CN117030904B - 液相色谱质谱联用测定环境样品中144种类固醇激素的方法 - Google Patents
液相色谱质谱联用测定环境样品中144种类固醇激素的方法 Download PDFInfo
- Publication number
- CN117030904B CN117030904B CN202311278599.0A CN202311278599A CN117030904B CN 117030904 B CN117030904 B CN 117030904B CN 202311278599 A CN202311278599 A CN 202311278599A CN 117030904 B CN117030904 B CN 117030904B
- Authority
- CN
- China
- Prior art keywords
- alpha
- acetate
- beta
- progesterone
- steroid hormones
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003270 steroid hormone Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 title claims abstract description 10
- 230000007613 environmental effect Effects 0.000 title claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 24
- 238000001819 mass spectrum Methods 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 13
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 13
- 238000004458 analytical method Methods 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- -1 testosterone lactone Chemical class 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 9
- 239000002352 surface water Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 5
- 238000004807 desolvation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229960002714 fluticasone Drugs 0.000 claims description 3
- MGNNYOODZCAHBA-GQKYHHCASA-N fluticasone Chemical compound C1([C@@H](F)C2)=CC(=O)C=C[C@]1(C)[C@]1(F)[C@@H]2[C@@H]2C[C@@H](C)[C@@](C(=O)SCF)(O)[C@@]2(C)C[C@@H]1O MGNNYOODZCAHBA-GQKYHHCASA-N 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000006978 adaptation Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000004704 ultra performance liquid chromatography Methods 0.000 claims description 2
- 238000002137 ultrasound extraction Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 6
- 229940092705 beclomethasone Drugs 0.000 claims 4
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 claims 4
- RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 claims 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 3
- MUMGGOZAMZWBJJ-DYKIIFRCSA-N Testostosterone Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 MUMGGOZAMZWBJJ-DYKIIFRCSA-N 0.000 claims 3
- AODPIQQILQLWGS-GXBDJPPSSA-N tetrahydrocortisol Chemical compound C1[C@H](O)CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CC[C@@H]21 AODPIQQILQLWGS-GXBDJPPSSA-N 0.000 claims 3
- XMRPGKVKISIQBV-UHFFFAOYSA-N (+-)-5- Pregnane-3,20-dione Natural products C1CC2CC(=O)CCC2(C)C2C1C1CCC(C(=O)C)C1(C)CC2 XMRPGKVKISIQBV-UHFFFAOYSA-N 0.000 claims 2
- FUFLCEKSBBHCMO-UHFFFAOYSA-N 11-dehydrocorticosterone Natural products O=C1CCC2(C)C3C(=O)CC(C)(C(CC4)C(=O)CO)C4C3CCC2=C1 FUFLCEKSBBHCMO-UHFFFAOYSA-N 0.000 claims 2
- BFZHCUBIASXHPK-ATWVFEABSA-N 11beta-hydroxyprogesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)C[C@@H]2O BFZHCUBIASXHPK-ATWVFEABSA-N 0.000 claims 2
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 claims 2
- DCMCEXCRUWBAFV-LDGASQGZSA-N 20beta-dihydrocorticosterone Chemical compound C[C@]12C[C@H](O)[C@H]3[C@@H](CCC4=CC(=O)CC[C@]34C)[C@@H]1CC[C@@H]2[C@H](O)CO DCMCEXCRUWBAFV-LDGASQGZSA-N 0.000 claims 2
- 229940022663 acetate Drugs 0.000 claims 2
- NBMKJKDGKREAPL-DVTGEIKXSA-N beclomethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(Cl)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O NBMKJKDGKREAPL-DVTGEIKXSA-N 0.000 claims 2
- CBGUOGMQLZIXBE-XGQKBEPLSA-N clobetasol propionate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)CCl)(OC(=O)CC)[C@@]1(C)C[C@@H]2O CBGUOGMQLZIXBE-XGQKBEPLSA-N 0.000 claims 2
- UWFYSQMTEOIJJG-FDTZYFLXSA-N cyproterone acetate Chemical compound C1=C(Cl)C2=CC(=O)[C@@H]3C[C@@H]3[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(C)=O)(OC(=O)C)[C@@]1(C)CC2 UWFYSQMTEOIJJG-FDTZYFLXSA-N 0.000 claims 2
- 229960000978 cyproterone acetate Drugs 0.000 claims 2
- 229960000890 hydrocortisone Drugs 0.000 claims 2
- 229960002985 medroxyprogesterone acetate Drugs 0.000 claims 2
- 229960004719 nandrolone Drugs 0.000 claims 2
- NPAGDVCDWIYMMC-IZPLOLCNSA-N nandrolone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 NPAGDVCDWIYMMC-IZPLOLCNSA-N 0.000 claims 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims 2
- 239000000186 progesterone Substances 0.000 claims 2
- 229960003387 progesterone Drugs 0.000 claims 2
- 229960003604 testosterone Drugs 0.000 claims 2
- WWYNJERNGUHSAO-XUDSTZEESA-N (+)-Norgestrel Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](CC)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 WWYNJERNGUHSAO-XUDSTZEESA-N 0.000 claims 1
- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 claims 1
- CBMYJHIOYJEBSB-UHFFFAOYSA-N (10S)-3t.17t-Dihydroxy-10r.13c-dimethyl-(5cH.8cH.9tH.14tH)-hexadecahydro-1H-cyclopenta[a]phenanthren Natural products C1C(O)CCC2(C)C3CCC(C)(C(CC4)O)C4C3CCC21 CBMYJHIOYJEBSB-UHFFFAOYSA-N 0.000 claims 1
- IWRPVTXREVYBHT-UHFFFAOYSA-N (17-acetyl-10,13-dimethyl-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-11-yl) acetate Chemical compound O=C1CCC2(C)C3C(OC(=O)C)CC4(C)C(C(C)=O)CCC4C3CCC2=C1 IWRPVTXREVYBHT-UHFFFAOYSA-N 0.000 claims 1
- AODPIQQILQLWGS-UHFFFAOYSA-N (3alpa,5beta,11beta,17alphaOH)-form-3,11,17,21-Tetrahydroxypregnan-20-one, Natural products C1C(O)CCC2(C)C3C(O)CC(C)(C(CC4)(O)C(=O)CO)C4C3CCC21 AODPIQQILQLWGS-UHFFFAOYSA-N 0.000 claims 1
- RHQQHZQUAMFINJ-UHFFFAOYSA-N (3alpha,5alpha,11beta)-3,11,21-Trihydroxypregnan-20-one Natural products C1C(O)CCC2(C)C3C(O)CC(C)(C(CC4)C(=O)CO)C4C3CCC21 RHQQHZQUAMFINJ-UHFFFAOYSA-N 0.000 claims 1
- RAJWOBJTTGJROA-UHFFFAOYSA-N (5alpha)-androstane-3,17-dione Natural products C1C(=O)CCC2(C)C3CCC(C)(C(CC4)=O)C4C3CCC21 RAJWOBJTTGJROA-UHFFFAOYSA-N 0.000 claims 1
- UUOHXXXJRQGPLC-QCQJMWNZSA-N (5r,8r,9s,10s,13s,14s,17r)-17-acetyl-17-hydroxy-10,13-dimethyl-2,4,5,6,7,8,9,11,12,14,15,16-dodecahydro-1h-cyclopenta[a]phenanthren-3-one Chemical compound C([C@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@@](C(=O)C)(O)[C@@]2(C)CC1 UUOHXXXJRQGPLC-QCQJMWNZSA-N 0.000 claims 1
- HFSZYSZYZVKKOX-CXICGXRGSA-N (6r,8s,9s,10r,13s,14s,17s)-17-acetyl-6-bromo-10,13-dimethyl-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one Chemical compound C1([C@H](Br)C2)=CC(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)C)[C@@]2(C)CC1 HFSZYSZYZVKKOX-CXICGXRGSA-N 0.000 claims 1
- RFDNAAHBIYPJCO-KVSHDJGKSA-N (8S,9S,10R,13R,14S)-10,13-dimethyl-3,5,6,7,8,9,11,12,14,15-decahydro-2H-cyclopenta[a]phenanthrene-1,4-dione Chemical compound C[C@@]12C=CC[C@H]1[C@@H]1CCC3C(CCC([C@]3(C)[C@H]1CC2)=O)=O RFDNAAHBIYPJCO-KVSHDJGKSA-N 0.000 claims 1
- SWNFRSGMYREPFG-XGXHKTLJSA-N (8r,9s,10r,13s,14s,17r)-17-ethynyl-17-hydroxy-13-methyl-1,2,8,9,10,11,12,14,15,16-decahydrocyclopenta[a]phenanthren-3-one Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3C=CC2=C1 SWNFRSGMYREPFG-XGXHKTLJSA-N 0.000 claims 1
- XBIDABJJGYNJTK-VDUMFTQRSA-N (8s,9s,10r,13s,14s,17r)-17-[(1s)-1,2-dihydroxyethyl]-17-hydroxy-10,13-dimethyl-1,2,6,7,8,9,12,14,15,16-decahydrocyclopenta[a]phenanthrene-3,11-dione Chemical compound O=C1CC[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)[C@@H](O)CO)[C@@H]4[C@@H]3CCC2=C1 XBIDABJJGYNJTK-VDUMFTQRSA-N 0.000 claims 1
- KKVPWYXKKAIBTN-FDIQSBBYSA-N (8s,9s,10r,13s,14s,17s)-17-acetyl-1-fluoro-10,13-dimethyl-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one Chemical compound C1CC2=CC(=O)CC(F)[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 KKVPWYXKKAIBTN-FDIQSBBYSA-N 0.000 claims 1
- JYYRDDFNMDZIIP-IDDWWOGSSA-N (8s,9s,10r,13s,14s,17s)-17-acetyl-10,13,16-trimethyl-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC(C)[C@H](C(C)=O)[C@@]1(C)CC2 JYYRDDFNMDZIIP-IDDWWOGSSA-N 0.000 claims 1
- JGMOKGBVKVMRFX-LEKSSAKUSA-N (8s,9s,10r,13s,14s,17s)-17-acetyl-10,13-dimethyl-1,2,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthren-3-one Chemical compound C1=CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 JGMOKGBVKVMRFX-LEKSSAKUSA-N 0.000 claims 1
- OKUWFSWDZQMETE-LEKSSAKUSA-N (8s,9s,10r,13s,14s,17s)-17-acetyl-10,13-dimethyl-8,9,11,12,14,15,16,17-octahydrocyclopenta[a]phenanthren-3-one Chemical compound C1=CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 OKUWFSWDZQMETE-LEKSSAKUSA-N 0.000 claims 1
- RZRPTBIGEANTGU-UHFFFAOYSA-N -Androst-4-ene-3,11,17-trione Natural products O=C1CCC2(C)C3C(=O)CC(C)(C(CC4)=O)C4C3CCC2=C1 RZRPTBIGEANTGU-UHFFFAOYSA-N 0.000 claims 1
- FUFLCEKSBBHCMO-KJQYFISQSA-N 11-dehydrocorticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3C(=O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 FUFLCEKSBBHCMO-KJQYFISQSA-N 0.000 claims 1
- ZESRJSPZRDMNHY-YFWFAHHUSA-N 11-deoxycorticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 ZESRJSPZRDMNHY-YFWFAHHUSA-N 0.000 claims 1
- WSCUHXPGYUMQEX-KCZNZURUSA-N 11beta-hydroxyandrost-4-ene-3,17-dione Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 WSCUHXPGYUMQEX-KCZNZURUSA-N 0.000 claims 1
- FZEAQJIXYCPBLD-UHFFFAOYSA-N 11beta-hydroxyandrostenedione Natural products C1C(=O)CCC2(C)C3C(O)CC(C)(C(CC4)=O)C4C3CCC21 FZEAQJIXYCPBLD-UHFFFAOYSA-N 0.000 claims 1
- VRRHHTISESGZFN-RKFFNLMFSA-N 16,17-didehydroprogesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC=C(C(=O)C)[C@@]1(C)CC2 VRRHHTISESGZFN-RKFFNLMFSA-N 0.000 claims 1
- LHNVKVKZPHUYQO-SRWWVFQWSA-N 16-alpha,17-Epoxypregn-4-ene-3,20-dione Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1C[C@H]3O[C@@]3(C(=O)C)[C@@]1(C)CC2 LHNVKVKZPHUYQO-SRWWVFQWSA-N 0.000 claims 1
- ABBVGECYEGYVPY-CEGNMAFCSA-N 17,21-Dihydroxypregn-4-en-3-one Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)CCO)[C@@H]4[C@@H]3CCC2=C1 ABBVGECYEGYVPY-CEGNMAFCSA-N 0.000 claims 1
- 229930182834 17alpha-Estradiol Natural products 0.000 claims 1
- GCKMFJBGXUYNAG-UHFFFAOYSA-N 17alpha-methyltestosterone Natural products C1CC2=CC(=O)CCC2(C)C2C1C1CCC(C)(O)C1(C)CC2 GCKMFJBGXUYNAG-UHFFFAOYSA-N 0.000 claims 1
- VOXZDWNPVJITMN-SFFUCWETSA-N 17α-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-SFFUCWETSA-N 0.000 claims 1
- XGUHPTGEXRHMQQ-BGJMDTOESA-N 19-hydroxyandrost-4-ene-3,17-dione Chemical compound O=C1CC[C@]2(CO)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 XGUHPTGEXRHMQQ-BGJMDTOESA-N 0.000 claims 1
- JIVPVXMEBJLZRO-CQSZACIVSA-N 2-chloro-5-[(1r)-1-hydroxy-3-oxo-2h-isoindol-1-yl]benzenesulfonamide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC([C@@]2(O)C3=CC=CC=C3C(=O)N2)=C1 JIVPVXMEBJLZRO-CQSZACIVSA-N 0.000 claims 1
- AODPIQQILQLWGS-FDSHTENPSA-N 5a-Tetrahydrocortisol Chemical compound C1[C@H](O)CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CC[C@H]21 AODPIQQILQLWGS-FDSHTENPSA-N 0.000 claims 1
- RAJWOBJTTGJROA-WZNAKSSCSA-N 5alpha-androstane-3,17-dione Chemical compound C1C(=O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC[C@H]21 RAJWOBJTTGJROA-WZNAKSSCSA-N 0.000 claims 1
- XMRPGKVKISIQBV-BJMCWZGWSA-N 5alpha-pregnane-3,20-dione Chemical compound C([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)C)[C@@]2(C)CC1 XMRPGKVKISIQBV-BJMCWZGWSA-N 0.000 claims 1
- RAJWOBJTTGJROA-QJISAEMRSA-N 5beta-androstane-3,17-dione Chemical compound C1C(=O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC[C@@H]21 RAJWOBJTTGJROA-QJISAEMRSA-N 0.000 claims 1
- ACSFOIGNUQUIGE-AIPUTVCKSA-N 5beta-dihydrocortisol Chemical compound C1C(=O)CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CC[C@@H]21 ACSFOIGNUQUIGE-AIPUTVCKSA-N 0.000 claims 1
- XMRPGKVKISIQBV-XWOJZHJZSA-N 5beta-pregnane-3,20-dione Chemical compound C([C@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)C)[C@@]2(C)CC1 XMRPGKVKISIQBV-XWOJZHJZSA-N 0.000 claims 1
- QGXBDMJGAMFCBF-HLUDHZFRSA-N 5α-Androsterone Chemical compound C1[C@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC[C@H]21 QGXBDMJGAMFCBF-HLUDHZFRSA-N 0.000 claims 1
- VHRSUDSXCMQTMA-PJHHCJLFSA-N 6alpha-methylprednisolone Chemical compound C([C@@]12C)=CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2[C@@H](O)C[C@]2(C)[C@@](O)(C(=O)CO)CC[C@H]21 VHRSUDSXCMQTMA-PJHHCJLFSA-N 0.000 claims 1
- PQSUYGKTWSAVDQ-ZVIOFETBSA-N Aldosterone Chemical compound C([C@@]1([C@@H](C(=O)CO)CC[C@H]1[C@@H]1CC2)C=O)[C@H](O)[C@@H]1[C@]1(C)C2=CC(=O)CC1 PQSUYGKTWSAVDQ-ZVIOFETBSA-N 0.000 claims 1
- PQSUYGKTWSAVDQ-UHFFFAOYSA-N Aldosterone Natural products C1CC2C3CCC(C(=O)CO)C3(C=O)CC(O)C2C2(C)C1=CC(=O)CC2 PQSUYGKTWSAVDQ-UHFFFAOYSA-N 0.000 claims 1
- KUVIULQEHSCUHY-XYWKZLDCSA-N Beclometasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(Cl)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)COC(=O)CC)(OC(=O)CC)[C@@]1(C)C[C@@H]2O KUVIULQEHSCUHY-XYWKZLDCSA-N 0.000 claims 1
- VOVIALXJUBGFJZ-KWVAZRHASA-N Budesonide Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1C[C@H]3OC(CCC)O[C@@]3(C(=O)CO)[C@@]1(C)C[C@@H]2O VOVIALXJUBGFJZ-KWVAZRHASA-N 0.000 claims 1
- HBSSQMGFYWXRJY-DADHALBJSA-N C(C)(=O)O.ClC1[C@@H]([C@]2(CC[C@@H]3[C@]4(CCC(C=C4CC[C@H]3[C@@H]2C1)=O)C)C)C(C)=O Chemical compound C(C)(=O)O.ClC1[C@@H]([C@]2(CC[C@@H]3[C@]4(CCC(C=C4CC[C@H]3[C@@H]2C1)=O)C)C)C(C)=O HBSSQMGFYWXRJY-DADHALBJSA-N 0.000 claims 1
- OMFXVFTZEKFJBZ-UHFFFAOYSA-N Corticosterone Natural products O=C1CCC2(C)C3C(O)CC(C)(C(CC4)C(=O)CO)C4C3CCC2=C1 OMFXVFTZEKFJBZ-UHFFFAOYSA-N 0.000 claims 1
- MFYSYFVPBJMHGN-ZPOLXVRWSA-N Cortisone Chemical compound O=C1CC[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 MFYSYFVPBJMHGN-ZPOLXVRWSA-N 0.000 claims 1
- MFYSYFVPBJMHGN-UHFFFAOYSA-N Cortisone Natural products O=C1CCC2(C)C3C(=O)CC(C)(C(CC4)(O)C(=O)CO)C4C3CCC2=C1 MFYSYFVPBJMHGN-UHFFFAOYSA-N 0.000 claims 1
- AEMOLEFTQBMNLQ-AQKNRBDQSA-N D-glucopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-AQKNRBDQSA-N 0.000 claims 1
- FMGSKLZLMKYGDP-UHFFFAOYSA-N Dehydroepiandrosterone Natural products C1C(O)CCC2(C)C3CCC(C)(C(CC4)=O)C4C3CC=C21 FMGSKLZLMKYGDP-UHFFFAOYSA-N 0.000 claims 1
- HCYAFALTSJYZDH-UHFFFAOYSA-N Desimpramine Chemical compound C1CC2=CC=CC=C2N(CCCNC)C2=CC=CC=C21 HCYAFALTSJYZDH-UHFFFAOYSA-N 0.000 claims 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 claims 1
- BFPYWIDHMRZLRN-SLHNCBLASA-N Ethinyl estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 BFPYWIDHMRZLRN-SLHNCBLASA-N 0.000 claims 1
- QGXBDMJGAMFCBF-UHFFFAOYSA-N Etiocholanolone Natural products C1C(O)CCC2(C)C3CCC(C)(C(CC4)=O)C4C3CCC21 QGXBDMJGAMFCBF-UHFFFAOYSA-N 0.000 claims 1
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 claims 1
- GCKMFJBGXUYNAG-HLXURNFRSA-N Methyltestosterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@](C)(O)[C@@]1(C)CC2 GCKMFJBGXUYNAG-HLXURNFRSA-N 0.000 claims 1
- IMONTRJLAWHYGT-ZCPXKWAGSA-N Norethindrone Acetate Chemical compound C1CC2=CC(=O)CC[C@@H]2[C@@H]2[C@@H]1[C@@H]1CC[C@](C#C)(OC(=O)C)[C@@]1(C)CC2 IMONTRJLAWHYGT-ZCPXKWAGSA-N 0.000 claims 1
- PDMMFKSKQVNJMI-BLQWBTBKSA-N Testosterone propionate Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](OC(=O)CC)[C@@]1(C)CC2 PDMMFKSKQVNJMI-BLQWBTBKSA-N 0.000 claims 1
- RHQQHZQUAMFINJ-DTDWNVJFSA-N Tetrahydrocorticosterone Chemical compound C1[C@H](O)CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CC[C@@H]21 RHQQHZQUAMFINJ-DTDWNVJFSA-N 0.000 claims 1
- XGMPVBXKDAHORN-RBWIMXSLSA-N Triamcinolone diacetate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](OC(C)=O)[C@@](C(=O)COC(=O)C)(O)[C@@]1(C)C[C@@H]2O XGMPVBXKDAHORN-RBWIMXSLSA-N 0.000 claims 1
- FPVRUILUEYSIMD-RPRRAYFGSA-N [(8s,9r,10s,11s,13s,14s,16r,17r)-9-fluoro-11-hydroxy-17-(2-hydroxyacetyl)-10,13,16-trimethyl-3-oxo-6,7,8,11,12,14,15,16-octahydrocyclopenta[a]phenanthren-17-yl] acetate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(OC(C)=O)[C@@]1(C)C[C@@H]2O FPVRUILUEYSIMD-RPRRAYFGSA-N 0.000 claims 1
- MULICLCRGFYQJF-LLTWYMBTSA-N [2-[(3r,5r,8s,9s,10s,13s,14s,17r)-3,17-dihydroxy-10,13-dimethyl-11-oxo-2,3,4,5,6,7,8,9,12,14,15,16-dodecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-oxoethyl] acetate Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@@](C(=O)COC(=O)C)(O)[C@@]2(C)CC1=O MULICLCRGFYQJF-LLTWYMBTSA-N 0.000 claims 1
- UZYCDQSWBJSKQK-CXKJNVJPSA-N acetic acid;(8s,9s,10r,13s,14s,17s)-17-(2-hydroxyacetyl)-10,13-dimethyl-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one Chemical compound CC(O)=O.O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 UZYCDQSWBJSKQK-CXKJNVJPSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- RZRPTBIGEANTGU-IRIMSJTPSA-N adrenosterone Chemical compound O=C1CC[C@]2(C)[C@H]3C(=O)C[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 RZRPTBIGEANTGU-IRIMSJTPSA-N 0.000 claims 1
- 229960002478 aldosterone Drugs 0.000 claims 1
- 229960002587 amitraz Drugs 0.000 claims 1
- QXAITBQSYVNQDR-ZIOPAAQOSA-N amitraz Chemical compound C=1C=C(C)C=C(C)C=1/N=C/N(C)\C=N\C1=CC=C(C)C=C1C QXAITBQSYVNQDR-ZIOPAAQOSA-N 0.000 claims 1
- AEMFNILZOJDQLW-QAGGRKNESA-N androst-4-ene-3,17-dione Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 AEMFNILZOJDQLW-QAGGRKNESA-N 0.000 claims 1
- 229960005471 androstenedione Drugs 0.000 claims 1
- AEMFNILZOJDQLW-UHFFFAOYSA-N androstenedione Natural products O=C1CCC2(C)C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 AEMFNILZOJDQLW-UHFFFAOYSA-N 0.000 claims 1
- 229940061641 androsterone Drugs 0.000 claims 1
- 229950000210 beclometasone dipropionate Drugs 0.000 claims 1
- 229960002537 betamethasone Drugs 0.000 claims 1
- UREBDLICKHMUKA-DVTGEIKXSA-N betamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-DVTGEIKXSA-N 0.000 claims 1
- AKUJBENLRBOFTD-QZIXMDIESA-N betamethasone acetate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)COC(C)=O)(O)[C@@]1(C)C[C@@H]2O AKUJBENLRBOFTD-QZIXMDIESA-N 0.000 claims 1
- 229960004648 betamethasone acetate Drugs 0.000 claims 1
- 229960004436 budesonide Drugs 0.000 claims 1
- UJVLDDZCTMKXJK-WNHSNXHDSA-N canrenone Chemical compound C([C@H]1[C@H]2[C@@H]([C@]3(CCC(=O)C=C3C=C2)C)CC[C@@]11C)C[C@@]11CCC(=O)O1 UJVLDDZCTMKXJK-WNHSNXHDSA-N 0.000 claims 1
- 229960005057 canrenone Drugs 0.000 claims 1
- IRKHFYZGVKPLBN-UHFFFAOYSA-N carboxy propanoate Chemical compound CCC(=O)OC(O)=O IRKHFYZGVKPLBN-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 229960001523 chlortalidone Drugs 0.000 claims 1
- 229960002842 clobetasol Drugs 0.000 claims 1
- 229960004703 clobetasol propionate Drugs 0.000 claims 1
- MOVRKLZUVNCBIP-RFZYENFJSA-N cortancyl Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)COC(=O)C)(O)[C@@]1(C)CC2=O MOVRKLZUVNCBIP-RFZYENFJSA-N 0.000 claims 1
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims 1
- FZCHYNWYXKICIO-FZNHGJLXSA-N cortisol 17-valerate Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)CO)(OC(=O)CCCC)[C@@]1(C)C[C@@H]2O FZCHYNWYXKICIO-FZNHGJLXSA-N 0.000 claims 1
- 229960004544 cortisone Drugs 0.000 claims 1
- ZESRJSPZRDMNHY-UHFFFAOYSA-N de-oxy corticosterone Natural products O=C1CCC2(C)C3CCC(C)(C(CC4)C(=O)CO)C4C3CCC2=C1 ZESRJSPZRDMNHY-UHFFFAOYSA-N 0.000 claims 1
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 claims 1
- 229940119740 deoxycorticosterone Drugs 0.000 claims 1
- 229960003914 desipramine Drugs 0.000 claims 1
- 229960003957 dexamethasone Drugs 0.000 claims 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 claims 1
- 229960003657 dexamethasone acetate Drugs 0.000 claims 1
- 229960004913 dydrogesterone Drugs 0.000 claims 1
- JGMOKGBVKVMRFX-HQZYFCCVSA-N dydrogesterone Chemical compound C1=CC2=CC(=O)CC[C@@]2(C)[C@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 JGMOKGBVKVMRFX-HQZYFCCVSA-N 0.000 claims 1
- 229960005309 estradiol Drugs 0.000 claims 1
- 229960003399 estrone Drugs 0.000 claims 1
- 229960002941 etonogestrel Drugs 0.000 claims 1
- GCKFUYQCUCGESZ-BPIQYHPVSA-N etonogestrel Chemical compound O=C1CC[C@@H]2[C@H]3C(=C)C[C@](CC)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 GCKFUYQCUCGESZ-BPIQYHPVSA-N 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 229960002011 fludrocortisone Drugs 0.000 claims 1
- AAXVEMMRQDVLJB-BULBTXNYSA-N fludrocortisone Chemical compound O=C1CC[C@]2(C)[C@@]3(F)[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 AAXVEMMRQDVLJB-BULBTXNYSA-N 0.000 claims 1
- SYWHXTATXSMDSB-GSLJADNHSA-N fludrocortisone acetate Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1CC[C@@](C(=O)COC(=O)C)(O)[C@@]1(C)C[C@@H]2O SYWHXTATXSMDSB-GSLJADNHSA-N 0.000 claims 1
- 229960000676 flunisolide Drugs 0.000 claims 1
- 229960001347 fluocinolone acetonide Drugs 0.000 claims 1
- FEBLZLNTKCEFIT-VSXGLTOVSA-N fluocinolone acetonide Chemical compound C1([C@@H](F)C2)=CC(=O)C=C[C@]1(C)[C@]1(F)[C@@H]2[C@@H]2C[C@H]3OC(C)(C)O[C@@]3(C(=O)CO)[C@@]2(C)C[C@@H]1O FEBLZLNTKCEFIT-VSXGLTOVSA-N 0.000 claims 1
- 229960003336 fluorocortisol acetate Drugs 0.000 claims 1
- 229940097043 glucuronic acid Drugs 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 229960004400 levonorgestrel Drugs 0.000 claims 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 claims 1
- RQZAXGRLVPAYTJ-GQFGMJRRSA-N megestrol acetate Chemical compound C1=C(C)C2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(C)=O)(OC(=O)C)[C@@]1(C)CC2 RQZAXGRLVPAYTJ-GQFGMJRRSA-N 0.000 claims 1
- 229960004296 megestrol acetate Drugs 0.000 claims 1
- 229960004584 methylprednisolone Drugs 0.000 claims 1
- 229960001566 methyltestosterone Drugs 0.000 claims 1
- 229960003248 mifepristone Drugs 0.000 claims 1
- VKHAHZOOUSRJNA-GCNJZUOMSA-N mifepristone Chemical compound C1([C@@H]2C3=C4CCC(=O)C=C4CC[C@H]3[C@@H]3CC[C@@]([C@]3(C2)C)(O)C#CC)=CC=C(N(C)C)C=C1 VKHAHZOOUSRJNA-GCNJZUOMSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229960001133 nandrolone phenpropionate Drugs 0.000 claims 1
- UBWXUGDQUBIEIZ-QNTYDACNSA-N nandrolone phenpropionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@H]4CCC(=O)C=C4CC3)CC[C@@]21C)C(=O)CCC1=CC=CC=C1 UBWXUGDQUBIEIZ-QNTYDACNSA-N 0.000 claims 1
- 229940053934 norethindrone Drugs 0.000 claims 1
- 229960001652 norethindrone acetate Drugs 0.000 claims 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims 1
- 229960000417 norgestimate Drugs 0.000 claims 1
- KIQQMECNKUGGKA-NMYWJIRASA-N norgestimate Chemical compound O/N=C/1CC[C@@H]2[C@H]3CC[C@](CC)([C@](CC4)(OC(C)=O)C#C)[C@@H]4[C@@H]3CCC2=C\1 KIQQMECNKUGGKA-NMYWJIRASA-N 0.000 claims 1
- 230000010355 oscillation Effects 0.000 claims 1
- 229960002847 prasterone Drugs 0.000 claims 1
- 229960004618 prednisone Drugs 0.000 claims 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 claims 1
- MIXMJCQRHVAJIO-TZHJZOAOSA-N qk4dys664x Chemical compound O.C1([C@@H](F)C2)=CC(=O)C=C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2C[C@H]3OC(C)(C)O[C@@]3(C(=O)CO)[C@@]2(C)C[C@@H]1O.C1([C@@H](F)C2)=CC(=O)C=C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2C[C@H]3OC(C)(C)O[C@@]3(C(=O)CO)[C@@]2(C)C[C@@H]1O MIXMJCQRHVAJIO-TZHJZOAOSA-N 0.000 claims 1
- 229960001487 rimexolone Drugs 0.000 claims 1
- QTTRZHGPGKRAFB-OOKHYKNYSA-N rimexolone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CC)(C)[C@@]1(C)C[C@@H]2O QTTRZHGPGKRAFB-OOKHYKNYSA-N 0.000 claims 1
- LXMSZDCAJNLERA-KVXIHFSQSA-N s-[(7s,8r,9s,10r,13s,14s,17r)-10,13-dimethyl-3,5'-dioxospiro[2,6,7,8,9,11,12,14,15,16-decahydro-1h-cyclopenta[a]phenanthrene-17,2'-oxolane]-7-yl] ethanethioate Chemical compound C([C@@H]1[C@]2(C)CC[C@@H]3[C@@]4(C)CCC(=O)C=C4C[C@@H]([C@@H]13)SC(=O)C)C[C@@]21CCC(=O)O1 LXMSZDCAJNLERA-KVXIHFSQSA-N 0.000 claims 1
- LXMSZDCAJNLERA-ZHYRCANASA-N spironolactone Chemical compound C([C@@H]1[C@]2(C)CC[C@@H]3[C@@]4(C)CCC(=O)C=C4C[C@H]([C@@H]13)SC(=O)C)C[C@@]21CCC(=O)O1 LXMSZDCAJNLERA-ZHYRCANASA-N 0.000 claims 1
- 229960002256 spironolactone Drugs 0.000 claims 1
- 229960001712 testosterone propionate Drugs 0.000 claims 1
- MEHHPFQKXOUFFV-OWSLCNJRSA-N trenbolone Chemical compound C1CC(=O)C=C2CC[C@@H]([C@H]3[C@@](C)([C@H](CC3)O)C=C3)C3=C21 MEHHPFQKXOUFFV-OWSLCNJRSA-N 0.000 claims 1
- 229960000312 trenbolone Drugs 0.000 claims 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 claims 1
- 229960002117 triamcinolone acetonide Drugs 0.000 claims 1
- YNDXUCZADRHECN-JNQJZLCISA-N triamcinolone acetonide Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H]3OC(C)(C)O[C@@]3(C(=O)CO)[C@@]1(C)C[C@@H]2O YNDXUCZADRHECN-JNQJZLCISA-N 0.000 claims 1
- 229960004320 triamcinolone diacetate Drugs 0.000 claims 1
- JUNDJWOLDSCTFK-MTZCLOFQSA-N trimegestone Chemical compound C1CC2=CC(=O)CCC2=C2[C@@H]1[C@@H]1CC[C@@](C(=O)[C@@H](O)C)(C)[C@@]1(C)CC2 JUNDJWOLDSCTFK-MTZCLOFQSA-N 0.000 claims 1
- 229950008546 trimegestone Drugs 0.000 claims 1
- 229940070710 valerate Drugs 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000004907 flux Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 18
- 238000000926 separation method Methods 0.000 description 8
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000003862 glucocorticoid Substances 0.000 description 3
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000003098 androgen Substances 0.000 description 2
- 229940030486 androgens Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000262 estrogen Substances 0.000 description 2
- 229940011871 estrogen Drugs 0.000 description 2
- 239000002395 mineralocorticoid Substances 0.000 description 2
- 229940037129 plain mineralocorticoids for systemic use Drugs 0.000 description 2
- 239000000583 progesterone congener Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003431 steroids Chemical class 0.000 description 2
- 229940037128 systemic glucocorticoids Drugs 0.000 description 2
- RJKFOVLPORLFTN-PQIPVKAESA-N (8s,9s,10r,13s,14s,17s)-2,2,4,6,6,17-hexadeuterio-10,13-dimethyl-17-(2,2,2-trideuterioacetyl)-7,8,9,11,12,14,15,16-octahydro-1h-cyclopenta[a]phenanthren-3-one Chemical compound C([C@]1(C)[C@@]([2H])(C(=O)C([2H])([2H])[2H])CC[C@H]1[C@@H]1CC2([2H])[2H])C[C@@H]1[C@]1(C)C2=C([2H])C(=O)C([2H])([2H])C1 RJKFOVLPORLFTN-PQIPVKAESA-N 0.000 description 1
- QTBSBXVTEAMEQO-FIBGUPNXSA-N 2,2,2-trideuterioacetic acid Chemical compound [2H]C([2H])([2H])C(O)=O QTBSBXVTEAMEQO-FIBGUPNXSA-N 0.000 description 1
- XBDQKXXYIPTUBI-ZBJDZAJPSA-N 2,2,3,3,3-pentadeuteriopropanoic acid Chemical compound [2H]C([2H])([2H])C([2H])([2H])C(O)=O XBDQKXXYIPTUBI-ZBJDZAJPSA-N 0.000 description 1
- 206010062016 Immunosuppression Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000012901 Milli-Q water Substances 0.000 description 1
- AUYYCJSJGJYCDS-LBPRGKRZSA-N Thyrolar Chemical class IC1=CC(C[C@H](N)C(O)=O)=CC(I)=C1OC1=CC=C(O)C(I)=C1 AUYYCJSJGJYCDS-LBPRGKRZSA-N 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- UDKABVSQKJNZBH-TWOXOXTASA-N [(8r,9s,10r,13s,14s,17r)-17-acetyl-6,10,13-trimethyl-16-methylidene-3-oxo-1,2,8,9,11,12,14,15-octahydrocyclopenta[a]phenanthren-17-yl] 2,2,2-trideuterioacetate Chemical compound C1=C(C)C2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC(=C)[C@](OC(=O)C([2H])([2H])[2H])(C(C)=O)[C@@]1(C)CC2 UDKABVSQKJNZBH-TWOXOXTASA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000011861 anti-inflammatory therapy Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000003246 corticosteroid Substances 0.000 description 1
- 229960001334 corticosteroids Drugs 0.000 description 1
- DUSHUSLJJMDGTE-ZJPMUUANSA-N cyproterone Chemical compound C1=C(Cl)C2=CC(=O)[C@@H]3C[C@@H]3[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2 DUSHUSLJJMDGTE-ZJPMUUANSA-N 0.000 description 1
- 229960003843 cyproterone Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003163 gonadal steroid hormone Substances 0.000 description 1
- 230000001506 immunosuppresive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000005495 thyroid hormone Substances 0.000 description 1
- 229940036555 thyroid hormone Drugs 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/52—Physical parameters
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/52—Physical parameters
- G01N30/54—Temperature
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
Abstract
本发明公开了液相色谱质谱联用同时测定环境样品中144种类固醇激素的方法，建立优化了144种类固醇激素的质谱参数，选取最佳质谱条件，优化色谱柱，确定流动相组成及比例，优化流速及柱温，最优化检测灵敏度及色谱峰及色谱质谱。与现有方法相比，本发明物质种类覆盖面广，检测通量高，可以满足多种类固醇激素在环境样品种的检测，最大程度确保样品的有效回收率及重复性。
Description
技术领域
本发明属于检测技术领域，具体涉及是一种液相色谱质谱联用同时测定环境样品中144种类固醇激素的方法。
背景技术
类固醇激素是一类具有生物活性的甾体物质，由胆固醇合成代谢而来，包括性激素（雌激素、雄激素、孕激素）和皮质激素（糖皮质激素、盐皮质激素），对人和动物的生命维持、生长发育、抗炎治疗、免疫抑制等方面具有重要作用。类固醇激素作为一类典型的环境内分泌干扰物，具有很强的内分泌干扰作用，对生态环境危害极大，它们主要来自包括人类在内的脊椎动物的排放，并在环境中不断被检测到。当水中的某些类固醇激素浓度极低时，甚至低于ng/L时，都会对水生生物生殖产生不利影响。
由于液相色谱-质谱法（LC-MS）适用于分析弱挥发性化合物，且无需衍生，增加了同时分析多种化合物的可能性，因此该分析方法广泛应用于类固醇激素的检测。但是目前大部分研究建立的分析方法中，类固醇种类单一，数量少，检测周期长，样品通量低，无法满足多类固醇激素筛查和定量的需求，导致大量的类固醇激素环境污染水平被忽略，尤其是仍具有生物活性的一些类固醇激素。目前对于类固醇激素的同时检测方法层出不穷，种类最多的方法可达六十几种，但对于数目繁多的类固醇激素检测种类仍较少，因此开发一种类型全面，数量种类多的分析检测方法至关重要。
发明内容
本发明的目的在于针对现有技术的不足，提供一种同时检测五大类共计144种类固醇激素的高效液相色谱-质谱串联法，应用于环境样品如地表水和沉积物中类固醇激素的检测。
为了达到上述目的，本发明采用如下技术方案：
一种液相色谱质谱联用测定环境样品中144种类固醇激素的方法，包括如下步骤：
S1：从地表水及沉积物中将类固醇激素通过固相萃取小柱提取出来，选取合适的洗脱溶剂，降低干扰；
S2：建立与优化144种类固醇激素的质谱参数，选取合适的质谱条件；
S3：确定色谱柱，优化色谱柱柱温条件，优化流动相组成和比例，最大程度上地分离144种类固醇激素。
优选的，作为一个较佳的实施方式，所述S1中固相萃取的洗脱溶剂为乙酸乙酯/乙腈（v/v, 1:1）。
优选的，作为一个较佳的实施方式，所述S2中质谱参数的选择与优化：在离子检测模式（MRM）下对于每种类固醇激素，选择两个强度高且稳定性强的MRM离子对，并优化锥孔电压、碰撞能量，两对MRM离子对同时用于定性分析，信号响应较高的离子对用于定量分析，从而建立正离子模式采集办法。
优选的，作为一个较佳的实施方式，所述S3中色谱峰分离度达到最优的方法为：根据所选144种类固醇激素的性质，选取对于同分异构体及相同质谱参数的物质分离效果最好的色谱柱，优化色谱柱柱温，并对流动相中的有机相进行选择调整水相及有机相比例，建立梯度洗脱程序，在此基础上，优化色谱柱的流速，在保证物质分离度的前提下，保证色谱峰峰型达到最优。
优选的，作为一个较佳的实施方式，所述色谱柱包括HSS T3色谱柱（100 mm×2.1mm,1.8µm, Waters）， BEH Phenyl色谱柱（100 mm×2.1 mm, 1.7µm, Waters）和HPH-C18色谱柱（100 mm×2.1 mm, 2.7µm, Agilent）；所述流动相有机相选取甲醇和乙腈，流速在仪器和色谱柱适配的范围内选择0.2或0.4或0.6 mL/min，色谱柱的柱温依据类固醇激素性质选择45 ℃以下。
优选的，作为一个较佳的实施方式，本发明首先在离子监测模式（MRM）下建立与优化144种类固醇激素的质谱参数，选取最佳质谱条件，其次对色谱条件进行对比，优化检测灵敏度和色谱峰分离度。
与现有技术相比，本发明的有益效果为：
建立了同时检测五类144种类固醇激素的高效液相色谱质谱串联法（UPLC-MS/MS），对多种同分异构体物质进行有效分离，实验高通量类固醇激素检测，满足多种类固醇激素的筛查和定量的需求，通过对质谱及色谱的优化大大提高了检测灵敏度。本发明可以丰富完善现有检测技术，物质检测全面，方法重现性好，大大满足了多种类固醇激素的检测和定量的需求。
附图说明
图1为对于难分离同分异构体及相同质谱参数的类固醇激素的色谱分离图谱。
具体实施方式
以下将以检测地表水及沉积物中类固醇激素浓度为例对本发明的技术方案进行更为详细的说明，但这些实施例不对本发明构成任何限制。
一、实施例1：地表水中类固醇激素浓度的检测
1、仪器与试剂：
超高效液相色谱串联质谱联用仪（Waters公司），包括ACQUITY超高效液相系统，TQ-S四级杆质谱；分析天平（美国Mettler公司）；氮吹仪；涡旋振荡器（Vortex-Genie 2），固相萃取装置（SUPELCO VISIPREP 24TM DL）。
甲醇（LC/MS级）、乙腈（LC/MS级）、乙酸乙酯（LC/MS级）、Milli-Q水。
类固醇激素标准品：包括表1中的雌激素、雄激素、孕激素、糖皮质激素、盐皮质激素，以及同位素内标：Estrone-d4、17β-Estradiol-d4、17a-Ethinyl Estradiol-d4、Testosterone-d4、Boldenone-d3、Spironolactone-d6、Cortisol-d4、FluticasonePropionate-d5、Melengestrol Acetate-d3, Norgestrel-d6, Mifepristone-d3,Cyproterone Acetate-d3, Ethisterone-13C2、Progesterone-d9，（纯度大于98%，TorontoResearch Chemicals，（Downsview，ON，Canada）；Steraloids， （Newport，RI， USA））。
2、样品处理（前处理）：
（1）固相萃取法处理地表水：取河水2000 mL，经玻璃纤维滤膜过滤后，用HLB固相萃取柱（500 mg，6 mL）同时富集所有目标类固醇激素。HLB柱首先用6 mL乙酸乙酯、6 mL甲醇及12 mL超纯水活化，过滤后的水样中添加10 ng同位素内标混合均匀，将水样以5-10mL/min的流速通过活化好的HLB柱，固相萃取后，用10 mL超纯水淋洗。然后将HLB柱吹干，吹干后的HLB柱用6 mL乙酸乙酯/乙腈（1:1, v/v）洗脱，将6 mL洗脱液用氮气吹干，用甲醇复溶至200 µL，进入仪器进行分析。
（2）超声萃取法处理沉积物：将沉积物样品冷冻干燥后研磨过80目筛，称取5g，加入到50mL离心管中，加入10 ng类固醇激素的同位素内标，放置12h后，加入20 mL甲醇/乙腈（1:1，v/v）提取液，于25 ℃超声振荡20 min，并离心10 min（5000 r/min, 10 min），收集上清液于200 mL茄形瓶中，重复上述步骤两次，共收集得到60 mL提取液。用旋转蒸发器将提取液在45℃蒸发至干燥，然后用2 mL甲醇润湿瓶壁，最后加入200 mL超纯水，后续步骤与采取样品处理（1）中的步骤相同。
3、超高效液相色谱-串联质谱联用仪进行（UPLC-MS/MS）检测：
（1）质谱分析条件：对于144种类固醇激素，采用电喷雾离子源（ESI），检测模式为正离子模式（ESI+），质谱检测采用多反应监测模式（MRM），离子源温度为150 ℃，脱溶剂气温度为450 ℃，脱溶剂气流量为900 L/h，碰撞气流量为150 L/h，毛细管电压为3.0 kV。主要的质谱参数见表1。
（2）UPLC液相条件：如图1所示，经过三种色谱柱对于难分离同分异构体及相同质谱参数类固醇激素分离情况的对比，最终选择HPH-C18色谱柱（100 mm×2.1 mm, 2.7µm,Agilent）；有机相经过乙腈和甲醇对物质的分离度及仪器响应程度的分析，最终流动相梯度采用甲醇（A）和超纯水（B），流动相梯度：0 min，40%A；0-4 min，40%-55%A；4-8 min，55%-70%A；8-13min，70-85%A；13-14 min，85%-100%A；17 min，100%A；17.1 min，100%-60%A；20min，60%A，经过对比不同流速下的柱压、峰宽、物质洗脱情况，最终流速为0.4 mL/min；柱温为40 °C，进样量为2 μL。
4、方法的考核参数及结果：
本发明采用高效液相色谱质谱联用的方法，通过保留时间和两对离子对对每一种类固醇激素进行确认，再根据标准品峰面积进行定量分析，并用对应的同位素内标校正目标物质在样品前处理过程和仪器分析过程中的损失，并且弥补进样过程中针与针之间的差异。具体参数如下：
（1）特异性分析：特异性是指分析方法是否具有区分待测组分、区分待测组分与干扰物区的能力，对于糖皮质激素，能否区分同分异构体、本体物质与代谢产物十分重要。本发明通过三种方法分析特异性。首先对标准溶液的色谱图进行分离度分析，判断物质尤其是同分异构体之间是否能够有效分离；其次，将空白水样（超纯水）按照整个样品前处理过程进行操作，包括使用相同的仪器设备、试剂、药品和玻璃器皿；此外，在空白水样（超纯水）中添加已知浓度的目标分析物，然后和样品一起分析，检查是否存在干扰物质。本方法通过优化液相色谱条件优化，显示分析物尤其是较难分离的同分异构体之间分离度良好。实验中的空白样品与标准溶液相比不存在干扰信号。
（2）标准曲线与最低定量限的测定：在空白基质中添加5 ng/L，10 ng/L，20 ng/L，50 ng/L，100ng/L的标准溶液，进样量为2μl进行UPLC-MS/MS分析，并对各物质峰面积与内标峰面积的比值（Y）和其浓度（X）进行线性回归分析，获得标准曲线。结果表明，物质的浓度与所测得相对内标的峰面积呈现良好的线性关系，相关系数（γ）基本大于0.99。依据信噪比（S/N）计算得各甲状腺激素的最低定量限（LOQ）在地表水和沉积物中的范围分别为0.02-3.36 ng/L，0.02-4.30 ng/g。
（3）回收率和重复性的测定：将一定50 ng/L浓度的标准品加入空白基质中，按照样品前处理及仪器分析方法进行检测，并计算该方法的回收率，以每个浓度重复测定6次的结果计算方法重现性，结果表明，在环境水体基质中，类固醇激素回收率为73-104%，相对标准偏差为（RSD）2.38-10.78%，在沉积物基质中，类固醇激素回收率为72-98%，相对标准偏差为2.16-11.28%。
综上所述，仅为本发明具体实施方式，但本发明的保护范围并不限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围内，因此，本发明的保护范围应以所述权利要求的保护范围为准。
Claims (1)
1.一种液相色谱质谱联用测定环境样品中144种类固醇激素的方法，其特征在于，包括如下步骤：
S1 样品处理
S11 固相萃取法处理地表水：取地表水经玻璃纤维滤膜过滤后，用HLB固相萃取柱同时富集所有目标类固醇激素，HLB固相萃取柱首先用乙酸乙酯、甲醇及超纯水活化，过滤后的水样中添加类固醇激素的同位素内标混合均匀，将水样以5-10 mL/min的流速通过活化好的HLB固相萃取柱，固相萃取后，用超纯水淋洗，然后将HLB固相萃取柱吹干，吹干后的HLB固相萃取柱用体积比为1:1的乙酸乙酯/乙腈洗脱，将洗脱液用氮气吹干，用甲醇复溶，进入仪器进行分析；
S12超声萃取法处理沉积物：将沉积物样品冷冻干燥后研磨过筛，称取样品加入到离心管中，加入类固醇激素的同位素内标，放置后加入体积比为1:1的甲醇/乙腈提取液，超声振荡并离心，收集上清液于瓶中，重复上述步骤两次，收集得到提取液；用旋转蒸发仪将提取液蒸发至干燥，然后用甲醇润湿瓶壁，最后加入超纯水，后续步骤与采取样品处理S11中的步骤相同；
S2 超高效液相色谱-串联质谱联用仪进行检测
质谱分析条件：对于144种类固醇激素，采用电喷雾离子源，检测模式为正离子模式，质谱检测采用多反应监测模式，离子源温度为150 ℃，脱溶剂气温度为450 ℃，脱溶剂气流量为900 L/h，碰撞气流量为150 L/h，毛细管电压为3.0 kV；
UPLC液相条件：色谱柱选择HPH-C18色谱柱，100 mm×2.1 mm, 2.7µm, 流动相梯度采用甲醇A和超纯水B，流动相梯度：0 min，40%A；0-4 min，40%-55%A；4-8 min，55%-70%A；8-13min，70-85%A；13-14 min，85%-100%A；17 min，100%A；流速在仪器和色谱柱适配的范围内选择0.2或0.4或0.6 mL/min，色谱柱的柱温依据类固醇激素性质选择45 ℃以下；
所述144种类固醇激素为：雌酮、17α-雌二醇、17β-雌二醇、17a-乙炔基雌二醇、甲睾酮、睾酮、雄烯二酮、雄酮、脱氢表雄酮、1,4-雄烯二酮、11β-羟雄烯二酮、5α-雄甾烷二酮、19-羟基雄烯二酮、5β-雄烷-3, 17-二酮、睾内酯、肾上腺甾酮、宝丹酮、群勃龙、司坦唑醇、苯丙酸去甲睾酮、丙酸睾酮、诺龙、去甲雄三烯醇酮、孕酮、20α-羟基孕酮、20β-羟基孕酮、2α-羟基孕酮、6β-羟孕酮、11α-羟基孕酮、11β-羟基孕酮、17α-羟孕酮、21α-羟基孕酮、4-孕烯-17α,20α-二醇-3-酮、4-孕烷-17α,20β-二醇-3-酮、5β-二氢-17-羟基孕酮、1,6-双脱氢孕酮、16-去氢黄体酮、Delta-6-黄体酮、地屈孕酮、16α-甲基孕酮、6-羰基黄体酮、11-酮孕甾酮、1-脱氢酮孕酮、5α-二氢酮孕酮、5β-二氢酮孕酮、6β-羟基酮孕酮、21-羟孕酮醋酸酯、11α-羟孕酮醋酸酯、6β-羟孕酮醋酸酯、6β-溴孕酮、羟孕酮甲苯磺酸、苯甲孕酮、炔诺酮、6,7-脱氢炔诺酮乙酸酯、醋酸炔诺酮、19-去甲睾酮、诺乙烯酮、炔孕酮、甲基炔诺酮l、孕二烯酮、依托孕烯、脱乙酰诺孕酯、诺孕酯、米非司酮、1,6-脱氢羟孕酮、甲羟孕酮、醋酸甲羟孕酮、差向醋酸甲羟孕酮、16, 17-环氧孕酮、17α-羟孕酮醋酸酯、17-羧基孕酮、羟基醋酸环丙孕酮、醋酸美仑孕酮、醋酸地马孕酮、醋酸环丙孕酮、醋酸氯孕酮、醋酸氟孕酮、四氢皮质酮、皮质醇、可的松、α-皮酮四醇、β-皮酮四醇、3α,20α-皮五醇、3α,20β-皮五醇、3β,20β-皮五醇、脱氧皮质酮、11-脱氢皮质酮、21-脱氧皮质醇、皮质脂酮、17-Desoxy-β-Cortolone、17-脱氧皮酮四醇、21-脱氧皮酮四醇、20α-二氢可的松、四氢可的松、11-四氢皮质醇、3β,5β-四氢皮质醇、3α,5α-四氢皮质醇、3α,5β-四氢皮质醇、二氢皮质醇、强的松、泼尼松龙、甲强龙、利美索隆、氨昔奈德、布地奈德、氟尼缩松、曲安奈德、氟轻松、己曲安奈德、皮质醇葡萄糖醛酸、倍他米松、地塞米松、倍氯米松、去羟米松，氯倍他索、氟米松、氟氢可的松、氟羟氢化泼尼松、醋酸倍他米松、醋酸地塞米松、醋酸倍氯米松、17-丙酸倍氯米松、21-丙酸倍氯米松、二丙酸倍氯米松、丙酸氯倍他索、丙酸氯硫卡松、丙酸氟替卡松、氧代丙酸氟替卡松、羧丙酸氟替卡松、醋酸氟米松、醋酸氟氢可的松、双乙酸曲安西龙、17-戊酸氢化可的松、21-戊酸氢化可的松、三醋酸皮酮四醇、醋酸脱氧皮质醇、醋酸四氢可的松、醋酸泼尼松、醛固酮、坎利酮、螺内酯、7β-螺内酯、硫代螺内酯、甲硫螺内酯。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311278599.0A CN117030904B (zh) | 2023-10-07 | 2023-10-07 | 液相色谱质谱联用测定环境样品中144种类固醇激素的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311278599.0A CN117030904B (zh) | 2023-10-07 | 2023-10-07 | 液相色谱质谱联用测定环境样品中144种类固醇激素的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117030904A CN117030904A (zh) | 2023-11-10 |
| CN117030904B true CN117030904B (zh) | 2023-12-19 |
Family
ID=88635769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311278599.0A Active CN117030904B (zh) | 2023-10-07 | 2023-10-07 | 液相色谱质谱联用测定环境样品中144种类固醇激素的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117030904B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117554536B (zh) * | 2024-01-12 | 2024-03-19 | 北京林业大学 | 一种环境水样中15种甲状腺激素的同时分析方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120076051A (ko) * | 2010-12-29 | 2012-07-09 | 재단법인 서울의과학연구소 | 타액 중의 스테로이드 호르몬의 정량 방법 |
| CN104965042A (zh) * | 2015-06-30 | 2015-10-07 | 中国环境科学研究院 | 地表水体中若干种痕量糖皮质激素及其衍生物的检测方法 |
| CN107543876A (zh) * | 2017-06-09 | 2018-01-05 | 上海市环境科学研究院 | 一种固相萃取‑液相色谱串联质谱法同时检测水体中9种雌激素类物质的方法 |
| CN111929387A (zh) * | 2020-08-24 | 2020-11-13 | 泉州南京大学环保产业研究院 | 沉积物中多种痕量雄激素的定量分析及生态风险评价方法 |
-
2023
- 2023-10-07 CN CN202311278599.0A patent/CN117030904B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120076051A (ko) * | 2010-12-29 | 2012-07-09 | 재단법인 서울의과학연구소 | 타액 중의 스테로이드 호르몬의 정량 방법 |
| CN104965042A (zh) * | 2015-06-30 | 2015-10-07 | 中国环境科学研究院 | 地表水体中若干种痕量糖皮质激素及其衍生物的检测方法 |
| CN107543876A (zh) * | 2017-06-09 | 2018-01-05 | 上海市环境科学研究院 | 一种固相萃取‑液相色谱串联质谱法同时检测水体中9种雌激素类物质的方法 |
| CN111929387A (zh) * | 2020-08-24 | 2020-11-13 | 泉州南京大学环保产业研究院 | 沉积物中多种痕量雄激素的定量分析及生态风险评价方法 |
Non-Patent Citations (4)
| Title |
|---|
| Validation of an isotope dilution mass spectrometry (IDMS) measurement procedure for the reliable quantification of steroid hormones in waters;Mirmont, Elodie 等;ANALYTICAL AND BIOANALYTICAL CHEMISTRY;第415卷(第16期);第3215-3229页 * |
| 固相萃取-LC-MS法检测水中痕量雌激素;常红 等;环境化学(第4期);第400-403页 * |
| 地表水体中同时分析18种糖皮质激素方法的建立;郭文景 等;环境科学;第36卷(第7期);第2719-2726页 * |
| 超高效液相色谱-串联质谱法测定环境水体/污泥中5种痕量雌激素;王秋英 等;分析试验室;第32卷(第8期);第31-34页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117030904A (zh) | 2023-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111366671B (zh) | 同时检测血清中18种类固醇激素的化学衍生-超高效液相色谱-串联质谱法 | |
| US8470602B2 (en) | Methods and systems for determining the presence or amount of delta 5 steroid compounds in a sample | |
| Keski-Rahkonen et al. | Fast and sensitive liquid chromatography–mass spectrometry assay for seven androgenic and progestagenic steroids in human serum | |
| CN104807920B (zh) | 一种试剂盒在利用高效液相色谱串联质谱技术检测血清中10种类固醇激素中的应用 | |
| CN117030904B (zh) | 液相色谱质谱联用测定环境样品中144种类固醇激素的方法 | |
| Volin | High-performance liquid chromatographic analysis of corticosteroids | |
| CN112051348B (zh) | 一种血清或血浆中类固醇激素的固相萃取方法 | |
| CN108709941B (zh) | 一种含羟基的神经类固醇的检测分析方法 | |
| Tölgyesi et al. | Quantitative determination of corticosteroids in bovine milk using mixed-mode polymeric strong cation exchange solid-phase extraction and liquid chromatography–tandem mass spectrometry | |
| Chang et al. | Quantitative measurement of male steroid hormones using automated on-line solid phase extraction-liquid chromatography-tandem mass spectrometry and comparison with radioimmunoassay | |
| CN112611828B (zh) | 一种血液中类固醇激素的纯化富集及其检测方法 | |
| CN111175419A (zh) | 一种同时检测血液样品中多种类固醇激素的方法及试剂盒 | |
| US11536733B2 (en) | Methods and systems for the detection of 11-oxo androgens by LC-MS/MS | |
| CN112986433A (zh) | 检测人血清样本中类固醇含量的方法 | |
| CN111323507A (zh) | 基于固相萃取法同时检测血清中11种类固醇的检测方法 | |
| CN114088859A (zh) | 一种分离多组同分异构体并检测29种类固醇激素的方法 | |
| CN114674961A (zh) | 一种非衍生化同步检测血清中17种类固醇激素的试剂盒及其应用 | |
| Appelblad et al. | Separation and detection of neuroactive steroids from biological matrices | |
| Speltini et al. | HA-C@ silica sorbent for simultaneous extraction and clean-up of steroids in human plasma followed by HPLC-MS/MS multiclass determination | |
| CN112162043A (zh) | 生物体液中糖皮质激素的液相色谱串联质谱检测方法 | |
| CN109856266A (zh) | 同时测定环境水样中多种痕量盐/糖皮质激素的分析方法 | |
| CN116519850B (zh) | 一种快速检测血清样本中16种激素浓度的方法 | |
| CN113514569A (zh) | 一种同时测定多种内源性激素及外源性激素的方法 | |
| CN113009036A (zh) | 一种检测性激素的试剂盒、性激素样品前处理方法及同时检测多种性激素的方法 | |
| Vicente et al. | Measurement of serum testosterone using high-performance liquid chromatography/tandem mass spectrometry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |