Bionanocomposites

Bionanocomposites

Integrating Biological Processes for Bioinspired Nanotechnologies

Edited by Carole Aimé and Thibaud Coradin

Sorbonne Universités UPMC Univ Paris 06 Collège de France UMR CNRS 7574 Laboratoire de Chimie de la Matière Condensée de Paris Paris, France

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Library of Congress Cataloging‐in‐Publication DataNames: Aimé, Carole, 1981– editor. | Coradin, Thibaud, editor.Title: Bionanocomposites : integrating biological processes for bioinspired nanotechnologies /

edited by Carole Aimé, Centre National de la Recherche Scientifique, Paris, France, Thibaud Coradin, Centre National de la Recherche Scientifique, Paris, France.

Description: First edition. | Hoboken, NJ, USA : John Wiley & Sons, Inc., 2017. | Includes bibliographical references and index.

Identifiers: LCCN 2017009006 (print) | LCCN 2017009534 (ebook) | ISBN 9781118942222 (cloth) | ISBN 9781118942253 (pdf) | ISBN 9781118942239 (epub)

Subjects: LCSH: Nanobiotechnology. | Nanocomposites (Materials) | Biomimetic materials.Classification: LCC TP248.25.N35 B564 2018 (print) | LCC TP248.25.N35 (ebook) |

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v

List of Contributors xv

1 What Are Bionanocomposites? 1Agathe Urvoas, Marie Valerio‐Lepiniec, Philippe Minard and Cordt Zollfrank

1.1 Introduction 11.2 A Molecular Perspective: Why Biological Macromolecules? 31.3 Challenges for Bionanocomposites 3 References 6

2 Molecular Architecture of Living Matter 9

2.1 Nucleic Acids 11Enora Prado, Mónika Ádok‐Sipiczki and Corinne Nardin

2.1.1 Introduction: A Bit of History 112.1.2 Definition and Structure 122.1.2.1 Nomenclature 122.1.2.2 Structure 132.1.3 DNA and RNA Functions 152.1.3.1 Introduction 152.1.3.2 Transcription–Translation Process 162.1.3.3 Replication Process 182.1.4 Specific Secondary Structures 192.1.4.1 Watson–Crick H‐Bonds 192.1.4.1.1 Stem‐Loop 192.1.4.1.2 Kissing Complex 202.1.4.2 Other Kinds of H‐Bonding 212.1.4.2.1 G‐Quartets 212.1.4.2.2 i‐Motifs 232.1.5 Stability 232.1.6 Conclusion 25 References 25

Contents

Contentsvi

2.2 Lipids 29Carole Aimé and Thibaud Coradin

2.2.1 Lipids Self‐Assembly 292.2.2 Structural Diversity of Lipids 302.2.2.1 Fatty Acyls (FA) 302.2.2.2 Glycerolipids (GL) 322.2.2.3 Glycerophospholipids (GP) 322.2.2.4 Sphingolipids (SP) 332.2.2.5 Sterol Lipids (ST) 342.2.2.6 Prenol Lipids (PR) 342.2.2.7 Saccharolipids (SL) 352.2.2.8 Polyketides (PK) 352.2.3 Lipid Synthesis and Distribution 352.2.4 The Diversity of Lipid Functions 362.2.4.1 Cellular Architecture 372.2.4.2 Lipid Rafts 372.2.4.3 Energy Storage 372.2.4.4 Regulating Membrane Proteins by Protein–Lipid Interactions 392.2.4.5 Signaling Functions 392.2.5 Lipidomics 39 References 40

2.3 Carbohydrates 41Mirjam Czjzek

2.3.1 Introduction 412.3.2 Monosaccharides 422.3.3 Oligosaccharides 442.3.3.1 Disaccharides 442.3.3.2 Protein Glycosylations 462.3.4 Polysaccharides 472.3.4.1 Cellulose 492.3.4.2 Hemicelluloses 502.3.4.2.1 Xyloglucan 502.3.4.2.2 Xylan 502.3.4.2.3 Mannan or Glucomannan 522.3.4.2.4 Mixed‐Linkage Glucan (MLG) 522.3.4.3 Pectins 532.3.4.4 Chitin 542.3.4.5 Alginate 542.3.4.6 Marine Galactans 552.3.4.7 Storage Polysaccharides: Starch, Glycogen, and Laminarin 55 References 56

Contents vii

2.4 Proteins: From Chemical Properties to Cellular Function: A Practical Review of Actin Dynamics 59Stéphane Romero and François‐Xavier Campbell‐Valois

2.4.1 Introduction 592.4.2 Molecular Architecture of Proteins 592.4.2.1 Amino Acids 602.4.2.2 Peptide Bond 602.4.2.3 Primary Structure 642.4.3 Protein Folding 662.4.3.1 Peptide and Protein: Secondary Structure 662.4.3.2 3D Folding: Tertiary Structure 672.4.3.3 Quaternary Structure 682.4.3.4 Protein Folding and De Novo Design 702.4.4 Interacting Proteins for Cellular Functions 732.4.4.1 Protein Interactions 732.4.4.2 Enzymatic Activity of Proteins 752.4.4.3 Molecular Motors 772.4.5 Self‐Assembly and Auto‐Organization:

Regulation of the Actin Cytoskeleton Assembly 782.4.5.1 Origin of the Actin Treadmilling 792.4.5.2 Regulation of Actin Treadmilling 832.4.5.3 Arp2/3 and Formin‐Initiated Actin Assembly

to Generate Mechanical Forces 832.4.5.4 Self‐Organization Properties and Force Generation

Understood Using In Vitro Reconstituted Actin‐Based Nanomovements 85

2.4.5.5 Applications in Bionanotechnologies 852.4.6 Conclusion 87 References 88

3 Functional Biomolecular Engineering 93

3.1 Nucleic Acid Engineering 95Enora Prado, Mónika Ádok‐Sipiczki and Corinne Nardin

3.1.1 Introduction 953.1.2 How to Synthetically Produce Nucleic Acids? 953.1.2.1 The Chemical Approach 953.1.2.2 Polymerase Chain Reaction 963.1.2.3 Combinatorial Synthesis of Oligonucleotides and Gene Libraries:

Aptamers 1003.1.3 Secondary Structures in Nanotechnologies 1023.1.3.1 Watson–Crick H‐Bonds 102

Contentsviii

3.1.3.1.1 Stem‐Loop 1023.1.3.1.2 Kissing Complex 1033.1.3.2 Other Kind of H‐Bonding 1033.1.3.2.1 G‐Quartets 1033.1.3.2.2 Origami: Nano‐architecture on Surface 1053.1.4 Conclusion 108 References 108

3.2 Protein Engineering 113Agathe Urvoas, Marie Valerio‐Lepiniec and Philippe Minard

3.2.1 Synthesis of Polypeptides: Chemical or Biological Approach? 1133.2.2 Proteins: From Natural to Artificial Sources 1143.2.2.1 How to Get the Coding Sequence of the Protein of Interest? 1143.2.2.2 E. coli: A Cheap “Protein Factory” with a Diversified Tool

Box 1143.2.2.3 Common Expression Plasmids 1163.2.2.4 Limits of Recombinant Protein Expression in E. coli 1173.2.2.5 Some Solutions Are Available to Solve these

Expression Problems 1183.2.3 Proteins: A Large Repertoire of Functional Objects 1183.2.3.1 Looking for Natural Proteins with Desired Function 1183.2.3.2 From Protein Engineering to Protein Design 1193.2.3.2.1 Modified Proteins Are Often Destabilized 1193.2.3.2.2 Natural or Engineered Proteins: From Small Step to Giant Leap

in Sequence Space 1203.2.3.2.3 Computational Protein Design 1203.2.3.2.4 Directed Evolution: A Diverse Repertoire Combined

with a Selection Process 1213.2.3.3 Combining Chemistry with Biological Objects 1233.2.3.3.1 Labeling Natural Amino Acids 1233.2.3.3.2 Bioorthogonal Labeling 1233.2.3.3.3 Tag‐Mediated Labeling and Enzymatic Coupling 1253.2.3.3.4 Enzyme‐Mediated Ligation 1263.2.3.3.5 Quality Control of Labeled Biomolecules 126 References 126

4 The Composite Approach 129

4.1 Inorganic Nanoparticles 131Carole Aimé and Thibaud Coradin

4.1.1 Introduction 1314.1.2 Overview of Inorganic Nanoparticles 1324.1.3 Synthesis of Inorganic Nanoparticles 132

Contents ix

4.1.3.1 Basic Principles 1324.1.3.2 Nanoparticles from Solutions 1384.1.3.2.1 Ionic Solids 1384.1.3.2.2 Metals 1394.1.3.2.3 Metal Oxides 1404.1.3.2.4 Morphological Control 1444.1.4 Some Specific Properties of Inorganic Nanoparticles 1454.1.5 Concluding Remarks 149 References 149

4.2 Hybrid Particles: Conjugation of Biomolecules to Nanomaterials 153Nikola Ž. Knežević, Laurence Raehm and Jean‐Olivier Durand

4.2.1 General Considerations 1534.2.2 Functionalization of Nanoparticle Surface 1544.2.2.1 Functionalization of Hydroxylated Surfaces 1544.2.2.2 Functionalization of Hydride‐Containing Surfaces 1544.2.2.3 Functionalization of Metal‐Containing Nanoparticles 1554.2.2.4 Functionalization of Carbon‐Based Nanomaterials 1554.2.3 Linker‐Mediated Conjugation of Biomolecules

to Nanoparticles 1554.2.3.1 Conjugation through Carbodiimide Chemistry 1554.2.3.2 Carbamate, Urea, and Thiourea Linkage 1564.2.3.3 Schiff Base Linkage 1584.2.3.4 Multicomponent Linkage Formation 1594.2.3.5 Biofunctionalization through Alkylation 1604.2.3.6 Bioorthogonal Linkage Formation 1614.2.3.7 Conjugation through Host–Guest Interactions 1624.2.3.8 Linkage through Metal Coordination 1624.2.3.9 Ligation through Complementary Base Pairing 1644.2.3.10 Electrostatic Interactions 1644.2.4 Conclusions 164 Acknowledgments 165 References 165

4.3 Biocomposites from Nanoparticles: From 1D to 3D Assemblies 169Carole Aimé and Thibaud Coradin

4.3.1 General Considerations 1694.3.2 One‐Dimensional Bionanocomposites 1704.3.3 Two‐Dimensional Organization of Nanoparticles 1754.3.4 Three‐Dimensional Organization of Particles 1754.3.5 Conclusion and Perspectives 180 References 180

Contentsx

5 Applications 185

5.1 Optical Properties 187Cordt Zollfrank and Daniel Van Opdenbosch

5.1.1 Introduction 1875.1.2 Interactions of Light with Matter 1895.1.3 Optics at the Nanoscale 1905.1.3.1 Nanoscale Optical Processes 1905.1.3.2 Nanoscale Confinement of Matter 1915.1.3.3 Nanoscale Confinement of Radiations 1915.1.4 Optical Properties of Bionanocomposites 1915.1.4.1 Absorption Properties of Bionanocomposites 1925.1.4.2 Emission Properties of Bionanocomposites 1955.1.4.3 Structural Colors with Bionanocomposites 2005.1.5 Conclusions 201 References 202

5.2 Magnetic Bionanocomposites: Current Trends, Scopes, and Applications 205Wei Li, Yuehan Wu, Xiaogang Luo and Shilin Liu

5.2.1 Introduction 2055.2.2 Construction Strategies for Magnetic Biocomposites 2085.2.2.1 The Blending Method 2085.2.2.2 In Situ Synthesis Method 2095.2.2.3 Grafting‐onto Method 2105.2.3 Applications of Magnetic Biocomposites 2125.2.3.1 Environmental Applications 2125.2.3.1.1 Removal of Toxic Metal Ions 2125.2.3.1.2 Removal of Dyes 2165.2.3.1.3 Biocatalysis and Bioremediation 2165.2.3.2 Biomedical Applications 2185.2.3.2.1 Magnetic Resonance Imaging (MRI) 2185.2.3.2.2 Cellular Therapy and Labeling 2195.2.3.2.3 Tissue Engineering Applications 2215.2.3.2.4 Drug Delivery 2215.2.3.2.5 Tissue Regeneration 2245.2.3.3 Biotechnological and Bioengineering Applications 2255.2.3.3.1 Biosensing 2265.2.3.3.2 Magnetically Responsive Films 2285.2.4 Concluding Remarks and Future Trends 228 Acknowledgments 229 References 229

Contents xi

5.3 Mechanical Properties of Natural Biopolymer Nanocomposites 235Biqiong Chen

5.3.1 Introduction 2355.3.2 Overview of Mechanical Properties of Polymer Nanocomposites

and Their Measurement Methods 2375.3.3 Solid Biopolymer Nanocomposites 2375.3.4 Porous Biopolymer Nanocomposites 2455.3.5 Biopolymer Nanocomposite Hydrogels 2475.3.6 Conclusions 249 References 251

5.4 Bionanocomposite Materials for Biocatalytic Applications 257Sarah Christoph and Francisco M. Fernandes

5.4.1 Bionanocomposites and Biocatalysis 2575.4.2 Form and Function in Bionanocomposite Materials

for Biocatalysis 2605.4.2.1 Bionanocomposites Structure 2605.4.2.1.1 Biopolymers 2605.4.2.1.2 The Inorganic Fraction 2645.4.2.2 Key Biocatalysts 2695.4.2.2.1 Nucleotides and Amino Acids 2695.4.2.2.2 Enzymes 2725.4.2.2.3 Whole Cells 2735.4.3 Applications 2775.4.3.1 Biosynthesis 2775.4.3.2 Sensing Applications 2815.4.3.3 Environmental Applications 2835.4.3.4 Energy Applications of Biocatalytic Bionanocomposites 2865.4.4 Conclusions and Perspectives 289 References 290

5.5 Nanocomposite Biomaterials 299Gisela Solange Alvarez and Martín Federico Desimone

5.5.1 Introduction 2995.5.2 Natural Nanocomposites 3015.5.2.1 Cellulosic Materials 3015.5.2.2 Chitosan 3055.5.2.3 Alginate 3055.5.2.4 Collagen 3075.5.2.5 Gelatin 307

Contentsxii

5.5.2.6 Silk Fibroin 3095.5.3 Synthetic Nanocomposites 3095.5.3.1 PLLA and PLGA 3095.5.3.2 Polyethylene Glycol 3125.5.3.3 Methacrylate 3125.5.3.4 Polyvinyl Alcohol 3145.5.3.5 Polyurethanes 3145.5.4 Conclusions 315 Acknowledgments 317 References 317

6 A Combination of Characterization Techniques 321Carole Aimé and Thibaud Coradin

6.1 Introductory Remarks 3216.2 Chemical Analyses 3226.2.1 Inductively Coupled Plasma 3226.2.2 Infrared Spectroscopy 3236.2.3 X‐Ray Photoelectron Spectroscopy and Auger Electron

Spectroscopy 3246.2.4 Energy–Dispersive X‐Ray Spectroscopy and Electron–Energy

Loss Spectroscopy 3286.3 Determining Size and Structure 3296.3.1 Imaging 3296.3.1.1 Electron Microscopy 3306.3.1.2 Atomic Force Microscopy 3336.3.2 Scattering Techniques 3356.3.2.1 Small Angle Scattering 3376.3.2.2 Dynamic Light Scattering and Zetametry 3376.3.3 Monitoring Particle–Biomolecule Interactions 3396.3.3.1 Electrophoresis 3396.3.3.2 Circular Dichroism Spectroscopy 3406.3.3.3 Isothermal Titration Calorimetry and Surface

Plasmon Resonance 3426.4 Materials Properties 3446.4.1 Optical Properties 3446.4.2 Mechanical Testing 3466.4.2.1 Rheology 3466.4.2.2 Compression Tests 3476.4.2.3 Tensile Tests 3486.4.2.4 Relaxation Tests 3486.4.2.5 Dynamic Mechanical Analysis 3496.4.2.6 Indentation 349

Contents xiii

6.4.2.7 Mechanical Testing of Hydrogels 3496.4.3 Magnetic Measurements 3506.4.4 Biological Properties 353 References 355

Index 359

xv

Mónika Ádok‐SipiczkiDepartment of Inorganic and Analytical Chemistry, University of Geneva, Geneva, Switzerland

Carole AiméSorbonne Universités, UPMC Univ Paris 06, Collège de France, UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée de Paris, Paris, France

Gisela Solange AlvarezUniversidad de Buenos Aires. Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Instituto de la Química y Metabolismo del Fármaco (IQUIMEFA). Facultad de Farmacia y Bioquímica. Buenos Aires, Argentina

François‐Xavier Campbell‐ValoisDépartement de Chimie et Sciences Biomoléculaires, Université d’Ottawa, Ottawa, Ontario, Canada

Biqiong ChenDepartment of Materials Science and Engineering, University of Sheffield, Sheffield, UK

Sarah ChristophSorbonne Universités, UPMC Univ Paris 06, Collège de France, UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée de Paris, Paris, France

Thibaud CoradinSorbonne Universités, UPMC Univ Paris 06, Collège de France, UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée de Paris, Paris, France

Mirjam CzjzekLaboratory of Integrative Biology of Marine Models, Station Biologique de Roscoff, University Sorbonne Paris VI and CNRS, Roscoff, France

Martín Federico DesimoneUniversidad de Buenos Aires. Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Instituto de la Química y Metabolismo del Fármaco (IQUIMEFA). Facultad de Farmacia y Bioquímica. Buenos Aires, Argentina

Jean‐Olivier DurandInstitut Charles Gerhardt Montpellier UMR‐5253 CNRS‐UM2‐ENSCM‐UM1cc, Montpellier, France

List of Contributors

List of Contributorsxvi

Francisco M. FernandesSorbonne Universités, UPMC Univ Paris 06, Collège de France, UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée de Paris, Paris, France

Nikola Ž. KneževićFaculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia

Wei LiCollege of Food Science and Technology, Huazhong Agricultural University, Wuhan, Hubei, China

Shilin LiuCollege of Food Science and Technology, Huazhong Agricultural University, Wuhan, Hubei, China

Xiaogang LuoSchool of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan, Hubei, China

Philippe MinardInstitute for Integrative Biology of the Cell (I2BC), UMR 9198, Université Paris‐Sud, CNRS, CEA, Orsay, France

Corinne NardinInstitut pluridisciplinaire de recherche sur l’environnement et les matériaux (IPREM), Equipe Physique Chimie des Polymères (EPCP), Université de Pau et des Pays de l’Adour (UPPA), Pau, France

Enora PradoInstitute of Physics Rennes, UMR UR1‐CNRS 6251, Rennes, France

Laurence RaehmInstitut Charles Gerhardt Montpellier UMR‐5253 CNRS‐UM2‐ENSCM‐UM1cc, Montpellier, France

Stéphane RomeroEquipe Communication Intercellulaire et Infections Microbiennes, Centre de Recherche Interdisciplinaire en Biologie (CIRB), Collège de France, Paris, FranceInstitut National de la Santé et de la Recherche Médicale U1050, Paris, FranceCentre National de la Recherche Scientifique UMR7241, Paris, FranceMEMOLIFE Laboratory of Excellence and Paris Science Lettre, Paris, France

Agathe UrvoasInstitute for Integrative Biology of the Cell (I2BC), UMR 9198, Université Paris‐Sud, CNRS, CEA, Orsay, France

Marie Valerio‐LepiniecInstitute for Integrative Biology of the Cell (I2BC), UMR 9198, Université Paris‐Sud, CNRS, CEA, Orsay, France

Daniel Van OpdenboschBiogenic Polymers, Technische Universität München, Straubing, Germany

List of Contributors xvii

Yuehan WuCollege of Food Science and Technology, Huazhong Agricultural University, Wuhan, Hubei, China

Cordt ZollfrankBiogenic Polymers, Technische Universität München, Straubing, Germany

Bionanocomposites: Integrating Biological Processes for Bioinspired Nanotechnologies, First Edition. Edited by Carole Aimé and Thibaud Coradin. © 2017 John Wiley & Sons, Inc. Published 2017 by John Wiley & Sons, Inc.

1

1

1.1 Introduction

Almost all natural materials, which are formed through metabolic processes of an organism, are nanocomposite materials, that is, materials associating at least two distinct phases, one of which being of nanometer scale dimension. The term “natural” is most often synonymously used with the term “biological.” Natural nanocomposite can be therefore characterized as bionanocomposites. Basically two kinds of solid composite materials are generated in natural systems: soft matter and hard matter (Figure 1.1). Natural soft matter compos-ites are composed of at least two types of organic biomacromolecules. The most prominent example here is wood, which is a hierarchically structured bionanocomposite consisting of polysaccharides (mainly cellulose) and lignin (Figure  1.1a). Biological hard matter is generally composed of an inorganic phase and an organic phase. Biominerals (sea shells) and hard tissue (bone) are two typical forms of appearance of biological hard matter (Figure 1.1b). Natural bionanocomposites combine a high resilience and tolerance toward failure, adaptation, modularity, and multifunctionality [1, 2]. They are originally designed and optimized for the needs of life and to meet the surrounding envi-ronmental conditions in order to guarantee the survival of the respective spe-cies they are associated with.

Nature provide a rich pool of raw materials for mankind with easily acces-sible constituents for habitation, clothes, weapons, and arts, among many

What Are Bionanocomposites?Agathe Urvoas1, Marie Valerio‐Lepiniec1, Philippe Minard1 and Cordt Zollfrank2

1 Institute for Integrative Biology of the Cell (I2BC), UMR 9198, Université Paris‐Sud, CNRS, CEA, Orsay, France2 Biogenic Polymers, Technische Universität München, Straubing, Germany

What Are Bionanocomposites?2

other examples. Further, the development of chemistry allowed for the transformation of this raw matter into synthetic materials. At the end of the last century, the conjunction of economic and environmental issues, com-bined with the growing development of multidisciplinary scientific research, has led to reconsider natural processes in general and natural materials in particular as an enormous pool of inspiration with an incredi-ble structural and functional variability. Such bioinspired materials, achieved by using Nature guidelines to tailor and design a novel class of bionanocomposites or nanostructured biohybrid materials, have the poten-tial to conquer complex multivariant environments [3–7].

However, it is interesting to note that under the constraints of living envi-ronments and required metabolic conversion processes, only a small number of organic compounds (based on the light elements carbon, hydrogen, oxygen, nitrogen, sulfur, and phosphorus) and a few inorganic phases (i.e., calcium phosphates and carbonates, silica, and iron oxides) are used for the formation of bionanocomposites [8]. This strongly contrasts with engineering materials that are prepared from almost all the elements of the periodic table. In paral-lel, structures and properties of biological polymers have been, and still are, studied by biologists mainly to understand their essential roles in biological systems. However, the potential applications of biological molecules in the design of bionanocomposites require to consider them as synthetic “building blocks” that may eventually be used in a context distant from their natural environment or function.

(a)

(b)

5 cm

Figure 1.1 Examples for biological soft and hard matter: (a) trunk disc of an oak tree and (b) lower jawbone of a cow (mandible).

1.3 Challenges for Bionanocomposites 3

1.2 A Molecular Perspective: Why Biological Macromolecules?

This is a relatively new view as biomolecules have long been considered, out-side the biological or biomedical field, as highly complex systems, difficult to modify, and too fragile to be of any practical utility. Indeed, proteins or nucleic acids have characteristic features that are not common in the syn-thetic chemical world. Their natural functionality in living cells and their potential applications outside biology precisely result from these properties:

● First, proteins and nucleic acids are very long copolymers in which the differ-ent monomers are linked with a defined order. In other words, these poly-mers have a defined “sequence,” a property that usually does not exist in polymers made by chemical synthesis.

● Second, the specific sequence of any nucleic acid or the coding sequence of a protein gene can be viewed and is actually used, by living cells as well as by biologists, not only as a substance but also as information: biological sequences can be duplicated, transmitted, eventually modified, and executed. Information processing occurs naturally between generations of cells and organisms that select, amplify, replicate genes, and control their expression. Information processing similarly occurs when a sequence is designed in a laboratory, transmitted by e‐mail, synthetized as a synthetic gene, amplified by PCR, and translated in protein in a recombinant microorganism.

● Third, biological polymers are self‐assembling materials. The information content embedded within each sequence is often sufficient to allow each nucleic acid or protein to reach its highly organized structure, and the func-tional properties of biological molecules directly result from their three‐dimensional structure.

● Fourth, nucleic acids or proteins can evolve. Each natural protein or nucleic acid sequence is not simply a molecule: its informational content is the prod-uct of a historical process. In the current structure and function of any natu-ral protein, there is the memory of all past successful trials that occurred during its evolution. It is this historical information accumulated over bil-lions of years that explains the amazing diversity and extreme sophistication of natural protein structures and functions.

1.3 Challenges for Bionanocomposites

Going back 50 years ago, the design of specific peptide or nucleic acid sequence to control the organization of gold nanoparticles into perfectly controlled crys-tals was probably as unexpected as the application of the same particles for cell imaging. Thus, the progresses made in the field of bionanocomposites over the

What Are Bionanocomposites?4

last decades largely result from the evolution of both chemistry and biology fields (but also of physics, engineering, and computer science) that, in some specific areas, has led to conceptual and experimental convergences. The pro-cessing of natural macromolecules in artificial conditions has been as fruitful as the confrontation of chemical and biological to define how the two worlds can cohabitate. This has led to an impressive list of “hybrid” objects that will be described in the following chapters.

However, there are several characteristics present in biology that have not been translated in engineering materials so far. The extraordinary structures and functions of biological materials strongly relate to their organization over several length scales. In particular, the importance of hierarchical structuring has long been identified and was widely investigated in the recent years [3, 9]. A variety of functional materials solutions relying on structural hierarchy were described in natural materials [10–14] (Figure  1.2). However, whereas such organizations could be obtained for organic or inorganic structures [15–17], they are still challenging to achieve in bionanocomposite systems.

(a1)

(a2)

(a3)

(a4)

(a5)

(b1) (b2)(b3)

(b4)

(b5)

Figure 1.2 Structural hierarchy of soft tissue (oak wood) and hard tissue (bone): (a1) tissue, (a2) cells, (a3) cell walls, (a4) elementary fibrils, and (a5) biomolecules (cellulose and lignin); (b1) compact and spongy bone, (b2) osteons, (b3) collagen fibril, (b4) mineralized collagen triple helices, and (b5) collagen molecule and calcium phosphate nanocrystal.

1.3 Challenges for Bionanocomposites 5

Another key feature of biological aspects yet to implement in materials science involves dynamic processes such as evolution, growth, and continuous structure formation (self‐organization, remodeling). This means that according to the local and temporal needs, the organism supplies the required material “on demand” with an extremely high spatiotemporal precision [18]. As a conse-quence, building blocks for the bionanocomposite formation (inorganic and organic phases) are continuously supplied and assembled from finely tuned cooperative interactions by regulatory processes as an answer to external and internal stimuli (Figure 1.3). This ultimately means that natural materials are dynamic in terms of structure and composition. These basic principles are related to two fundamental biological processes termed (i) ontogenesis and (ii) morphogenesis. Both processes are not known for engineering materials but

(a) (b)

(c) (d)

Collagen fibrilCells and othertissue elements

Figure 1.3 Fundamental biological and dynamic processes that are absent in engineering materials. The development of the material during the lifetime of an organism is termed ontogenesis: (a) juvenile bone (woven bone) with unoriented collagen fibrils and (b) adult bone (lamellar bone) with highly oriented collagen fibrils. Morphogenesis is the development of form: (c) juvenile skull and (d) adult skull.

What Are Bionanocomposites?6

might lead to advanced materials with unforeseen properties and open new horizons for high‐level applications.

To conclude, bionanocomposites are attracting more and more interest not only from the natural sciences but also from materials chemists and engineers. Although synthetic materials might never be as sophisticated as natural systems, integration of key processes involved in the building‐up of biological materials in the fabrication of bionanocomposites would pave the grounds for the development of a new generation of advanced materials that can cope with spatiotemporal multivariant environments and combine multiple properties.

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Guide for New Materials Technology. National Academy Press, Washington, DC: 1994.

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Burghammer, M.; Roth, S. V.; Stanzl‐Tschegg, S.; Fratzl, P. Nat. Mater. 2003, 2, 810–813.

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15 Zollfrank, C. Biotemplating: Polysaccharides in materials engineering. In Design and Nature V, Comparing Design in Nature with Science and Engineering, Brebbia, C. A., Carpi, A. (eds.) WIT Press, Southampton, 441–451, 2010.

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4093–4138. 18 Jeronimides, G. Chapters 1 and 2. In Structural Biological Materials. Design

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Molecular Architecture of Living Matter