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。 Example of chlordane component Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl O Cl Cl Cl Cl Cl Cl Cl Cl H H trans-chlordane Cl chiral oxychlordane Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl O Cl Cl Cl trans-nonachlor cis-nonachlor achiral Cl Cl Cl heptachlor Cl Cl Cl component-U82 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl trans-chlordane Cl Cl Cl component-MC4 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl cis-chlordane Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl component-MC5 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl trans-nonachlo Cl cis-nonachlor Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl component-MC7 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl component-MC6 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl heptachlor-exoepoxide Cl Cl Cl H Cl Cl C* C* H H Cl Cl H H Cl Cl H Cl H Cl Cl oxychlordene Cl Cl Cl Cl Cl O O Cl H H H Cl H Cl H H H H H H Cl H Cl H Cl Cl Cl H Cl Cl H Cl H Cl alpha-HCH O Cl Cl o,p’-DDD Cl Cl Cl O Cl Cl H Cl Cl Cl Cl Cl Cl H Cl H Cl H H O Cl Cl C* Cl Cl Cl Cl Cl Cl O Cl Cl oxychlordane Cl C* Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl o,p’-DDT Cl Cl Cl Cl Cl Cl Cl Cl Cl H Atropisomer of PCB 1 #45 (2,2’,3,6-TeCB) #84(2,2’,3,3’,6-PeCB) #95(2,2’,3,5’,6-PeCB) #91(2,2’,3,4’,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（ＢＧ Ｂ－１７２、20% tert-butyldimethylsilylated betacyclodextrin 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。 HRＧＣ／HRＭＳ and Column GC Hewlettpackard HP-5890II MS JEOL MS-700 Column： BGB-172 (BGB Analytik) 30mX0.25mmID,0.25μmFilmThickness （20%-tert-butyldimethylsilylatedbeta-cyclodextrin in 15%-phenyl-85%methyl-polysiloxane ） Table1 GC/MS conditions GC:HP6890Ⅱ Column:BGB-172 (BGB Analytik) 30mX0.25mmID, 0.25μmFilmThickness Carrier gas:Helium(1.0ml/min constant flow) Oven temp.:120℃(0min)-4℃/min-200℃(0min)-1℃/min230℃(25min), Inj.temp.:230℃ MS:JEOL JMS-800D Ionization mode:EI, Ion source temp.:250℃, Interface temp.:245℃, Ionization current:500μA, Ionization energy:38eV G#: 1 Repeat: 1.01[sec] m/z: 218.9 - 337.9 (1.54M) Ch.# Compound name m/z 1 HCH 218.9116 2 HCH 220.9087 3 13C6-HCH 224.9317 4 Mass Lock 230.9856 5 Lock Check 230.9856 6 DDT 235.0081 7 DDT 237.0053 8 D8ring-DDD 243.0575 9 13Cring-DDT 247.0484 10 heptachlor 271.8102 11 heptachlor 273.8072 12 13C-Heptachlor 276.8269 13 PCB4 289.9224 14 PCB4 291.9195 15 Chlordene 302.8883 16 13C-PCB4 303.9597 17 Chlordene 304.8853 18 13C-Chlordene 312.9218 19 Oxy-chlordene 318.8832 20 Oxy-chlordene 320.8803 21 PCB5 325.8805 22 PCB5 327.8775 23 13C-PCB5 337.9207 GC/MS channel list 1 (2 injections) 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 352.8442 2 heptachlor-O 354.8413 3 PCB6 359.8415 4 PCB6 361.8386 5 13C-Heptachlor362.8778 6 13C-PCB6 371.8818 7 CHL 372.826 8 CHL 374.8231 9 Mass Lock 380.976 10 Lock Check 380.976 11 13C-CHL 384.8566 12 Oxy-CHL 386.8052 13 Oxy-CHL 388.8023 14 PCB7 393.8025 15 PCB7 395.7996 16 13C-Oxy-CHL 398.8358 17 13C-PCB7 405.8428 18 nonachlor 406.787 19 nonachlor 408.7841 20 13C-Nonachlor 418.8176 21 PCB8 427.7636 22 PCB8 429.7606 23 13C-PCB8 441.7999 Technical chlordane import (tons) 2500 2000 1500 1000 500 technical chlordanes (including heptachlor) 1986 1984 1982 1979 1980 1972 1970 1968 1966 1964 1962 1960 1958 0 chlorine number Basic component of technical chlordane in Japan chlorine component ratio (%) α- chlordene 0.7 γ- chlordene 3 β- chlordene 3.6 Cl7 heptachlor 4.8 Cl8 MC-4 0.3 trans- chlordane 18 Cl6 MC-5 5.8 Cl7 cis-chlordane 16 MC-6 1.5 trans-nonachlor 14 cis-nonachlor 4.5 Cl8 Cl9 Cl6 Cl9 chlordane Cl Cl Cl Cl Cl Technical Chlordane trans- Cl Cl Cl trans- cis- cis- Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl MC-5 Cl racemic trans- MC-4 MC-4 trans- MC-5 racemic Cl Atmosphere cis- cisMC-5 Cl Cl Cl Cl MC-5 Cl Cl Cl Cl Cl MC-4 MC-4 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl transtranscis- cis- River Water Cl Cl Cl Cl Cl MC-5 MC-5 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl racemic MC-4 MC-4 trans- Cl Cl trans- River Sediment racemic MC-5 cis- cisMC-5 MC-4 MC-4 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl trans- Technical Chlordane trans- Cl Cl cis- cis- Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl MC-5 racemic MC-5 MC-5 Cl MC-4 MC-4 trans- nonracemic MC-5 Cl Cl Cl cistrans- Cl Serum cis- MC-4 MC-4 Cl chlordane Technical Chlordane Air racemic Water Sediment nonracemic Serum trans- cis- MC-5 heptachlor-epoxide and oxychlordane Cl Cl Cl Cl Cl oxychlordane O Cl Cl Cl H nonracemic exo- exoCl heptachlor-epoxide Cl Cl Cl Cl O Cl endo- endo- Cl H H heptachlorOxychlordane epoxide Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl O Cl Cl O Cl Air Cl H Cl H H Water nonracemic Serum Bivalve (corbicula) beta- Technical Chlordane Atmosphere alpha- gamma- chl6-2 chlordene 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 beta-chlordene 41 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 4,4'-DDD (2)2,4'-DDD (1)2,4'-DDD 4,4'-DDD 4,4'-DDD 4,4'-DDT (2)2,4'-DDT (1)2,4'-DDT (1)2,4'-DDD (2)2,4'-DDD (1)2,4'-DDD (2)2,4'-DDD DDD&DDT（Air） DDD&DDT（Water1） DDD&DDT（Water2） DQ Main View Page 1 DqData : h:\DiokData\POPsPCBChiralHi2new\07POPsChiralHi-003 Injection : 06EDAirItamiCityHVFeb PCB7 Intensity 80000 40000 0 34 36 38 40 42 44 46 48 Retention Time (min) 50 52 50 52 54 56 58 56 58 60 #189 #190 #170 #181 #172 (1)#171 #192 (2)#171 #173 #177 #193 #180 #191 #185 (1)#174 (2)#174 #187 (1)#183 (2)#183 #184 #188 #179 (1)/(2)#176 #186 #178 #182 (1)/(2)#175 Calculated Retention Time Intensity 13C-PCB7 8000 4000 0 34 36 38 40 42 44 46 48 Retention Time (min) 54 60 DQ Main View Page 1 DqData : h:\DiokData\POPsPCBChiralHi2new\07POPsChiralHi-003 Injection : 070208Fat98Yf PCB7 Intensity 20000 10000 0 34 36 38 40 42 44 46 48 Retention Time (min) 50 52 50 52 54 56 58 56 58 60 #189 #190 #170 #181 #172 (1)#171 #192 (2)#171 #173 #177 #193 #180 #191 #185 (1)#174 (2)#174 #187 (1)#183 (2)#183 #184 #188 #179 (1)/(2)#176 #186 #178 #182 (1)/(2)#175 Calculated Retention Time Intensity 13C-PCB7 2000 1000 34 36 38 40 42 44 46 48 Retention Time (min) 54 60 #170 (1)#183 (2)#183 PCB7 (adipose tissue) #180 (1)#174 (2)#174 #170 (1)#171 (2)#171 (1)#183 (2)#183 #180 #187 PCB7 (Air) #187 atropisomer (2)#174 (1)#174 #185 (2)#183 (1)#183 PCB7 (adipose tissue) #187 (2)#174 (1)#174 #185 (2)#183 (1)#183 #187 PCB7 (Air) E(+) EF = ---------E(+)+ E(-) EF (-) EFs of alpha-HCH in sea waters POPs in the oceans 0.5 The Japan Sea EF (-) 0.8 0.5 The South China Sea EF (-) 0.4 0.5 EF (-) The North Atlantic Ocean 0.5 The Pacific Ocean S-9 S-8 S-10 S-11 S-7 S-6 S-5 S-4 S-3 S-2 S-1 The correlation between EFs and alphaHCH/ΣHCHs ratios 0.6 POPs in the oceans The North Atlantic Ocean The South China Sea The Japan Sea The Pacific Ocean EF 北大西洋 日本海 南シナ海 太平洋 0.5 0.4 0.0 0.2 0.4 0.6 alpha -HCH/ΣHCH 0.8 1.0 POPs in the oceans The EFs of some POPs in the sea waters The North Atlantic Ocean The South China Sea The Japan Sea The Pacific Ocean 0.8 0.7 EF 0.6 0.5 0.4 0.3 0.2 Heptachlor-exo-epoxide trans-chlordane 0 1 2 3 4 5 6 7 8 9cis-chlordane 10 11 12 13 α 14-HCH 15 16 17
© Copyright 2024 ExpyDoc
