大孔吸附樹脂對(duì)貫葉金絲桃中苯并二蒽酮類成分的富集摘要目的考察大孔吸附樹脂對(duì)貫葉金絲桃中苯并二蒽酮類成分的富集方法,并確定工藝路線和吸附參數(shù)。方法本文以貫葉金絲桃中苯并二蒽酮類成分為考察指標(biāo)，采用動(dòng)態(tài)和靜態(tài)吸附試驗(yàn)相結(jié)合來考察大孔吸附樹脂對(duì)貫葉金絲桃中苯并二蒽酮類成分的富集工藝。結(jié)果本文得到穩(wěn)定可行的對(duì)貫葉金絲桃中苯并二蒽酮類成分富集的工藝路線和吸附參數(shù)。結(jié)論該方法可為貫葉金絲桃中苯并二蒽酮類成分的大孔樹脂精制工藝的確定提供參考。關(guān)鍵詞貫葉金絲桃；苯并二蒽酮；大孔吸附樹脂；靜態(tài)吸附；動(dòng)態(tài)吸附所屬專業(yè)中藥與天然藥物（中藥與天然藥物資源的開發(fā)利用和可持續(xù)發(fā)展）ENRICHMENTOFNAPHTHODIANTHRONESINHYPERICUMPERFORATUMLWITHMACROPOROUSRESINABSTRACTOBJECTIVETOSTUDYTHEENRICHMENTOFNAPHTHODIANTHRONESINHYPERICUMPERFORATUMLWITHMACROPOTOUSRESIN,ANDDEFINETHEREFINEMENTPROCESSANDADSORPTIONFACTORMETHODSTHEREFINEMENTPROCESSANDADSORPTIONFACTOROFTHESEPARATIONANDPURIFICATIONOFNAPHTHODIANTHRONESINHYPERICUMPERFORATUMLWITHMACROPOROUSRESINWERECOMPAREDBYSTATICANDDYNAMICADSORBINGEXPERIMENTSANDTHECONTENTOFNAPHTHODIANTHRONESWASDEVELOPEDASITSQUALITYSTANDARD,SCREENINGOUTTHEBESTREFINEMENTPROCESSANDADSORPTIONFACTORRESULTSTHEREFINEMENTPROCESSANDADSORPTIONFACTOROFTHEENRICHMENTOFNAPHTHODIANTHRONESINHYPERICUMPERFORATUMLWITHMACROPOROUSRESINARESTABLEANDFEASIBLECONCLUSIONTHEENRICHMENTMETHODCANOFFERINFORMATIONABOUTTHEDETERMINATIONOFREFINEMENTPROCESSOFA1A0A2A3A4A6A7A5A8A2A3A4A9A10A4A11A14A5A8LWITHMACROPOROUSRESINKEYWORDSHYPERICUMPERFORATUMLNAPHTHODIANTHRONESMACROPOTOUSRESINSTATICADSORPTIONDYNAMICADSORPTION貫葉金絲桃為藤黃科植物貫葉金絲桃HYPERICUMPERFORATUML的干燥地上2部分。貫葉金絲桃的主要化學(xué)成分包括苯并二蒽酮類化合物,如金絲桃素、偽金絲桃素、原金絲桃素、原偽金絲桃素等；黃酮類化合物,如蘆丁、金絲桃甙、槲皮素、異槲皮素、阿曼托黃素等；間苯三酚類化合物,包括貫葉金絲桃素、加貫葉金絲桃素等；還含有揮發(fā)油類、香豆素類化合物等A12A13A15A16A17。據(jù)文獻(xiàn)報(bào)道,貫葉金絲桃中的抗抑郁活性成分主要有苯并二蒽酮類、黃酮類、間苯三酚類等。其中，苯并二蒽酮類被普遍認(rèn)為是抗抑郁G1328用G17751G3921的成分，G3281G1881G3818對(duì)貫葉金絲桃提G2474物G3822以金絲桃素G16757的苯并二蒽酮類含G18339G993G1314G1122G19G17G22G8G1328為G17148G18339G6523制指標(biāo)。本文采用大孔吸附樹脂來考察貫葉金絲桃中苯并二蒽酮類的吸附G10317性，G1186G13792G17839G980G8505確定苯并二蒽酮類活性成分富集方法,得到G17751G20652G13443G5242的貫葉金絲桃有G6940部G1313。1儀器、試劑和材料HP6890G8680相G14406G16901G1214，HP7694G20042G12366G17839G7691G1214；G4719G8953UV2401PC；金絲桃素對(duì)G10043G2709G17153G14270G13666G3281SIGMAG1856G2508；試G2070G3355為分G7524G13443。大孔樹脂G3355為G3281G1147；貫葉金絲桃采G17153G1122G19497G16211G11477G8733中G5078。2實(shí)驗(yàn)部分21苯并二蒽酮類的含G18339G8991方法211供試G2709和對(duì)G10043G2709的制G3803供試G2709G9354G9094G726G2474G7691G2709G1343401G，精G4506G12228定，G1427950MLG7849G14406G18339G10954中，加G11014G1826740ML，G17241G3780G3800G10714G708G2163G10587350W、G20069G1058735KHZG70940分G19059，G6930G1931，加G11014G18267G14279G2063G5242，G6683G2260，G17819G9400。精G4506G18339G2474G13505G9400G90942ML，G1363410MLG7849G14406G18339G10954中，加G11014G18267G14279G2063G5242，G6683G2260。對(duì)G10043G2709G9354G9094G726精G4506G12228G2474G1128G8699化二G11979G1955G2399干燥G21G23G75的金絲桃素對(duì)G10043G2709，加G11014G18267G16G2549G2890G11G28G29G20G12G18209制成G8611G20G80G79含金絲桃素G21G19G的G9354G9094，G13634G7849G14406G18339G10954中，G1328為對(duì)G10043G2709G1660G3803G9094。212G8991定方法分G2047G2474供試G2709G9354G9094和對(duì)G10043G2709G9354G9094，以試G2070G1328G12366G11345，G10043分G1821G1821G5242法G708中G3281G146593G18682005G5192G10268G980部附G5417VBG709，G3324588NMG8886G19283G3800G8991定吸G6922G5242，G16757G12651，G2375得。213線性G14551G3272的考察分G2047精G4506G18339G2474對(duì)G10043G2709G1660G3803G909410ML、20ML、40ML、60ML、80MLG112210MLG7849G14406G18339G10954中，加G11014G18267G2549G289091G12244G18334G14279G2063G5242，G6683G2260，G10043分G1821G1821G5242法中G3281G14659G18682005G5192G10268G980部附G5417VB，G3324588NMG8886G19283G3800G8991定吸G6922G5242，以吸G6922G5242為G13449坐標(biāo)，濃G5242為橫坐標(biāo)，繪制標(biāo)準(zhǔn)曲線。結(jié)果得到回歸方程G726C029392353A，R09988。結(jié)果表明G3324198198G/MLG14551G3272G1881苯并二蒽酮類濃G5242與吸G6922G5242有良G3921的線性關(guān)系。22大孔吸附樹脂有機(jī)殘留物檢查G10043有機(jī)G9354G2070殘留G18339G8991定法G708中G3281G14659G18682005G5192G10268二部附G5417VIIIP第二法G709G8991定。221G14406G16901條件用鍵合/交聯(lián)聚乙二G18267毛細(xì)管G14406G16901柱G70830M025MM025MHPINNOWAXAGILENTG1856G2508G709；柱溫5G19，G17839G7691口及檢G8991器溫G5242分G2047為260及300；載G8680為氮G8680，流速G72620ML/MIN；G20042G12366G2474G7691G10954加熱條件G726120加熱15MIN。222供試G2709和對(duì)G10043G2709的制G3803供試G2709G9354G9094的制G3803G726G2474G7691G2709G1343402G，精G4506G12228定，G1363420MLG20042G12366G2474G7691G10954中，精G4506加入06十二烷基硫酸鈉G9354G90945ML，G6683G2260，G2375得。對(duì)G10043G2709G9354G9094的制G3803G726精G4506G12228G2474正己烷，苯，G11014苯，對(duì)二G11014苯，鄰二G11014苯，苯乙烯和G20,G21G16二乙基苯適G18339，加06十二烷基硫酸鈉G9354G9094G18209制成G86111ML分G2047含15G，10G，12G，12G，13G，16G和13G的G9354G9094，G6683G2260，精G4506G18339G24745ML，G1363420MLG20042G12366G2474G7691G10954中，G2375得。223G8991定法分G2047G2474對(duì)G10043G2709G9354G9094和供試G2709G9354G9094，G3324120加熱15MIN，依法G8991定，按G3818標(biāo)法以峰面積G16757G12651，G2375得。23貫葉金絲桃提G2474G9094的制G3803G2474貫葉金絲桃G14659材，加6G19G8乙G18267回流提G2474二次，G8611次G20G175G75，合并提G2474G9094，G9400G17819，G9400G9094G1955G2399濃縮G142791MLG9354G9094G13434相當(dāng)G11221GG14659材，離心，G3803用。24大孔樹脂的預(yù)G3800G107144以95乙G18267濕法裝柱,以95乙G18267洗脫，G993時(shí)檢G8991流出的乙G18267，當(dāng)流出的乙G18267與水混合后G993呈G11345G14406渾濁時(shí)G2375可，再以蒸餾水洗G14279無G18267味。實(shí)際操G1328中，乙G18267洗G14279柱體積的4倍時(shí)與水混合G993渾濁，洗G142796倍時(shí)，無樹脂味。25影響大孔樹脂靜態(tài)吸附的因素251樹脂型號(hào)的篩選選G24746種經(jīng)預(yù)G3800G10714的濕態(tài)樹脂5GG708D101、DA101、DA201、DB301、AB8、LSA20G709G13634100ML具塞錐形G10954中，G2474貫葉金絲桃提G2474G9094加入G10954中，G332425G6683床中振蕩24H，吸附達(dá)到平衡后，G9400去樹脂，定G18339移G2474清G9094，G8991定含G18339，G16757G12651吸附G10587。結(jié)果，吸附G10587依次為7G21G17G20G22，7G22G17G198，6G19G17G20G21，6G20G1778，65G175G20，8G19G17G225。本文根據(jù)吸附G10587結(jié)合樹脂成本綜合考慮，最終選擇LSA20型大孔吸附樹脂。252吸附時(shí)間的考察G247430G濕態(tài)LSA20型大孔吸附樹脂，G13634G1122100ML具塞錐形G10954中，加入貫葉金絲桃提G2474G9094，G332425G6683床中振蕩24H，G2474G7691時(shí)間依次為1，2，4，6，8，10，24H。G8991定吸附G10587，考察吸附時(shí)間對(duì)靜態(tài)吸附的影響。結(jié)果為，結(jié)合吸附G10587和時(shí)間成本綜合考慮，最終選擇吸附時(shí)間為G21G75。26影響大孔樹脂動(dòng)態(tài)吸附的因素261洗脫G9354G2070的篩選精G4506吸G2474貫葉金絲桃提G2474G9094100MLG8611ML含生G146591G上柱,依次用蒸餾水、20乙G18267、50乙G18267、70乙G18267、95乙G18267梯G5242洗脫,G8611G10954G6922集G980個(gè)柱體積的洗脫G9094,依次按1，2，G22編號(hào)，分G2047濃縮G14279干,G8991定G8611G1233洗脫G9094中苯并二蒽酮G18339。以G6922集G18339G10954編號(hào)X為橫坐標(biāo)，苯并二蒽酮G18339Y為G13449坐標(biāo),繪制洗脫曲線,G16277G32821。5A181A19A20A21A22A23A24A25A26A27A28A29A30A31A32A33A34A35A36A37A38A39A40A41A42A21A22A23A24A26A27A28A29A30A31A33A34A35A36A37A38A39A4015A43A44A45A46A47A48610A49A5020A51A52A46A47A481115A49A5050A51A52A46A47A481622A49A5070A51A52A46A47A482326A49A5095A51A52A46A47結(jié)果G7186G12046，50、70、95乙G18267洗脫G9094中苯并二蒽酮G18339G2356G5647G18339的94，G16840明苯并二蒽酮主要集中G332450、70、95乙G18267洗脫G9094中。G13792其中50乙G18267洗脫G9094和70乙G18267洗脫G9094中苯并二蒽酮G18339G2356G5647G18339的84，95乙G18267洗脫G9094中苯并二蒽酮G18339G17751G4581。70乙G18267的G7509性與50乙G18267G6521G17829，G1000G4579G112250乙G18267，相對(duì)G13792G16340可洗脫G991的水G9354性G7446G17148G1075G17751G4581，可基本G9097G1143450乙G18267洗脫G9094可洗脫的苯并二蒽酮G18339。因G8504，綜合考慮G1955G4581操G1328工G5219,G14422G13434生G1147成本等因素，G2033G8505確定洗脫條件為G1820用蒸餾水、20乙G18267洗去水G9354性G7446G17148，再以70乙G18267洗脫，G6922集70乙G18267洗脫部分。262洗脫G2070用G18339的確定精G4506吸G2474貫葉金絲桃提G2474G9094100MLG8611ML含生G146591G上柱,。G1820用蒸餾水、20乙G18267洗脫，再以70乙G18267洗脫，G8611G10954G6922集G980個(gè)柱體積的洗脫G9094,依次按1，2，G22編號(hào)，分G2047濃縮G14279干,G8991定G8611G1233洗脫G9094中苯并二蒽酮G18339。以G6922集G18339G10954編號(hào)X為橫坐標(biāo)，苯并二蒽酮G18339Y為G13449坐標(biāo),繪制洗脫曲線,G16277G32822。A53A54A55A56A57A58A59A60A61A62A63A64A65A64A66A64A67A64A68A64A69A64A70A64A71A64A72A64A63A73A64A63A63A64A63A65A64A63A66A64A63A67A64A63A68A64A63A69A64A63A70A64A63A71A64A63A72A64A65A73A64A65A63A64A65A65A64A65A66A64A65A67A64A65A68A64A65A69A64A74A75A76A77A78A79A80A81A82A83A846A85A86A87A88A89A90A85A90A86A90A87A90A88A90A89A90A91A86A91A92A91A87A91A93A91A88A91A94A91A89A91A95A91A90A85A91A90A90A91A90A86A91A90A92A91A90A87A91A90A93A91A90A88A91A90A94A91A90A89A91A90A95A91A96A91A97A98A99A100A101A102A103A104A105A106A1072A108A10970A110A111A112A113A114A115A116A117A118A119A120A121A122A123A112A113A124A125A126A127A128A110A111A113A114A115A116A117A118A120A121A122A123A124A125A127A12815A129A130A131A132A133610A12920A134A135A131A132A1331119A136A13770A138A139A140A141A142G32822結(jié)果G7186G12046，當(dāng)以水洗脫4倍柱體積、20乙G18267洗脫3倍柱體積時(shí)，洗脫曲線G5062G17829橫G17736G1000G6164G6922集的洗脫G9094G1972G1058無G14406，因G13792確定G19512去G7446G17148的水用G18339為4倍柱體積，20乙G18267用G18339為3倍柱體積。采用70乙G18267洗脫，洗脫G142797倍柱體積時(shí)曲線G5062G6521G17829橫G17736，G1000G20817倍柱體積洗脫G9094中苯并二蒽酮G18339G13434G235670乙G18267G5647洗脫G18339的96以上，G6937確定洗脫G9354G4198為7倍柱體積的70乙G18267。263影響大孔樹脂吸附性G14033因素的G11752G123622631大孔吸附樹脂的吸附性G14033的考察大孔吸附樹脂的吸附性G14033與G14659G9094濃縮G8616、上G7691流速、柱G5464G20652G8616等因素有關(guān)。本文采用L934正交試驗(yàn)篩選最G1351的上柱工藝條件。正交G16786G16757的因素水平表G16277表1。A1431L9A14434A145A146A147A148A149A150A151A152A153A154A147A148A152A153A155A156A157A158A159A160A161A162A163AA164A165A166A167A168A163BA169A170A171A172C11051A173201BV/H21A17311A173102BV/H31A17321A17353BV/H72632試驗(yàn)方法及結(jié)果本正交試驗(yàn)以70乙G18267洗脫G9094中苯并二蒽酮G18339G708以100G貫葉金絲桃G14659材G16757G709為考察指標(biāo)，結(jié)果G16277表2。A1742A175A176A177A178A179A180A181A182A183A175A176A178A179A180A181A184A185A186A187A188A189A190A191AA192A193A194A195A196A191BA197A198A199A200CA201A202DA203A204A205A206A207A208A209A210102G1111148621222447313333324212364952231498623124297313248283213422933213251X12651617133713092X15761367142113583X12291086131214031X4225394464362X5254564744533X40362437468R115177037032上G17860數(shù)據(jù)表明G726G3324G16786G13634水平G14551G3272G1881，以苯并二蒽酮G18339為指標(biāo),G11013G1122G7509G5058R的大G4579G7186G12046影響因素的主次，G6164以其影響G20046G5219為BAC；綜合分G7524，B為主要因素，A次G1055。G17902G17819G11464G16278分G7524，最G1260G13464合G5224為B1A2C2，G2375G2334G5464G726柱G20652G8616為120；G14659G9094濃縮G8616為11；G14659G9094上G7691流速為2BV/H。2633方G5058分G75248G11013G1122G14659G9094上G7691流速CG2027與G12366G11345DG2027的RG1552相G17829，G16840明G14659G9094上G7691流速對(duì)結(jié)果的影響G17751G4579。因G8504本文采用正交G16786G16757G2173G6175IIV31G17731件，G17839G13792以CG2027和DG2027G1328為G16835G5058G20045G17839行方G5058分G7524，結(jié)果G16277表3。A2113A212A213A214A215A216A213A214A215A216A217A218A219A220A221A218A222A217A223A224A225A226FA227FA228A229A230A231005A232A233A234A235A24321334694A236B47122585694A236A237A2380364G11013方G5058分G7524結(jié)果可G11705，AG2027G708G14659G9094濃縮G8616G709、BG2027G708G2334G5464A239柱G20652G8616G709對(duì)洗脫結(jié)果有G7186G14891性G5058異，CG2027G708G14659G9094上G7691流速G709無G7186G14891性G5058異。綜合G11464G16278分G7524和方G5058分G7524結(jié)果及生G1147實(shí)際，最終確定上柱工藝條件為G2334G5464G726柱G20652G8616為120；G14659G9094濃縮G8616為11；G14659G9094上G7691流速為3BV/H。27驗(yàn)G16789試驗(yàn)按G10043上G17860實(shí)驗(yàn)條件，G17839行驗(yàn)G16789試驗(yàn)，G8991定70乙G18267洗脫G9094的G9036G14179得G10587，G9036G14179中苯并二蒽酮類含G18339和大孔樹脂有機(jī)殘留G18339，結(jié)果G16277表4。A2404A241A242A243A241A244A245A243A241A244A245A246A247A248A249A250A251A252A253A254A255A55A0A1A249A44GA4570A57A58A2A3A4A5A62A6A7A8A9A252A44GA45A7A8A6A64A44A57A45A24A10A11A12A13A29A14A252A57A24A10A11A12A13A29A15A16A64A57A71A17A18A19A20A21A77A44A57A45110003833831465592A22A23A2500037A26A27A28A30A31210003333331525062A22A23A2500013A26A27A28A30A31310003783781485594A22A23A2500016A26A27A28A30A31上G17860數(shù)據(jù)可以G11487出，該條件穩(wěn)定可行。大孔樹脂殘留G1075G12538合G457G14659G2709G8892G1888的G3281際G6228G7427要G8726G708G17148G18339部分G709G458G708ICH指G4560G4008G2604G1262G2620G9035G19067主G16805G709。93討論G22G17G20苯并二蒽酮類的含G18339G8991定方法主要參考G13666G3281G14621G14659G18684,G7691G2709G9354G9094經(jīng)G8886G19283G6207G6563，其最大吸G6922G1552與對(duì)G10043G2709G980G14280,G3355為588NM，G12366G11345G9354G9094經(jīng)G6207G6563G3324588NMG8886G19283G3800無吸G6922。因G8504，選擇G8991定G8886G19283為588NM。G22G17G21綜合上G17860實(shí)驗(yàn)G11752G12362，大孔吸附樹脂對(duì)貫葉金絲桃中苯并二蒽酮類成分的分離G13443化工藝歸G13447如G991G726選用LSA20型大孔吸附樹脂，上柱G14659G9094濃縮G8616為11，柱G20652G8616為120，G14659G9094上G7691流速為3BV/H，吸附時(shí)間為G21G75。G1820用4倍柱體積蒸餾水和3倍柱體積20乙G18267洗脫G5335去，再選用7倍柱體積70乙G18267洗脫，G6922集洗脫G9094，G1955G2399干燥，G2375得。本文G25622貫葉金絲桃提G2474G9094的制G3803G257G20045G991G6164用貫葉金絲桃G14659材含苯并二蒽酮類G13434為010，G6164制G3803的上柱G14659G9094含苯并二蒽酮類G13434為026。本文G17902G17819大孔吸附樹脂富集后，G7691G2709中苯并二蒽酮類含G18339G13434達(dá)到148,為G14659材含G18339的148倍和上柱G14659G9094含G18339的57倍。G17902G17819驗(yàn)G16789試驗(yàn)G16840明該富集方法的工藝路線穩(wěn)定可行，吸附參數(shù)準(zhǔn)確可G19764。G22G17G22本文還G17839G980G8505考察G1114大孔樹脂的再生。為考察樹脂再生后是G2554G12538合要G8726,本文G17839行G1114樹脂再生后有G6940部G1313的G1457留G10587試驗(yàn)。經(jīng)G17819三次平行試驗(yàn)，苯并二蒽酮類的G1457留G1