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

1. ©2015 Waters Corporation 1
Understanding Complex Materials using
High Definition Mass Spectrometry
Eleanor Riches, Ph.D.
Principal Scientist
03 November 2014

2. ©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

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The SYNAPT G2-Si HDMS Instrument

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SYNAPT G2-Si HDMS Technology:
Ion sources

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SYNAPT G2-Si HDMS Technology:
Ion sources
MALDI
ESI
APCI
APPI
APGC
ASAP
DART
DESI
LDTD

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SYNAPT G2-Si HDMS Technology:
QuanToF
50k FWHM

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SYNAPT G2-Si HDMS Technology:
Ion mobility separation

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Ion Mobility and
Collisional Cross Section (CCS)

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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

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C16H26
Branched
structure
C16H26
Straight chain
structure
C7H8
Travelling Wave ion mobility separation

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C16H26
Branched
structure
C16H26
Straight chain
structure
C7H8
Travelling Wave ion mobility separation

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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

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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

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What is CCS?
• Chemical
Structure
(mass, size)
• 3-dimensional
Conformation
(shape)
Precise
Physicochemical
Property of an ion
Important
differentiating
Characteristic of
an ion

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CCS: A Useful Identification Point

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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

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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

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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

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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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Enhanced Structural Characterisation

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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

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Analysis of BDAVBi blue dopant
OLED01_047.raw : 1
A
A B
B
C
C D
D
Ion
isolated
by
quadrupole

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MS/MS in petroleomics applications

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MS/MS in petroleomics applications
With thanks to Dr. Priscila Lalli,
visiting researcher, NHMFL, FSU

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MS/MS in petroleomics applications
[C13H22S + 107Ag]+, DBE = 3
Ion
isolated
by
quadrupole
-H2S
-H2S
-C3H4
-CH2S
SHR
S
R
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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Comparing Complex Samples

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Ion mobility data:
Compared using HDMS Compare

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Asphaltene Sample 1
Ion mobility data:
Two different asphaltene samples
Asphaltene Sample 2

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Ion mobility data:
Compared using HDMS Compare

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Ion mobility data:
Compared using HDMS Compare

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PMMA infusion, ESI-SYNAPT G2
With thanks to Kirsten Craven
Ion mobility data:
Two different PMMA polymer samples

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Polymerix
With thanks to Kirsten Craven
Ion mobility data:
Two different PMMA polymer samples

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With thanks to Kirsten Craven
Ion mobility data:
Two different PMMA polymer samples

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PetroOrg:
Petroleum industry-specific software
With thanks to Dr. Yuri E. Corilo,
Developer of PetroOrg software, FFI & Omics LLC

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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

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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

43. ©2015 Waters Corporation 43
Thank you
for your attention!
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