![CHAPTER 1
From nature: Optics, nanotechnology,
and nano-optics
Ashin Shajia
, Jemy Jamesb,c
, Parvathy Nancyc,d
a
Institute of Physics, Slovak Academy of Sciences, Bratislava, Slovakia
b
FRE CNRS 3744, IRDL, University of Southern Brittany, Lorient, France
c
International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam,
Kerala, India
d
School of Pure and Applied Physics, Mahatma Gandhi University, Kottayam, Kerala, India
1. Introduction
Nanomaterials are abundant in nature, since everything in our world is composed of very
small particles. As a result, nanotechnology is always inspired by nature and natural phe-
nomena. The properties of the materials created by nature through evolutionary pro-
cesses are highly efficient or optimal, hence the use of natural materials directly in the
development of nanotechnology is of great importance. Now scientists have a clear idea
of how to create nanoscale materials with unique properties that never existed before.
Products using nanomaterials are now available in the market, such as nanoscale silver
as an antibacterial [1], sunscreen with nanoscale titanium dioxide that prevents sunburn
[2], application in the field of electronics as in batteries, targeted drug delivery, nanofilms
for coatings, water filtration, etc. [3] Molecular-level manipulation is the ultimate base of
nanotechnology, but that doesn’t mean that this field of science always deals only with
artificial materials.
In nature, molecules organize themselves into complex structures that could support
life, similar to the present nanotechnology that we are used to. Nature constructs every-
thing atom by atom, and understanding the basic principle of natural systems will help
nanoscientists to design artificial nanomaterials. For example, oncologists are looking into
nanotechnology as a potential way to treat cancer with targeted drug delivery by the use
of nanomedicine [4]. The inspiration for this is from the viruses that seek out a specific
type of cell to attack in a living organism. Similarly, optically transparent materials have
been improved by imitating the nanostructures found in the wings of insects. Finding
inspiration from nature’s nanotech is becoming big business nowadays.
Nano-optics or nanophotonics has become a serious topic of research over the past
decades. The interaction of light with nanometer-scale particles has developed into a new
and separate branch from conventional photonics research topics due to its massive pres-
ence in the natural world and also from an application point of view. On the nanometer
1
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![scale, materials including metals, semiconductors, dielectrics, and polymers exhibit inter-
esting properties, especially optical properties [5]. Particles that come under a size range of
nanometers show special phenomena that are not predictable as in their bulk counter-
parts. Making use of these properties of the nanoparticles in the field of optics and pho-
tonics is the core of nanophotonics [6]. The major aim of this chapter is to give a brief
introduction to the presence of nanotechnology and nanophotonics in the natural world
rather than the artificially created nano universe. Without going into deeper theoretical
aspects, this chapter presents an overall picture of the influence and existence of nano-
technology in nature.
2. Nature and optics
In nature, optical phenomena are observable as a result of the interaction of matter and
light; interactions of light from the sun and moon with particles in the atmosphere,
clouds, water, dust, etc. are the reason for some of the common natural optical phenom-
enon like mirages and rainbows (Fig. 1). Many of these natural phenomena in nature arise
from the optical properties of the atmosphere and due to the presence of other objects in
nature or sometimes even due to the visual illusion created by the human eye, such as
entoptic phenomena [7].
The particle and wave nature of the light also influences this kind of phenomenon.
Some are quite delicate and noticeable only by precise scientific measuring instruments.
One of the notable observations is the bending of light from a star by the sun, observed
during the time of the solar eclipse. This demonstrates that space is curved, as predicted by
Einstein in his theory of relativity. Most optical phenomena can be explained on the basis
of the classical electromagnetic explanation of light. But in practical applications, a
completely electromagnetic description of light is often difficult to apply in practice.
So for practical applications, optics is usually demonstrated using simplified models, like
geometric optics, that treat light as a collection of rays that travel in a straight line and
bend from a surface when they pass through or reflect from it. Wave optics or physical
optics is a more inclusive model of light, which explains the wave nature of such phe-
nomena as diffraction and interference, which cannot be explained using geometric
optics.
Based on the history of light in nature, the first accepted model to explain the nature
of light is the ray-based model of light, and later on, the wave model of light. The intro-
duction of the electromagnetic theory in the 19th century led to the rediscovery of light
waves as electromagnetic radiation. Even so, there are some phenomena in nature that
can be explained only by considering the fact that light has both wavelike and particle-
like nature (dual nature of light), effects that require quantum mechanical explanations.
Quantum optics is the field of science that deals with the application of quantum mechan-
ics to optical systems. When considering the particle-like nature of light, light is
2 Nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-15-320.jpg)
![considered as a collection of particles called photons. Optical science is an important and
applicable field of science in many related disciplines like astronomy, photography, var-
ious engineering fields, and especially in medical fields like optometry and ophthalmol-
ogy. Practical implementation of optics is found in everyday life and in a variety of
technologies like telescopes, mirrors, lenses, microscopes, lasers, optical fibers, etc.
Most colors in nature originate due to selective adsorption resulting from the pigmen-
tation embedded in the body or surface of an object. However, a certain range of intense
and bright contrast colors result from the interaction of light with nano- and microstruc-
tures, which leads to the appearance of color by coherent scattering, interference, and
diffraction without any absorption. These colors are commonly known as “structural
colors” [8]. The structures that help to modulate light leading to structural colors are part
of the family of photonic structures in nature.
Fig. 1 Some of the common optical phenomena happening in nature: (A) double rainbow and
supernumerary rainbows on the inside of the primary arc; (B) very bright sun dogs in Fargo, North
Dakota; (C) the reflection of Mount Hood in Mirror Lake; (D) a 22° halo around the sun, as seen in
the sky over Annapurna Base Camp, Annapurna, Nepal. ((A) Eric Rolph at English Wikipedia (https://
commons.wikimedia.org/wiki/File:Double-alaskan-rainbow.jpg), “Double-alaskan-rainbow,” size and
shape of the image by Ashin Shaji, https://creativecommons.org/licenses/by-sa/2.5/legalcode; (D) Anton
Yankovyi (https://commons.wikimedia.org/wiki/File:Halo_in_the_Himalayas.jpg), size and shape of the
image by Ashin Shaji, https://creativecommons.org/licenses/by-sa/4.0/legalcode.)
3
From nature: Optics, nanotechnology, and nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-16-320.jpg)
![Photonic structures can be defined as regular structures with periodicities matching
with the order of the wavelength of the light [9]. Structural colors have been a hot topic
of research for centuries, and the involvement of micro- and nanostructures in them was
introduced by Hooke (1665), Newton (1704), and Lord Rayleigh (1917) [8]. The first
ever imaging and a detailed study of structural elements that induce structural colors were
suggested by Anderson and Richards [10] after the introduction of the electron micro-
scope. The interest in natural structural colors was found to increase due to the fast
growth in the field of optical spectroscopy and scanning/transmission microscopy. These
spectroscopic techniques help to investigate the details of the complex nano and micro-
structures with unique optical characteristics that evolved and existed solely in nature for
millions of years [11].
Optical issues like high reflectivity or transmission, strong polarization of light,
dichroism, spectral filtering, etc., can be controlled with the help of the natural world
since nature provides solutions for all these in the form of nanostructures of different
morphological varieties. Thus, nature offers an abundant number of road maps for
multifunctional micro- and nanostructures that show outstanding dynamic and distinc-
tive coloration. This kind of structured material originates as a result of evolution over
millions of years and invites the interest of scientists to carry out deeper research that
may build the basis of future optical devices. It can find applications in medical diag-
nostics, communication, information processing, and devices with functionalities that
can go beyond the current stage. Therefore, the biomimetic approach is currently a hot
field of science. For the purpose of solving complex human problems, imitation or
copying the models, systems, or solutions from nature is known as biomimetic or bio-
mimicry [12].
3. Nanotechnology in nature
Nanoscience and nanotechnology always find inspiration from nature. Some common
nanostructures that are visible in nature include inorganic materials such as carbonaceous
soot, clay, organic natural thin films, and a variety of organic nanostructures such as pro-
teins, insects, and crustacean shells. These structures cause a range of behaviors in nature
together with the wettability of surfaces, the brightness of butterfly wings, and also the
adhesive properties of the lizard’s foot.
The coloration of many varieties of beetles and butterflies is created by sets of rigor-
ously spaced nanoscopic pillars. Fabricated from sugars like chitosan, or proteins like ker-
atin, the widths of slits between the pillars are designed to control light to attain certain
colors or effects like iridescence. One advantage of this strategy is resilience. Pigments
tend to bleach with exposure to light; however, structural colors are stable for remarkably
long periods.
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![A study of structural coloration in metallic-blue marble berries [13] where the spec-
imens collected in 1974, that had maintained their color despite being long dead. Sim-
ilarly, a lotus leaf is an example of an engineered surface because of its physical and
chemical conditions at the micro- and nanometer scale, able to provide a self-cleaning
effect. Wilhelm Barthlott, a German botanist, is considered to be the discoverer of the
Lotus effect [14] as he applied for its patent in 1994. He found out that the combination
of the chemical makeup of the surface and also the micro-and nano-projections on the
surface were the reason behind the effect. The protrusions [15] of the lotus leaf are
10 μm high, with every protrusion covered in bumps of a hydrophobic, waxy material
that is roughly 100 nm in height. The chitin polymer and epicuticular wax projections
allow the leaf to trap air. Water droplets ride on the tips of the projections and result in a
bed of air to make a super-hydrophobic surface (Fig. 2). Scientists designed this behavior
Fig. 2 Examples of self-cleaning surfaces in nature and their SEM images [16]. (Permission has been
granted through the Copyright Clearance Center’s Rights Link service.)
5
From nature: Optics, nanotechnology, and nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-18-320.jpg)
![into the product Lotusan®
, a self-cleaning paint. This paint mimics the microstructure of
the surface of a lotus leaf once it dries and cures within the environment. Small peaks and
valleys on the surface minimize the contact area for water and dirt, keeping the surface
clean. Various merchandise is currently on the market that mimics this hydrophobic
property, including consumer goods, spray coatings, plungers, toilet fixtures, automotive
components, etc.
Researchers at several universities are synthesizing biomimetic nanocomposites to
form robust materials to be used in lightweight armor systems, structures in transportation
systems, sturdy electronics, aerospace applications, etc. Nature has evolved an advanced
bottom-up approach for fabricating nanostructured materials that have great mechanical
strength and toughness. One of nature’s toughest materials is nacre, which is best known
as the iridescent mother-of-pearl made by mollusks. Mollusks produce nacre by depos-
iting amorphous calcium carbonate (CaCO3) onto porous layers of polysaccharide chitin.
The mineral then crystallizes, producing stacks of CaCO3 that are separated by layers of
organic material. Its strength comes from the brick-like assembly (interlocked) of the
molecules [17].
A lizard’s feet will bind firmly to any solid surface in a short time, and detach with no
apparent effort (Fig. 3). This adhesion is purely physical, with no chemical interaction
between the feet and the surface. The active adhesive layer of the gecko’s foot is a
branched nanoscopic layer of bristles known as “spatula” that measure about 200 nm
in length. Several thousand of those spatulae are connected to micron-sized “seta.” Both
spatulae and seta are fabricated from very flexible keratin. Although research into the finer
details of the spatulae’s attachment and detachment mechanism is in progress, the actual
fact is that they operate with no sticky chemicals. It is an impressive piece of design by
Mother Nature. That they are self-cleaning, immune to self-matting (the seta don’t stick
to each other), and detached by default (including from each other) are other interesting
features of geckos’ feet [18, 20]. These options have prompted ideas and suggestions that
in the future, glues, screws, and rivets may all be made by a single method, casting keratin
or similar material into completely different molds.
Magnetotactic bacteria possess the extraordinary ability to sense minute magnetic
fields, together with the Earth’s own magnetic field, using tiny chains of nanocrystals
known as magnetosomes (Fig. 4). These are grains sized between 30 and 50 nm, made
from either magnetite (a type of iron oxide) or, less commonly, greghite (an iron-sulfur
combo). Several types of magnetosomes work together to provide a foldable “compass
needle” that is many times more sensitive than its artificial counterparts. Magnetotactic
bacteria are pond-dwelling and only need to navigate short distances. However, their
precision is incredible. By varying the grain size, these bacteria can store information
since the growth is controlled by the most magnetically sensitive atomic arrangements
[22]. However, oxygen and sulfur combine rapidly with iron to provide magnetite,
greghite, or more than 50 other compounds, only a couple of which are magnetic. Hence
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![Fig. 3 Nanoengineered structures from nature: (A) microstructure and schematic illustration of gecko feet [18]; (B) micro/nanoarchitecture in the
wings of a butterfly [19]. (Permission has been granted through the Copyright Clearance Center’s Rights Link service.)](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-20-320.jpg)
![advanced technologies are needed to produce selectively the proper kind, and build the
magnetosome chains. Such manual skill is presently beyond our reach; however, in
future, scientists may learn a way to mimic these structures.
4. Presence of nano-optics in nature
The increasing research in nanotechnology makes it necessary to deal with the optical
phenomenon on the nanometer scale. Since the diffraction limit doesn’t enable us to
focus light to dimensions smaller than roughly one-half of the wavelength (200 nm), tra-
ditionally it was not practical to optically interact selectively with nanoscale structures.
However, in recent years, many new approaches have become available to reduce the
diffraction limit or even overcome it. A central goal of nano-optics is to extend the
utilization of optical techniques to length scales beyond the diffraction limit. The most
Fig. 4 Different morphology of magnetotactic bacteria: (A) vibrios; (B) rods (Bar ¼ 1.0 μm) and (D);
(C) coccoid (Bar ¼ 200 nm); (E) spirilla: (F) multicellular organism (Bar ¼ 1.0 μm) [21]. (Permission has
been granted through the Copyright Clearance Center’s Rights Link service.)
8 Nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-21-320.jpg)
![obvious potential technological applications that arise from breaking the diffraction bar-
rier are super-resolution microscopy and ultra-high-density information storage. How-
ever, the field of nano-optics is by no means restricted to technological applications and
instrumental design. Nano-optics additionally opens new doors to basic analysis on
nanometer-sized structures [23, 24].
Nature has developed numerous nanoscale structures to achieve distinctive optical
effects. An outstanding example is photosynthetic membranes that use light-harvesting
proteins to absorb daylight and then channel the excitation energy to different neighbor-
ing proteins [25]. The energy is guided to a so-called reaction center where it initiates a
charge transfer across the cell membrane. Other examples of nanophotonics in nature
include sophisticated nano diffractive structures commonly found in insects like butter-
flies and other animals to produce attractive colors and effects like those on a peacock’s
feather. Insect wings have ordered hexagonal close-packed array structures made of chi-
tin. The difference in spacing (from 200 nm to 1 μm) between these small structures
allows the wings to serve as self-cleaning and antireflective coatings, along with providing
improved mechanical strength and aerodynamics. It also functions as a diffraction grit-
ting, which produces iridescence. Iridescence originates as a result of the interaction
of light with the physical structure of the surface. In the Morpho butterfly, the spaces
between the ribs of the wing form natural photonic crystals, leading to a brilliant blue
color (Fig. 5). No pigments or chemicals are involved in this process. Researchers are
exploring these nanostructures as a way for controlling and manipulating the flow of
light, which is vital in optical communication.
Additionally, researchers have found that when they coat the Morpho wings with a
layer of heat-absorbing carbon nanotubes, the shift in reflected wavelength of light will
indicate very small temperature changes (Fig. 6). Hence, these sensors could someday be
used to discover inflamed or burned areas in people or points of wear and tear due to
friction in machines.
Another example is a moth’s eye, which has very small bumps on its surface. These
bumps are hexagonal-shaped structures that are a few hundred nanometers tall and
separated (Fig. 7). Since these patterns are smaller than the wavelength of visible light
(350–800 nm), the surface of the moth’s eye can absorb more light, since it has only very
low reflectance for visible light. Therefore, the visibility of a moth in dark conditions is
much better than a normal human eye because these nanostructures can absorb light very
efficiently. Scientists have been inspired to use similar artificial nanostructures to improve
the absorption of infrared light in a particular type of thermo-voltaic cell to make it more
efficient [29].
A new aim within the study of animal optical structures is to decipher and emulate the
animal’s genetic manufacturing process. Animals contain the ultimate factories within
them, which means they engineer via nanomachinery and molecular self-assembly,
and also the results are excellent, based on the previously reported results [30]. Maybe,
9
From nature: Optics, nanotechnology, and nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-22-320.jpg)
![in the near future, living cells will be cultured and photonic crystals can be grown and
harvested on an industrial basis. This successively would supply a chance for novel evo-
lutionary studies in the field of nanophotonics. According to the results obtained in pre-
vious research carried out by nanoscientists, it was found that the ability to manufacture
this kind of natural photonic crystal may be inherent among insect cells. Normally, there
is a single (minimal) mutation within the genes required to manage the developmental
process. The limited range of photonic crystals found in animals, compared with the
potential range in physics (where lattices may also contain sharp edges and corners,
etc.), further supports this concept. So, as a consequence of their production by single
cells, photonic crystals make ideal phenotypes for evolutionary study in the future.
Some of the applications of nature-inspired optical materials are listed below.
4.1 Light manipulation
Nature makes use of a large number of optical phenomena to produce attractive colors.
The most attractive and striking colors or optical effects are often created through the
manipulation of light with the help of intricate microstructures. These are usually known
Fig. 5 The Morpho didius butterfly: (A) image of the Morpho wings; (B) separated images of ground
scale and cover scale [26]. (Permission has been granted through the Copyright Clearance Center’s
Rights Link service.)
10 Nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-23-320.jpg)
![as structural colors. In particular, some types of three-dimensional natural photonic crys-
tals can create a photonic bandgap. This is a frequency band in dielectric structures in
which electromagnetic waves are prohibited, irrespective of their direction of propagation
in space. Theoretically, the three-dimensional periodicity of three-dimensional photonic
crystals can give rise to photonic band gaps in all directions and produce omnidirectional
reflection, which can produce bright color over a broad viewing angle [31, 32]. Compared
with pigment color, structural color offers ultrahigh saturation brightness and iridescence.
Moreover, as a result of not utilizing chemical dyes, structural color is environmentally
friendly and exhibits unlimited lightfastness (Fig. 8). Due to these distinctive properties,
tunable structural colors have opened new avenues to applications in areas like cosmetics,
textiles, printing and painting, displays, and security labeling.
Fig. 6 Wing scales of the painted lady, Vanessa cardui butterfly. The wing is covered in overlapping
layers of scale cells, as seen in the reflected light image in the region of one of the ventral
hindwing eyespots and high magnification SEM images showing the scale cell surfaces [27].
(A) Image of a V. cardui butterfly. Scale bar ¼ 1 cm. (B) Overlapping layers of scale cells in the wing
of a V. cardui butterfly. The scales themselves are made of chitin. Scale bar ¼ 2 mm. (C) Higher
magnification image of wing scales. The arrangement of scales are like overlapping tiles. Scale bar ¼
150 μm. (D) SEM image showing the attachment of scale cells to the wing of wing epithelium.
Scale bar ¼ 65 μm. (E) SEM image of base of scale cell where scale shaft is attached to the socket
cell. Scale bar ¼ 20 μm. (F) High magnification SEM showing the ornately patterned scale cell
surfaces. Scale bar ¼ 2 μm. (G) 6-day pupal wing scale stained with Wheat Germ Agglutinin (WGA),
a type of fluorescent. Scale bar ¼ 20 μm. (Permission has been granted through the Copyright
Clearance Center’s Rights Link service.)
11
From nature: Optics, nanotechnology, and nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-24-320.jpg)
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davg=170+18nm
davg=190+17nm
Nipple diameter (nm)
Nipple diameter (nm)
Counts
Counts
-
-
250 mm 10 mm
5 mm 400 mm
(A)
(C) (D)
(B) (E)
(F)
Fig. 7 The nano-nipple arrays of a Mourning Cloak butterfly eye, as revealed by SEM at different magnifications. The complete eye and its
enlarged regional topography are shown. The distribution of nano-nipple diameters for the Mourning Cloak butterfly and for the Question
Mark butterfly are shown in the graphs [28]. (A) Overview of butterfly eye. (B) Hexagonal facet lenses. (C) Junction in between three
hexagonal facets. (D) Nano-nipples present on a facet surface. (E) Arrangement of nano-nipple diameters for the Mourning Cloak butterfly.
(F) Arrangement of nano-nipple diameters for the Question Mark butterfly. (Permission has been granted through the Copyright Clearance
Center’s Rights Link service.)](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-25-320.jpg)
![L’Or
eal has manufactured a photonic cosmetic product [34] with a periodic nanoscale
structure that produces striking blue color without the help of any chemical pigments.
The light manipulation mechanism of butterfly Morpho scales is the inspiration behind
this. The structural color is feasibly tuned by modifying the periodicity of the layers.
The structural nature of the color also means it is more stable and sturdy than traditional
pigment color. Such structurally colored fabric thus has great potential for application in
the fashion industry and domestic furnishing textiles.
4.2 Antireflection
Antireflection films are widely used to reduce interface reflectance and to enhance the
performance of various kinds of optical devices, like LED displays and optic sensors. Con-
ventionally, interference coatings shaped by the deposition of single-layer and multilayer
stacks are widely adopted to obtain antireflection performance. Nevertheless, as well as
the lack of mechanical stability and the difficulty in fabrication, these antireflection films
are only effective over a narrow region of wavelengths at narrow incidence angles.
Thicker films are needed to suppress the Fresnel reflection of longer-wavelength light.
As an alternative, modern antireflection coatings with intricate microstructures within
the subwavelength range inspired by many natural species have helped us regarding
how to attain this. The presence of antireflection structures was first reported to exist
on the corneas of the eyes of many nocturnal insects [35] (Fig. 9). Thousands of omma-
tidia with size ranging from 10 to 30 μm are tightly packed on the spherical eye of an
insect. They are uniformly arranged with a fixed spatial periodicity of 170 nm. Similar
hierarchical subwavelength nanostructures are also observable on the transparent wings of
some cicadas and hawk moths [37].
This kind of antireflection structure consists of arrays of nanocones and nanopillars
arranged hexagonally. Due to their structured morphology, the Fresnel reflection can
be effectively reduced by the gradient refractive index profile. In addition, the spatial
periodicity is generally below the wavelength of the visible spectrum that can efficiently
Fig. 8 (A) Structure-based green color of butterfly wings; (B, C) different magnification times of the
optical ultrastructure in its wing scale surfaces [33]. (Permission has been granted through the
Copyright Clearance Center’s Rights Link service.)
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From nature: Optics, nanotechnology, and nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-26-320.jpg)
![prevent the light scattering. Inspired by the excellent antireflection subwavelength nano-
photonics structures in the compound eyes of insects and cicada wings, many kinds of
artificial nanostructured antireflective coatings have been produced on an industrial basis
including gratings, nanorods or nanocones, frustums of cones, nanotips, etc. [38]
4.3 Light focusing
Some nocturnal animals have the ability to focus the light from a wide range of angles of
incidence using biological microlenses as a solution to trap the light. The brittlestar
O. wendtii is a good example of a light-sensitive species in aquatic systems [39]. The
surface of each arm contains regular arrays of inorganic photonic structures, similar
to a characteristic double-lens design. Each of these microlenses is composed of single
anisotropic calcite crystals capable of focusing light toward the nerve photoreceptors,
which are 4–7 μm below them. These near-perfect calcite microlenses show a unique
focusing effect with significant signal enhancement and intensity adjustment. In addi-
tion, the surface design of each microlens and constituent calcite orientation decreases
the spherical aberration and birefringence that could degrade the optical function. Thus
O. wendtii can detect dark spots extremely sensitively, and quickly escape from pred-
ators into a dark area. Inspired by the unique microlens design and the outstanding
light-focusing properties in brittlestars, several biomimetic analogs were fabricated
by three-beam interference lithography.
For the compound eye of several insects, the close-packed micro-ommatidium arrays
arranged on the spherical macro basis also act as an effective light focusing tissue. Inspired by
this multi-lens focusing mechanism, an artificial compound eye was fabricated by a laser
direct writing method [40]. The artificial compound eye exhibits high uniformity, imaging,
and focusing capabilities. Moreover, it has the ability for distortion-free wide field of view
imaging and possesses high potential for applications in imaging devices and integrated
Fig. 9 (A) Photograph of the moth Cacostatia ossa—the translucent and matte parts show the
presence of an antireflective structure; (B, C) SEM images of the cross-section and the up-side of
the translucent part of the wings—this shows the non-close-packed nano conical arrays on
both sides of the wing membrane [36]. (Permission has been granted through the SciPris Scientific
Publishing and Remittance Integration Services.)
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![optical microsystems. The artificial compound eye structure can be combined with photo-
electrical micro receivers for wide-angle communication applications [38].
4.4 Chirality
As a result of the changes caused by evolution over millions of years, many natural species
such as beetles, shrimps, and butterflies have developed different types of three-
dimensional chiral photonic crystals sensitive to circularly polarized light (Fig. 10).
The eyes of insects have polarization-sensitive ommatidia, by which these chiral photonic
crystals probably contribute to their camouflage nature and communication systems. The
shrimp Gonodactylus smithii can communicate selectively to distinctly circularly polarized
light. The beetle species Chrysina gloriosa is significantly more brilliant when it is exposed
to left-handed circularly polarized (LCP) than right-handed circularly polarized (RCP)
light [42]. Mate-choice experiments performed by scientists proved that the polarized
light in the butterfly Heliconius cydno is used for sexual selection and speciation [43]. These
chiral biological organisms serve as novel motivations in the search for miniature chiral
optical devices.
5. Summary
Nature is capable of producing several complicated nanoscale structures. Currently,
researchers are exploring the natural world to find out its nanoscale secrets and using
nature as a model for producing these same complicated structures. Nanotechnology
can and will be used to enhance many products, several of which we interact with in
Fig. 10 Examples of 3D natural photonic crystals. On the left, the weevil Entimus imperialis; in the
center, the longhorn Prosopocera lactator; and on the right, the longhorn Pseudomyagrus
waterhousei [41]. Permission has been granted through the Copyright Clearance Center’s Rights Link
service.
15
From nature: Optics, nanotechnology, and nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-28-320.jpg)
![our daily lives. As this research using nature continues, there will be more breakthroughs
that may result in new devices and materials that can impact several aspects of the current
and future societies. Nature has always been efficient in developing numerous photonic
structures to fulfill specific biological functions and offers us plenty of technologically
unattainable photonic designs. To import them into materials systems, we need a com-
prehensive understanding of those structures. Although numerous efforts have been ded-
icated to adding comprehension to these biological structures, the physical difficulty of
the many natural systems makes it complex to create an accurate picture.
Thus, the structural mechanisms with underlying optical functions should be
completely investigated, which is also favorable to the extraction and simplification of
the photonic structures for nonnatural fabrication. Apart from the structural properties,
the physical properties of the material parts are also crucial for achieving specific optical
functions. Thus, we should get enough information concerning the materials utilized in
these natural systems, notably the dispersion properties of their real and imaginary refrac-
tive index parts across relevant frequency ranges. Fortunately, theoretical modeling and
calculation methods have matured to handle these issues. The fabrication of these struc-
tures in addition to targeting functional materials could be a key step toward applying
them. The biotemplating technique has been established as efficient to maintain the com-
plexness of the natural templates; however, it is not suitable for mass production with
high reproducibility. In recent years, biomimetic methods utilizing modern engineering
fabrication methods, like 3D lithography, nano-imprinting, and direct laser writing, have
made great progress with great improvements in resolution.
Nature has also shown various examples of practical integrity, like the iridescent but-
terfly wings, which not only demonstrate vivid structural color, but additionally possess
super-hydrophobicity, directional adhesion, self-cleaning, and fluorescence emission
functions. These enhanced biological solutions provide us with design principles for
the manufacturing of multifunctional artificial materials with multiscale structures. More-
over, by taking advantage of the practical integrations of structural properties from two or
more biological organisms, we are probably able to fabricate a new composite with mul-
tiple unique functions. Nature-inspired research is now at a growing stage and the present
achievements will function as proofs-of-principle and guides for future investigations.
References
[1] G.A. Sotiriou, S.E. Pratsinis, Antibacterial activity of Nanosilver ions and particles, Environ. Sci. Tech-
nol. 44 (2010) 5649–5654.
[2] J.F. Jacobs, I. van de Poel, P. Osseweijer, Sunscreens with titanium dioxide (TiO2) Nano-particles:
A societal experiment, NanoEthics 4 (2010) 103–113.
[3] M.J. Asim Kumar, Nanotechnology: A review of applications and issues, Int. J. Innov. Technol.
Explor. Eng. 3 (2013) 2278–3075.
[4] R. Singh, J.W. Lillard, Nanoparticle-based targeted drug delivery, Exp. Mol. Pathol. 86 (2009) 215–223.
[5] J. Hulla, S. Sahu, A. Hayes, Nanotechnology, Hum. Exp. Toxicol. 34 (2015) 1318–1321.
16 Nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-29-320.jpg)
![[6] Anon, ‘Plenty of room’ revisited, Nat. Nanotechnol. 4 (2009) 781.
[7] T.D. Rossing, C.J. Chiaverina, Light Science: Physics and the Visual Arts, Google eBook, Springer, 1999.
[8] M. Kolle, Photonic Structures Inspired by Nature. Photonic Structures Inspired by Nature, Springer,
Berlin, Heidelberg, 2011. https://doi.org/10.1007/978-3-642-15169-9.
[9] M.V. Berry, Nature’s optics and our understanding of light, Contemp. Phys. 56 (2014) 1–15.
[10] T.F. Anderson, A.G. Richards, An electron microscope study of some structural colors of insects,
J. Appl. Phys. 13 (1942) 748–758.
[11] A.R. Parker, 515 million years of structural colour, J. Opt. A Pure Appl. Opt. 2 (2000) R15–R28.
[12] J.F.V. Vincent, O.A. Bogatyreva, N.R. Bogatyrev, A. Bowyer, A.-K. Pahl, Biomimetics: Its practice
and theory, J. R. Soc. Interface 3 (2006) 471–482.
[13] S. Vignolini, et al., Pointillist structural color in Pollia fruit, Proc. Natl. Acad. Sci. 109 (2012)
15712–15715.
[14] W. Barthlott, C. Neinhuis, Purity of the sacred lotus, or escape from contamination in biological sur-
faces, Planta 202 (1997) 1–8.
[15] K. Balani, R.G. Batista, D. Lahiri, A. Agarwal, The hydrophobicity of a lotus leaf: a nanomechanical
and computational approach, Nanotechnology 20 (2009) 305707.
[16] M. Zhang, S. Feng, L. Wang, Y. Zheng, Lotus effect in wetting and self-cleaning, Biotribology
5 (2016) 31–43.
[17] E.M. Gerhard, et al., Design strategies and applications of nacre-based biomaterials, Acta Biomater.
54 (2017) 21–34.
[18] K. Takahashi, J.O.L. Berengueres, K.J. Obata, S. Saito, Geckos’ foot hair structure and their ability to
hang from rough surfaces and move quickly, Int. J. Adhes. Adhes. 26 (2006) 639–643.
[19] Y. Fang, G. Sun, Y. Bi, H. Zhi, Multiple-dimensional micro/nano structural models for hydropho-
bicity of butterfly wing surfaces and coupling mechanism, Sci. Bull. 60 (2015) 256–263.
[20] K. Autumn, Mechanisms of adhesion in geckos, Integr. Comp. Biol. 42 (2002) 1081–1090.
[21] L. Yan, et al., Magnetotactic bacteria, magnetosomes and their application, Microbiol. Res. 167 (2012)
507–519.
[22] D. Faivre, D. Sch€
uler, Magnetotactic bacteria and magnetosomes, Chem. Rev. 108 (2008) 4875–4898.
[23] L. Novotny, B. Hecht, Principles of Nano-optics. Cambridge University Press, Cambridge, UK, 2012,
https://doi.org/10.1017/CBO9780511813535.
[24] L. Wu, et al., Optical functional materials inspired by biology, Adv. Opt. Mater. 4 (2016) 195–224.
[25] D. Siefermann-Harms, The light-harvesting and protective functions of carotenoids in photosynthetic
membranes, Physiol. Plant. 69 (1987) 561–568.
[26] X. Yang, Z. Peng, H. Zuo, T. Shi, G. Liao, Using hierarchy architecture of Morpho butterfly scales for
chemical sensing: Experiment and modeling, Sensors Actuators A Phys. 167 (2011) 367–373.
[27] A. Dinwiddie, et al., Dynamics of F-actin prefigure the structure of butterfly wing scales, Dev. Biol.
392 (2014) 404–418.
[28] K.C. Lee, U. Erb, Remarkable crystal and defect structures in butterfly eye nano-nipple arrays, Arthro-
pod Struct. Dev. 44 (2015) 587–594.
[29] V.P. Khvostikov, et al., Photovoltaic cells based on GaSb and Ge for solar and thermophotovoltaic
applications, J. Sol. Energy Eng. 129 (2007) 291.
[30] A.R. Parker, Natural photonics for industrial inspiration, Philos. Trans. R. Soc. A Math. Phys. Eng.
Sci. 367 (2009) 1759–1782.
[31] J.W. Galusha, M.R. Jorgensen, M.H. Bartl, Diamond-structured Titania photonic-bandgap crystals
from biological templates, Adv. Mater. 22 (2010) 107–110.
[32] A. Blanco, et al., Large-scale synthesis of a silicon photonic crystal with a complete three-dimensional
bandgap near 1.5 micrometres, Nature 405 (2000) 437–440.
[33] Y. Liu, et al., Bio-inspired micro-nano structured surface with structural color and anisotropic wetta-
bility on cu substrate, Appl. Surf. Sci. 379 (2016) 230–237.
[34] S.M. Luke, P. Vukusic, An introduction to biomimetic photonic design, Europhys. News 42 (2011)
20–23.
[35] X. Gao, et al., The dry-style antifogging properties of mosquito compound eyes and artificial analogues
prepared by soft lithography, Adv. Mater. 19 (2007) 2213–2217.
17
From nature: Optics, nanotechnology, and nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-30-320.jpg)
![[36] O. Deparis, N. Khuzayim, A. Parker, J.P. Vigneron, Assessment of the antireflection property of moth
wings by three-dimensional transfer-matrix optical simulations, Phys. Rev. E 79 (2009) 041910.
[37] P.R. Stoddart, P.J. Cadusch, T.M. Boyce, R.M. Erasmus, J.D. Comins, Optical properties of chitin:
surface-enhanced Raman scattering substrates based on antireflection structures on cicada wings,
Nanotechnology 17 (2006) 680–686.
[38] Y.-F. Huang, et al., Improved broadband and quasi-omnidirectional anti-reflection properties with
biomimetic silicon nanostructures, Nat. Nanotechnol. 2 (2007) 770–774.
[39] J. Aizenberg, A. Tkachenko, S. Weiner, L. Addadi, G. Hendler, Calcitic microlenses as part of the pho-
toreceptor system in brittlestars, Nature 412 (2001) 819–822.
[40] D. Wu, et al., Bioinspired fabrication of high-quality 3D artificial compound eyes by voxel-modulation
femtosecond laser writing for distortion-free wide-field-of-view imaging, Adv. Opt. Mater. 2 (2014)
751–758.
[41] J.P. Vigneron, P. Simonis, Natural photonic crystals, Phys. B Condens. Matter 407 (2012) 4032–4036.
[42] V. Sharma, M. Crne, J.O. Park, M. Srinivasarao, Structural origin of circularly polarized iridescence in
jeweled beetles, Science 325 (2009) 449–451.
[43] A. Sweeney, C. Jiggins, S. Johnsen, Polarized light as a butterfly mating signal, Nature 423 (2003)
31–32.
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![when coming across obstacles, namely absorption, reflection, refraction, diffusion, and
dispersion. Sommerfeld defined this phenomenon conveniently as follows:
Diffraction is any deviation of light rays from the initial path which can be explained neither by
reflection nor by refraction.
The optical region of the electromagnetic spectrum, corresponding to wavelengths in the
visible, near-infrared, or ultraviolet spectrum, has long been considered attractive for
communications. The frequency of the light allows for high signal modulation frequency
and consequently high transmission speed.
In 1880, G.A. Bell patented an air-based optical telephone called the “Photophone,”
consisting of focusing sunlight on the surface of a flat mirror vibrating with sound. The
light was then sent to a detector of selenium coupled to a telephone receiver. A few later
ideas were also patented, one of them in Japan even suggesting quartz as a transmission
medium. In the 1950s, however, very few communication scientists considered optical
communication as a viable concept.
One hundred and twenty years ago, G. Marconi and K.F. Braun were awarded a
Nobel Prize “in recognition of their contributions to the development of wireless
telegraphy.” Sixty years ago, electronic and radio communications were in rapid
expansion. The first transatlantic cable was installed in 1956 and satellites would soon
allow even better coverage. The first communication satellite was launched in 1958.
Research in telecommunication concentrated mainly on shorter radio waves, in the
millimeter range, with the aim to reach higher transmission speeds. These waves could
not travel as easily in air as longer waves, and the research focused on designing practical
waveguides.
N.S. Kapany and H.H. Hopkins at Imperial College London constructed bundles of
thousands of fibers of length 75 cm and showed appreciable image transmission [1]. By
having a cladding to the fiber bundles, some applications, especially the gastroscope, went
into industrial production. The refractive index of the core is slightly higher than that of
the cladding. Typical dimensions are 10 or 50 μm for the core and 125 μm for the fiber.
In addition, a protecting plastic buffer is placed around the fiber went all the way to indus-
trial production. The theory of light propagation into fibers was described by N.S.
Kapany. His article on fiber optics in Scientific American in 1960 established the term
“fiber optics.”
The invention of the laser in the early 1960s (Nobel Prize in 1964 to C.H.
Townes, N.G. Basov, and A.M. Prokhorov) gave a new boost to the research in optical
communication. Shortly after the pulsed laser demonstrated in ruby by T.H. Maiman, A.
Javan built the first continuous-wave laser using a mixture of He and Ne gas. Semicon-
ductor lasers appeared almost at the same time, but were at first not so practical, since they
required high currents and could not work at room temperature. A few years later, the
introduction of heterostructures (Nobel Prize in 2000 to Z.I. Alferov and H. Kroemer)
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![1.6 Optical properties of nanoparticles
Focusing attention on interaction of light on particles on the nanometer scale, the field
of nano-optics has flourished greatly in recent times. On the nanometer scale, materials
including metals, semiconductors, dielectrics, and polymers exhibit interesting prop-
erties, especially optical properties. Among the various applications, innovative
methods to develop thin film coatings have garnered much attention. Nanocomposites
have been designed to achieve materials with tunable refractive indices and enhanced
optical properties.
Deeper and specific focus should be laid on the interaction of light with a material.
When light interacts with a material, there are three possible main effects: absorption,
transmission, and reflection of light. The nanoparticles exhibit higher specific surface
area, surface energy, and density compared to bulk materials. Hence introducing nano-
particles at even lower filler loadings will have tremendous effect on the physical, thermal,
and mechanical properties of the matrix [2]. Nanomaterials when combined with poly-
mers have enhanced mechanical and optical properties (e.g., refractive index and coef-
ficient of absorption) and find applications in light-emitting diodes, solar cells, polarizers,
light-stable color filters, optical sensors, etc. They also give rise to new characteristics like
light emission [3]. The optical properties of nanoparticles have been investigated for var-
ious applications like UV-filters, bio-imaging, photo thermal therapies, oxygen sensors,
etc. [4]. Ceria nanoparticles have attracted much attention as luminescent material and
material with a high refractive index [5]. Ceria nanoparticles are highly biocompatible
and hence several studies have focused on the use of cerium oxide nanoparticles as
Fig. 5 Schematic representing Brewster’s angle.
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![contrast agents for MRI [6]. Cerium is the most abundant element in the rare earth fam-
ily. Ce has electronic configuration [Xe] 4f2
6s2
and has two common oxidation states,
Ce3+
and Ce4+
[7]. Cerium has shielded 4f-electrons, which are responsible for the fas-
cinating properties of the rare earth element. PS/PMMA-grafted CeO2 nanocomposite
films were prepared by Parlak et al. using spin coating. It was observed that blending of PS
and CeO2 nanoparticles resulted in opaque films, whereas grafting of PMMA chains onto
CeO2 enhanced the transparency of the composite. This is because there is a strong
refractive index mismatch between PS and CeO2 particles. However, when PMMA with
a lower refractive index than PS and CeO2 is incorporated, the refractive index mismatch
is nullified [8].
2. Challenges: Nano-optics bottleneck
Electronic devices in principle work by the manipulation of the flow of electrons. Since
the size of an atom is around 0.1–0.5 nm, we can safely assume that the size profile of an
electron (if we can speak about the “size” of an electron at all) must be infinitesimally
smaller than nanometer dimensions. This effectively means that the electrons are capable
of working in dimensions smaller than the size of atoms.
Photonic devices, on the other hand, manipulate light, or more specifically electro-
magnetic radiation near or around visible light. Since the wavelength of light in the
region around visible light is in terms of hundreds of nanometers, no photonic devices
can therefore be smaller than the wavelength profile of light. This is a major obstacle that
limits the plethora of benefits offered by photonic technology while downscaling the size.
Though the size parameter is a major stumbling block, it has not limited the curiosity
and enthusiasm of physicists to investigate the interaction of light in subwavelength
dimensions, and what they found out was enthralling. Light in fact changed its behavior
in subwavelength dimensions.
Nano-optics emerged as the branch of science dealing with the study of the interac-
tion of light in nanometer dimensions. The branch requires a vivid and avid idea of the
complex and rigorous theoretical knowhow as nanoscale interaction of light can barely
be understood with the basic knowledge of the interaction of light in the daily life.
3. Trends: Current scenario in nano-optics
As stated above, it is impossible to downscale light beyond a limit, more precisely beyond
half the wavelength. If that is so, why should we bother about interaction of light on a
subwavelength scale?
Nano-optics researchers are exploiting this possibility of confining light in a single
spatial direction. The field has already branched out into many specific areas of interest.
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![• Spasers (surface plasmon amplification by stimulated emission of radiation), where the
oscillations are maintained by the stimulated emission of surface plasmons. Spasers are
nanoscale lasers.
4. The future: A world of possibilities
Nano-optics is still a very new topic, and experimental realization of the possibilities of
nanoscale interactions in the optical realm started only in 1984 when the optical coun-
terpart of scanning tunneling microscope (STM) was developed. Still not even 50 years
old, the science of nano-optics is now a multimillion dollar industry.
The possibilities are bigger when we go nanoscale, from immense medical advantages
to military applications and beyond. If we can control a nanometer-sized device perfectly,
it may even drive humanity to the doorstep of immortality. Nanoscale optical devices can
bring the vibrant colors of nature to our living rooms, and the manipulation of light might
overpower the electronics industry as we know it. Better and more efficient power
generation is another result worth mentioning.
5. Conclusion
Wonders of nano-optics are not at all new in nature. The vibrant hues we see in peacock
feathers, the magnificent colors on a butterfly’s wing, all make use of nano-optic prop-
erties of light. The technology is used in photosynthesis by plants. Understanding the
science behind nano-optics essentially bestows us with a better understanding of nature.
References
[1] H.H. Hopkins, N.S. Kapany, A flexible fibrescope, using static scanning, Nature 173 (1954) 39–41.
[2] A.M. Dı́ez-Pascual, Nanoparticle reinforced polymers, Polymers (Basel) 11 (2019) 625.
[3] I. Roppolo, M. Sangermano, A. Chiolerio, Optical properties of polymer nanocomposites, In: Functional
and Physical Properties of Polymer Nanocomposites (2016) 139–157.
[4] A. Gupta, S. Das, C.J. Neal, S. Seal, Controlling the surface chemistry of cerium oxide nanoparticles for
biological applications, J. Mater. Chem. B 4 (2016) 3195–3202.
[5] H. Gu, M.D. Soucek, Preparation and characterization of monodisperse cerium oxide nanoparticles in
hydrocarbon solvents, Chem. Mater. 19 (2007) 1103–1110.
[6] P. Eriksson, A.A. Tal, A. Skallberg, C. Brommesson, Z. Hu, R.D. Boyd, W. Olovsson, N. Fairley,
I.A. Abrikosov, X. Zhang, Cerium oxide nanoparticles with antioxidant capabilities and gadolinium
integration for MRI contrast enhancement, Sci. Rep. 8 (2018) 6999.
[7] C. Sun, H. Li, L. Chen, Nanostructured ceria-based materials: synthesis, properties, and applications,
Energy Environ. Sci. 5 (2012) 8475–8505.
[8] O. Parlak, M.M. Demir, Toward transparent nanocomposites based on polystyrene matrix and
PMMA-grafted CeO2 nanoparticles, ACS Appl. Mater. Interfaces 3 (2011) 4306–4314.
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![CHAPTER 3
Nano-optics for healthcare applications
Blessy Josepha
, Jemy Jamesa,b
, Nitin Eapena
, Nandakumar Kalarikkala
,
Sabu Thomasa
a
International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University,
Kottayam, Kerala, India
b
FRE CNRS 3744, IRDL, University of Southern Brittany, Lorient, France
1. Introduction
Nanotechnology is the art of making things smaller. The field of nanotechnology is
growing quickly and steadily. Nanoparticles have been used in the design of highly func-
tional materials due to their unique physical and chemical properties. Different types of
nanoparticles like metallic, non-metallic, and magnetic, carbon nanotubes, etc. are
widely used for various applications. However, inorganic nanoparticles (metallic and
metallic oxide nanoparticles) are of great interest due to their excellent physical and
chemical properties. They have been particularly effective in the strategic design of opti-
cal devices. The need for miniature-sized and lightweight optical components is increas-
ing day by day. This is possible by tailoring the size and shape of nanoparticles. Metallic
nanoparticles like gold nanoparticles show tunable radiation and absorption wavelength
depending on their aspect ratio, arising due to localized surface plasmon resonance
(LPSR) [1, 2]. When the incident light of certain frequency falls on metallic nanostruc-
tures, the free electrons in the material resonate at a frequency that is dependent on the
size and shape of the material (Fig. 1). The particles will strongly absorb or scatter light
when the wavelength of the incident light matches the oscillating frequency. This phe-
nomenon, described as LSPR, involving light matter interaction, a characteristic of plas-
monic nanostructures, is exploited for several applications in biomedical sector. The field
that studies this light matter interaction at nanometer scale—known as nanophotonics or
nano-optics—has been successful in developing new imaging modalities, especially for
medical imaging and diagnosis. The optical properties of nanoparticles were initially
described in 1857 by Michael Faraday. Studies on plasmonics started in 1899, and exper-
imental observations of plasmonic effects in light spectra were investigated by Robert
Wood in 1902 [3].
Inorganic nanoparticles exhibit superior material properties with functional versatil-
ity. They are being explored as potential tools for diagnostics as well as for treating dis-
eases due to their size features and advantages over conventional chemical imaging
techniques. They have been widely used for cellular delivery due to their versatile
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![features, such as wide availability, rich functionality, good biocompatibility, capability of
targeted drug delivery, and controlled release of drugs. For example, gold nanoparticles
have been extensively used in imaging, as drug carriers, and in thermotherapy of biolog-
ical targets. The interesting colors of metallic nanoparticle solutions are due to the red
shift of the plasmon band to visible frequencies, unlike that for bulk metals, where the
plasmon absorption is in the ultraviolet region. In fact, the optical properties of nanopar-
ticles depend significantly on their size and shape as well as on the dielectric constant of
the surrounding medium. Nanoparticles such as 20 nm sized gold (Au), platinum (Pt),
silver (Ag), and palladium (Pd) have characteristic wine red, yellowish gray, black,
and dark black colors, respectively [4]. Thus LSPR acts as a powerful tool to manipulate
light on the nanoscale. This chapter concentrates on the fundamental principles behind
nano-optics and the use of optically active nanomaterials for biomedical applications.
2. Nano-optics for bio imaging
The ultimate goal of bio imaging is to monitor and record structural and functional infor-
mation related to biological materials. Over the decades, several imaging systems have
been evolved to visualize biological specimens noninvasively, such as X-ray computed
tomography (CT), magnetic resonance imaging (MRI), optical coherence tomography
(OCT), etc. Optical techniques are highly desirable for bio imaging due to the fact that
they are safe, less expensive, and rapid when compared to other conventional techniques.
Nanoparticles present new opportunities for bio imaging, providing increased sensitivity
in detection through amplification of signal changes. They exhibit specific cellular uptake
Nanoparticle
Light
wave
Electric
field
+ +
+
+
+
+
+
– –
–
–
–
–
–
–
+
Fig. 1 Schematic diagram illustrating the localized surface plasmon on a nanoparticle surface.
(Reproduced with permission from S. Unser, I. Bruzas, J. He, L. Sagle, Localized surface plasmon
resonance biosensing: Current challenges and approaches, Sensors (Switzerland). 15 (2015)
15684–15716. https://doi.org/10.3390/s150715684.)
34 Nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-47-320.jpg)
![and possess properties that make them easily visible, such as quantum dots. Nanoparticles
act as tracers for improved visualization. Since light absorption from biologic tissues is at
its minimum at the near infrared (NIR) wavelengths, most nanoparticles like metal and
magnetic nanoparticles are designed to absorb strongly in the NIR region. Thus they
have proven to possess remarkable advantages for in vivo imaging [5].
Magnetic resonance imaging (MRI) is a noninvasive imaging modality that offers both
anatomical and functional information. Iron oxide nanoparticles are of considerable interest
as contrast agents for MRI due to their unique superparamagnetic properties [6, 7]. MRI
has been extensively studied for the successful tracking of stem cells. Lin et al. reported the
use of superparamagnetic iron oxide nanoparticles (SPIONs) to label mesenchymal stem
cells (MSCs). The distribution and migration of MSCs were evaluated using MRI for
up to 6 weeks [8]. Nickel ferrite nanoparticles also have been developed for MRI contrast
enhancement [9]. In order to alleviate the possible toxicity by nickel, ferrite nanoparticles
were coated with oleic acid and tetramethyl ammonium hydroxide (TMAH), where
TMAH also acted as a stabilizer. There are two particular types of contrast agents: T1
MRI and T2 MRI [10]. T1 MRI is also known as a positive contrast agent (CA) since
it gives brighter images. Gadolinium-based chelates belong to this class. Toxicity is a major
concern with this group of contrast agents [11]. The other class, T2 MRI CA, includes
dextran- or siloxane-coated super paramagnetic iron oxide nanoparticles [12]. This is also
known as negative CA due to the darker images obtained. T1 CA is preferred due to the
highly brightened images that are obtained. Several studies have focused on the alternatives
for T1 MRI contrast agents. Li et al. reported the advantages of pH-sensitive cross-linked
iron oxide nanoparticle assemblies (IONAs) as T1 MRI contrast agents for imaging tumors
[13]. The IONAs were extremely stable at neutral pH and had a blood circulation half-time
of nearly 2.2 h. Moreover the in vivo studies showed that the IONAs didn’t induce any
renal toxicity or hepatotoxicity.
The conversion of near-infrared radiations into visible light via nonlinear optical pro-
cesses, termed upconversion, has received considerable attention in biomedical applica-
tions. Among the nanoparticles that exhibit upconversion, rare-earth-doped
nanoparticles are considered as an alternative to traditional bio labels. The main advan-
tages include good chemical and physical stability, better spatial resolution, and low toxicity
[14]. It is particularly advantageous for background free biological sensing [15]. The main
advantages of this technique include improved sensitivity due to the absence of autofluor-
escence and deeper penetration into tissue, leading to less damage to biological tissues [14].
Upconversion nanoparticles doped with lanthanide ions received considerable attention in
this aspect [16]. Europium complex loaded polymer nanoparticles (ECP-NPs) were stud-
ied for live cell imaging [17]. PMMA-bearing carboxylate and sulfonate groups were
loaded with 1%–40% Europium complexes. The ECP-NPs were incubated with HeLa
cells for 3 h and TG (time-gated) imaging was done at a very low excitation power density
of 0.24 W cm 2
. It could be clearly seen that strong photoluminescence signals arise from
the endocytosed ECP-NPs (Fig. 2).
35
Nano-optics for healthcare applications](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-48-320.jpg)
![3. Nano-optics for biosensing
Nanotechnology is becoming a crucial driving force behind innovation in medicine and
healthcare, with a range of advances including nanoscale therapeutics, biosensors,
implantable devices, drug delivery systems, and imaging technologies. Nanophotonics
are particularly attractive in that they provide minimally invasive diagnostics for early
detection of diseases and help in real-time monitoring of drug intake.
Early detection of cancer can save more lives than any form of treatment at advanced
stages. Circulating tumor cells (CTCs) are viable cancer cells derived from tumors. The
origin of the metastatic disease is represented by these CTCs. Using nanotechnology, we
can develop devices that indicate when these CTCs appear in the body, and hence deliver
agents to reverse premalignant changes or kill those cells that have the potential to
become malignant.
Researchers have demonstrated a carbon nanotube chip that captures and analyses
circulating tumor cells in blood, rather than using magnetic and microfluidic methods
for the isolation of CTCs [18]. The schematic of the sensing technique is given in
Fig. 3. Some interesting works have been reported by Tseng et al., in which a
Fig. 2 Live-cell images of HeLa cells incubated with ECP-NPs. (A) TG PL images with PMMA-COOH 10%
(A1), PMMA-SO3H 3% (A2), and PMMA-SO3H 1% (A3) NPs at 40% [Eu(tta)3phen] loading. For a better
comparison between the different images, the intensity scale was fixed at 0 to 2 104 counts.
(B) Differential interference contrast (DIC) images. (C) Overlay of images from A and B (ECP-NP PL is
shown in red, PL intensities were normalized to the highest values in A1, A2, and A3). Scale bars in
all images: 10 μm. (Reproduced with permission from M. Cardoso Dos Santos, A. Runser, H. Bartenlian,
A.M. Nonat, L.J. Charbonnière, A.S. Klymchenko, N. Hildebrandt, A. Reisch, Lanthanide-complex-loaded
polymer nanoparticles for background-free single-particle and live-cell imaging, Chem. Mater. 31 (2019)
4034–4041. https://doi.org/10.1021/acs.chemmater.9b00576.)
36 Nano-optics](https://image.slidesharecdn.com/33865-250403134435-0e563584/85/Nano-Optics-Fundamentals-Experimental-Methods-and-Applications-Micro-and-Nano-Technologies-1st-Edition-Sabu-Thomas-Editor-49-320.jpg)
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- 6. NANO-OPTICS
- 7. NANO-OPTICS Fundamentals, Experimental Methods, and Applications Edited by SABU THOMAS YVES GROHENS GUILLAUME VIGNAUD NANDAKUMAR KALARIKKAL JEMY JAMES
- 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: 978-0-12-818392-2 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: Ana Claudia Garcia Production Project Manager: Kamesh Ramajogi Cover Designer: Christian J. Bilbow Typeset by SPi Global, India
- 9. Contributors Harith Ahmad Photonics Research Center, University of Malaya, Kuala Lumpur, Malaysia Stuart Bowden Quantum Energy for Sustainable Solar Technology (QESST) Engineering Research Center, Arizona State University, Tempe, AZ, United States Dermot Brabazon I-Form, Advanced Manufacturing Research Centre, & Advanced Processing Technology Research Centre, School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin, Ireland Jenu V. Chacko Laboratory for Optical and Computational Instrumentation (LOCI), University of Wisconsin at Madison, Madison, WI, United States Balu Chandra International School of Photonics, Cochin University of Science and Technology, Cochin, Kerala, India Judith M. Dawes MQ Photonics Research Center, Department of Physics and Astronomy, Macquarie University, Sydney, NSW, Australia Joydeep Dutta Functional Materials division, Materials and Nano-Physics Department, ICT School, KTH Royal Institute of Technology, Stockholm, Sweden Nitin Eapen International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India Karsten Fleischer I-Form, Advanced Manufacturing Research Centre, & Advanced Processing Technology Research Centre, School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin, Ireland Stephen Goodnick Quantum Energy for Sustainable Solar Technology (QESST) Engineering Research Center, Arizona State University, Tempe, AZ, United States Yves Grohens FRE CNRS 3744, IRDL, University of Southern Brittany, Lorient, France Banshi D. Gupta Physics Department, Indian Institute of Technology Delhi, New Delhi, India ix
- 10. Sulaiman Wadi Harun Department of Electrical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur, Malaysia Christiana Honsberg Quantum Energy for Sustainable Solar Technology (QESST) Engineering Research Center, Arizona State University, Tempe, AZ, United States Jemy James FRE CNRS 3744, IRDL, University of Southern Brittany, Lorient, France; International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India Jerry Jose International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India Blessy Joseph FRE CNRS 3744, IRDL, University of Southern Brittany, Lorient, France; International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India Nandakumar Kalarikkal School of Pure and Applied Physics; International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India Changhyoup Lee Institute of Theoretical Solid State Physics, Karlsruhe Institute of Technology, Karlsruhe, Germany Kwang-Geol Lee Department of Physics, Hanyang University, Seoul, Korea Juby Alphonsa Mathew International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India Eanna McCarthy I-Form, Advanced Manufacturing Research Centre, Advanced Processing Technology Research Centre, School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin, Ireland Waleed Soliman Mohammed Center of Research in Optoelectronics, Communication and Control Systems (BU-CROCCS), School of Engineering, Bangkok University, Pathum Thani, Thailand Rajesh V. Nair Department of Physics, Indian Institute of Technology Ropar, Rupnagar, Punjab, India Parvathy Nancy School of Pure and Applied Physics; International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India x Contributors
- 11. Anisha Pathak Physics Department, Indian Institute of Technology Delhi, New Delhi, India Hazli Rafis Abdul Rahim Department of Electrical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur; Universiti Teknikal Malaysia Melaka, Melaka, Malaysia Siti Aisyah Reduan Photonics Research Center, University of Malaya, Kuala Lumpur, Malaysia Carsten Rockstuhl Institute of Theoretical Solid State Physics; Institute of Nanotechnology, Karlsruhe Institute of Technology, Karlsruhe, Germany Swasti Saxena Department of Applied Physics, Sardar Valla Bhai National Institute of Technology, Surat, Gujarat, India Vivek Semwal Physics Department, Indian Institute of Technology Delhi, New Delhi, India Ashin Shaji Institute of Physics, Slovak Academy of Sciences, Bratislava, Slovakia Sithara P. Sreenilayam I-Form, Advanced Manufacturing Research Centre, Advanced Processing Technology Research Centre, School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin, Ireland Ankit Kumar Srivastava School of Applied Natural Science, Adama Science and Technology University, Adama, Ethiopia Mark Tame Department of Physics, Stellenbosch University, Stellenbosch, South Africa Kavintheran Thambiratnam Photonics Research Center, University of Malaya, Kuala Lumpur, Malaysia Siddharth Thokchom National Institute of Technology Manipur, Imphal, India Sabu Thomas School of Chemical Sciences; International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India Zian Cheak Tiu Photonics Research Center, University of Malaya, Kuala Lumpur, Malaysia Jijo P. Ulahannan Department of Physics, Government College, Kasaragod, Kerala, India Guillaume Vignaud FRE CNRS 3744, IRDL, University of Southern Brittany, Lorient, France xi Contributors
- 12. About the Editors Prof. Sabu Thomas is Vice Chancellor of Mahatma Gandhi University, Kottayam, Kerala, India. He is also Director of the School of Energy Materials, Professor at the School of Chemical Sciences and the founding Director of the International and Inter-University Centre for Nanoscience and Nanotechnology, at Mahatma Gandhi University, Kottayam, Kerala. Prof. Thomas is an outstanding leader with sustained international acclaim for his work in polymer science, polymer nanocomposites, elastomers, polymer blends, interpenetrating polymer networks, polymer membranes, nanoscience, nano- medicine, and green nanotechnology. Prof. Yves Grohens is Director of ComposiTIC Laboratory at the University of South Brittany, France. His research interests include interface science in nano and bio-composites. He is also involved in research on confinement in model thin films and its applications, (bio)polymers and their blends, and bio-composites. Interfaces and adhesion of polymers with natural reinforcing agents is one of the hot topics for applications in transportations and others. He is involved in many French and European networks focusing on these topics. He works with many French and some international companies including Arkema, PSA, Cooper Santard, CSP, and Airbus. xiii
- 13. Prof. Nandakumar Kalarikkal is Director of the International and Inter-University Centre for Nanoscience and Nanotechnology, and the School of Pure and Applied Physics, Mahatma Gandhi University, Kottayam, Kerala, India. The research works of his group include the syntheses, characteri- zation, and applications of various nanomaterials, LASER-matter interactions, ion irradiation effects on various novel materials, and phase transitions. Dr. Guillaume Vignaud is Assistant Professor of Physics at the University of South Brittany, France. His areas of expertise include polymer thin films, ultrathin films and interfaces, thin film deposition, material characterization, X-ray diffraction, and nanomaterials synthesis. Dr. Jemy James obtained his Ph.D. from the University of South Brittany, France, and is presently working at WITec GmbH, India. He was previously a junior research fellow at Mahatma Gandhi Univer- sity, Kottayam, Kerala, India. xiv About the Editors
- 14. CHAPTER 1 From nature: Optics, nanotechnology, and nano-optics Ashin Shajia , Jemy Jamesb,c , Parvathy Nancyc,d a Institute of Physics, Slovak Academy of Sciences, Bratislava, Slovakia b FRE CNRS 3744, IRDL, University of Southern Brittany, Lorient, France c International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India d School of Pure and Applied Physics, Mahatma Gandhi University, Kottayam, Kerala, India 1. Introduction Nanomaterials are abundant in nature, since everything in our world is composed of very small particles. As a result, nanotechnology is always inspired by nature and natural phe- nomena. The properties of the materials created by nature through evolutionary pro- cesses are highly efficient or optimal, hence the use of natural materials directly in the development of nanotechnology is of great importance. Now scientists have a clear idea of how to create nanoscale materials with unique properties that never existed before. Products using nanomaterials are now available in the market, such as nanoscale silver as an antibacterial [1], sunscreen with nanoscale titanium dioxide that prevents sunburn [2], application in the field of electronics as in batteries, targeted drug delivery, nanofilms for coatings, water filtration, etc. [3] Molecular-level manipulation is the ultimate base of nanotechnology, but that doesn’t mean that this field of science always deals only with artificial materials. In nature, molecules organize themselves into complex structures that could support life, similar to the present nanotechnology that we are used to. Nature constructs every- thing atom by atom, and understanding the basic principle of natural systems will help nanoscientists to design artificial nanomaterials. For example, oncologists are looking into nanotechnology as a potential way to treat cancer with targeted drug delivery by the use of nanomedicine [4]. The inspiration for this is from the viruses that seek out a specific type of cell to attack in a living organism. Similarly, optically transparent materials have been improved by imitating the nanostructures found in the wings of insects. Finding inspiration from nature’s nanotech is becoming big business nowadays. Nano-optics or nanophotonics has become a serious topic of research over the past decades. The interaction of light with nanometer-scale particles has developed into a new and separate branch from conventional photonics research topics due to its massive pres- ence in the natural world and also from an application point of view. On the nanometer 1 Nano-Optics © 2020 Elsevier Inc. https://doi.org/10.1016/B978-0-12-818392-2.00001-9 All rights reserved.
- 15. scale, materials including metals, semiconductors, dielectrics, and polymers exhibit inter- esting properties, especially optical properties [5]. Particles that come under a size range of nanometers show special phenomena that are not predictable as in their bulk counter- parts. Making use of these properties of the nanoparticles in the field of optics and pho- tonics is the core of nanophotonics [6]. The major aim of this chapter is to give a brief introduction to the presence of nanotechnology and nanophotonics in the natural world rather than the artificially created nano universe. Without going into deeper theoretical aspects, this chapter presents an overall picture of the influence and existence of nano- technology in nature. 2. Nature and optics In nature, optical phenomena are observable as a result of the interaction of matter and light; interactions of light from the sun and moon with particles in the atmosphere, clouds, water, dust, etc. are the reason for some of the common natural optical phenom- enon like mirages and rainbows (Fig. 1). Many of these natural phenomena in nature arise from the optical properties of the atmosphere and due to the presence of other objects in nature or sometimes even due to the visual illusion created by the human eye, such as entoptic phenomena [7]. The particle and wave nature of the light also influences this kind of phenomenon. Some are quite delicate and noticeable only by precise scientific measuring instruments. One of the notable observations is the bending of light from a star by the sun, observed during the time of the solar eclipse. This demonstrates that space is curved, as predicted by Einstein in his theory of relativity. Most optical phenomena can be explained on the basis of the classical electromagnetic explanation of light. But in practical applications, a completely electromagnetic description of light is often difficult to apply in practice. So for practical applications, optics is usually demonstrated using simplified models, like geometric optics, that treat light as a collection of rays that travel in a straight line and bend from a surface when they pass through or reflect from it. Wave optics or physical optics is a more inclusive model of light, which explains the wave nature of such phe- nomena as diffraction and interference, which cannot be explained using geometric optics. Based on the history of light in nature, the first accepted model to explain the nature of light is the ray-based model of light, and later on, the wave model of light. The intro- duction of the electromagnetic theory in the 19th century led to the rediscovery of light waves as electromagnetic radiation. Even so, there are some phenomena in nature that can be explained only by considering the fact that light has both wavelike and particle- like nature (dual nature of light), effects that require quantum mechanical explanations. Quantum optics is the field of science that deals with the application of quantum mechan- ics to optical systems. When considering the particle-like nature of light, light is 2 Nano-optics
- 16. considered as a collection of particles called photons. Optical science is an important and applicable field of science in many related disciplines like astronomy, photography, var- ious engineering fields, and especially in medical fields like optometry and ophthalmol- ogy. Practical implementation of optics is found in everyday life and in a variety of technologies like telescopes, mirrors, lenses, microscopes, lasers, optical fibers, etc. Most colors in nature originate due to selective adsorption resulting from the pigmen- tation embedded in the body or surface of an object. However, a certain range of intense and bright contrast colors result from the interaction of light with nano- and microstruc- tures, which leads to the appearance of color by coherent scattering, interference, and diffraction without any absorption. These colors are commonly known as “structural colors” [8]. The structures that help to modulate light leading to structural colors are part of the family of photonic structures in nature. Fig. 1 Some of the common optical phenomena happening in nature: (A) double rainbow and supernumerary rainbows on the inside of the primary arc; (B) very bright sun dogs in Fargo, North Dakota; (C) the reflection of Mount Hood in Mirror Lake; (D) a 22° halo around the sun, as seen in the sky over Annapurna Base Camp, Annapurna, Nepal. ((A) Eric Rolph at English Wikipedia (https:// commons.wikimedia.org/wiki/File:Double-alaskan-rainbow.jpg), “Double-alaskan-rainbow,” size and shape of the image by Ashin Shaji, https://creativecommons.org/licenses/by-sa/2.5/legalcode; (D) Anton Yankovyi (https://commons.wikimedia.org/wiki/File:Halo_in_the_Himalayas.jpg), size and shape of the image by Ashin Shaji, https://creativecommons.org/licenses/by-sa/4.0/legalcode.) 3 From nature: Optics, nanotechnology, and nano-optics
- 17. Photonic structures can be defined as regular structures with periodicities matching with the order of the wavelength of the light [9]. Structural colors have been a hot topic of research for centuries, and the involvement of micro- and nanostructures in them was introduced by Hooke (1665), Newton (1704), and Lord Rayleigh (1917) [8]. The first ever imaging and a detailed study of structural elements that induce structural colors were suggested by Anderson and Richards [10] after the introduction of the electron micro- scope. The interest in natural structural colors was found to increase due to the fast growth in the field of optical spectroscopy and scanning/transmission microscopy. These spectroscopic techniques help to investigate the details of the complex nano and micro- structures with unique optical characteristics that evolved and existed solely in nature for millions of years [11]. Optical issues like high reflectivity or transmission, strong polarization of light, dichroism, spectral filtering, etc., can be controlled with the help of the natural world since nature provides solutions for all these in the form of nanostructures of different morphological varieties. Thus, nature offers an abundant number of road maps for multifunctional micro- and nanostructures that show outstanding dynamic and distinc- tive coloration. This kind of structured material originates as a result of evolution over millions of years and invites the interest of scientists to carry out deeper research that may build the basis of future optical devices. It can find applications in medical diag- nostics, communication, information processing, and devices with functionalities that can go beyond the current stage. Therefore, the biomimetic approach is currently a hot field of science. For the purpose of solving complex human problems, imitation or copying the models, systems, or solutions from nature is known as biomimetic or bio- mimicry [12]. 3. Nanotechnology in nature Nanoscience and nanotechnology always find inspiration from nature. Some common nanostructures that are visible in nature include inorganic materials such as carbonaceous soot, clay, organic natural thin films, and a variety of organic nanostructures such as pro- teins, insects, and crustacean shells. These structures cause a range of behaviors in nature together with the wettability of surfaces, the brightness of butterfly wings, and also the adhesive properties of the lizard’s foot. The coloration of many varieties of beetles and butterflies is created by sets of rigor- ously spaced nanoscopic pillars. Fabricated from sugars like chitosan, or proteins like ker- atin, the widths of slits between the pillars are designed to control light to attain certain colors or effects like iridescence. One advantage of this strategy is resilience. Pigments tend to bleach with exposure to light; however, structural colors are stable for remarkably long periods. 4 Nano-optics
- 18. A study of structural coloration in metallic-blue marble berries [13] where the spec- imens collected in 1974, that had maintained their color despite being long dead. Sim- ilarly, a lotus leaf is an example of an engineered surface because of its physical and chemical conditions at the micro- and nanometer scale, able to provide a self-cleaning effect. Wilhelm Barthlott, a German botanist, is considered to be the discoverer of the Lotus effect [14] as he applied for its patent in 1994. He found out that the combination of the chemical makeup of the surface and also the micro-and nano-projections on the surface were the reason behind the effect. The protrusions [15] of the lotus leaf are 10 μm high, with every protrusion covered in bumps of a hydrophobic, waxy material that is roughly 100 nm in height. The chitin polymer and epicuticular wax projections allow the leaf to trap air. Water droplets ride on the tips of the projections and result in a bed of air to make a super-hydrophobic surface (Fig. 2). Scientists designed this behavior Fig. 2 Examples of self-cleaning surfaces in nature and their SEM images [16]. (Permission has been granted through the Copyright Clearance Center’s Rights Link service.) 5 From nature: Optics, nanotechnology, and nano-optics
- 19. into the product Lotusan® , a self-cleaning paint. This paint mimics the microstructure of the surface of a lotus leaf once it dries and cures within the environment. Small peaks and valleys on the surface minimize the contact area for water and dirt, keeping the surface clean. Various merchandise is currently on the market that mimics this hydrophobic property, including consumer goods, spray coatings, plungers, toilet fixtures, automotive components, etc. Researchers at several universities are synthesizing biomimetic nanocomposites to form robust materials to be used in lightweight armor systems, structures in transportation systems, sturdy electronics, aerospace applications, etc. Nature has evolved an advanced bottom-up approach for fabricating nanostructured materials that have great mechanical strength and toughness. One of nature’s toughest materials is nacre, which is best known as the iridescent mother-of-pearl made by mollusks. Mollusks produce nacre by depos- iting amorphous calcium carbonate (CaCO3) onto porous layers of polysaccharide chitin. The mineral then crystallizes, producing stacks of CaCO3 that are separated by layers of organic material. Its strength comes from the brick-like assembly (interlocked) of the molecules [17]. A lizard’s feet will bind firmly to any solid surface in a short time, and detach with no apparent effort (Fig. 3). This adhesion is purely physical, with no chemical interaction between the feet and the surface. The active adhesive layer of the gecko’s foot is a branched nanoscopic layer of bristles known as “spatula” that measure about 200 nm in length. Several thousand of those spatulae are connected to micron-sized “seta.” Both spatulae and seta are fabricated from very flexible keratin. Although research into the finer details of the spatulae’s attachment and detachment mechanism is in progress, the actual fact is that they operate with no sticky chemicals. It is an impressive piece of design by Mother Nature. That they are self-cleaning, immune to self-matting (the seta don’t stick to each other), and detached by default (including from each other) are other interesting features of geckos’ feet [18, 20]. These options have prompted ideas and suggestions that in the future, glues, screws, and rivets may all be made by a single method, casting keratin or similar material into completely different molds. Magnetotactic bacteria possess the extraordinary ability to sense minute magnetic fields, together with the Earth’s own magnetic field, using tiny chains of nanocrystals known as magnetosomes (Fig. 4). These are grains sized between 30 and 50 nm, made from either magnetite (a type of iron oxide) or, less commonly, greghite (an iron-sulfur combo). Several types of magnetosomes work together to provide a foldable “compass needle” that is many times more sensitive than its artificial counterparts. Magnetotactic bacteria are pond-dwelling and only need to navigate short distances. However, their precision is incredible. By varying the grain size, these bacteria can store information since the growth is controlled by the most magnetically sensitive atomic arrangements [22]. However, oxygen and sulfur combine rapidly with iron to provide magnetite, greghite, or more than 50 other compounds, only a couple of which are magnetic. Hence 6 Nano-optics
- 20. Fig. 3 Nanoengineered structures from nature: (A) microstructure and schematic illustration of gecko feet [18]; (B) micro/nanoarchitecture in the wings of a butterfly [19]. (Permission has been granted through the Copyright Clearance Center’s Rights Link service.)
- 21. advanced technologies are needed to produce selectively the proper kind, and build the magnetosome chains. Such manual skill is presently beyond our reach; however, in future, scientists may learn a way to mimic these structures. 4. Presence of nano-optics in nature The increasing research in nanotechnology makes it necessary to deal with the optical phenomenon on the nanometer scale. Since the diffraction limit doesn’t enable us to focus light to dimensions smaller than roughly one-half of the wavelength (200 nm), tra- ditionally it was not practical to optically interact selectively with nanoscale structures. However, in recent years, many new approaches have become available to reduce the diffraction limit or even overcome it. A central goal of nano-optics is to extend the utilization of optical techniques to length scales beyond the diffraction limit. The most Fig. 4 Different morphology of magnetotactic bacteria: (A) vibrios; (B) rods (Bar ¼ 1.0 μm) and (D); (C) coccoid (Bar ¼ 200 nm); (E) spirilla: (F) multicellular organism (Bar ¼ 1.0 μm) [21]. (Permission has been granted through the Copyright Clearance Center’s Rights Link service.) 8 Nano-optics
- 22. obvious potential technological applications that arise from breaking the diffraction bar- rier are super-resolution microscopy and ultra-high-density information storage. How- ever, the field of nano-optics is by no means restricted to technological applications and instrumental design. Nano-optics additionally opens new doors to basic analysis on nanometer-sized structures [23, 24]. Nature has developed numerous nanoscale structures to achieve distinctive optical effects. An outstanding example is photosynthetic membranes that use light-harvesting proteins to absorb daylight and then channel the excitation energy to different neighbor- ing proteins [25]. The energy is guided to a so-called reaction center where it initiates a charge transfer across the cell membrane. Other examples of nanophotonics in nature include sophisticated nano diffractive structures commonly found in insects like butter- flies and other animals to produce attractive colors and effects like those on a peacock’s feather. Insect wings have ordered hexagonal close-packed array structures made of chi- tin. The difference in spacing (from 200 nm to 1 μm) between these small structures allows the wings to serve as self-cleaning and antireflective coatings, along with providing improved mechanical strength and aerodynamics. It also functions as a diffraction grit- ting, which produces iridescence. Iridescence originates as a result of the interaction of light with the physical structure of the surface. In the Morpho butterfly, the spaces between the ribs of the wing form natural photonic crystals, leading to a brilliant blue color (Fig. 5). No pigments or chemicals are involved in this process. Researchers are exploring these nanostructures as a way for controlling and manipulating the flow of light, which is vital in optical communication. Additionally, researchers have found that when they coat the Morpho wings with a layer of heat-absorbing carbon nanotubes, the shift in reflected wavelength of light will indicate very small temperature changes (Fig. 6). Hence, these sensors could someday be used to discover inflamed or burned areas in people or points of wear and tear due to friction in machines. Another example is a moth’s eye, which has very small bumps on its surface. These bumps are hexagonal-shaped structures that are a few hundred nanometers tall and separated (Fig. 7). Since these patterns are smaller than the wavelength of visible light (350–800 nm), the surface of the moth’s eye can absorb more light, since it has only very low reflectance for visible light. Therefore, the visibility of a moth in dark conditions is much better than a normal human eye because these nanostructures can absorb light very efficiently. Scientists have been inspired to use similar artificial nanostructures to improve the absorption of infrared light in a particular type of thermo-voltaic cell to make it more efficient [29]. A new aim within the study of animal optical structures is to decipher and emulate the animal’s genetic manufacturing process. Animals contain the ultimate factories within them, which means they engineer via nanomachinery and molecular self-assembly, and also the results are excellent, based on the previously reported results [30]. Maybe, 9 From nature: Optics, nanotechnology, and nano-optics
- 23. in the near future, living cells will be cultured and photonic crystals can be grown and harvested on an industrial basis. This successively would supply a chance for novel evo- lutionary studies in the field of nanophotonics. According to the results obtained in pre- vious research carried out by nanoscientists, it was found that the ability to manufacture this kind of natural photonic crystal may be inherent among insect cells. Normally, there is a single (minimal) mutation within the genes required to manage the developmental process. The limited range of photonic crystals found in animals, compared with the potential range in physics (where lattices may also contain sharp edges and corners, etc.), further supports this concept. So, as a consequence of their production by single cells, photonic crystals make ideal phenotypes for evolutionary study in the future. Some of the applications of nature-inspired optical materials are listed below. 4.1 Light manipulation Nature makes use of a large number of optical phenomena to produce attractive colors. The most attractive and striking colors or optical effects are often created through the manipulation of light with the help of intricate microstructures. These are usually known Fig. 5 The Morpho didius butterfly: (A) image of the Morpho wings; (B) separated images of ground scale and cover scale [26]. (Permission has been granted through the Copyright Clearance Center’s Rights Link service.) 10 Nano-optics
- 24. as structural colors. In particular, some types of three-dimensional natural photonic crys- tals can create a photonic bandgap. This is a frequency band in dielectric structures in which electromagnetic waves are prohibited, irrespective of their direction of propagation in space. Theoretically, the three-dimensional periodicity of three-dimensional photonic crystals can give rise to photonic band gaps in all directions and produce omnidirectional reflection, which can produce bright color over a broad viewing angle [31, 32]. Compared with pigment color, structural color offers ultrahigh saturation brightness and iridescence. Moreover, as a result of not utilizing chemical dyes, structural color is environmentally friendly and exhibits unlimited lightfastness (Fig. 8). Due to these distinctive properties, tunable structural colors have opened new avenues to applications in areas like cosmetics, textiles, printing and painting, displays, and security labeling. Fig. 6 Wing scales of the painted lady, Vanessa cardui butterfly. The wing is covered in overlapping layers of scale cells, as seen in the reflected light image in the region of one of the ventral hindwing eyespots and high magnification SEM images showing the scale cell surfaces [27]. (A) Image of a V. cardui butterfly. Scale bar ¼ 1 cm. (B) Overlapping layers of scale cells in the wing of a V. cardui butterfly. The scales themselves are made of chitin. Scale bar ¼ 2 mm. (C) Higher magnification image of wing scales. The arrangement of scales are like overlapping tiles. Scale bar ¼ 150 μm. (D) SEM image showing the attachment of scale cells to the wing of wing epithelium. Scale bar ¼ 65 μm. (E) SEM image of base of scale cell where scale shaft is attached to the socket cell. Scale bar ¼ 20 μm. (F) High magnification SEM showing the ornately patterned scale cell surfaces. Scale bar ¼ 2 μm. (G) 6-day pupal wing scale stained with Wheat Germ Agglutinin (WGA), a type of fluorescent. Scale bar ¼ 20 μm. (Permission has been granted through the Copyright Clearance Center’s Rights Link service.) 11 From nature: Optics, nanotechnology, and nano-optics
- 25. 700 600 500 400 300 200 100 0 700 600 500 400 300 200 100 0 6 0 - 7 9 8 0 - 9 9 1 0 0 - 1 1 9 1 2 0 - 1 3 9 1 4 0 - 1 5 9 1 6 0 - 1 7 9 1 8 0 - 1 9 9 2 0 0 - 2 1 9 2 2 0 - 2 3 9 2 4 0 - 2 5 9 2 6 0 - 2 7 9 6 0 - 7 9 8 0 - 9 9 1 0 0 - 1 1 9 1 2 0 - 1 3 9 1 4 0 - 1 5 9 1 6 0 - 1 7 9 1 8 0 - 1 9 9 2 0 0 - 2 1 9 2 2 0 - 2 3 9 2 4 0 - 2 5 9 2 6 0 - 2 7 9 davg=170+18nm davg=190+17nm Nipple diameter (nm) Nipple diameter (nm) Counts Counts - - 250 mm 10 mm 5 mm 400 mm (A) (C) (D) (B) (E) (F) Fig. 7 The nano-nipple arrays of a Mourning Cloak butterfly eye, as revealed by SEM at different magnifications. The complete eye and its enlarged regional topography are shown. The distribution of nano-nipple diameters for the Mourning Cloak butterfly and for the Question Mark butterfly are shown in the graphs [28]. (A) Overview of butterfly eye. (B) Hexagonal facet lenses. (C) Junction in between three hexagonal facets. (D) Nano-nipples present on a facet surface. (E) Arrangement of nano-nipple diameters for the Mourning Cloak butterfly. (F) Arrangement of nano-nipple diameters for the Question Mark butterfly. (Permission has been granted through the Copyright Clearance Center’s Rights Link service.)
- 26. L’Or eal has manufactured a photonic cosmetic product [34] with a periodic nanoscale structure that produces striking blue color without the help of any chemical pigments. The light manipulation mechanism of butterfly Morpho scales is the inspiration behind this. The structural color is feasibly tuned by modifying the periodicity of the layers. The structural nature of the color also means it is more stable and sturdy than traditional pigment color. Such structurally colored fabric thus has great potential for application in the fashion industry and domestic furnishing textiles. 4.2 Antireflection Antireflection films are widely used to reduce interface reflectance and to enhance the performance of various kinds of optical devices, like LED displays and optic sensors. Con- ventionally, interference coatings shaped by the deposition of single-layer and multilayer stacks are widely adopted to obtain antireflection performance. Nevertheless, as well as the lack of mechanical stability and the difficulty in fabrication, these antireflection films are only effective over a narrow region of wavelengths at narrow incidence angles. Thicker films are needed to suppress the Fresnel reflection of longer-wavelength light. As an alternative, modern antireflection coatings with intricate microstructures within the subwavelength range inspired by many natural species have helped us regarding how to attain this. The presence of antireflection structures was first reported to exist on the corneas of the eyes of many nocturnal insects [35] (Fig. 9). Thousands of omma- tidia with size ranging from 10 to 30 μm are tightly packed on the spherical eye of an insect. They are uniformly arranged with a fixed spatial periodicity of 170 nm. Similar hierarchical subwavelength nanostructures are also observable on the transparent wings of some cicadas and hawk moths [37]. This kind of antireflection structure consists of arrays of nanocones and nanopillars arranged hexagonally. Due to their structured morphology, the Fresnel reflection can be effectively reduced by the gradient refractive index profile. In addition, the spatial periodicity is generally below the wavelength of the visible spectrum that can efficiently Fig. 8 (A) Structure-based green color of butterfly wings; (B, C) different magnification times of the optical ultrastructure in its wing scale surfaces [33]. (Permission has been granted through the Copyright Clearance Center’s Rights Link service.) 13 From nature: Optics, nanotechnology, and nano-optics
- 27. prevent the light scattering. Inspired by the excellent antireflection subwavelength nano- photonics structures in the compound eyes of insects and cicada wings, many kinds of artificial nanostructured antireflective coatings have been produced on an industrial basis including gratings, nanorods or nanocones, frustums of cones, nanotips, etc. [38] 4.3 Light focusing Some nocturnal animals have the ability to focus the light from a wide range of angles of incidence using biological microlenses as a solution to trap the light. The brittlestar O. wendtii is a good example of a light-sensitive species in aquatic systems [39]. The surface of each arm contains regular arrays of inorganic photonic structures, similar to a characteristic double-lens design. Each of these microlenses is composed of single anisotropic calcite crystals capable of focusing light toward the nerve photoreceptors, which are 4–7 μm below them. These near-perfect calcite microlenses show a unique focusing effect with significant signal enhancement and intensity adjustment. In addi- tion, the surface design of each microlens and constituent calcite orientation decreases the spherical aberration and birefringence that could degrade the optical function. Thus O. wendtii can detect dark spots extremely sensitively, and quickly escape from pred- ators into a dark area. Inspired by the unique microlens design and the outstanding light-focusing properties in brittlestars, several biomimetic analogs were fabricated by three-beam interference lithography. For the compound eye of several insects, the close-packed micro-ommatidium arrays arranged on the spherical macro basis also act as an effective light focusing tissue. Inspired by this multi-lens focusing mechanism, an artificial compound eye was fabricated by a laser direct writing method [40]. The artificial compound eye exhibits high uniformity, imaging, and focusing capabilities. Moreover, it has the ability for distortion-free wide field of view imaging and possesses high potential for applications in imaging devices and integrated Fig. 9 (A) Photograph of the moth Cacostatia ossa—the translucent and matte parts show the presence of an antireflective structure; (B, C) SEM images of the cross-section and the up-side of the translucent part of the wings—this shows the non-close-packed nano conical arrays on both sides of the wing membrane [36]. (Permission has been granted through the SciPris Scientific Publishing and Remittance Integration Services.) 14 Nano-optics
- 28. optical microsystems. The artificial compound eye structure can be combined with photo- electrical micro receivers for wide-angle communication applications [38]. 4.4 Chirality As a result of the changes caused by evolution over millions of years, many natural species such as beetles, shrimps, and butterflies have developed different types of three- dimensional chiral photonic crystals sensitive to circularly polarized light (Fig. 10). The eyes of insects have polarization-sensitive ommatidia, by which these chiral photonic crystals probably contribute to their camouflage nature and communication systems. The shrimp Gonodactylus smithii can communicate selectively to distinctly circularly polarized light. The beetle species Chrysina gloriosa is significantly more brilliant when it is exposed to left-handed circularly polarized (LCP) than right-handed circularly polarized (RCP) light [42]. Mate-choice experiments performed by scientists proved that the polarized light in the butterfly Heliconius cydno is used for sexual selection and speciation [43]. These chiral biological organisms serve as novel motivations in the search for miniature chiral optical devices. 5. Summary Nature is capable of producing several complicated nanoscale structures. Currently, researchers are exploring the natural world to find out its nanoscale secrets and using nature as a model for producing these same complicated structures. Nanotechnology can and will be used to enhance many products, several of which we interact with in Fig. 10 Examples of 3D natural photonic crystals. On the left, the weevil Entimus imperialis; in the center, the longhorn Prosopocera lactator; and on the right, the longhorn Pseudomyagrus waterhousei [41]. Permission has been granted through the Copyright Clearance Center’s Rights Link service. 15 From nature: Optics, nanotechnology, and nano-optics
- 29. our daily lives. As this research using nature continues, there will be more breakthroughs that may result in new devices and materials that can impact several aspects of the current and future societies. Nature has always been efficient in developing numerous photonic structures to fulfill specific biological functions and offers us plenty of technologically unattainable photonic designs. To import them into materials systems, we need a com- prehensive understanding of those structures. Although numerous efforts have been ded- icated to adding comprehension to these biological structures, the physical difficulty of the many natural systems makes it complex to create an accurate picture. Thus, the structural mechanisms with underlying optical functions should be completely investigated, which is also favorable to the extraction and simplification of the photonic structures for nonnatural fabrication. Apart from the structural properties, the physical properties of the material parts are also crucial for achieving specific optical functions. Thus, we should get enough information concerning the materials utilized in these natural systems, notably the dispersion properties of their real and imaginary refrac- tive index parts across relevant frequency ranges. Fortunately, theoretical modeling and calculation methods have matured to handle these issues. The fabrication of these struc- tures in addition to targeting functional materials could be a key step toward applying them. The biotemplating technique has been established as efficient to maintain the com- plexness of the natural templates; however, it is not suitable for mass production with high reproducibility. In recent years, biomimetic methods utilizing modern engineering fabrication methods, like 3D lithography, nano-imprinting, and direct laser writing, have made great progress with great improvements in resolution. Nature has also shown various examples of practical integrity, like the iridescent but- terfly wings, which not only demonstrate vivid structural color, but additionally possess super-hydrophobicity, directional adhesion, self-cleaning, and fluorescence emission functions. These enhanced biological solutions provide us with design principles for the manufacturing of multifunctional artificial materials with multiscale structures. More- over, by taking advantage of the practical integrations of structural properties from two or more biological organisms, we are probably able to fabricate a new composite with mul- tiple unique functions. Nature-inspired research is now at a growing stage and the present achievements will function as proofs-of-principle and guides for future investigations. References [1] G.A. Sotiriou, S.E. Pratsinis, Antibacterial activity of Nanosilver ions and particles, Environ. Sci. Tech- nol. 44 (2010) 5649–5654. [2] J.F. Jacobs, I. van de Poel, P. Osseweijer, Sunscreens with titanium dioxide (TiO2) Nano-particles: A societal experiment, NanoEthics 4 (2010) 103–113. [3] M.J. Asim Kumar, Nanotechnology: A review of applications and issues, Int. J. Innov. Technol. Explor. Eng. 3 (2013) 2278–3075. [4] R. Singh, J.W. Lillard, Nanoparticle-based targeted drug delivery, Exp. Mol. Pathol. 86 (2009) 215–223. [5] J. Hulla, S. Sahu, A. Hayes, Nanotechnology, Hum. Exp. Toxicol. 34 (2015) 1318–1321. 16 Nano-optics
- 30. [6] Anon, ‘Plenty of room’ revisited, Nat. Nanotechnol. 4 (2009) 781. [7] T.D. Rossing, C.J. Chiaverina, Light Science: Physics and the Visual Arts, Google eBook, Springer, 1999. [8] M. Kolle, Photonic Structures Inspired by Nature. Photonic Structures Inspired by Nature, Springer, Berlin, Heidelberg, 2011. https://doi.org/10.1007/978-3-642-15169-9. [9] M.V. Berry, Nature’s optics and our understanding of light, Contemp. Phys. 56 (2014) 1–15. [10] T.F. Anderson, A.G. Richards, An electron microscope study of some structural colors of insects, J. Appl. Phys. 13 (1942) 748–758. [11] A.R. Parker, 515 million years of structural colour, J. Opt. A Pure Appl. Opt. 2 (2000) R15–R28. [12] J.F.V. Vincent, O.A. Bogatyreva, N.R. Bogatyrev, A. Bowyer, A.-K. Pahl, Biomimetics: Its practice and theory, J. R. Soc. Interface 3 (2006) 471–482. [13] S. Vignolini, et al., Pointillist structural color in Pollia fruit, Proc. Natl. Acad. Sci. 109 (2012) 15712–15715. [14] W. Barthlott, C. Neinhuis, Purity of the sacred lotus, or escape from contamination in biological sur- faces, Planta 202 (1997) 1–8. [15] K. Balani, R.G. Batista, D. Lahiri, A. Agarwal, The hydrophobicity of a lotus leaf: a nanomechanical and computational approach, Nanotechnology 20 (2009) 305707. [16] M. Zhang, S. Feng, L. Wang, Y. Zheng, Lotus effect in wetting and self-cleaning, Biotribology 5 (2016) 31–43. [17] E.M. Gerhard, et al., Design strategies and applications of nacre-based biomaterials, Acta Biomater. 54 (2017) 21–34. [18] K. Takahashi, J.O.L. Berengueres, K.J. Obata, S. Saito, Geckos’ foot hair structure and their ability to hang from rough surfaces and move quickly, Int. J. Adhes. Adhes. 26 (2006) 639–643. [19] Y. Fang, G. Sun, Y. Bi, H. Zhi, Multiple-dimensional micro/nano structural models for hydropho- bicity of butterfly wing surfaces and coupling mechanism, Sci. Bull. 60 (2015) 256–263. [20] K. Autumn, Mechanisms of adhesion in geckos, Integr. Comp. Biol. 42 (2002) 1081–1090. [21] L. Yan, et al., Magnetotactic bacteria, magnetosomes and their application, Microbiol. Res. 167 (2012) 507–519. [22] D. Faivre, D. Sch€ uler, Magnetotactic bacteria and magnetosomes, Chem. Rev. 108 (2008) 4875–4898. [23] L. Novotny, B. Hecht, Principles of Nano-optics. Cambridge University Press, Cambridge, UK, 2012, https://doi.org/10.1017/CBO9780511813535. [24] L. Wu, et al., Optical functional materials inspired by biology, Adv. Opt. Mater. 4 (2016) 195–224. [25] D. Siefermann-Harms, The light-harvesting and protective functions of carotenoids in photosynthetic membranes, Physiol. Plant. 69 (1987) 561–568. [26] X. Yang, Z. Peng, H. Zuo, T. Shi, G. Liao, Using hierarchy architecture of Morpho butterfly scales for chemical sensing: Experiment and modeling, Sensors Actuators A Phys. 167 (2011) 367–373. [27] A. Dinwiddie, et al., Dynamics of F-actin prefigure the structure of butterfly wing scales, Dev. Biol. 392 (2014) 404–418. [28] K.C. Lee, U. Erb, Remarkable crystal and defect structures in butterfly eye nano-nipple arrays, Arthro- pod Struct. Dev. 44 (2015) 587–594. [29] V.P. Khvostikov, et al., Photovoltaic cells based on GaSb and Ge for solar and thermophotovoltaic applications, J. Sol. Energy Eng. 129 (2007) 291. [30] A.R. Parker, Natural photonics for industrial inspiration, Philos. Trans. R. Soc. A Math. Phys. Eng. Sci. 367 (2009) 1759–1782. [31] J.W. Galusha, M.R. Jorgensen, M.H. Bartl, Diamond-structured Titania photonic-bandgap crystals from biological templates, Adv. Mater. 22 (2010) 107–110. [32] A. Blanco, et al., Large-scale synthesis of a silicon photonic crystal with a complete three-dimensional bandgap near 1.5 micrometres, Nature 405 (2000) 437–440. [33] Y. Liu, et al., Bio-inspired micro-nano structured surface with structural color and anisotropic wetta- bility on cu substrate, Appl. Surf. Sci. 379 (2016) 230–237. [34] S.M. Luke, P. Vukusic, An introduction to biomimetic photonic design, Europhys. News 42 (2011) 20–23. [35] X. Gao, et al., The dry-style antifogging properties of mosquito compound eyes and artificial analogues prepared by soft lithography, Adv. Mater. 19 (2007) 2213–2217. 17 From nature: Optics, nanotechnology, and nano-optics
- 31. [36] O. Deparis, N. Khuzayim, A. Parker, J.P. Vigneron, Assessment of the antireflection property of moth wings by three-dimensional transfer-matrix optical simulations, Phys. Rev. E 79 (2009) 041910. [37] P.R. Stoddart, P.J. Cadusch, T.M. Boyce, R.M. Erasmus, J.D. Comins, Optical properties of chitin: surface-enhanced Raman scattering substrates based on antireflection structures on cicada wings, Nanotechnology 17 (2006) 680–686. [38] Y.-F. Huang, et al., Improved broadband and quasi-omnidirectional anti-reflection properties with biomimetic silicon nanostructures, Nat. Nanotechnol. 2 (2007) 770–774. [39] J. Aizenberg, A. Tkachenko, S. Weiner, L. Addadi, G. Hendler, Calcitic microlenses as part of the pho- toreceptor system in brittlestars, Nature 412 (2001) 819–822. [40] D. Wu, et al., Bioinspired fabrication of high-quality 3D artificial compound eyes by voxel-modulation femtosecond laser writing for distortion-free wide-field-of-view imaging, Adv. Opt. Mater. 2 (2014) 751–758. [41] J.P. Vigneron, P. Simonis, Natural photonic crystals, Phys. B Condens. Matter 407 (2012) 4032–4036. [42] V. Sharma, M. Crne, J.O. Park, M. Srinivasarao, Structural origin of circularly polarized iridescence in jeweled beetles, Science 325 (2009) 449–451. [43] A. Sweeney, C. Jiggins, S. Johnsen, Polarized light as a butterfly mating signal, Nature 423 (2003) 31–32. 18 Nano-optics
- 32. CHAPTER 2 Nano-optics: Challenges, trends, and future Jemy Jamesa,c , Balu Chandrab , Blessy Josephc , Parvathy Nancyc,e , Ashin Shajid , Jerry Josec , Nandakumar Kalarikkalc,e , Yves Grohensa , Guillaume Vignauda , Sabu Thomasc,f a FRE CNRS 3744, IRDL, University of Southern Brittany, Lorient, France b International School of Photonics, Cochin University of Science and Technology, Cochin, Kerala, India c International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India d Institute of Physics, Slovak Academy of Sciences, Bratislava, Slovakia e School of Pure and Applied Physics, Mahatma Gandhi University, Kottayam, Kerala, India f School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala, India 1. An outlook If technological advancements and their impact on the general public are considered, the last 200 years can clearly be described as the most progressive period of humankind. The advent of electricity and the subsequent emergence of electronic devices initiated a unique revolution. As technology advanced, the sizes of electronic devices became smaller and smaller. In 1960, when Theodore Maiman built the first laser, the world wit- nessed the metamorphosis of light as a counterpart to electricity. Devices that harness the nature of light are termed photonic devices, and just as electronic devices evolved over time, photonic devices are now evolving at a faster rate. As stated earlier, devices are getting smaller and smaller and right now, the minimum size parameters of electronic devices have reduced to a few tens of nanometers nm (1 nm ¼ 1 109 m). This was a fundamental problem when photonic devices started getting smaller. And as we found out more and more about the problem, the problem itself opened a doorway to completely unprecedented physical phenomena. It gave birth to a new branch of science, nano-optics, which deal with understanding and tailoring the complex behavior of light in nanometer dimensions. Global communication, and in particular internet and long-distance telephony, is now based primarily on optical fiber technology. The main advantage of optical waves compared to radio waves is the high frequency, which allows high data transmission rates. Nowadays, several terabits per second can be transmitted in a single fiber, which repre- sents an increase by a factor of 1 million to what could be achieved 50 years ago with radio signal transmission. The number of optical fiber cables being installed globally is increas- ing rapidly. Fiber optics is also important for a huge number of other applications, such as 19 Nano-Optics © 2020 Elsevier Inc. https://doi.org/10.1016/B978-0-12-818392-2.00002-0 All rights reserved.
- 33. in medicine, laser technology, and sensors. An interesting example of the use of fiber- optic communication in science is the advanced fiber optics network developed at the Large Hadron Collider at CERN in Geneva, which will transfer large amounts of information obtained by particle detectors to computer centers all over the world. 1.1 A historical perspective Let there be light and there was light Genesis 1:3 Historically, light was a center of interest for numerous inquisitive people: philosophers were interested in its nature and scientists wanted to interpret its associated phenomena. In antiquity, the Egyptians attempted to discover the mystery of light and to know its structure. From a philosophical point of view, their attempts were fruitless. However, in practice, they implemented impressive mechanisms based mainly on reflection. The Greeks also attempted to decode the enigma of light and considered it a contin- uous phenomenon propagating in the form of a substance current called the “visual ray.” Nevertheless, based on the work of the Egyptians, they established rules for light deflec- tion. One of the most impressive legacies of the Greeks in optics is the mirror of Archi- medes. Aristotle, interested in the sensation in general, refused to admit the existence of the visual ray and believed in the analogy between light and sound, whose vibratory nature was already known. In the 11th century, the thesis of the visual ray was definitively abandoned by the Iraqi Ibn Al-Haytham, whose work revolutionized optics. He detached optics from its philosophical envelope and embedded it in the framework of physics and mathematical sciences. He dealt at length with the theory of various physical phenomena like shadows, eclipses, and rainbows, and speculated on the physical nature of light. Al-Haytham’s optics entered Spain in the 12th century and was adopted by Grossteste, who affirmed the analogy between light and sound, and thoroughly investigated the matter of geometrical optics. After the contributions of the geometro-opticians, Snell and Descartes (see Fig. 1) studied the refraction phenomenon and stated that the speed of light is as high as the cov- ered medium is dense. This hypothesis was contested by Fermat, who attributed indices to the media. Foucault in the 19th century came out in favor of Fermat. This more mod- ern progress still dealt only with geometrical optics, which considered that the behavior of light with respect to obstacles is expressed uniquely in terms of absorption, reflection, or refraction. However, in the 17th century, Grimaldi, using a simple experiment, observed the progressive transition between light and shadow and regarded the corpuscular theory, supposing the rectilinear propagation of light, as insufficient to explain such an effect. Despite Newton’s support of the corpuscular theory (he believed that the light 20 Nano-optics
- 34. propagation is a movement of corpuscles that respects the rules of mechanics and notably that of the universal gravitation), Huygens advanced the undulatory theory based on Grimaldi’s observations. He explained Grimaldi’s observation by a purely intuitive pos- tulation, in which he regarded light propagation as an incessant creation of elementary spherical light sources. At the beginning of the 19th century, after some experiments on the colors of thin plates, T. Young came to the conclusion that the interaction between light rays may produce darkness, thereby discovering a wonderful phenomenon which he called “interference.” Like Huygens, Young supported the undulatory theory. He also devel- oped an elegant technique to handle refraction. His belief in the analogy between light and sound led him to state that light vibration is longitudinal. The famous A. Fresnel was of the same opinion. However, he considered that Huygens’ postulation did not explain the nonexistence of waves that have the same spec- ifications propagating backwards. He combined Huygens’ principle of “envelope” build- ing with the interference principle of Young and, for the purposes of putting forward a coherent theory, he made some supplementary hypotheses on the amplitude and phase of the new elementary waves. At the end of the 19th century, G. Kirchhoff gave a deeper mathematical basis to the diffraction theory introduced by Huygens and Fresnel, and considered Fresnel’s hypothesis as a logical consequence of the undulatory nature of light. Kirchhoff’s work was subjected a few years later to criticisms made by Sommerfeld, who considered the Kirchhoff formulation as a first approximation. He advanced with Rayleigh what was later called the “Rayleigh-Sommerfeld diffraction theory.” Hence a supplementary phenomenon called “diffraction” is added to those concerning the behavior of light Fig. 1 Some pioneers associated with the refraction. (Photo credit https://twitter.com/sahl_ibn; https:// en.wikipedia.org/wiki/Willebrord_Snellius; https://en.wikipedia.org/wiki/Ren e_Descartes.) 21 Nano-optics: challenges, trends, and future
- 35. when coming across obstacles, namely absorption, reflection, refraction, diffusion, and dispersion. Sommerfeld defined this phenomenon conveniently as follows: Diffraction is any deviation of light rays from the initial path which can be explained neither by reflection nor by refraction. The optical region of the electromagnetic spectrum, corresponding to wavelengths in the visible, near-infrared, or ultraviolet spectrum, has long been considered attractive for communications. The frequency of the light allows for high signal modulation frequency and consequently high transmission speed. In 1880, G.A. Bell patented an air-based optical telephone called the “Photophone,” consisting of focusing sunlight on the surface of a flat mirror vibrating with sound. The light was then sent to a detector of selenium coupled to a telephone receiver. A few later ideas were also patented, one of them in Japan even suggesting quartz as a transmission medium. In the 1950s, however, very few communication scientists considered optical communication as a viable concept. One hundred and twenty years ago, G. Marconi and K.F. Braun were awarded a Nobel Prize “in recognition of their contributions to the development of wireless telegraphy.” Sixty years ago, electronic and radio communications were in rapid expansion. The first transatlantic cable was installed in 1956 and satellites would soon allow even better coverage. The first communication satellite was launched in 1958. Research in telecommunication concentrated mainly on shorter radio waves, in the millimeter range, with the aim to reach higher transmission speeds. These waves could not travel as easily in air as longer waves, and the research focused on designing practical waveguides. N.S. Kapany and H.H. Hopkins at Imperial College London constructed bundles of thousands of fibers of length 75 cm and showed appreciable image transmission [1]. By having a cladding to the fiber bundles, some applications, especially the gastroscope, went into industrial production. The refractive index of the core is slightly higher than that of the cladding. Typical dimensions are 10 or 50 μm for the core and 125 μm for the fiber. In addition, a protecting plastic buffer is placed around the fiber went all the way to indus- trial production. The theory of light propagation into fibers was described by N.S. Kapany. His article on fiber optics in Scientific American in 1960 established the term “fiber optics.” The invention of the laser in the early 1960s (Nobel Prize in 1964 to C.H. Townes, N.G. Basov, and A.M. Prokhorov) gave a new boost to the research in optical communication. Shortly after the pulsed laser demonstrated in ruby by T.H. Maiman, A. Javan built the first continuous-wave laser using a mixture of He and Ne gas. Semicon- ductor lasers appeared almost at the same time, but were at first not so practical, since they required high currents and could not work at room temperature. A few years later, the introduction of heterostructures (Nobel Prize in 2000 to Z.I. Alferov and H. Kroemer) 22 Nano-optics
- 36. enabled operation at room temperature, making them ideal light sources for optical com- munication. Optical communications today have reached their present status thanks to a number of breakthroughs. 1.2 Photonics Light is primarily used for illumination and some common optical devices/elements are spectacles, mirrors, microscopes, magnifiers, telescopes, etc. Light is built out of photons, which are quantum mechanical and relativistic particles; light shows both a wave and particle nature in the sense of our understanding on a macroscopic level. Light moves at the maximum possible speed. The electromagnetic field of photons oscillates much faster than that is possible for electrons, as electrons are massive when compared to the mass-less photons. Some applications of the photonics are provided in Fig. 2. Optical switches enhance the speed of communication. Laser machining has a great impact on many technological applications in daily life. Micro-machining enables completely new approaches in biology and medicine. LIDAR (light detection and rang- ing) and laser spectroscopic techniques are being used for pollution estimation. Laser medicine is a developing area which enables treatment of most diseases and lasers are Applicaon of photonics Laser spectroscopy Laser medicine Material processing Communicaon Laser chemistry Fig. 2 Some everyday applications of photonics. 23 Nano-optics: challenges, trends, and future
- 37. highly popular in endoscopy and corrective eye surgery. The advantage is that these tech- niques are minimally invasive. Some of the advancements include: • rapid developments of optical switches; • optical fibers; • wavelength division multiplexers; • photodynamic therapy; • optical coherence tomography; • detection of single molecules; • detection of gravitational waves; and • optical sequencing of DNA. Light is usually described as a collection of photons or as electromagnetic waves, prop- agating with speed “c,” with its maximum in a vacuum and a lower speed in materials. 1.3 Speed of light Cvacuum ¼ 2:998108 ms1 Cmaterial ¼ Cvacuum=nmaterial where nmaterial is the conventional refractive index of the materials, Cvacuum is the speed of light in a vacuum, and Cmaterial is the speed of light in the material. curl E ¼ μo dH δt curl H ¼ ∂E ∂t + ∂P ∂t where H is the magnetic field vector, E is the electric field vector, and P is the magnetic polarization frequency (1013 –1015 Hz). The wave equation is described as: ΔE 1 c2 ∂2 E ∂t2 grad div E ¼ μo ∂2 P E ð Þ ∂t2 Δ ¼ Laplace operator ¼ ∂2 ∂x2 + ∂2 ∂y2 + ∂2 ∂z2 All material properties can be summarized by the refractive index n: ΔE 1 c2E grad div E ¼ 0 24 Nano-optics
- 38. c2 ¼ c2 0 εrμr ¼ c2 0 n2 ¼ 1 μoεoμrεr where εo is the vacuum permittivity. εo ¼ 8:8541012 ASεo ¼ 8:8541012 AS Vm ¼ 1 μoC2 o Vacuum permeability: μo ¼ 4π 107 VS Am where εr is electric permittivity, μr is magnetic permeability, μr is 1 for optical materials, and εr is 1 for a vacuum. 1.4 Focal length of thin spherical lens and refractive index Bioconvex lens with radius of curvature R at both sides have focal length as follows: f ¼ 1 2 n1 ð Þ R For a plano convex lens, the focal length is: f ¼ 1 n1 ð Þ R The influence of magnetic component of light can usually be neglected: μr 1 nreal ¼ ffiffiffiffi εr p as μr is neglected. Another way of representing the refractive index is: n ¼ ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1 + χphase iχabsorption q χ ¼ electrical susceptibility The imaginary part represents the absorption: χabsorption. The real part represents the phase change: χphase. Common optical elements like lenses, fibers, prisms, etc. are based on the refraction and dispersion of light as a result of the fact that the refractive index is greater than 1 in the material. The speed of light in a vacuum is different when compared to that in mate- rial. If the frequency of light is different than the resonance of the material, then the nonresonant interaction is dominated by phase changes of the light wave. This inter- action is based on the forced oscillation of electric dipoles in the matter with the light frequency. 25 Nano-optics: challenges, trends, and future
- 39. Phase velocity of light in a medium is given as: Cp ¼ Cvacuum nmatter ¼ 1 ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi oμ0rμr p ¼ ϑlightλinmatter where nmatter is usually the real refractive index: λinmatter ¼ λvacuum nmatter The refractive index of some of the common materials is given in Table 1. If the light is a mixture of frequency, then the speed of each component will be dif- ferent due to the varying refractive index. Refractive index variation as a function of the light frequency n(ν) or n(λ) is called dispersion. This can be understood by analyzing how the refraction at air glass interface results in spreading of white light (Fig. 3). For normal dispersion, dn dλ 0, refraction at shorter wavelength is more, as it can be demonstrated from Huygens’ principle. In anomalous dispersion, dn dλ 0, the refraction at higher wavelength will be more. In the range of absorption, the conventional refractive index increases with the wave- length of light and this is called anomalous dispersion. Velocity of a mixture of light is called group velocity, which is given as: Cg ¼ Cp λ dCp dλ Group refractive index: ngroup ¼ n λ ð Þλ dn λ ð Þ dλ Law of refraction: n1 sin θ1 ¼ n2 sin θ2 Table 1 Refractive index of common materials. Material Refractive index @ 546 nm Air 1.00029 CO2 1.00045 Water 1.33 Ethanol 1.36 Benzene 1.51 Quartz 1.46 Plexiglass 1.49 Diamond 2.42 26 Nano-optics
- 40. This is the very important law of refraction, the physical consequences of which have been studied, at least on record, for more than 1800 years. On the basis of some observations, Claudius Ptolemy of Alexandria attempted unsuc- cessfully to derive the expression. Kepler nearly succeeded in deriving the law of refrac- tion in his book Supplements to Vitello in 1604. Unfortunately he was misled by some erroneous data compiled by Vitello. The correct relationship seems to have been iden- tified first by Snell at the University of Leyden and then by the French mathematician Descartes. In English-speaking countries, this law is referred to as Snell’s law. Though unnoticed, in Baghdad, in the 10th century, an unknown scientist, Abu Sad Al Alla Ibn Sahl, excelled in optics and in his book Burning Mirrors and Lenses, in AD 984, he set out the present-day laws of refraction and how lenses and curved mirrors bend and focus light. However, this has not been much credited, and the law is still known by the name of Snell or Descartes. It is worth noting that Snell’s law (Fig. 4), discovered in Hol- land in the year 1621, was not well-known until Descartes published it in 1638. The wavelength dependence of the refractive indices is different for different mate- rials, and the dispersion compensation is possible by combining different glasses. If the total refraction is the same for two wavelengths, the system is called achromatic, and if the dispersion compensation works for three wavelengths, it is called apochromatic. Hartmann has given an explanation for the wavelength related dispersion as follows: n λ ð Þ ¼ n0 + Cdisp λλ0 ð Þα 0:5 α 2 where Cdisp and λ0 are constant. Fig. 3 Normal dispersion of white light into constituent colors. 27 Nano-optics: challenges, trends, and future
- 41. Sellmeir has described the refractive index in the wavelength range of ultra violet to infrared as follows: n λ ð Þ ¼ 1 + εm λ2 λ2 λ2 m Adisp,m where Adisp,m is the coefficient and λm is the resonance wavelength. 1.5 Brewster’s angle At a certain angle of incidence θB, the reflected light is perfectly polarized with the polar- ization direction parallel to the surface (Fig. 5) tanθB ¼ n2 n1 If the first medium is air, then n1 ¼ 1, and thus n2 ¼ tan θB. As Brewster’s angle can be determined precisely, the refractive index can be measured using this method, and this forms the basis of the ellipsometry technique, which is being used to measure the refractive index of thin films. We have up until now discussed optics and photonics, and can now briefly consider the role played by nanoparticles in optics. Fig. 4 Snell’s law. 28 Nano-optics
- 42. 1.6 Optical properties of nanoparticles Focusing attention on interaction of light on particles on the nanometer scale, the field of nano-optics has flourished greatly in recent times. On the nanometer scale, materials including metals, semiconductors, dielectrics, and polymers exhibit interesting prop- erties, especially optical properties. Among the various applications, innovative methods to develop thin film coatings have garnered much attention. Nanocomposites have been designed to achieve materials with tunable refractive indices and enhanced optical properties. Deeper and specific focus should be laid on the interaction of light with a material. When light interacts with a material, there are three possible main effects: absorption, transmission, and reflection of light. The nanoparticles exhibit higher specific surface area, surface energy, and density compared to bulk materials. Hence introducing nano- particles at even lower filler loadings will have tremendous effect on the physical, thermal, and mechanical properties of the matrix [2]. Nanomaterials when combined with poly- mers have enhanced mechanical and optical properties (e.g., refractive index and coef- ficient of absorption) and find applications in light-emitting diodes, solar cells, polarizers, light-stable color filters, optical sensors, etc. They also give rise to new characteristics like light emission [3]. The optical properties of nanoparticles have been investigated for var- ious applications like UV-filters, bio-imaging, photo thermal therapies, oxygen sensors, etc. [4]. Ceria nanoparticles have attracted much attention as luminescent material and material with a high refractive index [5]. Ceria nanoparticles are highly biocompatible and hence several studies have focused on the use of cerium oxide nanoparticles as Fig. 5 Schematic representing Brewster’s angle. 29 Nano-optics: challenges, trends, and future
- 43. contrast agents for MRI [6]. Cerium is the most abundant element in the rare earth fam- ily. Ce has electronic configuration [Xe] 4f2 6s2 and has two common oxidation states, Ce3+ and Ce4+ [7]. Cerium has shielded 4f-electrons, which are responsible for the fas- cinating properties of the rare earth element. PS/PMMA-grafted CeO2 nanocomposite films were prepared by Parlak et al. using spin coating. It was observed that blending of PS and CeO2 nanoparticles resulted in opaque films, whereas grafting of PMMA chains onto CeO2 enhanced the transparency of the composite. This is because there is a strong refractive index mismatch between PS and CeO2 particles. However, when PMMA with a lower refractive index than PS and CeO2 is incorporated, the refractive index mismatch is nullified [8]. 2. Challenges: Nano-optics bottleneck Electronic devices in principle work by the manipulation of the flow of electrons. Since the size of an atom is around 0.1–0.5 nm, we can safely assume that the size profile of an electron (if we can speak about the “size” of an electron at all) must be infinitesimally smaller than nanometer dimensions. This effectively means that the electrons are capable of working in dimensions smaller than the size of atoms. Photonic devices, on the other hand, manipulate light, or more specifically electro- magnetic radiation near or around visible light. Since the wavelength of light in the region around visible light is in terms of hundreds of nanometers, no photonic devices can therefore be smaller than the wavelength profile of light. This is a major obstacle that limits the plethora of benefits offered by photonic technology while downscaling the size. Though the size parameter is a major stumbling block, it has not limited the curiosity and enthusiasm of physicists to investigate the interaction of light in subwavelength dimensions, and what they found out was enthralling. Light in fact changed its behavior in subwavelength dimensions. Nano-optics emerged as the branch of science dealing with the study of the interac- tion of light in nanometer dimensions. The branch requires a vivid and avid idea of the complex and rigorous theoretical knowhow as nanoscale interaction of light can barely be understood with the basic knowledge of the interaction of light in the daily life. 3. Trends: Current scenario in nano-optics As stated above, it is impossible to downscale light beyond a limit, more precisely beyond half the wavelength. If that is so, why should we bother about interaction of light on a subwavelength scale? Nano-optics researchers are exploiting this possibility of confining light in a single spatial direction. The field has already branched out into many specific areas of interest. 30 Nano-optics
- 44. Nano-optics is an emerging area which deals with the manipulation of light at a scale which is much less than the wavelength of light itself. Some innovations in the areas of 3D optical lithography, microscopy beyond the diffraction limit, optical computing at the chip level, and energy efficient light to energy and energy to light conversion are some of the contributions in this research area of nano-optics. These innovations are giving rise to new fields of their own, like superresolution lithography and microscopy. The enhancement of interaction of light with nanoparticles is much sought after. Enhancement of solar energy conversion is being studied very rigorously these days and the improvements in the light guides or concentrators and innovation in the materials used for the light conversion are being sought out, such as making materials on the nano- scale, and making necessary morphological and structural changes to the materials. As a whole, the interaction of light with optical elements, the interaction of light with nanoparticles, and the manipulation of light emerging from nanoparticles are the broad areas of nano-optics. Some recent research has been carried out on the following areas. Further reading on these will be very useful, as detailed explanations on each topic are beyond the scope of this chapter. • Quantum control of atoms using ultra short pulses of laser and optical trapping and cooling of single nanoparticles, which is useful for precise and sensitive detection. • Magneto plasmonics where magnetic fields are used to influence the plasmonics. The magneto-refractive (MR) effect is also being researched, where the optical properties of a system can be controlled using magnetic field-controlled electrical resistivity. • Thermophotovoltaics (TPV), where a solar absorber or emitter is inducted in front of a photovoltaic cell in order to enhance the efficiency. • Nonlinear plasmonics, where nonlinear effects are explored when plasmonic nanos- tructures are used. • Spatio-temporal control of light where ultrafast optical sources are combined with scattering nearfield microscopes in the presence of 2D materials. • Optical antennas, which are used to enhance local light matter interaction, related to single quantum sources. • Near field optics and near field quantum optics, where evanescent fields are being exploited for sensing and analyzing the change in the properties of materials and light when the near field measurements are being carried out, leading to better control of the materials and photons at that level. • Nanocarbon photonics where the interaction of light with graphene, carbon nano- tubes, graphene quantum dots, etc. are being studied along with the effects of dopants and defects in carbon nanostructures. • Optofluidics in nano regimes where optical interferometery and nanofluidics are combined for ultra-precise measurements and detections. 31 Nano-optics: challenges, trends, and future
- 45. • Spasers (surface plasmon amplification by stimulated emission of radiation), where the oscillations are maintained by the stimulated emission of surface plasmons. Spasers are nanoscale lasers. 4. The future: A world of possibilities Nano-optics is still a very new topic, and experimental realization of the possibilities of nanoscale interactions in the optical realm started only in 1984 when the optical coun- terpart of scanning tunneling microscope (STM) was developed. Still not even 50 years old, the science of nano-optics is now a multimillion dollar industry. The possibilities are bigger when we go nanoscale, from immense medical advantages to military applications and beyond. If we can control a nanometer-sized device perfectly, it may even drive humanity to the doorstep of immortality. Nanoscale optical devices can bring the vibrant colors of nature to our living rooms, and the manipulation of light might overpower the electronics industry as we know it. Better and more efficient power generation is another result worth mentioning. 5. Conclusion Wonders of nano-optics are not at all new in nature. The vibrant hues we see in peacock feathers, the magnificent colors on a butterfly’s wing, all make use of nano-optic prop- erties of light. The technology is used in photosynthesis by plants. Understanding the science behind nano-optics essentially bestows us with a better understanding of nature. References [1] H.H. Hopkins, N.S. Kapany, A flexible fibrescope, using static scanning, Nature 173 (1954) 39–41. [2] A.M. Dı́ez-Pascual, Nanoparticle reinforced polymers, Polymers (Basel) 11 (2019) 625. [3] I. Roppolo, M. Sangermano, A. Chiolerio, Optical properties of polymer nanocomposites, In: Functional and Physical Properties of Polymer Nanocomposites (2016) 139–157. [4] A. Gupta, S. Das, C.J. Neal, S. Seal, Controlling the surface chemistry of cerium oxide nanoparticles for biological applications, J. Mater. Chem. B 4 (2016) 3195–3202. [5] H. Gu, M.D. Soucek, Preparation and characterization of monodisperse cerium oxide nanoparticles in hydrocarbon solvents, Chem. Mater. 19 (2007) 1103–1110. [6] P. Eriksson, A.A. Tal, A. Skallberg, C. Brommesson, Z. Hu, R.D. Boyd, W. Olovsson, N. Fairley, I.A. Abrikosov, X. Zhang, Cerium oxide nanoparticles with antioxidant capabilities and gadolinium integration for MRI contrast enhancement, Sci. Rep. 8 (2018) 6999. [7] C. Sun, H. Li, L. Chen, Nanostructured ceria-based materials: synthesis, properties, and applications, Energy Environ. Sci. 5 (2012) 8475–8505. [8] O. Parlak, M.M. Demir, Toward transparent nanocomposites based on polystyrene matrix and PMMA-grafted CeO2 nanoparticles, ACS Appl. Mater. Interfaces 3 (2011) 4306–4314. 32 Nano-optics
- 46. CHAPTER 3 Nano-optics for healthcare applications Blessy Josepha , Jemy Jamesa,b , Nitin Eapena , Nandakumar Kalarikkala , Sabu Thomasa a International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India b FRE CNRS 3744, IRDL, University of Southern Brittany, Lorient, France 1. Introduction Nanotechnology is the art of making things smaller. The field of nanotechnology is growing quickly and steadily. Nanoparticles have been used in the design of highly func- tional materials due to their unique physical and chemical properties. Different types of nanoparticles like metallic, non-metallic, and magnetic, carbon nanotubes, etc. are widely used for various applications. However, inorganic nanoparticles (metallic and metallic oxide nanoparticles) are of great interest due to their excellent physical and chemical properties. They have been particularly effective in the strategic design of opti- cal devices. The need for miniature-sized and lightweight optical components is increas- ing day by day. This is possible by tailoring the size and shape of nanoparticles. Metallic nanoparticles like gold nanoparticles show tunable radiation and absorption wavelength depending on their aspect ratio, arising due to localized surface plasmon resonance (LPSR) [1, 2]. When the incident light of certain frequency falls on metallic nanostruc- tures, the free electrons in the material resonate at a frequency that is dependent on the size and shape of the material (Fig. 1). The particles will strongly absorb or scatter light when the wavelength of the incident light matches the oscillating frequency. This phe- nomenon, described as LSPR, involving light matter interaction, a characteristic of plas- monic nanostructures, is exploited for several applications in biomedical sector. The field that studies this light matter interaction at nanometer scale—known as nanophotonics or nano-optics—has been successful in developing new imaging modalities, especially for medical imaging and diagnosis. The optical properties of nanoparticles were initially described in 1857 by Michael Faraday. Studies on plasmonics started in 1899, and exper- imental observations of plasmonic effects in light spectra were investigated by Robert Wood in 1902 [3]. Inorganic nanoparticles exhibit superior material properties with functional versatil- ity. They are being explored as potential tools for diagnostics as well as for treating dis- eases due to their size features and advantages over conventional chemical imaging techniques. They have been widely used for cellular delivery due to their versatile 33 Nano-Optics © 2020 Elsevier Inc. https://doi.org/10.1016/B978-0-12-818392-2.00003-2 All rights reserved.
- 47. features, such as wide availability, rich functionality, good biocompatibility, capability of targeted drug delivery, and controlled release of drugs. For example, gold nanoparticles have been extensively used in imaging, as drug carriers, and in thermotherapy of biolog- ical targets. The interesting colors of metallic nanoparticle solutions are due to the red shift of the plasmon band to visible frequencies, unlike that for bulk metals, where the plasmon absorption is in the ultraviolet region. In fact, the optical properties of nanopar- ticles depend significantly on their size and shape as well as on the dielectric constant of the surrounding medium. Nanoparticles such as 20 nm sized gold (Au), platinum (Pt), silver (Ag), and palladium (Pd) have characteristic wine red, yellowish gray, black, and dark black colors, respectively [4]. Thus LSPR acts as a powerful tool to manipulate light on the nanoscale. This chapter concentrates on the fundamental principles behind nano-optics and the use of optically active nanomaterials for biomedical applications. 2. Nano-optics for bio imaging The ultimate goal of bio imaging is to monitor and record structural and functional infor- mation related to biological materials. Over the decades, several imaging systems have been evolved to visualize biological specimens noninvasively, such as X-ray computed tomography (CT), magnetic resonance imaging (MRI), optical coherence tomography (OCT), etc. Optical techniques are highly desirable for bio imaging due to the fact that they are safe, less expensive, and rapid when compared to other conventional techniques. Nanoparticles present new opportunities for bio imaging, providing increased sensitivity in detection through amplification of signal changes. They exhibit specific cellular uptake Nanoparticle Light wave Electric field + + + + + + + – – – – – – – – + Fig. 1 Schematic diagram illustrating the localized surface plasmon on a nanoparticle surface. (Reproduced with permission from S. Unser, I. Bruzas, J. He, L. Sagle, Localized surface plasmon resonance biosensing: Current challenges and approaches, Sensors (Switzerland). 15 (2015) 15684–15716. https://doi.org/10.3390/s150715684.) 34 Nano-optics
- 48. and possess properties that make them easily visible, such as quantum dots. Nanoparticles act as tracers for improved visualization. Since light absorption from biologic tissues is at its minimum at the near infrared (NIR) wavelengths, most nanoparticles like metal and magnetic nanoparticles are designed to absorb strongly in the NIR region. Thus they have proven to possess remarkable advantages for in vivo imaging [5]. Magnetic resonance imaging (MRI) is a noninvasive imaging modality that offers both anatomical and functional information. Iron oxide nanoparticles are of considerable interest as contrast agents for MRI due to their unique superparamagnetic properties [6, 7]. MRI has been extensively studied for the successful tracking of stem cells. Lin et al. reported the use of superparamagnetic iron oxide nanoparticles (SPIONs) to label mesenchymal stem cells (MSCs). The distribution and migration of MSCs were evaluated using MRI for up to 6 weeks [8]. Nickel ferrite nanoparticles also have been developed for MRI contrast enhancement [9]. In order to alleviate the possible toxicity by nickel, ferrite nanoparticles were coated with oleic acid and tetramethyl ammonium hydroxide (TMAH), where TMAH also acted as a stabilizer. There are two particular types of contrast agents: T1 MRI and T2 MRI [10]. T1 MRI is also known as a positive contrast agent (CA) since it gives brighter images. Gadolinium-based chelates belong to this class. Toxicity is a major concern with this group of contrast agents [11]. The other class, T2 MRI CA, includes dextran- or siloxane-coated super paramagnetic iron oxide nanoparticles [12]. This is also known as negative CA due to the darker images obtained. T1 CA is preferred due to the highly brightened images that are obtained. Several studies have focused on the alternatives for T1 MRI contrast agents. Li et al. reported the advantages of pH-sensitive cross-linked iron oxide nanoparticle assemblies (IONAs) as T1 MRI contrast agents for imaging tumors [13]. The IONAs were extremely stable at neutral pH and had a blood circulation half-time of nearly 2.2 h. Moreover the in vivo studies showed that the IONAs didn’t induce any renal toxicity or hepatotoxicity. The conversion of near-infrared radiations into visible light via nonlinear optical pro- cesses, termed upconversion, has received considerable attention in biomedical applica- tions. Among the nanoparticles that exhibit upconversion, rare-earth-doped nanoparticles are considered as an alternative to traditional bio labels. The main advan- tages include good chemical and physical stability, better spatial resolution, and low toxicity [14]. It is particularly advantageous for background free biological sensing [15]. The main advantages of this technique include improved sensitivity due to the absence of autofluor- escence and deeper penetration into tissue, leading to less damage to biological tissues [14]. Upconversion nanoparticles doped with lanthanide ions received considerable attention in this aspect [16]. Europium complex loaded polymer nanoparticles (ECP-NPs) were stud- ied for live cell imaging [17]. PMMA-bearing carboxylate and sulfonate groups were loaded with 1%–40% Europium complexes. The ECP-NPs were incubated with HeLa cells for 3 h and TG (time-gated) imaging was done at a very low excitation power density of 0.24 W cm 2 . It could be clearly seen that strong photoluminescence signals arise from the endocytosed ECP-NPs (Fig. 2). 35 Nano-optics for healthcare applications
- 49. 3. Nano-optics for biosensing Nanotechnology is becoming a crucial driving force behind innovation in medicine and healthcare, with a range of advances including nanoscale therapeutics, biosensors, implantable devices, drug delivery systems, and imaging technologies. Nanophotonics are particularly attractive in that they provide minimally invasive diagnostics for early detection of diseases and help in real-time monitoring of drug intake. Early detection of cancer can save more lives than any form of treatment at advanced stages. Circulating tumor cells (CTCs) are viable cancer cells derived from tumors. The origin of the metastatic disease is represented by these CTCs. Using nanotechnology, we can develop devices that indicate when these CTCs appear in the body, and hence deliver agents to reverse premalignant changes or kill those cells that have the potential to become malignant. Researchers have demonstrated a carbon nanotube chip that captures and analyses circulating tumor cells in blood, rather than using magnetic and microfluidic methods for the isolation of CTCs [18]. The schematic of the sensing technique is given in Fig. 3. Some interesting works have been reported by Tseng et al., in which a Fig. 2 Live-cell images of HeLa cells incubated with ECP-NPs. (A) TG PL images with PMMA-COOH 10% (A1), PMMA-SO3H 3% (A2), and PMMA-SO3H 1% (A3) NPs at 40% [Eu(tta)3phen] loading. For a better comparison between the different images, the intensity scale was fixed at 0 to 2 104 counts. (B) Differential interference contrast (DIC) images. (C) Overlay of images from A and B (ECP-NP PL is shown in red, PL intensities were normalized to the highest values in A1, A2, and A3). Scale bars in all images: 10 μm. (Reproduced with permission from M. Cardoso Dos Santos, A. Runser, H. Bartenlian, A.M. Nonat, L.J. Charbonnière, A.S. Klymchenko, N. Hildebrandt, A. Reisch, Lanthanide-complex-loaded polymer nanoparticles for background-free single-particle and live-cell imaging, Chem. Mater. 31 (2019) 4034–4041. https://doi.org/10.1021/acs.chemmater.9b00576.) 36 Nano-optics
- 50. Other documents randomly have different content
- 54. The Project Gutenberg eBook of You Know Me Al: A Busher's Letters
- 55. This ebook is for the use of anyone anywhere in the United States and most other parts of the world at no cost and with almost no restrictions whatsoever. You may copy it, give it away or re-use it under the terms of the Project Gutenberg License included with this ebook or online at www.gutenberg.org. If you are not located in the United States, you will have to check the laws of the country where you are located before using this eBook. Title: You Know Me Al: A Busher's Letters Adapter: Ring Lardner Release date: July 29, 2016 [eBook #52670] Most recently updated: October 23, 2024 Language: English Credits: Produced by David Edwards, Graeme Mackreth and the Online Distributed Proofreading Team at http://www.pgdp.net (This file was produced from images generously made available by The Internet Archive) *** START OF THE PROJECT GUTENBERG EBOOK YOU KNOW ME AL: A BUSHER'S LETTERS ***
- 56. YOU KNOW ME AL A Busher's Letters BY RING W. LARDNER NEW YORK GEORGE H. DORAN COMPANY
- 57. Copyright, 1916, By George H. Doran Company PRINTED IN THE UNITED STATES OF AMERICA COPYRIGHT, 1914, BY THE CURTIS PUBLISHING COMPANY
- 58. CONTENTS CHAPTER PAGE I. A Busher's Letters Home 9 II. The Busher Comes Back 45 III. The Busher's Honeymoon 83 IV. A New Busher Breaks In 122 V. The Busher's Kid 166 VI. The Busher Beats It Hence 208
- 59. YOU KNOW ME AL
- 60. CHAPTER I A BUSHER'S LETTERS HOME Terre Haute, Indiana, September 6. Friend Al: Well, Al old pal I suppose you seen in the paper where I been sold to the White Sox. Believe me Al it comes as a surprise to me and I bet it did to all you good old pals down home. You could of knocked me over with a feather when the old man come up to me and says Jack I've sold you to the Chicago Americans. I didn't have no idea that anything like that was coming off. For five minutes I was just dum and couldn't say a word. He says We aren't getting what you are worth but I want you to go up to that big league and show those birds that there is a Central League on the map. He says Go and pitch the ball you been pitching down here and there won't be nothing to it. He says All you need is the nerve and Walsh or no one else won't have nothing on you. So I says I would do the best I could and I thanked him for the treatment I got in Terre Haute. They always was good to me here and though I did more than my share I always felt that my work was appresiated. We are finishing second and I done most of it. I can't help but be proud of my first year's record in professional baseball and you know I am not boasting when I say that Al. Well Al it will seem funny to be up there in the big show when I never was really in a big city before. But I guess I seen enough of life not to be scared of the high buildings eh Al?
- 61. I will just give them what I got and if they don't like it they can send me back to the old Central and I will be perfectly satisfied. I didn't know anybody was looking me over, but one of the boys told me that Jack Doyle the White Sox scout was down here looking at me when Grand Rapids was here. I beat them twice in that serious. You know Grand Rapids never had a chance with me when I was right. I shut them out in the first game and they got one run in the second on account of Flynn misjuging that fly ball. Anyway Doyle liked my work and he wired Comiskey to buy me. Comiskey come back with an offer and they excepted it. I don't know how much they got but anyway I am sold to the big league and believe me Al I will make good. Well Al I will be home in a few days and we will have some of the good old times. Regards to all the boys and tell them I am still their pal and not all swelled up over this big league business. Your pal, Jack. Chicago, Illinois, December 14. Old Pal: Well Al I have not got much to tell you. As you know Comiskey wrote me that if I was up in Chi this month to drop in and see him. So I got here Thursday morning and went to his office in the afternoon. His office is out to the ball park and believe me its some park and some office. I went in and asked for Comiskey and a young fellow says He is not here now but can I do anything for you? I told him who I am and says I had an engagement to see Comiskey. He says The boss is out of town hunting and did I have to see him personally? I says I wanted to see about signing a contract. He told me I could sign as well with him as Comiskey and he took me into another office. He says What salary did you think you ought to get? and I
- 62. says I wouldn't think of playing ball in the big league for less than three thousand dollars per annum. He laughed and says You don't want much. You better stick round town till the boss comes back. So here I am and it is costing me a dollar a day to stay at the hotel on Cottage Grove Avenue and that don't include my meals. I generally eat at some of the cafes round the hotel but I had supper downtown last night and it cost me fifty-five cents. If Comiskey don't come back soon I won't have no more money left. Speaking of money I won't sign no contract unless I get the salary you and I talked of, three thousand dollars. You know what I was getting in Terre Haute, a hundred and fifty a month, and I know it's going to cost me a lot more to live here. I made inquiries round here and find I can get board and room for eight dollars a week but I will be out of town half the time and will have to pay for my room when I am away or look up a new one when I come back. Then I will have to buy cloths to wear on the road in places like New York. When Comiskey comes back I will name him three thousand dollars as my lowest figure and I guess he will come through when he sees I am in ernest. I heard that Walsh was getting twice as much as that. The papers says Comiskey will be back here sometime to-morrow. He has been hunting with the president of the league so he ought to feel pretty good. But I don't care how he feels. I am going to get a contract for three thousand and if he don't want to give it to me he can do the other thing. You know me Al. Yours truly, Jack. Chicago, Illinois, December 16. Dear Friend Al: Well I will be home in a couple of days now but I wanted to write you and let you know how I come out with Comiskey. I signed my contract yesterday afternoon. He is a great
- 63. old fellow Al and no wonder everybody likes him. He says Young man will you have a drink? But I was to smart and wouldn't take nothing. He says You was with Terre Haute? I says Yes I was. He says Doyle tells me you were pretty wild. I says Oh no I got good control. He says Well do you want to sign? I says Yes if I get my figure. He asks What is my figure and I says three thousand dollars per annum. He says Don't you want the office furniture too? Then he says I thought you was a young ball-player and I didn't know you wanted to buy my park. We kidded each other back and forth like that a while and then he says You better go out and get the air and come back when you feel better. I says I feel O.K. now and I want to sign a contract because I have got to get back to Bedford. Then he calls the secretary and tells him to make out my contract. He give it to me and it calls for two hundred and fifty a month. He says You know we always have a city serious here in the fall where a fellow picks up a good bunch of money. I hadn't thought of that so I signed up. My yearly salary will be fifteen hundred dollars besides what the city serious brings me. And that is only for the first year. I will demand three thousand or four thousand dollars next year. I would of started home on the evening train but I ordered a suit of cloths from a tailor over on Cottage Grove and it won't be done till to-morrow. It's going to cost me twenty bucks but it ought to last a long time. Regards to Frank and the bunch. Your Pal, Jack. Paso Robles, California, March 2. Old Pal Al: Well Al we been in this little berg now a couple of days and its bright and warm all the time just like June. Seems funny to
- 64. have it so warm this early in March but I guess this California climate is all they said about it and then some. It would take me a week to tell you about our trip out here. We came on a Special Train De Lukes and it was some train. Every place we stopped there was crowds down to the station to see us go through and all the people looked me over like I was a actor or something. I guess my hight and shoulders attracted their attention. Well Al we finally got to Oakland which is across part of the ocean from Frisco. We will be back there later on for practice games. We stayed in Oakland a few hours and then took a train for here. It was another night in a sleeper and believe me I was tired of sleepers before we got here. I have road one night at a time but this was four straight nights. You know Al I am not built right for a sleeping car birth. The hotel here is a great big place and got good eats. We got in at breakfast time and I made a B line for the dining room. Kid Gleason who is a kind of asst. manager to Callahan come in and sat down with me. He says Leave something for the rest of the boys because they will be just as hungry as you. He says Ain't you afraid you will cut your throat with that knife. He says There ain't no extra charge for using the forks. He says You shouldn't ought to eat so much because you're overweight now. I says You may think I am fat, but it's all solid bone and muscle. He says Yes I suppose it's all solid bone from the neck up. I guess he thought I would get sore but I will let them kid me now because they will take off their hats to me when they see me work. Manager Callahan called us all to his room after breakfast and give us a lecture. He says there would be no work for us the first day but that we must all take a long walk over the hills. He also says we must not take the training trip as a joke. Then the colored trainer give us our suits and I went to my room and tried mine on. I ain't a bad looking guy in the White Sox uniform Al. I will have my picture taken and send you boys some.
- 65. My roommate is Allen a lefthander from the Coast League. He don't look nothing like a pitcher but you can't never tell about them dam left handers. Well I didn't go on the long walk because I was tired out. Walsh stayed at the hotel too and when he seen me he says Why didn't you go with the bunch? I says I was too tired. He says Well when Callahan comes back you better keep out of sight or tell him you are sick. I says I don't care nothing for Callahan. He says No but Callahan is crazy about you. He says You better obey orders and you will git along better. I guess Walsh thinks I am some rube. When the bunch come back Callahan never said a word to me but Gleason come up and says Where was you? I told him I was too tired to go walking. He says Well I will borrow a wheelbarrow some place and push you round. He says Do you sit down when you pitch? I let him kid me because he has not saw my stuff yet. Next morning half the bunch mostly vetrans went to the ball park which isn't no better than the one we got at home. Most of them was vetrans as I say but I was in the bunch. That makes things look pretty good for me don't it Al? We tossed the ball round and hit fungos and run round and then Callahan asks Scott and Russell and I to warm up easy and pitch a few to the batters. It was warm and I felt pretty good so I warmed up pretty good. Scott pitched to them first and kept laying them right over with nothing on them. I don't believe a man gets any batting practice that way. So I went in and after I lobbed a few over I cut loose my fast one. Lord was to bat and he ducked out of the way and then throwed his bat to the bench. Callahan says What's the matter Harry? Lord says I forgot to pay up my life insurance. He says I ain't ready for Walter Johnson's July stuff. Well Al I will make them think I am Walter Johnson before I get through with them. But Callahan come out to me and says What are you trying to do kill somebody? He says Save your smoke because you're going to need it later on. He says Go easy with the boys at first or I won't have no batters. But he was laughing and I guess he was pleased to see the stuff I had.
- 66. There is a dance in the hotel to-night and I am up in my room writing this in my underwear while I get my suit pressed. I got it all mussed up coming out here. I don't know what shoes to wear. I asked Gleason and he says Wear your baseball shoes and if any of the girls gets fresh with you spike them. I guess he was kidding me. Write and tell me all the news about home. Yours truly, Jack. Paso Robles, California, March 7. Friend Al: I showed them something out there to-day Al. We had a game between two teams. One team was made up of most of the regulars and the other was made up of recruts. I pitched three innings for the recruts and shut the old birds out. I held them to one hit and that was a ground ball that the recrut shortstop Johnson ought to of ate up. I struck Collins out and he is one of the best batters in the bunch. I used my fast ball most of the while but showed them a few spitters and they missed them a foot. I guess I must of got Walsh's goat with my spitter because him and I walked back to the hotel together and he talked like he was kind of jealous. He says You will have to learn to cover up your spitter. He says I could stand a mile away and tell when you was going to throw it. He says Some of these days I will learn you how to cover it up. I guess Al I know how to cover it up all right without Walsh learning me. I always sit at the same table in the dining room along with Gleason and Collins and Bodie and Fournier and Allen the young lefthander I told you about. I feel sorry for him because he never says a word. To-night at supper Bodie says How did I look to-day Kid? Gleason says Just like you always do in the spring. You looked like a cow. Gleason seems to have the whole bunch scared of him and they let him say anything he wants to. I let him kid me to but I ain't scared of him. Collins then says to me You got some fast ball there boy. I
- 67. says I was not as fast to-day as I am when I am right. He says Well then I don't want to hit against you when you are right. Then Gleason says to Collins Cut that stuff out. Then he says to me Don't believe what he tells you boy. If the pitchers in this league weren't no faster than you I would still be playing ball and I would be the best hitter in the country. After supper Gleason went out on the porch with me. He says Boy you have got a little stuff but you have got a lot to learn. He says You field your position like a wash woman and you don't hold the runners up. He says When Chase was on second base to-day he got such a lead on you that the little catcher couldn't of shot him out at third with a rifle. I says They all thought I fielded my position all right in the Central League. He says Well if you think you do it all right you better go back to the Central League where you are appresiated. I says You can't send me back there because you could not get waivers. He says Who would claim you? I says St. Louis and Boston and New York. You know Al what Smith told me this winter. Gleason says Well if you're not willing to learn St. Louis and Boston and New York can have you and the first time you pitch against us we will steal fifty bases. Then he quit kidding and asked me to go to the field with him early to-morrow morning and he would learn me some things. I don't think he can learn me nothing but I promised I would go with him. There is a little blonde kid in the hotel here who took a shine to me at the dance the other night but I am going to leave the skirts alone. She is real society and a swell dresser and she wants my picture. Regards to all the boys. Your friend, Jack. P.S. The boys thought they would be smart to-night and put something over on me. A boy brought me a telegram and I opened it and it said You are sold to Jackson in the Cotton States League. For just a minute they had me going but then I happened to think
- 68. that Jackson is in Michigan and there's no Cotton States League round there. Paso Robles, California, March 9. Dear Friend Al: You have no doubt read the good news in the papers before this reaches you. I have been picked to go to Frisco with the first team. We play practice games up there about two weeks while the second club plays in Los Angeles. Poor Allen had to go with the second club. There's two other recrut pitchers with our part of the team but my name was first on the list so it looks like I had made good. I knowed they would like my stuff when they seen it. We leave here to-night. You got the first team's address so you will know where to send my mail. Callahan goes with us and Gleason goes with the second club. Him and I have got to be pretty good pals and I wish he was going with us even if he don't let me eat like I want to. He told me this morning to remember all he had learned me and to keep working hard. He didn't learn me nothing I didn't know before but I let him think so. The little blonde don't like to see me leave here. She lives in Detroit and I may see her when I go there. She wants me to write but I guess I better not give her no encouragement. Well Al I will write you a long letter from Frisco. Yours truly, Jack. Oakland, California, March 19. Dear Old Pal: They have gave me plenty of work here all right. I have pitched four times but have not went over five innings yet. I
- 69. worked against Oakland two times and against Frisco two times and only three runs have been scored off me. They should only ought to of had one but Bodie misjuged a easy fly ball in Frisco and Weaver made a wild peg in Oakland that let in a run. I am not using much but my fast ball but I have got a world of speed and they can't foul me when I am right. I whiffed eight men in five innings in Frisco yesterday and could of did better than that if I had of cut loose. Manager Callahan is a funny guy and I don't understand him sometimes. I can't figure out if he is kidding or in ernest. We road back to Oakland on the ferry together after yesterday's game and he says Don't you never throw a slow ball? I says I don't need no slow ball with my spitter and my fast one. He says No of course you don't need it but if I was you I would get one of the boys to learn it to me. He says And you better watch the way the boys fields their positions and holds up the runners. He says To see you work a man might think they had a rule in the Central League forbidding a pitcher from leaving the box or looking toward first base. I told him the Central didn't have no rule like that. He says And I noticed you taking your wind up when What's His Name was on second base there to-day. I says Yes I got more stuff when I wind up. He says Of course you have but if you wind up like that with Cobb on base he will steal your watch and chain. I says Maybe Cobb can't get on base when I work against him. He says That's right and maybe San Francisco Bay is made of grapejuice. Then he walks away from me. He give one of the youngsters a awful bawling out for something he done in the game at supper last night. If he ever talks to me like he done to him I will take a punch at him. You know me Al. I come over to Frisco last night with some of the boys and we took in the sights. Frisco is some live town Al. We went all through China Town and the Barbers' Coast. Seen lots of swell dames but they was all painted up. They have beer out here that they call steam beer. I had a few glasses of it and it made me logey. A glass of that Terre Haute beer would go pretty good right now.
- 70. We leave here for Los Angeles in a few days and I will write you from there. This is some country Al and I would love to play ball round here. Your Pal, Jack. P.S.—I got a letter from the little blonde and I suppose I got to answer it. Los Angeles, California, March 26. Friend Al: Only four more days of sunny California and then we start back East. We got exhibition games in Yuma and El Paso, Texas, and Oklahoma City and then we stop over in St. Joe, Missouri, for three days before we go home. You know Al we open the season in Cleveland and we won't be in Chi no more than just passing through. We don't play there till April eighteenth and I guess I will work in that serious all right against Detroit. Then I will be glad to have you and the boys come up and watch me as you suggested in your last letter. I got another letter from the little blonde. She has went back to Detroit but she give me her address and telephone number and believe me Al I am going to look her up when we get there the twenty-ninth of April. She is a stenographer and was out here with her uncle and aunt. I had a run in with Kelly last night and it looked like I would have to take a wallop at him but the other boys seperated us. He is a bush outfielder from the New England League. We was playing poker. You know the boys plays poker a good deal but this was the first time I got in. I was having pretty good luck and was about four bucks to the good and I was thinking of quitting because I was tired and sleepy. Then Kelly opened the pot for fifty cents and I stayed. I had three sevens. No one else stayed. Kelly stood pat and I drawed two cards. And I catched my fourth seven. He bet fifty cents but I felt
- 71. pretty safe even if he did have a pat hand. So I called him. I took the money and told them I was through. Lord and some of the boys laughed but Kelly got nasty and begun to pan me for quitting and for the way I played. I says Well I won the pot didn't I? He says Yes and he called me something. I says I got a notion to take a punch at you. He says Oh you have have you? And I come back at him. I says Yes I have have I? I would of busted his jaw if they hadn't stopped me. You know me Al. I worked here two times once against Los Angeles and once against Venice. I went the full nine innings both times and Venice beat me four to two. I could of beat them easy with any kind of support. I walked a couple of guys in the forth and Chase drops a throw and Collins lets a fly ball get away from him. At that I would of shut them out if I had wanted to cut loose. After the game Callahan says You didn't look so good in there to-day. I says I didn't cut loose. He says Well you been working pretty near three weeks now and you ought to be in shape to cut loose. I says Oh I am in shape all right. He says Well don't work no harder than you have to or you might get hurt and then the league would blow up. I don't know if he was kidding me or not but I guess he thinks pretty well of me because he works me lots oftener than Walsh or Scott or Benz. I will try to write you from Yuma, Texas, but we don't stay there only a day and I may not have time for a long letter. Yours truly, Jack. Yuma, Arizona, April 1. Dear Old Al: Just a line to let you know we are on our way back East. This place is in Arizona and it sure is sandy. They haven't got no regular ball club here and we play a pick-up team this afternoon. Callahan told me I would have to work. He says I am using you
- 72. because we want to get through early and I know you can beat them quick. That is the first time he has said anything like that and I guess he is wiseing up that I got the goods. We was talking about the Athaletics this morning and Callahan says None of you fellows pitch right to Baker. I was talking to Lord and Scott afterward and I say to Scott How do you pitch to Baker? He says I use my fadeaway. I says How do you throw it? He says Just like you throw a fast ball to anybody else. I says Why do you call it a fadeaway then? He says Because when I throw it to Baker it fades away over the fence. This place is full of Indians and I wish you could see them Al. They don't look nothing like the Indians we seen in that show last summer. Your old pal, Jack. Oklahoma City, April 4. Friend Al: Coming out of Amarillo last night I and Lord and Weaver was sitting at a table in the dining car with a old lady. None of us were talking to her but she looked me over pretty careful and seemed to kind of like my looks. Finally she says Are you boys with some football club? Lord nor Weaver didn't say nothing so I thought it was up to me and I says No mam this is the Chicago White Sox Ball Club. She says I knew you were athaletes. I says Yes I guess you could spot us for athaletes. She says Yes indeed and specially you. You certainly look healthy. I says You ought to see me stripped. I didn't see nothing funny about that but I thought Lord and Weaver would die laughing. Lord had to get up and leave the table and he told everybody what I said. All the boys wanted me to play poker on the way here but I told them I didn't feel good. I know enough to quit when I am ahead Al. Callahan and I sat down to breakfast all alone this morning. He says Boy why don't you get to work? I says What do you mean? Ain't I
- 73. working? He says You ain't improving none. You have got the stuff to make a good pitcher but you don't go after bunts and you don't cover first base and you don't watch the baserunners. He made me kind of sore talking that way and I says Oh I guess I can get along all right. He says Well I am going to put it up to you. I am going to start you over in St. Joe day after to-morrow and I want you to show me something. I want you to cut loose with all you've got and I want you to get round the infield a little and show them you aren't tied in that box. I says Oh I can field my position if I want to. He says Well you better want to or I will have to ship you back to the sticks. Then he got up and left. He didn't scare me none Al. They won't ship me to no sticks after the way I showed on this trip and even if they did they couldn't get no waivers on me. Some of the boys have begun to call me Four Sevens but it don't bother me none. Yours truly, Jack. St. Joe, Missouri, April 7. Friend Al: It rained yesterday so I worked to-day instead and St. Joe done well to get three hits. They couldn't of scored if we had played all week. I give a couple of passes but I catched a guy flatfooted off of first base and I come up with a couple of bunts and throwed guys out. When the game was over Callahan says That's the way I like to see you work. You looked better to-day than you looked on the whole trip. Just once you wound up with a man on but otherwise you was all O.K. So I guess my job is cinched Al and I won't have to go to New York or St. Louis. I would rather be in Chi anyway because it is near home. I wouldn't care though if they traded me to Detroit. I hear from Violet right along and she says she can't hardly wait till I come to Detroit. She says she is strong for the Tigers but she will pull for me when I work against them. She is nuts over me and I guess she has saw lots of guys to.
- 74. I sent her a stickpin from Oklahoma City but I can't spend no more dough on her till after our first payday the fifteenth of the month. I had thirty bucks on me when I left home and I only got about ten left including the five spot I won in the poker game. I have to tip the waiters about thirty cents a day and I seen about twenty picture shows on the coast besides getting my cloths pressed a couple of times. We leave here to-morrow night and arrive in Chi the next morning. The second club joins us there and then that night we go to Cleveland to open up. I asked one of the reporters if he knowed who was going to pitch the opening game and he says it would be Scott or Walsh but I guess he don't know much about it. These reporters travel all round the country with the team all season and send in telegrams about the game every night. I ain't seen no Chi papers so I don't know what they been saying about me. But I should worry eh Al? Some of them are pretty nice fellows and some of them got the swell head. They hang round with the old fellows and play poker most of the time. Will write you from Cleveland. You will see in the paper if I pitch the opening game. Your old pal, Jack. Cleveland, Ohio, April 10. Old Friend Al: Well Al we are all set to open the season this afternoon. I have just ate breakfast and I am sitting in the lobby of the hotel. I eat at a little lunch counter about a block from here and I saved seventy cents on breakfast. You see Al they give us a dollar a meal and if we don't want to spend that much all right. Our rooms at the hotel are paid for. The Cleveland papers says Walsh or Scott will work for us this afternoon. I asked Callahan if there was any chance of me getting
- 75. into the first game and he says I hope not. I don't know what he meant but he may surprise these reporters and let me pitch. I will beat them Al. Lajoie and Jackson is supposed to be great batters but the bigger they are the harder they fall. The second team joined us yesterday in Chi and we practiced a little. Poor Allen was left in Chi last night with four others of the recrut pitchers. Looks pretty good for me eh Al? I only seen Gleason for a few minutes on the train last night. He says, Well you ain't took off much weight. You're hog fat. I says Oh I ain't fat. I didn't need to take off no weight. He says One good thing about it the club don't have to engage no birth for you because you spend all your time in the dining car. We kidded along like that a while and then the trainer rubbed my arm and I went to bed. Well Al I just got time to have my suit pressed before noon. Yours truly, Jack. Cleveland, Ohio, April 11. Friend Al: Well Al I suppose you know by this time that I did not pitch and that we got licked. Scott was in there and he didn't have nothing. When they had us beat four to one in the eight inning Callahan told me to go out and warm up and he put a batter in for Scott in our ninth. But Cleveland didn't have to play their ninth so I got no chance to work. But it looks like he means to start me in one of the games here. We got three more to play. Maybe I will pitch this afternoon. I got a postcard from Violet. She says Beat them Naps. I will give them a battle Al if I get a chance. Glad to hear you boys have fixed it up to come to Chi during the Detroit serious. I will ask Callahan when he is going to pitch me and let you know. Thanks Al for the papers. Your friend, Jack.
- 76. St. Louis, Missouri, April 15. Friend Al: Well Al I guess I showed them. I only worked one inning but I guess them Browns is glad I wasn't in there no longer than that. They had us beat seven to one in the sixth and Callahan pulls Benz out. I honestly felt sorry for him but he didn't have nothing, not a thing. They was hitting him so hard I thought they would score a hundred runs. A righthander name Bumgardner was pitching for them and he didn't look to have nothing either but we ain't got much of a batting team Al. I could hit better than some of them regulars. Anyway Callahan called Benz to the bench and sent for me. I was down in the corner warming up with Kuhn. I wasn't warmed up good but you know I got the nerve Al and I run right out there like I meant business. There was a man on second and nobody out when I come in. I didn't know who was up there but I found out afterward it was Shotten. He's the center-fielder. I was cold and I walked him. Then I got warmed up good and I made Johnston look like a boob. I give him three fast balls and he let two of them go by and missed the other one. I would of handed him a spitter but Schalk kept signing for fast ones and he knows more about them batters than me. Anyway I whiffed Johnston. Then up come Williams and I tried to make him hit at a couple of bad ones. I was in the hole with two balls and nothing and come right across the heart with my fast one. I wish you could of saw the hop on it. Williams hit it right straight up and Lord was camped under it. Then up come Pratt the best hitter on their club. You know what I done to him don't you Al? I give him one spitter and another he didn't strike at that was a ball. Then I come back with two fast ones and Mister Pratt was a dead baby. And you notice they didn't steal no bases neither. In our half of the seventh inning Weaver and Schalk got on and I was going up there with a stick when Callahan calls me back and sends Easterly up. I don't know what kind of managing you call that. I hit good on the training trip and he must of knew they had no chance to score off me in the innings they had left while they were liable to murder his other pitchers. I come back to the bench pretty
- 77. hot and I says You're making a mistake. He says If Comiskey had wanted you to manage this team he would of hired you. Then Easterly pops out and I says Now I guess you're sorry you didn't let me hit. That sent him right up in the air and he bawled me awful. Honest Al I would of cracked him right in the jaw if we hadn't been right out where everybody could of saw us. Well he sent Cicotte in to finish and they didn't score no more and we didn't neither. I road down in the car with Gleason. He says Boy you shouldn't ought to talk like that to Cal. Some day he will lose his temper and bust you one. I says He won't never bust me. I says He didn't have no right to talk like that to me. Gleason says I suppose you think he's going to laugh and smile when we lost four out of the first five games. He says Wait till to-night and then go up to him and let him know you are sorry you sassed him. I says I didn't sass him and I ain't sorry. So after supper I seen Callahan sitting in the lobby and I went over and sit down by him. I says When are you going to let me work? He says I wouldn't never let you work only my pitchers are all shot to pieces. Then I told him about you boys coming up from Bedford to watch me during the Detroit serious and he says Well I will start you in the second game against Detroit. He says But I wouldn't if I had any pitchers. He says A girl could get out there and pitch better than some of them have been doing. So you see Al I am going to pitch on the nineteenth. I hope you guys can be up there and I will show you something. I know I can beat them Tigers and I will have to do it even if they are Violet's team. I notice that New York and Boston got trimmed to-day so I suppose they wish Comiskey would ask for waivers on me. No chance Al. Your old pal, Jack. P.S.—We play eleven games in Chi and then go to Detroit. So I will see the little girl on the twenty-ninth.
- 78. Oh you Violet. Chicago, Illinois, April 19. Dear Old Pal: Well Al it's just as well you couldn't come. They beat me and I am writing you this so as you will know the truth about the game and not get a bum steer from what you read in the papers. I had a sore arm when I was warming up and Callahan should never ought to of sent me in there. And Schalk kept signing for my fast ball and I kept giving it to him because I thought he ought to know something about the batters. Weaver and Lord and all of them kept kicking them round the infield and Collins and Bodie couldn't catch nothing. Callahan ought never to of left me in there when he seen how sore my arm was. Why, I couldn't of threw hard enough to break a pain of glass my arm was so sore. They sure did run wild on the bases. Cobb stole four and Bush and Crawford and Veach about two apiece. Schalk didn't even make a peg half the time. I guess he was trying to throw me down. The score was sixteen to two when Callahan finally took me out in the eighth and I don't know how many more they got. I kept telling him to take me out when I seen how bad I was but he wouldn't do it. They started bunting in the fifth and Lord and Chase just stood there and didn't give me no help at all. I was all O.K. till I had the first two men out in the first inning. Then Crawford come up. I wanted to give him a spitter but Schalk signs me for the fast one and I give it to him. The ball didn't hop much and Crawford happened to catch it just right. At that Collins ought to of catched the ball. Crawford made three bases and up come Cobb. It was the first time I ever seen him. He hollered at me right off the reel. He says You better walk me you busher. I says I will walk you
- 79. back to the bench. Schalk signs for a spitter and I gives it to him and Cobb misses it. Then instead of signing for another one Schalk asks for a fast one and I shook my head no but he signed for it again and yells Put something on it. So I throwed a fast one and Cobb hits it right over second base. I don't know what Weaver was doing but he never made a move for the ball. Crawford scored and Cobb was on first base. First thing I knowed he had stole second while I held the ball. Callahan yells Wake up out there and I says Why don't your catcher tell me when they are going to steal. Schalk says Get in there and pitch and shut your mouth. Then I got mad and walked Veach and Moriarty but before I walked Moriarty Cobb and Veach pulled a double steal on Schalk. Gainor lifts a fly and Lord drops it and two more come in. Then Stanage walks and I whiffs their pitcher. I come in to the bench and Callahan says Are your friends from Bedford up here? I was pretty sore and I says Why don't you get a catcher? He says We don't need no catcher when you're pitching because you can't get nothing past their bats. Then he says You better leave your uniform in here when you go out next inning or Cobb will steal it off your back. I says My arm is sore. He says Use your other one and you'll do just as good. Gleason says Who do you want to warm up? Callahan says Nobody. He says Cobb is going to lead the league in batting and basestealing anyway so we might as well give him a good start. I was mad enough to punch his jaw but the boys winked at me not to do nothing. Well I got some support in the next inning and nobody got on. Between innings I says Well I guess I look better now don't I? Callahan says Yes but you wouldn't look so good if Collins hadn't jumped up on the fence and catched that one off Crawford. That's all the encouragement I got Al. Cobb come up again to start the third and when Schalk signs me for a fast one I shakes my head. Then Schalk says All right pitch
- 80. anything you want to. I pitched a spitter and Cobb bunts it right at me. I would of threw him out a block but I stubbed my toe in a rough place and fell down. This is the roughest ground I ever seen Al. Veach bunts and for a wonder Lord throws him out. Cobb goes to second and honest Al I forgot all about him being there and first thing I knowed he had stole third. Then Moriarty hits a fly ball to Bodie and Cobb scores though Bodie ought to of threw him out twenty feet. They batted all round in the forth inning and scored four or five more. Crawford got the luckiest three-base hit I ever see. He popped one way up in the air and the wind blowed it against the fence. The wind is something fierce here Al. At that Collins ought to of got under it. I was looking at the bench all the time expecting Callahan to call me in but he kept hollering Go on and pitch. Your friends wants to see you pitch. Well Al I don't know how they got the rest of their runs but they had more luck than any team I ever seen. And all the time Jennings was on the coaching line yelling like a Indian. Some day Al I'm going to punch his jaw. After Veach had hit one in the eight Callahan calls me to the bench and says You're through for the day. I says It's about time you found out my arm was sore. He says I ain't worrying about your arm but I'm afraid some of our outfielders will run their legs off and some of them poor infielders will get killed. He says The reporters just sent me a message saying they had run out of paper. Then he says I wish some of the other clubs had pitchers like you so we could hit once in a while. He says Go in the clubhouse and get your arm rubbed off. That's the only way I can get Jennings sore he says. Well Al that's about all there was to it. It will take two or three stamps to send this but I want you to know the truth about it. The way my arm was I ought never to of went in there. Yours truly, Jack.
- 81. Chicago, Illinois, April 25. Friend Al: Just a line to let you know I am still on earth. My arm feels pretty good again and I guess maybe I will work at Detroit. Violet writes that she can't hardly wait to see me. Looks like I got a regular girl now Al. We go up there the twenty-ninth and maybe I won't be glad to see her. I hope she will be out to the game the day I pitch. I will pitch the way I want to next time and them Tigers won't have such a picnic. I suppose you seen what the Chicago reporters said about that game. I will punch a couple of their jaws when I see them. Your pal, Jack. Chicago, Illinois, April 29. Dear Old Al: Well Al it's all over. The club went to Detroit last night and I didn't go along. Callahan told me to report to Comiskey this morning and I went up to the office at ten o'clock. He give me my pay to date and broke the news. I am sold to Frisco. I asked him how they got waivers on me and he says Oh there was no trouble about that because they all heard how you tamed the Tigers. Then he patted me on the back and says Go out there and work hard boy and maybe you'll get another chance some day. I was kind of choked up so I walked out of the office. I ain't had no fair deal Al and I ain't going to no Frisco. I will quit the game first and take that job Charley offered me at the billiard hall. I expect to be in Bedford in a couple of days. I have got to pack up first and settle with my landlady about my room here which I engaged for all season thinking I would be treated square. I am going to rest and lay round home a while and try to forget this rotten game. Tell the boys about it Al and tell them I never would of got let out if I hadn't worked with a sore arm.
- 82. I feel sorry for that little girl up in Detroit Al. She expected me there to-day. Your old pal, Jack. P.S. I suppose you seen where that lucky lefthander Allen shut out Cleveland with two hits yesterday. The lucky stiff.
- 83. CHAPTER II THE BUSHER COMES BACK. San Francisco, California, May 13. Friend Al: I suppose you and the rest of the boys in Bedford will be supprised to learn that I am out here, because I remember telling you when I was sold to San Francisco by the White Sox that not under no circumstances would I report here. I was pretty mad when Comiskey give me my release, because I didn't think I had been given a fair show by Callahan. I don't think so yet Al and I never will but Bill Sullivan the old White Sox catcher talked to me and told me not to pull no boner by refuseing to go where they sent me. He says You're only hurting yourself. He says You must remember that this was your first time up in the big show and very few men no matter how much stuff they got can expect to make good right off the reel. He says All you need is experience and pitching out in the Coast League will be just the thing for you. So I went in and asked Comiskey for my transportation and he says That's right Boy go out there and work hard and maybe I will want you back. I told him I hoped so but I don't hope nothing of the kind Al. I am going to see if I can't get Detroit to buy me, because I would rather live in Detroit than anywheres else. The little girl who got stuck on me this spring lives there. I guess I told you about her Al. Her name is Violet and she is some queen. And then if I got with the Tigers I wouldn't never have to pitch against Cobb and Crawford, though I believe I could show both of them up if I was
- 84. right. They ain't got much of a ball club here and hardly any good pitchers outside of me. But I don't care. I will win some games if they give me any support and I will get back in the big league and show them birds something. You know me, Al. Your pal, Jack. Los Angeles, California, May 20. Al: Well old pal I don't suppose you can find much news of this league in the papers at home so you may not know that I have been standing this league on their heads. I pitched against Oakland up home and shut them out with two hits. I made them look like suckers Al. They hadn't never saw no speed like mine and they was scared to death the minute I cut loose. I could of pitched the last six innings with my foot and trimmed them they was so scared. Well we come down here for a serious and I worked the second game. They got four hits and one run, and I just give them the one run. Their shortstop Johnson was on the training trip with the White Sox and of course I knowed him pretty well. So I eased up in the last inning and let him hit one. If I had of wanted to let myself out he couldn't of hit me with a board. So I am going along good and Howard our manager says he is going to use me regular. He's a pretty nice manager and not a bit sarkastic like some of them big leaguers. I am fielding my position good and watching the baserunners to. Thank goodness Al they ain't no Cobbs in this league and a man ain't scared of haveing his uniform stole off his back. But listen Al I don't want to be bought by Detroit no more. It is all off between Violet and I. She wasn't the sort of girl I suspected. She is just like them all Al. No heart. I wrote her a letter from Chicago
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