Dan Nielsen

February 19, 2010

Derivatization of Polar Organic Compounds for TD-GC/MS Analysis

0\\sidney\holmengroup\PresentationsByGroup\

Dan’s Presentations\Dreyfus_Final_Presentation.ppt

O

R1 R2

F F

F

F F

CH2

O NH2

+ + OH2

Ketone or

Aldehyde

F F

F

F F

CH2

O N

R1

R2

OximePFBHA

R

OH

Carboxylic Acid

or Alcohol

N

O(H3C)3Si

F3C Si(CH3)3

BSTFA

R

O

Si(CH3)3+

O

NH2F3CO

F3C NH

Si(CH3)3Silylated Derivative

+

CEMS COLLEGE OF Engineering and Mathematical SciencesCEMS COLLEGE OF Engineering and Mathematical SciencesCEMS COLLEGE OF Engineering and Mathematical Sciences

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

Accomplishments

2

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

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

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

Outline

• Background

• Experimental

• Results

• Conclusions

• Future Studies

5

Background

• Vehicle exhaust (150–300ºC) is primarily N2, O2, H2O and CO2.

• Minor constituents are CO, hydrocarbons, NOx and Particulate

Matter (PM).

Maricq, M. Journal of Aerosol Science, 2007, 38, 1079.

• 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.

6

Outline

• Background

• Experimental

• Results

• Conclusions

• Future Studies

7

One-Step Derivatizations

Ho, S.S.H. and J.Z. Yu. Anal. Chem., 2002, 74, 1232.

Forester, C.D., et al. Atmospheric Environment, 2007, 41, 1188.

+

Carboxylic Acid

or Alcohol

+

O

R1 R2

F F

F

F F

CH2

O NH2

+ OH2

Ketone or

Aldehyde

F F

F

F F

CH2

O N

R1

R2

Oxime (isomers)PFBHA

R

OH N

O(H3C)3Si

F3C Si(CH3)3

BSTFA

R

O

Si(CH3)3

O

NH2F3CO

F3C NH

Si(CH3)3Silylated Derivative

+

8

Two-Step Derivatization

Ortiz, R., et al. Atmospheric Research, 2006, 82, 709.

9

O

R1

OH

F F

F

F F

CH2

O NH2

+ + OH2

Multifunctional

Compound

F F

F

F F

CH2

O N

R1

O Si(CH3)3

Oxime (isomers)PFBHA

Oxime Derivative with Alcohol Group

N

O(H3C)3Si

F3C Si(CH3)3

BSTFA Two-Step Oxime Silylated Derivative

+

F F

F

F F

CH2

O N

R1

OH

F F

F

F F

CH2

O N

R1

OH

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

Recovery/Quantification Internal Standards

12

Compound Structure VPi VPf MWi MWf

IUPAC Name (Abbreviation) mm Hg mm Hg g/mol g/mol

Recovery Standards

1,2,3,4,5,6,7,8-

octadeuterionaphthalene

(Nap-d8)1.59E-1 1.59E-1 136 136

1,1,2,2,3,4,5,6,7,8-

decadeuterioacenaphthene

(Ace-d10)6.98E-3 6.98E-3 164 164

1,2,3,4,5,6,7,8,9,10-

decadeuteriophenanthrene

(Phe-d10)2.06E-4 2.06E-4 188 188

1,2,3,4,5,6,7,8,9,10,11,12-

dodecadeuteriochrysene

(Chr-d12)8.5E-8 8.5E-8 240 240

1,2,3,4,5,6,7,8,9,10,11,12-

dodecadeuterioperylene

(Per-d12)1.81E-8 1.81E-8 264 264

Quantification Standards

2-fluorobenzaldehyde

(2-FBA)1.16 Not Avail. 124.11 319

6-fluoro-4-chromanone

(6-F-4-C)3.47E-3 Not Avail. 166.15 361

5-fluoro-1-indanone

(5-F-1-I)2.63E-02 Not Avail. 150.15 345

O

O

F

O

O

F

O

F

D

D

D

D D

D

D

D

D

D

D

D

D

D

DD

D

D

D

D

D D D D

D

D

DD

D

D D

D

D

D

D

DD

D

D

D

D

D D D D

D

D

D D D D

D

PFBHA Reactive POC Surrogates

13

Compound Structure VPi VPf MWi MWf

IUPAC Name (Abbreviation) mm Hg mm Hg g/mol g/mol

Alkyl Ketone

Hexan-2-one

(H-2-O) 1.16E1 5.36E-3 100 295

Aryl Ketone

1-phenylethanone

(1-PE) 3.97E-1 Not Avail. 120 315

Alkyl Diketone

Hexane-2,5-dione

(H-2,5-D) 5.87E-1 Not Avail. 114 504

Quinone

1,4-benzoquinone

(1,4-BQ)9.00E-1 Not Avail. 108 498

Alkyl Aldehyde

Decanal

(DA)1.03E-1 6.91E-5 156 351

Phenyl Aldehyde

Benzaldehyde

(BA)1.27 7.09E-4 106 301

CH3 CH3

O

CH3

O

CH3

CH3

O

O

OO

H

O

CH3

O

H

Instrument Standards

14

Compound Structure VPi VPf MWi MWf

IUPAC Name (Abbreviation) mm Hg mm Hg g/mol g/mol

Instrument Standards

2,2-difluorobiphenyl

(2,2-DFB)4.65E-2 4.65E-2 190.19 190

Fluorene

(Flu)3E-3 3E-3 166.22 166.22

Phenanthrene

(Phe)2.06E-4 2.06E-4 178 178

F

F

DPM Extraction Procedure

15

Sonication Centrifugation Blowdown/Transfer Derivatization

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

16

Outline

• Background

• Experimental

• Results

• Conclusions

• Future Studies

17

Results: Native POCs (underivatized)

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

Results: TD-GC/MS Results

B2p12 %

ACN 89.4

DCM 10.2

MeOH 0.4

B2p15

ACN 65.9

DCM 7.3

MeOH 26.8

B2p16

ACN 65.9

DCM 14.6

MeOH 2.4

Hexane 17.1

% Yield PCI (Scan) B2p12, 15, 16 [using d-PAHs (IS) or phenylethanone oxime (PO) for quantitation]

0

20

40

60

80

100

120

Hex

anon

e_ox

ime

Phe

nyleth

anon

e_ox

ime

Dec

anon

e_ox

ime

Phe

nylpen

tano

ne_o

xim

e

Hex

aned

ione

_oxim

e

p-Ben

zoqu

inon

e_ox

ime

% r

ec

ov

ery

B2p12 IS

B2p12 PO

B215-1 IS

B2p15-1 PO

B2p15-2 IS

B2p15-2 PO

B2p16-1 IS

B2p16-1 PO

B2p16-2 IS

B2p16-2 PO

Results: TD-GC/MS Results

20

B2p12 %

ACN 89.4

DCM 10.2

MeOH 0.4

B2p15

ACN 65.9

DCM 7.3

MeOH 26.8

B2p16

ACN 65.9

DCM 14.6

MeOH 2.4

Hexane 17.1

% Yield EI (Scan) B2p12, 15, 16 [using d-PAHs (IS) or phenylethanone oxime (PO) for quantitation]

0

20

40

60

80

100

120

140

Hex

anon

e_ox

ime

Phe

nyleth

anon

e_ox

ime

Dec

anon

e_ox

ime

Phe

nylpen

tano

ne_o

xim

e

Hex

aned

ione

_oxim

e

p-Ben

zoqu

inon

e_ox

ime

% r

eco

very

B2p12 IS

B2p12 PO

B215-1 IS

B2p15-1 PO

B2p16-1 IS

B2p16-1 PO

Pulsed Injection Study

21

Pulsed injection study

0

100

200

300

400

500

600

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

Rela

tive p

erc

en

t ab

un

dan

ce

0.5min 1ml/min

0.5min 2ml/min

1min 1ml/min

1min 2ml/min

2min 1ml/min

2min 2ml/min

Concentration effect of PFBHA using large molar excess

22

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

GC/NCI-MS Percent Recovery Results

23

PFBHA Derivative

% 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

25pg at 48h 250pg at 48h

n=4 replicates using calibration curve samples 1 – 400pg

TD-GC/EI-MS versus GC/NCI and PCI-MS

24

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)

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 - - - - - - - - -

no blowdownblowndownno blowdownblowndownno blowdown

rsp/pg rsp/pg rsp/pg rsp/pg rsp/pg

TD-GC/EI-MS TD-GC/EI-MS GC/NCI-MS GC/NCI-MS GC/PCI-MS

TD-GC/EI-MS versus GC/NCI and PCI-MS

25

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)

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

Acetone Quench Study (TD-GC/EI-MS)

26

he

xan

-2-o

ne

_o

xim

e, 9

.51

5

un

kno

wn

_o

xim

e_

39

1, 1

2.8

19

2-f

luo

rob

en

zald

eh

yde

_o

xim

e, 1

3.1

92

be

nza

lde

hyd

e_

oxi

me

, 13

.33

5

1-p

he

nyl

eth

ano

ne

_o

xim

e, 1

3.6

31

1,4

-be

nzo

qu

ino

ne

_m

on

oo

xim

e, 1

3.8

73

de

can

al_

oxi

me

, 14

.16

9

5-f

luo

ro-1

-in

dan

on

e_

oxi

me

, 14

.94

8

6-f

luo

ro-4

-ch

rom

ano

ne

_o

xim

e, 1

5.3

43

8-F

luo

ro-1

-be

nzo

sub

ero

ne

, 15

.53

5 he

xan

e-2

,5-d

ion

e_

oxi

me

, 15

.73

9

1,4

-be

nzo

qu

ino

ne

_o

xim

e, 1

7.4

07

0.0E+00

2.0E+05

4.0E+05

6.0E+05

8.0E+05

1.0E+06

1.2E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

10ng POCs using acetone quench, EI-MS scan mode, ion 181m/z

Acetone Quench Study (TD-GC/EI-MS)

27

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

0.1ng POC using acetone quench, EI-MS scan mode, ion 181m/z

0.1ng AQ

Acetone Quench Study (TD-GC/EI-MS)

28

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

0.5ng POC using acetone quench, EI-MS scan mode, ion 181m/z

0.5ng AQ

Acetone Quench Study (TD-GC/EI-MS)

29

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

2ng POC using acetone quench, EI-MS scan mode, ion 181m/z

2ng AQ

Acetone Quench Study (TD-GC/EI-MS)

30

he

xan

-2-o

ne

_o

xim

e, 9

.51

5

un

kno

wn

_o

xim

e_

39

1, 1

2.8

19

2-f

luo

rob

en

zald

eh

yde

_o

xim

e, 1

3.1

92

be

nza

lde

hyd

e_

oxi

me

, 13

.33

5

1-p

he

nyl

eth

ano

ne

_o

xim

e, 1

3.6

31

1,4

-be

nzo

qu

ino

ne

_m

on

oo

xim

e, 1

3.8

73

de

can

al_

oxi

me

, 14

.16

9

5-f

luo

ro-1

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dan

on

e_

oxi

me

, 14

.94

8

6-f

luo

ro-4

-ch

rom

ano

ne

_o

xim

e, 1

5.3

43

8-F

luo

ro-1

-be

nzo

sub

ero

ne

, 15

.53

5h

exa

ne

-2,5

-dio

ne

_o

xim

e, 1

5.7

39

1,4

-be

nzo

qu

ino

ne

_o

xim

e, 1

7.4

07

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

10ng POC using acetone quench, EI-MS scan mode, ion 181m/z

10ng AQ

Acetone Quench Study (TD-GC/EI-MS)

31

he

xan

-2-o

ne

_o

xim

e, 9

.51

5

un

kno

wn

_o

xim

e_

39

1, 1

2.8

19

2-f

luo

rob

en

zald

eh

yde

_o

xim

e, 1

3.1

92

be

nza

lde

hyd

e_

oxi

me

, 13

.33

5

1-p

he

nyl

eth

ano

ne

_o

xim

e, 1

3.6

31

1,4

-be

nzo

qu

ino

ne

_m

on

oo

xim

e, 1

3.8

73

de

can

al_

oxi

me

, 14

.16

9

5-f

luo

ro-1

-in

dan

on

e_

oxi

me

, 14

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8

6-f

luo

ro-4

-ch

rom

ano

ne

_o

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e, 1

5.3

43

8-F

luo

ro-1

-be

nzo

sub

ero

ne

, 15

.53

5h

exa

ne

-2,5

-dio

ne

_o

xim

e, 1

5.7

39

1,4

-be

nzo

qu

ino

ne

_o

xim

e, 1

7.4

07

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

0.1 - 10ng POC using acetone quench, EI-MS scan mode, ion 181m/z

10ng AQ

2ng AQ

0.5ng AQ

0.1ng AQ

Acetone Quench Study (TD-GC/EI-MS)

32

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

0.1ng POC no acetone quench, EI-MS scan mode, ion 181m/z

0.1ng no AQ

Acetone Quench Study (TD-GC/EI-MS)

33

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

0.5ng POC no acetone quench, EI-MS scan mode, ion 181m/z

0.5ng no AQ

Acetone Quench Study (TD-GC/EI-MS)

34

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

2ng POC no acetone quench, EI-MS scan mode, ion 181m/z

2ng no AQ

Acetone Quench Study (TD-GC/EI-MS)

35

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

10ng POC no acetone quench, EI-MS scan mode, ion 181m/z

10ng no AQ

Acetone Quench Study (TD-GC/EI-MS)

36

he

xan

-2-o

ne

_o

xim

e, 9

.51

5

un

kno

wn

_o

xim

e_

39

1, 1

2.8

19

2-f

luo

rob

en

zald

eh

yde

_o

xim

e, 1

3.1

92

be

nza

lde

hyd

e_

oxi

me

, 13

.33

5

1-p

he

nyl

eth

ano

ne

_o

xim

e, 1

3.6

31

1,4

-be

nzo

qu

ino

ne

_m

on

oo

xim

e, 1

3.8

73

de

can

al_

oxi

me

, 14

.16

9

5-f

luo

ro-1

-in

dan

on

e_

oxi

me

, 14

.94

8

6-f

luo

ro-4

-ch

rom

ano

ne

_o

xim

e, 1

5.3

43

8-F

luo

ro-1

-be

nzo

sub

ero

ne

, 15

.53

5h

exa

ne

-2,5

-dio

ne

_o

xim

e, 1

5.7

39

1,4

-be

nzo

qu

ino

ne

_o

xim

e, 1

7.4

07

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

0.1 - 10ng POCs using acetone quench, EI-MS scan mode, ion 181m/z

10ng no AQ

2ng no AQ

0.5ng no AQ

0.1ng no AQ

Acetone Quench Study (TD-GC/EI-MS)

37

he

xan

-2-o

ne

_o

xim

e, 9

.51

5

un

kno

wn

_o

xim

e_

39

1, 1

2.8

19

2-f

luo

rob

en

zald

eh

yde

_o

xim

e, 1

3.1

92

be

nza

lde

hyd

e_

oxi

me

, 13

.33

5

1-p

he

nyl

eth

ano

ne

_o

xim

e, 1

3.6

31

1,4

-be

nzo

qu

ino

ne

_m

on

oo

xim

e, 1

3.8

73

de

can

al_

oxi

me

, 14

.16

9

5-f

luo

ro-1

-in

dan

on

e_

oxi

me

, 14

.94

8

6-f

luo

ro-4

-ch

rom

ano

ne

_o

xim

e, 1

5.3

43

8-F

luo

ro-1

-be

nzo

sub

ero

ne

, 15

.53

5h

exa

ne

-2,5

-dio

ne

_o

xim

e, 1

5.7

39

1,4

-be

nzo

qu

ino

ne

_o

xim

e, 1

7.4

07

0.0E+00

1.0E+06

2.0E+06

3.0E+06

4.0E+06

5.0E+06

6.0E+06

7.0E+06

7 9 11 13 15 17 19

Ab

un

dan

ce

Time (min)

0.1 - 10ng POC using acetone quench, EI-MS scan mode, ion 181m/z

10ng AQ

2ng AQ

0.5ng AQ

0.1ng AQ

NIST DPM (GC/NCI-MS)

38

hexa

n-2

-one

_ox

ime,

7.9

82

ben

zald

ehyd

e_ox

ime,

11.

366

1-p

heny

leth

anon

e_o

xim

e, 1

1.92

2

de

can

al_

oxi

me

, 12

.91

8

hex

ane-

2,5

-dio

ne_

oxi

me,

15

.78

1

1,4

-ben

zoq

uin

on

e_o

xim

e, 1

8.8

05

5-fl

uoro

-1-i

ndan

one_

oxi

me,

14.

263

2-f

luor

oben

zald

ehyd

e_ox

ime,

11.

122

6-f

luor

o-4

-chr

oman

one_

oxim

e, 1

4.97

0

0.0E+00

5.0E+04

1.0E+05

1.5E+05

2.0E+05

2.5E+05

3.0E+05

3.5E+05

4.0E+05

5 10 15 20 25 30

Ab

un

dan

ce

Time (min)

Calibration curve samples (0.1 - 10ng POC) NCI-MS SIM mode

200pg Inj

40pg Inj.

10pg Inj.

2pg Inj.

NIST DPM (GC/NCI-MS)

39

hexa

n-2

-one

_ox

ime,

7.9

82

ben

zald

ehyd

e_ox

ime,

11.

366

1-p

heny

leth

anon

e_o

xim

e, 1

1.92

2

de

can

al_

oxi

me

, 12

.91

8

hex

ane-

2,5

-dio

ne_

oxi

me,

15

.78

1

1,4

-ben

zoq

uin

on

e_o

xim

e, 1

8.8

05

5-fl

uoro

-1-i

ndan

one_

oxi

me,

14.

263

2-f

luor

oben

zald

ehyd

e_ox

ime,

11.

122

6-f

luor

o-4

-chr

oman

one_

oxim

e, 1

4.97

0

0.0E+00

5.0E+04

1.0E+05

1.5E+05

2.0E+05

2.5E+05

3.0E+05

3.5E+05

4.0E+05

5 10 15 20 25 30

Ab

un

dan

ce

Time (min)

Calibration curve samples (0.1 - 10ng POC) NCI-MS SIM mode

200pg Inj

40pg Inj.

10pg Inj.

2pg Inj.

NIST DPM (TD-GC/EI-MS)

40

0.0E+00

2.0E+06

4.0E+06

6.0E+06

8.0E+06

1.0E+07

1.2E+07

1.4E+07

1.6E+07

7 12 17 22 27 32

Ab

un

dan

ce

Time (min)

NIST DPM 0.1mg TD-GC/EI-MS, scan mode and ion 181m/z

Scan mode

ion 181m/z

NIST DPM (GC/PCI-MS)

41

0.0E+00

2.0E+03

4.0E+03

6.0E+03

8.0E+03

1.0E+04

1.2E+04

5 10 15 20 25 30

Ab

un

dan

ce

Time (min)

NIST DPM 0.5mg PCI-MS Scan mode, ions 181 and 155m/z

181m/z

155m/z

hex

an-2

-on

e_o

xim

e, 7

.89

2m

in

ben

zald

ehyd

e_ox

ime,

11.

366m

in

6-fl

uoro

-4-c

hrom

anon

e_ox

ime,

14.

970m

in

hexa

ne-2

,5-d

ione

_ox

ime,

15.

781m

in

1-ph

enyl

etha

none

_ox

ime,

11.

922m

in

deca

nal_

oxim

e, 1

2.91

8

5-fl

uo

ro-1

-in

da

no

ne

_o

xim

e, 1

4.2

63

min

2-fl

uo

rob

enza

ldeh

yde_

oxi

me,

11

.12

2m

in

0.0E+00

1.0E+05

2.0E+05

3.0E+05

4.0E+05

5.0E+05

6.0E+05

7.0E+05

8.0E+05

9.0E+05

1.0E+06

1.1E+06

1.2E+06

1.3E+06

1.4E+06

6 8 10 12 14 16

Ab

un

dan

ce

Time (min)

NIST DPM 0.5mg Scan mode, selected ions using PCI and NCI-MS

PCI 181m/z

NCI 167m/z

NCI 178m/z

NCI 181m/z

NCI 197m/z

NIST DPM (GC/PCI-MS and GC/NCI-MS)

42

+

Carboxylic Acid

or Alcohol

+

O

R1 R2

F F

F

F F

CH2

O NH2

+ OH2

Ketone or

Aldehyde

F F

F

F F

CH2

O N

R1

R2

Oxime (isomers)PFBHA

R

OH N

O(H3C)3Si

F3C Si(CH3)3

BSTFA

R

O

Si(CH3)3

O

NH2F3CO

F3C NH

Si(CH3)3Silylated Derivative

+

C6F5CH2-

Fragment Ion

C6F5CH2O-

C6F5CH2-

C6F5-

Dissociation ion

DPM POC Characterization

43Jakober, C.A., et al., Anal. Chem., 2006. 78(14): p. 5086-5093.

Recovery Standard

Ave % rec RSD

2-fluorobenzaldehyde 44 23

5-fluoro-1-indanone 91 33

GC/NCI-MS

All compounds analyzed as their oxime.

Compound Jakober

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

GC/NCI-MSTD-GC/EI-MS

BSTFA Derivatization Results

Compound Structure b.p. MWi MWf

# IUPAC Name (Synonms) ºC g/mo g/mo

16Decan-1-ol 1-Decanol

Caprinic alcohol

231 158 230

Aryl Carboxylic Acids

18Benzoic acid Benzenecarboxylic acid

Carboxylbenzene

249 122 194

Alkyl Carboxylic Acids

21Octanoic acid Caprylic acid

1-Heptanecarboxylic acid

237 144 216

Alkyl Dicarboxylic Acids

22Oxalic acid Ethanedioic acid

149 (sub.)

90 234

O

OH

OH

O

CH3

O

OH

O

OH

OHCH3

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

BSTFA Derivatization Results

45

Outline

• Background

• Experimental

• Results

• Conclusions

• Future Studies

46

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

47

Jakober, C.A., et al., Environ. Sci. Technol., 2007. 41(13): p. 4548-4554.

Outline

• Background

• Experimental

• Results

• Conclusions

• Future Studies

48

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