BIOINSPIRATION AND BIOMIMICRY IN CHEMISTRY BIOINSPIRATION AND BIOMIMICRY IN CHEMISTRY REVERSE-ENGINEERING NATURE Editedby Gerhard F. Swiegers A JOHN WILEY & SONS, INC., PUBLICATION Copyright©2012byJohnWiley&Sons,Inc.Allrightsreserved PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey PublishedsimultaneouslyinCanada Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmittedinanyform orbyanymeans,electronic,mechanical,photocopying,recording,scanning,orotherwise,exceptas permittedunderSection107or108ofthe1976UnitedStatesCopyrightAct,withouteithertheprior writtenpermissionofthePublisher,orauthorizationthroughpaymentoftheappropriateper-copyfee totheCopyrightClearanceCenter,Inc.,222RosewoodDrive,Danvers,MA01923,(978)750-8400, fax(978)750-4470,oronthewebatwww.copyright.com.RequeststothePublisherforpermission shouldbeaddressedtothePermissionsDepartment,JohnWiley&Sons,Inc.,111RiverStreet, Hoboken,NJ07030,(201)748-6011,fax(201)748-6008,oronlineat http://www.wiley.com/go/permission. LimitofLiability/DisclaimerofWarranty:Whilethepublisherandauthorhaveusedtheirbestefforts inpreparingthisbook,theymakenorepresentationsorwarrantieswithrespecttotheaccuracyor completenessofthecontentsofthisbookandspecificallydisclaimanyimpliedwarrantiesof merchantabilityorfitnessforaparticularpurpose.Nowarrantymaybecreatedorextendedbysales representativesorwrittensalesmaterials.Theadviceandstrategiescontainedhereinmaynotbe suitableforyoursituation.Youshouldconsultwithaprofessionalwhereappropriate.Neitherthe publishernorauthorshallbeliableforanylossofprofitoranyothercommercialdamages,including butnotlimitedtospecial,incidental,consequential,orotherdamages. Forgeneralinformationonourotherproductsandservicesorfortechnicalsupport,pleasecontactour CustomerCareDepartmentwithintheUnitedStatesat(800)762-2974,outsidetheUnitedStatesat (317)572-3993orfax(317)572-4002. Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprint maynotbeavailableinelectronicformats.FormoreinformationaboutWileyproducts,visitourweb siteatwww.wiley.com. LibraryofCongressCataloging-in-PublicationData: Bioinspirationandbiomimicryinchemistry:reverse-engineeringnature/ editedbyGerhardF.Swiegers. p.cm. Includesbibliographicalreferencesandindex. ISBN978-0-470-56667-1(cloth) 1. Biomimicry. 2. Biomimetics. 3. Biomedicalengineering. 4. Biomedical materials.I.Swiegers,GerhardF. QP517.B56B4782012 610.28–dc23 2011049801 PrintedintheUnitedStatesofAmerica 10987654321 DedicatedtoCrawfordLong,WilliamThomasGreenMorton, andWilhelmRo¨ntgen CONTENTS Foreword xvii Jean-MarieLehn Foreword xix JanineBenyus Preface xxiii Contributors xxv 1. Introduction: The Concept of Biomimicry and Bioinspiration in Chemistry 1 TimothyW.HanksandGerhardF.Swiegers 1.1 What is Biomimicry and Bioinspiration? 1 1.2 Why Seek Inspiration from, or Replicate Biology? 3 1.2.1 Biomimicry and Bioinspiration as a Means of Learning from Nature and Reverse-Engineering from Nature 3 1.2.2 Biomimicry and Bioinspiration as a Test of Our Understanding of Nature 4 1.2.3 Going Beyond Biomimicry and Bioinspiration 4 1.3 Other Monikers: Bioutilization, Bioextraction, Bioderivation, and Bionics 5 1.4 Biomimicry and Sustainability 5 1.5 Biomimicry and Nanostructure 7 1.6 Bioinspiration and Structural Hierarchies 9 1.7 Bioinspiration and Self-Assembly 11 1.8 Bioinspiration and Function 12 1.9 Future Perspectives: Drawing Inspiration from the Complex System that is Nature 13 References 14 vii viii CONTENTS 2. Bioinspired Self-Assembly I: Self-Assembled Structures 17 LeonardF.Lindoy,ChristopherRichardson,andJackK.Clegg 2.1 Introduction 17 2.2 Molecular Clefts, Capsules, and Cages 19 2.2.1 Organic Cage Systems 21 2.2.2 Metallosupramolecular Cage Systems 24 2.3 Enzyme Mimics and Models: The Example of Carbonic Anhydrase 28 2.4 Self-Assembled Liposome-Like Systems 30 2.5 Ion Channel Mimics 32 2.6 Base-Pairing Structures 34 2.7 DNA–RNA Structures 36 2.8 Bioinspired Frameworks 38 2.9 Conclusion 41 References 41 3. Bioinspired Self-Assembly II: Principles of Cooperativity in Bioinspired Self-Assembling Systems 47 GianfrancoErcolaniandLucaSchiaffino 3.1 Introduction 47 3.2 Statistical Factors in Self-Assembly 48 3.3 Allosteric Cooperativity 50 3.4 Effective Molarity 52 3.5 Chelate Cooperativity 55 3.6 Interannular Cooperativity 60 3.7 Stability of an Assembly 62 3.8 Conclusion 67 References 67 4. Bioinspired Molecular Machines 71 ChristopherR.Benson,AndrewI.Share,andAmarH.Flood 4.1 Introduction 71 4.1.1 Inspirational Antecedents: Biology, Engineering, and Chemistry 72