001-5
# 2020 Elsevier Inc. All rights reserved.
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![1.1.1 Types of nanosensors
During the short history of nanosensors, this technology has experienced substantial
developments. Since a variety of nanosensors are available today, classification can be
somewhat difficult. However, nanosensors can be classified based on two general
factors: (1) structure and (2) application.
Based on structure, nanosensors can be further classified into two groups:
Optical nanosensors: Optical nanosensors use the sensitivity of fluorescence for qualitative
and quantitative measurement.
Electrochemical nanosensors: This class of nanosensor mainly detects electronic or chemical
properties of a respective substance and transduces a signal. Recently, major developments
have taken place in this type of nanosensor technology.
Based on application, nanosensors can be classified into chemical nanosensors, nanoscale
electrometers, nanobiosensors, deployable sensors, and so on.
1.1.2 Applications of nanosensors
Nanosensors are gradually assuming roles in almost every aspect of human life. A number of
sensors can detect the presence of hazardous materials or microorganisms in food, water, and
air. These sensors are saving lives in different corners of the world. In the medical field
nanosensors are having a huge impact: for example, a variety of nanosensors are being used in
cancer detection, DNA and protein detection, and targeted drug delivery. Deployable sensors
have found applications in homeland security. Various chemical sensors are now added to
unmanned aerial vehicles to detect the presence of poisonous gas on the battlefield, to save the
lives of soldiers. Various tagging systems employ RFID chips, which are also an application of
nanosensors.
1.2 Nanomaterials for nanosensors
For centuries the beauty of the 400 CE Lycurgus Cup and the strength and beauty of a
Damascus steel blade have amazed people, but it has been only decades since we discovered the
secret behind these extraordinary ancient artifacts: nanomaterials [11,12]. Nanomaterials
are defined as those nanoparticles (NPs) that have at least one dimension in nanometer scale and
that exhibit some special property that is not available in the bulk form of the same
material. Though unknowingly used in several ancient artifacts, the modern-day extensive
research, informed fabrication, and utilization of nanomaterials began in 1857, when Michael
Faraday reported the synthesis of so-called “activated gold,” which was a colloidal solution
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![of Au NPs [13]. Since that time, the use of nanomaterials has slowly but surely spread,
due to their extraordinary properties associated with their size. Nanomaterials show
extraordinary properties different than their bulk size because of their nanoscale dimension.
The surface-to-volume ratio of nanomaterials is very high, which results in variations in
chemical, mechanical, optical, and magnetic nature [14]. To explore the properties and
applications of nanomaterials properly, it is judicious to classify them. However, several factors
can be considered in classifying nanomaterials, such as physical and chemical properties,
manufacturing process, dimensionality, uniformity, composition, and so forth [15]. From the
point of view of this chapter, we classify nanomaterials into four classes based on their
chemical composition: (1) carbon-based, (2) organic-based, (3) inorganic-based, and (4)
composite-based nanomaterials. In the following sections, we discuss different nanomaterials
that fall within these four categories and their applications, especially as nanosensors.
At this point, a brief introduction to nanosensors may be very helpful for those new to this
field. A sensor is a device that detects and responds to any change in its environment.
Daily life is full of sensors, such as light sensors, rain sensors, lane assist in automobiles,
smoke and fire alarm sensors, electrical sensors, and so forth. Nanosensors perform the
same function, but on a much smaller scale (1–100 nm), capable of sensing pathogens,
viruses, molecules, or even a single chemical element. The main advantages of nanosensors
are the minute sample quantities required, speed, portability, and low cost in mass
production, among others.
The history of nanosensors is only decades old. Since the beginning of the current century, the
world has experienced a rapid escalation of production and use of nanosensors as a consequence
of two factors. First, nanosensors, due to their excellent performance, have convinced the
world that they can be successfully used in different applications varying from the food
industry, fire and hazardous gas detection, to various critical fields like military and advanced
medical applications. Secondly, there is a tremendous advancement of different
manufacturing processes used for manufacturing nanosensors, increased availability, and
development of new nanomaterials and more clear understanding of nanoscale
phenomena [16].
1.2.1 Properties of nanomaterials for nanosensors
Nanomaterials, due to high surface-to-volume ratio and the manufacturing process, offer some
extraordinary properties that can be explored to produce various applications in drug
manufacturing, environmental sensing and protection, materials and manufacturing industries,
electronics, energy harvesting, etc. A few properties that are relevant to nanosensors are briefly
described in the following sections.
Introduction to nanomaterials and nanomanufacturing for nanosensors 3](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-16-320.jpg)
![1.2.1.1 Optical properties
Nanomaterials offer some excellent optical properties, such as light absorption, color, light
emission, and magnetooptical properties due to their sizes; these properties are quite different
from their bulk properties and make nanomaterials a good choice for optical nanosensors. One
of the first nanosensors devised to measure inhomogeneous pH distribution in three-
dimensional resolution was fluorescein-based, using a polyacrylamide nanoparticle
incorporated with pH-sensitive fluorescein-acrylamide [17]. Fluorescent nanosensors can
respond to some specific stimuli provided by the surrounding environment and transduce a
fluorescence signal to the detector to sense environmental changes. These nanosensors are used
to make oxygen sensors [18] and temperature sensors. The localized surface plasmon (LSP)
effect of the noble metal nanoparticle is a current active field of research for making
nanosensors (Fig. 1.1). When a nanoparticle confines surface plasmon, due to its dimension,
comparable to the wavelength of light, the free electron of the nanoparticle participates in
the collective oscillation. This phenomenon is called localized surface plasmon (LSP) [19].
The LSP effect greatly enhances the electric field near the nanoparticle surface and at the
plasmon resonant frequency the particle shows maximum optical extinction. A number of gas
sensors [20,21] and pH sensors [22,23] are manufactured using LSP.
1.2.1.2 Electronic properties
Nanomaterials can offer quite exceptional electronic properties that originate from the shape
and structure of the nanomaterial. When talking about exceptional electronic properties, the
name that comes to mind first is graphene. Graphene has a single-layer 2D honeycomb
structure in which both surfaces are available for molecule absorption. The structure causes the
electron seemly to be massless [24] and the electron moves at an average speed which is
300 times less than the speed of light at vacuum. This allows many relativistic events to be
e-
e- e- e-
e- e- e-
e- e- e-
e-
Electron cloud
Light wave
Electric
field
e-
Fig. 1.1
Schematic diagram of localized surface plasmon effect.
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![observable without a particle accelerator [15]. The carbon nanotube (CNT) in which graphene
acts as a building block also offers some excellent electronic properties. The sp2
hybridization
of the carbon orbitals in the CNT leaves free electrons at the surface of the tubes, which
yields these excellent properties. CNT can show metallic, semiconducting, or insulating
behavior, which can be controlled by controlling the diameter, chirality of the CNT, and any
functionalization or doping done on CNT [25]. Nanosensors using these properties detect using
two methods: (a) current enhancement, and (b) current inhibition. Various electrochemical
sensors have been developed for different purposes, such as detecting dopamine [26], histamine
[27], bacteria [28], glucose [29], and so forth, using the electronic properties of nanomaterials.
1.2.1.3 Magnetic properties
Due to the uneven arrangement and orientation of electrons in nanomaterials, and their size,
nanomaterials exhibit excellent magnetic properties too. Magnetic properties of nanomaterials
are becoming a center of interest in different branches of engineering, including but not limited
to different types of catalysis, biomedicine for cancer treatment, magnetic fluids, nuclear
magnetic resonance imaging (NMR), magnetic resonance imaging (MRI), and environmental
remediation [30]. Magnetic nanosensors use different techniques to perform detection, like the
effect magnetic particles exert on water proton relaxation rates, by determining the relaxation
of the magnetic moment within the magnetic particle, by detecting the presence of a magnetic
particle using magnetoresistivity, etc. Koh et al. explain different biosensors using the
previously mentioned methods. The following figures show schematic representations of the
three procedures [31]. Fig. 1.2A represents how magnetic nanoparticles dephase the protons of
water for a better MRI scan. Magnetic particles generally stay dispersed in a liquid solvent. But
when a target analyte (triangle in Fig. 1.2A) appears, the dispersed nanoparticles produce an
aggregate around it and eventually this aggregate dephases the spins of water protons more
efficiently than the dispersed state. This reduces the spin-spin relaxation time T2 to produce a
better MRI image. Fig. 1.2B shows the application of magnetic moment relaxation within a
magnetic nanoparticle for bacterial detection. The type of relaxation used here is Neel
relaxation. In the upper figure A, a magnetic field is applied to the nanoparticles and they orient
themselves along the applied field. Some of the nanoparticles are bonded with the target
bacteria. Later, in figure B, the field is removed and many of the particles experience Brownian
relaxation and randomly orient in a different direction. But the nanoparticles bonded to the
bacteria cannot undergo Brownian relaxation and rather show Neel relaxation, which is
comparatively slower and detectable. The superconducting quantum interference devices
(SQUIDs) detect the slower Neel relaxation and bacterial detection is performed. Fig. 1.2C
shows the operation of a magnetoresistive sensor. The basic principle that a magnetoresistive
sensor applies is that the magnetic particle bonds to the surface of the sensor and eventually
alters its magnetic field. This causes a change in sensor current and the detection is performed.
There are two mechanisms through which magnetic particles bind to the sensor surface: (i) direct
labeling, and (ii) indirect labeling. In the case of direct labeling, magnetic nanoparticles directly
Introduction to nanomaterials and nanomanufacturing for nanosensors 5](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-18-320.jpg)
![Sensor functionalization
Linker incubation
Capture antibody BSA Analyte Biotinylated antibody
Magnetoresistive Sensor
Streptavidin-coated magnetic nanotag
Nanotag-based quantification
Analyte incubation
Capture antibody BSA
Control
Control
Control
Control
Probe
Target bacterium
Magnetic particle
A
A
C
B
D
(A)
(B) (C)
B
Antibody
Probe
Probe
Probe
Fig. 1.2
(A) Magnetic property of nanomaterials used for sensing applications [31]. (B) Magnetic property of nanomaterials used for sensing
applications (working principle of SQUID) [31]. (C) Schematic diagram of giant magnetoresistive sensor application [31].](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-19-320.jpg)
![bindtothesurfacefunctionality,whileforindirectlabelingasandwichassayiscreated.Fig.1.2C
schematically shows the detection of protein by creating a sandwich assay.
Nanoparticles possess many more extraordinary properties including mechanical and thermal
properties, but these properties are not very important to the current subject point of view.
1.2.2 Different nanomaterials for nanosensors
To discuss and understand the use of nanomaterials in developing nanosensors, it is helpful to
classify them into different groups. But classifying nanomaterials into different groups is a
formidable job. Nanomaterials can be prepared using a number of bottom-up processes such as
cutting, ball milling, extruding, chipping, pounding, and many more [32] and top-down
approaches [33] resulting in different types of structures, with different surface coatings, which
can cause the classification to be obscure. For that reason, here we do not put too much
concentration on classifying nanomaterials, but rather we shed some light on some commonly
used nanomaterials. A schematic representation of carbon-based nanomaterials is provided in
Fig. 1.3 for a better understanding of the diverse nature of nanomaterials.
Fig. 1.3
Different carbon-based nanomaterials [34].
Introduction to nanomaterials and nanomanufacturing for nanosensors 7](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-20-320.jpg)
![1.2.2.1 Carbon nanotube
First developed in 1991 by Iijima, the carbon nanotube (CNT) is by far the most-used carbon-
based nanomaterial. It is a cylinder having diameters from fractions to tens of nanometers and a
length up to several micrometers. There exist both single-walled (SWCNTs) and multiwalled
(MWCNTs) nanotubes that are formed by single and multiple layers of graphene lamella,
respectively, seamlessly rolled up [14]. The CNT is commonly produced by a chemical vapor
deposition (CVD) technique or vaporization of graphite in a furnace in an inert (argon gas)
atmosphere. The CNT possesses some excellent properties, such as high strength caused by its
hexagonal structure, exceptional electronic properties caused by the free electron available
after sp2
hybridization, and ease of functionalization with different organic molecules that
provide a means to interact selectively with different analytes. This easy-to-functionalize
property enables CNTs to be used as probe tips for a wide range of chemical and biological
applications.
The main application of the CNT as a sensor is in the field-effect transistor (FET). Though
the CNT is robust and inert in nature, it is highly sensitive to chemical doping. A wide variety of
FETs are manufactured by chemical doping of CNTs. Fig. 1.4 shows a schematic diagram
of CNT-FET.
CNT-FETs are used to detect different types of gases like CO2, NH3, O2 [35], NO2, N2 [36], and
so forth. CNT-FETs are also used for detection in biological science. A variety of sensors
have already been developed by researchers for detecting proteins [37], enzymes, and β-D
glucose [38], among others.
1.2.2.2 Nanowires
Nanowires are also commonly used in making nanosensors, just like CNTs. Nanowires are
produced through a variety of processes such as chemical vapor deposition (CVD), laser
ablation, alternating current electrodeposition, and thermal evaporation [25]. Nanowires can be
made up of different materials but silicone nanowires have drawn recent interest. The electrical
properties and sensitivity of silicon nanowires can be tuned properly and reproducibly by
Si
SiO2
Gate
Drain
Source
CNT or net of CNTs
Fig. 1.4
Schematic diagram of CNT-FET [25].
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![controlling the nanowire diameter and dopant concentration [39]. Hahm et al. produced a
SiNW-based sensor to detect DNA and DNA mismatches [40] in which the silicon nanowire
devices were modified with peptide nucleic acid receptors. The gold nanocluster catalyzed
chemical vapor deposition technique was employed to prepare the nanowires used in this
sensor. The nanowires were assembled on the sensor along with peptide nucleic acid.
A schematic diagram of the device is given in Fig. 1.5 [40]. When a wild type or mutant DNA is
introduced to the sensor via the microfluidic channel, peptide nucleic acid binds with the DNA
and creates a tiny change of the conductance of the silicon nanowire. This change of
conductance enables the sensor to differentiate between fully complementary or
mismatched DNA.
Nanowires are also used to make gas sensors that can qualitatively detect NH3.
1.2.2.3 Nanoparticles
Nanoparticles are a commonly used nanomaterial not only in sensor manufacturing but also in
many other engineering applications. Although the name suggests a nanoparticle is a single
molecule, NPs are not just simply one molecule but rather a combination of three layers. These
layers are (a) the surface layer, which can be used to functionalize the nanoparticle; (b) the shell
layer; and (c) the core, which is essentially the central portion of the NP [41]. Nanoparticles are
PNA
(B) (C)
(A)
PNA-DNA
Fig. 1.5
(A) Schematic of a sensor device consisting of a SiNW (yellow) and a microfluidic channel (green),
where the arrows indicate the direction of sample flow. (B) The SiNW surface with PNA receptor.
(C) PNA-DNA duplex formation [40].
Introduction to nanomaterials and nanomanufacturing for nanosensors 9](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-22-320.jpg)
![prepared using various approaches like bottom-up synthesis, including but not limited to
chemical vapor deposition (CVD), spinning, plasma spraying synthesis, and laser pyrolysis,
and top-down approaches, including but not limited to mechanical milling, sputtering, and laser
ablation. Nanoparticles can be classified into various classes, for example (a) carbon-based
nanoparticle, (b) metal nanoparticle, (c) ceramic nanoparticle, (d) semiconductor nanoparticle,
and (e) polymer nanoparticle. Fig. 1.6 shows the SEM and TEM images of different
nanoparticles (NPs). Nanoparticles offer exceptional electronic, optical, magnetic, mechanical,
and thermal properties. Among these, the first three properties are exploited to produce many
sensors. Metallic nanoparticles are used to enhance surface plasmon resonance sensitivity. The
surface plasmon resonance technique is used in many optical sensors described in the previous
section. Palladium nanoparticles deposited on etched porous silicon are used to detect hydrogen
in the environment, while carbon electrodes with deposited gold nanoparticles are used to
detect copper in water [16].
Fig. 1.6
SEM image of (A) nonporous MA-SiO2 NPs, (B) mesoporous MA-SiO2 NPs. TEM images of
(C) nonporous MASiO2 NPs and (D) mesoporous MA-SiO2 NPs [18].
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![1.2.2.4 Fullerenes
Due to their unique properties, fullerenes are now receiving major attention from the scientific
community. Fullerenes have a hexagonal ground state with sp2
hybridization and are highly
symmetric with 120 symmetry operations. Fullerenes are very strong and bounce back to their
initial shape after deformation [15]. Among other properties, fullerenes have high surface-to-
volume ratio, high electron affinity, and a hydrophobic surface. A good number of sensors have
been developed using fullerenes along with other nanomaterials to form nanocomposites.
Brahman et al. developed a C60-MWCNT nanosensor for detecting pyruvic acid [42]. Another
electrochemical sensor was developed by the same researcher that uses a fullerene, copper
nanoparticle-fullerene, MWCNT composite to detect paracetamol [43]. Here they used a
pretreated carbon paste electrode (CPE) on which fullerene-C60 and multiwalled carbon
nanotubes (MWCNTs) were dropped to produce a modified CPE. Later copper nanoparticles
(CuNPs) were deposited electrochemically on the modified CPE and a nanocomposite film of
CuNPs/C60-MWCNTs/CPE was formed. This composite showed excellent performance in
paracetamol recognition and determination.
1.3 Nanomanufacturing
Nanomanufacturing is the process of manufacturing nanomaterials or various structures in
nanoscale for different applications. This can be considered an updated version of
micromanufacturing/microfabrication in which the dimension at which the manufacturing is done
is several orders smaller. The term nanofabrication is sometimes used as analogous to
nanomanufacturing,butsometimesnanofabricationrefersmore toa nanoscalefabricationprocess
that is used in funded research work and nanomanufacturing is used to refer to manufacturing
productsforrevenuegeneration[44].However,inthischapter,wearenotveryconcernedaboutthe
lack of a specific definition for the term nanomanufacturing; rather, we provide a general idea of
current prevailing nanomanufacturing processes for manufacturing nanosensors.
A schematic diagram of an ultrasonic assisted nanomanufacturing process is shown in Fig. 1.7.
In the figure, various possible types of vibration configurations are shown for the machining
process. The research group reported that this method can be successfully applied to produce
3D nanoobjects of discrete height levels and also of continuously varying height [45].
1.3.1 Nanomanufacturing processes
The main drive behind the nanomanufacturing process is the ever-increasing hunger of the
electronics industry to obtain smaller sizes. Currently, a microchip that we can hold on our
fingertips can store gigabytes of data. To satiate this hunger, different types of
nanomanufacturing processes have been developed that can be classified into three broad
Introduction to nanomaterials and nanomanufacturing for nanosensors 11](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-24-320.jpg)
![approaches: (1) top-down approach, (2) bottom-up approach, and (3) molecular assembly.
These three approaches are briefly described in the following sections.
1.3.1.1 Top-down approach
David, the famous statue created by Michelangelo, is one of the most notable sculptures of all
time. However, if someone asks how David or any other stone or wooden sculpture is made, the
answer is simple: a large block of stone or wood is gradually trimmed to the final shape. This is
a top-down approach. In nanomanufacturing, this approach is used when a large block of
material is taken and, by machining, the material is removed little by little till the final shape is
obtained. The top-down approach consists of two steps: (1) nanolithography and (2) transfer of
pattern.
In nanolithography, the desired pattern is created on a special type of sacrificial layer called a
resist. There are a number of nanolithography techniques, such as photolithography,
electron beam lithography, X-ray lithography, soft lithography, and so forth. The basic idea in
every case is similar. First, a layer of resist is applied to the substrate. Then with the help
of a pattern the photoresist is exposed to an energy source: for example, photolithography uses
ultraviolet rays while electron beam lithography uses an electron beam and X-ray
lithography uses an X-ray. Due to this patterned exposure, the resist undergoes a chemical
process and the chemical and mechanical properties vary throughout the whole coating.
Later, some part of the resist (exposed or unexposed part) is removed, depending on the
positive or negative resist, and a pattern is created. Now the metal layer (SiO2 in Fig. 1.8)
is ready for the etching process. After etching the pattern created by the resist is removed
mechanically or chemically. The simplified process is graphically represented in Fig. 1.8.
Circular vibration
Feed
(A)
(B) (C)
(D)
Ultrasonic
vibration
f < fr
f >> fr
Fig. 1.7
(A) Ultrasonic assisted AFM-based nanomanufacturing process. (B) Low-frequency tip-sample
interacting. (C) Ultrasonic tip-sample interaction while the tip is stationary. (D) SEM image of AFM
tip [45].
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![properties, charge, polarizability, and magnetic dipole of the molecule to drive them to
assemble together to form a particular structure. This is still a growing field and various
developments are required before this approach is used in industry.
Fig. 1.9
Bottom-up approach used in tissue engineering. (A) Complementary oligonucleotides were covalently
coupled to the surfaces of different cells by click chemistry. (B–E) Two nonadherent cell types were
mixed, and did not aggregate if their surfaces were modified with: (B) no oligonucleotides,
(C) noncomplementary oligonulceotides. However, specific aggregation was observed if the cell
surfaces were modified with complementary oligonucleotides (D, E). (F) Aggregation of DAPI stained
cells (blue), with the central cell modified with fluorescein-conjugated oligonucleotides (green). (G) 3D
reconstruction of an aggregate of Texas Red-labeled (red) and fluorescein-labeled cells (green) [46].
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![1.4.1 Electron beam lithography
Lithography is the technique of transferring patterns from one medium to another medium with
the help of a material called resist. Previously, different particle beams were used in
lithography, but with the application of the electron beam, nanometer-sized features have
become possible. Due to its precious pattern-making capability, electron beam lithography
(EBL) is frequently used in sensor manufacturing. Among various electron beam lithography
technologies, here we will discuss direct writing EBL technology due to its simplicity and
frequent use. In direct writing EBL, a finely focused Gaussian round beam is used that moves
with the wafer and a single pixel of the wafer is exposed at a time (Tseng et al., 2003). The basic
setup for direct writing EBL is shown in Fig. 1.11. The beam creates a desired pattern on
the wafer and, supported with the etching and deposition process, a very complicated
nanostructure can be produced. Though this technique is very cheap and popular, its main
drawback is the large time requirement. However, researchers are trying to improve the
technology to make this process more applicable.
1.4.2 Focused ion beam lithography
Focused ion beam lithography is another nanomanufacturing technique similar to electron
beam lithography, but here ions are used to perform the lithography instead of an electron
beam (Fig. 1.12). Since the ions are much heavier than electrons, focused ion beam
lithography can be more efficient than electron beam lithography. The focused ion beam
lithography technique also has some different classifications, but direct writing is the
simplest and cheapest one and hence that is the one discussed here. In this method, a resist is
not used and by varying the distance of the wafer, the dose of ions can be controlled, resulting
1
2
3
6
5
(A) (B)
NA
+ +
-
4
Fig. 1.11
(A) Conceptual diagram of DiVa: 1. Planar cathode, 2. Shaping apparatus, 3. Shaping apparatus
second set, 4. deflector, 5. Wafer, 6. Deflection plates; (B) Experimental DiVa apparatus at Stanford
University [47].
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![in a trench of different depth on the wafer. Heavy-ion species such as Ga+
and Au+
can also be
used in this lithography to produce a stronger effect. When a beam is passed over the wafer, a
trench having inverse Gaussian shape is obtained. With increase in strength, the trench
becomes more sharp, narrow, and V-shaped [48]. Multiple passes are also possible to create
complicated shapes.
1.4.3 X-ray lithography
X-ray lithography (XRL) is an advanced version of optical lithography in which shorter
wavelengths are used. In this method, a special type of mask is used with different local X-ray
absorption areas to define the pattern. This pattern is replicated on an X-ray sensitive material
called a resist, which is previously deposited on a substrate (usually a silicon wafer). When the
X-ray passing through the pattern falls on the resist, it may cause cross-linking (for negative
resists) or bond breaking (for positive resists), depending on the chemical nature of the resist.
After exposure, the whole thing is dipped in a specific solvent and, depending on its nature,
either the exposed area resist will dissolve and create a pattern or vice versa. The other part of
the resist will stay intact [49]. This is how X-ray lithography creates nanopatterns on the
substrate.
1.5 Conclusions and future directions
The beginnings of nanotechnology are popularly dated back to the famous lecture given by
Nobel laureate Richard Feynman, “There’s Plenty of Room at the Bottom,” in 1959. But the
application of this technology became evident at the beginning of 1980. Since then,
nanotechnology has gained huge momentum and currently is being applied in various aspects of
Fig. 1.12
Schematic diagram of focused ion beam lithography.
Introduction to nanomaterials and nanomanufacturing for nanosensors 17](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-30-320.jpg)
![our daily life. In this chapter, we mainly focused on different nanomaterials that are used in
making nanosensors, along with different nanomanufacturing processes used to develop those
sensors. In nanoscale, materials exhibit some extraordinary properties that are not visible in
bulk form and nanosensors take advantage of those properties. Nanosensors are gradually
making their way into various fields, including but not limited to biomedicine and
biotechnology, hazardous material detection, water purification, food industry, electronics and
optoelectronics, and forensics. The main advantages of nanosensors include (a) rapidness,
(b) low quantities of samples required, (c) robustness, (d) point of care capability, and (e) cost-
effectiveness. More and more research is being conducted to improve the current
nanomanufacturing methods, create new nanomaterials, and develop new sensors using the
properties of nanomaterials.
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![CHAPTER 2
Features and complex model of gold
nanoparticle fabrication for nanosensor
applications
Norma Alias, Hazidatul Akma Hamlan
Center for Sustainable Nanomaterials, Ibnu Sina Institute for Scientific and Industrial Research,
Universiti Teknologi Malaysia, Skudai, Malaysia
2.1 Introduction
In recent years, many researchers and engineers have been shifting the focus of their studies
toward nanosensors because of their unique sensitivity and selectivity, which mostly originate
from modifications and reactions that occur at nanoscales [1]. Due to their unique features,
nanosensors are widely chosen for detecting chemical and physical properties in many fields
such as environmental, biomedical, and food processing.
Dahman [2] expressed that nanosensors have a plethora of environmental applications. The
ability to detect chemical components of air and water strengthen the choice of nanosensors in
the environmental field. Nanosensors are mainly used in water monitoring quality [3],
monitoring plant signaling pathways [4], and detecting and determining quantities of
acetamiprid (insecticide) in food and the environment [5] and agriculture [6]. Vikesland [3]
stated that an abundance of existing nanosensors can be developed into consumer- and
operator-friendly tools. The author emphasized that nanotechnology-enabled sensors or
nanosensors can provide extensive and potentially low-cost monitoring of chemicals, microbes,
and other analytes in drinking water. Meanwhile, Kwak et al. [4] discussed how nanosensors
can act as monitoring tools to observe and monitor plant signaling pathways and metabolism.
Verdian [5] highlighted a current major concern of food safety experts, which is pesticide
residues. Despite the small amounts of toxicity from pesticide residues, insecticides that contain
acetamiprid can represent a health risk to human beings who are exposed to polluted food and
environments. Hence, nanosensors can be used in detecting and determining amounts of
acetamiprid in food and the environment.
Nanofabrication for Smart Nanosensor Applications. https://doi.org/10.1016/B978-0-12-820702-4.00002-7
# 2020 Elsevier Inc. All rights reserved.
21](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-34-320.jpg)
![Srivastava et al. [6] explained applications of nanosensors in agriculture in which wireless
nanosensors are used to monitor the soil fertility, moisture level, insects, temperature, crop
nutrient status, and diseases of crops. Using advances in nanotechnology, crop growth can be
monitored by employing networks of wireless nanosensors across cultivated fields. The
network can provide crucial data for agronomic intelligence processes such as optimal times for
crop planting and harvesting.
One of the most popular nanosensor technologies makes use of gold nanoparticles [7], whose
flexible surface chemistry allows them to be coated with biological recognition molecules,
polymers, and small molecules, hence broadening their range of applications. Gold
nanoparticles as substrates can also be used as a nanosensor technology for the detection of
pollutants and label-free detection of other molecules and proteins [8]. Based on the facts
described, this chapter presents established mathematical modeling based on partial differential
equations (PDEs) for nanoparticle materials fabrication, to control the process of gold
nanoparticle manufacturing. The modeling is created to investigate the feature properties and
boundaries in the development process. One-dimensional PDEs with respect to time and space
are employed to visualize the growth of gold nanoparticles (AuNPS).
An accurate and precise result can be achieved by governing complex mathematical modeling
and obtaining a large sparse matrix of linear system equations (LSEs). Meanwhile, the
parallelization of LSE is chosen in order to accelerate and speed up the simulation for a large
sparse matrix. Therefore, the main focus of this chapter is the parallelization of a mathematical
model of the fabrication of nanoparticles.
Nanoparticles have played an important role in advanced catalysts, ceramics, and electronic
devices as well as polymer composites and coatings for the last two decades [9]. Their physical
and chemical properties are different from those of conventional materials. A nanoparticle can
best be defined as a small object that behaves as a whole unit with regard to its properties, and is
classified according to its diameter.
Schmid [10] defined nanoparticles as nanomaterials with an average diameter that is less than
100 nm. Nowadays, nanoparticle technology plays an important role in providing opportunities
and possibilities for the development of a new generation of sensing tools. The targeted sensing of
selective biomolecules using functionalized gold nanoparticles (Au NPs) has become a major
research thrust in the last decade [11]. Researchers normally use gold nanoparticles due to their
stability and unique optical, electronic, biolabeling, and molecular-recognition properties.
In fabricating gold nanoparticles, several features need to be controlled – for example, size,
shape, and structure. The parameters will be changed according to functionality. This is due to
the strong correlation between the parameters and optical, electrical, and catalytic properties
[12]. Nanoparticles with controlled size and shape are of great interest because of their
morphology-dependent properties [10] and potential applications in a variety of fields.
22 Chapter 2](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-35-320.jpg)
![The application of gold growth is so significant that, in recent years, some researchers have
been reporting mainly on the analysis of gold growth, especially chemical properties. However,
only a few studies focus on mathematical modeling and simulation in visualizing the growth of
gold nanoparticles [13]. Due to this situation, this research investigates the rate of growth for
gold nanoparticles using a one-dimensional parabolic PDE approach.
Since nanoparticle fabrication is being dealt with through nanoscale approaches, the focus of
this chapter is on fine-grain parallelism involving a large-scale matrix from the mathematical
model discretization. In solving the problem of a large-scale matrix, parallel computing systems
with huge memory space are needed to produce a good result. Therefore, parallel computing
systems are employed throughout this study. The parameter change from phase change
simulation is the code from the Linux operating system using DPCS based on the
approximation of numerical scheme and parallel algorithms, as well as their sequential flows.
The PVM software integrated with the C language is used to support the message passing
paradigm and simulation for the parallel algorithm program.
2.1.1 Applications of nanoparticles
Nanotechnology deals with the particular technological goal of specifically manipulating atoms
and molecules for fabrication of macroscale merchandise. Nowadays, this is also known as
molecular nanotechnology [14]. In nanotechnology, sensitivity experiments are carried out for
various physical processes, involving a large-scale structure of modeling and reformation of the
nanoscale system, which appearance as nanoparticles [15].
Gold nanoparticles (AuNPs) display irreplaceable properties that make them a very attractive
material for nanosensing applications, especially in the environmental field. Besides that, the
“additional attractive feature of AuNPs is their interaction with thiols, providing effective and
selective means of controlled intracellular release” [16]. Liu et al. [17], Park et al. [18], and
Rejiya et al. [19] have investigated the application of gold particles as nanoparticles. Various
sizes of gold nanoparticles and their morphologies have attracted considerable interest for
researchers, especially in medical applications [20] and [21].
2.1.2 Growth of gold nanoparticles
As mentioned, gold nanoparticles (AuNPs) have attracted much attention among researchers,
due to their unique properties and encouraging applications in areas of biotechnology, catalysis
[22], and optoelectronics [23]. In preparing AuNPs, the homogeneous mixing of continuous
flows of an aqueous tetrachloroauric acid solution and a sodium borohydride solution is applied
using a microstructured static mixer [24]. Their studies have provided a profound
understanding of gold nanoparticle growth and small angle X-ray scattering (SAXS), combined
with X-ray absorption near-edge structure (XANES). In predicting the size, shape, and
Designing aspects of gold nanoparticles complex model investigation 23](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-36-320.jpg)
![polydispersity of gold nanoparticles, one paper [25] stressed that it is necessary to interpret the
underlying process using SAXS that offers integral information on the growth of nanoparticles.
However, Polte et al. [26], despite their widespread use, in countless cases and applications, a
deeper understanding and consideration of the underlying formation of the processes is missing.
Due to this phenomenon, the size and shape control of gold nanoparticles often remained.
Therefore, in this chapter, a great deal of attention has been focused on understanding the
process of gold nanoparticle formation pertaining to its growth rate. In predicting and
visualizing the growth of gold nanoparticles, mathematical modeling using one-dimensional
parabolic PDEs as the integrated methodology is proposed instead of conducting experimental
laboratory studies.
The gold nanoparticle fabrication correlates with longer systemic circulation and a high-cost
fabrication for small-scale limited process. Although the nanoparticles are small, mathematical
modeling and large sparse simulation can be presented in the fabrication process.
2.2 Mathematical model of gold nanoparticle fabrication
The focus of this chapter is on the application of one-dimensional parabolic equations from
PDEs to governing mathematical modeling. The prediction and visualization of the growth rate
of gold nanoparticles are obtained by employing one-dimensional parabolic PDEs with respect
to time, space, and some independent and dependent variables.
2.2.1 Governing equation of gold nanoparticle fabrication
This section deals with the mathematical modeling and simulation of one-dimensional
parabolic PDEs as an integrated methodology for predicting and visualizing the growth of gold
nanoparticles with respect to time and space. The modeling is formulated as a boundary value
problem of PDEs. The PDE modeling with significant features and its parameter identification
that influences on gold nanoparticles (AuNPs) of diameter Φ, ultraviolet radiation λ, and rate of
gold growth U are investigated.
The integrated methodology for predicting and visualizing the growth rate of gold nanoparticles
for nanosensor applications with respect to time and space involves predicting and visualizing
using one-dimensional parabolic PDEs. The governing equation of the mathematical model for
this problem is:
∂U
∂t
¼ Φ
∂2
U
∂x2
þλ, 0 x 1, t 0: (2.1)
Initial and boundary conditions are given by [27].
U x, 0
ð Þ ¼ sin πx
ð Þ, 0 x 1,
24 Chapter 2](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-37-320.jpg)
![U 0, t
ð Þ ¼ 0, 0 t 1,
U 1, t
ð Þ ¼ 0, 0 t 1:
The exact solution is given by
U x, t
ð Þ ¼ eπt
sin πx
ð Þ, (2.2)
where λ represents the incoherent ultraviolet radiation (nm), Φ is the diameter of gold growth, U
is the rate of gold growth, t is time (duration taken for the growth rate), and x is the spatial
coordinate of direction.
2.2.2 Nondimensionalized parameter for governing equations
In mathematics, a transformation from dimensional to nondimensional variables is required so
the relevant parameter identification and changes of the required parameters for mathematical
modeling can be specified. However, for engineering applications, nondimensionalizing the
governing equation is not necessary since real physical quantities are dealt with as the solution
progresses. Since this study focuses on mathematical analysis, the nondimensional rule is
needed because the nondimensionalized variables reduce the complexity of solving the
governing equation.
Therefore, Eqs. (2.1), (2.2) are nondimensionalized using the following dimensional scaling
from Blest et al. [28]. The nondimensional scaling is denoted with a tilde:
~
Ti ¼
Ti Tini
Tc Tini
, ~
x ¼
x
d
, ~
y ¼
y
d
, ~
ui
¼
ui
d
, ~
vi
¼
vi
d
, ~
t ¼
Krt
d2
, ~
L ¼
L
d
,
~
hk ¼
hk
d
, and ~
δk ¼
δk
d
,
where i = r, f are the respective resin and saturated fiber layer. By applying these
transformations and omitting tildes for clarity, Eqs. (2.1), (2.2) can be simplified as
∂Tf
∂t
þPe uf ∂Tf
∂x
þvf ∂Tf
∂y
¼ D
∂2
Tf
∂x2
þ
∂2
Tf
∂y2
þJ1
∂α
∂t
, (2.3)
∂Tr
∂t
þPe ur ∂Tr
∂x
þvr ∂Tr
∂y
¼
∂2
Tr
∂x2
þ
∂2
Tr
∂y2
þJ2
∂α
∂t
, (2.4)
and
∂α
∂t
¼ C1 þC2α
ð Þ 1α
ð Þ 0:47α
ð Þ for α 0:3, (2.5)
Designing aspects of gold nanoparticles complex model investigation 25](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-38-320.jpg)
![2.2.4 Linear system equation formulation for gold nanoparticle fabrication
The next steps of the numerical solution involve formulation of the linear system equation
(LSE) for Eq. (2.8). In addition, three important solution tools for solving LSEs—Jacobi,
Gauss-Seidel, and Alternating Group Explicit (AGE) by Evans and Sahimi [29], Abdurrahman
et al. [30], Sahimi et al. [31], and Abu Mansor et al. [32]—are focused on in this chapter.
The standard scheme for the three-point discretization of a one-dimensional parabolic PDE can
be visualized in matrix form as
AU ¼ F (2.9)
where U and f are one-dimensional vectors defined as
U ¼ U1, j + 1, U2, j + 1, U3, j + 1, …, Um, j + 1
T
,
F ¼ F1, F2, F3, …, Fm
ð Þ:
Eq. (2.7) can be written in matrix form as:
a
c
0
b
a
c
b
a
⋱
b
⋱
c
⋱
a
c
0
b
a
2
6
6
6
6
6
4
3
7
7
7
7
7
5
mm
ð Þ
U1
U2
U3
⋮
Um1
Um
2
6
6
6
6
6
4
3
7
7
7
7
7
5
m1
ð Þ
¼
F1
F2
F3
⋮
Fm1
Fm
2
6
6
6
6
6
4
3
7
7
7
7
7
5
m1
ð Þ
(2.10)
where
a ¼ 1 + 2rθ, b ¼ c ¼ rθ
and
F1 ¼ r 1θ
ð ÞUj
0 + 12r 1θ
ð Þ
ð ÞUj
1 + r 1θ
ð ÞUj
2 + rθUj + 1
0 + λΔt
Fi ¼ r 1θ
ð ÞUj
i1 + 12r 1θ
ð Þ
ð ÞUj
i + r 1θ
ð ÞUj
i + 1 + λΔt, for i ¼ 2,3,…:m1
Fm ¼ r 1θ
ð ÞUj
m1 + 12r 1θ
ð Þ
ð ÞUj
m + r 1θ
ð ÞUj
m + 1 + rθUj + 1
m + 1 + λΔt (2.11)
2.2.5 Visualization of the mathematical model for gold nanoparticle fabrication
Visualization of the mathematical model of the one-dimensional problem of gold nanoparticles
is acquired based on a simulation using Microsoft Visual Studio 2012 and the visualization
graphs are plotted using Matlab R2013b and Comsol Multiphysics. The results obtained are
validated using experimental data for the one-dimensional problem.
Designing aspects of gold nanoparticles complex model investigation 27](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-40-320.jpg)
![involved are alternating group explicit (AGE), red-black Gauss-Seidel (RBGS), and Jacobi (JB)
methods. These are then applied using sequential and parallel algorithms that are computed
using Parallel Virtual Machine (PVM) programming on a Linux platform by distributed parallel
computing systems. Numerical analysis and parallel performance evaluation based on
execution time, speed-up, efficiency, effectiveness, temporal performance, and granularity are
discussed at the end of this chapter.
2.3.1 Numerical implementation
This section is divided into three subsections: Section 2.3.1.1 discusses the alternating group
explicit (AGE) method, followed by the red-black Gauss-Seidel (RBGS) and Jacobi (JB)
methods for solving the LSE. In 1985, Evans introduced the AGE method for solving the
parabolic PDE problem [33]. It has been shown that this method is extremely powerful and
flexible, and provides users with many advantages. This so-called advanced iterative method
employs a fractional splitting strategy, which is applied alternately at each half time step on
tridiagonal systems of different schemes and which has proven to be stable. The Jacobi (JB) and
red-black Gauss-Seidel schemes represent basic numerical schemes and are the benchmarks for
simulating the AGE scheme.
2.3.1.1 Alternating group explicit (AGE)
As mentioned earlier, this iterative scheme employs a fractional splitting strategy which is
applied alternately at each half time step on tridiagonal systems of difference schemes. This
method has already proven to be stable. The linear system equation for the AGE scheme is
given by Au ¼ f, also illustrated.
The AGE method for obtaining the growth rate of a gold nanoparticle uses the Douglas-
Rachford (DR) variant instead of the Peaceman-Rachford (PR). This is so as to ensure its
unconditional stability [34] with stationary case (r is constant) and p 0 are given by the
following equations. The computational molecule for the AGE method in determining the value
of U at level p + 1
2 is (Fig. 2.4):
The molecule diagram of the AGE method for level p + 1 can be drawn as follows (Fig. 2.5):
2.3.1.2 Red-Black Gauss-Seidel method (RBGS)
The second iterative scheme of basic numerical analysis used for solving the linear system is the
Gauss-Seidel (GS) method. This method was modified and improved from the Jacobi method,
so it is no more difficult to apply and it often requires fewer iterations to produce the same
degree of accuracy.
When the Jacobi scheme is applied, the value of xi that is obtained in the nth
approximation
remains unchanged until the entire (n + 1)th
approximate has been calculated, while for the
30 Chapter 2](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-43-320.jpg)
![Gauss-Seidel scheme, new values of each xiwill be used as soon as they are known. Once x1 is
determined in the first equation, the value is then used in the second equation to obtain a new x2.
Similarly, the new x1 and x2 are used in the third equation to obtain the new x3 and so forth.
Tavakoli and Davami [35] considered a parallel Gauss-Seidel in solving a one-dimensional
elliptic partial differential equation with a Dirichlet boundary condition. The solution to the
linear system AU ¼ f can be obtained starting with U(0)
and using the iteration scheme
U k + 1
ð Þ
¼ MSUk
+ CS, (2.12)
where MS and CS are defined as
MS ¼ D + L
ð Þ1
U andCS ¼ D + L
ð Þ1
b:
This method is described using the formulae
U
k + 1
ð Þ
i ¼
1
aii
bi
X
ji
aijU
k
ð Þ
j
X
ji
aijU
k + 1
ð Þ
j
!
,i ¼ 1,2,3,…,m (2.13)
However, the GS scheme can only solve sequential algorithms of mathematical modeling, so
this scheme has been enhanced to solve algorithms in parallel, called the Red-Black Gauss-
Seidel (RBGS). The RBGS contains two subdomains ΩR
and ΩM
. The red point depends on the
black point, and vice versa. The loop starts by computing the odd points, from the bottom left,
and then going up to the next row and so on. As all of the odd points are finished, the
computation of the black ones continues. The red-black grid is illustrated in Figs. 2.6–2.8.
2.3.1.3 Jacobi method (JB)
The third numerical iterative method employed for solving LSEs is the Jacobi method (JB),
which is an algorithm for determining the solutions of a diagonally dominant system of linear
equations. Each diagonal element is solved and the approximate value is plugged in. The
Red point
Black point
Fig. 2.6
The grid for red and black points.
32 Chapter 2](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-45-320.jpg)
![Communication among processors is important for parallel computing, especially for sending
and receiving data domain. To ensure the programming runs smoothly, “master” will send the
information to data, left, right, start and end to every slave. Subsequently, as slaves receiving
the information, computing task would start automatically. The task-to-task communication
between slaves happened in sending and receiving neighbourhood data and it is done using
massage passing [36].
Besides communication activities and algorithm of data distribution between slaves, the
programming of parallel computing would be complete if the global and local convergence’s
algorithm of master and slave were written well.
2.3.2.1 1D parallel alternating group explicit method (1D PAGE)
AGE method is an advance numerical method that stands with independent domain for each
time level. The parallel algorithm for one-dimensional AGE is constructed based on domain
decomposition technique shown in Table 2.1A. While, synchronization of domain that
decomposed into p number of slave processors and sub-domain of one-dimensional Parallel
AGE disintegrated according to processors through Fig. 2.12.
Computation of one-dimensional Parallel AGE is begun by slave receiving the parameters
involved and initial condition from the master. Since this method consist of two time level, the
Table 2.1C: Domain decomposition of one-dimensional molecule for parallel JB algorithm.
One-dimensional Parallel Jacobi (1D-PJB)
i+1, j
i, j i, j i, j
i+1, j i +1, j
i –1, j
i–1, j
i–1, j
k
k + 1
TASK 1 TASK 2 TASK 3
P1
P2
=
Pp–1
Pp
Fig. 2.12
Data partitioning by number of processors.
Designing aspects of gold nanoparticles complex model investigation 37](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-50-320.jpg)
![algorithm defined it as U1[i] and U2[i] represent the time level of k + 1
2
and (k + 1)
respectively. According to Fig. 2.13, the communication between slaves is needed for sending
U1[i 1] and U1[i + 1] grid data at the time level of k + 1
2
to neighbour slaves. While, for
completing the computation at the time level of (k + 1) the grid points of U1[i 1] and U1[i + 1]
is anticipated. It is important to calculate the convergence for completing the computation
at time level (k + 1). The computation will generate until convergence criterion for local error,
|Ui
k+1
(p) Ui
k
((p) | ε(p) is satisfied.
2.3.2.2 1D parallel Red-Black Gauss-Seidel method (1D PRBGS)
Parallel RBGS is a method that has been modified from Gauss-Seidel (GS) iterative method.
Since Gauss-Seidel iterative method is not compatible for parallel computing the modification
has been made and approved to compute in parallel platform. This is due to the overlapping sub-
domain. However, by having the improvement method of GS, which is RBGS, the domain has
been partitioned into odd and even number known as red and black points respectively. By
having this scenario, the overlapping sub-domain has been avoided successfully. In order to
gain new updating value of Ui[1], which is red point, new value of black point is used and vice
versa. This phenomenon shown there is no data enslavements between groups. Fig. 2.14,
T1
T1
Start T1 Start Tp
Start Tp–1
• • • • • •
Start T2
End T1 End T2 End Tp–1 End Tp
T2 Tp–1
Tp–1
Tp
Tp
T2
Fig. 2.13
Communication activities of one-dimensional Parallel AGE in sending and receiving domain.
startR startR startR
startB
endR
P1 P2 P3
endR endR
endB endB endB
startB startB
Fig. 2.14
Molecule ordering for one-dimensional parallel RBGS.
38 Chapter 2](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-51-320.jpg)
![PAPAL
TEMPTATIONS.
ZWINGLE'S
FIRMNESS—
FABER'S
HOSTILITY.
CHAPTER II.
Papal Temptations—Progress of the Reformation—The Idol at
Stadelhofen—Sacrilege—The Ornaments of the Saints.
The Reformation had gained the day; it was now to
accelerate its conquests. After this battle of Zurich,
in which the most skilful champions of the papacy
were dumb, who would be bold enough to oppose the new doctrine?
But weapons of a different kind were tried. Zwingle's firmness and
republican bearing overawed his adversaries; accordingly they had
recourse to peculiar measures to subdue him. While Rome was
pursuing Luther with her anathemas, she endeavoured to win over
the reformer of Zurich by gentleness. The dispute was scarcely
ended when Zwingle received a visit from the captain of the pope's
guard—the son of the burgomaster Roust. He was accompanied by
the legate Einsius, the bearer of a papal brief, in which Adrian VI.
called Zwingle his beloved son, and assured him of his special
favour.[475] At the same time the pope urged Zink to gain over
Zwingle. And what has the pope commissioned you to offer him?
asked Oswald Myconius. Everything, replied Zink, except the
papal chair.[476]
There was no mitre, or crozier, or cardinal's hat,
that the pope would not have given to bribe the
reformer of Zurich. But Rome was strangely
mistaken in this respect; all her proposals were
unavailing. In Zwingle, the Romish Church had a
still more pitiless enemy than Luther. He cared far less than the
Saxon reformer for the ideas and ceremonies of former ages; it was
enough for him that any custom, however innocent in itself, was](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-56-320.jpg)
![THE CRUCIFIX OF
STADELHOFEN.
connected with some abuse; he fell violently upon it. The Word of
God (thought he) should stand alone.
But if Rome understood so imperfectly what was then taking place in
Christendom, she found counsellors who endeavoured to put her in
the way.
Faber, exasperated at seeing the pope thus humble himself before
his adversary, hastened to enlighten him. He was a courtier with a
constant smile upon his lips and honied words in his mouth; to judge
from his own language, he was everybody's friend, even of those
whom he accused of heresy. But his hatred was mortal. Accordingly,
the reformer, playing on his name (Faber), used to say, the Vicar of
Constance is a lie-smith. Let him openly take up arms, and see how
Christ defends us.[477]
These words were no mere idle boasting; for while the pope was
complimenting Zwingle on his eminent virtues, and the special
confidence he placed in him, the enemies of the reformer were
increasing in number throughout Switzerland. The veteran soldiers,
the great families, the herdsmen of the mountains, combined their
hatred against this doctrine which thwarted their tastes. At Lucerne,
the magnificent representation of Zwingle's passion was announced;
in effect, the people dragged the reformer's effigy to the scaffold,
shouting out that they were going to put the heretic to death; and
laying hands on some Zurichers who happened to be at Lucerne,
compelled them to be spectators of this mock execution. They shall
not trouble my repose, said Zwingle; Christ will never be wanting
to his followers.[478] Even the diet re-echoed with threats against
him. My dear confederates, said the councillor of Mullinen to the
cantons, make a timely resistance to the Lutheran cause......At
Zurich a man is no longer master in his own house!
This agitation among the enemy announced what
was passing in Zurich more loudly than any
proclamations could have done. The victory was
indeed bearing fruit; the conquerors were gradually taking](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-57-320.jpg)
![This daring action spread dismay on every side: one might have
thought that religion itself had fallen with the crucifix of Stadelhofen.
They are guilty of sacrilege! They deserve to be put to death!
exclaimed the friends of Rome. The council caused the image-
breakers to be apprehended.
No! cried Zwingle and his colleagues from their pulpits: Hottinger
and his friends are not guilty in the sight of God and worthy of
death.[479] But they may be punished for having acted with violence
and without the sanction of the magistrates.[480]
Meantime acts of a similar nature were continually taking place. A
curate of Saint Peter's, one day remarking in front of the church a
number of poor people ill fed and with tattered garments, said to
one of his colleagues, as he turned his eyes on the costly ornaments
of the saints: I should like to strip these idols of wood to procure
clothing for these poor members of Jesus Christ. A few days later,
at three o'clock in the morning, the saints and all their ornaments
disappeared. The council flung the curate into prison,
notwithstanding he protested his innocence of this proceeding.
What! exclaimed the people, is it these logs of wood that Jesus
ordered us to clothe? Is it on account of these images that he will
say to the righteous: I was naked, and ye clothed me?
Thus, the greater the resistance, the higher soared the Reformation;
and the more it was compressed, the more energetically did it spring
forward, and threaten to overthrow all that withstood it.](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-59-320.jpg)
![ZWINGLE ON THE
CHURCH.
Gospel as their fathers had done; that they would send no deputy to
Zwingle and his fellows; but that, if he fell into their hands, they
would treat him in such a manner as to deprive him of all wish to
relapse into the same faults.[481] Schaffhausen and St. Gall alone
sent representatives.
On the 26th of October, after the sermon, an
assembly of more than nine hundred persons,
composed of members of the Great Council and of
three hundred and fifty priests, filled the large hall of the town-
house. Zwingle and Leo Juda were seated at a table, on which lay
the Old and New Testament in the original languages. Zwingle spoke
first, and overthrowing with a vigorous arm the authority of the
hierarchy and of its councils, established the rights of every Christian
Church, and claimed the liberty of the primitive ages—of those times
when the Church knew neither general nor provincial councils. The
universal Church, said he, is spread over the whole world,
wherever there is faith in Christ, in India as well as at Zurich......And
as for particular churches, we have them at Berne, at Schaffhausen,
and even here. But the popes, with their cardinals and their councils,
form neither the universal Church nor a particular Church.[482] The
assembly before which I now speak, continued he with energy, is
the Church of Zurich; it desires to hear the Word of God, and it has
the right of ordering all that may appear to it conformable with the
Holy Scriptures.
Thus did Zwingle rely on the Church, but on the true Church; not on
the clergy alone, but on the assembly of Christians,—on the people.
All that the Scriptures say of the Church in general, he applied to
particular churches. He did not think that any church could err which
listened with docility to the Word of God. In his eyes, the Church
was represented politically and ecclesiastically by the Great Council.
[483] At first he explained every question from the pulpit; and when
his hearers' minds were convinced of the truth, he carried the matter](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-61-320.jpg)
![CANON HOFFMAN
—
PRESBYTERIANIS
M.
SILENCE OF
PRIESTS AND
MONKS.
before the Great Council, who, in harmony with the ministers of the
Church, formed such decisions as the Church called for.[484]
In the absence of the bishop's deputies, Conrad
Hoffmann, the same aged canon who had procured
Zwingle's election to Zurich, undertook the defence
of the pope. He maintained that the Church, the
flock, the third estate, had no right to discuss
such matters. I was thirteen years at Heidelberg, said he, living in
the house of a very great scholar, whose name was Doctor Joss, a
worthy and pious man, with whom I long ate and drank and led a
merry life; but I always heard him say that it was not proper to
discuss such matters; so you see...... All were ready to burst into
laughter; but the burgomaster checked them. Let us therefore wait
for a council, continued Hoffmann. For the present, I shall not
dispute, but obey the bishop's orders, even should he be a knave!
Wait for a council! replied Zwingle. And who will attend a council?
The pope with some sluggish and ignorant bishops who will do
nothing but what suits their fancy. No! the Church is not there! Höng
and Küssnacht (these were two Zurich villages) are certainly more of
a church than all the bishops and popes put together!
Thus did Zwingle vindicate the rights of the christian people, whom
Rome had deprived of their privileges. The assembly before which
he was speaking was not, in his judgment, the Church of Zurich, but
its first representative. This is the beginning of the Presbyterian
system in the age of the Reformation. Zwingle was withdrawing
Zurich from the jurisdiction of the Bishop of Constance, separating it
from the Latin hierarchy, and founding on this idea of the flock, of
the christian assembly, a new ecclesiastical constitution, to which
other countries were afterwards to adhere.
The disputation continued. Many priests having
risen to defend the images, but without having
recourse to Holy Writ, Zwingle and the other
reformers confuted them by the Bible. If no one](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-62-320.jpg)
![VICTORY.
stands forward to defend the use of images by arguments derived
from Scripture, said one of the presidents, we shall call upon some
of their advocates by name. As no one arose, the priest of
Wadischwyl was called. He is asleep, answered one of the
spectators. The priest of Horgen was next called. He has sent me in
his place, replied his curate, but I will not answer for him.
Evidently the power of God's Word was making itself felt in this
assembly. The partisans of the Reformation were full of energy,
liberty, and joy; their adversaries appeared speechless, uneasy, and
dejected. They summoned, one after another, the parish-priests of
Laufen, Glattfelden, Wetzikon, the rector and priest of Pfaffikon, the
dean of Elgg, the priest of Bäretschwyl, with the Dominicans and
Grayfriars, notorious for their preaching in defence of images, the
virgin, the saints, and the mass; but all made answer that they could
say nothing in their favour, and that henceforward they would apply
themselves to the study of the truth. Hitherto, said one of them, I
have put my trust in the old doctors; now, I will believe in the
new.—You should believe not in us, but in God's Word, exclaimed
Zwingle. It is Scripture alone that can never err! The sitting had
been long, and night was approaching. The president, Hofmeister of
Schaffhausen, stood up and said: Blessed be the Almighty and
Everlasting God for that in all things he has vouchsafed us the
victory; and he then exhorted the councillors of Zurich to pull down
all the images.
On Tuesday the assembly met again in order to discuss the doctrine
of the mass. Vadian was in the chair. My brethren in Christ, said
Zwingle, far from us be the thought that there is any deception or
falsehood in the body and blood of Christ.[485] Our only aim is to
show that the mass is not a sacrifice that one man can offer to God
for another, unless any one should maintain also that a man can eat
and drink for his friend.
Vadian having twice demanded if any there present
desired to uphold by Scripture the doctrine
impugned, and no one having replied, the canons](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-63-320.jpg)
![of Zurich, the chaplains, and many other ecclesiastics declared that
they agreed with Zwingle.
But scarcely had the reformers thus vanquished the partisans of the
old doctrines, than they had to contend against those impatient
spirits who call for sudden and violent innovations, and not for wise
and gradual reforms. The wretched Conrad Grebel rose and said: It
is not enough to have disputed about the mass, we must put an end
to its abuses.—The council will draw up an edict on the subject,
replied Zwingle. Upon this Simon Stumpf exclaimed: The Spirit of
God has already decided: why refer to the decision of the council?
[486]
The commander Schmidt of Küssnacht arose gravely, and in
language full of wisdom said, Let us teach Christians to receive
Christ in their hearts.[487] Until this hour, ye have all gone after idols.
The dwellers in the plain have run to the mountains, and those of
the mountains have gone to the plain; the French to Germany, and
the Germans to France. Now ye know whither ye ought to go. God
has combined all things in Christ. Ye noble citizens of Zurich! go to
the true source; and may Christ at length re-enter your territory, and
there resume his ancient empire.
This discourse made a deep impression, and no one stood up to
reply to it. Zwingle rose with emotion and said, Gracious lords, God
is with us......He will defend his cause. Now, then, forward in the
name of God. Here Zwingle's agitation became so great that he
could not proceed. He wept, and many joined their tears with his.
[488]
Thus ended the disputation. The presidents rose; the burgomaster
thanked them; and the aged warrior, turning to the council, said
gravely, with that voice which had so often been heard on the field
of battle, Now, then,......let us grasp the sword of God's Word, and
may the Lord prosper his work.](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-64-320.jpg)
![CHARACTER OF
THE SWISS
REFORMATION.
REVIVAL OF
LEARNING IN
ZURICH.
This dispute, which took place in the month of
October 1523, was decisive. The majority of the
priests, who had been present at it, returned full of
zeal to the different parts of the canton, and the
effect of these two days was felt throughout Switzerland. The
Church of Zurich, that had always preserved a certain independence
with respect to the see of Constance, was then entirely
emancipated. Instead of resting on the pope through the bishop, it
rested henceforward through the people on the Word of God. Zurich
recovered the privileges that Rome had taken from her. Town and
country vied with each other in interest for the work of the
Reformation, and the Great Council did but follow the movements of
the people. On all important occasions the city and the villages made
known their opinions. Luther had restored the Bible to the christian
world; Zwingle went farther, he restored their rights. This is a
characteristic feature of the Swiss Reformation. The maintenance of
sound doctrine was thus confided, under God, to the people; and
recent events have shown that a christian people can guard this
precious deposit better than priests and pontiffs.[489]
Zwingle did not allow himself to be elated by victory; on the
contrary, the Reformation, according to his wish, was carried on with
great moderation. God knows my heart, said he, when the council
asked his advice; He knows that I am inclined to build up, and not
to throw down. I am aware that there are timid souls who ought to
be conciliated; let the mass, therefore, for some time longer be read
on Sunday in all the churches, and let us avoid insulting the priests
who celebrate it.[490]
The council drew up an edict to this purport. Hottinger and
Hochrutiner, one of his friends, were banished from the canton for
two years, and forbidden to return without permission.
The Reformation at Zurich followed a prudent and
christian course. Daily raising this city more and
more, it surrounded her with glory in the eyes of all](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-65-320.jpg)
![THOMAS PLATER.
the friends of the Word of God. Accordingly those in Switzerland who
had saluted the new light that was dawning upon the Church felt
themselves powerfully attracted towards Zurich. Oswald Myconius,
expelled from Lucerne, had been residing for six months at
Einsidlen, when, as he was returning one day from a journey he had
made to Glaris,[491] oppressed by fatigue and by the heat of the
sun, he saw his little boy Felix running to meet him, and to tell him
that he had been invited to Zurich to superintend one of the schools.
Oswald could not believe such joyful tidings: he hesitated between
fear and hope.[492] I am thine, wrote he at last to Zwingle.
Geroldsek saw him depart with regret; gloomy thoughts filled his
mind. Alas! said he to Oswald, all those who confess Christ are
going to Zurich; I fear that one day we shall all perish there
together.[493] A melancholy presentiment, which by the death of
Geroldsek himself and of so many other friends of the Gospel, was
but too soon fulfilled on the plains of Cappel.
At Zurich, Myconius found at last a safe retreat. His predecessor,
who from his stature had been nicknamed at Paris the great devil,
had neglected his duties; Oswald devoted all his heart and strength
to their fulfilment. He explained the Greek and Latin classics, taught
rhetoric and logic, and the youth of the city listened to him with
delight.[494] Myconius was destined to become for the rising
generation what Zwingle was to those of riper years.
At first Myconius was alarmed at the advanced age
of the scholars under his care; but he had
gradually resumed his courage, and was not long in
distinguishing among his pupils a young man, twenty-four years of
age, from whose eyes beamed forth a love of study. Thomas Plater,
for such was his name, was a native of the Valais. In that beautiful
valley, where the torrent of the Viége rolls its noisy waters, after
issuing from the sea of ice and snow which encircles Mount Rosa,
between St. Nicholas and Stalden, on the lofty hill that rises on the
right bank of the river, may still be seen the village of Grächen. This](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-66-320.jpg)
![was Plater's birthplace. From the neighbourhood of these colossal
Alps was to proceed one of the most original of all the characters
that appeared in the great drama of the sixteenth century. At the
age of nine years, he had been placed under the care of a priest
who was his relation, by whom the little peasant was often so cruelly
beaten that he cried (as he tells us himself) like a kid under the
knife. He was taken by one of his cousins to attend the German
schools. But he had already attained the age of twenty years, and
yet, through running from school to school, he scarcely knew how to
read.[495] When he arrived at Zurich, he came to the determination
of gaining knowledge; and having taken his place in Oswald's school,
he said to himself, There shalt thou learn or die. The light of the
Gospel shone into his heart. One very cold morning, when he had no
fuel for the school-room stove, which it was his duty to keep up, he
thought to himself: Why should you want wood, while there are
many idols in the church! There was no one as yet in the church,
although Zwingle was to preach, and the bells were already
summoning the congregation. Plater entered very softly, laid hold of
an image of St. John that stood upon an altar, and thrust it into the
stove, saying: Down with you, for in you must go. Most assuredly
neither Myconius nor Zwingle would have sanctioned such a
proceeding.
It was in truth by better arms than these that incredulity and
superstition were to be combated. Zwingle and his colleagues had
given the hand of fellowship to Myconius; and the latter daily
expounded the New Testament in the church of Our Lady before an
eager and attentive crowd.[496] Another public disputation, held on
the 13th and 14th of January 1524, had again proved fatal to Rome;
and in vain did the canon Koch exclaim: Popes, cardinals, bishops,
councils—these are my church!
Everything was making progress in Zurich; men's minds were
becoming more enlightened, their hearts more decided, and the
Reformation was increasing in strength. Zurich was a fortress gained](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-67-320.jpg)
![DIET OF
LUCERNE.
CHAPTER IV.
Diet of Lucerne—Hottinger arrested—His Death—Deputation
from the Diet to Zurich—Abolition of religious Processions—
Abolition of Images—The Two Reformations—Appeal to the
People.
The adversaries were aware of what might be the
consequences of these changes in Zurich. They felt
that they must now decide upon striking a vigorous
blow. They had been silent spectators long enough. The iron-clad
warriors of Switzerland determined to rise at last; and whenever
they arose, the field of battle had been dyed with blood.
The diet had met at Lucerne; the clergy were endeavouring to excite
the chief council of the nation in their favour. Friburg and the Forest
Cantons proved their docile instruments; Berne, Basle, Soleure,
Glaris, and Appenzel were undecided. Schaffhausen was inclining
towards the Gospel; but Zurich alone stood forward boldly in its
defence. The partisans of Rome urged the assembly to yield to their
demands and prejudices. Let the people be forbidden, said they,
to preach or repeat any new or Lutheran doctrine in private or in
public, and to talk or dispute about such things in taverns and over
their wine.[497] Such was the ecclesiastical law they were desirous
of establishing in the confederation.
Nineteen articles were drawn up to this effect, approved of by all the
states, except Zurich, on the 26th of January 1523, and sent to all
the bailiffs with orders to see that they were strictly observed:
which caused great joy among the priests, says Bullinger, and
great sorrow among believers. A persecution, regularly organized
by the supreme authority of the confederation, was about to begin.](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-69-320.jpg)
![HOTTINGER
ARRESTED.
HOTTINGER'S
MARTYRDOM.
One of the first who received the mandate of the
diet was Henry Flackenstein of Lucerne, bailiff of
Baden. Hottinger, when banished from Zurich for
pulling down the crucifix of Stadelhofen, had retired to this bailiwick,
where he had not concealed his opinions. One day, as he chanced to
be dining at the Angel tavern in Zurzach, he had said that the priests
wrongly interpreted Holy Scripture, and that man should put his
trust in God alone.[498] The landlord, who was continually going in
and out to bring bread or wine, listened to what appeared to him
such very extraordinary language. Another day, Hottinger paid a visit
to his friend John Schutz of Schneyssingen. After they had eaten and
drunk together, Schutz asked him: What is this new faith that the
Zurich pastors are preaching? They preach, replied Hottinger,
that Christ was sacrificed once for all Christians; that by this one
sacrifice he has purified and redeemed them from all their sins; and
they show by Holy Scripture that the mass is a lie.
After this (in February 1523), Hottinger had quitted Switzerland, and
gone on business to Waldshut, on the other side of the Rhine.
Measures were taken to seize his person, and about the end of the
same month the poor unsuspecting Zuricher, having recrossed the
river, had scarcely reached Coblentz, a village on the left bank of the
Rhine, before he was arrested. He was taken to Klingenau, and as
he there frankly confessed his faith, the exasperated Flackenstein
said: I will take you to a place where you will find people to make
you a suitable answer.
In effect, the bailiff conducted him successively before the judges of
Klingenau, before the superior tribunal of Baden, and, since he could
find no one who would declare him guilty, before the diet sitting at
Lucerne. He was firmly resolved to seek judges who would condemn
his prisoner.
The diet lost no time, and condemned Hottinger to
be beheaded. When informed of his sentence, he
gave glory to God: That will do, said James](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-70-320.jpg)
![Troger, one of his judges, we do not sit here to listen to sermons.
You can have your talk some other time. He must have his head
taken off this once, said the bailiff Am Ort, with a laugh; if he
should ever get it on again, we will all embrace his faith. May God
forgive all those who have condemned me, said the prisoner. A
monk then presented a crucifix to his lips, but he put it away,
saying: It is in the heart that we must receive Jesus Christ.
When he was led out to execution, many of the spectators could not
refrain from tears. I am going to eternal happiness, said he,
turning towards them. On reaching the place where he was to die,
he raised his hands to heaven, exclaiming: Into thy hands, O my
Redeemer, I commit my spirit! In another minute his head rolled
upon the scaffold.
The blood of Hottinger was hardly cold before the enemies of the
Reformation seized the opportunity of still further inflaming the
anger of the confederates. It was in Zurich itself that the mischief
should be crushed. The terrible example that had just been given
must have filled Zwingle and his partisans with terror. Another
vigorous effort, and the death of Hottinger would be followed by
that of the Reform......The diet immediately resolved that a
deputation should be sent to Zurich, calling upon the councils and
the citizens to renounce their faith.
The deputation received an audience on the 21st of March. The
ancient christian unity is broken, said the deputies; the disease is
gaining ground; already have the clergy of the four Forest Cantons
declared, that unless the magistrates come to their aid, they must
discontinue their functions. Confederates of Zurich, join your efforts
to ours; stifle this new faith;[499] dismiss Zwingle and his disciples,
and then let us all unite to remedy the injuries that have been
inflicted on the popes and their courtiers.
Thus spoke the adversaries: and what would the citizens of Zurich
do? Would their hearts fail them? Had their courage cooled with the
blood of their fellow-citizen?](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-71-320.jpg)
![ABOLITION OF
PROCESSIONS
AND IMAGES.
Zurich did not leave her friends or enemies long in suspense. The
council announced calmly and nobly that they could make no
concessions in what concerned the Word of God; and then
proceeded to make a still more forcible reply.
Ever since the year 1351, it had been customary
for a numerous procession, each member of which
bore a cross, to go on Whitmonday on a pilgrimage
to Einsidlen to worship the Virgin. This festival,
which had been established in commemoration of the battle of
Tatwyll, was attended with great disorders.[500] The procession
should have taken place on the 7th of May. On the petition of the
three pastors it was prohibited by the council, and all the other
processions were reformed in their turn.
They did not stop here. The relics, that source of innumerable
superstitions, were honourably interred;[501] and then, at the
request of the three pastors, the council published a decree, to the
effect that honour being due to God alone, the images should be
removed from all the churches of the canton, and their ornaments
sold for the benefit of the poor. Twelve councillors, one from each
guild, the three pastors, the city-architect, blacksmiths, carpenters,
builders, and masons, went into the various churches, and having
closed the doors,[502] took down the crosses, defaced the frescoes,
whitewashed the walls, and took away the images, to the great
delight of the believers, who regarded this proceeding (says
Bullinger) as a striking homage paid to the true God. In some of the
country churches, the ornaments were burnt to the honour and
glory of God. Erelong the organs were taken down, on account of
their connexion with many superstitious practices; and a baptismal
service was drawn up, from which everything unscriptural was
excluded.[503]
The burgomaster Roust and his colleague, with their dying eyes
joyfully hailed the triumph of the Reformation. They had lived long](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-72-320.jpg)
![LUTHER AND
ZWINGLE.
The pagan element prevailed especially in that part of the christian
doctrine which relates to God. Paganism had corrupted in the
catholic church the idea of an infinite Deity, whose power, being
perfectly all-sufficient, is at work in all times and in all places. It had
established in the Church the reign of symbols, images, and
ceremonies; and the saints had become the demigods of popery.
Luther's reform was directed essentially against the
Jewish element. It was against this element that he
had been compelled to struggle, when an impudent
monk on behalf of the pope was making a trade of the salvation of
souls.
Zwingle's reform was particularly directed against the pagan
element. It was this element with which he had come in contact at
the temple of our Lady of Einsidlen, when a crowd, gathered
together from every side, fell down blindly before a gilded idol, as of
old in the temple of the Ephesian Diana.
The German reformer proclaimed the great doctrine of justification
by faith, and with it inflicted a death-blow on the pharisaical
righteousness of Rome. The reformer of Switzerland unquestionably
did the same; the inability of man to save himself forms the basis of
the work of all the reformers. But Zwingle did something more: he
established the sovereign, universal, and exclusive agency of God,
and thus inflicted a deadly blow on the pagan worship of Rome.
Roman-catholicism had exalted man and lowered God. Luther
lowered man, and Zwingle exalted God.
These two tasks, which were specially but not exclusively theirs,
were the complement of each other. Luther laid the foundation of
the building; Zwingle raised its crowning stone.
It was reserved for a still more capacious genius to impress, from
the banks of the Leman lake, these two characters conjointly upon
the Reformation.[504]](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-74-320.jpg)
![OPPOSITION.
But while Zwingle was thus advancing with mighty
strides to the head of the confederation, the
disposition of the cantons became daily more
hostile. The Zurich government felt the necessity of relying on the
people. The people, moreover, that is to say the assembly of
believers, was, according to Zwingle's principles, the highest power
to which there could be any appeal on earth. It was resolved to test
the state of public opinion, and the bailiffs were enjoined to demand
of all the parishes whether they were ready to suffer everything for
our Lord Jesus Christ, who, said the council, gave his life and his
blood for us sinners.[505] The whole canton had carefully followed
the progress of the Reformation in the city; and in many places, the
cottages of the peasants had become christian schools, wherein the
Holy Scriptures were read.
The proclamation of the council was read and enthusiastically
received in every parish. Let our lords, answered they, remain
fearlessly attached to the Word of God: we will aid them in
upholding it;[506] and if any one seeks to molest them, we will come
to their support like brave and loyal fellow-citizens. The peasantry
of Zurich showed then, that the strength of the Church is in the
christian people.
But the people were not alone. The man whom God had placed at
their head answered worthily to the call. Zwingle appeared to
multiply himself for the service of God. All that were enduring
persecution in the Helvetic cantons for the cause of the Gospel
addressed themselves to him.[507] The responsibility of public
affairs, the care of the churches, the anxieties of the glorious conflict
that was going on in every valley of Switzerland, weighed heavily
upon the evangelist of Zurich.[508] At Wittemberg, the news of his
courageous proceedings was received with joy. Luther and Zwingle
were two great lights, placed in Upper and Lower Germany; and the
doctrine of salvation, so powerfully proclaimed by both, filled the](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-75-320.jpg)
![A PATRIARCHAL
FAMILY.
were the first to break the federal unity. But threats and the rupture
of alliances were not enough. The fanaticism of the cantons called
for blood; and it was soon seen with what arms Rome intended
combating the Word of God.
One of Zwingle's friends, the worthy Œxlin,[509]
was pastor of Burg upon the Rhine, in the
neighbourhood of Stein. The bailiff Am-Berg, who
had appeared to listen to the Gospel with delight,[510] being
desirous of obtaining that bailiwick, had promised the leading men of
Schwytz to root out the new faith. Œxlin, although not within his
jurisdiction, was the first upon whom he exercised his severity.
About midnight, on the 7th of July 1524, some persons knocked at
the pastor's door; they were the bailiff's soldiers, who entered the
house, seized Œxlin, and carried him away prisoner, in defiance of
his cries. Thinking they meant to assassinate him, he cried Murder;
the inhabitants started from their beds in affright, and the village
soon became the scene of a frightful tumult, which was heard as far
as Stein. The sentinel on guard at the castle of Hohenklingen fired
the alarm-gun; the tocsin was rung, and the inhabitants of Stein,
Stammheim, and the adjoining places, were soon moving, and
inquiring of one another in the darkness what was the matter.
At Stammheim lived the deputy-bailiff Wirth, whose two eldest sons,
Adrian and John, both young priests full of piety and courage, were
preaching the Gospel with great unction. John especially abounded
in faith, and was ready to sacrifice his life for his Saviour. This was
truly a patriarchal family. Hannah, the mother, who had borne the
bailiff many children, and brought them up in the fear of the Lord,
was revered for her virtues throughout the whole district. At the
noise of the tumult in Burg, the father and the two eldest sons went
out like their neighbours. The father was indignant that the bailiff of
Frauenfeld should have exercised his authority in a manner contrary
to the laws of the country. The sons learned with sorrow that their
brother, their friend, the man whose good example they were](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-78-320.jpg)
![THE MOB IN THE
CONVENT OF
ITTINGEN.
delighted to follow, had been dragged away like a criminal. Each of
them seized a halberd, and in spite of the fears of a tender wife and
mother, the father and his two sons joined the band of citizens of
Stein with the determination of rescuing their pastor. Unhappily, a
number of those miscreants who make their appearance in every
disorder had joined the expedition; they pursued the bailiff's
officers; the latter, hearing the tocsin and the shouts of alarm,
redoubled their speed, dragging their victim after them, and soon
placed the river Thur between themselves and their pursuers.
When the people of Stein and Stammheim reached
the bank of the river, and found no means of
crossing, they halted, and resolved to send a
deputation to Frauenfeld. Oh! said the bailiff
Wirth, the pastor of Stein is so dear to us, that for his sake I would
willingly sacrifice my goods, my liberty, and my life.[511] The
populace, finding themselves near the Carthusian convent of
Ittingen, whose inmates were believed to have encouraged the
tyranny of the bailiff Am-Berg, entered the building and took
possession of the refectory. These miserable wretches soon became
intoxicated, and shameful disorders were the consequence. Wirth
vainly entreated them to leave the convent;[512] he was in danger of
being maltreated by them. His son Adrian remained outside the
cloister. John entered, but soon came out again, distressed at what
he had seen.[513] The drunken peasants proceeded to ransack the
wine-cellars and the store-rooms, to break the furniture, and burn
the books.
When the news of these disorders reached Zurich, some deputies
from the council hastened to the spot, and ordered all persons under
the jurisdiction of the canton to return to their homes. They did so
immediately. But a body of Thurgovians, attracted by the
disturbance, established themselves in the convent, for the sake of
its good cheer. On a sudden a fire broke out, no one knew how, and
the monastery was burnt to the ground.](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-79-320.jpg)
![THE DIET AT
ZUG.
THE WIRTHS
SURRENDERED
TO THE DIET.
Five days after this, the deputies of the cantons
met at Zug. Nothing was heard in the assembly but
threats of vengeance and of death. Let us march
with banners flying on Stein and Stammheim, said they, and put
the inhabitants to the sword. The deputy-bailiff and his two sons
had long been objects of especial dislike on account of their faith. If
any one is guilty, said the deputy of Zurich, he must be punished,
but according to the laws of justice, and not by violence. Vadian,
deputy of St. Gall, supported this opinion. Upon this the avoyer John
Hug of Lucerne, unable to contain himself any longer, exclaimed with
frightful imprecations:[514] The heretic Zwingle is the father of all
these insurrections; and you too, doctor of St. Gall, are favourable to
his infamous cause, and aid him in securing its triumphs......You
ought no longer to have a seat among us. The deputy of Zug
endeavoured to restore peace, but in vain. Vadian left the hall, and
as the populace had designs upon his life, he quitted the town
secretly, and reached the convent of Cappel by a circuitous route.
Zurich, intent on suppressing every disorder,
resolved to apprehend provisionally those persons
who were marked out by the rage of the
confederates. Wirth and his two sons were living
quietly at Stammheim. Never will the enemies of God be able to
vanquish His friends, said Adrian Wirth from the pulpit. The father
was warned of the fate impending over him, and was entreated to
flee with his two sons. No, answered he; I will wait for the
officers, putting my trust in God. And when the soldiers made their
appearance at his house, he said: My lords of Zurich might have
spared themselves all this trouble: if they had only sent a child I
should have obeyed their summons.[515] The three Wirths were
taken to Zurich and put in prison. Rutiman, bailiff of Nussbaum,
shared their fate. They were strictly examined, but nothing
reprehensible was found in their conduct.
As soon as the deputies of the cantons had heard of the
imprisonment of these four citizens, they required them to be sent to](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-80-320.jpg)
![EXAMINATION
AND TORTURE.
Baden, and ordered that in case of refusal their troops should march
upon Zurich and carry them off by force. To Zurich belongs the right
of ascertaining whether these men are guilty or not, said the
deputies of that state; and we have found no fault in them. On this
the deputies of the cantons exclaimed: Will you surrender them to
us? Answer yes or no, and not a word more. Two deputies of Zurich
mounted their horses, and rode off with all haste to their
constituents.
On their arrival, the whole town was in agitation. If the prisoners
were refused, the confederates would come and seek them with an
armed force; to give them up was consenting to their death.
Opinions were divided: Zwingle declared for their refusal. Zurich,
said he, ought to remain faithful to its constitution. At last it was
supposed a middle course had been found. We will deliver the
prisoners into your hands, said they to the diet, but on condition
that you will examine them solely with regard to the affair of
Ittingen, and not on their faith. The diet acceded to this
proposition, and on the Friday before St. Bartholomew's day (18th
August 1524) the three Wirths and their friend, accompanied by four
councillors of state and several armed men, quitted Zurich.
A deep concern was felt by all the city at the prospect of the fate
which awaited the two youths and their aged companions. Sobbing
alone was heard as they passed along. Alas! exclaims a
contemporary, what a mournful procession![516] The churches
were all filled. God will punish us! cried Zwingle. Let us at least
pray him to impart his grace to these poor prisoners, and to
strengthen them in the faith.[517]
On Friday evening the accused arrived at Baden,
where an immense crowd was waiting for them. At
first they were taken to an inn, and thence to
prison. They could scarcely advance, the crowd so pressed around to
catch a sight of them. The father, who walked in front, turned
towards his two sons, and observed to them meekly: See, my dear](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-81-320.jpg)
![children, we are (as the apostle says) men appointed to death; for
we are made a spectacle unto the world, and to angels, and to men
(1 Cor. iv. 9). Then, as he saw among the crowd his deadly enemy,
Am-Berg, the cause of all his misfortunes, he went up to him and
held out his hand, although the bailiff would have turned away:
There is a God in heaven who knows all things, said he calmly, as
he grasped his adversary's hand.
The examination began on the following day: the bailiff Wirth was
first brought in. He was put to the torture, without any regard to his
character or his age; but he persisted in declaring his innocence of
the pillage and burning of Ittingen. He was then accused of having
destroyed an image representing St. Anne. Nothing could be
substantiated against the other prisoners, except that Adrian Wirth
was married, and preached after the manner of Zwingle and Luther;
and that John Wirth had given the sacrament to a sick man without
bell and taper.[518]
But the more apparent their innocence, the greater was the fury of
their adversaries. From morning until noon they inflicted the cruelest
tortures on the old man. His tears could not soften his judges. John
Wirth was treated with still greater barbarity. Tell us, they asked
him in the midst of his anguish, whence did you learn this heretical
faith? From Zwingle or from any other person? And when he
exclaimed, O merciful and everlasting God, help and comfort me!
Where is your Christ now? said one of the deputies. When Adrian
appeared, Sebastian of Stein, the Bernese deputy, said to him:
Young man, tell us the truth; for if you refuse to do so, I swear by
the knighthood that I gained on the very spot where the Lord
suffered martyrdom, that we will open your veins one after another.
They then fastened the young man to a rope, and hoisted him into
the air: There, my little master, said Stein with a devilish sneer,
there is your wedding present;[519] alluding to the marriage of this
youthful servant of the Lord.](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-82-320.jpg)
![CONDEMNATION.
EXECUTION.
When the examination was ended, the deputies
returned to their cantons to deliver their report,
and did not meet again till four weeks after. The
bailiff's wife, the mother of the two priests, repaired to Baden,
carrying an infant child in her arms, to intercede with the judges.
John Escher of Zurich accompanied her as her advocate. Among the
judges he saw Jerome Stocker, landamman of Zug, who had been
twice bailiff of Frauenfeld: Landamman! said he, you know the
bailiff Wirth; you know that he has always been an upright
man.—You say the truth, my dear Escher, replied Stocker, he has
never injured anybody; fellow-citizens and strangers were always
kindly welcomed to his table; his house was a convent, an inn, and
an hospital;[520] and so, if he had committed robbery or murder, I
would have made every exertion to obtain his pardon. But seeing
that he has burnt Saint Anne, Christ's grandmother, he must
die!—The Lord have mercy upon us, exclaimed Escher.
The gates were now shut: it was the 28th September, and the
deputies of Berne, Lucerne, Uri, Schwytz, Unterwalden, Zug, Glaris,
Friburg, and Soleure, having proceeded to deliberate on their
judgment with closed doors, as was customary, passed sentence of
death on the bailiff Wirth, on his son John, who was the firmest in
his faith, and who appeared to have led away the others, and on the
bailiff Rutiman. Adrian, the second son, was granted to his mother's
tears.
The officers proceeded to the tower to fetch the prisoners. My son,
said the father to Adrian, never avenge our death, although we
have not deserved punishment. Adrian burst into tears. Brother,
said John, the cross of Christ must always follow his Word.[521]
After the sentence was read, the three Christians
were led back to prison; John Wirth walking first,
the two vice-bailiffs next, and a priest behind them.
As they were crossing the castle bridge, on which was a chapel
dedicated to St. Joseph, the priest called out to the two old men,](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-83-320.jpg)
![Fall down and call upon the saints. John Wirth, who was in front,
turned round at these words and said, Father, be firm. You know
that there is only one Mediator between God and man, the Lord
Jesus Christ.—Assuredly, my son, replied the old man, and by the
help of His grace I will continue faithful even to the end. Upon this
they all three began to repeat the Lord's Prayer, Our Father which
art in heaven, and so crossed the bridge.
They were next conducted to the scaffold. John Wirth, whose heart
was filled with the tenderest anxiety for his parent, bade him
farewell. My dearly beloved father, said he, henceforward thou art
no longer my father, and I am no longer thy son, but we are
brothers in Christ our Lord, for whose name we must suffer death.
[522] To-day, if it be God's pleasure, my beloved brother, we shall go
to Him who is the Father of us all. Fear nothing. Amen! replied
the old man, and may God Almighty bless thee, my beloved son
and brother in Christ!
Thus, on the threshold of eternity, did father and son take leave of
each other, hailing the new mansions in which they should be united
by everlasting ties. The greater part of those around them shed
floods of tears.[523] The bailiff Rutiman prayed in silence.
All three then knelt down in Christ's name, and their heads rolled
upon the scaffold.
The crowd, observing the marks of torture upon their bodies, gave
loud utterance to their grief. The two bailiffs left twenty-two children,
and forty-five grandchildren. Hannah was obliged to pay twelve
golden crowns to the executioner who had deprived her husband
and her son of life.
Thus blood, innocent blood, had been shed. Switzerland and the
Reformation were baptized with the blood of the martyrs. The great
enemy of the Gospel had done his work; but in doing it, his power
was broken. The death of the Wirths was to accelerate the triumphs
of the Reformation.](https://image.slidesharecdn.com/5604502-250520204317-be36bfdb/85/Nanofabrication-For-Smart-Nanosensor-Applications-Micro-And-Nano-Technologies-1st-Edition-Kaushik-Pal-Editor-84-320.jpg)
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- 6. Nanofabrication for Smart Nanosensor Applications
- 7. Nanofabrication for Smart Nanosensor Applications Edited by Kaushik Pal International and Inter University Centre for Nanoscience and Nanotechnology (IIUCN), School of Energy Materials, Mahatma Gandhi University, Kottayam, Kerala, India; Wuhan University, Wuchang District, Wuhan, Hubei Province, Republic of China Fernando Gomes Macromolecule Institute Professor Eloisa Mano; Civil Engineering Program, COPPE, Technology Center - University City, Federal University of Rio de Janeiro, Rio de Janeiro, Brazil
- 8. Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States © 2020 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library ISBN: 978-0-12-820702-4 For information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals Publisher: Matthew Deans Acquisitions Editor: Simon Holt Editorial Project Manager: Fernanda Oliveira Production Project Manager: Prem Kumar Kaliamoorthi Cover Designer: Greg Harris Typeset by SPi Global, India
- 9. Contributors M.M. Abdullah Promising Centre for Sensors and Electronic Devices (PCSED), Department of Physics, Faculty of Science and Arts, Najran University, Najran, Saudi Arabia Mostafa G. Aboelkheir Macromolecule Institute Professor Eloisa Mano, Technology Center - University City, Federal University of Rio de Janeiro, Rio de Janeiro, Brazil Gulzar Ahmad Department of Physics, University of Agriculture, Faisalabad, Pakistan Mazhar S. Al Zoubi Department of Basic Medical Studies, Yarmouk University, Irbid, Jordan Khalid M. Al-Batanyeh Department of Biological Sciences, Yarmouk University, Irbid, Jordan Norma Alias Center for Sustainable Nanomaterials, Ibnu Sina Institute for Scientific and Industrial Research, Universiti Teknologi Malaysia, Skudai, Malaysia Alaa A.A. Aljabali Department of Pharmaceutics and Pharmaceutical Technology, Faculty of Pharmacy, Yarmouk University, Irbid, Jordan Lorca Alzoubi Department of Pharmaceutics and Pharmaceutical Technology; Medicinal Chemistry and Pharmacognosy Department, Faculty of Pharmacy, Yarmouk University, Irbid, Jordan Nidhi Asthana National Centre of Experimental Mineralogy and Petrology, University of Allahabad, Allahabad, India Murthy Chavali Shree Velagapudi Rama Krishna Memorial College (PG Studies), Affiliated to Acharya Nagarjuna University, Nagaram; PG Department of Chemistry, Dharma Appa Rao College, Affiliated to Krishna University, Nuzvid; NTRC, MCETRC, Tenali, Andhra Pradesh, India Ramchander Chepyala FPC@DCU – Fraunhofer Project Centre for Embedded Bioanalytical Systems at Dublin City University, Dublin City University, Dublin, Ireland Shiplu Roy Chowdhury Tissue Engineering Centre, Faculty of Medicine, Universiti Kebangsaan Malaysia, Kuala Lumpur, Malaysia Vı́tor Corr^ ea da Costa Macromolecule Institute Professor Eloisa Mano, Technology Center - University City, Federal University of Rio de Janeiro, Rio de Janeiro, Brazil Michael K. Danquah Chemical Engineering Department, University of Tennessee, Chattanooga, TN, United States Krishna Chitanya Etika Department of Chemical Engineering, Birla Institute of Technology and Science, Pilani, Rajasthan, India Irene S. Fahim Industrial Engineering Department, Smart Engineering Systems Research Center (SESC), Nile University, Giza, Egypt Romildo Dias Toledo Filho Civil Engineering Program, COPPE, Technology Center - University City, Federal University of Rio de Janeiro, Rio de Janeiro, Brazil Sanjeev Gautam Netaji Subhas University of Technology, Delhi, India Ganesh Gollavelli Centre of Excellence of Nanotechnology; Department of Industrial Chemistry, College of Applied Sciences, Addis Ababa Science and Technology University, Addis Ababa, Ethiopia xv
- 10. Hazidatul Akma Hamlan Center for Sustainable Nanomaterials, Ibnu Sina Institute for Scientific and Industrial Research, Universiti Teknologi Malaysia, Skudai, Malaysia Ahmed M. Hassanein Nanoelectronics Integrated Systems Center (NISC), Nile University, Giza, Egypt Md Enamul Hoque Department of Biomedical Engineering, Military Institute of Science and Technology (MIST), Dhaka, Bangladesh Saiqa Ikram Bio/Polymer Research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi, India Purnima Jain Netaji Subhas University of Technology, Delhi, India Yasir Javed Department of Physics, University of Agriculture, Faisalabad, Pakistan Jaison Jeevanandam Department of Chemical Engineering, Curtin University, Miri, Sarawak, Malaysia Rocktotpal Konwarh Department of Biotechnology, College of Biological and Chemical Engineering; Centre of Excellence of Nanotechnology, Addis Ababa Science and Technology University, Addis Ababa, Ethiopia Samo Kralj Faculty of Natural Sciences and Mathematics, University of Maribor, Maribor, Slovenia Amit Kumar Dyal Singh College, University of Delhi, Delhi, India Enamala Manoj Kumar Bioserve Biotechnologies (India) Private Ltd., Hyderabad, Telangana, India Ahmed H. Madian Nanoelectronics Integrated Systems Center (NISC), Nile University, Giza; Radiation Engineering Department, NCRRT, Egyptian Atomic Energy Authority, Cairo, Egypt Tariq Mahbub Department of Mechanical Engineering, Military Institute of Science and Technology, Dhaka, Bangladesh Zaid Bin Mahbub Department of Mathematics and Physics, North South University, Dhaka, Bangladesh Ahmed Nawaz Department of Physics, University of Agriculture, Faisalabad, Pakistan Somia Nawaz Department of Physics, University of Agriculture, Faisalabad, Pakistan Mohammad A. Obeid Department of Pharmaceutics and Pharmaceutical Technology, Faculty of Pharmacy, Yarmouk University, Irbid, Jordan Kaushik Pal International and Inter University Centre for Nanoscience and Nanotechnology (IIUCN), School of Energy Materials, Mahatma Gandhi University, Kottayam, Kerala, India; Wuhan University, Wuchang District, Wuhan, Hubei Province, Republic of China Periasamy Palanisamy Department of Physics, Gnanamani College of Engineering, Namakkal, Tamil Nadu, India Suresh Babu Palanisamy Department of Biotechnology, College of Biological and Chemical Engineering, Addis Ababa Science and Technology University, Addis Ababa, Ethiopia Mamun Rabbani Department of Biomedical Physics and Technology, University of Dhaka, Dhaka, Bangladesh Lobna A. Said Nanoelectronics Integrated Systems Center (NISC), Nile University, Giza, Egypt M. Munir Sajid Department of Physics, Government College University, Faisalabad, Pakistan Naveed Akhtar Shad Department of Physics, Government College University, Faisalabad, Pakistan Bhasha Sharma Netaji Subhas University of Technology, Delhi, India Shreya Sharma Netaji Subhas University of Technology, Delhi, India xvi Contributors
- 11. Zayed Bin Zakir Shawon Department of Mathematics and Natural Sciences, BRAC University, Dhaka, Bangladesh Shashank Shekhar Netaji Subhas University of Technology, Delhi, India Asiya S.I. Bharath Institute of Higher Education and Research (BIHER), Bharath University, Chennai, Tamil Nadu, India Preeti Singh Bio/Polymer Research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi, India Fernando Gomes Macromolecule Institute Professor Eloisa Mano; Civil Engineering Program, COPPE, Technology Center - University City, Federal University of Rio de Janeiro, Rio de Janeiro, Brazil Murtaza M. Tambwala SAAD Centre for Pharmacy and Diabetes, School of Pharmacy and Pharmaceutical Science Ulster University, Coleraine, United Kingdom Sabu Thomas International and Inter University Centre for Nanoscience and Nanotechnology (IIUCN), School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala, India Contributors xvii
- 12. Editors’ biography Professor (Dr.) Kaushik Pal is an Indian citizen. He did his PH.D. in Physics (e.g. Nanotechnology, Multidisciplinary Sciences, Advanced Materials Science, Spectroscopy) from University of Kalyani, West-Bengal, India. Most recently he awarded with honorable DOCTOR OF SCIENCE (D.SC.) from Higher National Youth Skill Institute, Sepang, Selangor, Malaysia. He is the “Distinguish Research Professor” at Federal University of Rio de Janeiro, Brazil and acting as “Chair Professor and Group Leader, (Chief-Scientist & Faculty Fellow)” position in Wuhan University, Wuchang Dist., Hubei Province, Republic of China. Most recently, he has been a visiting professor working and contributing at the International and Inter University Centre for Nanoscience and Nanotechnology (IIUCN), School of Energy Materials, Mahatma Gandhi University, Kottayam, Kerala. He awarded international prestigious awards e.g. awarded the Marie-Curie Experienced Researcher (Postdoctoral Fellow) by the European Commission Network in Greece, and received the Brain Korea (BK-21) National Research Foundation Visiting Scientist Fellowship in South Korea. He was appointed Senior Postdoctoral Fellow at Wuhan University, China and within a year achieved the prestigious position of Chief-Scientist and Faculty (CAS) Fellow by the Chinese Academy of Science. He served as research professor (Group Leader and Independent Scientist), at Bharath University (BIHER), Research and Development, Chennai. His current research spans are focusing on e.g. Molecular Nanoscience and nanofabrication, functional materials, condensed matter physics (expt.), CNTs/graphene, liquid crystal, polymeric nanocomposite, switchable device, electron microscopy and spectroscopy, bioinspired materials, drug delivery, integration, switchable device modulation, stretchable electronics, supercapacitors, optoelectronics, green chemistry, and biosensor applications. He supervises a significant number of bachelor’s, master’s, PhD, and postdoctoral scholar’s theses, and his research has been published in several international top-tier journals from publishers e.g. Royal Chemical Society, Elsevier, Springer, IEEE, and InTech. He has edited 25 book chapters with significant publishers, contributed 10 review articles, and has edited several books for Elsevier, Apple Academic Press, and InTech. Dr. Pal is an expert group leader and the associate member of various scientific societies, organizations, and professional bodies. In his academic and professional research, he has received a number of significant xix
- 13. awards and prizes. He has been the chairperson of 30 national and international events, symposia, conferences, and workshops, and has contributed to 10 plenary, 28 keynote, and 30 invited lectures worldwide. Professor Fernando Gomes graduated in chemistry from the Federal University of Espı́rito Santo (1999), and received a Master in Engineering and Materials Science from the State University of the North Fluminense Darcy Ribeiro (2002), a PhD in Science and Technology of Polymers from the Federal University of Rio de Janeiro (2006), and a postdoctorate in the chemical engineering program at COPPE/UFRJ, Brazil. He is currently Associate Professor at the Macromolecules Institute at UFRJ, Collaborated Professor at the Civil Engineering Program at COPPE/UFRJ and Young Scientist in the State of Rio de Janeiro (FAPERJ-2015). He mainly works with polymeric nanocomposites obtained from renewable resources in three main lines: (I) in the field of environmental recovery, coordinating research projects focused on the use of renewable resources for the removal of oil in spills; (II) in the field of human health, coordinating projects that seek kinetic and spatial control of the drug release process; and (III) in the field of sensors, where he coordinates projects that seek to obtain plant fibers that conduct electricity for their use in sensors for intelligent devices. Supervisor of 103 undergraduate students; 28 M.Sc. students, 8 Ph.D. students and 5 Post Doc. Nowadays I am the supervisor of 4 undergraduate students; 2 M.Sc. students, 14 Ph.D. students and 2 Post Doc. Member of the editorial board of Current Applied Polymer Science (ISSN 2452-2716), Associate Editor of the MedCrave Online Journal (MOJ) Polymer Science (ISSN: 2574-9773), and Editor of the Academic Journal of Polymer Science. He also awarded Young Scientist of Rio de Janeiro State (FAPERJ 2011 and 2014), member of Post Graduate Program in Science and Technology of Polymers of the Federal University of Rio de Janeiro since 2008. Editors’ biography xx
- 14. CHAPTER 1 Introduction to nanomaterials and nanomanufacturing for nanosensors Tariq Mahbuba , Md Enamul Hoqueb a Department of Mechanical Engineering, Military Institute of Science and Technology, Dhaka, Bangladesh b Department of Biomedical Engineering, Military Institute of Science and Technology (MIST), Dhaka, Bangladesh 1.1 Nanosensors Sensors are devices used to detect the presence of a specific substance or to measure a physical property such as temperature, mass, or electrical or optical characteristics and produce a signal for recording or further postprocessing. The history of sensors is a long one. The first thermostat came into existence in the 1880s, and the first infrared sensor was developed in 1940. Nanosensors are similar to macrolevel sensors but have at least one dimension in nanoscale and can be used to measure signals available at that scale. Nanotechnology, with its rapid developments in recent years, has shown great potential in almost all industries. Various electronics industries have fueled these developments to satisfy their need for miniaturization, and the nanosensor field has taken advantage of these advances for its own development. A large volume of research has been conducted over the last two decades in the area of nanomaterials for wider applications, including nanosensors [1–10]. Since nanosensors can deal with signals produced at the nanoscale, the sample quantities needed are quite small and detection is very rapid. All of these qualities have helped the applications of various types of nanosensors in different fields, especially in the medical and homeland security fields. Gaining a clearer understanding of the special properties offered at the nanoscale by nanomaterials, evolution of the various techniques for nanomaterial production, and exploitation of the special properties of nanomaterials have all advanced nanosensor development. Nanofabrication for Smart Nanosensor Applications. https://doi.org/10.1016/B978-0-12-820702-4.00001-5 # 2020 Elsevier Inc. All rights reserved. 1
- 15. 1.1.1 Types of nanosensors During the short history of nanosensors, this technology has experienced substantial developments. Since a variety of nanosensors are available today, classification can be somewhat difficult. However, nanosensors can be classified based on two general factors: (1) structure and (2) application. Based on structure, nanosensors can be further classified into two groups: Optical nanosensors: Optical nanosensors use the sensitivity of fluorescence for qualitative and quantitative measurement. Electrochemical nanosensors: This class of nanosensor mainly detects electronic or chemical properties of a respective substance and transduces a signal. Recently, major developments have taken place in this type of nanosensor technology. Based on application, nanosensors can be classified into chemical nanosensors, nanoscale electrometers, nanobiosensors, deployable sensors, and so on. 1.1.2 Applications of nanosensors Nanosensors are gradually assuming roles in almost every aspect of human life. A number of sensors can detect the presence of hazardous materials or microorganisms in food, water, and air. These sensors are saving lives in different corners of the world. In the medical field nanosensors are having a huge impact: for example, a variety of nanosensors are being used in cancer detection, DNA and protein detection, and targeted drug delivery. Deployable sensors have found applications in homeland security. Various chemical sensors are now added to unmanned aerial vehicles to detect the presence of poisonous gas on the battlefield, to save the lives of soldiers. Various tagging systems employ RFID chips, which are also an application of nanosensors. 1.2 Nanomaterials for nanosensors For centuries the beauty of the 400 CE Lycurgus Cup and the strength and beauty of a Damascus steel blade have amazed people, but it has been only decades since we discovered the secret behind these extraordinary ancient artifacts: nanomaterials [11,12]. Nanomaterials are defined as those nanoparticles (NPs) that have at least one dimension in nanometer scale and that exhibit some special property that is not available in the bulk form of the same material. Though unknowingly used in several ancient artifacts, the modern-day extensive research, informed fabrication, and utilization of nanomaterials began in 1857, when Michael Faraday reported the synthesis of so-called “activated gold,” which was a colloidal solution 2 Chapter 1
- 16. of Au NPs [13]. Since that time, the use of nanomaterials has slowly but surely spread, due to their extraordinary properties associated with their size. Nanomaterials show extraordinary properties different than their bulk size because of their nanoscale dimension. The surface-to-volume ratio of nanomaterials is very high, which results in variations in chemical, mechanical, optical, and magnetic nature [14]. To explore the properties and applications of nanomaterials properly, it is judicious to classify them. However, several factors can be considered in classifying nanomaterials, such as physical and chemical properties, manufacturing process, dimensionality, uniformity, composition, and so forth [15]. From the point of view of this chapter, we classify nanomaterials into four classes based on their chemical composition: (1) carbon-based, (2) organic-based, (3) inorganic-based, and (4) composite-based nanomaterials. In the following sections, we discuss different nanomaterials that fall within these four categories and their applications, especially as nanosensors. At this point, a brief introduction to nanosensors may be very helpful for those new to this field. A sensor is a device that detects and responds to any change in its environment. Daily life is full of sensors, such as light sensors, rain sensors, lane assist in automobiles, smoke and fire alarm sensors, electrical sensors, and so forth. Nanosensors perform the same function, but on a much smaller scale (1–100 nm), capable of sensing pathogens, viruses, molecules, or even a single chemical element. The main advantages of nanosensors are the minute sample quantities required, speed, portability, and low cost in mass production, among others. The history of nanosensors is only decades old. Since the beginning of the current century, the world has experienced a rapid escalation of production and use of nanosensors as a consequence of two factors. First, nanosensors, due to their excellent performance, have convinced the world that they can be successfully used in different applications varying from the food industry, fire and hazardous gas detection, to various critical fields like military and advanced medical applications. Secondly, there is a tremendous advancement of different manufacturing processes used for manufacturing nanosensors, increased availability, and development of new nanomaterials and more clear understanding of nanoscale phenomena [16]. 1.2.1 Properties of nanomaterials for nanosensors Nanomaterials, due to high surface-to-volume ratio and the manufacturing process, offer some extraordinary properties that can be explored to produce various applications in drug manufacturing, environmental sensing and protection, materials and manufacturing industries, electronics, energy harvesting, etc. A few properties that are relevant to nanosensors are briefly described in the following sections. Introduction to nanomaterials and nanomanufacturing for nanosensors 3
- 17. 1.2.1.1 Optical properties Nanomaterials offer some excellent optical properties, such as light absorption, color, light emission, and magnetooptical properties due to their sizes; these properties are quite different from their bulk properties and make nanomaterials a good choice for optical nanosensors. One of the first nanosensors devised to measure inhomogeneous pH distribution in three- dimensional resolution was fluorescein-based, using a polyacrylamide nanoparticle incorporated with pH-sensitive fluorescein-acrylamide [17]. Fluorescent nanosensors can respond to some specific stimuli provided by the surrounding environment and transduce a fluorescence signal to the detector to sense environmental changes. These nanosensors are used to make oxygen sensors [18] and temperature sensors. The localized surface plasmon (LSP) effect of the noble metal nanoparticle is a current active field of research for making nanosensors (Fig. 1.1). When a nanoparticle confines surface plasmon, due to its dimension, comparable to the wavelength of light, the free electron of the nanoparticle participates in the collective oscillation. This phenomenon is called localized surface plasmon (LSP) [19]. The LSP effect greatly enhances the electric field near the nanoparticle surface and at the plasmon resonant frequency the particle shows maximum optical extinction. A number of gas sensors [20,21] and pH sensors [22,23] are manufactured using LSP. 1.2.1.2 Electronic properties Nanomaterials can offer quite exceptional electronic properties that originate from the shape and structure of the nanomaterial. When talking about exceptional electronic properties, the name that comes to mind first is graphene. Graphene has a single-layer 2D honeycomb structure in which both surfaces are available for molecule absorption. The structure causes the electron seemly to be massless [24] and the electron moves at an average speed which is 300 times less than the speed of light at vacuum. This allows many relativistic events to be e- e- e- e- e- e- e- e- e- e- e- Electron cloud Light wave Electric field e- Fig. 1.1 Schematic diagram of localized surface plasmon effect. 4 Chapter 1
- 18. observable without a particle accelerator [15]. The carbon nanotube (CNT) in which graphene acts as a building block also offers some excellent electronic properties. The sp2 hybridization of the carbon orbitals in the CNT leaves free electrons at the surface of the tubes, which yields these excellent properties. CNT can show metallic, semiconducting, or insulating behavior, which can be controlled by controlling the diameter, chirality of the CNT, and any functionalization or doping done on CNT [25]. Nanosensors using these properties detect using two methods: (a) current enhancement, and (b) current inhibition. Various electrochemical sensors have been developed for different purposes, such as detecting dopamine [26], histamine [27], bacteria [28], glucose [29], and so forth, using the electronic properties of nanomaterials. 1.2.1.3 Magnetic properties Due to the uneven arrangement and orientation of electrons in nanomaterials, and their size, nanomaterials exhibit excellent magnetic properties too. Magnetic properties of nanomaterials are becoming a center of interest in different branches of engineering, including but not limited to different types of catalysis, biomedicine for cancer treatment, magnetic fluids, nuclear magnetic resonance imaging (NMR), magnetic resonance imaging (MRI), and environmental remediation [30]. Magnetic nanosensors use different techniques to perform detection, like the effect magnetic particles exert on water proton relaxation rates, by determining the relaxation of the magnetic moment within the magnetic particle, by detecting the presence of a magnetic particle using magnetoresistivity, etc. Koh et al. explain different biosensors using the previously mentioned methods. The following figures show schematic representations of the three procedures [31]. Fig. 1.2A represents how magnetic nanoparticles dephase the protons of water for a better MRI scan. Magnetic particles generally stay dispersed in a liquid solvent. But when a target analyte (triangle in Fig. 1.2A) appears, the dispersed nanoparticles produce an aggregate around it and eventually this aggregate dephases the spins of water protons more efficiently than the dispersed state. This reduces the spin-spin relaxation time T2 to produce a better MRI image. Fig. 1.2B shows the application of magnetic moment relaxation within a magnetic nanoparticle for bacterial detection. The type of relaxation used here is Neel relaxation. In the upper figure A, a magnetic field is applied to the nanoparticles and they orient themselves along the applied field. Some of the nanoparticles are bonded with the target bacteria. Later, in figure B, the field is removed and many of the particles experience Brownian relaxation and randomly orient in a different direction. But the nanoparticles bonded to the bacteria cannot undergo Brownian relaxation and rather show Neel relaxation, which is comparatively slower and detectable. The superconducting quantum interference devices (SQUIDs) detect the slower Neel relaxation and bacterial detection is performed. Fig. 1.2C shows the operation of a magnetoresistive sensor. The basic principle that a magnetoresistive sensor applies is that the magnetic particle bonds to the surface of the sensor and eventually alters its magnetic field. This causes a change in sensor current and the detection is performed. There are two mechanisms through which magnetic particles bind to the sensor surface: (i) direct labeling, and (ii) indirect labeling. In the case of direct labeling, magnetic nanoparticles directly Introduction to nanomaterials and nanomanufacturing for nanosensors 5
- 19. Sensor functionalization Linker incubation Capture antibody BSA Analyte Biotinylated antibody Magnetoresistive Sensor Streptavidin-coated magnetic nanotag Nanotag-based quantification Analyte incubation Capture antibody BSA Control Control Control Control Probe Target bacterium Magnetic particle A A C B D (A) (B) (C) B Antibody Probe Probe Probe Fig. 1.2 (A) Magnetic property of nanomaterials used for sensing applications [31]. (B) Magnetic property of nanomaterials used for sensing applications (working principle of SQUID) [31]. (C) Schematic diagram of giant magnetoresistive sensor application [31].
- 20. bindtothesurfacefunctionality,whileforindirectlabelingasandwichassayiscreated.Fig.1.2C schematically shows the detection of protein by creating a sandwich assay. Nanoparticles possess many more extraordinary properties including mechanical and thermal properties, but these properties are not very important to the current subject point of view. 1.2.2 Different nanomaterials for nanosensors To discuss and understand the use of nanomaterials in developing nanosensors, it is helpful to classify them into different groups. But classifying nanomaterials into different groups is a formidable job. Nanomaterials can be prepared using a number of bottom-up processes such as cutting, ball milling, extruding, chipping, pounding, and many more [32] and top-down approaches [33] resulting in different types of structures, with different surface coatings, which can cause the classification to be obscure. For that reason, here we do not put too much concentration on classifying nanomaterials, but rather we shed some light on some commonly used nanomaterials. A schematic representation of carbon-based nanomaterials is provided in Fig. 1.3 for a better understanding of the diverse nature of nanomaterials. Fig. 1.3 Different carbon-based nanomaterials [34]. Introduction to nanomaterials and nanomanufacturing for nanosensors 7
- 21. 1.2.2.1 Carbon nanotube First developed in 1991 by Iijima, the carbon nanotube (CNT) is by far the most-used carbon- based nanomaterial. It is a cylinder having diameters from fractions to tens of nanometers and a length up to several micrometers. There exist both single-walled (SWCNTs) and multiwalled (MWCNTs) nanotubes that are formed by single and multiple layers of graphene lamella, respectively, seamlessly rolled up [14]. The CNT is commonly produced by a chemical vapor deposition (CVD) technique or vaporization of graphite in a furnace in an inert (argon gas) atmosphere. The CNT possesses some excellent properties, such as high strength caused by its hexagonal structure, exceptional electronic properties caused by the free electron available after sp2 hybridization, and ease of functionalization with different organic molecules that provide a means to interact selectively with different analytes. This easy-to-functionalize property enables CNTs to be used as probe tips for a wide range of chemical and biological applications. The main application of the CNT as a sensor is in the field-effect transistor (FET). Though the CNT is robust and inert in nature, it is highly sensitive to chemical doping. A wide variety of FETs are manufactured by chemical doping of CNTs. Fig. 1.4 shows a schematic diagram of CNT-FET. CNT-FETs are used to detect different types of gases like CO2, NH3, O2 [35], NO2, N2 [36], and so forth. CNT-FETs are also used for detection in biological science. A variety of sensors have already been developed by researchers for detecting proteins [37], enzymes, and β-D glucose [38], among others. 1.2.2.2 Nanowires Nanowires are also commonly used in making nanosensors, just like CNTs. Nanowires are produced through a variety of processes such as chemical vapor deposition (CVD), laser ablation, alternating current electrodeposition, and thermal evaporation [25]. Nanowires can be made up of different materials but silicone nanowires have drawn recent interest. The electrical properties and sensitivity of silicon nanowires can be tuned properly and reproducibly by Si SiO2 Gate Drain Source CNT or net of CNTs Fig. 1.4 Schematic diagram of CNT-FET [25]. 8 Chapter 1
- 22. controlling the nanowire diameter and dopant concentration [39]. Hahm et al. produced a SiNW-based sensor to detect DNA and DNA mismatches [40] in which the silicon nanowire devices were modified with peptide nucleic acid receptors. The gold nanocluster catalyzed chemical vapor deposition technique was employed to prepare the nanowires used in this sensor. The nanowires were assembled on the sensor along with peptide nucleic acid. A schematic diagram of the device is given in Fig. 1.5 [40]. When a wild type or mutant DNA is introduced to the sensor via the microfluidic channel, peptide nucleic acid binds with the DNA and creates a tiny change of the conductance of the silicon nanowire. This change of conductance enables the sensor to differentiate between fully complementary or mismatched DNA. Nanowires are also used to make gas sensors that can qualitatively detect NH3. 1.2.2.3 Nanoparticles Nanoparticles are a commonly used nanomaterial not only in sensor manufacturing but also in many other engineering applications. Although the name suggests a nanoparticle is a single molecule, NPs are not just simply one molecule but rather a combination of three layers. These layers are (a) the surface layer, which can be used to functionalize the nanoparticle; (b) the shell layer; and (c) the core, which is essentially the central portion of the NP [41]. Nanoparticles are PNA (B) (C) (A) PNA-DNA Fig. 1.5 (A) Schematic of a sensor device consisting of a SiNW (yellow) and a microfluidic channel (green), where the arrows indicate the direction of sample flow. (B) The SiNW surface with PNA receptor. (C) PNA-DNA duplex formation [40]. Introduction to nanomaterials and nanomanufacturing for nanosensors 9
- 23. prepared using various approaches like bottom-up synthesis, including but not limited to chemical vapor deposition (CVD), spinning, plasma spraying synthesis, and laser pyrolysis, and top-down approaches, including but not limited to mechanical milling, sputtering, and laser ablation. Nanoparticles can be classified into various classes, for example (a) carbon-based nanoparticle, (b) metal nanoparticle, (c) ceramic nanoparticle, (d) semiconductor nanoparticle, and (e) polymer nanoparticle. Fig. 1.6 shows the SEM and TEM images of different nanoparticles (NPs). Nanoparticles offer exceptional electronic, optical, magnetic, mechanical, and thermal properties. Among these, the first three properties are exploited to produce many sensors. Metallic nanoparticles are used to enhance surface plasmon resonance sensitivity. The surface plasmon resonance technique is used in many optical sensors described in the previous section. Palladium nanoparticles deposited on etched porous silicon are used to detect hydrogen in the environment, while carbon electrodes with deposited gold nanoparticles are used to detect copper in water [16]. Fig. 1.6 SEM image of (A) nonporous MA-SiO2 NPs, (B) mesoporous MA-SiO2 NPs. TEM images of (C) nonporous MASiO2 NPs and (D) mesoporous MA-SiO2 NPs [18]. 10 Chapter 1
- 24. 1.2.2.4 Fullerenes Due to their unique properties, fullerenes are now receiving major attention from the scientific community. Fullerenes have a hexagonal ground state with sp2 hybridization and are highly symmetric with 120 symmetry operations. Fullerenes are very strong and bounce back to their initial shape after deformation [15]. Among other properties, fullerenes have high surface-to- volume ratio, high electron affinity, and a hydrophobic surface. A good number of sensors have been developed using fullerenes along with other nanomaterials to form nanocomposites. Brahman et al. developed a C60-MWCNT nanosensor for detecting pyruvic acid [42]. Another electrochemical sensor was developed by the same researcher that uses a fullerene, copper nanoparticle-fullerene, MWCNT composite to detect paracetamol [43]. Here they used a pretreated carbon paste electrode (CPE) on which fullerene-C60 and multiwalled carbon nanotubes (MWCNTs) were dropped to produce a modified CPE. Later copper nanoparticles (CuNPs) were deposited electrochemically on the modified CPE and a nanocomposite film of CuNPs/C60-MWCNTs/CPE was formed. This composite showed excellent performance in paracetamol recognition and determination. 1.3 Nanomanufacturing Nanomanufacturing is the process of manufacturing nanomaterials or various structures in nanoscale for different applications. This can be considered an updated version of micromanufacturing/microfabrication in which the dimension at which the manufacturing is done is several orders smaller. The term nanofabrication is sometimes used as analogous to nanomanufacturing,butsometimesnanofabricationrefersmore toa nanoscalefabricationprocess that is used in funded research work and nanomanufacturing is used to refer to manufacturing productsforrevenuegeneration[44].However,inthischapter,wearenotveryconcernedaboutthe lack of a specific definition for the term nanomanufacturing; rather, we provide a general idea of current prevailing nanomanufacturing processes for manufacturing nanosensors. A schematic diagram of an ultrasonic assisted nanomanufacturing process is shown in Fig. 1.7. In the figure, various possible types of vibration configurations are shown for the machining process. The research group reported that this method can be successfully applied to produce 3D nanoobjects of discrete height levels and also of continuously varying height [45]. 1.3.1 Nanomanufacturing processes The main drive behind the nanomanufacturing process is the ever-increasing hunger of the electronics industry to obtain smaller sizes. Currently, a microchip that we can hold on our fingertips can store gigabytes of data. To satiate this hunger, different types of nanomanufacturing processes have been developed that can be classified into three broad Introduction to nanomaterials and nanomanufacturing for nanosensors 11
- 25. approaches: (1) top-down approach, (2) bottom-up approach, and (3) molecular assembly. These three approaches are briefly described in the following sections. 1.3.1.1 Top-down approach David, the famous statue created by Michelangelo, is one of the most notable sculptures of all time. However, if someone asks how David or any other stone or wooden sculpture is made, the answer is simple: a large block of stone or wood is gradually trimmed to the final shape. This is a top-down approach. In nanomanufacturing, this approach is used when a large block of material is taken and, by machining, the material is removed little by little till the final shape is obtained. The top-down approach consists of two steps: (1) nanolithography and (2) transfer of pattern. In nanolithography, the desired pattern is created on a special type of sacrificial layer called a resist. There are a number of nanolithography techniques, such as photolithography, electron beam lithography, X-ray lithography, soft lithography, and so forth. The basic idea in every case is similar. First, a layer of resist is applied to the substrate. Then with the help of a pattern the photoresist is exposed to an energy source: for example, photolithography uses ultraviolet rays while electron beam lithography uses an electron beam and X-ray lithography uses an X-ray. Due to this patterned exposure, the resist undergoes a chemical process and the chemical and mechanical properties vary throughout the whole coating. Later, some part of the resist (exposed or unexposed part) is removed, depending on the positive or negative resist, and a pattern is created. Now the metal layer (SiO2 in Fig. 1.8) is ready for the etching process. After etching the pattern created by the resist is removed mechanically or chemically. The simplified process is graphically represented in Fig. 1.8. Circular vibration Feed (A) (B) (C) (D) Ultrasonic vibration f < fr f >> fr Fig. 1.7 (A) Ultrasonic assisted AFM-based nanomanufacturing process. (B) Low-frequency tip-sample interacting. (C) Ultrasonic tip-sample interaction while the tip is stationary. (D) SEM image of AFM tip [45]. 12 Chapter 1
- 26. Currently, the top-down approach prevails as the most popular and widely used approach in the nanomanufacturing industry. But the other two approaches are also beginning to have their own positions in nanomanufacturing. 1.3.1.2 Bottom-up approach The bottom-up approach is similar to building up a house brick by brick (Fig. 1.9). In this approach, the final structure is developed by assembling or joining small components, even molecules. Typically there are several bottom-up approaches, including physical or chemical vapor deposition, contact printing, imprinting, assembly and joining, and coating. The bottom- up approach has high potential in healthcare and medical applications. Carbon nanomaterials and carbon nanotubes can be used for a bottom-up approach and a device that can work on an individual cell can be nanofabricated using this approach (Fig. 1.9). 1.3.1.3 Molecular self-assembly Molecular self-assembly is the newest approach, in which the components, especially molecules, assemble themselves in the desired fashion to produce a nanoobject without the direction of an outside force. This process involves different properties such as shape, surface Substrate x-ray x-ray Photoresist Pattern/Mask Development before Etching Etching and stripping of photoresist Negative photoresist Positive photoresist SiO2 layer Substrate Fig. 1.8 Image of positive and negative resist in X-ray lithography. Introduction to nanomaterials and nanomanufacturing for nanosensors 13
- 27. properties, charge, polarizability, and magnetic dipole of the molecule to drive them to assemble together to form a particular structure. This is still a growing field and various developments are required before this approach is used in industry. Fig. 1.9 Bottom-up approach used in tissue engineering. (A) Complementary oligonucleotides were covalently coupled to the surfaces of different cells by click chemistry. (B–E) Two nonadherent cell types were mixed, and did not aggregate if their surfaces were modified with: (B) no oligonucleotides, (C) noncomplementary oligonulceotides. However, specific aggregation was observed if the cell surfaces were modified with complementary oligonucleotides (D, E). (F) Aggregation of DAPI stained cells (blue), with the central cell modified with fluorescein-conjugated oligonucleotides (green). (G) 3D reconstruction of an aggregate of Texas Red-labeled (red) and fluorescein-labeled cells (green) [46]. 14 Chapter 1
- 28. 1.4 Nanomanufacturing processes for nanosensors Nanomanufacturing can be defined as the ability to measure, predict, and manufacture on atomic and molecular scales and to exploit the unique properties shown by nanomaterials at that scale. Nanomanufacturing is a multidisciplinary field and researchers from various backgrounds are contributing to it. Fig. 1.10 shows graphically how researchers from different, but strongly related, research disciplines approach the science of the nanomanufacturing process. However, in this chapter we are only concerned with the nanomanufacturing processes used in manufacturing nanosensors. In the previous section, it was shown that there are two broad approaches, namely the bottom-up approach and the top-down approach. A detailed discussion of these two approaches is not necessary here, as they have already been described. In this current section, we will discuss several nanomanufacturing processes that are commonly used in nanosensor preparation. Physics Surface plasmon reasonance, Molecular electronics etc. Food industry Antibacterial nanoparticle, Nano food packaging material etc. Medicine Biocompatible Nanoparticle, Nanobots etc. for diagnosis Energy and power Polycrystalline for solar cell, Thermocell, etc. Optics and engineering Surface plasmon polaritons, Photodetectors, Optoelectronics Materials Nanotubes Nanocomposite, Nanoparticle in different application Fig. 1.10 Nanomanufacturing approached from different disciplines. Introduction to nanomaterials and nanomanufacturing for nanosensors 15
- 29. 1.4.1 Electron beam lithography Lithography is the technique of transferring patterns from one medium to another medium with the help of a material called resist. Previously, different particle beams were used in lithography, but with the application of the electron beam, nanometer-sized features have become possible. Due to its precious pattern-making capability, electron beam lithography (EBL) is frequently used in sensor manufacturing. Among various electron beam lithography technologies, here we will discuss direct writing EBL technology due to its simplicity and frequent use. In direct writing EBL, a finely focused Gaussian round beam is used that moves with the wafer and a single pixel of the wafer is exposed at a time (Tseng et al., 2003). The basic setup for direct writing EBL is shown in Fig. 1.11. The beam creates a desired pattern on the wafer and, supported with the etching and deposition process, a very complicated nanostructure can be produced. Though this technique is very cheap and popular, its main drawback is the large time requirement. However, researchers are trying to improve the technology to make this process more applicable. 1.4.2 Focused ion beam lithography Focused ion beam lithography is another nanomanufacturing technique similar to electron beam lithography, but here ions are used to perform the lithography instead of an electron beam (Fig. 1.12). Since the ions are much heavier than electrons, focused ion beam lithography can be more efficient than electron beam lithography. The focused ion beam lithography technique also has some different classifications, but direct writing is the simplest and cheapest one and hence that is the one discussed here. In this method, a resist is not used and by varying the distance of the wafer, the dose of ions can be controlled, resulting 1 2 3 6 5 (A) (B) NA + + - 4 Fig. 1.11 (A) Conceptual diagram of DiVa: 1. Planar cathode, 2. Shaping apparatus, 3. Shaping apparatus second set, 4. deflector, 5. Wafer, 6. Deflection plates; (B) Experimental DiVa apparatus at Stanford University [47]. 16 Chapter 1
- 30. in a trench of different depth on the wafer. Heavy-ion species such as Ga+ and Au+ can also be used in this lithography to produce a stronger effect. When a beam is passed over the wafer, a trench having inverse Gaussian shape is obtained. With increase in strength, the trench becomes more sharp, narrow, and V-shaped [48]. Multiple passes are also possible to create complicated shapes. 1.4.3 X-ray lithography X-ray lithography (XRL) is an advanced version of optical lithography in which shorter wavelengths are used. In this method, a special type of mask is used with different local X-ray absorption areas to define the pattern. This pattern is replicated on an X-ray sensitive material called a resist, which is previously deposited on a substrate (usually a silicon wafer). When the X-ray passing through the pattern falls on the resist, it may cause cross-linking (for negative resists) or bond breaking (for positive resists), depending on the chemical nature of the resist. After exposure, the whole thing is dipped in a specific solvent and, depending on its nature, either the exposed area resist will dissolve and create a pattern or vice versa. The other part of the resist will stay intact [49]. This is how X-ray lithography creates nanopatterns on the substrate. 1.5 Conclusions and future directions The beginnings of nanotechnology are popularly dated back to the famous lecture given by Nobel laureate Richard Feynman, “There’s Plenty of Room at the Bottom,” in 1959. But the application of this technology became evident at the beginning of 1980. Since then, nanotechnology has gained huge momentum and currently is being applied in various aspects of Fig. 1.12 Schematic diagram of focused ion beam lithography. Introduction to nanomaterials and nanomanufacturing for nanosensors 17
- 31. our daily life. In this chapter, we mainly focused on different nanomaterials that are used in making nanosensors, along with different nanomanufacturing processes used to develop those sensors. In nanoscale, materials exhibit some extraordinary properties that are not visible in bulk form and nanosensors take advantage of those properties. Nanosensors are gradually making their way into various fields, including but not limited to biomedicine and biotechnology, hazardous material detection, water purification, food industry, electronics and optoelectronics, and forensics. The main advantages of nanosensors include (a) rapidness, (b) low quantities of samples required, (c) robustness, (d) point of care capability, and (e) cost- effectiveness. More and more research is being conducted to improve the current nanomanufacturing methods, create new nanomaterials, and develop new sensors using the properties of nanomaterials. References [1] A. Kumar, N. Das, N.K. Satija, K. Mandrah, S.K. Roy, R.G. Rayavarapu, A novel approach towards synthesis and characterization of non-cytotoxic gold nanoparticles using taurine as capping agent, Nanomaterials 10 (1) (2020) 45, https://doi.org/10.3390/nano10010045. [2] M.E. Hoque, A.M. Peiris, S.M. Atiqure Rahman, M.A. Wahab, New generation antibacterial nanofibrous membrane for potential water filtration, Curr. Anal. Chem. 14 (3) (2018) 278–284, https://doi.org/ 10.2174/1573411013666171009162832. [3] M. Golieskardi, M. Satgunam, D. Ragurajan, M.E. Hoque, A.M.H. Ng, L. Shanmuganantha, Advanced 3Y-TZP bioceramic doped with Al2O3 and CeO2 potentially for biomedical implant applications, Mater. Technol. 34 (8) (2019) 480–489, https://doi.org/10.1080/10667857.2019.1578912. [4] D. Ragurajan, et al., Advanced 3Y-TZP bioceramic doped with Al2O3 and MnO2 particles potentially for biomedical applications: study on mechanical and degradation properties, J. Mater. Res. Technol. 7 (4) (2018) 432–442, https://doi.org/10.1016/j.jmrt.2017.05.015. [5] A. Wahab, N. Islam, M.E. Hoque, D.J. Young, Recent advances in silver nanoparticle containing biopolymer nanocomposites for infectious disease control—a mini review, Curr. Anal. Chem. 14 (2018) 198–202. [6] S. Sagadevan, K. Pal, Z.Z. Chowdhury, M.E. Hoque, Structural, dielectric and optical investigation of chemically synthesized Ag-doped ZnO nanoparticles composites, J. Sol-Gel Sci. Technol. 83 (2) (2017) 394–404, https://doi.org/10.1007/s10971-017-4418-8. [7] F.M. Michael, M. Khalid, C.T. Ratnam, W. Rashmi, M.E. Hoque, M.R. Ketabchi, Nanohydroxyapatite synthesis using optimized process parameters for load-bearing implant, Bull. Mater. Sci. 39 (1) (2016) 133–145, https://doi.org/10.1007/s12034-015-1120-8. [8] S.M.M. Nainar, et al., Effect of compatibilizers on in vitro biocompatibility of PLA–HA bioscaffold, Bioinspired Biomim. Nanobiomater. 3 (4) (2014) 208–216, https://doi.org/10.1680/bbn.14.00014. [9] P. Malik, V. Katyal, V. Malik, A. Asatkar, G. Inwati, T.K. Mukherjee, Nanobiosensors: concepts and variations, ISRN Nanomater. 2013 (2013) 1–9, https://doi.org/10.1155/2013/327435. [10] L.M. Bellan, D. Wu, R.S. Langer, Current trends in nanobiosensor technology, Wiley Interdiscip. Rev. Nanomed. Nanobiotechnol. 3 (3) (2011) 229–246, https://doi.org/10.1002/wnan.136. [11] D.J. Barber, I.C. Freestone, An investigation of the origin of the colour of the Lycurgus cup by analytical transmission electron microscopy, Archaeometry 32 (1990) 33–45, https://doi.org/10.1111/j.1475-4754.1990. tb01079.x. [12] J.D. Verhoeven, D.T. Peterson, What is a Damascus steel? Mater. Charact. 29 (1992) 335–341, https://doi.org/ 10.1016/1044-5803(92)90105-Q. [13] M. Faraday, The Bakerian lecture: experimental relations of gold (and other metals) to light, Philos. Trans. R. Soc. Lond. 147 (1857) 145–181. 18 Chapter 1
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- 34. CHAPTER 2 Features and complex model of gold nanoparticle fabrication for nanosensor applications Norma Alias, Hazidatul Akma Hamlan Center for Sustainable Nanomaterials, Ibnu Sina Institute for Scientific and Industrial Research, Universiti Teknologi Malaysia, Skudai, Malaysia 2.1 Introduction In recent years, many researchers and engineers have been shifting the focus of their studies toward nanosensors because of their unique sensitivity and selectivity, which mostly originate from modifications and reactions that occur at nanoscales [1]. Due to their unique features, nanosensors are widely chosen for detecting chemical and physical properties in many fields such as environmental, biomedical, and food processing. Dahman [2] expressed that nanosensors have a plethora of environmental applications. The ability to detect chemical components of air and water strengthen the choice of nanosensors in the environmental field. Nanosensors are mainly used in water monitoring quality [3], monitoring plant signaling pathways [4], and detecting and determining quantities of acetamiprid (insecticide) in food and the environment [5] and agriculture [6]. Vikesland [3] stated that an abundance of existing nanosensors can be developed into consumer- and operator-friendly tools. The author emphasized that nanotechnology-enabled sensors or nanosensors can provide extensive and potentially low-cost monitoring of chemicals, microbes, and other analytes in drinking water. Meanwhile, Kwak et al. [4] discussed how nanosensors can act as monitoring tools to observe and monitor plant signaling pathways and metabolism. Verdian [5] highlighted a current major concern of food safety experts, which is pesticide residues. Despite the small amounts of toxicity from pesticide residues, insecticides that contain acetamiprid can represent a health risk to human beings who are exposed to polluted food and environments. Hence, nanosensors can be used in detecting and determining amounts of acetamiprid in food and the environment. Nanofabrication for Smart Nanosensor Applications. https://doi.org/10.1016/B978-0-12-820702-4.00002-7 # 2020 Elsevier Inc. All rights reserved. 21
- 35. Srivastava et al. [6] explained applications of nanosensors in agriculture in which wireless nanosensors are used to monitor the soil fertility, moisture level, insects, temperature, crop nutrient status, and diseases of crops. Using advances in nanotechnology, crop growth can be monitored by employing networks of wireless nanosensors across cultivated fields. The network can provide crucial data for agronomic intelligence processes such as optimal times for crop planting and harvesting. One of the most popular nanosensor technologies makes use of gold nanoparticles [7], whose flexible surface chemistry allows them to be coated with biological recognition molecules, polymers, and small molecules, hence broadening their range of applications. Gold nanoparticles as substrates can also be used as a nanosensor technology for the detection of pollutants and label-free detection of other molecules and proteins [8]. Based on the facts described, this chapter presents established mathematical modeling based on partial differential equations (PDEs) for nanoparticle materials fabrication, to control the process of gold nanoparticle manufacturing. The modeling is created to investigate the feature properties and boundaries in the development process. One-dimensional PDEs with respect to time and space are employed to visualize the growth of gold nanoparticles (AuNPS). An accurate and precise result can be achieved by governing complex mathematical modeling and obtaining a large sparse matrix of linear system equations (LSEs). Meanwhile, the parallelization of LSE is chosen in order to accelerate and speed up the simulation for a large sparse matrix. Therefore, the main focus of this chapter is the parallelization of a mathematical model of the fabrication of nanoparticles. Nanoparticles have played an important role in advanced catalysts, ceramics, and electronic devices as well as polymer composites and coatings for the last two decades [9]. Their physical and chemical properties are different from those of conventional materials. A nanoparticle can best be defined as a small object that behaves as a whole unit with regard to its properties, and is classified according to its diameter. Schmid [10] defined nanoparticles as nanomaterials with an average diameter that is less than 100 nm. Nowadays, nanoparticle technology plays an important role in providing opportunities and possibilities for the development of a new generation of sensing tools. The targeted sensing of selective biomolecules using functionalized gold nanoparticles (Au NPs) has become a major research thrust in the last decade [11]. Researchers normally use gold nanoparticles due to their stability and unique optical, electronic, biolabeling, and molecular-recognition properties. In fabricating gold nanoparticles, several features need to be controlled – for example, size, shape, and structure. The parameters will be changed according to functionality. This is due to the strong correlation between the parameters and optical, electrical, and catalytic properties [12]. Nanoparticles with controlled size and shape are of great interest because of their morphology-dependent properties [10] and potential applications in a variety of fields. 22 Chapter 2
- 36. The application of gold growth is so significant that, in recent years, some researchers have been reporting mainly on the analysis of gold growth, especially chemical properties. However, only a few studies focus on mathematical modeling and simulation in visualizing the growth of gold nanoparticles [13]. Due to this situation, this research investigates the rate of growth for gold nanoparticles using a one-dimensional parabolic PDE approach. Since nanoparticle fabrication is being dealt with through nanoscale approaches, the focus of this chapter is on fine-grain parallelism involving a large-scale matrix from the mathematical model discretization. In solving the problem of a large-scale matrix, parallel computing systems with huge memory space are needed to produce a good result. Therefore, parallel computing systems are employed throughout this study. The parameter change from phase change simulation is the code from the Linux operating system using DPCS based on the approximation of numerical scheme and parallel algorithms, as well as their sequential flows. The PVM software integrated with the C language is used to support the message passing paradigm and simulation for the parallel algorithm program. 2.1.1 Applications of nanoparticles Nanotechnology deals with the particular technological goal of specifically manipulating atoms and molecules for fabrication of macroscale merchandise. Nowadays, this is also known as molecular nanotechnology [14]. In nanotechnology, sensitivity experiments are carried out for various physical processes, involving a large-scale structure of modeling and reformation of the nanoscale system, which appearance as nanoparticles [15]. Gold nanoparticles (AuNPs) display irreplaceable properties that make them a very attractive material for nanosensing applications, especially in the environmental field. Besides that, the “additional attractive feature of AuNPs is their interaction with thiols, providing effective and selective means of controlled intracellular release” [16]. Liu et al. [17], Park et al. [18], and Rejiya et al. [19] have investigated the application of gold particles as nanoparticles. Various sizes of gold nanoparticles and their morphologies have attracted considerable interest for researchers, especially in medical applications [20] and [21]. 2.1.2 Growth of gold nanoparticles As mentioned, gold nanoparticles (AuNPs) have attracted much attention among researchers, due to their unique properties and encouraging applications in areas of biotechnology, catalysis [22], and optoelectronics [23]. In preparing AuNPs, the homogeneous mixing of continuous flows of an aqueous tetrachloroauric acid solution and a sodium borohydride solution is applied using a microstructured static mixer [24]. Their studies have provided a profound understanding of gold nanoparticle growth and small angle X-ray scattering (SAXS), combined with X-ray absorption near-edge structure (XANES). In predicting the size, shape, and Designing aspects of gold nanoparticles complex model investigation 23
- 37. polydispersity of gold nanoparticles, one paper [25] stressed that it is necessary to interpret the underlying process using SAXS that offers integral information on the growth of nanoparticles. However, Polte et al. [26], despite their widespread use, in countless cases and applications, a deeper understanding and consideration of the underlying formation of the processes is missing. Due to this phenomenon, the size and shape control of gold nanoparticles often remained. Therefore, in this chapter, a great deal of attention has been focused on understanding the process of gold nanoparticle formation pertaining to its growth rate. In predicting and visualizing the growth of gold nanoparticles, mathematical modeling using one-dimensional parabolic PDEs as the integrated methodology is proposed instead of conducting experimental laboratory studies. The gold nanoparticle fabrication correlates with longer systemic circulation and a high-cost fabrication for small-scale limited process. Although the nanoparticles are small, mathematical modeling and large sparse simulation can be presented in the fabrication process. 2.2 Mathematical model of gold nanoparticle fabrication The focus of this chapter is on the application of one-dimensional parabolic equations from PDEs to governing mathematical modeling. The prediction and visualization of the growth rate of gold nanoparticles are obtained by employing one-dimensional parabolic PDEs with respect to time, space, and some independent and dependent variables. 2.2.1 Governing equation of gold nanoparticle fabrication This section deals with the mathematical modeling and simulation of one-dimensional parabolic PDEs as an integrated methodology for predicting and visualizing the growth of gold nanoparticles with respect to time and space. The modeling is formulated as a boundary value problem of PDEs. The PDE modeling with significant features and its parameter identification that influences on gold nanoparticles (AuNPs) of diameter Φ, ultraviolet radiation λ, and rate of gold growth U are investigated. The integrated methodology for predicting and visualizing the growth rate of gold nanoparticles for nanosensor applications with respect to time and space involves predicting and visualizing using one-dimensional parabolic PDEs. The governing equation of the mathematical model for this problem is: ∂U ∂t ¼ Φ ∂2 U ∂x2 þλ, 0 x 1, t 0: (2.1) Initial and boundary conditions are given by [27]. U x, 0 ð Þ ¼ sin πx ð Þ, 0 x 1, 24 Chapter 2
- 38. U 0, t ð Þ ¼ 0, 0 t 1, U 1, t ð Þ ¼ 0, 0 t 1: The exact solution is given by U x, t ð Þ ¼ eπt sin πx ð Þ, (2.2) where λ represents the incoherent ultraviolet radiation (nm), Φ is the diameter of gold growth, U is the rate of gold growth, t is time (duration taken for the growth rate), and x is the spatial coordinate of direction. 2.2.2 Nondimensionalized parameter for governing equations In mathematics, a transformation from dimensional to nondimensional variables is required so the relevant parameter identification and changes of the required parameters for mathematical modeling can be specified. However, for engineering applications, nondimensionalizing the governing equation is not necessary since real physical quantities are dealt with as the solution progresses. Since this study focuses on mathematical analysis, the nondimensional rule is needed because the nondimensionalized variables reduce the complexity of solving the governing equation. Therefore, Eqs. (2.1), (2.2) are nondimensionalized using the following dimensional scaling from Blest et al. [28]. The nondimensional scaling is denoted with a tilde: ~ Ti ¼ Ti Tini Tc Tini , ~ x ¼ x d , ~ y ¼ y d , ~ ui ¼ ui d , ~ vi ¼ vi d , ~ t ¼ Krt d2 , ~ L ¼ L d , ~ hk ¼ hk d , and ~ δk ¼ δk d , where i = r, f are the respective resin and saturated fiber layer. By applying these transformations and omitting tildes for clarity, Eqs. (2.1), (2.2) can be simplified as ∂Tf ∂t þPe uf ∂Tf ∂x þvf ∂Tf ∂y ¼ D ∂2 Tf ∂x2 þ ∂2 Tf ∂y2 þJ1 ∂α ∂t , (2.3) ∂Tr ∂t þPe ur ∂Tr ∂x þvr ∂Tr ∂y ¼ ∂2 Tr ∂x2 þ ∂2 Tr ∂y2 þJ2 ∂α ∂t , (2.4) and ∂α ∂t ¼ C1 þC2α ð Þ 1α ð Þ 0:47α ð Þ for α 0:3, (2.5) Designing aspects of gold nanoparticles complex model investigation 25
- 39. ∂α ∂t ¼ C3 1α ð Þ for α 0:3, (2.6) where D, J1 and J2 are dimensionless constants given by D ¼ Kf Kr , J1 ¼ øρrHR ρf cf Tc Tini ð Þ , J2 ¼ HR cr Tc Tini ð Þ Pe, which is the Peclet number, and the constant Ci are given by Pe ¼ Vd Kr Ci ¼ d2 ci Kr , i ¼ 1,2,3 2.2.3 Discretization using finite difference method for gold nanoparticle fabrication problem The specific parameter value of the finite difference method (FDM) is a numerical strategy for discretizing the parabolic equation. Approximate derivatives in Eq. (2.3) produce the approximation solution of the gold growth, which can be analyzed to be used in environmental analysis for nanosensors. The discretization of Eq. (2.3) is given by Ui, j + 1 Ui, j Δt ¼ Φ θ δ2 x Ui, j + 1 + 1θ ð Þ δ2 x Ui, j + λ, (2.7) where 0 θ 1 2 and 1 2 θ 1: Transferring the continuity equation of the PDE into the discrete solution by FDM with the forward difference formula for a first-order derivative and three points discretization for a second-order derivative, Eq. (2.7) is expanded as follows: rθUi1, j + 1 + 1 + 2rθ ð ÞUi, j + 1 rθUi + 1, j + 1 ¼ r 1θ ð ÞUi1, j + 12r 1θ ð Þ ð ÞUi, j + r 1θ ð ÞUi + 1, j + λΔt (2.8) with i ¼ 1, 2, …, m and j ¼ 1, 2, …, n. The step sizes of nanoscale gold nanoparticle growth during the photochemical reduction process can be considered as explicit, implicit, and Crank-Nicolson methods with respect to time and space variables. In equation, the convergent explicit methodology is able to express the growth dynamics of a particle at a new time step, depending on the few forms of points at the previous time. The explicit scheme of the FDM is uniquely designed in the closed domain and available to generate a large sparse fine domain for high resolution of the growth visualization. 26 Chapter 2
- 40. 2.2.4 Linear system equation formulation for gold nanoparticle fabrication The next steps of the numerical solution involve formulation of the linear system equation (LSE) for Eq. (2.8). In addition, three important solution tools for solving LSEs—Jacobi, Gauss-Seidel, and Alternating Group Explicit (AGE) by Evans and Sahimi [29], Abdurrahman et al. [30], Sahimi et al. [31], and Abu Mansor et al. [32]—are focused on in this chapter. The standard scheme for the three-point discretization of a one-dimensional parabolic PDE can be visualized in matrix form as AU ¼ F (2.9) where U and f are one-dimensional vectors defined as U ¼ U1, j + 1, U2, j + 1, U3, j + 1, …, Um, j + 1 T , F ¼ F1, F2, F3, …, Fm ð Þ: Eq. (2.7) can be written in matrix form as: a c 0 b a c b a ⋱ b ⋱ c ⋱ a c 0 b a 2 6 6 6 6 6 4 3 7 7 7 7 7 5 mm ð Þ U1 U2 U3 ⋮ Um1 Um 2 6 6 6 6 6 4 3 7 7 7 7 7 5 m1 ð Þ ¼ F1 F2 F3 ⋮ Fm1 Fm 2 6 6 6 6 6 4 3 7 7 7 7 7 5 m1 ð Þ (2.10) where a ¼ 1 + 2rθ, b ¼ c ¼ rθ and F1 ¼ r 1θ ð ÞUj 0 + 12r 1θ ð Þ ð ÞUj 1 + r 1θ ð ÞUj 2 + rθUj + 1 0 + λΔt Fi ¼ r 1θ ð ÞUj i1 + 12r 1θ ð Þ ð ÞUj i + r 1θ ð ÞUj i + 1 + λΔt, for i ¼ 2,3,…:m1 Fm ¼ r 1θ ð ÞUj m1 + 12r 1θ ð Þ ð ÞUj m + r 1θ ð ÞUj m + 1 + rθUj + 1 m + 1 + λΔt (2.11) 2.2.5 Visualization of the mathematical model for gold nanoparticle fabrication Visualization of the mathematical model of the one-dimensional problem of gold nanoparticles is acquired based on a simulation using Microsoft Visual Studio 2012 and the visualization graphs are plotted using Matlab R2013b and Comsol Multiphysics. The results obtained are validated using experimental data for the one-dimensional problem. Designing aspects of gold nanoparticles complex model investigation 27
- 41. In this section, the visualization of the growth of gold nanoparticles from the mathematical model simulation is compared with the experimental data. From the data obtained, the growth of the gold nanoparticles is described in Fig. 2.1, which shows the spectral absorption measured using photon correlation spectroscopy for Samples A and D. Samples A and D used different synthesis methods, such as UVA and UVC photo-initiation. In the experiment involving photochemical synthesis of AuNPs, tri-sodium citrate was added into a boiling gold chloride dilution and produced relatively monodisperse AuNPs with diameter between 10 and 20 nm. The changes in solution appearance during the experiment were carried out in order to indicate the presence of AuNP size for each sample used. Different diameters of AuNPs are used in order to visualize the rate of growth for gold nanoparticles. Hence, the computational molecule for AGE methodology at level p+1, as depicted in Fig. 2.5, an average particle size (diameter) from 5 nm to 100 nm, depending on ultraviolet wavelength, was used. In this study, six different sizes of AuNPs were measured: 5, 20, 40, 60, 80 and 100 nm. From Fig. 2.1, it can be concluded that the largest diameter Φ gives the highest rate of gold growth U(x,t). By focusing on the highest rate of gold growth, with a diameter of 100 nm, the mathematical model simulation of Eq. (2.1) is charged by a different amount of UV radiation, with wavelengths of 366 nm and 253.7 nm. The visualization graph from the simulation of the governing equation is described by Figs. 2.2 and 2.3. 2.3 Numerical implementation and parallelization for gold nanoparticle fabrication This section consists of the numerical implementation of the solution of the governing equation of the one-dimensional parabolic model for growth of gold nanoparticles, which will aid in promoting the usage of nanosensors in environmental analysis. The numerical implementations Fig. 2.1 Experimental data for particle size distribution (diameter) of gold nanoparticle growth using different samples. 28 Chapter 2
- 42. Fig. 2.2 Visualization of gold nanoparticle growth based on the mathematical model with different values of diameters. 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0 3 6 9 12 15 18 21 Time (s) U(x,t), Growth rate of gold nanoparticle (%) UV radiation (2.573e-7) UV radiation (3.66e-7) Fig. 2.3 Visualization of gold nanoparticle growth with different UV light radiation wavelengths (366 and 253.7 nm) using AGE method. Designing aspects of gold nanoparticles complex model investigation 29
- 43. involved are alternating group explicit (AGE), red-black Gauss-Seidel (RBGS), and Jacobi (JB) methods. These are then applied using sequential and parallel algorithms that are computed using Parallel Virtual Machine (PVM) programming on a Linux platform by distributed parallel computing systems. Numerical analysis and parallel performance evaluation based on execution time, speed-up, efficiency, effectiveness, temporal performance, and granularity are discussed at the end of this chapter. 2.3.1 Numerical implementation This section is divided into three subsections: Section 2.3.1.1 discusses the alternating group explicit (AGE) method, followed by the red-black Gauss-Seidel (RBGS) and Jacobi (JB) methods for solving the LSE. In 1985, Evans introduced the AGE method for solving the parabolic PDE problem [33]. It has been shown that this method is extremely powerful and flexible, and provides users with many advantages. This so-called advanced iterative method employs a fractional splitting strategy, which is applied alternately at each half time step on tridiagonal systems of different schemes and which has proven to be stable. The Jacobi (JB) and red-black Gauss-Seidel schemes represent basic numerical schemes and are the benchmarks for simulating the AGE scheme. 2.3.1.1 Alternating group explicit (AGE) As mentioned earlier, this iterative scheme employs a fractional splitting strategy which is applied alternately at each half time step on tridiagonal systems of difference schemes. This method has already proven to be stable. The linear system equation for the AGE scheme is given by Au ¼ f, also illustrated. The AGE method for obtaining the growth rate of a gold nanoparticle uses the Douglas- Rachford (DR) variant instead of the Peaceman-Rachford (PR). This is so as to ensure its unconditional stability [34] with stationary case (r is constant) and p 0 are given by the following equations. The computational molecule for the AGE method in determining the value of U at level p + 1 2 is (Fig. 2.4): The molecule diagram of the AGE method for level p + 1 can be drawn as follows (Fig. 2.5): 2.3.1.2 Red-Black Gauss-Seidel method (RBGS) The second iterative scheme of basic numerical analysis used for solving the linear system is the Gauss-Seidel (GS) method. This method was modified and improved from the Jacobi method, so it is no more difficult to apply and it often requires fewer iterations to produce the same degree of accuracy. When the Jacobi scheme is applied, the value of xi that is obtained in the nth approximation remains unchanged until the entire (n + 1)th approximate has been calculated, while for the 30 Chapter 2
- 44. Fig. 2.4 Computational molecule for AGE method at level p + 1 2. Fig. 2.5 Computational molecule for AGE method at level p + 1.
- 45. Gauss-Seidel scheme, new values of each xiwill be used as soon as they are known. Once x1 is determined in the first equation, the value is then used in the second equation to obtain a new x2. Similarly, the new x1 and x2 are used in the third equation to obtain the new x3 and so forth. Tavakoli and Davami [35] considered a parallel Gauss-Seidel in solving a one-dimensional elliptic partial differential equation with a Dirichlet boundary condition. The solution to the linear system AU ¼ f can be obtained starting with U(0) and using the iteration scheme U k + 1 ð Þ ¼ MSUk + CS, (2.12) where MS and CS are defined as MS ¼ D + L ð Þ1 U andCS ¼ D + L ð Þ1 b: This method is described using the formulae U k + 1 ð Þ i ¼ 1 aii bi X ji aijU k ð Þ j X ji aijU k + 1 ð Þ j ! ,i ¼ 1,2,3,…,m (2.13) However, the GS scheme can only solve sequential algorithms of mathematical modeling, so this scheme has been enhanced to solve algorithms in parallel, called the Red-Black Gauss- Seidel (RBGS). The RBGS contains two subdomains ΩR and ΩM . The red point depends on the black point, and vice versa. The loop starts by computing the odd points, from the bottom left, and then going up to the next row and so on. As all of the odd points are finished, the computation of the black ones continues. The red-black grid is illustrated in Figs. 2.6–2.8. 2.3.1.3 Jacobi method (JB) The third numerical iterative method employed for solving LSEs is the Jacobi method (JB), which is an algorithm for determining the solutions of a diagonally dominant system of linear equations. Each diagonal element is solved and the approximate value is plugged in. The Red point Black point Fig. 2.6 The grid for red and black points. 32 Chapter 2
- 46. process is then iterated until it converges. The solution to the linear system Au ¼ b can be obtained by beginning with U(0) and using iteration with U k + 1 ð Þ ¼ MJuk + CJ (2.14) where vector MJ and CJ can be defined as MJ ¼ D1 L + U ð ÞandCJ ¼ D1 b If U(0) is carefully chosen, a sequence U(1) , U(2) , U(3) … is generated, which converges to the solution ^ U: A sufficient condition for the method to be applied is that A is a strictly diagonally dominant matrix. Before implementing the simulation of the numerical scheme, an algorithm must be constructed. The purpose of constructing this algorithm is to monitor our programming language. In this study, we develop sequential and parallel algorithms to assist in monitoring our programming. If constructed the programming having error, that can be solved by help of algorithms. 2.3.2 Parallelization of iterative methods for solving one-dimensional mathematical model A parallel algorithm is constructed based upon the combination of several sequential algorithms. However, this algorithm has two types of server, the “master” and “slave.” The “master” will control all the activities that are conducted by the “slave,” such as receiving and sending the data. The parallel algorithm is constructed based on a SIMD architecture. A SIMD processor has a single control unit reading instructions pointed to by a single program counter, parallel decoding and sending control signals to the processing elements (PEs). The principle of SIMD is illustrated in Fig. 2.9. The SIMD architecture based on distributed computing system is shown in Fig. 2.10. Fig. 2.7 Molecule diagram at ΩR . Fig. 2.8 Molecule diagram at ΩM . Designing aspects of gold nanoparticles complex model investigation 33
- 47. In this research, C is used as a language that is planted in PVM with the Linux Fedora 21 operating system. The program is linked with the PVM library using the #include pvm3. h command for starting the program. From Fig. 2.11, it is clearly seen that the “master” sends the data of the start, end, initial, and boundary conditions for all slaves. The computational task is run by the “slave” until the local stopping criteria ε is fulfilled by each slave. The results obtained by slaves are sent toward the master. The master will process and store the results. If the global stopping criterion that is declared in the master is satisfied, the computation task is then stopped. The computation will be running if the condition (global stopping criterion) is still not satisfied. The servers will perform the calculation until the condition declared by the master is reached. The file programs contain message passing in order to communicate the purpose between master and slave as the program is compiled in the host pool for each architecture. The resulting object files are located at a location accessible by machines in the host pool. The PVM header file should be included with every PVM program. This is due to the important information regarding the interface of PVM programming. The techniques for the one- dimensional algorithm were illustrated in Fig. 2.11A, while the communication between processors is shown in Fig. 2.11B. In this research, techniques of domain decomposition were employed due to the presence of independent domains in the problem proposed. The grid of domain decomposition for each Data items Instructions Fig. 2.9 Principle of SIMD processor. Fig. 2.10 The SIMD architecture based on distributed computer systems. 34 Chapter 2
- 48. one-dimensional parallel algorithm is shown in Tables 2.1A, 2.1B, and 2.1C, which are AGE, RBGS, and JB, respectively. Based on Table 2.1A, we can conclude that the grid of domain decomposition for one-dimensional parallel AGE and JB was similar since the domain is independent. This differs from one-dimensional parallel RBGS since the domain decomposition for those algorithms involves even and odd domain partitioning. This is to avoid the overlapping subdomain problem. The mapping subdomain processes for sending and receiving data from the one-dimensional parallel algorithm at each time level were summarized in Tables 2.1A–2.1C. Based on that illustrated in Tables 2.1A, 2.1B, and 2.1C, the grid point of ui required data from the x-direction, which is left and right, while the updating activities are needed for implementing the latest iteration of time level (k + 1). Thus, for this case, the algorithm for sending and receiving data from neighborhood processors ui1 is needed to make sure the program functions well. X Y T1 Start T1 Start T2 Start Tn End T1 End T2 End Tn T2 Tn (A) (B) Fig. 2.11 (A) Domain decomposition technique for one-dimensional. (B) Communication between slaves. Designing aspects of gold nanoparticles complex model investigation 35
- 49. Table 2.1A: Domain decomposition of one-dimensional molecule for parallel AGE algorithm. TASK 1 At time level At time level (k + 1): 1 2 + : k i– 1, j k i, j i +1, j i +1, j i, j i+1, j i +1, j i +2, j i–1, j i+1, j i +1, j i, j i +2, j i, j i +2, j i–1, j i, j i, j TASK 1 TASK 2 TASK 2 TASK 3 TASK 3 k + 1 2 k + 1 2 k k + 1 One-dimensional Parallel Alternating Group Explicit (1D-PAGE) Table 2.1B: Domain decomposition of one-dimensional molecule for parallel RBGS algorithm. i+1, j i+1, j i+1, j i–1, j i–1, j i, j i +1, j i+1, j i, j i, j i, j i, j i –1, j i–1, j i +1, j i, j i –1, j k k k + 1 k + 1 i –1, j TASK 1 TASK 1 TASK 2 TASK 2 TASK 3 TASK 3 One-dimensional Parallel Red-BlackGauss-Seidel (1D-PRBGS) Notes:
- 50. Communication among processors is important for parallel computing, especially for sending and receiving data domain. To ensure the programming runs smoothly, “master” will send the information to data, left, right, start and end to every slave. Subsequently, as slaves receiving the information, computing task would start automatically. The task-to-task communication between slaves happened in sending and receiving neighbourhood data and it is done using massage passing [36]. Besides communication activities and algorithm of data distribution between slaves, the programming of parallel computing would be complete if the global and local convergence’s algorithm of master and slave were written well. 2.3.2.1 1D parallel alternating group explicit method (1D PAGE) AGE method is an advance numerical method that stands with independent domain for each time level. The parallel algorithm for one-dimensional AGE is constructed based on domain decomposition technique shown in Table 2.1A. While, synchronization of domain that decomposed into p number of slave processors and sub-domain of one-dimensional Parallel AGE disintegrated according to processors through Fig. 2.12. Computation of one-dimensional Parallel AGE is begun by slave receiving the parameters involved and initial condition from the master. Since this method consist of two time level, the Table 2.1C: Domain decomposition of one-dimensional molecule for parallel JB algorithm. One-dimensional Parallel Jacobi (1D-PJB) i+1, j i, j i, j i, j i+1, j i +1, j i –1, j i–1, j i–1, j k k + 1 TASK 1 TASK 2 TASK 3 P1 P2 = Pp–1 Pp Fig. 2.12 Data partitioning by number of processors. Designing aspects of gold nanoparticles complex model investigation 37
- 51. algorithm defined it as U1[i] and U2[i] represent the time level of k + 1 2 and (k + 1) respectively. According to Fig. 2.13, the communication between slaves is needed for sending U1[i 1] and U1[i + 1] grid data at the time level of k + 1 2 to neighbour slaves. While, for completing the computation at the time level of (k + 1) the grid points of U1[i 1] and U1[i + 1] is anticipated. It is important to calculate the convergence for completing the computation at time level (k + 1). The computation will generate until convergence criterion for local error, |Ui k+1 (p) Ui k ((p) | ε(p) is satisfied. 2.3.2.2 1D parallel Red-Black Gauss-Seidel method (1D PRBGS) Parallel RBGS is a method that has been modified from Gauss-Seidel (GS) iterative method. Since Gauss-Seidel iterative method is not compatible for parallel computing the modification has been made and approved to compute in parallel platform. This is due to the overlapping sub- domain. However, by having the improvement method of GS, which is RBGS, the domain has been partitioned into odd and even number known as red and black points respectively. By having this scenario, the overlapping sub-domain has been avoided successfully. In order to gain new updating value of Ui[1], which is red point, new value of black point is used and vice versa. This phenomenon shown there is no data enslavements between groups. Fig. 2.14, T1 T1 Start T1 Start Tp Start Tp–1 • • • • • • Start T2 End T1 End T2 End Tp–1 End Tp T2 Tp–1 Tp–1 Tp Tp T2 Fig. 2.13 Communication activities of one-dimensional Parallel AGE in sending and receiving domain. startR startR startR startB endR P1 P2 P3 endR endR endB endB endB startB startB Fig. 2.14 Molecule ordering for one-dimensional parallel RBGS. 38 Chapter 2
- 52. illustrated the computational molecule for computation of RBGS ordering toward three processors. The ordering is not simplest as JB method since it involves red and black points. One-dimensional parallel RBGS is classified into two groups of grid-points through the different colour point red and black represent the odd and even number of grid respectively. In order for obtaining good load balancing, the alternate numbers for the red and black need to be same for conveying toward processors as shown in the figure above. Depending on the colour of the grid-point, the first two starting grid points in a processor were labelled as “startR” and followed by “startB”. While the other two end grid points were labelled as “endR” followed by “endB”. The computation using this method begin by computing the red point from the bottom left (refer Fig. 2.15A) until finished, then followed black point (refer Fig. 2.15B). In computing black points, the updated value of red points at grid (i 1) and (i + 1) is needed. The algorithm begins by providing slave the initial condition as well as independent parameters involve from the master and end up by calculating the global error of the computation. As receiving the initial condition and parameters from the slave, the computation for this method started by computing new value of odd grid (red points) through the communication with neighbourhood slave for sending and receiving data purpose. The computation will carried out until the solution is converged as the global maximum error satisfied the convergence criteria. 2.3.2.3 1D parallel Jacobi method (1D PJB) One-dimensional Parallel JB method dealing with an independent sub-domain. This method is the simplest method compared with another two iterative method employed for this research. Based on Fig. 2.16 below, we can summarize that the new updating value of U, at time level of k + 1, this method hold on value from previous time level of k which are ui1 and ui+1. Fig. 2.16 illutrated the sending and receiving data in order of computing new value for i 1 grid form T1 T1 T2 T2 Start T1 End T1 End T2 End Tp–1 Tp–1 Tp T1 T2 End Tp–1 End Tp End T1 End Tp End T2 Start T2 Start Tp–1 Tp–1 Tp–1 Tp–1 Tp Tp Tp T1 T2 Start Tp–1 Start Tp Start T1 Start Tp Start T2 (A) (B) Fig. 2.15 (A) Communication activities of one-dimensional Parallel RBGS in sending and receiving red points. (B) Communication activities of one-dimensional Parallel RBGS in sending and receiving black points. Designing aspects of gold nanoparticles complex model investigation 39
- 53. left and right neighbourhood which are (T1) and (T2) respectively. While, that figure also clearly shows the transferring data for i + 1. This Parallel Jacobi algorithm is implemented in the slave’s command in order for computing the approximation solution. The algorithm begins by receiving parameters involves from the master such as independent parameters, initial condition and matrix size for computation. Then, the computation will start calculating the new value of Ui based on specified equation. The computation will generate as the approximation solution converged by satisfying the condition ofjUi k+1 Ui k j ε. Value of ε, is constant as it is defined by the master. For this research, we use ε ¼ 1 1010 . However, the slaves have to communicate with the neighbour slaves to pass up the neighbourhood data if the solution still not converged. Thus the iteration will be calculated in order for computing new updating value of Ui. As the solution converged, the local maximum error will be sent to master in order to calculate the global maximum error of the parallel algorithms. If the condition of global maximum error were satisfied, the computation will stopped and the result were printed. 2.3.3 Parallel performance evaluation for fabricating gold nanoparticles By comprising eight number of processors, Parallel Virtual Machine (PVM) with the Fedora version of 21 is installed in distributed memory architecture in order to test and implement the advance as well as the classical numerical methods. The parallel performance that evaluated based on the simulation from parallel algorithm are examined through solving the large sparse problem. Both case studies are being simulated using parallel evaluation and the comparisons of each method known as PAGE, PRBGS and PJB are analyse based on run time, speedup, efficiency, effectiveness, temporal performance and granularity. In order to examine and Fig. 2.16 Communication activities of one-dimensional Parallel JB in sending and receiving points. 40 Chapter 2
- 54. measure the performance of the parallel algorithm by the use of numerical methods, the computational complexity and communication cost are calculated. If the computational complexity and communication cost is higher, the longer computational time takes for solving the model problem. Before the matrix size are being decided, the simulation are test for different values of matrix size. Below, in Fig. 2.17 is the speedup results for six value of matrix size that tested using AGE methods. Based on the graft shown in Fig. 2.17, the performance of the linear speedup and graft value of m ¼ 50000, 100000, 150000, 200000, 250000, and 5000000 were reasonable. However, the size matrix for m ¼ 5000000 is categorized as superlative size matrix since Sp p and that size of the matrix was not appropriate for large sparse implementation due to some reasons such as the optimization of the usage of cache memory in parallel systems, poor sequential and parallel coding program, and unstable parallel system. For this research, the selected matrix size for undergo the parallelization is m ¼ 250000 since the speedup line is converged, stable and has approximately small difference between the linear speedup compared with other size matrix. Since PRBGS and PJB are considered as benchmark methods for PAGE method, thus the size matrixes chosen should be the similar to all methods in this experiment. The performance evaluation of the parallel algorithms for the 1D problem was done by solving a large sparse matrix size, where m ¼ 250000 as an optimum large sparse matrix for predicting the growth of gold nanoparticles (AuNPs). While the other parameters involved were Δx ¼ 0.000004, Δt ¼ 0.01,r ¼ Δx =Δt Δt and ε ¼ 1010 . In addition, the additional calculation that required for the artificial boundary value on the overlapping subdomains also influence the results. Fig. 2.17 Speedup versus number of processors for different values of matrix size, m for one-dimensional problem. Designing aspects of gold nanoparticles complex model investigation 41
- 55. Other documents randomly have different content
- 56. PAPAL TEMPTATIONS. ZWINGLE'S FIRMNESS— FABER'S HOSTILITY. CHAPTER II. Papal Temptations—Progress of the Reformation—The Idol at Stadelhofen—Sacrilege—The Ornaments of the Saints. The Reformation had gained the day; it was now to accelerate its conquests. After this battle of Zurich, in which the most skilful champions of the papacy were dumb, who would be bold enough to oppose the new doctrine? But weapons of a different kind were tried. Zwingle's firmness and republican bearing overawed his adversaries; accordingly they had recourse to peculiar measures to subdue him. While Rome was pursuing Luther with her anathemas, she endeavoured to win over the reformer of Zurich by gentleness. The dispute was scarcely ended when Zwingle received a visit from the captain of the pope's guard—the son of the burgomaster Roust. He was accompanied by the legate Einsius, the bearer of a papal brief, in which Adrian VI. called Zwingle his beloved son, and assured him of his special favour.[475] At the same time the pope urged Zink to gain over Zwingle. And what has the pope commissioned you to offer him? asked Oswald Myconius. Everything, replied Zink, except the papal chair.[476] There was no mitre, or crozier, or cardinal's hat, that the pope would not have given to bribe the reformer of Zurich. But Rome was strangely mistaken in this respect; all her proposals were unavailing. In Zwingle, the Romish Church had a still more pitiless enemy than Luther. He cared far less than the Saxon reformer for the ideas and ceremonies of former ages; it was enough for him that any custom, however innocent in itself, was
- 57. THE CRUCIFIX OF STADELHOFEN. connected with some abuse; he fell violently upon it. The Word of God (thought he) should stand alone. But if Rome understood so imperfectly what was then taking place in Christendom, she found counsellors who endeavoured to put her in the way. Faber, exasperated at seeing the pope thus humble himself before his adversary, hastened to enlighten him. He was a courtier with a constant smile upon his lips and honied words in his mouth; to judge from his own language, he was everybody's friend, even of those whom he accused of heresy. But his hatred was mortal. Accordingly, the reformer, playing on his name (Faber), used to say, the Vicar of Constance is a lie-smith. Let him openly take up arms, and see how Christ defends us.[477] These words were no mere idle boasting; for while the pope was complimenting Zwingle on his eminent virtues, and the special confidence he placed in him, the enemies of the reformer were increasing in number throughout Switzerland. The veteran soldiers, the great families, the herdsmen of the mountains, combined their hatred against this doctrine which thwarted their tastes. At Lucerne, the magnificent representation of Zwingle's passion was announced; in effect, the people dragged the reformer's effigy to the scaffold, shouting out that they were going to put the heretic to death; and laying hands on some Zurichers who happened to be at Lucerne, compelled them to be spectators of this mock execution. They shall not trouble my repose, said Zwingle; Christ will never be wanting to his followers.[478] Even the diet re-echoed with threats against him. My dear confederates, said the councillor of Mullinen to the cantons, make a timely resistance to the Lutheran cause......At Zurich a man is no longer master in his own house! This agitation among the enemy announced what was passing in Zurich more loudly than any proclamations could have done. The victory was indeed bearing fruit; the conquerors were gradually taking
- 58. SACRILEGE— ORNAMENTS OF THE SAINTS. possession of the country, and every day the Gospel made fresh progress. Twenty-four canons and a great number of chaplains voluntarily petitioned the council to reform their statutes. It was decided to replace these sluggish priests by pious and learned men, with commission to give the Zurich youth a Christian and liberal education, and to establish in the place of their vespers and Latin masses, a daily explanation of a chapter in the Bible, according to the Hebrew and Greek texts, first for the learned, and afterwards for the people. There are unfortunately in every army a number of those desperate heroes who leave their ranks and make unseasonable attacks on points that ought still to be respected. A young priest, Louis Hetzer, had published a treatise in German entitled, The judgment of God against Images, which produced a great sensation, and the images wholly engrossed the thoughts of a part of the people. It is only to the detriment of those essentials that ought to occupy his mind, that man can fix his attention on secondary matters. At a place called Stadelhofen, outside the city gates, stood a crucifix elaborately carved and richly ornamented. The most zealous partisans of the Reformation, shocked at the superstitions to which this image gave rise, could not pass by without giving vent to their indignation. A citizen named Claude Hottinger, a worthy man, says Bullinger, and well read in the Holy Scriptures, having fallen in with the miller of Stadelhofen, to whom the crucifix belonged, asked him when he intended to throw down his idols. No one compels you to worship them, replied the miller.—But do you not know, retorted Hottinger, that the Word of God forbids us to have any graven images?—Well then, said the miller, if you are authorized to remove them, I abandon them to you. Hottinger thought himself empowered to act, and shortly after, about the end of September, he was seen to pass the gates with a body of citizens. On arriving at the crucifix, they deliberately dug round it, until the image, yielding to their efforts, fell to the earth with a loud crash.
- 59. This daring action spread dismay on every side: one might have thought that religion itself had fallen with the crucifix of Stadelhofen. They are guilty of sacrilege! They deserve to be put to death! exclaimed the friends of Rome. The council caused the image- breakers to be apprehended. No! cried Zwingle and his colleagues from their pulpits: Hottinger and his friends are not guilty in the sight of God and worthy of death.[479] But they may be punished for having acted with violence and without the sanction of the magistrates.[480] Meantime acts of a similar nature were continually taking place. A curate of Saint Peter's, one day remarking in front of the church a number of poor people ill fed and with tattered garments, said to one of his colleagues, as he turned his eyes on the costly ornaments of the saints: I should like to strip these idols of wood to procure clothing for these poor members of Jesus Christ. A few days later, at three o'clock in the morning, the saints and all their ornaments disappeared. The council flung the curate into prison, notwithstanding he protested his innocence of this proceeding. What! exclaimed the people, is it these logs of wood that Jesus ordered us to clothe? Is it on account of these images that he will say to the righteous: I was naked, and ye clothed me? Thus, the greater the resistance, the higher soared the Reformation; and the more it was compressed, the more energetically did it spring forward, and threaten to overthrow all that withstood it.
- 60. DISPUTATION OF OCTOBER. CHAPTER III. The Disputation of October—Zwingle on the Church—The Church—Commencement of Presbyterianism—Discussion on the Mass—Enthusiasts—The Language of Discretion— Victory—A Characteristic of the Swiss Reformation— Moderation—Oswald Myconius at Zurich—Revival of Literature—Thomas Plater of the Valais. Even these excesses were destined to be salutary; a new combat was needed to secure fresh triumphs; for in the things of the Spirit, as in the affairs of the world, there is no conquest without a struggle; and as the soldiers of Rome stood motionless, the conflict was to be brought on by the undisciplined sons of the Reformation. In fact, the magistrates were embarrassed and agitated; they felt the necessity of having their consciences enlightened, and with this view they resolved to appoint another public disputation in the German language, in which the question of idols should be examined according to Scripture. The Bishops of Coire, Constance, and Basle, the university of the latter city, and the twelve cantons, were accordingly requested to send deputies to Zurich. But the bishops declined the invitation, and calling to mind the wretched figure their deputies had made at the former disputation, they had little inclination to repeat such humiliating scenes. Let the evangelicals dispute if they please, but let them dispute alone. On the first occasion, the Romish party had kept silence; on the second they were resolved not to appear. Rome may possibly have imagined that the great combat would cease for want of combatants. The bishops were not alone in refusing to attend. The men of Unterwalden replied that they had no scholars among them, but only worthy and pious priests, who explained the
- 61. ZWINGLE ON THE CHURCH. Gospel as their fathers had done; that they would send no deputy to Zwingle and his fellows; but that, if he fell into their hands, they would treat him in such a manner as to deprive him of all wish to relapse into the same faults.[481] Schaffhausen and St. Gall alone sent representatives. On the 26th of October, after the sermon, an assembly of more than nine hundred persons, composed of members of the Great Council and of three hundred and fifty priests, filled the large hall of the town- house. Zwingle and Leo Juda were seated at a table, on which lay the Old and New Testament in the original languages. Zwingle spoke first, and overthrowing with a vigorous arm the authority of the hierarchy and of its councils, established the rights of every Christian Church, and claimed the liberty of the primitive ages—of those times when the Church knew neither general nor provincial councils. The universal Church, said he, is spread over the whole world, wherever there is faith in Christ, in India as well as at Zurich......And as for particular churches, we have them at Berne, at Schaffhausen, and even here. But the popes, with their cardinals and their councils, form neither the universal Church nor a particular Church.[482] The assembly before which I now speak, continued he with energy, is the Church of Zurich; it desires to hear the Word of God, and it has the right of ordering all that may appear to it conformable with the Holy Scriptures. Thus did Zwingle rely on the Church, but on the true Church; not on the clergy alone, but on the assembly of Christians,—on the people. All that the Scriptures say of the Church in general, he applied to particular churches. He did not think that any church could err which listened with docility to the Word of God. In his eyes, the Church was represented politically and ecclesiastically by the Great Council. [483] At first he explained every question from the pulpit; and when his hearers' minds were convinced of the truth, he carried the matter
- 62. CANON HOFFMAN — PRESBYTERIANIS M. SILENCE OF PRIESTS AND MONKS. before the Great Council, who, in harmony with the ministers of the Church, formed such decisions as the Church called for.[484] In the absence of the bishop's deputies, Conrad Hoffmann, the same aged canon who had procured Zwingle's election to Zurich, undertook the defence of the pope. He maintained that the Church, the flock, the third estate, had no right to discuss such matters. I was thirteen years at Heidelberg, said he, living in the house of a very great scholar, whose name was Doctor Joss, a worthy and pious man, with whom I long ate and drank and led a merry life; but I always heard him say that it was not proper to discuss such matters; so you see...... All were ready to burst into laughter; but the burgomaster checked them. Let us therefore wait for a council, continued Hoffmann. For the present, I shall not dispute, but obey the bishop's orders, even should he be a knave! Wait for a council! replied Zwingle. And who will attend a council? The pope with some sluggish and ignorant bishops who will do nothing but what suits their fancy. No! the Church is not there! Höng and Küssnacht (these were two Zurich villages) are certainly more of a church than all the bishops and popes put together! Thus did Zwingle vindicate the rights of the christian people, whom Rome had deprived of their privileges. The assembly before which he was speaking was not, in his judgment, the Church of Zurich, but its first representative. This is the beginning of the Presbyterian system in the age of the Reformation. Zwingle was withdrawing Zurich from the jurisdiction of the Bishop of Constance, separating it from the Latin hierarchy, and founding on this idea of the flock, of the christian assembly, a new ecclesiastical constitution, to which other countries were afterwards to adhere. The disputation continued. Many priests having risen to defend the images, but without having recourse to Holy Writ, Zwingle and the other reformers confuted them by the Bible. If no one
- 63. VICTORY. stands forward to defend the use of images by arguments derived from Scripture, said one of the presidents, we shall call upon some of their advocates by name. As no one arose, the priest of Wadischwyl was called. He is asleep, answered one of the spectators. The priest of Horgen was next called. He has sent me in his place, replied his curate, but I will not answer for him. Evidently the power of God's Word was making itself felt in this assembly. The partisans of the Reformation were full of energy, liberty, and joy; their adversaries appeared speechless, uneasy, and dejected. They summoned, one after another, the parish-priests of Laufen, Glattfelden, Wetzikon, the rector and priest of Pfaffikon, the dean of Elgg, the priest of Bäretschwyl, with the Dominicans and Grayfriars, notorious for their preaching in defence of images, the virgin, the saints, and the mass; but all made answer that they could say nothing in their favour, and that henceforward they would apply themselves to the study of the truth. Hitherto, said one of them, I have put my trust in the old doctors; now, I will believe in the new.—You should believe not in us, but in God's Word, exclaimed Zwingle. It is Scripture alone that can never err! The sitting had been long, and night was approaching. The president, Hofmeister of Schaffhausen, stood up and said: Blessed be the Almighty and Everlasting God for that in all things he has vouchsafed us the victory; and he then exhorted the councillors of Zurich to pull down all the images. On Tuesday the assembly met again in order to discuss the doctrine of the mass. Vadian was in the chair. My brethren in Christ, said Zwingle, far from us be the thought that there is any deception or falsehood in the body and blood of Christ.[485] Our only aim is to show that the mass is not a sacrifice that one man can offer to God for another, unless any one should maintain also that a man can eat and drink for his friend. Vadian having twice demanded if any there present desired to uphold by Scripture the doctrine impugned, and no one having replied, the canons
- 64. of Zurich, the chaplains, and many other ecclesiastics declared that they agreed with Zwingle. But scarcely had the reformers thus vanquished the partisans of the old doctrines, than they had to contend against those impatient spirits who call for sudden and violent innovations, and not for wise and gradual reforms. The wretched Conrad Grebel rose and said: It is not enough to have disputed about the mass, we must put an end to its abuses.—The council will draw up an edict on the subject, replied Zwingle. Upon this Simon Stumpf exclaimed: The Spirit of God has already decided: why refer to the decision of the council? [486] The commander Schmidt of Küssnacht arose gravely, and in language full of wisdom said, Let us teach Christians to receive Christ in their hearts.[487] Until this hour, ye have all gone after idols. The dwellers in the plain have run to the mountains, and those of the mountains have gone to the plain; the French to Germany, and the Germans to France. Now ye know whither ye ought to go. God has combined all things in Christ. Ye noble citizens of Zurich! go to the true source; and may Christ at length re-enter your territory, and there resume his ancient empire. This discourse made a deep impression, and no one stood up to reply to it. Zwingle rose with emotion and said, Gracious lords, God is with us......He will defend his cause. Now, then, forward in the name of God. Here Zwingle's agitation became so great that he could not proceed. He wept, and many joined their tears with his. [488] Thus ended the disputation. The presidents rose; the burgomaster thanked them; and the aged warrior, turning to the council, said gravely, with that voice which had so often been heard on the field of battle, Now, then,......let us grasp the sword of God's Word, and may the Lord prosper his work.
- 65. CHARACTER OF THE SWISS REFORMATION. REVIVAL OF LEARNING IN ZURICH. This dispute, which took place in the month of October 1523, was decisive. The majority of the priests, who had been present at it, returned full of zeal to the different parts of the canton, and the effect of these two days was felt throughout Switzerland. The Church of Zurich, that had always preserved a certain independence with respect to the see of Constance, was then entirely emancipated. Instead of resting on the pope through the bishop, it rested henceforward through the people on the Word of God. Zurich recovered the privileges that Rome had taken from her. Town and country vied with each other in interest for the work of the Reformation, and the Great Council did but follow the movements of the people. On all important occasions the city and the villages made known their opinions. Luther had restored the Bible to the christian world; Zwingle went farther, he restored their rights. This is a characteristic feature of the Swiss Reformation. The maintenance of sound doctrine was thus confided, under God, to the people; and recent events have shown that a christian people can guard this precious deposit better than priests and pontiffs.[489] Zwingle did not allow himself to be elated by victory; on the contrary, the Reformation, according to his wish, was carried on with great moderation. God knows my heart, said he, when the council asked his advice; He knows that I am inclined to build up, and not to throw down. I am aware that there are timid souls who ought to be conciliated; let the mass, therefore, for some time longer be read on Sunday in all the churches, and let us avoid insulting the priests who celebrate it.[490] The council drew up an edict to this purport. Hottinger and Hochrutiner, one of his friends, were banished from the canton for two years, and forbidden to return without permission. The Reformation at Zurich followed a prudent and christian course. Daily raising this city more and more, it surrounded her with glory in the eyes of all
- 66. THOMAS PLATER. the friends of the Word of God. Accordingly those in Switzerland who had saluted the new light that was dawning upon the Church felt themselves powerfully attracted towards Zurich. Oswald Myconius, expelled from Lucerne, had been residing for six months at Einsidlen, when, as he was returning one day from a journey he had made to Glaris,[491] oppressed by fatigue and by the heat of the sun, he saw his little boy Felix running to meet him, and to tell him that he had been invited to Zurich to superintend one of the schools. Oswald could not believe such joyful tidings: he hesitated between fear and hope.[492] I am thine, wrote he at last to Zwingle. Geroldsek saw him depart with regret; gloomy thoughts filled his mind. Alas! said he to Oswald, all those who confess Christ are going to Zurich; I fear that one day we shall all perish there together.[493] A melancholy presentiment, which by the death of Geroldsek himself and of so many other friends of the Gospel, was but too soon fulfilled on the plains of Cappel. At Zurich, Myconius found at last a safe retreat. His predecessor, who from his stature had been nicknamed at Paris the great devil, had neglected his duties; Oswald devoted all his heart and strength to their fulfilment. He explained the Greek and Latin classics, taught rhetoric and logic, and the youth of the city listened to him with delight.[494] Myconius was destined to become for the rising generation what Zwingle was to those of riper years. At first Myconius was alarmed at the advanced age of the scholars under his care; but he had gradually resumed his courage, and was not long in distinguishing among his pupils a young man, twenty-four years of age, from whose eyes beamed forth a love of study. Thomas Plater, for such was his name, was a native of the Valais. In that beautiful valley, where the torrent of the Viége rolls its noisy waters, after issuing from the sea of ice and snow which encircles Mount Rosa, between St. Nicholas and Stalden, on the lofty hill that rises on the right bank of the river, may still be seen the village of Grächen. This
- 67. was Plater's birthplace. From the neighbourhood of these colossal Alps was to proceed one of the most original of all the characters that appeared in the great drama of the sixteenth century. At the age of nine years, he had been placed under the care of a priest who was his relation, by whom the little peasant was often so cruelly beaten that he cried (as he tells us himself) like a kid under the knife. He was taken by one of his cousins to attend the German schools. But he had already attained the age of twenty years, and yet, through running from school to school, he scarcely knew how to read.[495] When he arrived at Zurich, he came to the determination of gaining knowledge; and having taken his place in Oswald's school, he said to himself, There shalt thou learn or die. The light of the Gospel shone into his heart. One very cold morning, when he had no fuel for the school-room stove, which it was his duty to keep up, he thought to himself: Why should you want wood, while there are many idols in the church! There was no one as yet in the church, although Zwingle was to preach, and the bells were already summoning the congregation. Plater entered very softly, laid hold of an image of St. John that stood upon an altar, and thrust it into the stove, saying: Down with you, for in you must go. Most assuredly neither Myconius nor Zwingle would have sanctioned such a proceeding. It was in truth by better arms than these that incredulity and superstition were to be combated. Zwingle and his colleagues had given the hand of fellowship to Myconius; and the latter daily expounded the New Testament in the church of Our Lady before an eager and attentive crowd.[496] Another public disputation, held on the 13th and 14th of January 1524, had again proved fatal to Rome; and in vain did the canon Koch exclaim: Popes, cardinals, bishops, councils—these are my church! Everything was making progress in Zurich; men's minds were becoming more enlightened, their hearts more decided, and the Reformation was increasing in strength. Zurich was a fortress gained
- 68. by the new doctrine, and from her walls it was about to spread over the whole confederation.
- 69. DIET OF LUCERNE. CHAPTER IV. Diet of Lucerne—Hottinger arrested—His Death—Deputation from the Diet to Zurich—Abolition of religious Processions— Abolition of Images—The Two Reformations—Appeal to the People. The adversaries were aware of what might be the consequences of these changes in Zurich. They felt that they must now decide upon striking a vigorous blow. They had been silent spectators long enough. The iron-clad warriors of Switzerland determined to rise at last; and whenever they arose, the field of battle had been dyed with blood. The diet had met at Lucerne; the clergy were endeavouring to excite the chief council of the nation in their favour. Friburg and the Forest Cantons proved their docile instruments; Berne, Basle, Soleure, Glaris, and Appenzel were undecided. Schaffhausen was inclining towards the Gospel; but Zurich alone stood forward boldly in its defence. The partisans of Rome urged the assembly to yield to their demands and prejudices. Let the people be forbidden, said they, to preach or repeat any new or Lutheran doctrine in private or in public, and to talk or dispute about such things in taverns and over their wine.[497] Such was the ecclesiastical law they were desirous of establishing in the confederation. Nineteen articles were drawn up to this effect, approved of by all the states, except Zurich, on the 26th of January 1523, and sent to all the bailiffs with orders to see that they were strictly observed: which caused great joy among the priests, says Bullinger, and great sorrow among believers. A persecution, regularly organized by the supreme authority of the confederation, was about to begin.
- 70. HOTTINGER ARRESTED. HOTTINGER'S MARTYRDOM. One of the first who received the mandate of the diet was Henry Flackenstein of Lucerne, bailiff of Baden. Hottinger, when banished from Zurich for pulling down the crucifix of Stadelhofen, had retired to this bailiwick, where he had not concealed his opinions. One day, as he chanced to be dining at the Angel tavern in Zurzach, he had said that the priests wrongly interpreted Holy Scripture, and that man should put his trust in God alone.[498] The landlord, who was continually going in and out to bring bread or wine, listened to what appeared to him such very extraordinary language. Another day, Hottinger paid a visit to his friend John Schutz of Schneyssingen. After they had eaten and drunk together, Schutz asked him: What is this new faith that the Zurich pastors are preaching? They preach, replied Hottinger, that Christ was sacrificed once for all Christians; that by this one sacrifice he has purified and redeemed them from all their sins; and they show by Holy Scripture that the mass is a lie. After this (in February 1523), Hottinger had quitted Switzerland, and gone on business to Waldshut, on the other side of the Rhine. Measures were taken to seize his person, and about the end of the same month the poor unsuspecting Zuricher, having recrossed the river, had scarcely reached Coblentz, a village on the left bank of the Rhine, before he was arrested. He was taken to Klingenau, and as he there frankly confessed his faith, the exasperated Flackenstein said: I will take you to a place where you will find people to make you a suitable answer. In effect, the bailiff conducted him successively before the judges of Klingenau, before the superior tribunal of Baden, and, since he could find no one who would declare him guilty, before the diet sitting at Lucerne. He was firmly resolved to seek judges who would condemn his prisoner. The diet lost no time, and condemned Hottinger to be beheaded. When informed of his sentence, he gave glory to God: That will do, said James
- 71. Troger, one of his judges, we do not sit here to listen to sermons. You can have your talk some other time. He must have his head taken off this once, said the bailiff Am Ort, with a laugh; if he should ever get it on again, we will all embrace his faith. May God forgive all those who have condemned me, said the prisoner. A monk then presented a crucifix to his lips, but he put it away, saying: It is in the heart that we must receive Jesus Christ. When he was led out to execution, many of the spectators could not refrain from tears. I am going to eternal happiness, said he, turning towards them. On reaching the place where he was to die, he raised his hands to heaven, exclaiming: Into thy hands, O my Redeemer, I commit my spirit! In another minute his head rolled upon the scaffold. The blood of Hottinger was hardly cold before the enemies of the Reformation seized the opportunity of still further inflaming the anger of the confederates. It was in Zurich itself that the mischief should be crushed. The terrible example that had just been given must have filled Zwingle and his partisans with terror. Another vigorous effort, and the death of Hottinger would be followed by that of the Reform......The diet immediately resolved that a deputation should be sent to Zurich, calling upon the councils and the citizens to renounce their faith. The deputation received an audience on the 21st of March. The ancient christian unity is broken, said the deputies; the disease is gaining ground; already have the clergy of the four Forest Cantons declared, that unless the magistrates come to their aid, they must discontinue their functions. Confederates of Zurich, join your efforts to ours; stifle this new faith;[499] dismiss Zwingle and his disciples, and then let us all unite to remedy the injuries that have been inflicted on the popes and their courtiers. Thus spoke the adversaries: and what would the citizens of Zurich do? Would their hearts fail them? Had their courage cooled with the blood of their fellow-citizen?
- 72. ABOLITION OF PROCESSIONS AND IMAGES. Zurich did not leave her friends or enemies long in suspense. The council announced calmly and nobly that they could make no concessions in what concerned the Word of God; and then proceeded to make a still more forcible reply. Ever since the year 1351, it had been customary for a numerous procession, each member of which bore a cross, to go on Whitmonday on a pilgrimage to Einsidlen to worship the Virgin. This festival, which had been established in commemoration of the battle of Tatwyll, was attended with great disorders.[500] The procession should have taken place on the 7th of May. On the petition of the three pastors it was prohibited by the council, and all the other processions were reformed in their turn. They did not stop here. The relics, that source of innumerable superstitions, were honourably interred;[501] and then, at the request of the three pastors, the council published a decree, to the effect that honour being due to God alone, the images should be removed from all the churches of the canton, and their ornaments sold for the benefit of the poor. Twelve councillors, one from each guild, the three pastors, the city-architect, blacksmiths, carpenters, builders, and masons, went into the various churches, and having closed the doors,[502] took down the crosses, defaced the frescoes, whitewashed the walls, and took away the images, to the great delight of the believers, who regarded this proceeding (says Bullinger) as a striking homage paid to the true God. In some of the country churches, the ornaments were burnt to the honour and glory of God. Erelong the organs were taken down, on account of their connexion with many superstitious practices; and a baptismal service was drawn up, from which everything unscriptural was excluded.[503] The burgomaster Roust and his colleague, with their dying eyes joyfully hailed the triumph of the Reformation. They had lived long
- 73. THE TWO REFORMATIONS. enough, and they died at the very time of this great renovation of public worship. The Swiss Reformation here presents itself under an aspect somewhat different from that of the German Reformation. Luther had risen up against the excesses of those who had broken the images in the churches of Wittemberg; and in Zwingle's presence the idols fell in the temples of Zurich. This difference is explained by the different lights in which the two reformers viewed the same object. Luther desired to maintain in the Church all that was not expressly contrary to the Scriptures, and Zwingle to abolish all that could not be proved by them. The German reformer wished to remain united to the Church of the preceding ages, and was content to purify it of all that was opposed to the Word of God. The Zurich reformer passed over these ages, returned to the apostolic times, and, carrying out an entire transformation of the Church, endeavoured to restore it to its primitive condition. Zwingle's Reformation was therefore the more complete. The work that Providence had confided to Luther, the restoration of the doctrine of justification by faith, was doubtless the great work of the Reformation; but when this was accomplished, others remained to be done, which, although secondary, were still important; and to these Zwingle's exertions were more especially directed. In fact, two mighty tasks had been imposed on the reformers. Christian Catholicism, born in the midst of Jewish pharisaism and Greek paganism, had gradually felt the influence of these two religions, which had transformed it into Roman-catholicism. The Reformation that was called to purify the Church, was destined to purge it alike from the Jewish and the pagan element. The Jewish element prevailed chiefly in that part of the christian doctrine which relates to man. Catholicism had received from Judaism the pharisaical ideas of self-righteousness, of salvation by human strength or works.
- 74. LUTHER AND ZWINGLE. The pagan element prevailed especially in that part of the christian doctrine which relates to God. Paganism had corrupted in the catholic church the idea of an infinite Deity, whose power, being perfectly all-sufficient, is at work in all times and in all places. It had established in the Church the reign of symbols, images, and ceremonies; and the saints had become the demigods of popery. Luther's reform was directed essentially against the Jewish element. It was against this element that he had been compelled to struggle, when an impudent monk on behalf of the pope was making a trade of the salvation of souls. Zwingle's reform was particularly directed against the pagan element. It was this element with which he had come in contact at the temple of our Lady of Einsidlen, when a crowd, gathered together from every side, fell down blindly before a gilded idol, as of old in the temple of the Ephesian Diana. The German reformer proclaimed the great doctrine of justification by faith, and with it inflicted a death-blow on the pharisaical righteousness of Rome. The reformer of Switzerland unquestionably did the same; the inability of man to save himself forms the basis of the work of all the reformers. But Zwingle did something more: he established the sovereign, universal, and exclusive agency of God, and thus inflicted a deadly blow on the pagan worship of Rome. Roman-catholicism had exalted man and lowered God. Luther lowered man, and Zwingle exalted God. These two tasks, which were specially but not exclusively theirs, were the complement of each other. Luther laid the foundation of the building; Zwingle raised its crowning stone. It was reserved for a still more capacious genius to impress, from the banks of the Leman lake, these two characters conjointly upon the Reformation.[504]
- 75. OPPOSITION. But while Zwingle was thus advancing with mighty strides to the head of the confederation, the disposition of the cantons became daily more hostile. The Zurich government felt the necessity of relying on the people. The people, moreover, that is to say the assembly of believers, was, according to Zwingle's principles, the highest power to which there could be any appeal on earth. It was resolved to test the state of public opinion, and the bailiffs were enjoined to demand of all the parishes whether they were ready to suffer everything for our Lord Jesus Christ, who, said the council, gave his life and his blood for us sinners.[505] The whole canton had carefully followed the progress of the Reformation in the city; and in many places, the cottages of the peasants had become christian schools, wherein the Holy Scriptures were read. The proclamation of the council was read and enthusiastically received in every parish. Let our lords, answered they, remain fearlessly attached to the Word of God: we will aid them in upholding it;[506] and if any one seeks to molest them, we will come to their support like brave and loyal fellow-citizens. The peasantry of Zurich showed then, that the strength of the Church is in the christian people. But the people were not alone. The man whom God had placed at their head answered worthily to the call. Zwingle appeared to multiply himself for the service of God. All that were enduring persecution in the Helvetic cantons for the cause of the Gospel addressed themselves to him.[507] The responsibility of public affairs, the care of the churches, the anxieties of the glorious conflict that was going on in every valley of Switzerland, weighed heavily upon the evangelist of Zurich.[508] At Wittemberg, the news of his courageous proceedings was received with joy. Luther and Zwingle were two great lights, placed in Upper and Lower Germany; and the doctrine of salvation, so powerfully proclaimed by both, filled the
- 76. vast tracts that extend from the summit of the Alps to the shores of the Baltic and of the North Sea.
- 77. NEW OPPOSITION. CHAPTER V. New Opposition—Abduction of Œxlin—The Family of the Wirths —The Populace at the Convent of Ittingen—The Diet of Zug —The Wirths apprehended and given up to the Diet—Their Condemnation. The Word of God could not thus invade extensive countries, without its triumphs exasperating the pope in his palace, the priest in his presbytery, and the Swiss magistrates in their councils. Their terror increased from day to day. The people had been consulted; the christian people became of consequence in the Christian Church, and appeals were made to their sympathy and faith and not to the decrees of the Roman chancery! So formidable an attack required a still more formidable resistance. On the 18th of April, the pope addressed a brief to the confederates, and the diet, which met at Zug in the month of July, yielding to the urgent exhortations of the pontiff, sent a deputation to Zurich, Schaffhausen, and Appenzel, commissioned to acquaint these states with the firm resolve of the diet to crush the new doctrine, and to prosecute its adherents to the forfeiture of their goods, their honours, and even of their lives. Zurich did not hear this warning without emotion; but a firm reply was made, that, in matters of faith, the Word of God alone must be obeyed. On receiving this answer, Lucerne, Schwytz, Uri, Unterwalden, Friburg, and Zug, trembled with rage; and, unmindful of the reputation and strength the accession of Zurich had formerly given to the infant confederation, forgetting the precedence that had been immediately accorded to her, the simple and solemn oaths that had been made to her, and of the many victories and reverses they had shared with her,—these states declared that they would no longer sit in diet with Zurich. Thus in Switzerland, as in Germany, the partisans of Rome
- 78. A PATRIARCHAL FAMILY. were the first to break the federal unity. But threats and the rupture of alliances were not enough. The fanaticism of the cantons called for blood; and it was soon seen with what arms Rome intended combating the Word of God. One of Zwingle's friends, the worthy Œxlin,[509] was pastor of Burg upon the Rhine, in the neighbourhood of Stein. The bailiff Am-Berg, who had appeared to listen to the Gospel with delight,[510] being desirous of obtaining that bailiwick, had promised the leading men of Schwytz to root out the new faith. Œxlin, although not within his jurisdiction, was the first upon whom he exercised his severity. About midnight, on the 7th of July 1524, some persons knocked at the pastor's door; they were the bailiff's soldiers, who entered the house, seized Œxlin, and carried him away prisoner, in defiance of his cries. Thinking they meant to assassinate him, he cried Murder; the inhabitants started from their beds in affright, and the village soon became the scene of a frightful tumult, which was heard as far as Stein. The sentinel on guard at the castle of Hohenklingen fired the alarm-gun; the tocsin was rung, and the inhabitants of Stein, Stammheim, and the adjoining places, were soon moving, and inquiring of one another in the darkness what was the matter. At Stammheim lived the deputy-bailiff Wirth, whose two eldest sons, Adrian and John, both young priests full of piety and courage, were preaching the Gospel with great unction. John especially abounded in faith, and was ready to sacrifice his life for his Saviour. This was truly a patriarchal family. Hannah, the mother, who had borne the bailiff many children, and brought them up in the fear of the Lord, was revered for her virtues throughout the whole district. At the noise of the tumult in Burg, the father and the two eldest sons went out like their neighbours. The father was indignant that the bailiff of Frauenfeld should have exercised his authority in a manner contrary to the laws of the country. The sons learned with sorrow that their brother, their friend, the man whose good example they were
- 79. THE MOB IN THE CONVENT OF ITTINGEN. delighted to follow, had been dragged away like a criminal. Each of them seized a halberd, and in spite of the fears of a tender wife and mother, the father and his two sons joined the band of citizens of Stein with the determination of rescuing their pastor. Unhappily, a number of those miscreants who make their appearance in every disorder had joined the expedition; they pursued the bailiff's officers; the latter, hearing the tocsin and the shouts of alarm, redoubled their speed, dragging their victim after them, and soon placed the river Thur between themselves and their pursuers. When the people of Stein and Stammheim reached the bank of the river, and found no means of crossing, they halted, and resolved to send a deputation to Frauenfeld. Oh! said the bailiff Wirth, the pastor of Stein is so dear to us, that for his sake I would willingly sacrifice my goods, my liberty, and my life.[511] The populace, finding themselves near the Carthusian convent of Ittingen, whose inmates were believed to have encouraged the tyranny of the bailiff Am-Berg, entered the building and took possession of the refectory. These miserable wretches soon became intoxicated, and shameful disorders were the consequence. Wirth vainly entreated them to leave the convent;[512] he was in danger of being maltreated by them. His son Adrian remained outside the cloister. John entered, but soon came out again, distressed at what he had seen.[513] The drunken peasants proceeded to ransack the wine-cellars and the store-rooms, to break the furniture, and burn the books. When the news of these disorders reached Zurich, some deputies from the council hastened to the spot, and ordered all persons under the jurisdiction of the canton to return to their homes. They did so immediately. But a body of Thurgovians, attracted by the disturbance, established themselves in the convent, for the sake of its good cheer. On a sudden a fire broke out, no one knew how, and the monastery was burnt to the ground.
- 80. THE DIET AT ZUG. THE WIRTHS SURRENDERED TO THE DIET. Five days after this, the deputies of the cantons met at Zug. Nothing was heard in the assembly but threats of vengeance and of death. Let us march with banners flying on Stein and Stammheim, said they, and put the inhabitants to the sword. The deputy-bailiff and his two sons had long been objects of especial dislike on account of their faith. If any one is guilty, said the deputy of Zurich, he must be punished, but according to the laws of justice, and not by violence. Vadian, deputy of St. Gall, supported this opinion. Upon this the avoyer John Hug of Lucerne, unable to contain himself any longer, exclaimed with frightful imprecations:[514] The heretic Zwingle is the father of all these insurrections; and you too, doctor of St. Gall, are favourable to his infamous cause, and aid him in securing its triumphs......You ought no longer to have a seat among us. The deputy of Zug endeavoured to restore peace, but in vain. Vadian left the hall, and as the populace had designs upon his life, he quitted the town secretly, and reached the convent of Cappel by a circuitous route. Zurich, intent on suppressing every disorder, resolved to apprehend provisionally those persons who were marked out by the rage of the confederates. Wirth and his two sons were living quietly at Stammheim. Never will the enemies of God be able to vanquish His friends, said Adrian Wirth from the pulpit. The father was warned of the fate impending over him, and was entreated to flee with his two sons. No, answered he; I will wait for the officers, putting my trust in God. And when the soldiers made their appearance at his house, he said: My lords of Zurich might have spared themselves all this trouble: if they had only sent a child I should have obeyed their summons.[515] The three Wirths were taken to Zurich and put in prison. Rutiman, bailiff of Nussbaum, shared their fate. They were strictly examined, but nothing reprehensible was found in their conduct. As soon as the deputies of the cantons had heard of the imprisonment of these four citizens, they required them to be sent to
- 81. EXAMINATION AND TORTURE. Baden, and ordered that in case of refusal their troops should march upon Zurich and carry them off by force. To Zurich belongs the right of ascertaining whether these men are guilty or not, said the deputies of that state; and we have found no fault in them. On this the deputies of the cantons exclaimed: Will you surrender them to us? Answer yes or no, and not a word more. Two deputies of Zurich mounted their horses, and rode off with all haste to their constituents. On their arrival, the whole town was in agitation. If the prisoners were refused, the confederates would come and seek them with an armed force; to give them up was consenting to their death. Opinions were divided: Zwingle declared for their refusal. Zurich, said he, ought to remain faithful to its constitution. At last it was supposed a middle course had been found. We will deliver the prisoners into your hands, said they to the diet, but on condition that you will examine them solely with regard to the affair of Ittingen, and not on their faith. The diet acceded to this proposition, and on the Friday before St. Bartholomew's day (18th August 1524) the three Wirths and their friend, accompanied by four councillors of state and several armed men, quitted Zurich. A deep concern was felt by all the city at the prospect of the fate which awaited the two youths and their aged companions. Sobbing alone was heard as they passed along. Alas! exclaims a contemporary, what a mournful procession![516] The churches were all filled. God will punish us! cried Zwingle. Let us at least pray him to impart his grace to these poor prisoners, and to strengthen them in the faith.[517] On Friday evening the accused arrived at Baden, where an immense crowd was waiting for them. At first they were taken to an inn, and thence to prison. They could scarcely advance, the crowd so pressed around to catch a sight of them. The father, who walked in front, turned towards his two sons, and observed to them meekly: See, my dear
- 82. children, we are (as the apostle says) men appointed to death; for we are made a spectacle unto the world, and to angels, and to men (1 Cor. iv. 9). Then, as he saw among the crowd his deadly enemy, Am-Berg, the cause of all his misfortunes, he went up to him and held out his hand, although the bailiff would have turned away: There is a God in heaven who knows all things, said he calmly, as he grasped his adversary's hand. The examination began on the following day: the bailiff Wirth was first brought in. He was put to the torture, without any regard to his character or his age; but he persisted in declaring his innocence of the pillage and burning of Ittingen. He was then accused of having destroyed an image representing St. Anne. Nothing could be substantiated against the other prisoners, except that Adrian Wirth was married, and preached after the manner of Zwingle and Luther; and that John Wirth had given the sacrament to a sick man without bell and taper.[518] But the more apparent their innocence, the greater was the fury of their adversaries. From morning until noon they inflicted the cruelest tortures on the old man. His tears could not soften his judges. John Wirth was treated with still greater barbarity. Tell us, they asked him in the midst of his anguish, whence did you learn this heretical faith? From Zwingle or from any other person? And when he exclaimed, O merciful and everlasting God, help and comfort me! Where is your Christ now? said one of the deputies. When Adrian appeared, Sebastian of Stein, the Bernese deputy, said to him: Young man, tell us the truth; for if you refuse to do so, I swear by the knighthood that I gained on the very spot where the Lord suffered martyrdom, that we will open your veins one after another. They then fastened the young man to a rope, and hoisted him into the air: There, my little master, said Stein with a devilish sneer, there is your wedding present;[519] alluding to the marriage of this youthful servant of the Lord.
- 83. CONDEMNATION. EXECUTION. When the examination was ended, the deputies returned to their cantons to deliver their report, and did not meet again till four weeks after. The bailiff's wife, the mother of the two priests, repaired to Baden, carrying an infant child in her arms, to intercede with the judges. John Escher of Zurich accompanied her as her advocate. Among the judges he saw Jerome Stocker, landamman of Zug, who had been twice bailiff of Frauenfeld: Landamman! said he, you know the bailiff Wirth; you know that he has always been an upright man.—You say the truth, my dear Escher, replied Stocker, he has never injured anybody; fellow-citizens and strangers were always kindly welcomed to his table; his house was a convent, an inn, and an hospital;[520] and so, if he had committed robbery or murder, I would have made every exertion to obtain his pardon. But seeing that he has burnt Saint Anne, Christ's grandmother, he must die!—The Lord have mercy upon us, exclaimed Escher. The gates were now shut: it was the 28th September, and the deputies of Berne, Lucerne, Uri, Schwytz, Unterwalden, Zug, Glaris, Friburg, and Soleure, having proceeded to deliberate on their judgment with closed doors, as was customary, passed sentence of death on the bailiff Wirth, on his son John, who was the firmest in his faith, and who appeared to have led away the others, and on the bailiff Rutiman. Adrian, the second son, was granted to his mother's tears. The officers proceeded to the tower to fetch the prisoners. My son, said the father to Adrian, never avenge our death, although we have not deserved punishment. Adrian burst into tears. Brother, said John, the cross of Christ must always follow his Word.[521] After the sentence was read, the three Christians were led back to prison; John Wirth walking first, the two vice-bailiffs next, and a priest behind them. As they were crossing the castle bridge, on which was a chapel dedicated to St. Joseph, the priest called out to the two old men,
- 84. Fall down and call upon the saints. John Wirth, who was in front, turned round at these words and said, Father, be firm. You know that there is only one Mediator between God and man, the Lord Jesus Christ.—Assuredly, my son, replied the old man, and by the help of His grace I will continue faithful even to the end. Upon this they all three began to repeat the Lord's Prayer, Our Father which art in heaven, and so crossed the bridge. They were next conducted to the scaffold. John Wirth, whose heart was filled with the tenderest anxiety for his parent, bade him farewell. My dearly beloved father, said he, henceforward thou art no longer my father, and I am no longer thy son, but we are brothers in Christ our Lord, for whose name we must suffer death. [522] To-day, if it be God's pleasure, my beloved brother, we shall go to Him who is the Father of us all. Fear nothing. Amen! replied the old man, and may God Almighty bless thee, my beloved son and brother in Christ! Thus, on the threshold of eternity, did father and son take leave of each other, hailing the new mansions in which they should be united by everlasting ties. The greater part of those around them shed floods of tears.[523] The bailiff Rutiman prayed in silence. All three then knelt down in Christ's name, and their heads rolled upon the scaffold. The crowd, observing the marks of torture upon their bodies, gave loud utterance to their grief. The two bailiffs left twenty-two children, and forty-five grandchildren. Hannah was obliged to pay twelve golden crowns to the executioner who had deprived her husband and her son of life. Thus blood, innocent blood, had been shed. Switzerland and the Reformation were baptized with the blood of the martyrs. The great enemy of the Gospel had done his work; but in doing it, his power was broken. The death of the Wirths was to accelerate the triumphs of the Reformation.
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