金沢大学大学院自然科学研究科分子作用学金沢大学薬学部日本分析化学会の許諾を得て登

Mitamura Kuniko

Mizuguchi Tatsuhito

Narukawa Hitomi

Shimada Kazutake

Analytical Sciences

Kanazawa University Repository for Academic Resources

Degradation of Estrogen Conjugates UsingTitanium Dioxide as a Photocatalyst著者 Mitamura Kuniko, Narukawa Hitomi, MizuguchiTatsuhito, Shimada Kazutakejournal orpublication titleAnalytical Sciencesvolume 20number 1page range 3-4year 2004-01-01URL http://hdl.handle.net/2297/3901ＡＮＡＬＹＴＩＣＡＬＳＣｍＮＣＥＳＪＡＮＵＡＲＹ２００４,VOL20 2004cTheJapanSocietyfOrAnalyticalChemistry ３ RqpiclCommunicotions De=radationofEstrogenConiugatesUsingTitaniumDioxidMsaPhotocatalyst ＫⅢikoMITAMuRA,THitomiNARuKAwA,ntsuhitoMIzuGucHI,andKazutakeSHIMADA RzJc"/Jyq/Ｐ/zα'wzac〃icaJScje"ces,KZJ"αＺｑｗａ肋加e耐､ﾉ;１３－１脈ａｍ－ｍａｃｈｊ,KZJ"αZawa920LO93午,〃pα〃EstrogenconIugates（estradiol-3-glucuronide，-17-glucuronide，estrone-glucuronideand‐sulfate）weresubjectedto photodegradationusingtitaniumdioxideimmobilizedonglassbeadsasacatalyst・TheirtimecoursesweremeasuredbyHPLCandcomparedwiththoseoftheuncolUugatedestrogens、Estradiol,iｔｓｌ７-glucuronideandestrone,whichhaveanuncol0ugatedphenolichydroxygroupattheC-3position,werealmostcompletelydegradedbyUVilTadiationwithin4h Ontheotherhand,significantamountsofestradiol-andestrone-3-glucuronidｅ(CCZ､２０％,２５％)andestronesulfate(cα、90％),whichwerecolUugatedatthe3-hydroxygroup,remainedaftera65hirradiation・Theseresultssupportedthehypothesisthatthephotodegradationofestrogenswasinitiatedatthephenolichydroxygroup． (ReceivedDecember9,2003;AcceptedDeceInberlO,2003） wasmonitoredbymeasuringtheremainingsubstratebyUV-HPLC． Introduction lnrecentyears，thelehasbeenincreasingconcernoverthe endocrinedisluptingeffectoftheendogenousestrogensand xenoestrogensinenvironmentalwaterthroughtheexcretionsof humans，domesticandfannanimals・Amongtheendogenousestrogens,estradiol(E2)showsthehighestestrogenicpotential fOllowedbyestrone（E]）whicharefOundinmanywater systems，suchasriversandtheeffluentfromsewagetreatment plants・l-51tisnotedthatestrogensaremamlyexcretedascoIUugatessuchasglucuronideandsulfate､6,7Althoughthe estrogenconjugatesdonothaveestrogenicactivities,theycan actasthehorlnoneprecursorsbydeconjugationduringthe processofsewagetreatmentusingactivatedsludge・ItisdifficulttocompletelyremovethesesubstancesfTom environmentalwaterbytheusualmethodsusingsewage treatment,4,8andtherefOrethedevelopmentofnovel technologiesisnecessarytoovercomethisproblem・Photodegradationusingasemiconductorphotocatalystas typifiedbytitaniumdioxide(TiO2)isoneofthesafe,effective andpromisingenvironmentalcleanuptechnologies・ItwasreportedthatE2inanaqueoussolutionwasphotodegradedand mineralizedtocarbondioxideusingTiO2particlesorfilms underUVlightirradiation9JoThemechanismofthe photocatalyticoxidativedegradationofE2suggestedthatthe phenolichydroxymoietyofE2wasimtiallyattackedbythe hydroxylradicaLwhichwasgeneratedbytheUVilTadiationof TiO2mwater.，’''’'２However,ｉｔｈａｓｎｏｔｂｅｅｎｃｌarifiedthatthe estrogenscolUugatedatthephenolichydroxygroupareableto bedegradedbyphotocatalyticdegradationusingTiO2、Ｉｎｔｈｉｓｐａｐｅｒｗｅｄｅｓｃｒｉｂｅｔｈｅｔｉｍｅｃｏursesofthe photodegradationofestrogencolUugatesusingTiO2 immobilizedonglassbeadsasacatalyst,whichwerecompared withthoseoftheuncolUugatedestrogens(Fig.１)．Thereaction Experimental ＭＺＪｒｅｒｊａＪｓα"‘だage"応E2andE1weredonatedfromTeikokuＨｏｌｍｏｎｅＭｆｇ (Kawasaki,Japan)．E23-glucuronide(E23G),E217-glucuronide (E217G)andEIglucuronide(ＥｌＧ)werepurchasedfromSigma‐ Aldrich(St・Louis,ＭＱＵＳＡ)．EIsulfate(EIS)waspreparedinourlaboratolyfromElbytheusualproceduleusingthe chlorosulfOnicacid-pyridinecomplex Thephotocatalyst,ＢＬ２５ＤＸ（diameter,２．５ｍｍ;membrane thickness，ＬＯＵｍ；TiO2immobilizedonglassbeads)，was purchasedfTomPhoto-CatalyticMaterials(Komaki,Japan)． OasisHLBcartridges（６０ｍｇ,３ｍl）(Waters,MilfOrd,ＭＡ， USA)weresuccessivelyconditionedwithmethanol(ZmDand water(２ｍl)priortouse． A〃αmtLlsHPLCwaspeIfOrmedusinｇａＰＵ－９８０ｐｕｍｐ(JASCOTokyo， Japan)equippedwithaJ，spheleODS-H80column(４１１，，１５０ ×４．６ｍｍｉ,..）（YMC，Kyoto，Japan）andaSPD-10AUV detector(Shimadzu,Kyoto)．E23GandElSweremonitoredat 275ｎｍａｎｄ２６９ｎｍ,respectively・Theothercompoundswere牙F～ ○ Ｒ１Ｏ 雪熱;iii$illw1il;;二二aへＯＨ Ｅ１：Ｒ,＝Ｈ，Ｒ２=Ｏ Ｅ１Ｇ：ＲＦＧ，Ｒ２＝Ｏ Ｅ１Ｓ：Ｒ１＝Ｓ，Ｒ２=ＯＳ－ＳＯ３Ｈ ThispaperisdedicatedtoProfessoｒＨｅｉｎｚＧ、Floss(WashingtonUniv.，ＷＡ，ＵＳＡ）ontheoccasionofhis70th birthday・fTowhomcorrespondenceshouldbeaddressed E-mail:mitamura＠pkanazawa-u・acjp FiglStructuresofE2,EIandtheircolﾘugates． ● ＡＮＡＬＹＴＩＣＡＬＳＣＩＥＮＣＥＳＪＡＮＵＡＲＹ２００４,ＶＯＬ２０ ４ 2(〃＝２，mean)．Ｅ2,E217GandEI,whichhaveanunconjugatedphenolichydroxygroupattheC-3positio､，werealmost completelydegradedafler4hofUVirradiationbyfirst-order kinetics・Theirdegradationrateconstantsｗｅｒｅ1.7×l0-2min-1[coefficientofdetermmation(戸)＝0984],１．５×l0-2min-l(72＝0.991）ａｎｄ１．５×10-2min-l（津＝0.991),respectively、Ontheotherhand,thedegradationratesofE23G,ＥｌＧａｎｄＥｌＳ，which areconjugatedatthe3-hydroxygroup,welemuchlowerthan thoseoftheaboveestrogens・E23GandElGweredegradedslowlybyfirst-orderkinetics[3.6×10-3min-I（r2＝0.967)ａｎｄ 3.4×l03min-l(涙＝0.938),respectively],andca20and25％ofthesubstratesremainedaftera6､Shirradiation,respectivelyln thecaseofElS,Ｃａ､９０％ofthesubstratestillremainedattheend oftheirradiationanditsdegradationorderwasuncleamE2was almostquantitativelyrecoveredfromthereactionmixtureunder thecontrolconditions，ｓｕｃｈａｓｎｏＵＶｌｉｇｈｔｏｒｃａｔａｌｙｓｔ・Thesedatashowedthattheadsorptionofestrogenonaphotocatalyst wasnegligibleandthephotocatalysteffectivelyfimctioned Asdescribedabove,thehydroxylradicalwasgeneratedwhen TiO2wasirradiatedbyUVlightinanaqueoussolution・lL12Theoxidationofthephenolichydroxymoietyofestrogensbythe hydroxylradicalwaslegardedastheinitiationofthe photocatalyticdegradationoftheestrogens､gTheresults describedinthispapersupportedtheabovehypothesisand showedthatthe3-hydroxygroupofestrogenisimportantfOr thephotodegradationThecatalyticeffectoftheother photocatalystsonthedegradationoftheestrogensconjugatedat the3-hydroxygroupandtheinvestigationofthefOnned degradationproductsarenowinprogressinourlaboratory． ０８ ６４２ １０ ０００ 己ニユ一目○目］口』］臣⑪。巨○９0６０１２０１８０２４０３００３６０ Ｔｉｍｅ/ｍiｎ Fig2Photocatalyticdegradationofestrogensusingphotocatalyst underUVirradiation（〃＝２，mean)．●，Ｅ２；○，Ｅ,；■，Ｅｚ３Ｇ；□，E217G；▼，ＥＩＣ；▲,ＥｌＳ monitoreｄａｔ２８０ｎｍＴｈｅＨｏｗｒａｔｅａｎｄｃｏｌｕｍｎｔｅｍperature weresetatLOmlmin-land４０°Ｃ，respectivelyAsamobile phase,methanol-water(7:3,Ｖ/V)wasusedfOrthedetennination ofuncoIljugatedestrogens[E2(ｊＲ４３ｍｉｎ)ａｎｄＥ,('R４．６ｍin)]， andmethanol-watercontaining5mＭｏｆＨＣＯ２ＮＨ４ｗａｓｕｓｅｄ ｆＯｒｔｈｅｄetelminationofconjugatedestrogens｛ＥＩＳ（l:1,Ｖ/ＷＲ ５３ｍｉｎ),Ｅ２Ｇ［Z:3,Ｖ/v;/Ｒ７３ｍｉｎ（3Ｇ),７．８ｍiｎ（l7G)］ａｎｄ ＥｌＧ(2:3,Ｖ/ＷＲ７９ｍｉｎ)}・AVL-4LCblacklightlamp(３６５，，，４Ｗ)(VilberLounnat， Cedex,France)wasusedasthelightsource． P/zorode8m〃jo〃q/esjmge"sTheethanolsolutionofestrogenwasdilutedwithwatertol UM（theethanolconcentrationwaslessｔｈａｎ0.396,Ｖ/v)． Photocatalyticglassbeads(cα､１３．６９)werespreadtocoverthe bottomofaglasspetridish(diameter,８ｃｍ),andtheestrogen solution（111Ｍ,１５ｍl)wasplacedinthedishThepetridish wasplacedinalightshieldedbox[22.5(wide)×１３．５(depth)× １６ｃｍ（height)Landirradiatedbyablacklightlamｐｌ６ｃｍ ａｗａｙｆＯｒ６､５hFivehundredmicrolitersofsolutionwas sampledevery30minandthensubjectedtoanOasisHLB cartridge・Afterwashingwithwater(２ｍl),estrogenwaselutedwithmethanol（1.5ｍl)ａｎｄevaporatedunderaN2gasstream Theresiduewasdissolvedinmethanol（５０Ⅱl）andanaliquot wasappliedtoanHPLC Acknowledgements TheauthorsaIcgratefUltoDrs．Ｒ・NakagakiandSKohtani(KanazawaUniversity）fOrtheirhelpfUldiscussions，Our thanksarealsoduetoDr.ＳＨｏｎｍａ(TbikokuHonnoneMfg.） fOrsupplyingestrogens． References １．Ｙ､Nakamura,Ｋ・Onda,CTakatoh,ａｎｄＡ・Miya,Ｂ""sekjKngalE",2003,52,107. 2.Ｋ．Majima，Ｔ・Fukui，IYuan，Ｇ、Wang，andKMatsumoto,Ａ"αＬＳｃｊ.,2002,18,869. 3.Ｇ.-Ｇ．Yin９，Ｒ、Ｓ、Kookana，ａｎｄＹ.-J・Ｒｕ，Ｅ"Ｗ'ｗ２．ｍZ.，2002,28,545. 4.Ｆ､Tilton,Ｗ､Ｈ、Benson,andDSchlenk,Ａ９"αr､T1axjcoJ.，２００２，６１，２１１． ５．Ｈ,Ｍ､ＫｕｃｈａｎｄＫ・Ballschmiter,Ｆ花se"ｊ"ｓノＬＡ"αﾉ.Ｃ/jem.，2000,366,392. 6.Ｋ．Wright，，．Ｃ・Collms，ａｎｄＪ、ＲＫ・Preedy，SreMdS，1979,卿,４４５．７．Ｋ．Shimada,Ｋ､Mitamura,ａｎｄＴ・Higashi,Ｊ・Chro伽aro8r．Ａ,2001,935,141. 8.Ｔ、Ａ・Ｔｅmes，Ｈ・Andersen，Ｄ・Gilberg，andMBonerz，Ａ"αﾉ.Che"0.,2002,刀,３４９８．９．Ｙ・Ohko,Ｋ､Iuchi,Ｃ・Ｎｉｗａ,Ｔ・Tatsuma,Ｔ､Nakashima,TIguchi，Ｙ、Kubota，andAFUjishima，Ｅ'Mro〃Scj，TCC/、oﾉ.,2002,36,4175.10.Ｈ、MColeman，Ｂ、Ｒ・Eggins，』．Ａ、Byrne，Ｆ・LPalmer，andEKing,APP/､Catα【.B:E"virolu.,2000,2午,L1.11.Ｃ・RichardandPBoule,ハノビ1,1ﾉＪＪＣ/z2,.,1994,ノ8,547.12.Ｎ・Watanabe,SHorikoshi,Ｈ､Kawabe,Ｙ・Sugie,Ｊ・Zhao，ａｎｄＨ・Hidaka,ChemoSphe”,2003,52,851.比coveDW・esrmge"sTheestrogensolutions（１ＩＬＭ,500111)ｗｅｒｅsuhjectedtoan OasisHLBcartridge,concentratedandthenanalyzedbyHPLC asdescribedabovewhichwereusedastheOminilluminated samples・Thepeakareasoftheestrogensinthesesampleswerecomparedwiththoseoftheexpectedamountofauthentic estrogens,andtheobtainedrecoveryrates(cα､８０％)wereused fbrcolTectionoftheConcentrationinthefOllowingexperiments． ResultsandDiscussion Thetimecoursesofthephotocatalyticdegradationsofthe estrogensusingthephotocatalyticglassbeadsweremonitored bymeasuringthe1℃mainingsubstratebyUV-HPLC、Analiquotofthereactionmixturewassubjectedtothesolid-phase extraction，concentratedandthenanalyzedbyHPLC，because theUVdetectordidnothaveenoughsensitivitytodetect estrogenswithoutpretreatment、TheresultsofthephotocatalyticdegradationareshowninFig． 

Degradation of Estrogen Conjugates Using Titanium Dioxide as a Photocatalyst

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Degradation of Estrogen Conjugates Using Titanium Dioxide as a Photocatalyst

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