Summary of activities and research conducted at the University of Vermont, funded by the Henry and Camille Dreyfus Foundation

1. Derivatization of Polar Organic Compounds for TD-GC/MS Analysis
R1
F F
F F R2
O NH2
O N
+ F CH2 + H2O
F CH2
F F Dan Nielsen
F F
PFBHA February 19, 2010 Oxime
O
(H3C)3Si O
F 3C NH2
O
N O
+ R Si(CH3)3 +
F 3C Si(CH3)3
F 3C NH
Acid
ol BSTFA Silylated Derivative Si(CH3)3
sidneyholmengroupPresentationsByGroup
Dan’s PresentationsDreyfus_Final_Presentation.ppt 0
CEMS COLLEGE OF Engineering and Mathematical Sciences

2. Acknowledgments
Dr. Britt Holmén
Ron Tackett and many others (Agilent Technologies)
Floyd Vilmont (Eng. Machinist, UVM)
Bruce O’Rourke (Chemistry, UVM)
Chris Jakober (CA, Air Resources Board)
The Dreyfus Foundation
1

3. Accomplishments
Setting up lab:
- Chemical storage
- Glassware cleaning station
- SFE setup (repaired dual piston pump)
- Coy chamber improvements
- CI upgrade on 5973MS
- Overhauled diffusion pump on 5972MS
- GC/FID setup and configuration
- Maintained both GC/MSs
- Nitrogen blowdown station
2

4. Accomplishments
Assisted with Holmén group activities:
- Melanoma detection grant research
- Protection devices grant research and proposal writing
- Safety representative (received model lab status for Votey 122B)
- Completed final budget tally for the Career grant
- Assisted students:
Kate Johannesen, Mike Kreigh, Timothy Kelly, Kristofer Kretsch
Tucker Stevens, Paul Montane, Matt Casari, Mitchell Robinson,
Karen Sentoff, John Kasumba, Jiangjiang Zhu, Anna Conterato,
Damon Lane, Courtney Giles, and Vaishali Sharma
3

5. Accomplishments
• Presented research:
- CEMS: Oct. 10, 2008
- AAAR conference: Oct. 22,2008
- Holmén group: Mar. 3, 2008, Jul. 28, 2008, Sep. 17, 2008,
Jan. 7, 2009, Jun. 29, 2009, Sep. 28, 2009, Feb. 8, 2010.
• Developed micro-derivatization procedure for hydroxylated
compounds utilizing BSTFA (potentially for TD-GC/NCI-MS).
• Developed micro-derivatization procedure for carbonylated
compounds using PFBHA (potentially for TD-GC/NCI-MS).
• Successfully tested PFBHA procedure using NIST DPM,
optimized scale down and work-up procedure for 0.1 – 1mg DPM
quantities.
4

6. Outline
• Background
• Experimental
• Results
• Conclusions
• Future Studies
5

7. Background
• Vehicle exhaust (150–300ºC) is primarily N2, O2, H2O and CO2.
• Minor constituents are CO, hydrocarbons, NOx and Particulate
Matter (PM).
• Many POCs have been identified as
products of incomplete combustion.
• POCs additionally generated as
secondary products from reaction
with O3, OH, NO3, light (>290nm).
• The high polarity of many species
prohibits or negatively affects
separation by gas chromatography
due to adsorption to injector and
column active sites.
Maricq, M. Journal of Aerosol Science, 2007, 38, 1079.
6

8. Outline
• Background
• Experimental
• Results
• Conclusions
• Future Studies
7

9. One-Step Derivatizations
R1
F F
F F R2
O O NH2
O N
+ F CH2 + H2O
R1 R2 F CH2
F F
Ketone or F F
Aldehyde PFBHA Oxime (isomers)
O
(H3C)3Si O
F 3C NH2
O
OH N O
+ R Si(CH 3)3 +
R F 3C Si(CH 3)3
F 3C NH
Carboxylic Acid
or Alcohol BSTFA Silylated Derivative Si(CH 3)3
Ho, S.S.H. and J.Z. Yu. Anal. Chem., 2002, 74, 1232.
Forester, C.D., et al. Atmospheric Environment, 2007, 41, 1188. 8

10. Two-Step Derivatization
R1
F F
F F
O O NH2
O N OH H2O
OH + F CH2 +
R1 F CH2
F F
Multifunctional F F
Compound PFBHA Oxime (isomers)
R1
R1
F F
(H3C)3Si O F F
O N OH
O N O Si(CH 3)3
N
F CH2 +
F CH2
F 3C Si(CH 3)3
F F
F F
Oxime Derivative with Alcohol Group BSTFA Two-Step Oxime Silylated Derivative
Ortiz, R., et al. Atmospheric Research, 2006, 82, 709.
9

11. Experimental Variables
PFBHA: 1. Extraction technique
2. Solvent composition
3. Concentration and Excess of reagent
4. Time
BSTFA: 1 – 4. (Above)
5. Heating reaction (60ºC, 2h)
6. Blowdown between derivatization reactions
7. Use of drying agents (e.g., Na2SO4, molecular sieves)
10

13. Recovery/Quantification Internal Standards
Compound Structure VPi VPf MWi MWf
IUPAC Name (Abbreviation) mm Hg mm Hg g/mol g/mol
Recovery Standards
D D
D D
1,2,3,4,5,6,7,8-
octadeuterionaphthalene 1.59E-1 1.59E-1 136 136
D D
(Nap-d8)
D D
D D
D D
1,1,2,2,3,4,5,6,7,8- D D
decadeuterioacenaphthene 6.98E-3 6.98E-3 164 164
(Ace-d10) D D
D D
D D
D D
1,2,3,4,5,6,7,8,9,10-
decadeuteriophenanthrene D D 2.06E-4 2.06E-4 188 188
(Phe-d10)
D D D D
D D
D D
1,2,3,4,5,6,7,8,9,10,11,12- D
D
dodecadeuteriochrysene D 8.5E-8 8.5E-8 240 240
(Chr-d12) D D
D
D D
D D D D
1,2,3,4,5,6,7,8,9,10,11,12- D D
dodecadeuterioperylene 1.81E-8 1.81E-8 264 264
(Per-d12) D D
D D D D
Quantification Standards
O
F
2-fluorobenzaldehyde
1.16 Not Avail. 124.11 319
(2-FBA)
O
O
F
6-fluoro-4-chromanone
3.47E-3 Not Avail. 166.15 361
(6-F-4-C)
O
O
5-fluoro-1-indanone 12
2.63E-02 Not Avail. 150.15 345
(5-F-1-I)
F

14. PFBHA Reactive POC Surrogates
Compound Structure VPi VPf MWi MWf
IUPAC Name (Abbreviation) mm Hg mm Hg g/mol g/mol
Alkyl Ketone
O
Hexan-2-one
1.16E1 5.36E-3 100 295
(H-2-O) H3C CH3
Aryl Ketone
O
1-phenylethanone
CH3 3.97E-1 Not Avail. 120 315
(1-PE)
Alkyl Diketone
O
Hexane-2,5-dione CH3
H3C 5.87E-1 Not Avail. 114 504
(H-2,5-D)
O
Quinone
1,4-benzoquinone O O 9.00E-1 Not Avail. 108 498
(1,4-BQ)
Alkyl Aldehyde
O
Decanal
1.03E-1 6.91E-5 156 351
(DA) H3C H
Phenyl Aldehyde
O
Benzaldehyde
H 1.27 7.09E-4 106 301
13
(BA)

15. Instrument Standards
Compound Structure VPi VPf MWi MWf
IUPAC Name (Abbreviation) mm Hg mm Hg g/mol g/mol
Instrument Standards
F
2,2-difluorobiphenyl
4.65E-2 4.65E-2 190.19 190
(2,2-DFB)
F
Fluorene
3E-3 3E-3 166.22 166.22
(Flu)
Phenanthrene
2.06E-4 2.06E-4 178 178
(Phe)
14

16. DPM Extraction Procedure
Sonication Centrifugation Blowdown/Transfer Derivatization
15

17. Instrumental Analysis (TD-GC/EI-MS and GC/CI-MS)
16

18. Outline
• Background
• Experimental
• Results
• Conclusions
• Future Studies
17

19. Results: Native POCs (underivatized)
Jakober, C.A., et al., Anal. Chem., 2006. 78(14): p. 5086-5093.
18

20. Results: TD-GC/MS Results
% Yield PCI (Scan) B2p12, 15, 16
[using d-PAHs (IS) or phenylethanone oxime (PO) for quantitation]
B2p12 % 120
B2p12 IS
ACN 89.4
DCM 10.2 100 B2p12 PO
MeOH 0.4 B215-1 IS
80 B2p15-1 PO
% recovery
B2p15 B2p15-2 IS
60
ACN 65.9 B2p15-2 PO
DCM 7.3
40 B2p16-1 IS
MeOH 26.8
B2p16-1 PO
20 B2p16-2 IS
B2p16
ACN 65.9 0
B2p16-2 PO
DCM 14.6
e
e
e
e
e
e
m
m
m
m
im
m
xi
i
i
xi
i
MeOH 2.4
ox
ox
x
ox
o
_o
_o
_
_
e_
_
ne
ne
ne
e
ne
on
on
Hexane 17.1
o
o
no
o
di
an
an
n
an
ui
ta
e
ex
ec
h
an
oq
n
et
pe
H
D
ex
nz
yl
yl
en
H
Be
en
Ph
p-
Ph

21. Results: TD-GC/MS Results
% Yield EI (Scan) B2p12, 15, 16
[using d-PAHs (IS) or phenylethanone oxime (PO) for quantitation]
B2p12 % 140
ACN 89.4
120
DCM 10.2 B2p12 IS
MeOH 0.4 100 B2p12 PO
% recovery
B215-1 IS
B2p15 80
ACN 65.9 B2p15-1 PO
60
DCM 7.3 B2p16-1 IS
MeOH 26.8 40
B2p16-1 PO
20
B2p16
ACN 65.9 0
DCM 14.6
e
e
e
e
e
e
m
im
im
m
m
im
xi
xi
xi
MeOH 2.4
ox
ox
ox
_o
_o
_o
e_
e_
_
ne
ne
e
ne
on
on
on
Hexane 17.1
io
no
no
an
an
n
ed
ui
ha
ta
ex
ec
an
oq
n
et
pe
H
D
ex
nz
yl
yl
en
H
Be
en
Ph
p-
Ph
20

22. Pulsed Injection Study
Pulsed injection study
600
500
Relative percent abundance
400 0.5min 1ml/min
0.5min 2ml/min
1min 1ml/min
300
1min 2ml/min
2min 1ml/min
200 2min 2ml/min
100
0
4-FBA-Ox 6-F-4-C-Ox BA-Ox 1-PE-Ox 1-PP-1-O-Ox H-2,5-D-Ox
Oxime Derivative
21

23. Concentration effect of PFBHA using large molar excess
0.5mM 5mM 5:0.5mM
Rsp/pg Rsp/pg Factor
hexan-2-one_oxime 15 83 5
benzaldehyde_oxime 68 210 3
1-phenylethanone_oxime 18 161 9
decanal_oxime 62 165 3
hexane-2,5-dione_oxime 27 109 4
1,4-benzoquinone_oxime 0.4 214 514
22

24. GC/NCI-MS Percent Recovery Results
PFBHA Derivative 25pg at 48h 250pg at 48h
% Rec RSD % Rec RSD
hexan-2-one oxime 99 2.9 101 5.7
2-fluorobenzaldehyde oxime 96 1.9 98 2.9
benzaldehyde oxime 94 2.5 98 4.3
1-phenylethanone oxime 94 2.2 96 3.0
decanal oxime 95 2.2 99 2.8
1-phenylpentan-1-one oxime 92 2.1 96 2.6
5-fluoro-1-indanone oxime 94 2.3 99 3.1
hexane-2,5-dione oxime 91 2.4 96 3.8
1,4-benzoquinone oxime 95 3.8 99 2.9
n=4 replicates using calibration curve samples 1 – 400pg
23

25. TD-GC/EI-MS versus GC/NCI and PCI-MS
TD-GC/EI-MS TD-GC/EI-MS GC/NCI-MS GC/NCI-MS GC/PCI-MS
no blowdown blowndown no blowdown blowndown no blowdown
rsp/pg rsp/pg rsp/pg rsp/pg rsp/pg
min max min max min max min max min max
hexan-2-one-oxime - - 15 105 100 619 9 389 7 20
2-fluorobenzaldehyde-oxime - - 41 163 671 817 118 817 - -
benzaldehyde-oxime - - 14 210 710 1675 168 1675 2 4
1-phenylethanone-oxime - - 15 161 650 1459 158 985 3 4
decanal-oxime - - 27 165 135 513 41 513 3 5
6-fluoro-4-chromanone-oxime - - 4 193 700 1419 193 1027 5 6
hexane-2,5-dione-oxime - - 27 109 62 389 48 299 2 2
1,4-benzoquinone-oxime - - 0.4 281 106 600 107 600 1 6
1,4-napthoquinone (native) 14 - - - - - - - - -
4-fluorobenzophenone (native) 26 - - - - - - - - -
Approximate response/pg injected factors for NCI:EI:PCI ≈ 200:40:1
Liquid injection: 0.1 – 10% sample mass analyzed
TD injection: 100% sample mass analyzed (minus blowdown losses)
24

26. TD-GC/EI-MS versus GC/NCI and PCI-MS
TD-GC/EI-MS GC/NCI-MS GC/PCI-MS
LOD (pg) LOD (pg) LOD (pg)
hexan-2-one_oxime 10 1 51
benzaldehyde_oxime 5 0.3 256
1-phenylethanone_oxime 6 0.5 286
decanal_oxime 6 1 213
6-fluoro-4-chromanone_oxime 5 0.5 159
hexane-2,5-dione_oxime 9 2 423
1,4-benzoquinone_oxime 4 0.8 172
Approximate injection LOD factors for NCI:EI:PCI ≈ 1:10:350
Liquid injection: 0.1 – 10% sample mass analyzed
Thermal desorption injection: 100% sample mass analyzed
(minus blowdown losses)
25

27. Abundance
0.0E+00
2.0E+05
4.0E+05
6.0E+05
8.0E+05
1.0E+06
1.2E+06
7
9
hexan-2-one_oxime, 9.515
11
unknown_oxime_391, 12.819
13
2-fluorobenzaldehyde_oxime, 13.192
benzaldehyde_oxime, 13.335
Time (min)
1-phenylethanone_oxime, 13.631
1,4-benzoquinone_monooxime, 13.873
decanal_oxime, 14.169
5-fluoro-1-indanone_oxime, 14.948
15
6-fluoro-4-chromanone_oxime, 15.343
8-Fluoro-1-benzosuberone, 15.535
hexane-2,5-dione_oxime, 15.739
10ng POCs using acetone quench, EI-MS scan mode, ion 181m/z
17
1,4-benzoquinone_oxime, 17.407
19
Acetone Quench Study (TD-GC/EI-MS)
26

28. Acetone Quench Study (TD-GC/EI-MS)
0.1ng POC using acetone quench, EI-MS scan mode, ion 181m/z
7.0E+06
6.0E+06
5.0E+06
Abundance
4.0E+06
0.1ng AQ
3.0E+06
2.0E+06
1.0E+06
0.0E+00
7 9 11 13 15 17 19
Time (min)
27

29. Acetone Quench Study (TD-GC/EI-MS)
0.5ng POC using acetone quench, EI-MS scan mode, ion 181m/z
7.0E+06
6.0E+06
5.0E+06
Abundance
4.0E+06
0.5ng AQ
3.0E+06
2.0E+06
1.0E+06
0.0E+00
7 9 11 13 15 17 19
Time (min)
28

30. Acetone Quench Study (TD-GC/EI-MS)
2ng POC using acetone quench, EI-MS scan mode, ion 181m/z
7.0E+06
6.0E+06
5.0E+06
Abundance
4.0E+06
2ng AQ
3.0E+06
2.0E+06
1.0E+06
0.0E+00
7 9 11 13 15 17 19
Time (min)
29

31. Abundance
1.0E+06
3.0E+06
5.0E+06
6.0E+06
7.0E+06
0.0E+00
2.0E+06
4.0E+06
7
9
hexan-2-one_oxime, 9.515
11
unknown_oxime_391, 12.819
13
2-fluorobenzaldehyde_oxime, 13.192
benzaldehyde_oxime, 13.335
Time (min)
1-phenylethanone_oxime, 13.631
1,4-benzoquinone_monooxime, 13.873
decanal_oxime, 14.169
5-fluoro-1-indanone_oxime, 14.948
15
6-fluoro-4-chromanone_oxime, 15.343
8-Fluoro-1-benzosuberone, 15.535
hexane-2,5-dione_oxime, 15.739
17
1,4-benzoquinone_oxime, 17.407
10ng POC using acetone quench, EI-MS scan mode, ion 181m/z
19
10ng AQ
Acetone Quench Study (TD-GC/EI-MS)
30

32. Abundance
0.0E+00
2.0E+06
4.0E+06
6.0E+06
1.0E+06
3.0E+06
5.0E+06
7.0E+06
7
9
hexan-2-one_oxime, 9.515
11
unknown_oxime_391, 12.819
13
2-fluorobenzaldehyde_oxime, 13.192
benzaldehyde_oxime, 13.335
Time (min)
1-phenylethanone_oxime, 13.631
1,4-benzoquinone_monooxime, 13.873
decanal_oxime, 14.169
5-fluoro-1-indanone_oxime, 14.948
15
6-fluoro-4-chromanone_oxime, 15.343
8-Fluoro-1-benzosuberone, 15.535
hexane-2,5-dione_oxime, 15.739
17
1,4-benzoquinone_oxime, 17.407
0.1 - 10ng POC using acetone quench, EI-MS scan mode, ion 181m/z
19
2ng AQ
10ng AQ
0.1ng AQ
0.5ng AQ
Acetone Quench Study (TD-GC/EI-MS)
31

33. Acetone Quench Study (TD-GC/EI-MS)
0.1ng POC no acetone quench, EI-MS scan mode, ion 181m/z
7.0E+06
6.0E+06
5.0E+06
Abundance
4.0E+06
0.1ng no AQ
3.0E+06
2.0E+06
1.0E+06
0.0E+00
7 9 11 13 15 17 19
Time (min)
32

34. Acetone Quench Study (TD-GC/EI-MS)
0.5ng POC no acetone quench, EI-MS scan mode, ion 181m/z
7.0E+06
6.0E+06
5.0E+06
Abundance
4.0E+06
0.5ng no AQ
3.0E+06
2.0E+06
1.0E+06
0.0E+00
7 9 11 13 15 17 19
Time (min)
33

35. Acetone Quench Study (TD-GC/EI-MS)
2ng POC no acetone quench, EI-MS scan mode, ion 181m/z
7.0E+06
6.0E+06
5.0E+06
Abundance
4.0E+06
2ng no AQ
3.0E+06
2.0E+06
1.0E+06
0.0E+00
7 9 11 13 15 17 19
Time (min)
34

36. Acetone Quench Study (TD-GC/EI-MS)
10ng POC no acetone quench, EI-MS scan mode, ion 181m/z
7.0E+06
6.0E+06
5.0E+06
Abundance
4.0E+06
10ng no AQ
3.0E+06
2.0E+06
1.0E+06
0.0E+00
7 9 11 13 15 17 19
Time (min)
35

37. Abundance
0.0E+00
2.0E+06
4.0E+06
6.0E+06
1.0E+06
3.0E+06
5.0E+06
7.0E+06
7
9
hexan-2-one_oxime, 9.515
11
unknown_oxime_391, 12.819
13
2-fluorobenzaldehyde_oxime, 13.192
benzaldehyde_oxime, 13.335
Time (min)
1-phenylethanone_oxime, 13.631
1,4-benzoquinone_monooxime, 13.873
decanal_oxime, 14.169
5-fluoro-1-indanone_oxime, 14.948
15
6-fluoro-4-chromanone_oxime, 15.343
8-Fluoro-1-benzosuberone, 15.535
hexane-2,5-dione_oxime, 15.739
17
1,4-benzoquinone_oxime, 17.407
0.1 - 10ng POCs using acetone quench, EI-MS scan mode, ion 181m/z
19
2ng no AQ
10ng no AQ
0.1ng no AQ
0.5ng no AQ
Acetone Quench Study (TD-GC/EI-MS)
36

38. Abundance
0.0E+00
2.0E+06
4.0E+06
6.0E+06
1.0E+06
3.0E+06
5.0E+06
7.0E+06
7
9
hexan-2-one_oxime, 9.515
11
unknown_oxime_391, 12.819
13
2-fluorobenzaldehyde_oxime, 13.192
benzaldehyde_oxime, 13.335
Time (min)
1-phenylethanone_oxime, 13.631
1,4-benzoquinone_monooxime, 13.873
decanal_oxime, 14.169
5-fluoro-1-indanone_oxime, 14.948
15
6-fluoro-4-chromanone_oxime, 15.343
8-Fluoro-1-benzosuberone, 15.535
hexane-2,5-dione_oxime, 15.739
17
1,4-benzoquinone_oxime, 17.407
0.1 - 10ng POC using acetone quench, EI-MS scan mode, ion 181m/z
19
2ng AQ
10ng AQ
0.1ng AQ
0.5ng AQ
Acetone Quench Study (TD-GC/EI-MS)
37

39. Abundance
0.0E+00
1.0E+05
2.0E+05
3.0E+05
4.0E+05
5.0E+04
1.5E+05
2.5E+05
3.5E+05
5
hexan-2-one_oxime, 7.982
10
2-fluorobenzaldehyde_oxime, 11.122
benzaldehyde_oxime, 11.366
1-phenylethanone_oxime, 11.922
decanal_oxime, 12.918
5-fluoro-1-indanone_oxime, 14.263
15
6-fluoro-4-chromanone_oxime, 14.970
hexane-2,5-dione_oxime, 15.781
Time (min)
1,4-benzoquinone_oxime, 18.805
20
NIST DPM (GC/NCI-MS)
25
Calibration curve samples (0.1 - 10ng POC) NCI-MS SIM mode
30
2pg Inj.
10pg Inj.
40pg Inj.
200pg Inj
38

40. Abundance
0.0E+00
1.0E+05
2.0E+05
3.0E+05
4.0E+05
5.0E+04
1.5E+05
2.5E+05
3.5E+05
5
hexan-2-one_oxime, 7.982
10
2-fluorobenzaldehyde_oxime, 11.122
benzaldehyde_oxime, 11.366
1-phenylethanone_oxime, 11.922
decanal_oxime, 12.918
5-fluoro-1-indanone_oxime, 14.263
15
6-fluoro-4-chromanone_oxime, 14.970
hexane-2,5-dione_oxime, 15.781
Time (min)
1,4-benzoquinone_oxime, 18.805
20
NIST DPM (GC/NCI-MS)
25
Calibration curve samples (0.1 - 10ng POC) NCI-MS SIM mode
30
2pg Inj.
10pg Inj.
40pg Inj.
200pg Inj
39

41. NIST DPM (TD-GC/EI-MS)
NIST DPM 0.1mg TD-GC/EI-MS, scan mode and ion 181m/z
1.6E+07
1.4E+07
1.2E+07
1.0E+07
Abundance
8.0E+06
Scan mode
ion 181m/z
6.0E+06
4.0E+06
2.0E+06
0.0E+00
7 12 17 22 27 32
Time (min)
40

42. NIST DPM (GC/PCI-MS)
NIST DPM 0.5mg PCI-MS Scan mode, ions 181 and 155m/z
1.2E+04
1.0E+04
8.0E+03
Abundance
181m/z
6.0E+03
155m/z
4.0E+03
2.0E+03
0.0E+00
5 10 15 20 25 30
Time (min)
41

43. NIST DPM (GC/PCI-MS and GC/NCI-MS)
NIST DPM 0.5mg Scan mode, selected ions using PCI and NCI-MS
R1
1.4E+06
F F
F F R2
benzaldehyde_oxime, 11.366min
1.3E+06 O O NH2
O N
1.2E+06 + F CH2 + H
R1 R2 F CH2
1.1E+06
1-phenylethanone_oxime, 11.922min
hexan-2-one_oxime, 7.892min
1.0E+06
F F
Ketone or F F Fragment Ion
2-fluorobenzaldehyde_oxime, 11.122min
9.0E+05
PCI 181m/z C6F5CH2-
5-fluoro-1-indanone_oxime, 14.263min
Aldehyde PFBHA Oxime (isomers)
6-fluoro-4-chromanone_oxime, 14.970min
Abundance
8.0E+05
NCI 167m/z C6F5- O
7.0E+05 NCI 178m/z Dissociation ion
hexane-2,5-dione_oxime, 15.781min
NCI 181m/z C6F5CH2-
6.0E+05
(H3C)3Si O NCI 197m/z C6F5CH2O-
5.0E+05 F 3C NH2
O
OH N O
decanal_oxime, 12.918
4.0E+05
+ R Si(CH 3)3 +
R F 3C Si(CH 3)3
3.0E+05
F 3C NH
2.0E+05
Carboxylic Acid
1.0E+05
or Alcohol BSTFA Silylated Derivative Si(C
0.0E+00
6 8 10 12 14 16
Time (min)
42

44. DPM POC Characterization
Compound Jakober TD-GC/EI-MS GC/NCI-MS
2mg min max min max
ppmm ng/mg ng/mg ng/mg ng/mg
hexan-2-one 190 4 32 1 551
benzaldehyde 63 23 117 5 921
1-phenylethanone 5 40 95 7 597
decanal 58 1 4 3 106
hexane-2,5-dione 310 0.4 2 1 22
1,4-benzoquinone 460 0.4 1 0 5
Recovery Standard GC/NCI-MS
Ave % rec RSD
2-fluorobenzaldehyde 44 23
5-fluoro-1-indanone 91 33
All compounds analyzed as their oxime.
Jakober, C.A., et al., Anal. Chem., 2006. 78(14): p. 5086-5093.
43

45. BSTFA Derivatization Results
Compound Structure b.p. MWi MWf
# IUPAC Name (Synonms) ºC g/mo g/mo
Decan-1-ol
16 1-Decanol H3C OH
231 158 230
Caprinic alcohol
Aryl Carboxylic Acids
O
Benzoic acid
18 Benzenecarboxylic acid OH 249 122 194
Carboxylbenzene
Alkyl Carboxylic Acids
O
Octanoic acid
21 Caprylic acid 237 144 216
1-Heptanecarboxylic acid H3C OH
Alkyl Dicarboxylic Acids
O
Oxalic acid HO 149
22 Ethanedioic acid OH (sub.)
90 234
O
Compound (retention time) Na2SO4_4h Na2SO4_24h no Na2SO4_3h no Na2SO4_26h
% yield % yield % yield % yield
Decafluorobiphenyl (13.5min) 120 63 27 31
Pyrene (27.9min) 185 102 89 82
Ethanedioic_acid_bis(trimethylsilyl)ester (14.1min) 0 0 0 1
Benzoic_acid_trimethylsilyl_ester (16.5min) 134 77 26 44
Octanoic_acid_trimethylsilyl_ester (16.9min) 136 90 36 44
(Decyloxy)trimethylsilane (18.8min) 49 31 11 23
44

46. BSTFA Derivatization Results
45

47. Outline
• Background
• Experimental
• Results
• Conclusions
• Future Studies
46

48. Conclusions
• Carbonyl compounds using PFBHA:
- Limit of Detection
Jakober 1,4-BQ: 12pg (46 HPLC-APCI-ITMS)
Nielsen 1,4-BQ: <2pg w/out DPM matrix using NCI-MS
- Range of Detection
hexanone to 1,4-benzoquinone
possibly napthoquinone with higher injector temp. (>320°C)
• Hydroxyl compounds using BSTFA:
– Further investigations needed
– Derivatives may be lost with blowdown
– Water may be a concern
• Vehicle Exhaust Particulate Matter:
– TD-GC/EI-MS: ~ 50 – 500ug DPM (100% injection)
– GC/NCI-MS: ~ 50 – 500ug DPM (2% Injection)
– LODs less than 2pg/inj. for all tested compounds
– Potentially utilize TD-GC/NCI-MS for ppbm POCs in DPM samples
Jakober, C.A., et al., Environ. Sci. Technol., 2007. 41(13): p. 4548-4554.
47

49. Outline
• Background
• Experimental
• Results
• Conclusions
• Future Studies
48

50. Future Studies
• Acetone quench study for GC/NCI-MS:
1. Acetone quench with complete blowdown
2. Acetone quench without complete blowdown
3. No acetone quench
• Deactivate glassware to minimize adsorption to
silanol sites
• Distill solvents to remove impurities
• Dr. Sharma utilizing derivatization procedure for
continuing research with DPM toxicity to rat cells.
49