Advances in CHEMICAL ENGINEERING ENGINEERING ASPECTS OF SELF-ORGANIZING MATERIALS 35 VOLUME Editedby RUDY J. KOOPMANS PolyUrethane R&D, Freienbach Dow Europe GmbH, Switzerland Amsterdam(cid:129)Boston(cid:129)Heidelberg(cid:129)London(cid:129)NewYork(cid:129)Oxford Paris(cid:129)SanDiego(cid:129)SanFrancisco(cid:129)Singapore(cid:129)Sydney(cid:129)Tokyo AcademicPressisanimprintofElsevier ADVANCES IN CHEMICAL ENGINEERING Editor-in-Chief GUY B. MARIN Department of Chemical Engineering Ghent University Ghent, Belgium Editorial Board DAVID H. WEST Research and Development The Dow Chemical Company Freeport, Texs, U.S.A. PRATIM BISWAS Department of Chemical and Civil Engineering Washington University St. Louis, Missouri, U.S.A. JINGHAI LI Institute of Process Engineering Chinese Academy of Sciences Beijing, P.R. China SHANKAR NARASIMHAN Department of Chemical Engineering Indian Institute of Technology Chennai, India AcademicPressisanimprintofElsevier Radarweg29,POBox211,1000AEAmsterdam,TheNetherlands 32JamestownRoad,LondonNW17BY,UK 30CorporateDrive,Suite400,Burlington,MA01803,USA 525BStreet,Suite1900,SanDiego,CA92101-4495,USA Firstedition2009 Copyright(cid:2)2009ElsevierInc.Allrightsreserved Nopartofthispublicationmaybereproduced,storedinaretrievalsystem ortransmittedinanyformorbyanymeanselectronic,mechanical,photocopying, recordingorotherwisewithoutthepriorwrittenpermissionofthepublisher PermissionsmaybesoughtdirectlyfromElsevier’sScience&TechnologyRights DepartmentinOxford,UK:phone(þ44)(0)1865843830;fax(þ44)(0)1865853333; email:permissions@elsevier.com.Alternativelyyoucansubmityourrequestonlineby visitingtheElsevierwebsiteathttp://www.elsevier.com/locate/permissions,andselecting ObtainingpermissiontouseElseviermaterial Notice Noresponsibilityisassumedbythepublisherforanyinjuryand/ordamagetopersons orpropertyasamatterofproductsliability,negligenceorotherwise,orfromanyuse oroperationofanymethods,products,instructionsorideascontainedinthematerial herein.Becauseofrapidadvancesinthemedicalsciences,inparticular,independent verificationofdiagnosesanddrugdosagesshouldbemade LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress BritishLibraryCataloguinginPublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary ISBN:978-0-12-374752-5 ISSN:0065-2377 ForinformationonallAcademicPresspublications visitourwebsiteatbooks.elsevier.com PrintedandboundinUSA 09 10 11 12 10 9 8 7 6 5 4 3 2 1 Working together to grow libraries in developing countries www.elsevier.com | www.bookaid.org | www.sabre.org PREFACE About10yearsago,ImetwithProfessorNevilleBodenatLeedsUniversity when he had just inaugurated the SelfOrganizing Molecular Systems Cen- tre(http://www.soms.leeds.ac.uk/).Hisambition,asIunderstooditatthe time, was to create a focused research effort on the physico-chemistry of shortamino-acidsequences(peptidesoflessthen25residues)anddevelop understandingonhowmolecules,throughintermolecularinteractions,may aggregate at various length and time scales. To an industrial researcher scouting for new materials and applications, the effort in place looked interestingbutquiteacademicwithverylimitedvalueifanytothechemical industry.However,theenthusiasmandmotivationofProfessorBodenand histeam,togetherwithsomefurtherdetailed discussions,mademerealize thatinfactallmaterialsatthemacroscospicscaleperformasaconsequence oftheveryspecific,oftenhierarchicalorganizationpotentialofthecompos- ing atoms or molecules. Furthermore, the opportunity of learning from nature including the reuse of molecular building blocks looked like a way to innovate synthetic materials as to chemistry, application performance, andsustainability.Exploringsuchavastspace,particularlyforanindustrial setting,requiresfocusinawaythatwhileworkingtowardatargetapplica- tion, knowledge and other opportunities would be revealed. Since those days and across the world many more research groups (cid:2) mainly in acade- mia (cid:2) have started working on different aspects of self-organization of nature’s building blocks. The list of publications is expansive, which makes it opportune to bring together a number of key papers that cover the state of the art as well as the thinking about the main technical challenges. Withadecadeofexperience,Ihavebroughttogethersevenpaperswitha scope limited to self-assembly of peptides, but covering key issues for advancing materials research into product development. The patent litera- tureactivityistypicallyanindicatorofcommercialinterestandapplication space. Chapter 1 covers in some detail, but without being comprehensive, what self-assembled peptides may bring in terms of material applications. Chapters2and3explaintheunderlyingprinciplesofpeptideself-assembly and how experiment can be used to model the hierarchy of structure formation. Typically, the work on peptides requires a tailored molecular ix x Preface configurationandChapter4coverstheoptionsavailableforpreparingthem insufficientquantities.Theremainingchaptersfocusonthetechnologyand use of the self-assembly mechanism to create specific applications such as ‘‘silk fibers,’’ coatings, and scaffolds to name a few. Either an ‘‘all’’ peptide composition can be used or combinations of peptide with synthetic oligo- mersor polymers(cid:2) hybrid systems. The idea to bring this topical volume together was suggested by David West, member of the editorial board but also a very good friend and long time colleague at The Dow Chemical Company. The volume provided a platform to write up most of the things that is known in this field of research,forwhichIamverygratefulasIbelievethatpeptideswillbecome thenew materialsof the future in view of their versatility Rudy Koopmans Horgen, February 2009 CONTRIBUTORS Numbers in parenthesis indicate the pages on which the authors’ contributions begins. A. Aggeli, Centre for Self-Organising Molecular Systems, School of Chemistry, Universityof Leeds,Leeds LS2 9JT, United Kingdom (11) N. Boden, Centre for Self-Organising Molecular Systems, School of Chemistry, Universityof Leeds,Leeds LS2 9JT, United Kingdom (11) R.P.W. Davies, Centre for Self-Organising Molecular Systems, School of Chemistry, University of Leeds, Leeds LS2 9JT, United Kingdom (11) Conan J. Fee, Department of Chemical & Process Engineering, University of Canterbury, Christchurch8020, New Zealand(211) Sally L. Gras, Department of Chemical and Biomolecular Engineering and The Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne,Victoria 3010,Australia (161) Lei Huang, Department of Macromolecular Science, Key Laboratory of Molecular EngineeringofPolymersofMinistryofEducation,AdvancedMaterialsLaboratory, FudanUniversity,Shanghai200433,People’sRepublicofChina(119) KierJames,AstburyCentreforStructuralMolecularBiology,UniversityofLeeds, Leeds LS2 9JT, United Kingdom (79) Rudy J. Koopmans, PolyUrethane R&D, Freienbach, Dow Europe GmbH, Switzerland(1) Stuart Kyle, Astbury Centre for Structural Molecular Biology, University of Leeds, Leeds LS2 9JT, United Kingdom (79) BoxunLeng,DepartmentofMacromolecularScience,KeyLaboratoryofMolecular EngineeringofPolymersofMinistryofEducation,AdvancedMaterialsLaboratory, FudanUniversity,Shanghai200433,People’sRepublicofChina(119) T.C.B.Mcleish,DepartmentofPhysicsandAstronomy;CentreforSelf-Organising MolecularSystems,UniversityofLeeds,LeedsLS29JT,UnitedKingdom(11) MichaelJ.McPherson, AstburyCentreforStructuralMolecularBiology;Centre forPlant Sciences,University of Leeds, LeedsLS2 9JT, United Kingdom (79) vii viii Contributors Anton P.J. Middelberg, The University of Queensland, Centre for Biomolecular Engineering, St. Lucia, Australia(1) I.A. Nyrkova, Institut CharlesSadron,Strasbourg Cedex, France(11) Stephen Parsons, Centre for Plant Sciences, University of Leeds, Leeds LS2 9JT, United Kingdom (79) Jessica Riley, Astbury Centre for Structural Molecular Biology, University of Leeds, Leeds LS2 9JT, United Kingdom (79) A.N. Semenov, InstitutCharlesSadron,Strasbourg Cedex, France(11) Zhengzhong Shao, Department of Macromolecular Science, Key Laboratory of MolecularEngineeringofPolymersofMinistryofEducation,AdvancedMaterials Laboratory,FudanUniversity,Shanghai200433,People’sRepublicofChina(119) Paul van der Schoot, Group Theoretical and Polymer Physics, Department of Applied Physics, Technische Universiteit Eindhoven, Postbus 513, 5600 MB Eindhoven,the Netherlands (45) ACKNOWLEDGMENTS Funding under the Sixth European Framework (project NMP3-CT-2005- 516961 (cid:2) Bio-based functional materials from engineered self-assembled peptides (BASE)) together with a number of bilateral conections allowed not only advancing the science and technology of self-assembly peptides butalsobroughttogethermanycreativepeopleonmanyoccasions.Itwasin fact a symposium in 2007 organised by Prof. Anton Middelberg at Univer- sity of Queensland, Australia, that connected many of the authors and set the frame for the structure of this volume. I thank all the contributing authors for their time and efforts (cid:2) a nice piece of work! Writing about science and technology is nothing without the people that make the pub- lication possible. In particular Professor Guy Marin provided continued encouragementtosticktothetimeline.TheElsevierstaffwasalwayshelpful to make things happen in order to turn the words into print. Obviously, there are those many invisible hands and minds that contributed to this process and whom I also want to thank. Finally, I want to thank you the reader for taking up interest in this fascinating world of peptide self- assembly. Enjoy the reading! xi 1 CHAPTER Engineering Materials from the Bottom Up – Overview Rudy J. Koopmans1,* and Anton P.J. Middelberg2 Contents 1. Introduction 1 2. HistoricalContext 2 3. Self-AssemblingPeptideLiterature 4 4. AFutureofChallengesandOpportunities 7 References 8 1. INTRODUCTION Self-assembly is a concept receiving significant attention in a variety of researchfieldsrangingfrombiologytocyberneticstosocialsciences.Despite its seemingly self-explanatory simplicity, implying a level of spontaneous assembly or ordering beyond the individual, composing molecules, this process is difficult to formally express in mathematical terms. Still the phe- nomenon in the natural sciences where atoms and molecules aggregate into higher order structures at various time and length scales is an observable reality. It offers significant potential for designing highly functional and diversematerialsoncetheunderlyingmechanismsareunderstood. Self-organizationisoftenconsideredassynonymoustoself-assemblyand for many practical purposes indistinct (Anderson, 2002). However, self- assembly maybetakenas the simple collection andaggregationofcompo- nents into a confined entity, while self-organization can be considered as spontaneous but information-directed generation of organized functional 1 PolyUrethaneR&D,Freienbach,DowEuropeGmbH.,Switzerland 2 TheUniversityofQueensland,CentreforBiomolecularEngineering,StLucia,Australia *Correspondingauthor. E-mailaddress:[email protected] AdvancesinChemicalEngineering,Volume35 (cid:2)2009ElsevierInc. ISSN0065-2377,DOI:10.1016/S0065-2377(08)00201-9 Allrightsreserved. 1 2 RudyJ.KoopmansandAntonP.J.Middelberg structures in equilibrium conditions (Lehn, 2002). For the purpose of these papers, self-assembly will be used to mean any form of organization that comesaboutthroughforcesdirectinghierarchicalstructureformationfrom themolecular level up. Atthemacroscale,suchorganizedfunctionalstructuresmanifestasphy- sicalsubstances,thatis,materialsthatformthebasisforengineer-specified productsandapplications.Forexample,woolisamaterialthatcanbetaken to make yarn for use in cloth making. At the molecular level, wool is a keratin composed of protein molecules with very specific amino acid sequences that have been spontaneously ordered into fibrous structures allowing the mechanical operation of yarn forming (Block, 1939; Corfield and Robson, 1955). However, in contrast to conventional use of either natural or synthetic materials, where a transformation process is needed toshapetheproductandapplication,forpeptidesandproteinsthebound- aryconditions(e.g.temperature,pH,andsolvent)directtheaggregationof suchmoleculesintoorganized structuresatvariouslengthandtimescales, andwithdifferingordersofcomplexity.Thesestructuresarethefunctional intermediates or potential end products that can be applied in multiple applicationsfor differentmarkets. Thefollowingpapersfocusmainlyonvariousaspectsassociatedwiththe self-assembly of peptides. Peptides are relatively short sequences of amino acids, typically less than 50. The limited number of residues brings simpli- citybutstillallowsforsufficientdifferentiationtostudyself-assemblyinits variousdetails.Thecompositionalfreedomoftheprimarymoleculeallows forasufficientlyrichhierarchicalstructurecreationthroughaggregationof individual peptides into supramolecular constructs resulting in interesting materials.Thischapterlooksintorelevantpatentliteratureasareflectionof thestate of the art of technology inpeptide self-assembly. 2. HISTORICAL CONTEXT Materials definethe faceof society. Initially,since prehistoric times – and to this day – materials were selected amongst those available in nature. These included, besides stonesand metals, basic ingredientsobtained from plants, crops,andanimalsintheformof,forexample,wood,flax,wool,andleather. Materials use was a skills-based activity perfected by artists and guild- membershandedfromonegenerationtothenext. Notuntilthelate18thandbeginningofthe19thcentury,commencingwith the Industrial Revolution and with an increasing need for natural products, did the search for more and other materials begin. Empire building, com- merce,andpopulationgrowthstimulatedinvestigationsintotheuseofmore novel natural products such as rubber and cellulose. Entrepreneurialism combined with scientific understanding and discovery gave rise to new