2013 Waters Corporation 1

Transcription

1 High Definition Mass Spectrometry (HDMS) application of ion mobility in oil and petroleum analysis Patrice Lemire Waters Corporation WCTOW Vancouver, May 13, Waters Corporation 1

2 Introduction Overview of SYNAPT HDMS Technology Focus on Ion Mobility DriftScope Software Oil & Petroleum Example Data 2013 Waters Corporation 2

3 SYNAPT HDMS Technology ESI APCI APPI ASAP APGC MALDI LDTD DESI DART 2013 Waters Corporation 3

4 UPLC/HDMS E Ion mobility 2013 Waters Corporation 4

5 Separation by Drift Time 2013 Waters Corporation 5

6 IMS Increases Peak Capacity: The Datacube Peak capacity = NLC x NIM x Nm/z x F F = fraction of bins occupied Nm/z > NLC > NIM Waters Corporation However, LC, m/z and IM not completely orthogonal 6

7 Travelling Wave Ion Mobility Separation C 16 H 26 Branched structure C 16 H 26 Straight chain structure C 7 H Waters Corporation 7

8 DriftScope: Data Viewing & Interaction NAPHTHENIC ACID STANDARD Not mass resolved Ion mobility resolved Mass (m/z) Single mass peak at m/z 571 has five mobility resolved peaks under it 2013 Waters Corporation 8

9 DriftScope: Data Viewing & Interaction A 1B 2A 2B 2C 3B 3A 4A 4B m/z Drift time (ms) Small cut asphaltene, m/z Waters Corporation 9 2.5

10 CCS CALCULATIONS Relating Drift Time to Size 2013 Waters Corporation 10

11 DriftScope: CCS Calculation 2013 Waters Corporation 11

12 DriftScope: CCS Calculation *These data were collected using Waters ASAP a thermal desorption technique, so no chromatographic separation * Peak Intensity (cps) Drift Time (Bins) Exact Mass (m/z) Retention Time (mins) Collision Cross Section (Å 2 ) Charge on the ion 2013 Waters Corporation 12

13 DriftScope: Exporting Data CCS values in Å Waters Corporation 13

14 EXAMPLE DATA IFPEN Collaboration IFP Energies nouvelles is a public-sector research, innovation and training center active in the fields of energy, transport and the environment Waters Corporation 14

15 Analysis of Crude Oil Fraction IFPEN uses FTICR-MS to analyse crude oils & their fractions Collaboration: samples provided by IFPEN and comparative analyses made with FTICR-MS & SYNAPT HDMS Samples: with thanks to Jérémie Ponthus, IFPEN 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 2013 Waters Corporation 15

16 IFPEN FT ICR-MS Analysis Typical data treatment: Kendrick plots using their in-house KendrickInside software Double Bond Equivalen nt Aromaticity # C : Alkylation exact Kendrick mass = IUPAC mass x (14/ ) E. Kendrick, Anal. Chem., 1963, 35, C.A. Hughey, C.L. Hendrickson, R.P. Rodgers, A.G. Marshall, Anal. Chem., 2001, 73, Kendrick mass defect = (nominal Kendrick mass - exact Kendrick mass) 2013 Waters Corporation 16

17 IFPEN Analysis: Egina Resins ESI+ FTICR-MS analysis 1 mg/ml sample MeOH:Toluene (1:1) + 0.5% formic acid Resolving power m/z 400 Results C 18 to C 60 DBE from 5 to 23 C20 C30 C40 C50 C Waters Corporation 17

18 IFPEN Analysis: Egina Resins Total Mass Spectrum 1 dimethyl pyridine 2 isoquinoline 3 benzoquinoline 4 dibenzacridine 5 crude oil N containing compounds Mass Spectrum Jérémie Ponthus Waters Oil & Petroleum Seminar Day 6th October Manchester 2013 Waters Corporation 18

19 IFPEN Analysis: Egina Resins 2013 Waters Corporation 19

20 Waters Analysis: Egina Resins SYNAPT HDMS analysis 40K resolution Ion mobility enabled ASAP+ Direct deposit of solution, 6 mg/ml in toluene Thermal desorption and gas phase APCI Thermal ramp from 250 o C to 650 o C ESI+ 1 mg/ml MeOH:Toluene (1:1) Calibrations External mass: leucine enkephalin, m/z , <2 ppm Mobility cell: Polyalanine, over range ~ approx. 85 Å 2 to 250 Å Waters Corporation 20

21 Waters Analysis: Egina Resins ASAP ESI 2013 Waters Corporation 21

22 Waters Analysis: Egina Resins Oil fraction mobilogram: an organised area 2013 Waters Corporation 22

23 Waters Analysis: Egina Resins Kendrick plot of the Synapt G2 HDMS data Extraction of a nitrogen containing series (family 1) with thanks to Jérémie Ponthus 2013 Waters Corporation 23

24 Waters Analysis: Egina Resins Excel plot of the DriftScope family Waters Corporation 24

25 Waters Analysis: Egina Resins Excel plot of the DriftScope family 1: series characterisation CH 2 DBE= m/z bins m/z bins DBE=1 DBE=6 DBE=7 DBE=8 DBE=9 DBE=0 DBE=10 DBE=11 DBE=10 DBE=12 DBE=2 DBE=3 DBE=4 DBE=5 60 -H Waters Corporation 25

26 Waters Analysis: Egina Resins Excel plot of the DriftScope family 1: C number characterisation 130 C13 C C15 C16 C C18 C19 C C21 C22 90 C 22 (DBE 0) bins 141Ų C Ų C23 C24 C25 C26 C27 80 C28 C29 C30 70 C31 C32 60 C Ų C34 C35 C33 50 C 22 (DBE 10) bins 123Ų C36 C37 C38 C39 C Waters Corporation

27 Summary Ion mobility separates species according to: Size Shape Charge DriftScope helps to visualise mobility data 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 Waters Corporation 27

28 Conclusion IFPEN 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 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 Waters Corporation 28

29 Acknowledgements Jeremy Phontus IFP Energies Nouvelles, Rond-point de l échangeur de Solaize BP 3, Solaize, France Eleanor Riches 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: Waters Corporation 29

30 Thank You For Your Attention 2013 Waters Corporation 30