Dendrimers: Towards Catalytic, Material and Biomedical Uses

This book will be mainly focussed on the properties and uses of dendrimers and dendrons. The aim of this book is to be the reference book about dendrimers applications. It will not describe all details, but it will give the reader a unique overview of what has currently been done with dendrimers, with numerous references and illustrations. It will be divided in four main parts: Part 1) Generalities, syntheses, characterizations and properties; Part 2) Applications in catalysis; Part 3) Applications for the elaboration or modification of materials; and Part 4) Applications in biology/medicine. The role of the nanometric size and the multiple functions of dendrimers on the properties will be emphasized.

Table of Contents:
Preface xv Part 1 Generalities, Syntheses, Characterizations, and Physicochemical Properties 1 1 Syntheses of Dendrimers and Dendrons 3 Anne-Marie Caminade 1.1 Introduction: What Are Dendrimers and Dendrons? 3 1.2 Syntheses of Poly(propyleneimine) Dendrimers (PPI) 5 1.3 Synthesis of Poly(amidoamine) Dendrimers (PAMAM) 5 1.4 Syntheses of Poly(ether) Dendrimers 7 1.5 Syntheses of Poly(ester) Dendrimers 10 1.6 Synthesis of Poly(lysine) Dendrimers 14 1.7 Syntheses of Silicon-Containing Dendrimers 15 1.8 Syntheses of Phosphorus-Containing Dendrimers 16 1.9 Syntheses of Carbon-Based Dendrimers 17 1.10 Syntheses of Dendrimers Constituted of Nitrogen Heterocycles 19 1.11 Syntheses by Self-Assembly 21 1.12 Accelerated Syntheses 26 1.13 Conclusion 30 References 30 2 Methods of Characterization of Dendrimers 35 Anne-Marie Caminade 2.1 Introduction 35 2.2 Spectroscopy and Spectrometry 36 2.2.1 Nuclear Magnetic Resonance (NMR) 36 2.2.2 Mass Spectrometry 40 2.2.3 X-ray Diffraction 41 2.2.4 Infrared (IR) and Raman Spectroscopy 42 2.2.5 Ultraviolet–Visible (UV–vis) Spectroscopy 43 2.2.6 Fluorescence 44 2.2.7 Chirality, Optical Rotation, and Circular Dichroism (CD) 45 2.2.8 Electron Paramagnetic Resonance (EPR) 45 2.2.9 Electrochemistry 46 2.2.10 Magnetometry 46 2.2.11 Mössbauer Spectroscopy 46 2.2.12 X-ray Spectroscopies 47 2.3 Scattering Techniques 47 2.3.1 Laser Light Scattering (LLS) 47 2.3.2 Small-Angle Neutron Scattering (SANS) 47 2.3.3 Small-Angle X-ray Scattering (SAXS) and Wide-Angle X-ray Scattering (WAXS) 48 2.4 Microscopy 48 2.4.1 Transmission Electron Microscopy (TEM) 49 2.4.2 Atomic Force Microscopy (AFM) 49 2.4.3 Polarizing Optical Microscopy (POM) 50 2.5 Rheology and Physical Characterizations 50 2.5.1 Intrinsic Viscosity 50 2.5.2 Differential Scanning Calorimetry (DSC) 50 2.5.3 Dielectric Spectroscopy (DS) 51 2.5.4 Dipole Moments 51 2.6 Separation Techniques 52 2.6.1 Size Exclusion Chromatography 52 2.6.2 Electrophoresis 53 2.7 Conclusion 53 References 54 3 Luminescent Dendrimers 67 Anne-Marie Caminade 3.1 Introduction 67 3.2 Dendrimers with Fluorescent Terminal Groups 68 3.2.1 Fully Substituted Dendrimers 68 3.2.2 Partially Substituted Dendrimers 69 3.3 Luminescent Group at the Core of Dendrimers and Energy/Light-Harvesting Properties 74 3.3.1 Organic Fluorophores as Cores 74 3.3.2 Porphyrins and Phthalocyanines as Cores 77 3.3.3 Metallic Cores 78 3.4 Fluorescent Groups inside the Structure of Dendrimers 79 3.5 Intrinsically Fluorescent Dendrimers 81 3.5.1 Fluorescent Groups throughout the Dendrimeric Structure 81 3.5.2 Fluorescence of Dendrimers without Known Fluorophores 86 3.6 Two-Photon-Excited Fluorescence of Dendrimers 86 3.7 Conclusion 89 References 90 4 Stimuli-Responsive Dendrimers 99 Anne-Marie Caminade 4.1 Introduction 99 4.2 Photoresponsive Dendrimeric Structures 100 4.2.1 Azobenzene-Containing Dendrimers and Dendrons 101 4.2.2 Other Types of Photoresponsive Dendrimers 108 4.3 Thermoresponsive Dendrimeric Structures 110 4.3.1 Thermoresponsive Properties of Dendrimers 110 4.3.2 Thermoresponsive Properties of Dendrons and Dendronized Polymers 112 4.4 Dendrimers Responsive to Solution Media Changes 114 4.4.1 pH-Responsive Dendrimers 114 4.4.2 Dendrimers Disassembly 115 4.5 Conclusion 117 References 118 5 Liquid Crystalline Dendrimers 125 Anne-Marie Caminade 5.1 Introduction 125 5.2 Mesogenic Groups as Terminal Functions of Dendrons 126 5.3 Mesogenic Groups as Terminal Functions of Dendrimers 131 5.4 Mesogenic Groups as Branches of Dendrimers 134 5.5 Conclusion 135 References 136 6 Dendrimers and Nanoparticles 141 Cédric-Olivier Turrin and Anne-Marie Caminade 6.1 Introduction 141 6.2 Dendrimers or Dendrons for Coating Nanoparticles 142 6.2.1 Dendronization of Nanoparticles by Ligand Exchange 142 6.2.2 Direct Synthesis of Dendronized Nanoparticles 147 6.2.3 Dendrimer Coated Nanoparticles 149 6.2.4 Nanocomposites with Interdendrimer Nanoparticles 151 6.3 Dendrimers as Templates for the Synthesis of Dendrimer-Encapsulated Nanoparticles (DENs) 152 6.3.1 Catalysis with Dendrimer-Encapsulated Nanoparticles 153 6.3.2 Other Uses of Dendrimer-Encapsulated Nanoparticles 154 6.4 Conclusion and Perspectives 154 References 155 Part 2 Applications in Catalysis 163 7 Terminal Groups of Dendrimers as Catalysts for Homogeneous Catalysis 165 Armelle Ouali and Anne-Marie Caminade 7.1 General Introduction 165 7.1.1 The “Dendrimer Effect” 165 7.1.2 Recycling the Catalysts 166 7.2 Catalytic Organometallic Sites as Catalysts for Homogeneous Catalysis 167 7.2.1 Formation of C–X Bonds (X = C, N, O) 167 7.2.2 Addition Reactions on a C=X Double Bond (X = C, O) 175 7.2.3 Oxidation Reactions 177 7.3 Organocatalysis with Dendrimers 178 7.4 Conclusion 178 References 179 8 Catalytic Sites inside the Dendrimeric Structure for Homogeneous Catalysis 183 Armelle Ouali and Anne-Marie Caminade 8.1 Introduction 183 8.2 Catalytic Sites as the Core of Dendrimers 184 8.2.1 Dendrimers Bearing a Transition-Metal-Based Complex at the Core 184 8.2.2 Dendrimers Bearing an Organocatalyst at the Core 188 8.3 Catalytic Sites inside the Branches of Dendrimers 191 8.3.1 Formation of C–X Bonds (X = C, N, O) 191 8.3.2 Addition Reactions on a C=C Double Bond: Olefi n Hydrogenation 192 8.4 Conclusion 192 References 193 9 Dendrimers as Homogeneous Enantioselective Catalysts 197 Armelle Ouali and Anne-Marie Caminade 9.1 Introduction 197 9.2 Catalytic Organometallic Sites as Catalysts for Homogeneous Catalysis 198 9.2.1 Formation of C–X Bonds (X = C, N, O) 198 9.2.2 Addition Reactions on a C=X Double Bond (X = C, O) 204 9.3 Organocatalysis with Dendrimers 209 9.3.1 Aldolizations 209 9.3.2 Aza–Morita–Baylis–Hillmann Reactions 209 9.3.3 Transaminations 210 9.4 Conclusion 210 References 210 10 Catalysis with Dendrimers in Particular Media 215 Régis Laurent and Anne-Marie Caminade 10.1 Introduction 215 10.2 Two-Phase (Liquid–Liquid) Media 216 10.3 Catalysis in Ionic Liquids 219 10.4 Catalysis in Supercritical Media 220 10.5 Catalysis in Aqueous Media 221 10.6 Conclusion 234 References 234 11 Heterogeneous Catalysis with Dendrimers 239 Régis Laurent and Anne-Marie Caminade 11.1 Introduction 239 11.2 Catalysis with Dendrons Synthesized from a Solid Material 240 11.2.1 Silica as an Inorganic Support 240 11.2.2 Polymers and Resins as Organic Supports 248 11.3 Catalysis with Dendrons or Dendrimers Grafted on to a Solid Surface 254 11.4 Catalysis with Insoluble Dendrimers 257 11.5 Conclusion 260 References 261 Part 3 Applications for the Elaboration or Modification of Materials 267 12 Dendrimers inside Materials 269 Régis Laurent and Anne-Marie Caminade 12.1 Introduction 269 12.2 Dendrimers for the Elaboration of Gels 270 12.2.1 Dendrimers for the Elaboration of Supramolecular Hygrogels 270 12.2.2 Dendrimers for the Elaboration of Polymer-Type Hygrogels 273 12.2.3 Dendrimers for the Elaboration of Organogels 276 12.3 Dendrimers inside Silica Gels 280 12.4 Dendrimers inside Other Types of Materials 285 12.5 Dendrimers for the Elaboration of OLEDs 288 12.5.1 Fluorescent Dendrimers for the Elaboration of OLEDs 290 12.5.2 Phosphorescent Dendrimers for the Elaboration of OLEDs 295 12.6 Conclusion 298 References 299 13 Self-Assembly of Dendrimers in Layers 313 Béatrice Delavaux-Nicot and Anne-Marie Caminade 13.1 Introduction 313 13.2 Langmuir–Blodgett Films of Dendrons and Dendrimers 314 13.2.1 Poly(benzyl ether) Derivatives 316 13.2.2. Poly(amidoamine) and Poly(propyleneimine) Derivatives 319 13.2.3 Azobenzene Derivatives 320 13.2.4 Poly(carbosilane) Dendrimer Derivatives 321 13.2.5 Fullerene C60 Derivatives 322 13.2.6 Other Examples 325 13.3 Assemblies of Dendrons and Dendrimers on Solid Surfaces 326 13.3.1 Assembly of Dendrons and Dendrimers on Gold Surfaces 327 13.3.2 Assembly of Dendrons and Dendrimers on Silicon Substrates or Related Substrates 330 13.4 Several Routes for the Formation of Dendron or Dendrimer Multilayers 334 13.5 Nanoimprinting with Dendrons and Dendrimers on Solid Surfaces 342 13.5.1 Dendrimer-Based Self-Assembled Monolayers as Resists for Scanning Probe Lithography 342 13.5.2 Microprinting, Transfer Printing, and Dip-Pen Nanolithography with Dendrimers 344 13.6 Conclusion 350 References 351 14 Dendrimers as Chemical Sensors 361 Anne-Marie Caminade 14.1 Introduction 361 14.2 Dendrimers as Chemical Sensors in Solution 362 14.2.1 Porphyrins and Other Macrocyclic Derivatives as the Core or Branches of Dendrimeric Sensors 362 14.2.2 Terminal Groups of Dendrimers as Sensors in Solution 363 14.3 Dendrimers as Electrochemical Sensors 365 14.4 Dendrimers on Modifi ed Surfaces as Chemical Sensors 367 14.4.1 Dendrimers on Surfaces at the Interface with a Solution 367 14.4.2 Dendrimers on Surfaces at the Interface with a Vapor 368 14.5 Conclusion 370 References 370 15 Dendrimers as Biological Sensors 375 Anne-Marie Caminade 15.1 Introduction 375 15.2 Dendrimers as Sensors in Solutions of Biological Media 375 15.3 Detection by Electrochemical Methods 378 15.4 Dendrimers or Dendrons for DNA Microarrays 380 15.5 Dendrimers for Other Types of Biomicroarrays 383 15.6 Dendrimers on Other Types of Support 384 15.7 Dendrimers as Multiply Labeled Entities Connected to the Target 385 15.8 Conclusion 386 References 387 Part 4 Applications in Biology/Medicine 393 16 Dendrimers for Imaging 395 Cédric-Olivier Turrin and Anne-Marie Caminade 16.1 Introduction 395 16.2 Magnetic Resonance Imaging with Dendrimers 395 16.2.1 Paramagnetic Dendrimer-Based Contrast Agents 398 16.2.2 PARACEST Dendrimer-Based Contrast Agents 402 16.2.3 Superparamagnetic Dendrimer-Based Contrast Agents 402 16.2.4 Dendrimer-Based 129Xe HYPER-CEST MRI Contrast Agents 403 16.2.5 19F Dendrimer-Based MRI Contrast Agents 403 16.3 Other Types of Imaging with Dendrimers 403 16.3.1 Dendrimers for Optical Imaging 403 16.3.2 Dendrimers for Nuclear Medicine (NM) Imaging and Computed Tomography X-Ray Imaging (CT) 405 16.4 Conclusion and Perspectives 407 References 407 17 Dendrimers as Transfection Agents 413 Cédric-Olivier Turrin and Anne-Marie Caminade 17.1 Introduction 413 17.2 Gene Transfection with PAMAM Dendrimers 415 17.2.1 Pioneering Results 415 17.2.2 Gene Transfection with Surface-Modifi ed PAMAM 416 17.2.3 Gene Transfection with Core-Modifi ed PAMAM 418 17.2.4 Gene Transfection with PAMAM-Functionalized Nanoparticles 419 17.2.5 Gene Transfection with PAMAM-Like Hyperbranched Polymers 420 17.3 Gene Transfection with Other Dendrimers 421 17.3.1 Gene Transfection with PPI Dendrimers 421 17.3.2 Gene Transfection with Peptide-Based Dendrimers 422 17.3.3 Gene Transfection with Phosphorus-Based Dendrimers 423 17.3.4 Gene Transfection with Silane-Based Dendrimers 424 17.4 Conclusion and Perspective 426 References 426 18 Dendrimer Conjugates for Drug Delivery 437 Cédric-Olivier Turrin and Anne-Marie Caminade 18.1 Introduction 437 18.2 Improving Bioavailability with Dendrimers 438 18.3 Passive Targeting in Tumors with Dendrimer–Drug Conjugates 440 18.3.1 Dendrimer–Drug Bioconjugates and the EPR Effect 440 18.3.2 PEGylated Dendrimeric Scaffolds 442 18.4 Active Targeting with Site-Specifi c Dendrimer–Drug Conjugates 446 18.4.1 Addressing with Folic Acid (FA) 446 18.4.2 Addressing with Tumor-Homing Peptides 448 18.4.3 Addressing with Monoclonal Antibodies 449 18.5 Dendrimers for Photodynamic Therapy (PDT) 449 18.6 Dendrimers for Boron Neutron Capture Therapy (BNCT) 451 18.7 Conclusion and Perspectives 452 References 453 19 Encapsulation of Drugs inside Dendrimers 463 Cédric-Olivier Turrin and Anne-Marie Caminade 19.1 Introduction 463 19.2 From Dendritic Boxes to Dendrimer-Based Formulations 464 19.3 Improving Bioavailability with Dendrimers? 464 19.4 Toxicological Issues 465 19.5 Dendrimer-Based Formulations for Drug Delivery 466 19.5.1 Nontargeted Formulations 466 19.5.2 Supramolecular Assemblies Involving Surface Ionic Interactions 473 19.5.3 Targeted Formulations 475 19.6 Conclusion and Perspectives 477 References 477 20 Unexpected Biological Applications of Dendrimers and Specifi c Multivalency Activities 485 Cédric-Olivier Turrin and Anne-Marie Caminade 20.1 Introduction 485 20.2 Dendrimers and Multivalency 486 20.2.1 Multivalent Effects and Dendrimeric Effects 486 20.2.2 Glycodendrimers 487 20.3 Antimicrobial Dendrimers 488 20.3.1 Polycationic Dendrimers 489 20.3.2 Polyanionic Dendrimers 491 20.4 From Immunomodulation to Regenerative Medicine 494 20.4.1 Immunomodulation and Anti-Inflammation 494 20.4.2 Dendrimers and Regenerative Medicine 498 20.5 Conclusion and Perspectives 501 References 502 21 General Conclusions and Perspectives 511 Anne-Marie Caminade Index 515