new generation gc-hrtofms “accutof gcv 4g” gcv 4g automatic isolation valve gas clean or change...
TRANSCRIPT
New generation GC-HRTOFMS
“AccuTOF GCv 4G”
Outline • JEOL Mass Spectrometers
• AccuTOF GCv 4G – Overview
– Ion transfer and analyzer schematic
– Standard ion source
– EI/FI/FD combination ion source
– Direct Probes
– Specifications
• Applications – GC/MS
– Direct MS
– Pyrolysis GC/MS
– Comprehensive 2DGC/MS
• Summary
JMS-T100GCV AccuTOF GCV 4G
JEOL Mass spectrometers
TOFMS series GC-MS series
JMS-800D UltraFOCUS, GC-HRMS for Dioxin analysis
JMS-Q1050GC, GC-QMS
JMS-S3000 MALDI-SpiralTOF
JMS-T100LP AccuTOF-DART
JMS-T100GCV AccuTOF GCV 4G
AccuTOF GCv 4G
Automatic isolation valve clean or change sources without
breaking analyzer vacuum Direct inlet flange
for both GC/MS
and Direct MS
Thermally-stabilized flight
tube for enhanced stability
All pumps contained
in chassis Turbo pump x 2
Rough pump x 2
Gas Chromatograph Agilent 7890A
High-resolution TOF,
ADC-based 4 GHz Digitizer,
4 orders dynamic range
Reservoir for a Calibrant
Ion Transfer and Analyzer Schematic
Rough
pump
Ion source and
ion transfer
Rough
pump
Turbo
pump
Isolation valve
Analyzer
Turbo
pump
Detector
• Low-acceleration ion transfer system removes
99% of helium carrier gas ions for longer MCP
lifetime.
• Auto tuning for all ionization modes.
• JEOL’s orthogonal acceleration-TOFMS
system provides a higher duty cycle for
continuous beam ion sources.
High sensitivity
• Special focusing by 2-stage acceleration
system.
• Energy focusing by single stage reflectron.
High mass resolution
Available Ionization Methods on the
AccuTOF GCv 4G • Hard Ionization:
Good for structural analysis using the
generated fragment ions.
– EI (Electron Ionization)
– DEI (Desorption EI) using DEP
• Soft Ionization: Provides molecular weight information.
– CI (Chemical Ionization)
– DCI (Desorption CI) using DEP
– FI/FD (Field Ionization/
Field Desorption)
The history of ionizations
1921 A. J. Dempster, EI (Electron Ionization)
1950 E. W. Müller, FI (Field Ionization)
1956 F. P. Lossing, PI (Photo Ionization)
1963 R. E. Honig, LD (Laser Desorption)
1966 M. S. B. Munson,
CI (Chemical Ionization)
1969 H. D. Beckey, FD (Field Desorption)
1977 D. F. Hunt,
DCI (Desorption Chemical Ionization)
1981 M. Barber,
FAB(Fast Atom Bombardment)
1984 J. B. Fenn, ESI (Electrospray Ionization)
1987 F. Hillenkamp, K. Tanaka,
MALDI (Matrix-assisted Laser Desorption
Ionization)
2005 R.B. Cody, J.A. Laramée,
DART (Direct Analysis in Real Time)
Standard EI ion source
EI socket chamber
CI socket chamber
• Easy to remove and clean
• Easy to replace the filament
• Quickly switch between EI and CI
EI/FI/FD combination ion source
• The only EI/FI/FD combination ion source available on the market
• Three measurement modes: GC/EI, GC/FI and FD
• Quickly switch between EI, FI and FD modes without breaking vacuum
Cathode for FI/FD
Filament for EI
Lens unit
Direct Probes Glass tube
Direct Inlet Probe (DIP) • EI and CI
• For insoluble compounds and solids
Direct Exposure Probe (DEP) • DEI and DCI
• For thermolabile compounds
Field Desorption Probe (FDP) • GC/FI and FD
• It is suited to Hydrocarbon analysis
Liquid Injection FD Probe (LIFDI) • FD
• Quick sampling
Pt filament
Carbon emitter Carbon emitter
Capillary tube
AccuTOF GCv 4G Spec
State-of-the-arts GC-HRTOFMS
Reflectron Time-of-Flight MS system
Usable as both GC/MS and Direct MS
Resolving power: R≥8,000 (FWHM) @ m/z 617
Mass range: m/z 4 – 5,000
Mass accuracy: 1.5 mDa or 4 ppm (RMS)
Sensitivity: S/N ≥ 100 for 1pg OFN (GC/EI)
Acquisition rate: up to 50 spectra/s
Auto tuning for all ionization modes
GC/MS Applications
Impurity Analysis Using GC/EI and
Ammonia CI
Mode No. Obs. m/z Error
(mDa) Formula
EI+ 1 31.0187 0.3 CH3O
2 45.0346 0.6 C2H5O
3 73.0290 0.0 C3H5O2
4 87.0444 -0.2 C4H7O2
5 104.0471 -0.2 C4H8O3
CI+ 6 124.0987 1.3 C4H14NO3
7 210.1336 -0.6 C8H20NO5
EI+
CI+
Unknown
1
2
3
4
5
6
7 [M+NH4]
+
2-Methoxyethanol
Diethylene glycol
monomethyester
Diethylene glycol Ethylene glycol
1,4-Dioxane-2-ol
Triethylene glycol (main component)
Suggested impurity
unknown component
m/z 73
m/z 87
m/z 104
m/z 45
m/z 31
Triethylene glycol
Liquid Crystal Analysis Using GC/EI
and Isobutane CI
Unknown
Mode No. Obs. m/z Error
(mDa) Formula
EI+ 1 69.0715 1.1 C5H9
2 111.1187 1.3 C8H15
3 195.0689 1.4 C13H9NO
4 333.1743 1.4 C22H23NO2
CI+ 5 334.1802 -0.5 C22H24NO2
1 2
3
5 [M+H]+
GC/EI
TIC
GC/CI
TIC
EI+
CI+
Calculator LCD
Suggested unknown component
m/z 69
m/z 111
m/z 195
4
UV-Curing Adhesive Analysis Using
GC/EI and FI
m/z
UV-curing
adhesive
Mode No. Obs. m/z Error
(mDa)
Formula
EI+ 1 119.0853 -0.8 C9H11
2 147.0801 -0.9 C10H11O
3 201.0475 0.6 C12H10OP
FI+ 4 348.1283 0.4 C22H21O2P
1
2
3
4, [M]+・
EI+
FI+
Unknown GC/EI TIC
GC/FI TIC
m/z 119
m/z 147
m/z 201
Suggested unknown component
m/z
Time (min)
Time (min)
No molecule ion
Organic Fluorine Compounds Analysis
Using GC/EI and FI Hydrofluorocarbon ether
Trifluoroethanol
EI+
FI+
EI+
FI+
m/z 150.0107
[M]+・, C3H3F5O
(Error: 0.3 mDa)
m/z 149
[M-H]+
m/z 100.0142
[M]+・, C2H3F3O
(Error: 0.6 mDa)
m/z 100
[M]+・
m/z
Time (min)
m/z
m/z
m/z
m/z 131
[M-F]+
m/z 69
[CF3]+
m/z 69
[CF3]+
Diesel Oil Analysis Using GC/EI and FI TIC[1]; / EI+(eiFi) / EI+(eifi)_DieselOil_1023_003 0.2uL Inj, Split200
0
2
4
6
8
10
12
14
16
Intensity (17885739)x106
9.819.22
8.61 10.89
4.907.96 11.39
5.74 6.53 7.27
11.87
9.50
4.01 12.339.00
8.357.53
12.766.23 7.065.38 11.114.59 13.19
TIC[1]; / FI+(eiFi) / FI+(eifi)_DieselOil_1024_002 0.2uL Inj, Split200
2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0Time[min]
0
500
1000
1500
2000
2500
Intensity (2515297)x103
9.23 9.81 10.37
8.61
11.39
7.96
11.87
7.27
6.5312.33
5.75 9.014.9012.778.36
GC/EI
GC/FI
C11H24 C12H26 C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C10H22
+
C9H12
C24H50
C25H52
C26H54
C9H20
C9H20
C10H22
+
C9H12 C11H24
C12H26
C13H28
C14H30
C15H32
C16H34 C17H36 C18H38
C19H40
C20H42
C21H44
C22H46
C24H50
C25H52
C23H48 C26H54
m/z 207.0329 (Background)
is used as external calibrant
m/z 226.26605 (C16H34)
is used as external calibrant
Next slide
Next slide
Mass Spectra of the Component at R.T. 4.90 min MS[1];4.89..4.91;-1.0*MS[1];4.93..4.94; / EI+(eiFi) / EI+(eif i)_DieselOil_1023_003
0.2uL Inj, Split200
0
50
100
150
200
Intensity (244804)x103
57.07143.055
105.070
71.085
85.100
120.093
56.062
70.07755.054
84.093
119.085142.17299.11691.054
58.07351.023
MS[1];4.89..4.91; / FI+(eiFi) / FI+(eif i)_DieselOil_1024_002
0.2uL Inj, Split200
40 60 80 100 120 140 160 180 200
m/z
0
5
10
15
20
25
Intensity (27559)x103
142.172
120.095
143.176
121.100
EI+
FI+
M+・, C10H22
(0.8 mDa)
M+・, C9H12
(1.6 mDa)
M+・, C10H22
(-0.2 mDa)
M+・, C9H12
(-0.7 mDa)
C8H9
(-0.4 mDa)
C6H13
(-1.0 mDa)
C5H11
(-0.8 mDa)
C4H9
(0.9 mDa) C3H7
(0.6 mDa)
No fragment ions
FI spectrum showed that
the component at R.T. 4.90 (min)
consists of different two
hydrocarbons.
Direct MS Applications
Tristearin Analysis Using DEP
200 300 400 500 600 700 800 900質量電荷比(m/z)
0
10
20
30
強度 (36551)x103
200 300 400 500 600 700 800 900質量電荷比(m/z)
0
100
200
300
400
強度 (412610)x103
x 50
Direct Exposure Probe (DEP) • EI and CI
• For high boiling point compounds
• For thermolabile compounds
Pt filament Desorption EI+
Desorption CI+ with Ammonia
[M]+・
890
[M-H2O]+
872
607
607
341
341
267
[M+NH4]+
908
m/z 607
m/z 395
395
m/z 267
Synthetic Organic Pigment Analysis
Using Direct Probes
Pigment Yellow 83(C36H32Cl4N6O8)
NHOCCH N N
ClCl
N N CHCOHN
COCH3
Cl
H3CO
OCH3
Cl
H3CO
OCH3
COCH3
Pigment Red 144(C40H23Cl5N6O4)
N N
HOCl
Cl
CONH
Cl
NHOC OH
N N
Cl
Cl
Desorption EI+ Desorption EI+
FD+ FD+ [M]+・ [M]+・
Liquid Crystal Analysis Using
Direct Probes
200 400 600 800質量電荷比(m/z)
0
20
40
60
80
100相対強度
830.49
590.46
EI+
CI+
FD+ [M]+・
No molecular ion
No protonated
molecule
PEG600
(Internal calibrant)
Mode Obs. m/z Error
(mDa)
Formula
FD+ 830.4864 -0.6 C52H66N2O7
m/z m/z
m/z
Organic Electro-Luminescence (OEL) and
Ionic Liquid Analysis Using Direct Probes
Desorption EI+
FD+
[M]+・
m/z 510.2338, [M]+・
(Error: -1.0 mDa)
Mass Spectra of OEL
FD+
N
C4H9
CH3
S
O
O
F3C
N S
O
O
CF3
m/z 150.1289
[Cation]+
(Error 0.6 mDa) m/z 580.1766
[M+Cation]+
(Error 2.8 mDa) [Cation]2+
FD Mass Spectrum of Ionic liquid
OEL
Ionic liquid
Polymer Analysis Using FD
Polystyrene 4,000
FD mode on the “AccuTOF
GCv 4G” can measure
heavier ions than m/z 5,000 !
1000 2000 3000 4000 5000 m/z
FD+
Copolymer Analysis Using FD
Ethylene Oxide (EO)/ Propylene Oxide (PO)
block copolymer
m/z
H OCH2CH2 OCH2CH
CH3
OCH2CH2 OHx y z
Repeat A
PO: (C3H6O)n
Repeat B, EO: (C2H4O)n
Copolymer distribution and type analysis results using the Polymerix Software (Sierra)
FD+
Mn Mw Mz PD
1053.2 1077.1 1100.9 1.03
Mn:Number-average M.W.
Mw:Weight-average M.W.
Mz:Z-average M.W.
PD:Mw/Mn
Microcrystalline Wax Analysis Using FD
Series Mn Mw Mz PD %
Total 657.0 686.9 718.9 1.0 100
CnH2n+2 571.1 617.3 665.3 1.1 17.3
CnH2n 529.7 655.0 680.8 1.0 24.2
CnH2n-2 670.5 692.3 715.6 1.0 13.1
CnH2n-4 715.6 739.0 764.7 1.0 8.4
CnH2n-6 688.3 717.9 751.1 1.0 22.5
CnH2n-8 710.0 739.6 772.8 1.0 14.5
Mn:Number-average M.W.
Mw:Weight-average M.W.
Mz:Z-average M.W.
PD:Mw/Mn
Microcrystalline
Wax
It is possible to determine the
component ratio and the average
M.W. in the microcrystalline wax
using FD type analysis.
Pyrolysis GC/MS
Applications
Pyrolysis System
Pyrolysis GC/MS • For material and polymer science
• Any material samples can be
introduced into the temperature
controlled furnace.
• Pyrolysis measurements with higher
temperatures (400 - 600 ⁰C)
• Thermal extraction measurements
with lower temperatures (200 - 400 ⁰C)
• Generated components by pyrolysis
and/or thermal extraction are separated
by the capillary GC column.
• This technique provides useful
information about the material
composition of the samples. to MS
Pyrolysis GC/EI of the
Brominated Flame Retardant “FRPC” TIC[1]; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
2000
4000
6000
8000
強度 (8593437)x103
13.63
0.36
3.30
2.99
17.20
10.44
1.16 4.35 12.958.60 9.505.294.77
TIC[1]; / EI+ / FRPC(溶液)+TMAH_01 10mg/mLを2uL導入, TMAH2uL導入, Split200, 2400V
0 2 4 6 8 10 12 14 16 18 20経過時間[min]
50
100
強度 (124694505)x106
9.74
0.32
9.23
8.79
8.222.82
4.36
熱分解GC
誘導体化熱分解GC
HBr
OH BrOH
Br
Br Br
Br
HO OH
Br
Br Br
Br
HO O
O
O
O
O
O
Br
Br
Br
Br
O
O
O
Monomer
O
H
Br Br
Br
HO OH
H
Br Br
Br
O O
Br
Br Br
Br
O O
Br
Br H
H
O O
H
Br H
H
O O
H
Br H
Br
O O
etc…
TIC[1]; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
2000
4000
6000
8000
強度 (8593437)x103
13.63
0.36
3.30
2.99
17.20
10.44
1.16 4.35 12.958.60 9.505.294.77
TIC[1]; / EI+ / FRPC(溶液)+TMAH_01 10mg/mLを2uL導入, TMAH2uL導入, Split200, 2400V
0 2 4 6 8 10 12 14 16 18 20経過時間[min]
50
100
強度 (124694505)x106
9.74
0.32
9.23
8.79
8.222.82
4.36
熱分解GC
誘導体化熱分解GC
HBr
OH BrOH
Br
Br Br
Br
HO OH
Br
Br Br
Br
HO O
O
O
O
O
O
Br
Br
Br
Br
O
O
O
Monomer
O
H
Br Br
Br
HO OH
H
Br Br
Br
O O
Br
Br Br
Br
O O
Br
Br H
H
O O
H
Br H
H
O O
H
Br H
Br
O O
etc…
[min]
MS[1];9.50..9.51;-1.0*MS[1];9.54..9.55; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
448.8 450.8
446.8 452.8181.1 369.9215.0152.1 467.8289.0
MS[1];10.46;-1.0*MS[1];10.48; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
528.7526.7
543.8524.7292.9448.879.9 152.0
MS[1];13.64;-1.0*MS[1];13.66; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
660.8135.1658.8
528.7107.0
656.8 664.8150.1 292.9 448.8344.9
719.8
MS[1];17.22;-1.0*MS[1];17.27..17.27; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
200 400 600 800 1000質量電荷比(m/z)
0
100相対強度
135.1107.0
836.9150.1 660.8
792.9580.9 895.9
Br
Br Br
Br
HO OH
Br
Br Br
Br
HO O
O
O
O
O
O
Br
Br
Br
Br
O
O
O
H
Br Br
Br
HO OH
m/z
m/z
m/z
m/z
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
MS[1];9.50..9.51;-1.0*MS[1];9.54..9.55; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
448.8 450.8
446.8 452.8181.1 369.9215.0152.1 467.8289.0
MS[1];10.46;-1.0*MS[1];10.48; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
528.7526.7
543.8524.7292.9448.879.9 152.0
MS[1];13.64;-1.0*MS[1];13.66; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
660.8135.1658.8
528.7107.0
656.8 664.8150.1 292.9 448.8344.9
719.8
MS[1];17.22;-1.0*MS[1];17.27..17.27; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
200 400 600 800 1000質量電荷比(m/z)
0
100相対強度
135.1107.0
836.9150.1 660.8
792.9580.9 895.9
Br
Br Br
Br
HO OH
Br
Br Br
Br
HO O
O
O
O
O
O
Br
Br
Br
Br
O
O
O
H
Br Br
Br
HO OH
m/z
m/z
m/z
m/z
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
HBr
Monomer
EI mass spectrum of Monomer
Obs. Isotopic pattern
Calc. Isotopic pattern
of C37H36O6Br4
O O
Br
BrBr
Br
O O
OO
n
Brominated Flame Retardant “FRPC” (m/z)
(m/z)
[M]+・
FRPC
only
Derivatization Pyrolysis GC/EI of the
Brominated Flame Retardant “FRPC”
TIC[1]; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
2000
4000
6000
8000
強度 (8593437)x103
13.63
0.36
3.30
2.99
17.20
10.44
1.16 4.35 12.958.60 9.505.294.77
TIC[1]; / EI+ / FRPC(溶液)+TMAH_01 10mg/mLを2uL導入, TMAH2uL導入, Split200, 2400V
0 2 4 6 8 10 12 14 16 18 20経過時間[min]
50
100
強度 (124694505)x106
9.74
0.32
9.23
8.79
8.222.82
4.36
熱分解GC
誘導体化熱分解GC
HBr
OH BrOH
Br
Br Br
Br
HO OH
Br
Br Br
Br
HO O
O
O
O
O
O
Br
Br
Br
Br
O
O
O
Monomer
O
H
Br Br
Br
HO OH
H
Br Br
Br
O O
Br
Br Br
Br
O O
Br
Br H
H
O O
H
Br H
H
O O
H
Br H
Br
O O
etc…
TIC[1]; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
2000
4000
6000
8000
強度 (8593437)x103
13.63
0.36
3.30
2.99
17.20
10.44
1.16 4.35 12.958.60 9.505.294.77
TIC[1]; / EI+ / FRPC(溶液)+TMAH_01 10mg/mLを2uL導入, TMAH2uL導入, Split200, 2400V
0 2 4 6 8 10 12 14 16 18 20経過時間[min]
50
100
強度 (124694505)x106
9.74
0.32
9.23
8.79
8.222.82
4.36
熱分解GC
誘導体化熱分解GC
HBr
OH BrOH
Br
Br Br
Br
HO OH
Br
Br Br
Br
HO O
O
O
O
O
O
Br
Br
Br
Br
O
O
O
Monomer
O
H
Br Br
Br
HO OH
H
Br Br
Br
O O
Br
Br Br
Br
O O
Br
Br H
H
O O
H
Br H
H
O O
H
Br H
Br
O O
etc…
[min]MS[1];2.81..2.84;-1.0*MS[1];2.89..2.91; / EI+ / FRPC(溶液)+TMAH_01 10mg/mLを2uL導入, TMAH2uL導入, Split200, 2400V
0
50
100相対強度
149.1121.0
164.1
109.077.0
65.0MS[1];10.22;-1.0*MS[1];10.24..10.24; / EI+ / FRPC(溶液)+TMAH_01 10mg/mLを2uL導入, TMAH2uL導入, Split200, 2400V
200 400 600 800 1000質量電荷比(m/z)
0
50
100相対強度
556.8
554.8 558.8
571.8552.8306.9
MS[1];9.50..9.51;-1.0*MS[1];9.54..9.55; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
448.8 450.8
446.8 452.8181.1 369.9215.0152.1 467.8289.0
MS[1];10.46;-1.0*MS[1];10.48; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
528.7526.7
543.8524.7292.9448.879.9 152.0
MS[1];13.64;-1.0*MS[1];13.66; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
660.8135.1658.8
528.7107.0
656.8 664.8150.1 292.9 448.8344.9
719.8
MS[1];17.22;-1.0*MS[1];17.27..17.27; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
200 400 600 800 1000質量電荷比(m/z)
0
100相対強度
135.1107.0
836.9150.1 660.8
792.9580.9 895.9
Br
Br Br
Br
HO OH
Br
Br Br
Br
HO O
O
O
O
O
O
Br
Br
Br
Br
O
O
O
H
Br Br
Br
HO OH
m/z
m/z
m/z
m/z
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
MS[1];9.50..9.51;-1.0*MS[1];9.54..9.55; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
448.8 450.8
446.8 452.8181.1 369.9215.0152.1 467.8289.0
MS[1];10.46;-1.0*MS[1];10.48; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
528.7526.7
543.8524.7292.9448.879.9 152.0
MS[1];13.64;-1.0*MS[1];13.66; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
0
100相対強度
660.8135.1658.8
528.7107.0
656.8 664.8150.1 292.9 448.8344.9
719.8
MS[1];17.22;-1.0*MS[1];17.27..17.27; / EI+ / FRPC(溶液)_01 10mg/mLを2uL導入, Split200, 2400V
200 400 600 800 1000質量電荷比(m/z)
0
100相対強度
135.1107.0
836.9150.1 660.8
792.9580.9 895.9
Br
Br Br
Br
HO OH
Br
Br Br
Br
HO O
O
O
O
O
O
Br
Br
Br
Br
O
O
O
H
Br Br
Br
HO OH
m/z
m/z
m/z
m/z
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
Rel
ativ
e in
ten
sity
(%)
B A
A
B
A
B
EI mass spectra of chemicals that show structure
A (m/z)
Brominated Flame Retardant “FRPC” monomer
FRPC
+ Tetramethylammonium
hydroxide (Derivatizing Agent)
Thermal Extraction GC/EI
of Wire Coating Material
Squalene
(Lubricant)
Decabromodiphenyl Ethane
(Flame retardant)
Irganox1330
(Antioxidant)
Unknown
C50H70O3 Isotopic pattern Red: Measured
Blue: Calculated
Wire coating
Irganox1330
Unknown
-263 u
-555 u
[M]+・
-263 u -555 u
m/z 718.5340, [M]+・ ?
C50H70O3, Error: 1.5 mDa
Irganox1330 Suggested unknown
component
Pyrolysis GC/EI, CI and FI of ABS Polymer TIC[1]; / EI+ / 1024-ABS
8 10 12 14 16 18 20 22経過時間[min]
40
50
強度 (55480000)x106
20.130
17.882
Unknown
Mode No. Obs. m/z Error
(mDa) Formula
EI+ 1 77.0392 0.1 C6H5
2 104.0629 0.3 C8H8
3 168.0808 -0.5 C12H10N
4 183.1035 -1.3 C13H13N
CI+ 5 184.1127 0.1 C13H14N
FI+ 6 183.1055 0.7 C13H13N
1
2 EI+
CI+
Benzenepropane
-nitrile
Dimers
β-Methyl-styrene
α-Methylstyrene
Methylene glutaronitrile
FI+
3
5 [M+H]+
6 [M]+・
4 [M]+・
m/z 168 m/z 104
m/z 77
Suggested unknown component
(min) (m/z)
Comprehensive 2DGC/MS
Applications
2DGC(GCxGC) System
2DGC/MS
• Higher separation power than normal
GC/MS.
• 2DGC measurement can be done with one
GC. A second GC oven is unnecessary.
• Time-of-flight mass spectrometer (TOFMS)
is the best detector for 2DGC/MS.
• For many applications including: Petroleum,
Flavors, Metabolomics, Environmental.
• Any GC inlet technique, such as
Split/Splitless, Pyrolyser, Head-Space, etc.,
can be utilized.
• This technique provides useful informations
for a wide range of chemicals all at once.
GC Oven
GC Inlet Cold jet Hot jet
Modulator
Trap time: 3-8 sec
to MS or other detector
1st Column
Meas. time:
30-90 min
2nd Column
Meas. time:
3-8 sec
Rosemary Aroma Oil Analysis
Using GCxGC/EI
2D TIC
3D TIC 1st column (Nonpolar) separation
2n
d c
olu
mn
(P
ola
r) s
ep
ara
tio
n
(sec
)
(min)
6
45 35 25 15 0
3
0
Petroleum Liquids Analysis
Using GCxGC/EI Merged 2D mass chromatogram
of Dibenzothiophenes
A B
C
Kerosene 2D TIC
Light Oil 2D TIC
m/z 184.0343
C12H8S
Error: -0.4 mDa
m/z 198.0495
C13H10S
Error: -0.8 mDa
m/z 212.0654
C14H12S
Error: -0.6 mDa
A
B
C
GCxGC/FI Technique with a
Normal Column Set
1st column: Nonpolar column
(BPX5, 30m x 0.25mm, I.D. 0.25um)
2n
d c
olu
mn
: P
ola
r co
lum
n
(BP
X50, 2m
x 0
.1m
m, I.
D. 0.1
mm
)
GCxGC/FI Technique with a
Reverse Column Set
1st column: Polar column
(DB-WAXETR, 30m x 0.25mm, I.D. 0.1um)
2n
d c
olu
mn
: N
on
po
lar
co
lum
n
(DB
-1, 1m
x 0
.1m
m, I.
D. 0.1
um
)
PAHs Analysis in Exhaust Gas
Using GCxGC/EI
3D Mass chromatogram (m/z 228.0930±0.01)
m/z 228.0933
C18H12
(Error: 0.3 mDa)
2D TIC
(a)
3D TIC
Pyrolysis GCxGC/EI and FI Analysis of
Nylon 6,6
100 200 300
質量電荷比(m/z)
0
100相対面積
82.155.1
41.0110.1
56.1
100.158.1 127.1 167.1
2D TIC
Unknown
m/z 210.1729
C12H22N2O
Error: -0.4 mDa
(m/z)
(m/z)
EI+
FI+
H8C4
Suggested unknown component 1st column (Nonpolar) separation
2n
d c
olu
mn
(P
ola
r) s
ep
ara
tio
n
No molecule ion
Summary AccuTOF GCv 4G is a state-of-the-art GC-
HRTOFMS.
This latest GC-TOFMS simultaneously
provides high-sensitivity, high mass resolution,
high mass accuracy and high speed data
acquisition capabilities for each analysis.
EI/FI/FD combination ion source is a unique
capability that is only offered by JEOL.
AccuTOF GCv 4G can be used as both a
GC/MS and Direct MS system.
It is very easy to perform accurate mass
measurement in all ionization modes.
JMS-T100GCV AccuTOF GCv 4G