Triple Quadrupole Gas Chromatography-Mass Spectrometry/Mass Spectrometry Re-imagined: Increased...
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Transcript of Triple Quadrupole Gas Chromatography-Mass Spectrometry/Mass Spectrometry Re-imagined: Increased...
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The world leader in serving science
Increased Simplicity and Productivity
Triple Quadrupole GC-MS/MS Re-imagined
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Tough challenges faced in the laboratory
• High sample loads/short deadlines
• Keeping sample analysis costs down with more and more challenging LODs and matrices
• Integrating and maintaining new methods and technologies into production workflows to remain competitive
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What‘s required...
• Realization of the productivity advantages of high performance GC-MS/MS
• Minimizing the impact of adoption and implementation to current laboratory operations
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Triple Quadrupole GC-MS/MS is an essential part of a cost-effective, high productivity analytical method in today’s laboratory
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Many laboratories are already investing in and exploring GC-MS/MS as a tool to obtain a competitive edge in their analyses
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GC-MS/MS – What’s so special?
• Low detection limits
• Reduced sample preparation
• Consolidated analytical methods
• Faster, automated data processing
...it is a high selectivity technique...
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Selectivity in a method
McLafferty circa. 1980
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Method performance requirement
• Target compounds
• Matrices
• Sensitivity
Method performance requirement
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First sample prep..
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Method performance requirement
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...then instrument detection...
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Total method selectivity
Method performance requirement
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Analytical Benefits for Single Quadrupole GC-MS
• Robust• Run more samples between cleaning
• Sensitive Precision• Accurate and reproducible results at the lowest levels
• Unknown Analysis• Full scan for unknown library searches
• Alternating full scan/SIM for unknowns and low level analysis
• Flexibility• Switch quickly between dedicated EI and CI sources
• Easy to Use and Maintain
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Full Scan/SIM Methodology for Drinking Water
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Challenging Samples for Single Quadrupole GC-MS
• Matrix Challenges• Concentration
challenges• Difficult to prove
contamination
Gamma BHC
Methiocarb Mevinphos
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...what about GC-MS/MS?...
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Total method selectivity
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Method performance requirement
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Use GC-MS/MS to reduce clean-up...
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Total method selectivity
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Method performance requirement
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Use GC-MS/MS to consolidate methods...
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Method 1performance requirement
Method 2performance requirement
Method 3performance requirement
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Use GC-MS/MS to consolidate methods...
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Consolidated multi-residue method
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What will GC-MS/MS do for my lab?
High selectivity
• Possibility the reduce selectivity in sample preparation
• Reduced sample prep steps creates a more generic sample prep method – more compounds & matrices
• Consolidated GC-MS methods due to high performance – buffer against requirements
• Compressed chromatography possible
• Easy peak evaluation – auto-integrators
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Step 1: Ions are produced in the source
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Step 2: Ions are focused in the s-shaped prefilter
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Step 2: Ions focused by prefilter, removing neutrals
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Step 3: Ions are isolated by molecular weight in Q1
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Step 3: Ions are isolated by molecular weight in Q1
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Step 4: Ions further fragmented in collision cell
(With same mass as analyte)
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Step 4: Ions further fragmented in collision cell
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Step 5: Unique ions to analytes chosen in Q3
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Only unique fragments to analyte detected
Step 5: Unique ions to analytes chosen in Q3
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AutoSRM Overview
1) Precursor ion selection
2) Product ion selection
3) Collision energy optimization
SR
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Step 1 – Pick Your Precursor Ions
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Step 1 – Pick Your Precursor Ions
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Step 1 – Pick Your Precursor Ions
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Step 2 – Pick Your Product Ions
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Step 2 – Pick Your Product Ions
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Step 3 – Optimize Your Transitions
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Step 3 – Optimize Your Transitions
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Export from AutoSRM to Instrument Method
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Timed-SRM Method Overview
Acquisition Windows centered around retention time and Window
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Timed-SRM Method Overview
Acquisition windows allowed to overlap
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Timed-SRM Advantages
Segmented SRM
Timed SRM
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Timed-SRM Advantages
Acquisition Windows
Segmented SRM
Timed SRM
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Timed-SRM Advantages
• Removes wasted dwell time
• Allow higher overall dwell times
• Leads to higher sensitivity
Wasted Dwell Time
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Timed-SRM Advantages
• Peaks centered in acquisition window
• No peak elutes near acquisition break
• Allows for retention time shift (e.g. due to heavy matrix)
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Instrument Parameters
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Timed-SRM from Thermo Scientific TSQ 8000 GC-MS
Screenshot of a section of the analytical run showing the “acquisition map” automatically created by the TSQ™ 8000 System using t-SRM.
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Calibration Curves
• All calibration curves correlation coefficients greater than 0.99
• Example calibration curve for Cyfluthrin, R2 = 0.9996
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Transitions for Pesticides from PAR ver 2
• SRM peaks at 4 ppb from Terbacil (left, 161.1 > 88.0, CE 15 V) and Alachlor(right, 188.1 > 130.1, CE 25 V)
• SRM peaks at 4 ppb from Tolylfluanid (left, 238.1 > 137.1, CE 15 V) and Pyridaben (right, 309.1 > 147.1, CE 15 V)
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The world leader in serving science
A Second Level of Selectivity
Structure and Mass Defect
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Thermo Scientific TSQ Quantum XLS Ultra – HyperQuad™ Technology Inside
Patented HyperQuad technology meets with GC/MS for the first time to create highest performing GC Triple on the market
6 mm hyperbolic precision quads allow excellent ion transmission at standard resolution as well as opportunity to use enhanced mass resolution to 0.1 Da peak width
Effective pre-cursor ion filtering with strongly reduced matrix interference
Improved signal/noise & quantitative precision
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U-SRM: Two Modes of Selectivity
• Ultra selective-Single Reaction
Monitoring (U-SRM)
• Offers a unique opportunity to increase selectivity using triple quadrupole.
• Combination• Increased Q1 mass resolution • MS/MS Structural based
selectivity
• For use when standard SRM does not provide enough selectivity
m/z
Increased mass resolution
Structural selectivity (MS/MS)
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Precursor Ion Selection Q1 (Standard SRM mode)
• At standard mass resolution precursor selection • Q1 = 0.7 Da FWHM• Higher probability that interfering
species are transmitted to the collision cell with the target compound mass
• These matrix interferents are often orders of magnitude higher than target compounds
• If they are not completely discriminated against in by CID then the resulting product ion detection can have a higher background noise present
Matrix components transmitted through Q1 during SRM
Q1= 218.9 m/z (0.7 Da res.)
Q1 Transmission Window
Q1= 0.7Da
219217
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Precursor Ion Selection Q1 (U-SRM mode)
HyperQuad does not allow matrix through through Q1 during U-SRM
• When operated in U-SRM mode, the TSQ Quantum XLS Ultra narrows the pre-cursor mass window to <0.2Da
• This increased resolution allows the HyperQuad to discriminate against common matrix component masses for targets showing a large enough
Δmass defect.
• This allows for better collision cell performance and robustness as well as reducing chemical noise
• Lindane carries a Δmass defect and can be isolated from matrix in this example
Q1= 0.1Da
219217 221
Q1= 218.86 m/z (0.1 Da res.)
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U-SRM: Effect of Increasing Q1 Resolution
• Real life effect of the lindane example…
• Lindane isomers in green tea
• As Q1 resolution is increased into the ultra range signal/noise ratio increases dramatically
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U-SRM in action
• PCB 28 in industrial soil sample at ca.100fg (ASE extraction with no clean-up)
• Continuum full scan spectrum shows background removed with HyperQuad at increased resolution
contocpSCAN003 #1594-1597 RT: 13.68-13.69 AV: 4 SM: 7B NL: 4.04E7T: + p EI Q1MS [200.000-300.000]
255.0 255.2 255.4 255.6 255.8 256.0 256.2 256.4 256.6 256.8 257.0 257.2
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XLSULTRA_NPV_OCP00016_110329102653 3/29/2011 10:26:53 AM
RT: 13.33 - 15.12 SM: 7G
13.4 13.6 13.8 14.0 14.2 14.4 14.6 14.8 15.0
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RT: 13.69
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TIC F: + c EI SRM ms2 255.960 [185.965-185.975] MS XLSULTRA_NPV_OCP00016_110329102653
SRM (Q1 0.7Da)
0.7 Da
256 m/z
Q1 precursor selection
2,4,4'-Trichlorobiphenyl
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U-SRM in action
• PCB 28 in industrial soil sample at ca.100 fg (ASE extraction with no clean-up)
• Continuum full scan spectrum shows background removed with HyperQuad at increased resolution.
• Dramatically improved detection using U-SRM
C:\XCALIBUR\...\contocpSCAN004 4/14/2011 5:27:58 PM
contocpSCAN004 #1469-1471 RT: 13.68-13.69 AV: 3 SM: 7B NL: 3.02E6T: + p EI Q1MS [200.000-300.000]
255.0 255.2 255.4 255.6 255.8 256.0 256.2 256.4 256.6 256.8 257.0 257.2
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contocpSCAN003 #1594-1597 RT: 13.68-13.69 AV: 4 SM: 7B NL: 4.04E7T: + p EI Q1MS [200.000-300.000]
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XLSULTRA_NPV_OCP00011_110329074139 3/29/2011 7:41:39 AM
RT: 13.33 - 15.12 SM: 7G
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RT: 13.69 NL: 3.21E3
TIC F: + c EI SRM ms2 255.960 [185.965-185.975] MS ICIS XLSULTRA_NPV_OCP00011_110329074139
XLSULTRA_NPV_OCP00016_110329102653 3/29/2011 10:26:53 AM
RT: 13.33 - 15.12 SM: 7G
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RT: 13.69
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TIC F: + c EI SRM ms2 255.960 [185.965-185.975] MS XLSULTRA_NPV_OCP00016_110329102653
U-SRM (Q1 0.1Da)
Matrix interefent transmitted in standard mode (0.7Da) but rejected during U-SRM (0.1Da) precursor selection
PCB 28 Precursor mass 2 55.96 m/z selected
0.1
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0.7 Da
0.1 Da
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Environmental: Polychlorinated Biphenyls (PCBS)XLSULTRA_NPV_OCP00017_110329105955 3/29/2011 10:59:55 AM
RT: 13.17 - 16.75 SM: 7G
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RT: 14.04AA: 725579SN: 97
RT: 14.35AA: 37646SN: 280
RT: 14.78AA: 201199SN: 229
RT: 15.03AA: 140023SN: 185
RT: 14.38AA: 94563SN: 88
RT: 16.03AA: 24964SN: 94
RT: 16.03AA: 26376SN: 160
NL: 1.01E5
TIC F: + c EI SRM ms2 255.960 [185.965-185.975] MS XLSULTRA_NPV_OCP00017_110329105955
NL: 1.53E5
TIC F: + c EI SRM ms2 257.960 [185.965-185.975] MS ICIS XLSULTRA_NPV_OCP00017_110329105955
NL: 1.37E4
TIC F: + c EI SRM ms2 289.920 [219.935-219.945] MS ICIS XLSULTRA_NPV_OCP00017_110329105955
NL: 7.06E4
TIC F: + c EI SRM ms2 291.920 [219.935-219.945] MS ICIS XLSULTRA_NPV_OCP00017_110329105955
NL: 1.01E4
TIC F: + c EI SRM ms2 323.880 [253.905-253.915] MS ICIS XLSULTRA_NPV_OCP00017_110329105955
NL: 1.42E4
TIC F: + c EI SRM ms2 325.880 [255.905-255.915] MS ICIS XLSULTRA_NPV_OCP00017_110329105955
XLSULTRA_NPV_OCP00011_110329074139 3/29/2011 7:41:39 AM
RT: 13.17 - 16.75 SM: 7G
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RT: 13.69AA: 5479SN: 859
RT: 13.70AA: 5485SN: 862
RT: 14.37AA: 4122SN: 1454
RT: 14.36AA: 1393SN: 393
RT: 16.05AA: 2033SN: 352
RT: 16.04AA: 3693SN: 412
NL: 3.21E3
TIC F: + c EI SRM ms2 255.960 [185.965-185.975] MS ICIS XLSULTRA_NPV_OCP00011_110329074139
NL: 2.87E3
TIC F: + c EI SRM ms2 257.960 [185.965-185.975] MS ICIS XLSULTRA_NPV_OCP00011_110329074139
NL: 2.74E3
TIC F: + c EI SRM ms2 289.920 [219.935-219.945] MS ICIS XLSULTRA_NPV_OCP00011_110329074139
NL: 1.02E3
TIC F: + c EI SRM ms2 291.920 [219.935-219.945] MS ICIS XLSULTRA_NPV_OCP00011_110329074139
NL: 1.54E3
TIC F: + c EI SRM ms2 323.880 [253.905-253.915] MS ICIS XLSULTRA_NPV_OCP00011_110329074139
NL: 2.53E3
TIC F: + c EI SRM ms2 325.880 [255.905-255.915] MS ICIS XLSULTRA_NPV_OCP00011_110329074139
Tri, Tetra, Penta PCBs 100 fg in Contaminated land (industrial soil) sample
Standard SRM ( Q1=0.7 Da)
TSQ Quantum XLS Ultra U-SRM
( Q1=0.1Da )
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Environmental: Pesticides
Endrin 1pg in contaminated land sample ran both in SRM (Q1 0.7 amu) and U-SRM (Q1 0.1 amu)
U-SRM
SRM
C:\Xcalibur\...\XLSULTRA_NPV_0104OCP048 4/2/2011 7:39:50 PM
RT: 16.93 - 17.25 SM: 3G
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NL: 1.68E5
m/z= 190.43-191.43 F: + c EI SRM ms2 262.910 [190.925-190.935, 192.925-192.935] MS XLSULTRA_NPV_0104OCP048
NL: 1.83E5
m/z= 192.43-193.43 F: + c EI SRM ms2 262.910 [190.925-190.935, 192.925-192.935] MS XLSULTRA_NPV_0104OCP048
NL: 1.25E4
m/z= 190.43-191.43 F: + c EI SRM ms2 262.910 [190.925-190.935, 192.925-192.935] MS ICIS xlsultra_npv_0104ocp031
NL: 1.86E4
m/z= 192.43-193.43 F: + c EI SRM ms2 262.910 [190.925-190.935, 192.925-192.935] MS ICIS xlsultra_npv_0104ocp031
XLSULTRA_NPV_OCP00015_110329095349 3/29/2011 9:53:49 AM
RT: 15.48 - 17.07 SM: 7G
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RT: 16.56AA: 28533SN: 31RMS
RT: 15.95AA: 29627SN: 31RMS
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NL: 1.74E4
m/z= 175.47-176.47 F: + c EI SRM ms2 245.950 [175.965-175.975] MS ICIS XLSULTRA_NPV_OCP00015_110329095349
NL: 7.78E3
m/z= 245.45-246.45 F: + c EI SRM ms2 317.940 [245.945-245.955] MS XLSULTRA_NPV_OCP00015_110329095349
XLSULTRA_NPV_OCP00013_110329084745 3/29/2011 8:47:45 AM
RT: 15.48 - 17.07 SM: 7G
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RT: 16.56AA: 12784SN: 708RMS
RT: 15.95AA: 7444SN: 412RMS
RT: 16.86AA: 380SN: 22RMS
RT: 16.67AA: 198SN: 19RMS
RT: 16.52AA: 129SN: 14RMS
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NL: 6.83E3
m/z= 175.47-176.47 F: + c EI SRM ms2 245.950 [175.965-175.975] MS ICIS XLSULTRA_NPV_OCP00013_110329084745
NL: 1.16E3
m/z= 245.45-246.45 F: + c EI SRM ms2 317.940 [245.945-245.955] MS XLSULTRA_NPV_OCP00013_110329084745
U-SRM
SRM
o,p-DDE & p,p-DDE 100fg in contaminated land sample ran both in SRM (Q1 0.7 amu) and U-SRM (Q1 0.1 amu)
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• New technology• Sample through-put
• Time savings
• Lower detection limits
• Triple Quadrupole GC-MS/MS provides selectivity with flexibility
• Advanced Triple Quadrupole GC-MS/MS can deliver two modes of selectivity• Increased resolution
• Structural selectivity through MS/MS
Conclusion
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Thank You for Your Attention!
Questions?
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