Ion mobility & PetroOrg software : Novel techniques for petroleomics investigations

©2015 Waters Corporation 1

ANALYTICAL FRONTIERS:

Eleanor Riches, Ph.D.

pETROLEOMICS


Ion Mobility & PetroOrg Software: Novel Techniques for

Petroleomics Investigations

Eleanor Riches, Ph.D. Principal Scientist

January 2015


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


The SYNAPT G2-Si HDMS Instrument

Click Here for Product Information

http://www.waters.com/waters/en_US/SYNAPT-G2-Si-High-Definition-Mass-Spectrometry/nav.htm?cid=134740622�


SYNAPT G2-Si HDMS Technology: Ion sources


SYNAPT G2-Si HDMS Technology: Ion sources

MALDI

ESI

APCI

APPI

APGC

ASAP

DART

DESI

LDTD


SYNAPT G2-Si HDMS Technology: StepWave ion guide

Elec

tric

Fie

ld

Diffuse Ion Cloud


SYNAPT G2-Si HDMS Technology: Quadrupole

MS/MS


SYNAPT G2-Si HDMS Technology: Triwave ion mobility region


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


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



SENSITIVITY RESOLUTION



HIGH RESOLUTION

ENHANCED RESOLUTION

50k FWHM


Ion Mobility and Collision Cross Section (CCS)


Travelling Wave ion mobility separation


Turbomolecular Pumps

Trap IMS Transfer

Gate

N2

Ar

Ions In

Ions Out 0.05mbar

He

0.05mbar 3mbar



C16H26 Branched structure

C16H26 Straight chain

structure

C7H8





structure

C7H8



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


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


What is CCS?

Important differentiating characteristic of an ion

— Chemical structure (mass, size)

— Dimensional information (shape)

Precise physicochemical property of an ion


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 Å²

C36 175 Å²

C14 100 Å²

C22 (DBE 10) 62.71 bins 122.80 Å²

Excel plot of the DriftScope N1 family: C number characterisation

Waters analysis of Egina resin


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


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


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


Application of Ion Mobility to Petroleomics


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


Ion Mobility in Petroleum Analysis

Use of ion mobility-mass spectrometry is relatively recent in petroleomics

– Drift tube ion mobility:

– TWIM:


Typical petroleum mass spectrum

Mobilogram

Ion mobility data in DriftScope

Mass & ion mobility detected peaks

Ion Mobility Data: Electrospray


Ion Mobility Data: APPI

ML and DS spectra


Ion Mobility Data: Electrospray


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


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


MS/MS in petroleomics applications

S1 Class, DBE = 3 With thanks to Dr. Priscila Lalli, visiting researcher, NHMFL, FSU


Introducing PetroOrg


Introduction to PetroOrg

Click Here for Further Information

http://www.waters.com/waters/en_US/Omics-LLC/nav.htm?cid=134812553�


Ion Mobility Data in PetroOrg


Ion Mobility Data in PetroOrg

The long diagonals correspond to DBE groups

The short diagonals correspond to C number groups


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


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


Custom Reporting


Application Examples


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


APPI(+) – Safaniya Vacuum Residue

160

80

40

0

120

Drif

t Tim

e

10 20 30 40 50 60

Carbon Number

S1

DBE


APPI(+) – Safaniya Vacuum Residue

40

20

10

0

30

DB

E

10 20 30 40 50 60

Carbon Number

S1


S

S

S


ASAP(+) – Boscan Vacuum Residue

50 oC

250 oC

350 oC

450 oC

550 oC 650 oC



250 oC

10 20 30 50 60

Drif

t Tim

e

160

0

120

DBE

40

Carbon Number

HC

80

40



10 20 30 40 50 60

HC

Carbon Number

Drif

t Tim

e

160

80

40

0

120

DBE

350 oC



10 20 30 40 50 60

HC

Carbon Number

Drif

t Tim

e

160

80

40

0

120

DBE

450 oC



10 20 30 40 50 60

HC

Carbon Number

Drif

t Tim

e

160

80

40

0

120

DBE

550 oC



160

80

40

0

120

Drif

t Tim

e

10 20 30 40 50 60

HC

Carbon Number DBE

650 oC



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




350 oC



40

20

10

0

30

DB

E

10 20 30 40 50 60

Carbon Number

HC




450 oC



40

20

10

0

30

DB

E

10 20 30 40 50 60

HC

Carbon Number




550 oC



40

20

10

0

30

DB

E

10 20 30 40 50 60

HC

Carbon Number




650 oC



40

20

10

0

30

DB

E

10 20 30 40 50 60

HC

Carbon Number


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


Ion Mobility Coupled with Separation Techniques: The Next Step?


Instrumentation: Chromatography

Binary Solvent Manager

Sample Manager

Convergence Manager

Column Oven/Manager

PDA Detector

UPLC UPC2


Instrumentation: UPC2-MS

MS splitter

From the Column manager or PDA

From the makeup pump

To the convergence Manager

To the MS


Instrumentation: UPC2-MS


Chromatography: UPLC-IMS-MS

m/z

Dri

ft T

ime

(Bin

s)

Typical UPLC chromatogram

“Mobilogram”

Total combined spectrum

Boscan (ESI+)


Chromatography: UPLC-IMS-MS

Typical UPLC chromatogram

Total combined spectrum

“Mobilogram”

Retention Time (Mins)

Dri

ft T

ime

(Bin

s)

Boscan (ESI+)


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


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


Summary & Conclusions


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


Petroleomics Solution Web Page www.waters.com > Chemical > Fuel and Energy

www.waters.com/petroleomics

http://www.waters.com/�

http://www.waters.com/petroleomics�


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


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


Acknowledgements

Thank you for your attention!

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Ion mobility & PetroOrg software : Novel techniques for petroleomics investigations

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