ASMS 2014 poster final
1
Standard mixture is composed of: 2-methyl furan, Furfuryl Alcohol, Shikimic Acid, Vanillic Acid, P-Cresol, 3,5-dimethoxy toluene, Eugenol, 5- (hydroxymethel) furfural, Syringol, Apocynin, Levoglucosan, Syringaldehyde, Acetosyringone, Coniferyl Aldehyde, Pyrene • Pyrolysis of lignocellulosic biomass has shown promise as an alternative energy source to fossil fuels. • Comprehensive characterization of biomass pyrolyzates is critical for producing high quality biofuels. • Traditional GC-EI-MS has many limitations, especially in identifying the compounds that are not in the database. • Dopant assisted atmospheric pressure chemical ionization (dAPCI) coupled to GC-TOFMS is a complementary tool; however, structural information is limited. Exploring Structural Information using In-source CID on Micropyrolyzer-GC-dAPCI-TOF Mass Spectrometry Nathan R. Bond 1 ; Daniel P. Cole 1 ; Carolyn P. Hutchinson 1 ; Young Jin Lee 1 1 Department of Chemistry, Iowa State University, Ames, IA Overview Results • To explore the use of in-source CID for structural analysis of biomass pyrolyzates in Py-GC-dAPCI-TOFMS. Instrumentation Materials • Standards are obtained from Sigma Aldrich (see first chromatograph) • Standard mix is prepared at 1 mM per compound with 5 μL injection. Methods • Red oak pyrolysis: 500° C on Frontier micropyrolyzer. • GC programing: Oven temp. held at 35 ° for 5 min, increased at 4 ° per min to 260 ° , and held for 5 min. • Standard condition: Fragmenter -95V, Skimmer -65V • Fragmentation conditions: Fragmenter -160V, Skimmer -145V Experimental Conclusions Autosampler or micropyrolyzer TOF MS Agilent 6200 series Ammonia gas APCI interface GC DB-1701 column (J& W, 30 m x 0.25 mm x 0.25 μm) • Understanding MS/MS of standard compounds allows to interpret fragmentation pattern of unknowns. • Most ammonium adducts are resulted in the loss of ion signals in fragmentation condition. Thus, it is not effective for levoglucosan or other cellulose pyrolysis products. Acknowledgements Future Direction • Test tentative identifications against standards • Run replicate experiment • Study the effect of changing other parameters • Examine other standard compounds to observe fragmentation patterns 6 x10 0 0. 0. 0. 0. 0. 0. 0. 0. 0. 1 +APCI TIC Scan Frag=95.0V 01_1mM std mix_5ul ALS_GCsep.d 1 Counts vs. Acquisition Time (min) 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 Acetosyringone (RT:46.5 min) Syringaldehyde (RT:44.7 min) 3,5-dimethoxytoluene (RT:29.3 min) Coniferyl Aldehyde (RT:47.35 min) Unknown at 44.8 min.(Syringaldehyde) Unknown at 40.5 min (3,5-dimethoxyphenone) Unknown at 32.4 min (4-hydroxy-3-methoxystyrene) Unknown at 36.4 min (2-methoxy-4-propenylphenol) 5 x10 0 1 1 2 2 3 3 4 4 5 5 +APCI TIC Scan Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d 1 Counts vs. Acquisition Time (min) 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 197.0756 213.0944 207.0301 190 195 200 205 210 215 220 183.0608 199.0793 208.0378 175.0495 4 160 165 170 175 180 185 190 195 200 205 210 215 220 225 4 x10 0 0. 0. 0. 0. 0. 0. 0. 0. 0. 1 1. 1. 1. 1. 1. 1. 1. 1. 1. 2 2. +APCI Scan (46.291-46.658 min, 520 Scans) Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d Subtract 181.0480 196.0715 140.0459 155.0689 125.0224 108.0200 167 0322 Counts vs. Mass-to-Charge (m/z) 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 6 x10 0 0 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 +APCI TIC Scan Frag=95.0V 04_py_3rods_redoak_nonacid_infused_GC sep_frag95V_skimmer65V.d 1 Counts vs. Acquisition Time (min) 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 6 x10 0 0 0 0 1 1 1 1 2 2 2 2 3 3 3 3 4 4 4 +APCI TIC Scan Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d 1 Counts vs. Acquisition Time (min) 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 Micropyrolyzer-GC-dAPCI- TOFMS CID 153.0874 0980 160 1653 45 150 155 160 3 x10 0 0. 0. 0. 0. 1 1. 1. 1. 1. 2 2. 2. 2. 2. 3 3. 3. +APCI Scan (29.241-29.365 min, 176 Scans) Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d Subtract (2) 153.0894 138.0661 123.0789 109.0637 Counts vs. Mass-to-Charge (m/z) 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 179.0656 195.0844 213 170 0766 170 175 180 185 190 195 200 205 210 2 3 x10 0 0 0 0 0 1 1 1 1 1 2 2 2 2 2 +APCI Scan (46.861-47.762 min, 1274 Scans) Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d Subtract 179.0689 147.0429 161.0584 119.0484 107.0487 135.0431 124.0508 Counts vs. Mass-to-Charge (m/z) 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 180.0758 198.1097 167 0658 208 0345 170 175 180 185 190 195 200 205 210 4 x10 0 0. 1 1. 2 2. 3 3. 4 4. +APCI Scan (40.412-40.674 min, 372 Scans) Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d Subtract 180.0757 165.0525 137.0580 121.0636 149.0580 105.0439 115.0383 197.0769 129 0508 207 0974 Counts vs. Mass-to-Charge (m/z) 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210 151.0732 158.0793 146.0791 45 150 155 160 4 x10 0 0 0 0 0 1 1 1 1 1 2 +APCI Scan (32.281-32.478 min, 280 Scans) Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d Subtract 151.0735 135.0428 107.0485 119.0482 140.0452 166.0443 115.0384 Counts vs. Mass-to-Charge (m/z) 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 NRB acknowledges Alice & Donald Hudson Scholarship to support undergraduate research and Professor Emeritus Robert Angelici to support the travel to attend the 2014 American Society for Mass Spectrometry Conference. 3 x10 0 0. 0. 0. 0. 1 1. 1. 1. 1. 2 2. 2. +APCI Scan (44.611-44.886 min, 390 Scans) Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d Subtract 182.0557 123.0431 167.0324 140.0453 155.0687 111.0434 Counts vs. Mass-to-Charge (m/z) 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 CID CID CID CID CID CID [MH] + [M . NH 3 ]+ . [MH] + [MH] + [MH] + ~ -C3H2O -C4H8O -C4H8O2 -C2H4O -C 2 H 2 O -C 3 H 2 O M+ . M+ . ~ [MH] + [MH] + -H2O 150.0661 -C3H4O2 -C3H2O -CHO C 9 H 10 O 2 -C 2 H 4 O -CH 4 -C2H3O2 -CH 4 O -CH3O -C2H3O -CH3 C 10 H 12 O 3 Purpose Overview GC-TIC Chromatograms MS and MS/MS spectra of selected compounds Standard mix without fragmentation Standard mix with fragmentation Pyrolysis of red oak without fragmentation Pyrolysis of red oak with fragmentation M +. [MNH 4 ] + [MNH 4 ] + [M . NH 3 ]+ . M +. [MNH 4 ] + [M . NH 3 ]+ . M +. 4 x10 0 0 0 0 0 1 1 1 1 1 2 2 +APCI Scan (44.727-44.940 min, 301 Scans) Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d Subtract 182.0538 105.0442 123.0429 140.0451 155.0683 167.0316 111.0431 131.0476 151.0730 115.0389 163.0727 Counts vs. Mass-to-Charge (m/z) 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 183.0617 200.0881 9 0471 70 175 180 185 190 195 200 205 21 M +. M +. [MH] + [M . NH 3 ]+ . [MNH 4 ] + M +. M +. [MH] + -C 2 H 2 O -C 3 H 2 O M +. [MH] + -C 2 H 4 O2 -CH 4 -CO Acetosyringone Syringaldehyde Coniferyl Aldehyde 3,5-dimethoxytoluene immer65V.d Subtract 164.0811 182.1151 0738 172.0945 188 0 155 160 165 170 175 180 185 19 4 x10 0 0 0 0 0 1 1 1 1 1 2 2 2 2 +APCI Scan (36.295-36.429 min, 190 Scans) Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d Subtract 164.0814 149.0580 105.0675 137.0583 133.0634 121.0637 115.0390 Counts vs. Mass-to-Charge (m/z) 102 104 106 108 110 112 114 116 118 120 122 124 126 128 130 132 134 136 138 140 142 144 146 148 150 152 154 156 158 160 162 164 166 168 M +. [MH] + [MNH 4 ] + -CH 4 -CH 4 O -C 2 H 4 -C 2 H 4 O2 -C 2 H 4 O M +. M +. C 10 H 12 O 2 44.8 36.4 40.5 32.4 3 Pyrene P-Cresol Levoglucosan 1 9, 10 2 4 Compounds listed numerically: Lactic Acid, 2-Butonic Acid, 2,5-Dimethyl-3-methylene P-dioxane, 3-Oxobutanoic Acid, 2-(5H) Furanone, a-Methyl furan, Furfural, p-/o-dioxanone, 2-propenoic Acid, Ethyl ester, 5-Methyl 2(3H)-furanone, Vanillic Acid, Levoglucosane Compounds listed numerically: 5-methoxy-2-furoic Acid, Maltol, Syringol, Vanillyl methylcetone, Ethyl vanillylether, Acetosyringone, Phenol, Methyl 10-hydroxydec-trans-8-ene-4,6-diynoate 12 5 6 11 7,8 13 1 1 3 3 2 2 4 6 4 7 7 6 8 8 5 5
-
Upload
nathan-bond -
Category
Documents
-
view
16 -
download
0
Transcript of ASMS 2014 poster final
Standard mixture is composed of: 2-methyl furan, Furfuryl Alcohol, Shikimic Acid, Vanillic Acid, P-Cresol, 3,5-dimethoxy toluene, Eugenol, 5-
(hydroxymethel) furfural, Syringol, Apocynin, Levoglucosan, Syringaldehyde, Acetosyringone, Coniferyl Aldehyde, Pyrene
• Pyrolysis of lignocellulosic biomass has shown promise as an alternative energy source to fossil fuels.
• Comprehensive characterization of biomass pyrolyzates is critical for producing high quality biofuels.
• Traditional GC-EI-MS has many limitations, especially in identifying the compounds that are not in the database.
• Dopant assisted atmospheric pressure chemical ionization (dAPCI) coupled to GC-TOFMS is a complementary tool; however, structural information is limited.
Exploring Structural Information using In-source CID on Micropyrolyzer-GC-dAPCI-TOF Mass Spectrometry
Nathan R. Bond1; Daniel P. Cole1; Carolyn P. Hutchinson1; Young Jin Lee1 1 Department of Chemistry, Iowa State University, Ames, IA
Overview Results
• To explore the use of in-source CID for structural analysis of biomass pyrolyzates in Py-GC-dAPCI-TOFMS.
Instrumentation
Materials • Standards are obtained from Sigma Aldrich (see first chromatograph) • Standard mix is prepared at 1 mM per compound with 5 μL injection. Methods • Red oak pyrolysis: 500°C on Frontier micropyrolyzer. • GC programing: Oven temp. held at 35° for 5 min, increased at
4° per min to 260°, and held for 5 min. • Standard condition: Fragmenter -95V, Skimmer -65V • Fragmentation conditions: Fragmenter -160V, Skimmer -145V
Experimental
Conclusions
Autosampler or micropyrolyzer
TOF MS Agilent 6200
series
Ammonia gas
APCI interface
GC
DB-1701 column (J& W, 30 m x 0.25 mm x 0.25 μm)
• Understanding MS/MS of standard compounds allows to interpret fragmentation pattern of unknowns.
• Most ammonium adducts are resulted in the loss of ion signals in fragmentation condition. Thus, it is not effective for levoglucosan or other cellulose pyrolysis products.
Acknowledgements Future Direction
• Test tentative identifications against standards • Run replicate experiment • Study the effect of changing other parameters • Examine other standard compounds to observe
fragmentation patterns
6x10
0
0.
0.
0.
0.
0.
0.
0.
0.
0.
1
+APCI TIC Scan Frag=95.0V 01_1mM std mix_5ul ALS_GCsep.d
1
Counts vs. Acquisition Time (min)
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56
Acetosyringone (RT:46.5 min) Syringaldehyde (RT:44.7 min)
3,5-dimethoxytoluene (RT:29.3 min) Coniferyl Aldehyde (RT:47.35 min)
Unknown at 44.8 min.(Syringaldehyde) Unknown at 40.5 min (3,5-dimethoxyphenone)
Unknown at 32.4 min (4-hydroxy-3-methoxystyrene) Unknown at 36.4 min (2-methoxy-4-propenylphenol)
5x10
0
1
1
2
2
3
3
4
4
5
5
+APCI TIC Scan Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d
1
Counts vs. Acquisition Time (min)
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56
197.0756
213.0944
207.0301
190 195 200 205 210 215 220
183.0608
199.0793
208.0378175.0495
4
160 165 170 175 180 185 190 195 200 205 210 215 220 225
4x10
0
0.
0.
0.
0.
0.
0.
0.
0.
0.
1
1.
1.
1.
1.
1.
1.
1.
1.
1.
2
2.
+APCI Scan (46.291-46.658 min, 520 Scans) Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d Subtract
181.0480
196.0715140.0459
155.0689125.0224108.0200
167 0322
Counts vs. Mass-to-Charge (m/z)
100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200
6x10
0
0
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8
+APCI TIC Scan Frag=95.0V 04_py_3rods_redoak_nonacid_infused_GC sep_frag95V_skimmer65V.d
1
Counts vs. Acquisition Time (min)
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
6x10
0
0
0
0
1
1
1
1
2
2
2
2
3
3
3
3
4
4
4
+APCI TIC Scan Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d
1
Counts vs. Acquisition Time (min)
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
Micropyrolyzer-GC-dAPCI-
TOFMS
CID
153.0874
0980 160 1653
45 150 155 160
3x10
0
0.
0.
0.
0.
1
1.
1.
1.
1.
2
2.
2.
2.
2.
3
3.
3.
+APCI Scan (29.241-29.365 min, 176 Scans) Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d Subtract (2)
153.0894
138.0661123.0789
109.0637
Counts vs. Mass-to-Charge (m/z)
85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165
179.0656
195.0844
213170 0766
170 175 180 185 190 195 200 205 210 2
3x10
0
0
0
0
0
1
1
1
1
1
2
2
2
2
2
+APCI Scan (46.861-47.762 min, 1274 Scans) Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d Subtract
179.0689
147.0429
161.0584119.0484
107.0487 135.0431
124.0508
Counts vs. Mass-to-Charge (m/z)
85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190
180.0758
198.1097
167 0658 208 0345
170 175 180 185 190 195 200 205 210
4x10
0
0.
1
1.
2
2.
3
3.
4
4.
+APCI Scan (40.412-40.674 min, 372 Scans) Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d Subtract
180.0757
165.0525
137.0580
121.0636
149.0580105.0439
115.0383 197.0769129 0508 207 0974
Counts vs. Mass-to-Charge (m/z)
80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210
151.0732
158.0793
146.0791
45 150 155 160
4x10
0
0
0
0
0
1
1
1
1
1
2
+APCI Scan (32.281-32.478 min, 280 Scans) Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d Subtract
151.0735
135.0428
107.0485
119.0482
140.0452
166.0443115.0384
Counts vs. Mass-to-Charge (m/z)
80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180
NRB acknowledges Alice & Donald Hudson Scholarship to support undergraduate research and Professor Emeritus Robert Angelici to support the travel to attend the 2014 American Society for Mass Spectrometry Conference.
3x10
0
0.
0.
0.
0.
1
1.
1.
1.
1.
2
2.
2.
+APCI Scan (44.611-44.886 min, 390 Scans) Frag=160.0V 02_1mM std mix_5ul ALS_GCsep_frag160V_skimmer145V.d Subtract
182.0557
123.0431
167.0324140.0453155.0687
111.0434
Counts vs. Mass-to-Charge (m/z)
100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200
CID CID
CID
CID
CID CID
[MH]+
[M.NH3]+.
[MH]+
[MH]+
[MH]+
~
-C3H2O
-C4H8O -C4H8O2
-C2H4O
-C2H2O -C3H2O
M+.
M+.
~
[MH]+ [MH]+
-H2O
150.0661
-C3H4O2
-C3H2O
-CHO
C9H10O2
-C2H4O -CH4
-C2H3O2
-CH4O
-CH3O
-C2H3O -CH3
C10H12O3
Purpose
Overview
GC-TIC Chromatograms MS and MS/MS spectra of selected compounds
Standard mix without fragmentation
Standard mix with fragmentation
Pyrolysis of red oak without fragmentation
Pyrolysis of red oak with fragmentation
M+.
[MNH4]+
[MNH4]+
[M.NH3]+. M+.
[MNH4]+
[M.NH3]+.
M+.
4x10
0
0
0
0
0
1
1
1
1
1
2
2
+APCI Scan (44.727-44.940 min, 301 Scans) Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d Subtract
182.0538
105.0442 123.0429
140.0451155.0683 167.0316
111.0431
131.0476 151.0730115.0389 163.0727
Counts vs. Mass-to-Charge (m/z)
80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190
183.0617
200.0881
9 0471
70 175 180 185 190 195 200 205 21
M+.
M+.
[MH]+
[M.NH3]+.
[MNH4]+
M+.
M+.
[MH]+
-C2H2O -C3H2O
M+.
[MH]+
-C2H4O2
-CH4 -CO
Acetosyringone
Syringaldehyde
Coniferyl Aldehyde
3,5-dimethoxytoluene
kimmer65V.d Subtract
164.0811
182.1151
0738 172.0945188 0
155 160 165 170 175 180 185 19
4x10
0
0
0
0
0
1
1
1
1
1
2
2
2
2
+APCI Scan (36.295-36.429 min, 190 Scans) Frag=160.0V 05_py_3rods_redoak_nonacid_infused_GC sep_frag160V_skimmer145V.d Subtract
164.0814
149.0580105.0675
137.0583
133.0634121.0637
115.0390
Counts vs. Mass-to-Charge (m/z)
102 104 106 108 110 112 114 116 118 120 122 124 126 128 130 132 134 136 138 140 142 144 146 148 150 152 154 156 158 160 162 164 166 168
M+.
[MH]+
[MNH4]+
-CH4
-CH4O
-C2H4 -C2H4O2
-C2H4O
M+.
M+.
C10H12O2
44.8 36.4 40.5
32.4
3
Pyrene
P-Cresol
Levoglucosan
1
9, 10 2
4
Compounds listed numerically: Lactic Acid, 2-Butonic Acid, 2,5-Dimethyl-3-methylene P-dioxane, 3-Oxobutanoic Acid, 2-(5H) Furanone, a-Methyl furan, Furfural, p-/o-dioxanone, 2-propenoic Acid, Ethyl ester, 5-Methyl 2(3H)-furanone, Vanillic Acid, Levoglucosane Compounds listed numerically: 5-methoxy-2-furoic Acid, Maltol, Syringol, Vanillyl methylcetone, Ethyl vanillylether, Acetosyringone, Phenol, Methyl 10-hydroxydec-trans-8-ene-4,6-diynoate
12
5
6 11
7,8
13
1
1
3
3
2
2
4
6
4
7
7
6
8
8
5
5
