Tomorrow's chemistry today : concepts in nanoscience, organic materials and environmental chemistry

Providing a glimpse into the future, the young scientists contributing here were considered to be the most important for tomorrow's chemistry and materials science. They present the state of the art in their particular fields of research, with topics ranging from new synthetic pathways and nanotechnology to green chemistry. Of major interest to organic chemists, materials scientists and biochemists.Content: Chapter 1 Subcomponent Self?Assembly as a Route to New Structures and Materials (pages 1–29): Jonathan R. NitschkeChapter 2 Molecular Metal Oxides and Clusters as Building Blocks for Functional Nanoscale Architectures and Potential Nanosystems (pages 31–46): Leroy CroninChapter 3 Nanostructured Porous Materials: Building Matter from the Bottom Up (pages 47–71): Javier Garcia?MartinezChapter 4 Strategies toward Hierarchically Structured Optoelectronically Active Polymers (pages 73–100): Eike Jahnke and Holger FrauenrathChapter 5 Mimicking Nature: Bio?Inspired Models of Copper Proteins (pages 101–127): Iryna A. Koval, Patrick Gamez and Jan ReedijkChapter 6 From the Past to the Future of Rotaxanes (pages 129–159): Andreea R. SchmitzerChapter 7 Multiphoton Processes and Nonlinear Harmonic Generations in Lanthanide Complexes (pages 161–184): Ga?Lai LawChapter 8 Light?Emitting Organic Nanoaggregates from Functionalized para?Quaterphenylenes (pages 185–213): Manuela SchiekChapter 9 Plant Viral Capsids as Programmable Nanobuilding Blocks (pages 215–236): Nicole F. SteinmetzChapter 10 New Calorimetric Approaches to the Study of Soft Matter 3D Organization (pages 237–261): J. M. Nedelec and M. BabaChapter 11 Naphthalenediimides as Photoactive and Electroactive Components in Supramolecular Chemistry (pages 263–293): Sheshanath Vishwanath BhosaleChapter 12 Coordination Chemistry of Phosphole Ligands Substituted with Pyridyl Moieties: From Catalysis to Nonlinear Optics and Supramolecular Assemblies (pages 295–319): Christophe Lescop and Muriel HisslerChapter 13 Selective Hydrogen Transfer Reactions over Supported Copper Catalysts Leading to Simple, Safe, and Clean Protocols for Organic Synthesis (pages 321–336): Federica Zaccheria and Nicoletta RavasioChapter 14 Selective Oxido?Reductive Processes by Nucleophilic Radical Addition under Mild Conditions (pages 337–351): Cristian Gambarotti and Carlo PuntaChapter 15 Speeding Up Discovery Chemistry: New Perspectives in Medicinal Chemistry (pages 353–373): Matteo Colombo and Ilaria PerettoChapter 16 Overview of Protein?Tannin Interactions (pages 375–394): Elisabete Barros de Carvalho, Victor Armando Pereira de Freitas and Nuno Filipe da Cruz Batista MateusChapter 17 Photochemical Transformation Processes of Environmental Significance (pages 395–419): Davide Vione Tomorrow’s Chemistry Today: Concepts in Nanoscience, Organic Materials and Environmental Chemistry, Second Edition......Page 5 Contents......Page 7 Preface......Page 15 List of Contributors......Page 21 Member Societies......Page 25 Part One: Self-Organization, Nanoscience and Nanotechnology......Page 29 1.1 Introduction......Page 31 1.2 Aqueous Cu(I)......Page 33 1.3 Chirality......Page 35 1.4.1 Dicopper Helicates......Page 36 1.4.2 Tricopper Helicates......Page 38 1.4.3 Catenanes and Macrocycles......Page 39 1.4.4 [2 × 2] Tetracopper(I) Grid......Page 40 1.5.2 Simultaneous Syntheses of Helicates......Page 41 1.5.3 Sorting within a Structure......Page 42 1.5.4 Cooperative Selection by Iron and Copper......Page 45 1.6.1 New Cascade Reaction......Page 48 1.6.2 Hammett Effects......Page 50 1.6.3 Helicate Reconfigurations......Page 51 1.6.4 Substitution as a Route to Polymeric Helicates......Page 52 1.8 Acknowledgments......Page 55 2.1 Introduction......Page 59 2.2 From POM Building Blocks to Nanoscale Superclusters......Page 61 2.3 From Building Blocks to Functional POM Clusters......Page 65 2.3.1 Host–Guest Chemistry of POM-based Superclusters......Page 66 2.3.2 Magnetic and Conducting POMs......Page 67 2.3.3 Thermochromic and Thermally Switchable POM Clusters......Page 68 2.4 Bringing the Components Together – Towards Prototype Polyoxometalate-based Functional Nanosystems......Page 70 2.5 Acknowledgments......Page 72 3.1 Introduction......Page 75 3.2 Synthesis by Organic Molecule Templates......Page 76 3.3 Synthesis by Molecular Self-Assembly: Liquid Crystals and Cooperative Assembly......Page 78 3.4.2 Capping Agents......Page 85 3.4.3 Foams......Page 86 3.5 Multiscale Self-Assembly......Page 87 3.6 Biomimetic Synthesis: Toward a Multidisciplinary Approach......Page 89 3.7 Acknowledgments......Page 97 4.1 Hierarchically Structured Organic Optoelectronic Materials via Self-Assembly......Page 101 4.2 Toward Hierarchically Structured Conjugated Polymers via the Foldamer Approach......Page 102 4.3 “Self-Assemble, then Polymerize” – A Complementary Approach and Its Requirements......Page 106 4.3.1 Topochemical Polymerization Using Self-Assembled Scaffolds......Page 107 4.3.2 Self-Assembly of β-Sheet Forming Oligopeptides and Their Polymer Conjugates......Page 108 4.4 Macromonomer Design and Preparation......Page 110 4.5 Hierarchical Self-Organization in Organic Solvents......Page 113 4.6 A General Model for the Hierarchical Self-Organization of Oligopeptide–Polymer Conjugates......Page 117 4.7 Conversion to Conjugated Polymers by UV Irradiation......Page 120 4.9 Acknowledgments......Page 123 5.1 Environmental Pollution: How Can “Green” Chemistry Help?......Page 129 5.2.1 Type 1 Active Site......Page 130 5.2.2 Type 2 Active Site......Page 131 5.2.5 The CuA Active Site......Page 132 5.3 Catechol Oxidase: Structure and Function......Page 133 5.3.1 Catalytic Reaction Mechanism......Page 135 5.4 Model Systems of Catechol Oxidase: Historic Overview......Page 136 5.5.2 Copper(I) and Copper(II) Complexes with [22]py4pz: Structural Properties and Mechanism of the Catalytic Reaction......Page 142 5.5.3 Copper(I) and Copper(II) Complexes with [22]pr4pz: Unraveling Catalytic Mechanisms......Page 146 5.6 Concluding Remarks......Page 152 5.7 Acknowledgments......Page 153 6.1 Introduction......Page 157 6.2 Synthesis of Rotaxanes......Page 159 6.2.1 Van der Waals Interactions in the Synthesis of Rotaxanes......Page 160 6.2.2 Hydrophobic Interactions in the Synthesis of Rotaxanes......Page 161 6.2.3 Hydrogen Bonding in Rotaxane Synthesis......Page 162 6.2.4 Donor–Acceptor Interactions in the Synthesis of Rotaxanes......Page 163 6.2.5 Transition-Metal Coordination in the Synthesis of Rotaxanes......Page 164 6.3.1 Rotaxanes as Molecular Shuttles......Page 165 6.3.1.1 Acid–Base-controlled Molecular Shuttle......Page 167 6.3.1.2 A Light-driven Molecular Shuttle......Page 168 6.3.2 Molecular Lifts......Page 170 6.3.3 Artificial Molecular Muscles......Page 171 6.3.4 Redox-activated Switches for Dynamic Memory Storage......Page 172 6.3.5 Bioelectronics......Page 175 6.3.6 Membrane Transport......Page 177 6.3.7 Catalytically Active Rotaxanes as Processive Enzyme Mimics......Page 179 6.4 Conclusion and Perspectives......Page 180 7.1 Introduction......Page 189 7.2 Types of Nonlinear Processes......Page 190 7.3 Selection Rules for Multiphoton Absorption......Page 192 7.4 Multiphoton Absorption Induced Emission......Page 193 7.5 Nonlinear Harmonic Generation......Page 204 7.7 Acknowledgments......Page 209 8.1 Introduction to para-Phenylene Organic Nanofibers......Page 213 8.2 General Aspects of Nanofiber Growth......Page 215 8.3 Synthesis of Functionalized para-Quaterphenylenes......Page 217 8.4 Variety of Organic Nanoaggregates from Functionalized para-Quaterphenylenes......Page 221 8.5 Symmetrically Functionalized p-Quaterphenylenes......Page 222 8.6 Differently Di-functionalized p-Quaterphenylenes......Page 225 8.7 Monofunctionalized p-Quaterphenylenes......Page 227 8.8 Tailoring Morphology: Nanoshaping......Page 228 8.9 Tailoring Optical Properties: Linear Optics......Page 229 8.10 Creating New Properties: Nonlinear Optics......Page 231 8.12 Acknowledgments......Page 233 9.1 Nanobiotechnology – A Definition......Page 243 9.3 General Introduction to CPMV......Page 244 9.4 Advantages of Plant Viral Particles as Nanoscaffolds......Page 247 9.5 Addressable Viral Nanobuilding Block......Page 248 9.6 From Labeling Studies to Applications......Page 250 9.7 Immobilization of Viral Particles and the Construction of Arrays on Solid Supports......Page 257 9.8 Outlook......Page 259 9.9 Acknowledgments......Page 260 10.1 Introduction......Page 265 10.2 Transitions in Confined Geometries......Page 266 10.2.1.1 Confinement Effect on Triple-point Temperature......Page 267 10.2.2 Porosity Measurements via Determination of the Gibbs–Thomson Relation......Page 268 10.2.2.3 Surface Force Apparatus......Page 269 10.2.3 Thermoporosimetry and Pore Size Distribution Measurement......Page 270 10.3.1 Analogy and Limitations......Page 271 10.3.2.1 Elastomers......Page 272 10.3.2.4 Crosslinking of Polyolefins......Page 274 10.4.2 Photocuring and Photopolymerization Investigations......Page 275 10.5.1.1 Correlation between Oxidation and Crystallinity......Page 279 10.5.1.2 Crosslinking and Crystallizability......Page 281 10.5.1.3 Photo-aging Study by Macroperoxide Concentration Monitoring......Page 282 10.5.2 Kinetics of Chain Scissions during Accelerated Aging of Poly(ethylene oxide)......Page 283 10.5.2.1 Chain Scission Kinetics from Melting......Page 284 10.6 Conclusion......Page 286 Part Two: Organic Synthesis, Catalysis and Materials......Page 291 11.1 Introduction......Page 293 11.2 General Syntheses and Reactivity......Page 294 11.2.2 General Chemical and Physical Properties......Page 296 11.3 Redox and Optical Properties of NDIs......Page 299 11.3.2 NDI-DAN Foldamers......Page 300 11.3.3 Ion Channels......Page 301 11.3.4 NDIs in Material Chemistry......Page 303 11.4 Catenanes and Rotaxanes......Page 304 11.4.1 NDIs Used as Sensors......Page 305 11.4.2 Nanotubes......Page 307 11.5.2 Covalent Models......Page 309 11.5.3 Noncovalent Models......Page 312 11.6 Applications of Core-Substituted NDIs......Page 315 11.8 Acknowledgment......Page 318 12.1 Introduction......Page 323 12.2.1 Synthesis and Physical Properties......Page 324 12.2.2 Fine Tuning of the Physical Properties via Chemical Modifications of the Phosphole Ring......Page 326 12.3.1 Syntheses and Catalytic Tests......Page 328 12.3.2 Isomerization of Coordinated Phosphole Ring into 2-Phospholene Ring......Page 329 12.3.3 Square-Planar Complexes Exhibiting Nonlinear Optical Activity......Page 331 12.3.4 Ruthenium Complexes......Page 332 12.4.1 Bimetallic Coordination Complexes Bearing a Bridging Phosphane Ligand......Page 333 12.4.1.1 Pd(I) and Pt(I) Bimetallic Complexes......Page 334 12.4.1.2 Cu(I) Bimetallic Complexes......Page 335 12.4.2 Supramolecular Organization of π-Conjugated Chromophores via Coordination Chemistry: Synthesis of Analogues of [2.2]-Paracyclophanes......Page 338 12.5 Conclusions......Page 342 12.6 Acknowledgments......Page 343 13: Selective Hydrogen Transfer Reactions over Supported Copper Catalysts Leading to Simple, Safe, and Clean Protocols for Organic Synthesis......Page 349 13.1 Chemoselective Reduction of Polyunsaturated Compounds via Hydrogen Transfer......Page 351 13.2 Alcohol Dehydrogenation......Page 353 13.4 Isomerization of Allylic Alcohols......Page 359 13.5 Conclusions......Page 361 14.1 Introduction......Page 365 14.2.1 Acylation of N-heteroaromatic Bases......Page 366 14.2.2 Acylation of N-heteroaromatic Bases Catalyzed by N-hydroxyphthalimide......Page 368 14.2.3 Photoinduced Nucleophilic Radical Substitution in the Presence of TiO2......Page 369 14.2.4 Hydroxymethylation of N-heteroaromatic Bases......Page 371 14.2.5 Perfluoroalkylation of N-heteroaromatic Bases and Quinones......Page 372 14.3.1 Nucleophilic Radical Addition Promoted by TiCl3/PhN2+ Systems......Page 373 14.3.2 Nucleophilic Radical Addition Promoted by TiCl3/Pyridine Systems......Page 375 14.3.3 Nucleophilic Radical Addition Promoted by TiCl3/Hydroperoxide Systems......Page 376 Part Three: Health, Food, and Environment......Page 381 15: Speeding Up Discovery Chemistry: New Perspectives in Medicinal Chemistry......Page 383 15.1 Solid-phase Extraction......Page 384 15.2 Polymer-assisted Solution-phase Synthesis......Page 386 15.3 Microwave-assisted Organic Synthesis......Page 389 15.4 Flow Chemistry......Page 394 15.5 Analytical Instrumentation......Page 398 15.6 Conclusions......Page 399 16.1 Phenolic Compounds......Page 403 16.2 Tannin Structures......Page 404 16.2.1 Dietary Burden and Properties of Phenolic Compounds......Page 405 16.4 Experimental Studies of the Interactions between Proteins and Tannins......Page 406 16.4.1 Nephelometric Studies of BSA and Condensed Tannin Aggregation......Page 407 16.5.2 pH and Ionic Strength......Page 409 16.5.3 Influence of Polysaccharide on the Interactions between Protein and Tannin......Page 411 16.6 Flow Nephelometric Analysis of Protein–Tannin Interactions......Page 413 16.7 Interactions of Tannins with Salivary Proteins–Astringency......Page 415 16.8 Polysaccharides and Astringency......Page 417 16.9 Acknowledgments......Page 419 17.1.1 Photochemical Processes in the Atmosphere......Page 423 17.1.2 Photochemical Reactions in Ice and Snow......Page 428 17.1.3 Photochemical Reactions in Surface Waters......Page 429 17.2.1 Reactions Induced by ·OH......Page 431 17.2.2 Reactions Induced by ·NO2......Page 439 17.2.3 Reactions Induced by Cl2·-......Page 440 17.3 Conclusions......Page 442 17.4 Acknowledgments......Page 443 Index......Page 449

Providing a glimpse into the future, the young scientists contributing here were considered to be the most important for tomorrow's chemistry and materials science. They present the state of the art and the perspectives in their particular fields of research, with topics ranging from new synthetic pathways and nanotechnology to green chemistry.

Clearly divided into three main areas of discussion, the first part deals with self-organization, nanoscience and nanotechnology, culminating in new approaches of the study of soft matter 3D organization. Part Two looks at organic synthesis, catalysis and materials, while the final part covers health, food, and the environment, including future perspectives for medical chemistry and photochemical transformation processes of environmental significance.

Of major interest to physical- and organic chemists, materials scientists and biochemists.