Post on 19-Jul-2015
©2015 Waters Corporation 1
ANALYTICAL FRONTIERS:
Eleanor Riches, Ph.D.
pETROLEOMICS
©2015 Waters Corporation 2
Ion Mobility & PetroOrg Software: Novel Techniques for
Petroleomics Investigations
Eleanor Riches, Ph.D. Principal Scientist
January 2015
©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
©2015 Waters Corporation 4
The SYNAPT G2-Si HDMS Instrument
Click Here for Product Information
©2015 Waters Corporation 5
SYNAPT G2-Si HDMS Technology: Ion sources
©2015 Waters Corporation 6
SYNAPT G2-Si HDMS Technology: Ion sources
MALDI
ESI
APCI
APPI
APGC
ASAP
DART
DESI
LDTD
©2015 Waters Corporation 7
SYNAPT G2-Si HDMS Technology: StepWave ion guide
Elec
tric
Fie
ld
Diffuse Ion Cloud
©2015 Waters Corporation 8
SYNAPT G2-Si HDMS Technology: Quadrupole
MS/MS
©2015 Waters Corporation 9
SYNAPT G2-Si HDMS Technology: Triwave ion mobility region
©2015 Waters Corporation 10
SYNAPT G2-Si HDMS Technology: Triwave ion mobility region
©2015 Waters Corporation 11
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
©2015 Waters Corporation 12
SYNAPT G2-Si HDMS Technology: QUANTOF Time-of-Flight region
©2015 Waters Corporation 13
SYNAPT G2-Si HDMS Technology: QUANTOF Time-of-Flight region
SENSITIVITY RESOLUTION
©2015 Waters Corporation 14
SYNAPT G2-Si HDMS Technology: QUANTOF Time-of-Flight region
HIGH RESOLUTION
ENHANCED RESOLUTION
50k FWHM
©2015 Waters Corporation 15
Ion Mobility and Collision Cross Section (CCS)
©2015 Waters Corporation 16
Travelling Wave ion mobility separation
©2015 Waters Corporation 17
Turbomolecular Pumps
Trap IMS Transfer
Gate
N2
Ar
Ions In
Ions Out 0.05mbar
He
0.05mbar 3mbar
Travelling Wave ion mobility separation
©2015 Waters Corporation 18
Travelling Wave ion mobility separation
©2015 Waters Corporation 19
C16H26 Branched structure
C16H26 Straight chain
structure
C7H8
Travelling Wave ion mobility separation
©2015 Waters Corporation 20
C16H26 Branched structure
C16H26 Straight chain
structure
C7H8
Travelling Wave ion mobility separation
©2015 Waters Corporation 21
C16H26 Branched structure
C16H26 Straight chain
structure
C7H8
Travelling Wave ion mobility separation
©2015 Waters Corporation 22
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
©2015 Waters Corporation 23
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
©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
©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
©2015 Waters Corporation 26
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
©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
©2015 Waters Corporation 28
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
©2015 Waters Corporation 29
Application of Ion Mobility to Petroleomics
©2015 Waters Corporation 30
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
©2015 Waters Corporation 31
Ion Mobility in Petroleum Analysis
Use of ion mobility-mass spectrometry is relatively recent in petroleomics
– Drift tube ion mobility:
– TWIM:
©2015 Waters Corporation 32
Typical petroleum mass spectrum
Mobilogram
Ion mobility data in DriftScope
Mass & ion mobility detected peaks
Ion Mobility Data: Electrospray
©2015 Waters Corporation 33
Ion Mobility Data: APPI
ML and DS spectra
©2015 Waters Corporation 34
Ion Mobility Data: Electrospray
©2015 Waters Corporation 35
MS/MS in petroleomics applications With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU
©2015 Waters Corporation 36
MS/MS in petroleomics applications
[C13H22S + 107Ag]+, DBE = 3 Ion isolated
by quadrupole
-H2S
-H2S -C3H4
SHR
SR
With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU
-CH2S
©2015 Waters Corporation 37
MS/MS in petroleomics applications
S1 Class, DBE = 3 With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU
©2015 Waters Corporation 38
Introducing PetroOrg
©2015 Waters Corporation 39
Introduction to PetroOrg
Click Here for Further Information
©2015 Waters Corporation 40
Introduction to PetroOrg
©2015 Waters Corporation 41
Introduction to PetroOrg
©2015 Waters Corporation 42
Ion Mobility Data in PetroOrg
©2015 Waters Corporation 43
Ion Mobility Data in PetroOrg
The long diagonals correspond to DBE groups
The short diagonals correspond to C number groups
©2015 Waters Corporation 44
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
©2015 Waters Corporation 45
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
©2015 Waters Corporation 46
Custom Reporting
©2015 Waters Corporation 47
Custom Reporting
©2015 Waters Corporation 48
Application Examples
©2015 Waters Corporation 49
ESI(+) - VGO Hydrotreatment Effluent
40
20
10
0
30
DB
E
10 20 30 40 50 60
N1
Carbon Number
Relative Abundance (% Total)
20
10
5
0
15
Drif
t Tim
e (m
s)
10 20 30 40 50 60
N1
Carbon Number
DBE
©2015 Waters Corporation 50
APPI(+) – Safaniya Vacuum Residue
160
80
40
0
120
Drif
t Tim
e
10 20 30 40 50 60
Carbon Number
S1
DBE
©2015 Waters Corporation 51
APPI(+) – Safaniya Vacuum Residue
40
20
10
0
30
DB
E
10 20 30 40 50 60
Carbon Number
S1
Relative Abundance (% Total)
S
S
S
©2015 Waters Corporation 52
ASAP(+) – Boscan Vacuum Residue
50 oC
250 oC
350 oC
450 oC
550 oC 650 oC
©2015 Waters Corporation 53
ASAP(+) – Boscan Vacuum Residue
250 oC
10 20 30 50 60
Drif
t Tim
e
160
0
120
DBE
40
Carbon Number
HC
80
40
©2015 Waters Corporation 54
ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
Drif
t Tim
e
160
80
40
0
120
DBE
350 oC
©2015 Waters Corporation 55
ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
Drif
t Tim
e
160
80
40
0
120
DBE
450 oC
©2015 Waters Corporation 56
ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
Drif
t Tim
e
160
80
40
0
120
DBE
550 oC
©2015 Waters Corporation 57
ASAP(+) – Boscan Vacuum Residue
160
80
40
0
120
Drif
t Tim
e
10 20 30 40 50 60
HC
Carbon Number DBE
650 oC
©2015 Waters Corporation 58
ASAP(+) – Boscan Vacuum Residue
40
20
10
0
30
DB
E
10 20 30 40 50 60
HC
Carbon Number Relative Abundance (% Total)
Possible result of fragmentation
Alkylated parent ions
250 oC
©2015 Waters Corporation 59
Relative Abundance (% Total)
ASAP(+) – Boscan Vacuum Residue
350 oC
Possible result of fragmentation
Alkylated parent ions
40
20
10
0
30
DB
E
10 20 30 40 50 60
Carbon Number
HC
©2015 Waters Corporation 60
ASAP(+) – Boscan Vacuum Residue
Relative Abundance (% Total)
450 oC
Possible result of fragmentation
Alkylated parent ions
40
20
10
0
30
DB
E
10 20 30 40 50 60
HC
Carbon Number
©2015 Waters Corporation 61
ASAP(+) – Boscan Vacuum Residue
Relative Abundance (% Total)
550 oC
Possible result of fragmentation
Alkylated parent ions
40
20
10
0
30
DB
E
10 20 30 40 50 60
HC
Carbon Number
©2015 Waters Corporation 62
ASAP(+) – Boscan Vacuum Residue
Relative Abundance (% Total)
650 oC
Possible result of fragmentation
Alkylated parent ions
40
20
10
0
30
DB
E
10 20 30 40 50 60
HC
Carbon Number
©2015 Waters Corporation 63
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 45 5
©2015 Waters Corporation 64
Ion Mobility Coupled with Separation Techniques: The Next Step?
©2015 Waters Corporation 65
Instrumentation: Chromatography
Binary Solvent Manager
Sample Manager
Convergence Manager
Column Oven/Manager
PDA Detector
UPLC UPC2
©2015 Waters Corporation 66
Instrumentation: UPC2-MS
MS splitter
From the Column manager or PDA
From the makeup pump
To the convergence Manager
To the MS
©2015 Waters Corporation 67
Instrumentation: UPC2-MS
©2015 Waters Corporation 68
Chromatography: UPLC-IMS-MS
m/z
Dri
ft T
ime
(Bin
s)
Typical UPLC chromatogram
“Mobilogram”
Total combined spectrum
Boscan (ESI+)
©2015 Waters Corporation 69
Chromatography: UPLC-IMS-MS
Typical UPLC chromatogram
Total combined spectrum
“Mobilogram”
Retention Time (Mins)
Dri
ft T
ime
(Bin
s)
Boscan (ESI+)
©2015 Waters Corporation 70
Chromatography: UPLC-IMS-MS Boscan (ESI+)
©2015 Waters Corporation 71
Chromatography: UPLC-IMS-MS Boscan (ESI+)
©2015 Waters Corporation 72
Chromatography: UPLC-IMS-MS Boscan (ESI+)
©2015 Waters Corporation 73
Chromatography: UPLC-IMS-MS Boscan (ESI+)
©2015 Waters Corporation 74
Chromatography: UPC2-IMS-MS Boscan (APPI+)
©2015 Waters Corporation 75
Chromatography: UPC2-IMS-MS Boscan (APPI+)
©2015 Waters Corporation 76
Chromatography: UPC2-IMS-MS Boscan (APPI+)
©2015 Waters Corporation 77
Chromatography: UPC2-IMS-MS Boscan (APPI+)
©2015 Waters Corporation 78
Chromatography: UPC2-IMS-MS Boscan (APPI+)
©2015 Waters Corporation 79
Summary & Conclusions
©2015 Waters Corporation 80
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 tools Powerful, industry-specific information from Waters’ ion mobility data
©2015 Waters Corporation 81
Petroleomics Solution Web Page www.waters.com > Chemical > Fuel and Energy
www.waters.com/petroleomics
©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
©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
©2015 Waters Corporation 84
Acknowledgements
Thank you for your attention!
Follow Chemical Materials on Twitter @WatersChemical