Carlos Afonso, Université de Rouen, Laboratoire COBRA, Plateau technique C2iorga In this presentation, Carlos Afonso describes the analysis of polymers and petroleum by ion mobility mass spectrometry and utilises novel sample introduction techniques such as the Atmospheric Solids Analysis Probe (ASAP).

1. Rapid analysis of polymers and petroleum by
I bilit t tIon-mobility mass spectrometry
Carlos AfonsoCarlos Afonso
Université de Rouen
Laboratoire COBRA
Pl t t h i C2iPlateau technique C2iorga
1

2. Context
Carlos AFONSO Pierre GIUSTI Brice BOUYSSIERECarlos AFONSO, Pierre GIUSTI, Brice BOUYSSIERE
2

3. Ionization of polymers
• Polymer : large molecular
diversitydiversity
– Heteroatoms (PEG, PMMA…)
– Unsaturated (PB)
A ti (PS)
PMMA 2
CH3
O O
CH3
n
PS 7
n
PDMS 1
n
Si
O
CH3
CH3
– Aromatics (PS)
– Saturated (PE, PP…)
• Ionization
– M+•
– [M+H]+, [M+Na]+, [M+Met]+
Solubility• Solubility
– In mass spectrometry the majority of
ionization methods implies to
l bili lsolubilize samples
3

4. ASAP: Atmospheric Solids Analysis Probe
• Sample deposited onto glass tube
– Use of pure sample
no solvent required– no solvent required
• Desorption using a hot N2 flux
• Ionization from plasma generated
by a corona dischargeby a corona discharge
Charge transfer (M+•)
N2 + e– → N2
+• + 2e–
N +• + 2N → N +• + NN2 + 2N2 → N4 + N2
N4
+• (or N2
+•) + M → M+• + xN2
Proton transfer (MH+)
N4
+• + H2O → H2O+• + 2N2
H2O+• + H2O → H3O+ + HO•
H3O+ + n(H2O)+N2 → H+(H2O)n+N2
H+(H O) M MH+ (H O)
Proton transfer (MH )
H+(H2O)n + M → MH+ + n(H2O)
C.N. McEwen, R.G. McKay, and B.S. Larsen, Anal. Chem. 2005, 77, 7826-7831
4

5. ASAP: examples
Paraffins
C72
2×CH2
• Change conditions to control ionization
N2 + MeOH MH+
M+•
M+•M+•
MH+MH+MH+
N2 MM+•
M+•
M+ 2
5

6. APPI, APCI, ASAP, ESI
• ESI
– Polar compounds
L l l t i
Complementary ion sources to analyse
molecular diversity
– Large molecules, proteins,
polymers…
– Fragile Molecules
• APCI ESI
100,000
10 000
DP-APCI
(pyrolysis)
• APCI
– Low polarity
– < 2000u
Small molecules
ESI
APPI
10,000
1,000
Mass(u)
(pyrolysis)
– Small molecules
• APPI/ASAP
– Non polar molecules
ASAP l l l
APPI
DP-APCI APCI
100
– ASAP can analyze low polar
high mass molecules
(pyrolysis)
Non polar very polar
Polarity
6

7. Chromatographic separation ?
• Drift tube
– Electric field and buffer gas
IM spectrum
• Ion mobility
vd  K  E
• Ω Collision cross section (Å2)
– Related to size and shape
d
7

8. IMS
TR1000 Handheld Explosive
Trace Detector
• Homeland
securityy
Smiths Detection (Ionscan 400B)Smiths Detection (Ionscan 400B)
8
G. Reid Asbury et al. / Talanta 50 (2000) 1291–1298
T. Khayamian et al. / Talanta 69 (2006) 795–799

9. Ion Mobility - Mass Spectrometry
2D map
ntensity
Mass
spectrum
m/z
in
9
• Ion coordinats = m/z + drift time + intensity

10. Molecular mapping by ASAP-IM/MS
• The 2D-MAP allows to spread the ions
– Increase peak capacity
1103084.raw : 1
Ion detection
algorithm
DBE:
n-paraffins: CnH2n+2
CcHhNnOoSs
DBE = c – h/2 + n/2 + 1
DBE
perylene
10

11. Polypropylene (PP) and additives
Recycling ?
11
C. Barrere, F. Maire, C. Afonso, P. Giusti, Anal. Chem. 2012, 84, 9349-9354

12. ASAP-IMMS of PP1: stabilizers study
TWIM
m/z mobility plotASAP-MS spectrum
TWIM allo additionalNo pyrolysis residue ? TWIM allow additional
signals to be evidenced
C. Barrere, F. Maire, C. Afonso, P. Giusti, Anal. Chem. 2012, 84, 9349-9354
12

13. ASAP-IMMS of PP2: polymer and stabilizers
(- 4.9 ppm)
m/z mobility plot
(+ 4.9 ppm)
Pyrolysis
residues
(+ 1 1 ppm)
(- 2.2 ppm)
(+ 1.1 ppm)
2 stabilizers identified
Pyrolysis residues distributions similar to PP1
13

14. ASAP or DIP-APCI: a complex ionization
processprocess
e−
Ionization
By charge exchange
N2 N2
+•
e
Traces of O2
pyrolysis
Traces of O2
and H2O
?
PP
PyrolysisPyrolysis
products
R.B. Cody, Anal. Chem. 2009, 81, 1101–1107
14

15. PE/PPPE PP
339.3621 391.2842
295.2995
323.3308
339.3621353.3414365.3778
379.3934
391.2842
(a)
PE
PE PP
419.3155
300 325 350 375 m/z
353.3414
395 3884
(b)
PP
311.2945
395.3884
437.4353479.4823
521.5292
563.5762
C3
H6
C3
H6
C3
H6
PP
269.2475
605.6231
647.67010
689.7170
731.7640
200 300 400 500 600 700 m/z
15
Differentiation of PP and PE

16. PE-PP
PE
DBE 0 5
DBE 0.5
DBE 0.5
PPPP
16
Oxygen containing species for PE and PP
Low DBE species detected for PE not for PP

17. PP vs PEPE PPPE PP
17
C. Afonso, M. Farenc, M. Witt, K. Craven, C. Barrère-Mangote, P. Giusti, 63rd ASMS
conf. 2015 Saint Louis, USA

18. IM-MS m/z 300-400
18

19. IM-MS m/z 313-327
19

20. IM-MS m/z 323
DBE 2.5
DBE 1.5
DBE 0.5
DBE 2.5
DBE 3.5
DBE 4.5
20
Cyclic species at low drift time ?

21. Biodegradable polymers and blends: on
the road of materiomicsthe road of materiomics
• Aliphatic polyesters
hydrolysable ester bonds– hydrolysable ester bonds
• Renewable Resource:
polylactic acid (PLA)
HO
O
O
H
n
• Polyethylene
72.0211
21

22. ASAP MS of PLA-PE blend 30:70
[PLA6+H]+
[PLA +H]+
[PLA10+H]+
[PLA5+H]+
[PLA +H]+
• No detection of PE ions !
[PLA16+H]
• Only PLA ions detected
22
C. Barrère, W. Selmi, M. Hubert-Roux, T. Coupin, B. Assumani, C. Afonso and P. Giusti,
Polym. Chem., 2014, 5, 3576

23. ASAP-IMSMS PLA-PE blend 30/70
PE
PLA
PLA ions are easily distinguished from PE ions as they are
significantly more compact (folded)
23

24. Polymer chemistry (back cover)
24

25. Oil and petroleum distillates
25

26. Diesel hydrodesulfurization (HDS)
Catal. Sci. Technol., 2011, 1, 23–42
26
F. Maire, K. Neeson, R. Denny, M. McCullagh, C. Lange, C. Afonso, and P. Giusti, Anal. Chem.
2013, 85, 5530−5534

27. Molecular map
Hydrodesulfurization
• Comparison of 2D map
• Collaboration with Waters
– Developement of HDMS compare.
27

28. Comparaison Moléculaire• HDMS compare• HDMS compare
SS
S
28
F. Maire, K. Neeson, R. Denny, M. McCullagh, C. Lange, C. Afonso, and P. Giusti, Anal. Chem.
2013, 85, 5530−5534

29. Petroleum analysis in refineries
0
Conventional crude
composition
(Arabian Light)
0
Market
demand
Increase of middle fractions cuts (diesel) demand:
conversion units
Need for hydrodemetallation, hydrodesulfuration,
0
10
20
Light
fractions
0
10
20
Light
fractions
hydrodenitrogenation and hydrocracking process
understanding at the molecular level :
30
40
Middle
fractions
30
40
50
60
70
50
60
70
Middle
fractions Better feed and products
h t i ti i d d80
90
Heavy
fractions 80
90
Heavy
fractions
characterization is needed
100
wt %
100
fractions
wt %
29

30. Analysis of heavy petroleum product
Ultra high resolution Ion mobility spectrometry
ttime(ms)
2D separation1D separation
Ultra high resolution
FT-ICR
• Expensive
• Rare
Ion mobility spectrometry
High resolution Mass Spectrometry
Synapt G2 Waters (QToF) m/z
Drift
30

31. Comparison of ultra high resolution mass spectrometry
and ion mobility spectrometry coupled with mass
spectrometry
330.2353
330 23754
spectrometry
• Ultra High Resolution mass
spectrometry
• Ion mobility spectrometry-mass
spectrometry
2D separation330.23754
330.23417
+CH2
ms)
o 2D separation
R=900000
R= 40000
DBE
rifttime(m
330.1996
330 20 330 25/
m/z
Dr
DBE=double bond equivalent
330.20 330.25
m/z
m/z
Structural information
-Organization of ion in series
Separation of isomers
1 peak = 1 elemental composition
Chemical formula assignment of all
resolved species -Separation of isomersresolved species
31

32. METHODS: Atmospheric pressure ionization
techniques
• APPI
Atmospheric Pressure Photo Ionization
• APCI
Atmospheric Pressure Chemical Ionization
• ESI
Electrospray Ionization
Gas phase ionization
Using a corona discharge
Gas phase ionization
Using a UV lamp hυ = 10.6 eV
Liquid phase ionization
32

33. Sources comparison: heavy petroleum fraction sample
2942205
C21H28N+
• ESI : only nitrogen
containing species are
ESI
%
100
294.2205
294 1867294 1304
observed
ASAP
%
100
m/z
294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260
0
294.1867294.1304
294.2343
294.1442
C23H18
+•
C H O+•
C22H30
+•
• ASAP and APPI show
the same ionization 100
m/z
294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260%
0
294.1105
294.2005
294.2358
C21H26O+•
C H N+
C H +•
C H +•
profile APPI
m/z
294 100 294 120 294 140 294 160 294 180 294 200 294 220 294 240 294 260
%
0
294.1420
294.1082
294.1983
C21H28N
C21H26O+•
C22H30C23H18
+
• APCI ionized several
species but ions overlap
APCI
%
100
294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260
294.2230
294.1405
294.2305
C21H28N+
12
C21
13
C1
H29
+
C23H18
+•
33
m/z
294.100 294.120 294.140 294.160 294.180 294.200 294.220 294.240 294.260
0
294.1967

34. Data treatment
• Collaboration with the Future Fuel Institute, Tallahassee, Florida:
• PetroOrg: software development in progress
o Treatment of 2D data
o Peak assignment
o Data display
.
Targeting settings
p y
.
330..20 330.25
m/z
34

35. Data treatment
• Collaboration with the Future Fuel Institute, Tallahassee, Florida:
• PetroOrg: software development in progress
o Treatment of ion mobility data
o Peak assignment
o Data displayp y
F l l i i h dl
35
From a mass spectrum to elemental composition more easy to handle

36. PetroOrg: data representation
• Data representation based on the elemental composition:
Double Bond Equivalent vs C#:o Double Bond Equivalent vs C#:
AromaticDBE
AromaticD
Paraffin
C#
Paraffin
36

37. Application 1 : sulfur speciation
• Analyze of a heavy petroleum fraction using APPI-IMMS
• Comparison before and after hydrotreatment of the S1 class :
Feed Effluent
 Effect of the hydrodesulfurization
37

38. Application 1 : sulfur speciation
• 2D plot Carbon number vs. DBE for the feed:
DBE = 12
DBE = 9
DBE = 6
DBE 9
 M l l h t i ti
DBE = 6
 Molecular characterization
38

39. Application 2: nitrogen speciation
• ESI in positive mode:
• Ion mobility display :
cans)
cans)
C=31
Drifttime(sc
• C=22
Drifttime(sc
• DBE 6
C=22
H h C A H d i k C L R d R P M h ll A G E & F l 2001 15 (5) 1186 1193
m/z
• C=31
C#
• DBE 8
Hughey, C. A.; Hendrickson, C. L.; Rodgers, R. P.; Marshall, A. G., Energy & Fuels 2001, 15 (5), 1186-1193.
39

40. Application 2: isomeric separation
s)fttime(scansDrif
• DBE 8
C#
• The lines might correspond to two isomer families:
R
• Work in progress
N
R
R
NR
DBE = 8
N1
40

41. Conclusion on ASAP-IMMS of polymers
• ASAP source
– No sample preparation
No sol ent– No solvent
– Ionization saturated → polar (universal)
– robustness (atmospheric pressure, no spray)
• ASAP of polymers and oil• ASAP of polymers and oil
– Pyrolysis products or small oligomers
– Py-CI/MS)
– Results can be compared with previous dataResults can be compared with previous data
– Much easier and faster than most analytical
methods
• IM-MS couplingp g
– 2D separation
– Identification of ion families with different size
– Investigation of differential molecular content
41

42. Acknowledgments
Florian Maire
Marie Hubert-Roux
Florian Maire
Caroline Barrère
Mathilde Farenc
Pierre Giusti
Eleanor Riches
Kirsten Craven
EFRD
42Normandy region
Kieran Neeson,
Richard Denny,
Michael McCullagh