High Definition Mass Spectrometry (HDMS) application … WCTOW... · High Definition Mass Spectrometry (HDMS) application of ion mobility in oil and ... Single mass peak at m/z 571

High Definition Mass Spectrometry (HDMS) High Definition Mass Spectrometry (HDMS)

application of ion mobility in oil and application of ion mobility in oil and

petroleum analysispetroleum analysis

©2013 Waters Corporation 1

petroleum analysispetroleum analysis

Patrice Patrice LemireLemire

Waters CorporationWaters Corporation

WCTOWWCTOW

Vancouver, May 13, 2013Vancouver, May 13, 2013

Overview of SYNAPTOverview of SYNAPT®® HDMS™ TechnologyHDMS™ Technology

Focus on Ion MobilityFocus on Ion Mobility

DriftScope SoftwareDriftScope Software

Introduction Introduction


DriftScope SoftwareDriftScope Software

Oil & Petroleum Example DataOil & Petroleum Example Data

ESI

APCI

APPI

SYNAPTSYNAPT®® HDMS™ TechnologyHDMS™ Technology


DARTDESILDTD

APGC

MALDI

ASAP

UPLC/HDMSUPLC/HDMSE E


Ion mobility

Separation by Drift TimeSeparation by Drift Time


IMS Increases IMS Increases PPeak Capacity: eak Capacity: The The DatacubeDatacube


2

� Peak capacity = NLC x NIM x Nm/z x F

F = fraction of bins occupied

� Nm/z > NLC > NIM

� However, LC, m/z and IM not completely orthogonal

C16H26

C16H26

Straight chainstructure

Travelling Wave Ion Mobility SeparationTravelling Wave Ion Mobility Separation


C16H26

Branchedstructure

structure

C7H8

Not mass resolved Ion mobility resolved

DriftScope: Data Viewing & InteractionDriftScope: Data Viewing & Interaction

NAPHTHENIC ACID STANDARD


Mass (m/z)

Single mass peak at m/z 571 hasfive mobility resolved peaks under it

1A 1B

2A2B

2C

3A3B

4A4B

1 2 3 4

DriftScope: Data Viewing & InteractionDriftScope: Data Viewing & Interaction


335.0

335.5

m/z

2.5

Drift time(ms)

8.0

Small cut asphaltene, m/z 335 – 335.5

CCS CALCULATIONSCCS CALCULATIONS


CCS CALCULATIONSCCS CALCULATIONS

Relating Drift Time to SizeRelating Drift Time to Size

DriftScope: CCS CalculationDriftScope: CCS Calculation


*These data were collected

DriftScope: CCS CalculationDriftScope: CCS Calculation


PeakIntensity(cps)

DriftTime(Bins)

ExactMass(m/z)

CollisionCrossSection(Å2)

Chargeon theion

RetentionTime(mins)

*

*These data were collectedusing Waters ASAP – a thermaldesorption technique, so nochromatographic separation

CCS valuesin Å2

DriftScope: Exporting DataDriftScope: Exporting Data


EXAMPLE DATAEXAMPLE DATA


EXAMPLE DATAEXAMPLE DATA

IFPEN CollaborationIFPEN Collaboration

IFP Energies IFP Energies nouvellesnouvelles is a publicis a public--sector sector

research, innovation and training center active research, innovation and training center active

in the fields of energy, transport and the in the fields of energy, transport and the

environment.environment.

� IFPEN uses FTICR-MS to analyse crude oils & their fractions

� Collaboration: samples provided by IFPEN and comparative analyses made with FTICR-MS & SYNAPT HDMS

� SAR fraction:

� Samples: with thanks to Jérémie Ponthus, IFPEN

Analysis of Crude Oil FractionAnalysis of Crude Oil Fraction


� SAR fraction:

— Saturated 44.5%

— Aromatics 36.3%

— Resins 16.4%

� Sample: from Nigerian Egina oil field

— Vacuum residue

— Resins fraction

— Most polar fraction

— Particularly nitrogen-rich oil

� Typical data treatment: Kendrick plots using their in-house “KendrickInside” software

Double Bond Equivalent

Aromaticity

IFPEN FT ICRIFPEN FT ICR--MS AnalysisMS Analysis


� exact Kendrick mass = IUPAC mass x (14/14.01565)

� Kendrick mass defect = (nominal Kendrick mass - exact Kendrick mass)

# C : AlkylationDouble Bond Equivalent

• E. Kendrick, Anal. Chem., 1963, 35, 2146-2154• C.A. Hughey, C.L. Hendrickson, R.P. Rodgers, A.G. Marshall, Anal. Chem., 2001, 73, 4676-4681

� ESI+ FTICR-MS analysis

— 1 mg/mL sample

— MeOH:Toluene (1:1)

+ 0.5% formic acid

— Resolving power 100,000 @ m/z 400

IFPEN Analysis: IFPEN Analysis: EginaEgina ResinsResins


� Results

— C18 to C60— DBE from 5 to 23

C20 C30 C40 C50 C60

1 dimethyl pyridine

2 isoquinoline

3 benzoquinoline

4 dibenzacridine

5 crude oil

Total Mass Spectrum



N containing compounds Mass Spectrum

Jérémie Ponthus – Waters Oil & Petroleum Seminar Day – 6th October 2011 - Manchester



� SYNAPT HDMS analysis

— 40K resolution

— Ion mobility enabled

� ASAP+

— Direct deposit of solution, 6 mg/mL in toluene

Waters Analysis: Waters Analysis: EginaEgina ResinsResins


— Thermal desorption and gas phase APCI

— Thermal ramp from 250 oC to 650 oC

� ESI+

— 1 mg/mL

— MeOH:Toluene (1:1)

� Calibrations

— External mass: leucine enkephalin, m/z 556.2771, <2 ppm

— Mobility cell: Polyalanine, over range ~ approx. 85 Å2 to 250 Å2

ASAP ESI



� Oil fraction mobilogram: an organised area




� Kendrick plot of the Synapt G2 HDMS data


� Extraction of a nitrogen containing series (family 1) – with thanks to Jérémie Ponthus


140

160

180

100

110

120

130

� Excel plot of the DriftScope family 1


20

40

60

80

100

120

100 200 300 400 500 600 700 800 900 100040

50

60

70

80

90

100

220 270 320 370 420 470 520 570


100

110

120

130

DBE=0

DBE=1100

110

120

130

+CH2

� Excel plot of the DriftScope family 1: series characterisation


40

50

60

70

80

90

100

220 270 320 370 420 470 520 570

DBE=1

DBE=6

DBE=7

DBE=8

DBE=9

DBE=10

DBE=11

DBE=12

DBE=2

DBE=3

DBE=4

DBE=5

40

50

60

70

80

90

100

220 270 320 370 420 470 520 570

DBE=0

DBE=1

DBE=10

m/z 400.377283.66 bins

m/z 400.376775.55 bins

-H2


100

110

120

130

C13

C14

C15

C16

C17

C18

C19

C20

C21

� Excel plot of the DriftScope family 1: C number characterisation


40

50

60

70

80

90

100

220 270 320 370 420 470 520 570

C22

C23

C24

C25

C26

C27

C28

C29

C30

C31

C32

C33

C34

C35

C36

C37

C38

C39

C40

C22 (DBE 0)77.38 bins141Å²

C36175 Å²

C14100 Å²

C22 (DBE 10)62.71 bins123Å²

� DriftScope helps to visualise mobility data

— 3D: m/z, drift time, intensity

� Ion mobility separates species according to:

— Size

— Shape

— Charge

SummarySummary


— 3D: m/z, drift time, intensity

— 4D: m/z, retention time, drift time, intensity

� Ion mobility offers:

— Increased peak capacity due to additional separation

— Comprehensive characterisation of samples

— Ion size information from CCS calculations following the

calibration of the mobility cell.

ConclusionConclusionIFPEN collaborationIFPEN collaboration

� Ion Mobility mass spectrometry is applicable and offers benefits to the

analysis of oil and petroleum samples.

� The Synapt HDMS exact mass data can be used to generate Kendrick

plots.

� When mass and drift time are taken into consideration, it enables the


� When mass and drift time are taken into consideration, it enables the

identification of incorrect assignments of ions provided by high

resolution data alone.

� The calibration of the mobility cell with polyalanine allowed the

calculation of the size of species within the sample.

� The knowledge of size distribution in the sample could lead to novel

catalyst design – of vital importance in the quality of the products

generated from crude oil.

AcknowledgementsAcknowledgements

� Jeremy Phontus

IFP Energies Nouvelles, Rond-point de l’échangeur de Solaize–BP 3,

69360 Solaize, France

� Eleanor Riches

Waters Corporation, Atlas Park, Simonsway,


Waters Corporation, Atlas Park, Simonsway,

Manchester M22 5PP, UK

Evaluating the multiple benefits offered by ion mobility-mass

spectrometry in oil and petroleum analysis

Int. J. Ion Mobil. Spec. (2013) 16:95–103


Thank You For Your AttentionThank You For Your Attention

High Definition Mass Spectrometry (HDMS) application … WCTOW... · High Definition Mass Spectrometry (HDMS) application of ion mobility in oil and ... Single mass peak at m/z 571

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