冠醚輔助萃取細(xì)胞色素c

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1、Anal.Chem.2006,78,7735-7742ExtractiveSolubilization,StructuralChange,and FunctionalConversionofCytochromecinIonic LiquidsviaCrownEtherComplexationKojiroShimojo,*,?NorihoKamiya,?FumitoTani,§HirochikaNaganawa,?YoshinoriNaruta,§and MasahiroGoto*,?DivisionofEnvironmentandR

2、adiationSciences,NuclearScienceandEngineeringDirectorate,JapanAtomicEnergy Agency,Tokai-mura,Ibaraki,319-1195,Japan,DepartmentofAppliedChemistry,GraduateSchoolofEngineeringand CenterforFutureChemistry,KyushuUniversity,744Motooka,Fukuoka,819-0395,Japan,andInstituteforMa

3、terials ChemistryandEngineering,KyusyuUniversity,Higashi-ku,Fukuoka812-8581,JapanThisarticlereportsontheextractionbehaviorofhemeproteinsfromanaqueousphaseintoionicliquids(ILs)withdicyclohexano-18-crown-6(DCH18C6),andthestructure-functionrelationshipofcytochromec(Cyt-c)

4、dissolvedinILs.WehavefoundthatDCH18C6enablestransferofLys-richproteinsintoILsviasupramolecularcomplexation.ThehydrophobicityandfunctionalgroupsofILshaveagreatinfluenceonproteinpartitioning,andahydroxylgroup-containingILwithDCH18C6iscapableofthequantitativepartitioningo

5、fCyt-c.Ontheotherhand,proteintransferusingconventionalorganicsolventsisnegligiblysmall.UV-visible,CD,andresonanceRamanspectroscopiccharacterizationsindicatethatthesixthligandMet80inthehemegroupoftheCyt-c-DCH18C6complexinILisreplacedbyotheraminoacidresiduesofthepeptidec

6、hainandthatanon-natural,six-coordinate,low-spinferrichemestructureisinducedinIL.Solubi-lizationofCyt-cinILcausestheenvironmentalchangeofthehemevicinityofCyt-c,whichtriggersthefunctionalconversionofCyt-cfromanelectron-transferproteintoperoxidase.TheCyt-c-DCH18C6complexi

7、nILprovidesremarkablyhighperoxidaseactivitycomparedwithnativeCyt-c,becauseofenhancementoftheaffinityforH2O2.Ionicliquids(ILs)haveemergedasanewclassofsolventsinmanyfieldsofchemistryandindustry.ILs,whicharesaltsandthereforeentirelycomposedofions,possessattractiveproperti

8、es,e.g.,negligiblevolatility,nonflammability,andhighthermalstability.Furthermore,theirchemicalandphysicalproperties(w