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Introduction of 7200 Q-TOF.pdf

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This document provides information about the 7200 Series Q-TOF for GC/MS, a new mass spectrometry instrument from Agilent. The 7200 combines a quadrupole mass filter with time-of-flight mass analyzer to provide high resolution and accurate mass capabilities. It offers improved sensitivity, mass accuracy, and dynamic range over previous instruments. The document describes the instrument's design features and provides examples of how it can be used for applications like pesticide residue analysis, metabolomics, and structural elucidation of unknown compounds.

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Page 1 7200 Series Q-TOF for GC/MS June 2011 A new analytical tool for solving complex analytical problems
Page 2 7200 GC/Q-TOF Breakfast Seminar ASMS Conference on Mass Spectrometry and Allied Topics June 5-9, 2011 Colorado Convention Center, Denver, CO
Page 3 Hospitality Suite “There’s Something Brewing at Agilent” BrewPub Theme Super Sensitive Stout Heavy Matrix Hefeweizen Clearly Better Bitter
Page 4 240 IT 7000 TQ 220 IT 5975E SQ 5975T LTM SQ 5975C SQ 7200 Q-TOF More Choices – Better Solutions Agilent GC/MS & GC/MS/MS ASMS Agilent Restricted
Page 5 = + What is it? 7890 + 7000 + 6500 = 7200 GC/Q-TOF Quadrupole Time of Flight MS Time of Flight MS Triple Quadrupole MS
Page 6 What Will The 7200 Q-TOF Do For You? • TOF mode • High resolution full scan spectra • Accurate mass measurements • Fast full spectrum acquisition • MS/MS mode • Product ion spectra – high resolution, accurate mass • Sensitivity > TQ product ion methods • Ideal tool for solving complex analytical problems • New tools for structural elucidation of unknowns and confirmation of non-targets
Page 7 = + 7890 + 7000 + 6500 = 7200 GC/Q-TOF It‟s our newest GC/MS . . . built upon many well proven parts: Almost one thousand 7000 TQs Over one thousand TOFs and Q-TOFs Many thousand 7890 GCs
Page 8 7200 Analyzer 7000B TQ 6500 Q-TOF NEW Optics
Page 9 New . . . Yet Totally Proven Dual-stage ion mirror improves second-order time focusing for high mass resolution. Hexapole collision cell accelerates ion through the cell to enable faster generation of high-quality MS/MS spectra without cross-talk Split-flow turbo differentially pumps the ion source and quadrupole analyzer compartments 4GHz ADC electronics enable a high sampling rate (32 Gbit/s) which improves the resolution, mass accuracy, and sensitivity for low-abundance samples. Dual gain amplifiers simultaneously process detector signals through both low- gain and high gain channels, extending the dynamic range to 105. Analog-to-digital (ADC) Detector: Unlike time-to-digital (TDC) detectors which record single ion events, ADC detection records multiple ion events, allowing very accurate mass assignments over a wide mass range and dynamic range of concentrations. Proprietary INVAR flight tube sealed in a vacuum-insulated shell eliminates thermal mass drift due to temperature changes to maintain excellent mass accuracy, 24/7. Added length improves mass resolution. Hot, quartz monolithic quadrupole analyzer and collision cell identical to the 7000 Quadrupole MS/MS
Page 10 Other New . . . And Improved New Removable Ion Source includes repeller, ion volume, extraction lens and dual filaments New Internal Reference Mass can be delivered to the source at a low and high concentration Two 300L/s turbos pump the focusing optics and flight tube
Page 11 • Allows swap of complete ion source, including filaments, in ~30 minutes without venting • Allows fast EI/CI source swapping without venting Removable Ion Source (RIS)
Page 12 Removable Ion Source (RIS) Automated Retractable Transfer Line RIS Automated Gate Valve
Page 13 30 minute source swap with RIS New Clean Ion Source Original Dirty Ion Source 1pg OFN Ventcool ion sourceopen chamber and replace/maintain source components close chamberpump outheat source stabilize vacuum and source temperature
Page 14 Spectral presentation (Tune File) Centroid View Profile View Most users think in “centroid”, but the MS operates in “profile”
Page 15 Comparing Quad & TOF 10 100 1000 10000 100000 0 200 400 600 800 1000 1200 Resolving Power Mass (amu) Resolving Power Quad TOF 0.001 0.01 0.1 1 0 200 400 600 800 1000 1200 peak width, amu Mass (amu) PeakWidth Quad TOF TOF has constant Resolving Power (peak-width changes with mass) Quads operate with constant peak-width (Resolving Power changes with mass)
Page 16 Resolving power & mass accuracy R = 614/0.68 = 903 Δmz = 0.1/614 = 160 ppm Pw=0.68 Mz=614 SQ TQ IT TOF Q-TOF R = 614/0.0423 = 14522 Δmz = 0.0004/613.96 = 0.7 ppm Resolving Power: R=mz/FWHM Mass Accuracy: Δmz=dm/mz*106 , parts per million (ppm) PFTBA mass 614 C12F24N=613.964203 1 Da. 1 Da.
Page 17 OFN Results theoretical masss = 271.986677 error = -0.5 ppm 1pg OFN Theoretical Mass = 271.986677 error = -0.5 ppm Resolving Power = 13464 0.25 u Later Prototype Q-TOF
Page 18 Large dynamic range detection system Threshold Time to Digital Converter Counts “1” when above Threshold 1-2 Orders Magnitude Dynamic Range 2-8 Gbit/sec of information Analog to Digital Converter Measures each point 4-5 Orders Magnitude Dynamic Range 32 Gbit/sec of information TDC ADC
Page 19 Response linearity and mass accuracy ADC advantages 5 Hz acquisition, RIS LOD about 0.01 pg R^2=0.9991
Page 20 Accurate mass makes mass defect important X Hydrogen H 1 1.0078 99.99 0.0078 D or 2 H 2 2.0141 0.01 0.0141 X+1 Carbon 12 C 12 12 98.91 0 13 C 13 13.0034 1.1 1.1nC 0.0060nC 2 0.0034 X+1 Nitrogen 14 N 14 14.0031 99.6 0.0031 15 N 15 15.0001 0.4 0.37nN 0.0001 X+2 Oxygen 16 O 16 15.9949 99.76 -0.0051 17 O 17 16.9991 0.04 0.04nO -0.0009 18 O 18 17.9992 0.2 0.20nO -0.0008 X Fluorine F 19 18.9984 100 -0.0016 X+2 Silicon 28 Si 28 27.9769 92.2 -0.0231 29 Si 29 28.9765 4.7 5.1nSi -0.0235 30 Si 30 29.9738 3.1 3.4nSi -0.0262 X Phosphorus P 31 30.9738 100 -0.0262 X+2 Sulfur 32 S 32 31.9721 95.02 -0.0279 33 S 33 32.9715 0.76 0.8nS -0.0285 34 S 34 33.9679 4.22 4.4nS -0.0321 X+2 Chlorine 35 Cl 35 34.9689 75.77 -0.0311 37 Cl 37 36.9659 24.23 32.5nCl -0.0341 X+2 Bromine 79 Br 79 78.9183 50.5 -0.0817 81 Br 81 80.9163 49.5 98.0nBr -0.0837 X Iodine I 127 126.9045 100 -0.0955 X+1 Factor X+2 Factor Mass Defect Type Element Symbol Abundance Integer Mass Exact Mass
Page 21 Many possible formulas with an MSD or IT But only a few with TOF 1 10 100 1000 10000 0.1 1 10 100 1000 # Possible Chemical Formulas mass uncertainty, ppm Possible Number of Chemical Formulas at m/z 272 Formulas made of: C,H,N,O,F, & Cl mass uncertainty ppm amu # of Possible Formulas 1000 0.3 7657 368 0.1 4050 100 0.03 1223 37 0.01 466 10 0.003 120 4 0.001 43 1 0.0003 11 0.4 0.0001 5 0.1 0.00003 2 Octafluoronaphthalene (CAS 313-72-4) C10F8 = 271.98667 Accurate mass reduces risk of investing effort on the wrong molecule
Page 22 Internal Reference Mass (IRM) • The goal for the 7200 is for easy and reliable ~2-5ppm mass accuracy under all conditions • Agilent has developed a proprietary Internal Reference Mass (IRM) delivery system for “on the fly” mass axis correction • IRM is the use of known background ions to “lock” the mass axis for each scan • Requires reliable IRM calibration signals with and without matrix
Page 23 7200 provisional instrument performance Specifications… • Resolving Power: >10K at m/z 272 (>13K typical) • Mass Accuracy: <5 ppm at m/z 272 (<2ppm typical) • MS Sensitivity: 1 pg OFN S/N > 400:1 • Dynamic Range: > 3 orders of magnitude • Quad Mass range: 20-1050 Da (0.7-4.0 Da FWHM) • TOF Mass range: 20-1700 Da • Spectral Rate: 1-50 spectra/sec All specifications subject to change
Page 24 Mass accuracy Number of Ions Mass Accuracy Limited by ion statistics Limited by detector non-linearity TDC ADC Required mass accuracy
Page 25 7200 Series Q-TOF for GC/MS How is this new capability used - application results Pesticides in Food Tom Doherty, Phil Wylie, Chris Sandy, Bill Russ Fluorotelomer Alcohols in Biosolids (PCI) Anthony Macherone Volatile Sulfur-containing Compounds in Beverages Nobuo Ochiai, Kikuo Sasamoto – Gerstel KK, Japan Ryo Ogasawara, Hajime Kawakami – Agilent Volatile Photodegradation Products in Beer Stephan Baumann Metabolomics Oscar Yanes, Maria Vinaixa, Jesus Breznes – Tarragona University, Spain
Page 26 Pesticides in Food
Page 27 Internal reference mass correction in matrix 100ppb pesticides in Okra extract Measured Accurate Mass (Da)Mass Error, ppm Analyte RT Theoretical Mass No IRM With IRM No IRM With IRM Trifluralin 5.83 306.0696 306.0638 306.0698 -18.9 0.7 Ethion 13.03 230.9732 230.9689 230.9744 -18.6 5.2 Iprodione 14.26 314.0094 314.0030 314.0101 -20.4 2.2 Indoxacarb18.06 527.0702 527.0603 527.0730 -18.8 5.3 Trifluralin No IRM, -18.9ppm IRM, -0.7ppm +EI TIC +EI EIC(306.0696)
Page 28 Okra QuEChERS Extract Matrix interferant ion (b-Tocopherol) 150.06839 Da Analyte Indoxacarb ion (100pg) 150.01195 Da (fragment ion) +/-0.5 amu (~ 300ppm) Indoxacarb b-Tocopherol Indoxacarb TOF Accurate Mass to Eliminate Matrix Interferants Tocopherol interference eliminated in MS mode If even more selectivity is needed, option of MS/MS Extraction window 5 ppm MS/MS with high resolution and accurate mass! Dm = 0.0564 Da.
Page 29 Fludioxonil in Frozen Blueberry Extract 38 ppb in extract TIC EIC: 248.0392 +/- 0.5 amu EIC: 248.0392 +/- 10 ppm Signal/Noise = 108 Signal/Noise = 1154
Page 30 Add „Q+CID‟ to TOF solution Sometimes the combined power of GC Resolution (Agilent) + MS Resolving Power (Agilent) Is not enough based upon: Small ΔMass Defect (Nature) + Intense Matrix Ions (Sample) High resolution MS/MS can solve some of these problems Why add „Q‟ to TOF to make Q-TOF?
Page 31 • Structural Elucidation from product Ion spectra using high resolution and accurate mass • Start with full scan EI spectrum • Use CID on each fragment mass to confirm structure of fragment • Select Fragment 1 to be precursor 1  Product ions • Select Fragment 2 to be precursor 2  Product ions Precursor-product ion relationship is documented and ion molecular formula confirmed by accurate mass Requires multiple analyses and much more sensitive than NMR Will not replace NMR, but will complement nicely CID CID How is it used? Structure elucidation
Page 32 MS/MS chemical noise reduction If resolution and accurate mass are not enough EI MS m/z 272 54:1 S/N Analyte ions Matrix ions MS/MS 272222 216:1 S/N Analyte ions with minimal matrix ions 1pg OFN in PFTBA Background
Page 33 TIC Chromatogram NIST MS Search NIST MS Interpreter MassHunter Formula Calculator Accurate Mass Library Workflow Using NIST MS Interpreter and MassHunter Qual Formula Calculator
Page 34 Formula Calculator Determine all possible formulas consistent with measured mass C7H2Cl5 -1.67 ppm diff
Page 35 Molecular Ion Fragment Ions 1 2 3 4 Pesticide m/z Formula Δ ppm Formula Δ ppm Formula Δ ppm Formula Δ ppm Formula Chlorpyrifos -methyl 320.8944 C7H7Cl3NO3PS -0.7 C7 H7 Cl [37Cl] N O3 P S 0.0 C7 H7 Cl2 N O3 P S 0.0 C2 H6 O2 P S 215.4 C6 H2 Cl3 N O2 P S Dichlorvos 219.9454 C4H7Cl2O4P 1.6 C4H7ClO4P -0.9 C2H6O3P 3.7 C4 H7[37Cl] O4 P 336.5 C3 H2 Cl2 O3 P Endosulfan sulfate 419.8112 C9 H6 Cl6 O4 S -2.1 C9 H6 Cl4[37Cl] O4 S -0.7 C5 Cl5[37Cl] 0.0 C5 Cl4[37Cl]2 -220.9 C8 H3 Cl5 Propachlor 211.0758 C11 H14 Cl N O -1.0 C10 H11 Cl N O 1.1 C11 H14 N O 1.8 C8 H8 Cl N O -3.9 C6 H5 771.6 C2 H2 Cl O Fluazifop-p- butyl 383.1339 C19 H20 F3 N O4 -2.2 C19 H20 F2 N O4 -1.1 C14 H11 F3 N O2 -1.3 C12 H7 F3 N O 2.1 C6 H3 F3 N -494.2 C7 H14 O3 Triazophos 313.0645 C12 H16 N3 O3 P S -1.4 C10 H12 N3 O3 P S -2.7 C8 H8 N3 O3 P S -0.6 C8 H7 N3 O -1.9 C8 H8 N3 O -47.7 C11 H14 N2 O3 P S -54.1 C9 H10 N2 O3 P S Fragment ion mass with high mass accuracy Helps unambiguously identify corresponding formula and hence exact mass of a fragment Examples from building accurate mass pesticide library Most probable fragment ion
Page 36 Fluorotelomer Alcohols in Biosolids
Page 37 Fluorotelomer Alcohols • Source unknown, but probably intermediate degradation products of fluorinated polymers • Oxidize to form fluorinated carboxylic acid, some of which are toxic • Methods needed for studying their transport and fate in the environment • Have the form F3C(CF2)N-1(CH2)MOH • N:M FTOH is the shorthand notation • Positive CI, 20% CH4
Page 38 Fluorotelomer Alcohol Mass Accuracy Protonated Molecular Ion (PCI) Acronym Formula Exact Mass + H Observed Mass DΔ ppmpm 4:2 FTOH C6H5F9O 265.0269 265.0270 -0.38 6:2 FTOH C8H5F13O 365.0206 365.0206 0 8:2 FTOH C10H5F17O 465.0142 465.0140 0.43 10:2 FTOH C12H5F21O 565.0078 565.0078 0 7:2 sFTOH C9H5F15O 415.0174 415.0190 -3.85 5:1 FTOH C6H3F11O 301.0081 301.0079 0.66 6:1 FTOH C7H3F13O 351.0049 351.0050 -0.28 7:1 FTOH C8H3F15O 401.0017 401.0016 0.25 8:1 FTOH C9H3F17O 450.9985 450.9985 0 9:1 FTOH C10H3F19O 500.9953 500.9956 -0.60 10:1 FTOH C11H3F21O 550.9921 550.9922 -0.18 11:1 FTOH C12H3F23O 600.9889 600.9896 -1.16 MeFOSE C11H8F17NO3S 558.0026 558.0042 -2.87 EtFOSE C12H10F17NO3S 572.0183 572.0167 2.80
Page 39 Fluorotelomer Neutral Loss Mechanism Inferred PCI, methane -H20, -HF F F F F F F F F F OH2 + -F2 F F F F F F F OH2 + CH2 + F F F F F F F F -H2O -HF Exact Mass: 265.0269 Exact Mass: 38.0168 Exact Mass: 227.0102 Exact Mass: 227.0301 C+ F F F F F F F F Exact Mass: 37.9968 Dm = 38.0166 Da. Dm = 0.020 Da. Acronym Observed Base Peak m/z Molecular ion -F2 m/z Dppm Molecular ion -H20, -HF m/z Dppm 4:2 FTOH 227.0104 227.0301 86.77 227.0102 -0.88
Page 40 11:1 FTOH Spiked in Biosolid Extract PCI, methane Spiked at 50 pg/ml level Excellent qualifier ratio in the presence of nearly 103 excess of matrix. EIC of m/z=580.9784 overlaid on m/z=600.9845 Quant ion m/z = 580.9784 EIC Qualifier ion m/z = 600.9845
Page 41 10:2 FTOH Fluorotelomer Alcohol MS/MS PCI, methane -H20, -HF Dm = 38.0166 Da. Acronym Precursor m/z CE Transition m/z Dppm Loss 10:2 FTOH 565 10V 526.9918 -1.3 -H2O, -HF 565.0078 TIC EIC for m/z 526.9918
Page 42 Identification and Quantification of Sulfur-Containing Compounds in Beverages
Page 43 Compounds affecting taste and flavor • 2-formyl thiophene and 2-acetyl thiazole are common contaminants • Low sensory threshold and can have negative effect on product flavor or aroma • Easy to separate from each other • Often requires sophisticated extraction/enrichment procedures and/or powerful 2D GC techniques for separation from matrix for quantitation • Method highlights • Simple L/L extraction in dichloromethane (10:1 enrichment) • 1:10 split injection with SSL inlet • DB-5MS column 30 m x 0.25 mm x 0.25 μm
Page 44 Standards at 100 pg On Column 2-formyl thiophene Formula C5H4OS MW: 112 2-acetyl thiazole Formula C5H5NOS MW: 127
Page 45 TIC and EICs of Coffee Extract 2-formyl thiophene m/z 111.9983 ± 100 ppm 2-acetyl thiazole m/z 127.0092 ± 100 ppm
Page 46 2-Acetyl Thiazole calibration STD addition calibration curve for 2-acetyl thiazole in spiked coffee (STD amount: 1, 2, 5, 10, 20, 50, 100, 200, 500, 1000 pg) m/z 127.0092 Mass window: ±20 ppm Average mass error = 1.1 ppm (max 1.6) over entire concentration range
Page 47 Photodegradation Products in Beer
Page 48 Photodegradation Products in Beer • Completely untargeted (initially) study of beer photodegradation • Method highlights • 30 min extraction at 30 ˚C using manual SPME holder and conditioned 50/30 µm DVB/Carboxen/PDMS StableFlex SPME fiber (Supelco), no agitation • Desorption at 300 ˚C for 2 min in the SSL injector; 1:10 split • Agilent J&W column DB-5MS 30 m x 0.25 mm x 0.25 µm
Page 49 Changes in the Chromatogram No exposure to direct sunlight 3 hours 6 hours Appears following the exposure of the sample to direct sunlight. Peak height is dependent on the duration of exposure to the sun Molecular ion m/z=165.1120 C10H15NO
Page 50 Summary of MS/MS Experiments C4H5 C10H14N C9H14N C7H8N C9H11N C6H7NO C6H8N C6H6NO C5H6N C5H7N C4H5 C4H6N mine, N-(2-furanylmethylene)-3-methyl- 100 150 200 250 300 350 400 7 81 95 109 122 136 164 O N C10H15NO 109 C6H7NO 122 C7H8NO 136 C9H14N 148 C10H14N 133 C9H11N 80 C5H6N 94 C6H8N 108 C6H6N O 81 C5H7N 55 C3H5N 53 41 C3H 5 66 C4H4N 78 C5H4N MS MS/MS
Page 51 Summary of MS/MS Experiments C4H5 C10H14N C9H14N C7H8N C9H11N C6H7NO C6H8N C6H6NO C5H6N C5H7N C4H5 C4H6N mine, N-(2-furanylmethylene)-3-methyl- 100 150 200 250 300 350 400 7 81 95 109 122 136 164 O N C10H15NO 109 C6H7NO 122 C7H8NO 136 C9H14N 148 C10H14N 133 C9H11N 80 C5H6N 53 78 C5H4N MS MS/MS
Page 52 Summary of MS/MS Experiments C4H5 C10H14N C9H14N C7H8N C9H11N C6H7NO C6H8N C6H6NO C5H6N C5H7N C4H5 C4H6N mine, N-(2-furanylmethylene)-3-methyl- 100 150 200 250 300 350 400 7 81 95 109 122 136 164 O N C10H15NO 109 C6H7NO 122 C7H8NO 136 C9H14N 148 C10H14N 133 C9H11N 80 C5H6N 94 C6H8N 108 C6H6NO 81 C5H7N 55 C3H5N 53 41 C3H5 66 C4H4N 78 C5H4N MS MS/MS
Page 53 Metabolomics: Unknowns Analysis Tool to Identify Components of Bovine Plasma
Page 54 Unknowns Analysis (MassHunter Quant) Using deconvolution and spectral library matching to identify unknowns - Using NIST library search - Not using RT match (in this particular example)
Page 55 Unknowns Analysis (MassHunter Quant) Using deconvolution and spectral library matching to identify unknowns Asparagine
Page 56 Bovine plasma Unknowns Analysis results (partial) Component RT Compound Name CAS# Formula Match Factor 9.73 L-Isoleucine, N-(trimethylsilyl)-, trimethylsilyl ester 7483-92-3 C12H29NO2Si2 78.22 9.81 L-Proline, 1-(trimethylsilyl)-, trimethylsilyl ester 7364-47-8 C11H25NO2Si2 75.45 10.03 Butanedioic acid, bis(trimethylsilyl) ester 40309-57-7 C10H22O4Si2 81.68 10.11 2-Phenyl-1-(p-tolyl)benzimidazole 3510-25-6 C20H16N2 58.53 10.21 Methyl 8-methyl-decanoate 1000336-49-1 C12H24O2 61.59 10.43 Phosphoric acid, 2-isothiocyanatoethyl bis(trimethylsilyl) ester 56051-85-5 C9H22NO4PSSi2 51.03 10.63 Serine tritms 64625-17-8 C12H31NO3Si3 85.27 10.68 Nonanoic acid, trimethylsilyl ester 82326-11-2 C12H26O2Si 88.03 10.85 Glycine, N-formyl-N-(trimethylsilyl)-, trimethylsilyl ester 55517-31-2 C9H21NO3Si2 50.55 10.96 N,O,O-Tris(trimethylsilyl)-L-threonine 2--2-7537 C13H33NO3Si3 78.77 11.15 Dodecyl trifluoroacetate 1000351-74-5 C14H25F3O2 64.8 11.29 Decanedioic acid, bis(tert-butyldimethylsilyl) ester 104255-98-3 C22H46O4Si2 71.42 11.48 Glyoxime, bis(trimethylsilyl)- 54731-39-4 C8H20N2O2Si2 51.54 11.7 2,4(1H,3H)-Pyrimidinedione, dihydro-1,3-bis(trimethylsilyl)- 74810-47-2 C10H22N2O2Si2 63.24 11.91 2-Piperidone, 1-(trimethylsilyl)-3-[(trimethylsilyl)amino]- 32565-12-1 C11H26N2OSi2 51.39 11.95 Decanoic acid, trimethylsilyl ester 55494-15-0 C13H28O2Si 73.52 12.05 Cycloheptasiloxane, tetradecamethyl- 107-50-6 C14H42O7Si7 54.25 12.19 (Z,Z)-3-Methyl-3H-cyclonona(def)biphenylene 110823-80-8 C18H14 51.04 12.29 Butanedioic acid, [(trimethylsilyl)oxy]-, bis(trimethylsilyl) ester 38166-11-9 C13H30O5Si3 68.14 12.33 Pyrazine, 3,6-dihydro-3,6-dimethyl-2,5-bis(trimethylsilyloxy)- 1000156-30-2 C12H26N2O2Si2 50.63 12.49 3,6,9,12-Tetraoxa-2,13-disilatetradecane, 2,2,13,13-tetramethyl- 62185-58-4 C12H30O4Si2 68.69 12.59 2-Hydroxymandelic acid, ethyl ester, di-TMS 1000071-88-8 C16H28O4Si2 53.02 12.72 L-Proline, 5-oxo-1-(trimethylsilyl)-, trimethylsilyl ester 30274-77-2 C11H23NO3Si2 70.45
Page 57 What about TOF SPEED? TOF always collects full mass range Q-TOF always display full product ion spectrum • Acquisition Rate: transients (pulses) /second • 10,000 transients/second • Sum of transients = Spectral Rate: • Typical max rate: 25-200 spectra/sec (Hz) to disk • Usable rate is limited by signal level (ion count) • New analysis opportunities for GC/MS: • High Throughput: ~20 Hz • Ultra high resolution GC: ~ 40Hz • GCxGC: ~50-200 Hz
Page 58 “Speed” enhances deconvolution Time Deconvolution Requires Time Offset
Page 59 High data rate = better deconvolution Slow data rate will not pick each peak apex Fast data rate will allow deconvolution of closely eluting peaks Time Time
Page 60 High data rate = better deconvolution Slow data rate will not pick each peak apex Fast data rate will allow deconvolution of closely eluting peaks Time Time The 7200 Q-TOF in TOF mode will have: •Faster Data Rates •Maintain Excellent S/N •New MassHunter Deconvolution
Page 61 And What about Q-TOF File Size? • Typical file sizes for pesticide analysis • MSD SIM – 0.8-1 MB/18-min run • MSD scan – 3-5 MB/40-min run • TQ MRM – 5 MB/20-min run • TQ scan – 8 MB/20-min run • IT MS/MS – 2.5 MB/45-min run (99 compounds) • TOF or Q-TOF Typical run • 800-1200 MB/20-min run at 5 Hz, profile • Centroid only reduces 5-10X Note: File size depends on the threshold, number of target compounds, number of masses/compound, and runtime etc.
Page 62 • Can accurate mass measurements be made in a real matrix? • What are the limitations?
Page 63 Successful Applications Require the Correct Combination of: GC Resolution (Agilent) + MS Resolving Power (Agilent) + ΔMass Defect (Mother Nature) + Relative Ion Intensities (Sample) We may have a little to learn about these new apps.
Page 64 240.1218 240.0785 Flurenol methyl ester m/z = 240.0781 Mass error = 1.7 ppm Dimetilan m/z = 240.1217 Mass error = 0.4 ppm ~13,500 resolution FWHM How much “R” and “Defect” is enough? Intensity Ratio = 1:1 No IRM corrections applied Dm = 0.043 Da.
Page 65 Intensity affects the rResult Two mass peaks with FWHM 0.7 u with 0.5 u between centroided m/z value Two mass peaks with FWHM 0.05 u with 0.5 u between centroided m/z value m/z m/z
Page 66 GC or MS: Relative intensity affects the result Centroid view of mass peaks obscures this fact m/z m/z m/z m/z Profile view of mass peaks Centroid Centroid Centroid Centroid
Page 67 240.1218 240.0785 Flurenol methyl ester m/z = 240.0781 Mass error = 1.7 ppm Dimetilan m/z = 240.1217 Mass error = 0.4 ppm ~13,500 resolution FWHM How much “R” and “Defect” is enough? Intensity Ratio = 1:1
Page 68 240.1184 240.0780 Flurenol methyl ester m/z = 240.0781 Mass error = -0.4 ppm Dimetilan m/z = 240.1217 Mass error = -13.7 ppm Improved results will require a better GC separation or MS/MS How much “R” and “Defect” is enough? Intensity Ratio = 1:0.02
Page 69 Future Webinars: Balancing Performance Criteria • Resolving Power: >10K at m/z 272 (>13K typical) • Mass Accuracy: <5 ppm at m/z 272 (<2ppm typical) • MS Sensitivity: 1 pg OFN S/N > 400:1 • Dynamic Range: > 3 orders of magnitude • Quad Mass range: 20-1050 Da (0.7-4.0 Da FWHM) • TOF Mass range: 20-1700 Da • Spectral Rate: 1-50 spectra/sec All specifications subject to change
Page 70 1. Internal Reference Mass for routine sub 5ppm mass accuracy even in heavy matrix 2. Removable Ion Source (including filaments) 3. Q-TOF MS/MS: • Chemical noise reduction • Selectivity • Structural information • Method development 4. Removable Ion Source for quick source cleaning and EI/CI swapping without breaking vacuum 5. Software tools – formula calculator Key Features of the 7200
Page 71 240 IT 7000 TQ 220 IT 5975E SQ 5975T LTM SQ 5975C SQ 7200 Q-TOF More Choices – Better Solutions Agilent GC/MS & GC/MS/MS ASMS Agilent Restricted

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Introduction of 7200 Q-TOF.pdf

  • 1. Page 1 7200 Series Q-TOF for GC/MS June 2011 A new analytical tool for solving complex analytical problems
  • 2. Page 2 7200 GC/Q-TOF Breakfast Seminar ASMS Conference on Mass Spectrometry and Allied Topics June 5-9, 2011 Colorado Convention Center, Denver, CO
  • 3. Page 3 Hospitality Suite “There’s Something Brewing at Agilent” BrewPub Theme Super Sensitive Stout Heavy Matrix Hefeweizen Clearly Better Bitter
  • 4. Page 4 240 IT 7000 TQ 220 IT 5975E SQ 5975T LTM SQ 5975C SQ 7200 Q-TOF More Choices – Better Solutions Agilent GC/MS & GC/MS/MS ASMS Agilent Restricted
  • 5. Page 5 = + What is it? 7890 + 7000 + 6500 = 7200 GC/Q-TOF Quadrupole Time of Flight MS Time of Flight MS Triple Quadrupole MS
  • 6. Page 6 What Will The 7200 Q-TOF Do For You? • TOF mode • High resolution full scan spectra • Accurate mass measurements • Fast full spectrum acquisition • MS/MS mode • Product ion spectra – high resolution, accurate mass • Sensitivity > TQ product ion methods • Ideal tool for solving complex analytical problems • New tools for structural elucidation of unknowns and confirmation of non-targets
  • 7. Page 7 = + 7890 + 7000 + 6500 = 7200 GC/Q-TOF It‟s our newest GC/MS . . . built upon many well proven parts: Almost one thousand 7000 TQs Over one thousand TOFs and Q-TOFs Many thousand 7890 GCs
  • 8. Page 8 7200 Analyzer 7000B TQ 6500 Q-TOF NEW Optics
  • 9. Page 9 New . . . Yet Totally Proven Dual-stage ion mirror improves second-order time focusing for high mass resolution. Hexapole collision cell accelerates ion through the cell to enable faster generation of high-quality MS/MS spectra without cross-talk Split-flow turbo differentially pumps the ion source and quadrupole analyzer compartments 4GHz ADC electronics enable a high sampling rate (32 Gbit/s) which improves the resolution, mass accuracy, and sensitivity for low-abundance samples. Dual gain amplifiers simultaneously process detector signals through both low- gain and high gain channels, extending the dynamic range to 105. Analog-to-digital (ADC) Detector: Unlike time-to-digital (TDC) detectors which record single ion events, ADC detection records multiple ion events, allowing very accurate mass assignments over a wide mass range and dynamic range of concentrations. Proprietary INVAR flight tube sealed in a vacuum-insulated shell eliminates thermal mass drift due to temperature changes to maintain excellent mass accuracy, 24/7. Added length improves mass resolution. Hot, quartz monolithic quadrupole analyzer and collision cell identical to the 7000 Quadrupole MS/MS
  • 10. Page 10 Other New . . . And Improved New Removable Ion Source includes repeller, ion volume, extraction lens and dual filaments New Internal Reference Mass can be delivered to the source at a low and high concentration Two 300L/s turbos pump the focusing optics and flight tube
  • 11. Page 11 • Allows swap of complete ion source, including filaments, in ~30 minutes without venting • Allows fast EI/CI source swapping without venting Removable Ion Source (RIS)
  • 12. Page 12 Removable Ion Source (RIS) Automated Retractable Transfer Line RIS Automated Gate Valve
  • 13. Page 13 30 minute source swap with RIS New Clean Ion Source Original Dirty Ion Source 1pg OFN Ventcool ion sourceopen chamber and replace/maintain source components close chamberpump outheat source stabilize vacuum and source temperature
  • 14. Page 14 Spectral presentation (Tune File) Centroid View Profile View Most users think in “centroid”, but the MS operates in “profile”
  • 15. Page 15 Comparing Quad & TOF 10 100 1000 10000 100000 0 200 400 600 800 1000 1200 Resolving Power Mass (amu) Resolving Power Quad TOF 0.001 0.01 0.1 1 0 200 400 600 800 1000 1200 peak width, amu Mass (amu) PeakWidth Quad TOF TOF has constant Resolving Power (peak-width changes with mass) Quads operate with constant peak-width (Resolving Power changes with mass)
  • 16. Page 16 Resolving power & mass accuracy R = 614/0.68 = 903 Δmz = 0.1/614 = 160 ppm Pw=0.68 Mz=614 SQ TQ IT TOF Q-TOF R = 614/0.0423 = 14522 Δmz = 0.0004/613.96 = 0.7 ppm Resolving Power: R=mz/FWHM Mass Accuracy: Δmz=dm/mz*106 , parts per million (ppm) PFTBA mass 614 C12F24N=613.964203 1 Da. 1 Da.
  • 17. Page 17 OFN Results theoretical masss = 271.986677 error = -0.5 ppm 1pg OFN Theoretical Mass = 271.986677 error = -0.5 ppm Resolving Power = 13464 0.25 u Later Prototype Q-TOF
  • 18. Page 18 Large dynamic range detection system Threshold Time to Digital Converter Counts “1” when above Threshold 1-2 Orders Magnitude Dynamic Range 2-8 Gbit/sec of information Analog to Digital Converter Measures each point 4-5 Orders Magnitude Dynamic Range 32 Gbit/sec of information TDC ADC
  • 19. Page 19 Response linearity and mass accuracy ADC advantages 5 Hz acquisition, RIS LOD about 0.01 pg R^2=0.9991
  • 20. Page 20 Accurate mass makes mass defect important X Hydrogen H 1 1.0078 99.99 0.0078 D or 2 H 2 2.0141 0.01 0.0141 X+1 Carbon 12 C 12 12 98.91 0 13 C 13 13.0034 1.1 1.1nC 0.0060nC 2 0.0034 X+1 Nitrogen 14 N 14 14.0031 99.6 0.0031 15 N 15 15.0001 0.4 0.37nN 0.0001 X+2 Oxygen 16 O 16 15.9949 99.76 -0.0051 17 O 17 16.9991 0.04 0.04nO -0.0009 18 O 18 17.9992 0.2 0.20nO -0.0008 X Fluorine F 19 18.9984 100 -0.0016 X+2 Silicon 28 Si 28 27.9769 92.2 -0.0231 29 Si 29 28.9765 4.7 5.1nSi -0.0235 30 Si 30 29.9738 3.1 3.4nSi -0.0262 X Phosphorus P 31 30.9738 100 -0.0262 X+2 Sulfur 32 S 32 31.9721 95.02 -0.0279 33 S 33 32.9715 0.76 0.8nS -0.0285 34 S 34 33.9679 4.22 4.4nS -0.0321 X+2 Chlorine 35 Cl 35 34.9689 75.77 -0.0311 37 Cl 37 36.9659 24.23 32.5nCl -0.0341 X+2 Bromine 79 Br 79 78.9183 50.5 -0.0817 81 Br 81 80.9163 49.5 98.0nBr -0.0837 X Iodine I 127 126.9045 100 -0.0955 X+1 Factor X+2 Factor Mass Defect Type Element Symbol Abundance Integer Mass Exact Mass
  • 21. Page 21 Many possible formulas with an MSD or IT But only a few with TOF 1 10 100 1000 10000 0.1 1 10 100 1000 # Possible Chemical Formulas mass uncertainty, ppm Possible Number of Chemical Formulas at m/z 272 Formulas made of: C,H,N,O,F, & Cl mass uncertainty ppm amu # of Possible Formulas 1000 0.3 7657 368 0.1 4050 100 0.03 1223 37 0.01 466 10 0.003 120 4 0.001 43 1 0.0003 11 0.4 0.0001 5 0.1 0.00003 2 Octafluoronaphthalene (CAS 313-72-4) C10F8 = 271.98667 Accurate mass reduces risk of investing effort on the wrong molecule
  • 22. Page 22 Internal Reference Mass (IRM) • The goal for the 7200 is for easy and reliable ~2-5ppm mass accuracy under all conditions • Agilent has developed a proprietary Internal Reference Mass (IRM) delivery system for “on the fly” mass axis correction • IRM is the use of known background ions to “lock” the mass axis for each scan • Requires reliable IRM calibration signals with and without matrix
  • 23. Page 23 7200 provisional instrument performance Specifications… • Resolving Power: >10K at m/z 272 (>13K typical) • Mass Accuracy: <5 ppm at m/z 272 (<2ppm typical) • MS Sensitivity: 1 pg OFN S/N > 400:1 • Dynamic Range: > 3 orders of magnitude • Quad Mass range: 20-1050 Da (0.7-4.0 Da FWHM) • TOF Mass range: 20-1700 Da • Spectral Rate: 1-50 spectra/sec All specifications subject to change
  • 24. Page 24 Mass accuracy Number of Ions Mass Accuracy Limited by ion statistics Limited by detector non-linearity TDC ADC Required mass accuracy
  • 25. Page 25 7200 Series Q-TOF for GC/MS How is this new capability used - application results Pesticides in Food Tom Doherty, Phil Wylie, Chris Sandy, Bill Russ Fluorotelomer Alcohols in Biosolids (PCI) Anthony Macherone Volatile Sulfur-containing Compounds in Beverages Nobuo Ochiai, Kikuo Sasamoto – Gerstel KK, Japan Ryo Ogasawara, Hajime Kawakami – Agilent Volatile Photodegradation Products in Beer Stephan Baumann Metabolomics Oscar Yanes, Maria Vinaixa, Jesus Breznes – Tarragona University, Spain
  • 27. Page 27 Internal reference mass correction in matrix 100ppb pesticides in Okra extract Measured Accurate Mass (Da)Mass Error, ppm Analyte RT Theoretical Mass No IRM With IRM No IRM With IRM Trifluralin 5.83 306.0696 306.0638 306.0698 -18.9 0.7 Ethion 13.03 230.9732 230.9689 230.9744 -18.6 5.2 Iprodione 14.26 314.0094 314.0030 314.0101 -20.4 2.2 Indoxacarb18.06 527.0702 527.0603 527.0730 -18.8 5.3 Trifluralin No IRM, -18.9ppm IRM, -0.7ppm +EI TIC +EI EIC(306.0696)
  • 28. Page 28 Okra QuEChERS Extract Matrix interferant ion (b-Tocopherol) 150.06839 Da Analyte Indoxacarb ion (100pg) 150.01195 Da (fragment ion) +/-0.5 amu (~ 300ppm) Indoxacarb b-Tocopherol Indoxacarb TOF Accurate Mass to Eliminate Matrix Interferants Tocopherol interference eliminated in MS mode If even more selectivity is needed, option of MS/MS Extraction window 5 ppm MS/MS with high resolution and accurate mass! Dm = 0.0564 Da.
  • 29. Page 29 Fludioxonil in Frozen Blueberry Extract 38 ppb in extract TIC EIC: 248.0392 +/- 0.5 amu EIC: 248.0392 +/- 10 ppm Signal/Noise = 108 Signal/Noise = 1154
  • 30. Page 30 Add „Q+CID‟ to TOF solution Sometimes the combined power of GC Resolution (Agilent) + MS Resolving Power (Agilent) Is not enough based upon: Small ΔMass Defect (Nature) + Intense Matrix Ions (Sample) High resolution MS/MS can solve some of these problems Why add „Q‟ to TOF to make Q-TOF?
  • 31. Page 31 • Structural Elucidation from product Ion spectra using high resolution and accurate mass • Start with full scan EI spectrum • Use CID on each fragment mass to confirm structure of fragment • Select Fragment 1 to be precursor 1  Product ions • Select Fragment 2 to be precursor 2  Product ions Precursor-product ion relationship is documented and ion molecular formula confirmed by accurate mass Requires multiple analyses and much more sensitive than NMR Will not replace NMR, but will complement nicely CID CID How is it used? Structure elucidation
  • 32. Page 32 MS/MS chemical noise reduction If resolution and accurate mass are not enough EI MS m/z 272 54:1 S/N Analyte ions Matrix ions MS/MS 272222 216:1 S/N Analyte ions with minimal matrix ions 1pg OFN in PFTBA Background
  • 33. Page 33 TIC Chromatogram NIST MS Search NIST MS Interpreter MassHunter Formula Calculator Accurate Mass Library Workflow Using NIST MS Interpreter and MassHunter Qual Formula Calculator
  • 34. Page 34 Formula Calculator Determine all possible formulas consistent with measured mass C7H2Cl5 -1.67 ppm diff
  • 35. Page 35 Molecular Ion Fragment Ions 1 2 3 4 Pesticide m/z Formula Δ ppm Formula Δ ppm Formula Δ ppm Formula Δ ppm Formula Chlorpyrifos -methyl 320.8944 C7H7Cl3NO3PS -0.7 C7 H7 Cl [37Cl] N O3 P S 0.0 C7 H7 Cl2 N O3 P S 0.0 C2 H6 O2 P S 215.4 C6 H2 Cl3 N O2 P S Dichlorvos 219.9454 C4H7Cl2O4P 1.6 C4H7ClO4P -0.9 C2H6O3P 3.7 C4 H7[37Cl] O4 P 336.5 C3 H2 Cl2 O3 P Endosulfan sulfate 419.8112 C9 H6 Cl6 O4 S -2.1 C9 H6 Cl4[37Cl] O4 S -0.7 C5 Cl5[37Cl] 0.0 C5 Cl4[37Cl]2 -220.9 C8 H3 Cl5 Propachlor 211.0758 C11 H14 Cl N O -1.0 C10 H11 Cl N O 1.1 C11 H14 N O 1.8 C8 H8 Cl N O -3.9 C6 H5 771.6 C2 H2 Cl O Fluazifop-p- butyl 383.1339 C19 H20 F3 N O4 -2.2 C19 H20 F2 N O4 -1.1 C14 H11 F3 N O2 -1.3 C12 H7 F3 N O 2.1 C6 H3 F3 N -494.2 C7 H14 O3 Triazophos 313.0645 C12 H16 N3 O3 P S -1.4 C10 H12 N3 O3 P S -2.7 C8 H8 N3 O3 P S -0.6 C8 H7 N3 O -1.9 C8 H8 N3 O -47.7 C11 H14 N2 O3 P S -54.1 C9 H10 N2 O3 P S Fragment ion mass with high mass accuracy Helps unambiguously identify corresponding formula and hence exact mass of a fragment Examples from building accurate mass pesticide library Most probable fragment ion
  • 37. Page 37 Fluorotelomer Alcohols • Source unknown, but probably intermediate degradation products of fluorinated polymers • Oxidize to form fluorinated carboxylic acid, some of which are toxic • Methods needed for studying their transport and fate in the environment • Have the form F3C(CF2)N-1(CH2)MOH • N:M FTOH is the shorthand notation • Positive CI, 20% CH4
  • 38. Page 38 Fluorotelomer Alcohol Mass Accuracy Protonated Molecular Ion (PCI) Acronym Formula Exact Mass + H Observed Mass DΔ ppmpm 4:2 FTOH C6H5F9O 265.0269 265.0270 -0.38 6:2 FTOH C8H5F13O 365.0206 365.0206 0 8:2 FTOH C10H5F17O 465.0142 465.0140 0.43 10:2 FTOH C12H5F21O 565.0078 565.0078 0 7:2 sFTOH C9H5F15O 415.0174 415.0190 -3.85 5:1 FTOH C6H3F11O 301.0081 301.0079 0.66 6:1 FTOH C7H3F13O 351.0049 351.0050 -0.28 7:1 FTOH C8H3F15O 401.0017 401.0016 0.25 8:1 FTOH C9H3F17O 450.9985 450.9985 0 9:1 FTOH C10H3F19O 500.9953 500.9956 -0.60 10:1 FTOH C11H3F21O 550.9921 550.9922 -0.18 11:1 FTOH C12H3F23O 600.9889 600.9896 -1.16 MeFOSE C11H8F17NO3S 558.0026 558.0042 -2.87 EtFOSE C12H10F17NO3S 572.0183 572.0167 2.80
  • 39. Page 39 Fluorotelomer Neutral Loss Mechanism Inferred PCI, methane -H20, -HF F F F F F F F F F OH2 + -F2 F F F F F F F OH2 + CH2 + F F F F F F F F -H2O -HF Exact Mass: 265.0269 Exact Mass: 38.0168 Exact Mass: 227.0102 Exact Mass: 227.0301 C+ F F F F F F F F Exact Mass: 37.9968 Dm = 38.0166 Da. Dm = 0.020 Da. Acronym Observed Base Peak m/z Molecular ion -F2 m/z Dppm Molecular ion -H20, -HF m/z Dppm 4:2 FTOH 227.0104 227.0301 86.77 227.0102 -0.88
  • 40. Page 40 11:1 FTOH Spiked in Biosolid Extract PCI, methane Spiked at 50 pg/ml level Excellent qualifier ratio in the presence of nearly 103 excess of matrix. EIC of m/z=580.9784 overlaid on m/z=600.9845 Quant ion m/z = 580.9784 EIC Qualifier ion m/z = 600.9845
  • 41. Page 41 10:2 FTOH Fluorotelomer Alcohol MS/MS PCI, methane -H20, -HF Dm = 38.0166 Da. Acronym Precursor m/z CE Transition m/z Dppm Loss 10:2 FTOH 565 10V 526.9918 -1.3 -H2O, -HF 565.0078 TIC EIC for m/z 526.9918
  • 42. Page 42 Identification and Quantification of Sulfur-Containing Compounds in Beverages
  • 43. Page 43 Compounds affecting taste and flavor • 2-formyl thiophene and 2-acetyl thiazole are common contaminants • Low sensory threshold and can have negative effect on product flavor or aroma • Easy to separate from each other • Often requires sophisticated extraction/enrichment procedures and/or powerful 2D GC techniques for separation from matrix for quantitation • Method highlights • Simple L/L extraction in dichloromethane (10:1 enrichment) • 1:10 split injection with SSL inlet • DB-5MS column 30 m x 0.25 mm x 0.25 μm
  • 44. Page 44 Standards at 100 pg On Column 2-formyl thiophene Formula C5H4OS MW: 112 2-acetyl thiazole Formula C5H5NOS MW: 127
  • 45. Page 45 TIC and EICs of Coffee Extract 2-formyl thiophene m/z 111.9983 ± 100 ppm 2-acetyl thiazole m/z 127.0092 ± 100 ppm
  • 46. Page 46 2-Acetyl Thiazole calibration STD addition calibration curve for 2-acetyl thiazole in spiked coffee (STD amount: 1, 2, 5, 10, 20, 50, 100, 200, 500, 1000 pg) m/z 127.0092 Mass window: ±20 ppm Average mass error = 1.1 ppm (max 1.6) over entire concentration range
  • 48. Page 48 Photodegradation Products in Beer • Completely untargeted (initially) study of beer photodegradation • Method highlights • 30 min extraction at 30 ˚C using manual SPME holder and conditioned 50/30 µm DVB/Carboxen/PDMS StableFlex SPME fiber (Supelco), no agitation • Desorption at 300 ˚C for 2 min in the SSL injector; 1:10 split • Agilent J&W column DB-5MS 30 m x 0.25 mm x 0.25 µm
  • 49. Page 49 Changes in the Chromatogram No exposure to direct sunlight 3 hours 6 hours Appears following the exposure of the sample to direct sunlight. Peak height is dependent on the duration of exposure to the sun Molecular ion m/z=165.1120 C10H15NO
  • 50. Page 50 Summary of MS/MS Experiments C4H5 C10H14N C9H14N C7H8N C9H11N C6H7NO C6H8N C6H6NO C5H6N C5H7N C4H5 C4H6N mine, N-(2-furanylmethylene)-3-methyl- 100 150 200 250 300 350 400 7 81 95 109 122 136 164 O N C10H15NO 109 C6H7NO 122 C7H8NO 136 C9H14N 148 C10H14N 133 C9H11N 80 C5H6N 94 C6H8N 108 C6H6N O 81 C5H7N 55 C3H5N 53 41 C3H 5 66 C4H4N 78 C5H4N MS MS/MS
  • 51. Page 51 Summary of MS/MS Experiments C4H5 C10H14N C9H14N C7H8N C9H11N C6H7NO C6H8N C6H6NO C5H6N C5H7N C4H5 C4H6N mine, N-(2-furanylmethylene)-3-methyl- 100 150 200 250 300 350 400 7 81 95 109 122 136 164 O N C10H15NO 109 C6H7NO 122 C7H8NO 136 C9H14N 148 C10H14N 133 C9H11N 80 C5H6N 53 78 C5H4N MS MS/MS
  • 52. Page 52 Summary of MS/MS Experiments C4H5 C10H14N C9H14N C7H8N C9H11N C6H7NO C6H8N C6H6NO C5H6N C5H7N C4H5 C4H6N mine, N-(2-furanylmethylene)-3-methyl- 100 150 200 250 300 350 400 7 81 95 109 122 136 164 O N C10H15NO 109 C6H7NO 122 C7H8NO 136 C9H14N 148 C10H14N 133 C9H11N 80 C5H6N 94 C6H8N 108 C6H6NO 81 C5H7N 55 C3H5N 53 41 C3H5 66 C4H4N 78 C5H4N MS MS/MS
  • 53. Page 53 Metabolomics: Unknowns Analysis Tool to Identify Components of Bovine Plasma
  • 54. Page 54 Unknowns Analysis (MassHunter Quant) Using deconvolution and spectral library matching to identify unknowns - Using NIST library search - Not using RT match (in this particular example)
  • 55. Page 55 Unknowns Analysis (MassHunter Quant) Using deconvolution and spectral library matching to identify unknowns Asparagine
  • 56. Page 56 Bovine plasma Unknowns Analysis results (partial) Component RT Compound Name CAS# Formula Match Factor 9.73 L-Isoleucine, N-(trimethylsilyl)-, trimethylsilyl ester 7483-92-3 C12H29NO2Si2 78.22 9.81 L-Proline, 1-(trimethylsilyl)-, trimethylsilyl ester 7364-47-8 C11H25NO2Si2 75.45 10.03 Butanedioic acid, bis(trimethylsilyl) ester 40309-57-7 C10H22O4Si2 81.68 10.11 2-Phenyl-1-(p-tolyl)benzimidazole 3510-25-6 C20H16N2 58.53 10.21 Methyl 8-methyl-decanoate 1000336-49-1 C12H24O2 61.59 10.43 Phosphoric acid, 2-isothiocyanatoethyl bis(trimethylsilyl) ester 56051-85-5 C9H22NO4PSSi2 51.03 10.63 Serine tritms 64625-17-8 C12H31NO3Si3 85.27 10.68 Nonanoic acid, trimethylsilyl ester 82326-11-2 C12H26O2Si 88.03 10.85 Glycine, N-formyl-N-(trimethylsilyl)-, trimethylsilyl ester 55517-31-2 C9H21NO3Si2 50.55 10.96 N,O,O-Tris(trimethylsilyl)-L-threonine 2--2-7537 C13H33NO3Si3 78.77 11.15 Dodecyl trifluoroacetate 1000351-74-5 C14H25F3O2 64.8 11.29 Decanedioic acid, bis(tert-butyldimethylsilyl) ester 104255-98-3 C22H46O4Si2 71.42 11.48 Glyoxime, bis(trimethylsilyl)- 54731-39-4 C8H20N2O2Si2 51.54 11.7 2,4(1H,3H)-Pyrimidinedione, dihydro-1,3-bis(trimethylsilyl)- 74810-47-2 C10H22N2O2Si2 63.24 11.91 2-Piperidone, 1-(trimethylsilyl)-3-[(trimethylsilyl)amino]- 32565-12-1 C11H26N2OSi2 51.39 11.95 Decanoic acid, trimethylsilyl ester 55494-15-0 C13H28O2Si 73.52 12.05 Cycloheptasiloxane, tetradecamethyl- 107-50-6 C14H42O7Si7 54.25 12.19 (Z,Z)-3-Methyl-3H-cyclonona(def)biphenylene 110823-80-8 C18H14 51.04 12.29 Butanedioic acid, [(trimethylsilyl)oxy]-, bis(trimethylsilyl) ester 38166-11-9 C13H30O5Si3 68.14 12.33 Pyrazine, 3,6-dihydro-3,6-dimethyl-2,5-bis(trimethylsilyloxy)- 1000156-30-2 C12H26N2O2Si2 50.63 12.49 3,6,9,12-Tetraoxa-2,13-disilatetradecane, 2,2,13,13-tetramethyl- 62185-58-4 C12H30O4Si2 68.69 12.59 2-Hydroxymandelic acid, ethyl ester, di-TMS 1000071-88-8 C16H28O4Si2 53.02 12.72 L-Proline, 5-oxo-1-(trimethylsilyl)-, trimethylsilyl ester 30274-77-2 C11H23NO3Si2 70.45
  • 57. Page 57 What about TOF SPEED? TOF always collects full mass range Q-TOF always display full product ion spectrum • Acquisition Rate: transients (pulses) /second • 10,000 transients/second • Sum of transients = Spectral Rate: • Typical max rate: 25-200 spectra/sec (Hz) to disk • Usable rate is limited by signal level (ion count) • New analysis opportunities for GC/MS: • High Throughput: ~20 Hz • Ultra high resolution GC: ~ 40Hz • GCxGC: ~50-200 Hz
  • 58. Page 58 “Speed” enhances deconvolution Time Deconvolution Requires Time Offset
  • 59. Page 59 High data rate = better deconvolution Slow data rate will not pick each peak apex Fast data rate will allow deconvolution of closely eluting peaks Time Time
  • 60. Page 60 High data rate = better deconvolution Slow data rate will not pick each peak apex Fast data rate will allow deconvolution of closely eluting peaks Time Time The 7200 Q-TOF in TOF mode will have: •Faster Data Rates •Maintain Excellent S/N •New MassHunter Deconvolution
  • 61. Page 61 And What about Q-TOF File Size? • Typical file sizes for pesticide analysis • MSD SIM – 0.8-1 MB/18-min run • MSD scan – 3-5 MB/40-min run • TQ MRM – 5 MB/20-min run • TQ scan – 8 MB/20-min run • IT MS/MS – 2.5 MB/45-min run (99 compounds) • TOF or Q-TOF Typical run • 800-1200 MB/20-min run at 5 Hz, profile • Centroid only reduces 5-10X Note: File size depends on the threshold, number of target compounds, number of masses/compound, and runtime etc.
  • 62. Page 62 • Can accurate mass measurements be made in a real matrix? • What are the limitations?
  • 63. Page 63 Successful Applications Require the Correct Combination of: GC Resolution (Agilent) + MS Resolving Power (Agilent) + ΔMass Defect (Mother Nature) + Relative Ion Intensities (Sample) We may have a little to learn about these new apps.
  • 64. Page 64 240.1218 240.0785 Flurenol methyl ester m/z = 240.0781 Mass error = 1.7 ppm Dimetilan m/z = 240.1217 Mass error = 0.4 ppm ~13,500 resolution FWHM How much “R” and “Defect” is enough? Intensity Ratio = 1:1 No IRM corrections applied Dm = 0.043 Da.
  • 65. Page 65 Intensity affects the rResult Two mass peaks with FWHM 0.7 u with 0.5 u between centroided m/z value Two mass peaks with FWHM 0.05 u with 0.5 u between centroided m/z value m/z m/z
  • 66. Page 66 GC or MS: Relative intensity affects the result Centroid view of mass peaks obscures this fact m/z m/z m/z m/z Profile view of mass peaks Centroid Centroid Centroid Centroid
  • 67. Page 67 240.1218 240.0785 Flurenol methyl ester m/z = 240.0781 Mass error = 1.7 ppm Dimetilan m/z = 240.1217 Mass error = 0.4 ppm ~13,500 resolution FWHM How much “R” and “Defect” is enough? Intensity Ratio = 1:1
  • 68. Page 68 240.1184 240.0780 Flurenol methyl ester m/z = 240.0781 Mass error = -0.4 ppm Dimetilan m/z = 240.1217 Mass error = -13.7 ppm Improved results will require a better GC separation or MS/MS How much “R” and “Defect” is enough? Intensity Ratio = 1:0.02
  • 69. Page 69 Future Webinars: Balancing Performance Criteria • Resolving Power: >10K at m/z 272 (>13K typical) • Mass Accuracy: <5 ppm at m/z 272 (<2ppm typical) • MS Sensitivity: 1 pg OFN S/N > 400:1 • Dynamic Range: > 3 orders of magnitude • Quad Mass range: 20-1050 Da (0.7-4.0 Da FWHM) • TOF Mass range: 20-1700 Da • Spectral Rate: 1-50 spectra/sec All specifications subject to change
  • 70. Page 70 1. Internal Reference Mass for routine sub 5ppm mass accuracy even in heavy matrix 2. Removable Ion Source (including filaments) 3. Q-TOF MS/MS: • Chemical noise reduction • Selectivity • Structural information • Method development 4. Removable Ion Source for quick source cleaning and EI/CI swapping without breaking vacuum 5. Software tools – formula calculator Key Features of the 7200
  • 71. Page 71 240 IT 7000 TQ 220 IT 5975E SQ 5975T LTM SQ 5975C SQ 7200 Q-TOF More Choices – Better Solutions Agilent GC/MS & GC/MS/MS ASMS Agilent Restricted