Ion mobility- mass spectrometry can help to offer an additional orthogonal dimension of separation, and can help to deconvolute isomeric species in the ion mobility dimension, which, in turn, helps to simplify the analysis of these highly complex samples, and map the compositional space of petroleum samples, and can also characterise the shapes and sizes, or collisional cross sections, of molecules of interest. The most important component of this work was the development of novel software that helps the user to visualise, interact with, and process ion mobility data – so, for the first time, we are able to utilise the ion mobility dimension in comprehensive petroleomics analyses.

1. ©2015 Waters Corporation 1
ANALYTICAL FRONTIERS:
Eleanor Riches, Ph.D.
pETROLEOMICS

2. ©2015 Waters Corporation 2
Ion Mobility & PetroOrg Software:
Novel Techniques for
Petroleomics Investigations
Eleanor Riches, Ph.D.
Principal Scientist
January 2015

3. ©2015 Waters Corporation 3
Presentation Overview
PetroOrg Software
Overview of the SYNAPT G2-Si HDMS Instrument
Introduction to Ion Mobility & CCS
The Application of Ion Mobility to Petroleomics
Summary & Acknowledgements
Ion Mobility Coupled with Separation Techniques

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The SYNAPT G2-Si HDMS Instrument
Click Here for Product Information

5. ©2015 Waters Corporation 5
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:
StepWave ion guide
ElectricField
Diffuse
Ion Cloud

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SYNAPT G2-Si HDMS Technology:
Quadrupole
MS/MS

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SYNAPT G2-Si HDMS Technology:
Triwave ion mobility region

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SYNAPT G2-Si HDMS Technology:
Triwave ion mobility region

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SYNAPT G2-Si HDMS Technology:
Travelling Wave ion transfer optics
 A repeating train of DC pulses propels the ions
 Ions ‘surf’ on the wave front
 Less mobile ions are overtaken by the wave more
often than more mobile ions
SIMION picture of the travelling wave device
Poster 720002666en, Kevin Giles, Jason Wildgoose & David Langridge

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SYNAPT G2-Si HDMS Technology:
QUANTOF Time-of-Flight region

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SYNAPT G2-Si HDMS Technology:
QUANTOF Time-of-Flight region
SENSITIVITY RESOLUTION

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SYNAPT G2-Si HDMS Technology:
QUANTOF Time-of-Flight region
HIGH
RESOLUTION
ENHANCED
RESOLUTION
50k FWHM

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Ion Mobility and
Collision Cross Section (CCS)

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Travelling Wave ion mobility separation

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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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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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Travelling Wave ion mobility separation
 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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Travelling Wave ion mobility separation
 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

24. ©2015 Waters Corporation 24
What is CCS?
 Important differentiating
characteristic of an ion
— Chemical structure
(mass, size)
— Dimensional information
(shape)
 Precise physicochemical
property of an ion

25. ©2015 Waters Corporation 25
40
50
60
70
80
90
100
110
120
130
220 270 320 370 420 470 520 570
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
C31
C32
C33
C34
C35
C36
C37
C38
C39
C40
C22 (DBE 1)
77.38 bins
140.88 Ų
C36
175 Ų
C14
100 Ų
C22 (DBE 10)
62.71 bins
122.80 Ų
 Excel plot of the DriftScope N1 family: C number characterisation
Waters analysis of Egina resin

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Analysis of Egina resin
 Ion Mobility MS
– Size and identification of the molecule
+
 3D TEM
– Calculation of the catalyst's porosity
– Determination of the pore size
=
 % of active sites of the catalyst
accessible to the molecule
(ie. efficiency)
 Size information
– Size distribution of the molecules in a sample
– Link to catalyst porosity
– Analytical tool for catalyst screening
– Comprehension of feed/product behaviour

27. ©2015 Waters Corporation 27
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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Using the IMS region for fragmentation
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

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Application of Ion Mobility to Petroleomics

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The Challenges of Petroleum Analysis
 Petroleum samples provide one of the biggest challenges for scientists
in the field of analytical chemistry
5 3
8 18
10 75
12 355
15 8347
20 36.6 x 104
25 36.7 x 106
30 41.1 x 108
35 49.3 x 1010
40 62.4 x 1012
45 82.2 x 1014
60 221.5 x 1020
80 1056 x 1028
100 5920 x 1038
Carbon
Number
Number of
Isomers
Fractions
Gasoline
Diesel
VGO
VR

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Ion Mobility in Petroleum Analysis
 Use of ion mobility-mass spectrometry is relatively recent in petroleomics
– Drift tube ion mobility:
– TWIM:

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Typical petroleum
mass spectrum
Mobilogram
Ion mobility data
in DriftScope
Mass & ion mobility
detected peaks
Ion Mobility Data: Electrospray

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Ion Mobility Data: APPI
ML and DS spectra

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Ion Mobility Data: Electrospray

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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
SHR
S
R
With thanks to Dr. Priscila Lalli,
visiting researcher, NHMFL, FSU
-CH2S

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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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Introducing PetroOrg

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Introduction to PetroOrg
Click Here for Further Information

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Introduction to PetroOrg

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Introduction to PetroOrg

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Ion Mobility Data in PetroOrg

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Ion Mobility Data in PetroOrg
The long diagonals
correspond to DBE groups
The short diagonals
correspond to C number groups

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Generating Industry-Specific Diagrams
A fully interactive user interface enables quick and simple
generation of industry-specific diagrams
Classes found
2D or 3D Different plots

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Generating Industry-Specific Diagrams
Example of a Carbon Number vs DBE plot
for the N1 Class
Example of a Van Krevelen diagram
for the N1 Class

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Custom Reporting

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Custom Reporting

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Application Examples

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ESI(+) - VGO Hydrotreatment Effluent
40
20
10
0
30
DBE
10 20 30 40 50 60
N1
Carbon Number
Relative Abundance (% Total)
20
10
5
0
15
DriftTime(ms)
10 20 30 40 50 60
N1
Carbon Number
DBE

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APPI(+) – Safaniya Vacuum Residue
160
80
40
0
120
DriftTime
10 20 30 40 50 60
Carbon Number
S1
DBE

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APPI(+) – Safaniya Vacuum Residue
40
20
10
0
30
DBE
10 20 30 40 50 60
Carbon Number
S1
Relative Abundance (% Total)
S
S
S

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ASAP(+) – Boscan Vacuum Residue
50 oC
250 oC
350 oC
450 oC
550 oC
650 oC

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ASAP(+) – Boscan Vacuum Residue
250 oC
10 20 30 50 60
DriftTime
160
0
120
DBE
40
Carbon Number
HC
80
40

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ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
DriftTime
160
80
40
0
120
DBE
350 oC

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ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
DriftTime
160
80
40
0
120
DBE
450 oC

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ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
DriftTime
160
80
40
0
120
DBE
550 oC

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ASAP(+) – Boscan Vacuum Residue
160
80
40
0
120
DriftTime
10 20 30 40 50 60
HC
Carbon NumberDBE
650 oC

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ASAP(+) – Boscan Vacuum Residue
40
20
10
0
30
DBE
10 20 30 40 50 60
HC
Carbon NumberRelative Abundance (% Total)
Possible result
of fragmentation
Alkylated
parent ions
250 oC

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Relative Abundance (% Total)
ASAP(+) – Boscan Vacuum Residue
350 oC
Possible result
of fragmentation
Alkylated
parent ions
40
20
10
0
30
DBE
10 20 30 40 50 60
Carbon Number
HC

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ASAP(+) – Boscan Vacuum Residue
Relative Abundance (% Total)
450 oC
Possible result
of fragmentation
Alkylated
parent ions
40
20
10
0
30
DBE
10 20 30 40 50 60
HC
Carbon Number

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ASAP(+) – Boscan Vacuum Residue
Relative Abundance (% Total)
550 oC
Possible result
of fragmentation
Alkylated
parent ions
40
20
10
0
30
DBE
10 20 30 40 50 60
HC
Carbon Number

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ASAP(+) – Boscan Vacuum Residue
Relative Abundance (% Total)
650 oC
Possible result
of fragmentation
Alkylated
parent ions
40
20
10
0
30
DBE
10 20 30 40 50 60
HC
Carbon Number

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In Agreement with the Literature
DBE 10
DBE 17
DBE 23
DBE 26
DBE 9
DBE 15
DBE 21
DBE 25
DBE 12
DBE 18
Carbon Number
HC Class
Double Bond Equivalents vs. C#
IRMPD APPI(+) FT-ICR MS.
Total de-alkylation revealing the core structures
DBE 20
DBE 7
DBE 14
Image shown with kind permission from the authors. Ref: Podgorski, D. C., et al., Energy & Fuels, 2013, 27, pp 1268 - 1276
15 25 35 455

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Ion Mobility Coupled with Separation
Techniques: The Next Step?

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Instrumentation: Chromatography
Binary Solvent Manager
Sample Manager
Convergence Manager
Column Oven/Manager
PDA Detector
UPLC UPC2

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Instrumentation: UPC2-MS
MS splitter
From the Column
manager or PDA
From the
makeup pump
To the
convergence
Manager
To the MS

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Instrumentation: UPC2-MS

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Chromatography: UPLC-IMS-MS
m/z
DriftTime(Bins)
Typical UPLC chromatogram
“Mobilogram”
Total combined spectrum
Boscan (ESI+)

69. ©2015 Waters Corporation 69
Chromatography: UPLC-IMS-MS
Typical UPLC chromatogram
Total combined spectrum
“Mobilogram”
Retention Time (Mins)
DriftTime(Bins)
Boscan (ESI+)

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Chromatography: UPLC-IMS-MS
Boscan (ESI+)

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Chromatography: UPLC-IMS-MS
Boscan (ESI+)

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Chromatography: UPLC-IMS-MS
Boscan (ESI+)

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Chromatography: UPLC-IMS-MS
Boscan (ESI+)

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Chromatography: UPC2-IMS-MS
Boscan (APPI+)

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Chromatography: UPC2-IMS-MS
Boscan (APPI+)

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Chromatography: UPC2-IMS-MS
Boscan (APPI+)

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Chromatography: UPC2-IMS-MS
Boscan (APPI+)

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Chromatography: UPC2-IMS-MS
Boscan (APPI+)

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Summary & Conclusions

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PetroOrg Summary
The power of multidimensional separation
using ion mobility-mass spectrometry with
Waters’ SYNAPT HDMS
Quickly and simply import
Waters’ ion mobility data, and
other data formats
Interactive and versatile reporting toolsPowerful, industry-specific information from
Waters’ ion mobility data

81. ©2015 Waters Corporation 81
Petroleomics Solution Web Page
www.waters.com > Chemical > Fuel and Energy
www.waters.com/petroleomics

82. ©2015 Waters Corporation 82
Conclusions
 Novel software tools help to visualize, interact with, and
process ion mobility-mass spectrometry data for
comprehensive, petroleomics-specific data analysis
 Ion mobility-mass spectrometry can help to…
— Offer an additional orthogonal dimension of separation
— Deconvolute isomeric species in the ion mobility dimension
— Simplify the analysis of very complex samples
— Map the compositional space of petroleum samples
— Characterise the shapes and/or sizes of materials

83. ©2015 Waters Corporation 83
Acknowledgements
 Collaborators: Jérémie Ponthus, Jérémie Barbier and
Laure Boursier, IFP Energies nouvelles, France
 Collaborator Dr. Kim Sunghwan, Kyungpook University,
Korea
 Collaborator: Ryan Rodgers, FFI, FSU, Tallahassee, USA
 Collaborator: Yuri E. Corilo, FFI, FSU, Tallahassee, USA
particularly for the development of PetroOrg software

84. ©2015 Waters Corporation 84
Acknowledgements
Thank you
for your attention!
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