Petroleomic Characterization using an Ion Mobility-Orbitrap Platform

Yehia M. Ibrahim1, Roza Wojcik1, Spencer A. Prost1, Sandilya V.B. Garimella1, Randolph V. Norheim1, Erin S. Baker1, Noor A. Aly1, Hans Ketelslegers2, Fabian Grimm3, Ivan Rusyn3, Richard D. Smith1

1Biological Sciences Division, Pacific Northwest National Laboratory, Richland, WA2Concawe, Brussels, Belgium3Department of Veterinary Integrative Biosciences, Texas A&M University, College Station, TX

August 2, 2017 1

High Resolution Mass Analyzers

Marshall A.G. et al. PNAS (2008) 105, 1809 Zhurov K.O. et al. Energy & Fuels (2008) 105, 1809

OrbitrapFT-ICR

Ion mobility-TOF MS

Santos J.M. et al. Anal. Methods (2015) 7, 4450

Fernandez-Lima A. et al. Anal. Chem. (2009) 81, 9941

Time

𝐾𝐾 =𝐿𝐿2

(𝑉𝑉 ∗ 𝑡𝑡)

𝐾𝐾 = 𝐶𝐶(𝑞𝑞𝑁𝑁

)( 2𝜋𝜋𝜇𝜇𝜇𝜇𝜇𝜇

)1/2(1Ω)

Ω depend on:size/charge,ion-neutral interaction,rotationally-averaged shape

Ion Mobility Spectrometry (IMS)

Electric field, E

Buffer gas

𝑣𝑣 = 𝐾𝐾 ∗ 𝐸𝐸

IMS & Multidimensional Separation

21 22 23 24 25 26 27 28 29

Time (ms)

200 µs

May J.C. and McLean J.A. Anal. Chem. (2015) 87, 1422

Timing challenges with Orbitrap

100ms- 1sOrbitrap MS

Previous Efforts

Clowers B.H. et al. Anal. Chem. (2005) 77, 5877Donohoe G.C. et al. Anal. Chem. (2014) 86, 8121

Karasak F.W. et al. Anal. Chem. (1971) 43, 1441

RT: 0.00 - 4.89

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

N5T US60

1 2 3 4 5 6 7 8 9 10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

The Dual Gate Approach

Gating grid

Exactive Orbitrap

C-Trap

OrbitrapMass Analyzer

ESI Sprayer

Tube Lens

90o Flatapole

Multipole

PNNL-Drift tube IMS

Ion Funnel (9.7 Torr)

Inlet (1 mm i.d. )

Inlet (0.5 mm i.d.)Ion Funnel Trap (4 Torr)

Ion Funnel (4 Torr)

Segmented quadrupole(80 mtorr)

Quadrupole (300 mtorr)

Tang K. et al. Anal. Chem. (2005) 77, 3330Ibrahim Y.M. et al. Int. J. Mass Spectrom. (2015) 377, 655

Buffer gas: N2Field: E = 18 V/cm

DT-IMS-Orbitrap

RIMS ~75RExactive 100,000

Data processing

RT: 0.00 - 4.89

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

N5T US60

Mobility chromatogram (Thermo .raw)

Time-m/z heat map

convert

Modes of IMS Operation

1. Signal averaging single packet single pulse

2. Single multiplexing encoding multiple packets single pulse

3. Double multiplexing encoding* multiple packets multiple pulses

*Belov M.E. et al. ASMS 2011

1. Signal AveragingHeavy gas oil

2. Single MultiplexingHeavy gas oil

3. Double MultiplexingHeavy gas oil

Comparison of the Three Modes (after decoding)

Signal averaging Single decoding double decoding

Increased Sampling and S/N

Signal averaging Single decoding double decoding

IMS of Petroleum Samples

Straight RunGas Oils

Vacuum &Hydrotreated Gas oils

HeavyGas Oils

Trendlines in Petroleomic Data

Structural Changes

IMS-TOF IMS-Orbitrap

IMS-TOF vs IMS-Orbitrap

Benefits of High Mass Resolution & IMS

19 20 21 22 23 24 25

Time (ms)

304.2000

304.2050

304.2100

304.2150m

/z

304.200

304.205

304.210

304.215

--

Benefits of High Mass Resolution & IMS

19 20 21 22 23 24 25

Time (ms)

304.2000

304.2050

304.2100

304.2150m

/z

304.200

304.205

304.210

304.215

--

304.20917

19 20 21 22 23 24 25

Time (ms)

304.2000

304.2050

304.2100

304.2150m

/z

304.200

304.205

304.210

304.215

--

Benefits of High Mass Resolution & IMS

304.20584

Theo. Mass Exp. Mass Error (ppm)

DBE Mol. Formula Class

304.20935 304.20917 0.59 5.5 C19H30N1S1 N1S1

304.20598 304.20584 0.46 10.5 C22H26N1 N1

C3 vs. SH4

Benefits of High Mass Resolution & IMS

19 20 21 22 23 24 25

Time (ms)

304.2000

304.2050

304.2100

304.2150m

/z

304.200

304.205

304.210

304.215

--

The Next Leap in Ion Mobility

13 m SLIM-IMS

~45 cm

~32 cm

• Structures for Lossless Ion Manipulations (SLIM)

• Peak capacity ~250 as compared to ~30 for DTIMS

• Drift time of seconds for better matching with Orbitrapsee oral presentation TOD pm

94 cm DTIMS 13 m DTIMS

Summary

• Ion mobility is complementary to Orbitrap (and FT-ICR)

• Improved S/N was obtained using double multiplexing

• Ion mobility spread ions into bands of chemical classes (trend lines) for improved diagnostics/identifications

• Faster Orbitrap acquisition and/or slower ion mobility separation improves the matching

• Higher mobility resolution is possible in Structures for Lossless Ion Manipulations (SLIM)

Acknowledgment

PNNL

Daniel OrtonMalak TfailyRosalie Chu

Thermo Scientific

Satendra PrasadJean Jacques DunyachAlexander Makarov

Composer softwareDavid Stranz-Sierra Analytics, Inc.

William R. Wiley Environmental Molecular Sciences Laboratory

FundingPNNL Laboratory Directed Research & Development