自组装有机纳米管

Asymmetric organic nanotubes with different inner and outer surfaceswere discussed in terms of molecular design, immobilization of functional moieties, and molecular packing.

Self-AssembledOrganicNanotubes:TowardAttoliterChemistry

TOSHIMISHIMIZU

NanoarchitectonicsResearchCenter(NARC),NationalInstituteofAdvancedIndustrialScienceandTechnology(AIST),Tsukuba,Ibaraki305-8565,Japan

Received16January2008;accepted25January2008

DOI:10.1002/pola.22652

PublishedonlineinWileyInterScience(http://doc.guandang.net).

ABSTRACT:Diversechemi-calfunctionalizationoftheinnerandoutersurfacesofthenano-tubesenablesustosenseandvis-ualizetheencapsulationandtransportbehaviorofbiomacro-molecularguests.Theeventoccursspeci http://doc.guandang.netparisonoftheorganicnano-tubehistorywiththatofwell-knowncarbonnanotubesandavarietyofmolecularbuildingblocksastube-formingcom-poundswere rstintroduced.Asymmetricorganicnanotubeswithdifferentinnerandoutersur-faceswerediscussedintermsofmoleculardesign,immobilizationoffunctionalmoieties,andmolec-ularpacking.Finally,thepracticalexamplesoftheorganicnano-tubesasananocontainer,nano-

channel,andnanopipettewerealsodescribedtofeaturethecon-ceptof‘‘attoliterchemistry.’’

C2008WileyPeriodicals,Inc.JPolymV

SciPartA:PolymChem46:2601–2611,2008

Keywords:attoliterchemistry;hollowcylinder;host-guestsys-tems;nanotechnology;self-assem-bly

TOSHIMISHIMIZU

ToshimiShimizuiscurrentlythedirectorofNanoarchitectonicsResearchCenter(NARC),NationalInstituteofAdvancedIndustrialScienceandTechnology(AIST)inTsukuba,Japan.HereceivedhisB.S.andM.S.degreesinpolymerchemistryfromKyotoUniversity,Japan,in1975and1977,respectively,andobtainedhisPh.D.degreefromKyotoUniversity,Japan,in1983.In1977,hejoinedtheResearchInstituteofPolymersandTextiles,AgencyofIndustrialSci-enceandTechnology(AIST),MinistryofInternationalTradeandIndustry(MITI),Japan.AfterhispostdoctoralresearchatFreeUniver-sityBerlinwithProf.J.-H.Fuhrhop,hejoinedtheNationalInstitute

of

Correspondenceto:T.Shimizu(E-mail:tshmz-shimizu@aist.go.jp)

JournalofPolymerScience:PartA:PolymerChemistry,Vol.46,2601–2611(2008)

2601

Asymmetric organic nanotubes with different inner and outer surfaceswere discussed in terms of molecular design, immobilization of functional moieties, and molecular packing.

2602J.POLYM.SCI.PARTA:POLYM.CHEM.:VOL.46(2008)

MaterialsandChemicalResearch,AIST,MITIin1993.Since2001,heisthedirectoroftheNARC,AIST.HehasbeenpromotingtheCoreResearchforEvolutionalScienceandTechnology(CREST)andthesubsequentSolutionOrientedResearchforScienceandTechnology(SORST)projectsasaprojectleader, nancedbyJapanScienceandTechnologyCorporation(JST)since2001.Hisresearchfocusesonthenoncovalentsynthesisandstructuralanalysesofhigh-axial-rationano-structuresthroughtheself-assemblyofamphiphilicmonomers.Inpar-ticular,heisnowengagedindevelopingorganicnanotubematerials.HeistherecipientoftheMinister’sAwardofMITI,2000,theAwardoftheSocietyofPolymerScience2001,Japan,andtheChemicalSoci-etyofJapan(CSJ)AwardforCreativeWorkfor2006.Hehasbeentheauthorofover240publications,includingoriginalresearchpapers,reviews,and15chaptersofbooks.

INTRODUCTION

Asinglecellisexpectedtopossesswatercontentcorre-spondingto1pL(pL¼10À12L)volumeinsidethehol-lowcavitywhenconsideringitasacubewithawidthof10lm(Fig.1).Tomanipulatestillultrasmallervolumesofliquidsinsuchperse eldsascellbiology,micro- uidics,capillarychromatography,andnanolithography,oneneedsabetterunderstandingof uidbehaviorcon nedinattolitervolume.1–7Indeed,waterinnano-meter-sizedrestrictedgeometries,suchasmicellesandmicroemulsions,8,9nanometer lms,10,11andnanoporoussilica,12oftenshowsdifferentandsometimesunex-pectedfeaturesincomparisontobulkwater.Thetrendofminiaturizationinconventionalmicrochipdevicesconsistingofpoly(dimethylsiloxane),silicone,andglasshasthusdirectedgrowingattentiontonewfemtoliter(fL¼10À15L)orattoliter(aL¼10À18L)vesselslikecar-bon13andsilicananotubes.14

Ontheotherhand,theseneedshaveinspiredmanyinvestigationsonmolecularassemblieswithwell-de neddimensionsandmorphologiesinsupramolecularchemistry.15Self-assembledlipidnanotubes(LNTs)with10nminnerdiametersand1lmlengthcanprovidethecon nedwatervolumecorrespondingto1aL,whichissmallerbyfactorof103and106thanthoseofthefem-toliterchamber16andsinglecell,respectively(Fig.1).Con nedliquidnanospaceshapedbyaLNTshouldbefavorabletofeaturethechemicaleventsinattolitervol-ume,whichisassociatedwith‘‘attoliterchemistry.’’Self-assemblednanotubearchitecturesfromperseor-ganicmoleculesincludingproteins,17DNA,18syntheticpolymers,19,20andamphiphiles(lipids)15haverecentlybeendevelopedinlargenumbers.Theyaregraduallydemonstratingattractivepotentialforpracticaluseindifferent eldsfromthoserelatedtocarbonnano-tubes.21,22Recentadvancesinthenanotubeworldhavethusenteredanewera,inwhichonecanproduceany

nanotubesconsistingofallmaterialsandelements.Herewedescribethehistory,classi cation,andourrecenttopicsonself-assembledorganicnanotubes.Inparticu-lar,wefocusontheorganicnanotubescapableofper-formingendo-sensingforencapsulationandtransportofbiomacromoleculesinanattolitervolumenanochannel,whoseinnersurfacesarerationallymodi edwithpersefunctionalities.

NANOTUBESWITH10nmINNERDIAMETERS

Thenanotubestructureswith10nmscaledinnerdiame-tersmaybeclassi edintofourcategories(Fig.2).Typi-calnanotubeisamultiwallcarbonnanotube(MW-CNT).21TheinnerdiametersoftheMW-CNTsare10timesaslongasthatofasingle-wallCNT(SW-CNT).22Self-organizationcanallowproteinstoassembleintotu-bulararchitectures.Forexample,dimersofa-andb-tubulinproteinshelicallyarrangetoformacirclewithinvolving13dimersandfurtherassembleintotubularstructures.23Physicalproceduresthatincludeone-dimensionalgrowingprocessofanatomspeciesfabri-catecarbonnanotubes,whereasbiologicalprocesspro-ducesnaturalproteinnanotubes.

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