Two- and Three-Dimensional Smectic Ordering of Single-Handed Helical Polymers

Two- and Three-Dimensional Smectic Ordering of Single-Handed Helical Polymers

PublishedonWeb12/13/2007

Two-andThree-DimensionalSmecticOrderingof

Single-HandedHelicalPolymers

HisanariOnouchi, KentoOkoshi,*, TakashiKajitani, Shin-ichiroSakurai,

KanjiNagai, , JiroKumaki, KiyotakaOnitsuka,§andEijiYashima*, ,

YashimaSuper-structuredHelixProject,ExploratoryResearchforAdVancedTechnology(ERATO),JapanScienceandTechnologyAgency(JST),101CreationCoreNagoya,2266-22Anagahora,Shimoshidami,Moriyama-ku,Nagoya463-0003,Japan,DepartmentofMolecularDesignandEngineering,GraduateSchoolofEngineering,NagoyaUniVersity,Chikusa-ku,Nagoya464-8603,Japan,andTheInstituteofScientificandIndustrialResearch,Osaka

UniVersity,8-1Mihogaoka,Ibaraki,Osaka567-0047,Japan

ReceivedJune25,2007;E-mail:kokoshi@yp-jst.jp;yashima@apchem.nagoya-u.ac.jp

Abstract:Rodlikepolymerswithpreciselydefinedarchitecturesareidealbuildingblocksforself-assembledstructuresleadingtonovelnanometer-scaledevices.WefoundthatthelivingpolymerizationofasingleisocyanideenantiomerbearinganL-alaninependantwithalongn-decylchainsimultaneouslyproduceddiastereomericright-andleft-handedheliceswithdifferentmolecularweightsandnarrowmolecularweightdistributions.Eachsingle-handed,rodlikehelicalpolymerwithacontrolledlengthandhandednessisolatedbyafacilesolventfractionationmethodwithacetoneself-assembledtoformwell-definedtwo-andthree-dimensionalsmecticorderingonthenanometerscaleonasubstrateandinaliquidcrystallinestateasevidencedbydirectatomicforcemicroscopicobservationsandX-raydiffractionmeasurements,respectively.

Introduction

Biologicalmacromolecules,suchasDNAandsomeviruses,possessawell-definedrodlikestructurewithaone-handedhelicalsense,whichprovidesaccesstoidealbuildingblocksforself-assemblednanomaterialsanddevices.Nucleicacidshavebeensuccessfullyusedintheself-assemblyofsupramo-leculararraysthroughtheirhighlyspecificbindingproperties.1Somevirusesarealsoknowntoformsmecticliquidcrystalline(LC)phases,inwhichrodlikevirusesarepackedintolayersperpendiculartothedirectionoftheirorientation,duetotheiruniformmolecularlengths.2Althoughabacterialsyntheticmethodhasbeenreportedtoproducemonodispersepolypeptideswithastate-of-the-artcontrolofthemolecularlengthsandstructures,3itremainsagreatchallengetocontrolthoseoftheartificialhelicalpolymerstosuchanextentinaconventionalsyntheticway,4notonlytomimicthestructuresofbiologicalhelicesbutalsotodevelopnovelfunctions.5

Fullysyntheticopticallyactivehelicalpolymershavebeenpreparedeitherbythepolymerizationofopticallyactive

monomers,suchasisocyanates,5gsilanes,5eacetylenes,5corbythehelix-senseselectivepolymerizationofachiralmethacrylates,5fisocyanides,5d,6andcarbodiimides7bearingbulkysubstituentsbychiralcatalystsorinitiators.Theformerpolymerizationproducesdynamichelicalpolymerscomposedofinterconvertingright-andleft-handedhelicalsegmentsseparatedbyrarelyoccurringhelicalreversals,5c,e,gandthelatterstatichelicalpolymerswhosehelicalconformationsarelockedduringthepolymerizationunderkineticcontrol.5f,6

Inearlierstudies,wereportedtheconventionalpolymerizationofanenantiomericallypurephenylisocyanidebearinganL-alaninependantwithalongn-decylchainthroughanamidelinkage(L-1)withNiCl2asacatalyst,whichproducedarodlikestatichelicalpolyisocyanidewithabroadmolecularweight

(4)(a)Kim,K.T.;Park,C.;Kim,C.;Winnik,M.A.;Manners,I.Chem.

Commun.2006,1372-1374.(b)Okoshi,K.;Sano,N.;Suzaki,G.;Tokita,M.;Magoshi,J.;Watanabe,J.Jpn.J.Appl.Phys.2002,41,L720-L722.(c)Okoshi,K.;Kamee,H.;Suzaki,G.;Tokita,M.;Fujiki,M.;Watanabe,J.Macromolecules2002,35,4556-4559.

(5)(a)Yashima,E.;Maeda,ldamers:Structure,Properties,and

Applications;Hecht,S.,Huc,I.,Eds.;Wiley:Weinheim,2007;pp331-366.(b)Hoeben,F.J.M.;Jonkheijm,P.;Meijer,E.W.;Schenning,P.H.J.Chem.ReV.2005,105,1491-1546.(c)Yashima,E.;Maeda,K.;Nishimura,T.Chem.sEur.J.2004,10,42-51.(d)Elemans,J.A.A.W.;Rowan,A.E.;Nolte,R.J.M.J.Mater.Chem.2003,13,2661-2670.(e)Fujiki,M.Macromol.RapidCommun.2001,22,539-563.(f)Nakano,T.;Okamoto,Y.Chem.ReV.2001,101,4013-4038.(g)Green,M.M.;Park,J.-W.;Sato,T.;Teramoto,A.;Lifson,S.;Selinger,R.L.B.;Selinger,J.V.Angew.Chem.,Int.Ed.1999,38,3138-3154.

(6)(a)Amabilino,D.B.;Serrano,J.-L.;Sierra,T.;Veciana,J.J.Polym.Sci.,

PartA:Polym.Chem.2006,44,3161-3174.(b)Suginome,M.;Ito,Y.AdV.Polym.Sci.2004,17,77-136.(c)Cornelissen,J.J.L.M.;Rowan,A.E.;Nolte,R.J.M.;Sommerdijk,N.A.J.M.Chem.ReV.2001,101,4039-4070.

(7)(a)Tang,H.-Z.;Boyle,P.D.;Novak,B.M.J.Am.Chem.Soc.2005,127,

2136-2142.(b)Tian,G.;Lu,Y.;Novak,B.M.J.Am.Chem.Soc.2004,126,4082-

4083.

J.AM.CHEM.SOC.2008,130,229-236

9

(1)(a)Seeman,N.C.Int.J.Nanotechnol.2005,2,348-370.(b)Winfree,E.;

Liu,F.;Wenzler,L.A.;Seeman,N.C.Nature1998,394,539-544.(2)(a)Lee,S.-W.;Wood,B.M.;Belcher,ngmuir2003,19,1592-1598.(b)Lee,S.-W.;Mao,C.;Flynn,C.E.;Belcher,A.M.Science2002,296,892-895.(c)Dogic,Z.;Faden,S.Phys.ReV.Lett.1997,78,2417-2420.(d)Wen,X.;Meyer,R.B.;Casper,D.L.D.Phys.ReV.Lett.1989,63,2760-2763.

(3)(a)Yu,S.M.;Conticello,V.P.;Zhang,G.;Kayser,C.;Fournier,M.J.;

搜索“diyifanwen.net”或“第一范文网”即可找到本站免费阅读全部范文。收藏本站方便下次阅读，第一范文网，提供最新教学研究Two- and Three-Dimensional Smectic Ordering of Single-Handed Helical Polymers全文阅读和word下载服务。