pops 類における 光学異性体分析の検討
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POPs 類における光学異性体分析の検討
○ 松村千里、鈴木元治、鶴川正寛、奥野俊博、中野 武
(兵庫県立健康環境科学研究センター)
光学異性体• クロルデン異性体には光学異性体が存在。生体
内で一方の異性のみが選択的に代謝されることにより光学異性対比 ER ( (+) / ( - ) )が変化することが知られている。これらの光学異性体の把握は、生体中での代謝情報やリスク評価に役立つことから、重要なファクターになると考えられる。
Cl
ClCl
Cl
Cl
ClCl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
Cl
Cl Cl
ClCl
Cl
Cl
trans-nonachlor cis-nonachlorachiral
trans-chlordane chiral oxychlordane
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
O
H
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
O
H
Example of chlordane component
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
ClCl
Cl
Cl
ClCl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
Cl
Cl Cl
ClCl
Cl
Cl
Cl
Cl Cl
ClCl
Cl
Cl
Cl
Cl
Cl Cl
ClCl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
ClCl
Cl
Cl
Cl
Cl Cl
ClCl
Cl
Cl
Cl Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
Cl Cl
ClCl
Cl
Cl
Cl
heptachlor component-U82
trans-chlordane component-MC4
cis-chlordane component-MC5
trans-nonachlo cis-nonachlor component-MC7
Cl
ClCl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl Cl
ClCl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
O
H
O
H
H
Cl
Cl Cl
ClCl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
O
H
O
H
H
Cl
ClCl
Cl
Cl
Cl
O
H
H
Cl
Cl Cl
Cl
Cl
Cl
O
H
H
H
Cl
H
H
Cl
H
Cl
Cl
Cl
H
Cl
HH
Cl
H
H
Cl
H
Cl
Cl
Cl
H
Cl
H
Cl
Cl
H
Cl
C*
Cl
Cl
Cl
Cl
C*
Cl
Cl
H
H
Cl
Cl
H
Cl
C*
Cl
Cl
Cl
Cl
C*
Cl
Cl
H
H
component-MC6 o,p’-DDT
oxychlordane o,p’-DDD
heptachlor-exo- alpha-HCH epoxide
oxychlordene
Atropisomer of PCB 1
#45 (2,2’,3,6-TeCB)
#84(2,2’,3,3’,6-PeCB) #91(2,2’,3,4’,6-PeCB)
#95(2,2’,3,5’,6-PeCB) #88(2,2’,3,4,6-PeCB)
Atropisomer of PCB 2
#132(2,2’,3,3’,4,6’-HxCB) #135(2,2’,3,3’,5,6’-HxCB)
#136(2,2’,3,3’,6,6’-HxCB) #149(2,2’,3,4’,5’,6-HxCB)
#131(2,2’,3,3’,4,6-HxCB) #139(2,2’,3,4,4’,6-HxCB)
#144(2,2’,3,4,5’,6-HxCB)
Atropisomer of PCB 3
#171(2,2’,3,3’,4,4’,6-HpCB) #175(2,2’,3,3’,4,5’,6-HpCB)
#183(2,2’,3,4,4’,5’,6-HpCB) #176(2,2’,3,3’,4,6,6’-HpCB)
#174(2,2’,3,3’,4,5,6’-HpCB)
#196(2,2’,3,3’,4,4’,5,6’-OcCB) #197(2,2’,3,3’,4,4’,6,6’-OcCB)
P309 ~P312
光学異性体• 今回は、GC/MS分析用キャピラリーカラ
ムとして液相に β -シクロデキストリンを用いたカラム(BGB-172、 20% tert-butyldimethylsilylated beta-cyclodextrin in methylphenylcyanopropylpolysiloxane )を使用することにより、クロルデン類および Atropisomer ( PCB )の光学異性体分析を行った。人血清、クロルデン製品や環境試料の光学異性体パターンを比較したのでその結果を報告する。
HR GC/ HR MS and Column
GC Hewlettpackard HP-5890IIMS JEOL MS-700
Column : BGB-172 (BGB Analytik)30mX0.25mmID,0.25μmFilmThickness
( 20%-tert-butyldimethylsilylated-beta-cyclodextrin in 15%-phenyl-85%-me
thyl-polysiloxane )
Table1 GC/MS conditions
GC:HP6890ⅡColumn:BGB-172 (BGB Analytik) 30mX0.25mmID, 0.25μmFilmThicknessCarrier gas:Helium(1.0ml/min constant flow)Oven temp.:120℃(0min)-4℃/min-200℃(0min)-1℃/min-230℃(25min), Inj.temp.:230℃MS:JEOL JMS-800DIonization mode:EI, Ion source temp.:250℃, Interface temp.:245℃, Ionization current:500μA, Ionization energy:38eV
GC/MS channel list 1 (2 injections)
G#: 1 Repeat: 1.01[sec] m/ z: 218.9 - 337.9 (1.54M)Ch.# Compound name m/ z
1 HCH 218.91162 HCH 220.90873 13C6-HCH 224.93174 Mass Lock 230.98565 Lock Check 230.98566 DDT 235.00817 DDT 237.00538 D8ring-DDD 243.05759 13Cring-DDT 247.048410 heptachlor 271.810211 heptachlor 273.807212 13C-Heptachlor 276.826913 PCB4 289.922414 PCB4 291.919515 Chlordene 302.888316 13C-PCB4 303.959717 Chlordene 304.885318 13C-Chlordene 312.921819 Oxy-chlordene 318.883220 Oxy-chlordene 320.880321 PCB5 325.880522 PCB5 327.877523 13C-PCB5 337.9207
GC/MS channel list 2 (2 injections)
G#: 1 Repeat: 1.01[sec] m/ z: 352.8 - 441.8 (1.25M)Ch.# Compound name m/ z
1 heptachlor-O 352.84422 heptachlor-O 354.84133 PCB6 359.84154 PCB6 361.83865 13C-Heptachlor- 362.87786 13C-PCB6 371.88187 CHL 372.8268 CHL 374.82319 Mass Lock 380.97610 Lock Check 380.97611 13C-CHL 384.856612 Oxy-CHL 386.805213 Oxy-CHL 388.802314 PCB7 393.802515 PCB7 395.799616 13C-Oxy-CHL 398.835817 13C-PCB7 405.842818 nonachlor 406.78719 nonachlor 408.784120 13C-Nonachlor 418.817621 PCB8 427.763622 PCB8 429.760623 13C-PCB8 441.7999
0
500
1000
1500
2000
250019
58
1960
1962
1964
1966
1968
1970
1972
1979
1980
1982
1984
1986
technical chlordanes (including heptachlor)
Technical chlordane import (tons)
Basic component of technical chlordane in Japan
chlorine component ratio (%)
Cl6 α- chlordene 0.7
γ- chlordene 3
β- chlordene 3.6
Cl7 heptachlor 4.8
Cl8 MC-4 0.3
trans- chlordane 18
MC-5 5.8
cis-chlordane 16
Cl9 MC-6 1.5
trans-nonachlor 14
cis-nonachlor 4.5Cl9
Cl8
Cl7
Cl6
ch
lori
ne
nu
mb
er
Technical Chlordane
Atmosphere
chlordane transtrans-- transtrans--
ciscis- - ciscis--
MC-5MC-5 MC-5MC-5 MC-4 MC-4
transtrans-- transtrans--
ciscis- - ciscis--
MC-5MC-5 MC-5MC-5 MC-4 MC-4
racemic
racemic
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
Cl
ClCl
ClClCl
Cl
Cl
ClCl
ClClCl
Cl
ClCl
ClCl
ClCl
Cl
Cl
Cl
River Water
River Sediment
transtrans-- transtrans-- ciscis- - ciscis--
MC-5MC-5 MC-5MC-5
MC-4 MC-4
transtrans-- transtrans--
ciscis- - ciscis--
MC-5MC-5 MC-5MC-5 MC-4 MC-4
racemic
racemic
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
Cl
ClCl
ClClCl
Cl
Cl
ClCl
ClClCl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
Technical Chlordane
Serum
transtrans-- transtrans--
ciscis- - ciscis--
MC-5MC-5 MC-5MC-5 MC-4 MC-4
MC-5 MC-5 transtrans-- ciscis--
transtrans-- MC-5 MC-5 ciscis-- MC-4 MC-4
racemic
nonracemic
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
Cl
ClCl
ClClCl
Cl
Cl
ClCl
ClClCl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl
chlordane transtrans-- cis cis- - MC-5MC-5 Technical
Chlordane
Air
Water
Sediment
Serum
racemic
nonracemic
heptachlor-epoxide and oxychlordane
heptachlor-epoxide
oxychlordane
exo- exo-
endo- endo-
nonracemic
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
O
H
Cl
ClCl
ClCl
Cl
Cl
O
H
H
Oxychlordane
Air
Water
Serum
nonracemic
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
O
H
Cl
ClCl
ClCl
Cl
Cl
O
H
H
heptachlor-epoxide
Bivalve(corbicula)
beta- gamma-
alpha- chl6-2
chlordene
Technical Chlordane
Atmosphere
River Water
River Sediment
Serum
Figure2 GC/MS-SIM chromatogram showing elution of chlordene on BGB-172 HRGC column. (average of m/z 302.8883 and 304.8853)
Table1 The enantiomeric excess (EE is absolute of 100 X [Area-first – Area-last]/[Area-first + Area-last]) values of chlordane component in serum sample. (%)
chl6-2*3 41
beta-chlordene 3.8
gamma-chlordene 21
heptachlor-exo-epoxide 50
MC-5 71
trans-chlordane 24
cis-chlordane 48
oxy-chlordane 21
•1 Area-first : area of first eluted enantiomer•2 Area-last : area of last eluted enantiomer•3 unknown isomer on chlordane
DDD&DDT ( Air )
(1)2
,4'-D
DD
(2)2
,4'-D
DD
4,4'
-DD
D
(1)2
,4'-D
DT
(2)2
,4'-D
DT
4,4'
-DD
T
DDD&DDT ( Water1 )
(1)2
,4'-D
DD
(2)2
,4'-D
DD
4,4'
-DD
D
DDD&DDT ( Water2 )
(1)2
,4'-D
DD
(2)2
,4'-D
DD
4,4'
-DD
D
DQ Main View Page 1DqData : h:\DiokData\POPsPCBChiralHi2new\07POPsChiralHi-003Injection : 06EDAirItamiCityHVFeb
34 36 38 40 42 44 46 48 50 52 54 56 58 60Retention Time (min)
0
40000
80000
Inte
nsi
ty
PCB7
Calculated Retention Time
#1
84
#1
88
#1
79
(1)/
(2)#
17
6#
18
6#
17
8
#1
82
(1)/
(2)#
17
5
#1
87
(1)#
18
3(2
)#1
83
#1
85
(1)#
17
4(2
)#1
74
#1
81
#1
72
(1)#
17
1#
19
2(2
)#1
71
#1
73
#1
77
#1
93
#1
80
#1
91
#1
70
#1
90
#1
89
34 36 38 40 42 44 46 48 50 52 54 56 58 60Retention Time (min)
0
4000
8000
Inte
nsi
ty
13C-PCB7
DQ Main View Page 1DqData : h:\DiokData\POPsPCBChiralHi2new\07POPsChiralHi-003Injection : 070208Fat98Yf
34 36 38 40 42 44 46 48 50 52 54 56 58 60Retention Time (min)
0
10000
20000
Inte
nsi
ty
PCB7
Calculated Retention Time
#1
84
#1
88
#1
79
(1)/
(2)#
17
6#
18
6#
17
8
#1
82
(1)/
(2)#
17
5
#1
87
(1)#
18
3(2
)#1
83
#1
85
(1)#
17
4(2
)#1
74
#1
81
#1
72
(1)#
17
1#
19
2(2
)#1
71
#1
73
#1
77
#1
93
#1
80
#1
91
#1
70
#1
90
#1
89
34 36 38 40 42 44 46 48 50 52 54 56 58 60Retention Time (min)
1000
2000
Inte
nsi
ty
13C-PCB7
PCB7(adiposetissue)
#187
(1)#
183
(2)#
183
#180
#170
PCB7(Air) #1
87
(1)#
183
(2)#
183
(1)#
174
(2)#
174
(1)#
171
(2)#
171
#180
#170
atropisomer
PCB7(Air) #1
87
(1)#
183
(2)#
183
#185
(1)#
174
(2)#
174
PCB7(adiposetissue)
#187
(1)#
183
(2)#
183
#185
(1)#
174
(2)#
174
0.4
0.8
S- 9 S- 8 S- 10 S- 11 S- 7 S- 6 S- 5 S- 4 S- 3 S- 2 S- 1
EFs of alpha-HCH in sea waters
The North Atlantic OceanThe North Atlantic Ocean
The South China Sea
The Pacific OceanThe Pacific Ocean
The Japan SeaThe Japan Sea
POPs in the oceansE(+)
E(+)+ E(-)EF = ----------
0.5
0.5
0.5
0.5
EF
(-)
EF
(-)
EF
(-)
EF
(-)
The correlation between EFs and alpha-HCH/ΣHCHs ratios
POPs in the oceans
0.4
0.5
0.6
0.0 0.2 0.4 0.6 0.8 1.0alpha-HCH/ ΣHCH
EF
北大西洋 日本海 南シナ海 太平洋
The North Atlantic Ocean The South China Sea
The Japan Sea The Pacific Ocean
The North Atlantic Ocean The South China Sea
The Pacific OceanThe Japan Sea
The EFs of some POPs in the sea waters POPs in the oceans
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
EF
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