understanding complex materials using high definition mass spectrometry
TRANSCRIPT
©2015 Waters Corporation 1
Understanding Complex Materials using High Definition Mass Spectrometry
Eleanor Riches, Ph.D. Principal Scientist
03 November 2014
©2015 Waters Corporation 2
Presentation Overview
Enhanced Structural Characterisation
Comparing Complex Samples
Overview of the SYNAPT G2-Si HDMS Instrument
Introduction to Ion Mobility & Collisional Cross Section
CCS: A Useful Identification Point
©2015 Waters Corporation 5
SYNAPT G2-Si HDMS Technology: Ion sources
MALDI
ESI
APCI
APPI
APGC
ASAP
DART
DESI
LDTD
©2015 Waters Corporation 9
Turbomolecular Pumps
Trap IMS Transfer
Gate
N2
Ar
Ions In
Ions Out 0.05mbar
He
0.05mbar 3mbar
Travelling Wave ion mobility separation
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C16H26 Branched structure
C16H26 Straight chain
structure
C7H8
Travelling Wave ion mobility separation
©2015 Waters Corporation 11
C16H26 Branched structure
C16H26 Straight chain
structure
C7H8
Travelling Wave ion mobility separation
©2015 Waters Corporation 12
C16H26 Branched structure
C16H26 Straight chain
structure
C7H8
Travelling Wave ion mobility separation
©2015 Waters Corporation 13
Collision Cross Section (CCS) Ion mobility MS measures an ion’s DRIFT TIME
— Applying a calibration gives us COLLISION CROSS SECTION (CCS), a key physicochemical property of the species
Polyalanine calibration CCS value Measured
Drift Time
©2015 Waters Corporation 14
Collision Cross Section (CCS) Ion mobility MS measures an ion’s DRIFT TIME
— Applying a calibration gives us COLLISION CROSS SECTION (CCS), a key physicochemical property of the species
Time-of-Flight MS measures an ion’s FLIGHT TIME
— Applying a calibration gives us MASS TO CHARGE RATIO (m/z), and hence the ion’s mass: a key physicochemical property of the species
Polyalanine calibration CCS value Measured
Drift Time
Sodium formate calibration m/z value Measured
Flight Time
©2015 Waters Corporation 15
What is CCS?
• Chemical Structure
(mass, size)
• 3-dimensional Conformation
(shape)
Precise Physicochemical
Property of an ion
Important differentiating
Characteristic of an ion
©2015 Waters Corporation 17
CCS: a useful identification point
Matrix Rt (mins) %Error Pear 7.48 1.73
Boscalid expected retention time (Rt) 7.35 mins (standard): Matrix dependent retention time shifts
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CCS: a useful identification point
Matrix Rt (mins) %Error Pear 7.48 1.73 Mandarin 7.55 2.65
Boscalid expected retention time (Rt) 7.35 mins (standard): Matrix dependent retention time shifts
©2015 Waters Corporation 19
CCS: a useful identification point
Matrix Rt (mins) %Error Pear 7.48 1.73 Mandarin 7.55 2.65 Leek 7.68 4.30
Boscalid expected retention time (Rt) 7.35 mins (standard): Matrix dependent retention time shifts
©2015 Waters Corporation 20
CCS: a useful identification point
Matrix Rt (mins) %Error Pear 7.48 1.73 Mandarin 7.55 2.65 Leek 7.68 4.30 Ginger 7.78 5.53
Boscalid expected retention time (Rt) 7.35 mins (standard): Matrix dependent retention time shifts
©2015 Waters Corporation 21
CCS: a useful identification point
Without CCS Without CCS With CCS m/z tolerance +/-
5ppm 10ppm 10ppm
Rt tolerance +/- 2.5% 2.5% 2.5% CCS tolerance +/-
- - 2%
Correct IDs 7 8 8 False negatives 1 0 0 False positives 1 1 0
Using CCS filtering: 0% false positives and false negatives observed for pesticide formulation
With thanks to Dr. Mike McCullagh
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m/z
Drift time
Using the IMS region for fragmentation
Precursor ions separated
by IMS
m/z
Drift time
Precursor and product ions
are TIME ALIGNED
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m/z
Drift time
m/z
Drift time
1st & 2nd generation product ions
are TIME ALIGNED
Ion isolated
by quadrupole
Product ions separated
by IMS
Precursor ion FRAGMENTED
Using the IMS region for fragmentation
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BDAVBi Blue Dopant
C52H40N2
693
693
616
448 525
256 168
MS Spectrum
MS/MS Spectrum
356
N
N
Analysis of BDAVBi blue dopant
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Analysis of BDAVBi blue dopant
OLED01_045.raw : 1
168
356
256
448
616
525
693
Drift time (Bins)
m/z
Separation of isomers
N
N
Ion isolated
by quadrupole
©2015 Waters Corporation 27
Analysis of BDAVBi blue dopant
OLED01_047.raw : 1
A
A B
B C
C D
D
Ion isolated
by quadrupole
©2015 Waters Corporation 29
MS/MS in petroleomics applications With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU
©2015 Waters Corporation 30
MS/MS in petroleomics applications
[C13H22S + 107Ag]+, DBE = 3 Ion isolated
by quadrupole
-H2S
-H2S -C3H4
-CH2S
SHR
SR
With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU
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MS/MS in petroleomics applications
S1 Class, DBE = 3 With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU
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Asphaltene Sample 1
Ion mobility data: Two different asphaltene samples
Asphaltene Sample 2
©2015 Waters Corporation 37
PMMA infusion, ESI-SYNAPT G2
With thanks to Kirsten Craven
Ion mobility data: Two different PMMA polymer samples
©2015 Waters Corporation 38
Polymerix
With thanks to Kirsten Craven
Ion mobility data: Two different PMMA polymer samples
©2015 Waters Corporation 39 With thanks to Kirsten Craven
Ion mobility data: Two different PMMA polymer samples
©2015 Waters Corporation 40
PetroOrg: Petroleum industry-specific software
With thanks to Dr. Yuri E. Corilo, Developer of PetroOrg software, FFI & Omics LLC
©2015 Waters Corporation 41
PetroOrg: Petroleum industry-specific software
Example of a Carbon Number vs DBE plot for the N1 Class
Example of a Van Krevelen diagram for the N1 Class
With thanks to Dr. Yuri E. Corilo, Developer of PetroOrg software, FFI & Omics LLC
©2015 Waters Corporation 42
Summary
Waters’ SYNAPT G2-Si HDMS instrument, with its quadrupole – ion mobility-ToF geometry, is an unrivalled tool for the characterisation of complex materials
The orthogonal separation offered by ion mobility enables powerful structural elucidation workflows
Collisional Cross Section (CCS) measurements provide valuable confirmatory data points
Ion mobility-specific software allows interactive data evaluation and processing
Partnering and collaborating with key thought leaders has resulted in the development of unique petroleum industry-specific data processing software
©2015 Waters Corporation 43
Thank you for your attention!
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