蚕丝素蛋白及其应用

王佳培胡建恩白雪芳杜昱光(中国科学院大连化学物理研究所,辽宁大连116023):,:;;SilkFibroinanditsApplicationWANGJiapei,HUJianen,BAIXuefang,DUYuguang(DalianInstituteofChemicalPhysics,ChineseAcademyofSciences,Dalian116023,China)Abstract:Thecomposition,structure,property,preparationandcurrentsituationofcomprehensiveutilizationofsilkfibroinhavebeenreviewedinthispaper.Thedevelopmentresearchonapplicationofsilkfibroin,akindofnaturalresource,inmedicine,foodstuffandotherwisehasgreatprofoundsignificanceinpractice.Keywords:silkfibroin;silk;aminoacid2,,,,,70%~80%5000,,,68t87t,70%1!;90%,,,11118,8,,112!%25854284411324152303040068038087129147047151050010023003901118047115047063175036021045513090822173212174156032∀13∀收稿日期:20040517作者简介:(1963),,,,1212Vol.12,No.122004621FineandSpecialtyChemicals,,1!12,2,silk#silk∃silk#,,:a=449,b=720,c=908;silk∃,,:a=944,b=697,c=920,=90%,,silk∃3!silk∃,,,,,,,,,,,,4!,10~50nm,,100,,ReginaV,silk&,∃,,,350KD25KD,P25,P2527KD5!280KD230KD25KDabc3,ac90%6!7!TGSSGFGPYVADGGYSRREGYEAWSSKSDFET,GASSGS8!,,:2,,100∋,175∋,,280∋,305∋,,,,,45∋silk#;45∋,silk#silk∃,silk#,silk∃;,50∋,;pH5,;pH5,silk∃;,silk∃;,,silk∃;7kV,,silk∃,,silk∃pH,Ni2+silk∃;Viney(ICP)Ca2+silk∃;NMR,Ca2+Cu2+silk∃9!;PaolaTaddeiCo2+10!32:11!;(,∀14∀1212,,2:31(1)马赛热皂液法(Marseillessoap)05%03%Na2CO3,100∋1h,,12~13!PaolaTaddei:7g/L,98∋1h;3g/LNa2CO33g/LNa2SiO32g/L,98∋1h(2)Na2CO3脱胶法Na2CO33:005%Na2CO398~100∋30min,3;(005%Na2CO3,()()50,60min,214!;)05%Na2CO3,()()50,30min,215!,,;05%NaHCO330min,,,16!(3)酶解脱胶法1%Alkalase25mg/mL,60∋30min,()()50(4)尿素脱胶法8mol/L004mol/LTris(pH=7)05mol/L,()()30(5)皂液脱胶法005%,100∋30min,()()100(6)水脱胶法100∋,5~60min,120∋5~30min,()()3032(1)Ajisawa∗s法17!Ajisawa∗sn(CaCl2)+n(EtOH)+n(H2O)=1+2+8!,75∋,,,()Ajisawa∗s()15,AgNO3Cl-Ajisawa∗s40%CaCl2,(2)LiBr溶解法LiBr3:m(LiBr)+m(C2H5OH)+m(H2O)=45+44+11;(m(LiBr)+m(C2H5OH)=40+60;)95mol/LLiBrH2O(3)LiSCN溶解法:9mol/LLiSCN,,()Ajisawa∗s()30~100,5mol/L2h:60%LiSCN,,()Ajisawa∗s()100,20mmol/LTrisHCl5mol/LLiSCN,,LiSCN,NaSCN18!LiCl/N,N,1~2h18!(4)Ca(NO3)2溶解法Ca(NO3)2MeOHH2O,mCa(NO3)2∀4H2O!+m(CH3OH)=3+1,,Ca(NO3)2MeOHH2O∀15∀2004621,:,19!4,:ZnCl2H3PO4Cu(NH3)4(OH)24,2:41(1)酶的固定化载体(),,,,20!3:,,:2122!23!24!25!26!(2)生物传感器,:,,,,,,,pH,,pH,,,,(3)组织工程支撑材料,,,,,,,,,,,27!28!:;,;,,;,,;,,,,,,,MinouraL929,,2930!;,,,,31!;Gregory,,32!;DavidKaplan,ArgGlyAsp33!,,,,∀16∀121242(1)人工器官或组织,,,,,,,,34~36!,,,,,,,,,,10,37!(2)抗凝血活性,,,,100,20%,,37!,38,39!(3)化妆品,,,,−.;,(:,OH,COOH,NH2),;,,,()(4)药物的控释材料,37!,,,pH5,,,,;,;,,,,,,,485%,;;;,40!,,/1!,,,.J!.,1998,3:17~232!.J!.,2003,1:24~263!,.J!.,2000,5:37~40∀17∀2004621,:4!,,.J!.,2002,6:818~8235!TanakaK,KajiyamaN,IshikuraK,etal.DeterminationofthesiteofdisulfidelinkagebetweenheavyandlightchainsofsilkfibroinproducedbyBombyxmoriJ!.BiochimicaetBiophysicaActc,1999,1432:92~1036!,,,.J!.,1997,5:629~6327!MinouraN,AibaS,HiguchiM.AttachmentandgrowthoffibroblastcellsonsilkfibroinJ!.BiochemBiophysResCommun,1995,208:511~5168!LiM,OgisoM,MinouraN.EnzymaticdegradationbehaviorofporoussilkfibroinsheetsJ!.Biomaterials,2003,24:357~3659!,,,.J!.,2001,55:860~86210!TaddeiP,MontiP,FreddiG,etal.IRstudyonthebindingmodeofmetalcationstochemicallymodifiedBombyxmoriandTussahsilkfibresJ!.Molecularstructure,2003,651653:433~44111!DattaA,GhoshAK,KunduSC.PurificationandcharacterizationoffibroinfromthetropicalSaturniidsilkworm,AntheraeamylittaJ!.InsectBiochemistryandMolecularBiology,2001,31:1013~101812!UmIC,KweonHY,ParkYH,etal.StructuralcharacteristicsandpropertiesoftheregeneratedsilkfibroinpreparedfromformicacidJ!.InternationalJournalofBiologicalMacromolecules,2001,29:91~9713!YeoJH,LeeKG,LeeYW,etal.SimplepreparationandcharacteristicsofsilkfibroinmicrosphereJ!.EuropeanPolymerJournal,2003,39:1195~119914!YamadaH,NakaoH,TakasuY,etal.PreparationofundegradednativemolecularfibroinsolutionfromsilkwormcocoonsJ!.MaterialsScienceandEngineeringC,2001,14:41~4615!,,.J!.,2000,19(2):146~14916!ChenX,KnightDP,ShaoZ,etal.RegeneratedBombyxsilksolutionswithrheometryandFTIRJ!.Polymer,2001,42:9969~997417!AjisawaA.Dissolutionofsilkfibroinwithcalciumchloride/ethanolaqueoussolutionJ!.SericSciJpn,1998,67:91~9418!FreddiG,PessinaG,TsukadaM.SwellinganddissolutionofsilkfibroininNmethylmorpholineNoxideJ!.BiologicalMacromolecules,1999,24:251~26319!KweonHY,UmIC,ParkYH.ThermalbehaviorofregeneratedAntheraeapernyisilkfibroinfilmtreatedwithaqueousmethanolJ!.Polymer,2000,41:7361736720!ZhangYQ.NaturalsilkfibroinasasupportforenzymeimmobilizationJ!.BiotechnologyAdvances,1998,16(5/6):961~97121!YingL,KangET,NeohKG.Covalentimmobilizationofglucoseoxidaseonmicroporousmembranespreparedfrompoly(vinylidenefluoride)withgraftedpoly(acrylicacid)sidechainsJ!.JournalofMembraneScience,2002,208:361~37422!TzanovT,CostaSA,GubitzGM,etal.HydrogenperoxidegenerationwithimmobilizedglucoseoxidasefortextilebleachingJ!.JournalofBiotechnology,2002,93:87~9423!QianJ,LiuY,LiuH,etal.ImmobilizationofhorseradishperoxidasewitharegeneratedsilkfibroinmembraneanditsapplicationtoatetrathiafulvalenemediatingH2O2sensorJ!.Biosensors&Bioelectronics,1997,12(12):1213~121824!,.J!.,2002,28(1):64~6925!,,,.J!.,1996,8:13~1926!.J!.,2002,12(5):27~2827!LangerR,VacantiJP.Tissueengineering.J