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GC×GC principle
injector detector
modulator
1st columnconventional
(30 m × 0.25 mm × 0.25 µm)
2nd columnfast
(1 m × 0.1 mm × 0.1 µm)
2nd dimension retention time
2nd dimension retention time1st dimension retention time
1st dimension retention time
GC×GC principle
GC×GC principle
187167
185
2nddi
men
sion
rete
ntio
n tim
e (s
ec)
1st dimension retention time (min)
201 180
198
187 183
128167
185
171
156 157
180
198173
201202
187187183183
128128
167167 185185171171
156156 157157180180
198198
173173
201201
202202
Contour plot
GC×GC principle
187167
185 201 180
198
187187183183
128128
167167 185185171171
156156 157157180180
198198
173173
201201
202202
2nddi
men
sion
rete
ntio
n tim
e (s
ec)
1st dimension retention time (min)
187 183
128167
185
171
156 157
180
198173
201202
APEX plot
GC × enantio-GC: (normal) set-up
Non-polar phase
1st columnconventional
(30 m × 0.25 mm × 0.25 µm)
Enantio selective phase
2nd columnfast
(1 m × 0.1 mm × 0.1 µm)
injector detector
modulator
Fast enantioseparationColumn:EtTBS-βCD phase1m × 0.1mm × 0.1µm
Isothermal:70°C
Linear carrier gas velocity:60 cm/s = ūopt(2ūopt or 3ūopt ⇒ 58 s or 37 s)
limon
ene
cam
phor
linal
ool
linal
ylac
etat
e
retention time (s)
R. Shellie, Ph.J. Marriott, Anal. Chem. 74 (2002) 5426.
GC × enantio-GC: (alternative) set-up
Non-polar phase
1st columnconventional DB-5
(10 m × 0.10 mm × 0.10 µm)
Enantio selective phase
2nd columnfast EtTBS-βCD
(1 m × 0.25 mm × 0.25 µm)
MS detector(vacuum)injector
modulator
GC × enantio-GC: (alternative) set-up
(-) linalool
(+) limonene
(-) limonene
(+) linalool
(-) linalylacetat
(+) linalylacetat1,
8-ci
neol
e(±
)α-p
inen
e
1,8-cineole
(-)limonene
(-) limonene
(+) limonene
1,8-cineole(+) limonene
(-) limonene (+) limonene
6136 14028
30156894= =
Rs (limonene) = 1.4(linalool) = 1.6(linalyl acetat) = 0.8
= 0.437
2tR ((+) linalyl acetat, MS) = 38 s2tR ((+) linalyl acetat, FID) = 154 s
R. Shellie, Ph.J. Marriott, Anal. Chem. 74 (2002) 5426.
GC × enantio-GC: conclusions
• Enantiomeric separation is worse compared to heart-cut MDGC
• Separation of enantiomeric pair from other co-elutants is questionable
• Suitable only for well resolved pairs of enantiomers
• Vacuum set-up is rather difficult to operate
• Not really a viable option ?
GC × enantio-GC: SolGel × Cyclodex-B
traditional Chinese medicine• more than 800 peak detected• 394 compounds positively identified• some of those compounds are enantiomers
J. Wu, X. Lu, W. Tang, H. Kong, S. Zhou, G. Xu, J. Chromatogr. A 1034 (2004) 199.
enantio-GC × GC
Enantio selective phase
1st columnconventional
(30 m × 0.25 mm × 0.25 µm)
Polar or shape selective phase
2nd columnfast
(1 m × 0.1 mm × 0.1 µm)
injector detector
modulator
(EtTBS-β-CD+CycloSil B) × BPX-50Red wine volatiles
Y. Shao, Ph. Mariott, Anal. Bioanal. Chem. 375 (2003) 635.
(EtTBS-β-CD+CycloSil B) × BPX-50Strawberry volatiles
linalool
2,5-dimethyl-4-hydroxy-(2H)-furan-3-one(DMHF)
A. Williams, D. Ryan, A.O. Guasca, Ph. Mariott, E. Pang, J. Chromatogr. B 817 (2005) 97.
Xenobiotics: PCBs on Chirasil-Dex
M. Harju, A. Bergman, M. Olsson, A. Roos, P. Haglund, J. Chromatogr. A 1019 (2003) 127.
Chirasil-Dex × LC-50
Standard of the 144 Aroclor CBs
Grey seal blubber sample
M. Harju, A. Bergman, M. Olsson, A. Roos, P. Haglund, J. Chromatogr. A 1019 (2003) 127.
Chirasil-Dex × VF-23ms
Standard of the 144 Aroclor CBs
Grey seal blubber sample
M. Harju, A. Bergman, M. Olsson, A. Roos, P. Haglund, J. Chromatogr. A 1019 (2003) 127.
Quantitative parameters
M. Harju, A. Bergman, M. Olsson, A. Roos, P. Haglund, J. Chromatogr. A 1019 (2003) 127.
Quantitative parameters
M. Harju, A. Bergman, M. Olsson, A. Roos, P. Haglund, J. Chromatogr. A 1019 (2003) 127.
enantio-GC × GC: conclusions
• Enantiomeric separation is not improved but 1D-GC separation is maintained
• Excellent and fast separation of the enantiomersfrom other sample constituents
• GCxGC – excellent tool for determination of isomers well separated in the 1D-GC
• Heart-cut MDGC still the method of choice if isomers are eluting very closely
• Method development • select chiral column • select second column
DB-1×007-65HT: overlay
20 30 40 50 60 700
1
2
3
4
5
6
7
8
10
9
10 PBDEsPCBsPCNsPCDTsPCDEsPBBsPCDD/FsToxaphene
2nddi
men
sion
rete
ntio
n tim
e (s
ec)
1st dimension retention time (min)
OCPs
DB-1×007-65HT: PCAs Clx
1
2
3
4
5
6
010 20 30 40 50 60
2nd
dim
ensi
on re
tent
ion
time
(s)
1st dimension retention time (min)
C10–C13 with 52, 56 and 63 wt.% Cl content
C14–C17 with 42 and 57 wt.% Cl content
C18–C20 with 36 wt.% Cl content
1920
21
14
15
1617
1819
2021 22
23
2322
18
17
24
21
2223
24
25
26
C18Cl5
C18Cl6C19Cl5C14Cl5 C14Cl6
C15Cl5
C11Cl8C12Cl7C13Cl6
DB-1×007-65HT: PCAs Clx
A – Slovak dust
B – Spanish dust
2nddi
men
sion
rete
ntio
n tim
e (s
)
1st dimension retention time (min)
shortmedium long
shortmedium long
O
Brx BryDB-1×007-65HT: PBDEs
0
1
2
3
4
5
6
7
8
10 15 20 25 30 35 40
2nd
dim
ensi
on re
tent
ion
time
(s)
1st dimension retention time (min)
0
1
2
3
4
5
6
7
8
45 50 55 60 65 70
155
105
126
85
114106
127
116
124
99104
103121
102100
101120
125
88109
98,119
40,77
81
55
78
42,66
58,79
74
47
67
80
49
68
7146,48
726F-47
62
51
53
69,73
50
22,37
20,35
38
30
27 19
18
34
32
2629
36
17
39
16,33
28
10
4
9
14
12,13
1511
8
23
115
76
7
6
25,31
97,118
108,123
8687
4MeO-49
4OH-42
3F-100
6F-664’F-69
2OH-28
BB52
BB49
4’F-27BB15
1 4’F-253’F-28
BB101
6OH-47
4OH-49
154
me-TBBP-A
BB153
6OH-99
144161
168
153TBBP-A
139
131,158,140
141
160142
159 167
HBCD
138
166
156184
128
BB169183
182185
192
191
181
173,190204
4’,6F-1992,4’F-198
198
203205
208207 206
4’F-208
209
80
4’F-160
3F-119
6MeO-47
203
198
183 181
PCAs
HBCD138
139
153
TBBP-A
144154
85116
99101
100
DB-1×007-65HT: dust extract
203
183181
138
139
153HBCD
144
154
85116
99101
10042 or 66
47
46 or 48
28
7
PCAs
TBBP-A 198
DB-1×007-65HT: PCTs, toxaphene, PCAs
0
1
2
3
4
5
6
7
8
15 25 35 45 55 65 75 85
PCAs
Toxaphene
PCTs
2nddi
men
sion
rete
ntio
n tim
e (s
ec)
1st dimension retention time (min)
DB-1xLC-50: overlay
20 30 40 50 60 700
1
2
3
4
5
6
7
8
10
9
10
11PCDD/FsPCBs
81
77 126 169
123,118114
105
167
156157
189
2nddi
men
sion
rete
ntio
n tim
e (s
ec)
1st dimension retention time (min)
PBBsPBBs
15
5249
169
101 153
PBDEsPCDEsOCPsToxaphenesPCNsPCDTs
DB-XLBxLC-50
20 30 40 50 60 700
1
2
3
4
5
6
7
8Sediment sample – dioxin fraction
2nddi
men
sion
rete
ntio
n tim
e (s
ec)
1st dimension retention time (min)
4F1 4D1
5F1
5F2
5D1
6F1
6F2
6F3
6D16D2
6D3
7F1
6F4
7D1
7F2
OCDD
OCDF
DB-1xVF-23: overlay2nd
dim
ensi
on re
tent
ion
time
(sec
)
1st dimension retention time (min)20 30 40 50 60 70
0
1
2
3
4
5
6
7
8
10 80
OCPsPBDEsPCBsPCNsPCDTsPCDEsPCDD/FsPBBs
DB-1xVF-23: toxaphene2nd
dim
ensi
on re
tent
ion
time
(sec
)
1st dimension retention time (min)20 30 40 50 60 70
0
1
2
3
4
5
6
7
8
10 80