Table Of ContentAdvances in
CHEMICAL ENGINEERING
ENGINEERING ASPECTS OF SELF-ORGANIZING MATERIALS
35
VOLUME
Editedby
RUDY J. KOOPMANS
PolyUrethane R&D, Freienbach
Dow Europe GmbH, Switzerland
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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
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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