Dendrimer Chemistry Concepts, Syntheses, Properties, Applications

by Vögtle, Fritz; Richardt, Gabriele; Werner, Nicole; Rackstraw, Anthony J.

• ISBN13: 9783527320660
• ISBN10: 3527320660
• Edition: 1st
• Format: Paperback
• Copyright: 2009-03-23
• Publisher: Wiley-VCH

Summary

Written by internationally acclaimed authors, this textbook contains everything you need to know about this versatile class of compounds. Starting with a historical overview, definitions and other fundamentals, it goes on to look at characterization, analysis and properties of dendrimers. While the focus is on synthesis and applications, it also contains chapters on analytics and other applications. Essential reading for organic and polymer chemists, undergraduate and graduate students, students and lecturers in chemistry.

Author Biography

After his graduation in Freiburg Fritz V+¦gtle was awarded his Ph.D at the University of Heidelberg in 1965 where he became Professor in 1969. After staying at the Universtiy of Wuerzburg from 1970-1975 he became Professor and Director at the Kekule-Institute for Organic Chemistry of Bonn since 1975.

Table of Contents

Preface	p. xi
Introduction	p. 1
Historical - Cascade molecules and dendrimers	p. 1
Dendritic architectures	p. 7
Perfection, defects, dispersity	p. 13
Definition and classification of dendritic molecules	p. 15
Nomenclature of dendritic molecules	p. 16
Newkome nomenclature	p. 16
Cascadane nomenclature	p. 17
Bibliography and Notes for Chapter 1 "Introduction"	p. 22
Synthetic methods for dendritic molecules	p. 25
Divergent synthesis	p. 25
Convergent synthesis	p. 27
Recent synthetic methods	p. 28
Orthogonal synthesis	p. 28
Double-stage convergent method	p. 29
Double-exponential method	p. 29
Hypermonomer method	p. 30
Click chemistry	p. 31
Solid phase synthesis	p. 31
Coordination-chemical synthesis	p. 33
Metal complex as core unit	p. 33
Metal complex as branching unit	p. 34
Supramolecular synthesis	p. 35
Hyperbranched polymers	p. 38
Dendronised linear polymers	p. 39
Polymer-analogous method	p. 39
Macromonomer method	p. 41
Dendro-Isomers	p. 42
Bibliography and Notes for Chapter 2 "Synthetic methods for dendritic molecules"	p. 44
Functional dendrimers	p. 49
Monofunctional dendrimers	p. 50
Functional core	p. 50
Functional periphery	p. 51
Functionalisation of terminal groups	p. 52
Introduction of peripheral groups prior to dendrimer growth	p. 54
Functional units in the dendrimer scaffold	p. 55
Modification prior to dendrimer growth	p. 55
Internal modification on conclusion of dendrimer growth	p. 58
Multifunctional dendrimers	p. 61
Bifunctionalised molecular periphery	p. 62
Two different functional units in different parts of the molecule	p. 67
More than two different functional units	p. 67
Overview of functional dendrimers and their synthesis	p. 71
Bibliography and Notes for Chapter 3 "Functional dendrimers"	p. 75
Types of dendrimers and their syntheses	p. 81
Achiral dendrimers	p. 81
POPAM	p. 81
PAMAM	p. 85
POMAM	p. 89
Polylysine dendrimers	p. 90
Dendritic hydrocarbons	p. 93
Condensed arene components - Iptyceness	p. 93
Dendrimers from arene and multiply bonded building blocks	p. 93
Stilbenoid dendrimers	p. 97
Hyperbranched polybenzenes	p. 102
Carbon/oxygen-based (and Fréchet) dendrimers	p. 102
Polyether dendrimers	p. 102
Polyester dendrimers	p. 104
Carbohydrate dendrimers (glycodendrimers)	p. 108
Porphyrin-based dendrimers	p. 109
Ionic dendrimers	p. 111
Polyanionic dendrimers	p. 111
Polyanionic dendrimers	p. 114
Silicon-based dendrimers	p. 118
Silane dendrimers	p. 118
Carbosilane dendrimers	p. 120
Carbosiloxane dendrimers	p. 123
Siloxane dendrimers	p. 127
Hyperbranched silicon-based polymers	p. 128
Phosphorus-based dendrimers	p. 130
Metallodendrimers (and Newkome dendrimers)	p. 133
Bibliography and Notes for Section 4.1 "Achiral dendrimers"	p. 138
Chiral dendrimers	p. 143
Classification of chiral dendrimers	p. 143
Studies on the chirality of dendritic molecules	p. 145
Chiroptical studies	p. 145
Possible applications of chiral dendrimers	p. 146
Dendrimers with chiral core and achiral branching scaffold	p. 146
Chiroptical studies on dendrimers with chiral cores	p. 147
Possible applications of chiral-core dendrimers	p. 153
Dendrimers with chiral building blocks as spacers or branching units	p. 156
Chiroptical studies on dendrimers with chiral dendrimer scaffold	p. 156
Possible applications of dendrimers with chiral branching scaffold	p. 158
Chirality in the periphery	p. 158
Chiroptical studies on dendrimers with peripheral chiral units	p. 158
Possible applications of dendrimers with peripheral chiral units	p. 160
Chiral dendrimers for asymmetric catalysis	p. 161
Interpretation of the chirality of dendritic molecules	p. 161
Bibliography and Notes for Section 4.2 "Chiral Dendrimers"	p. 165
Photophysical properties of dendirtic molecules	p. 169
Luminescence and energy transfer	p. 169
Luminescence	p. 169
Energy transfer	p. 172
Dexter mechanism: Energy transfer by radiative emission	p. 172
Förster mechanism: Energy transfer by dipole-dipole interactions	p. 172
Examples from the field of dendritic molecules	p. 173
Antenna effect and photoisomerisation of dendrimers	p. 176
Antenna effect	p. 176
Photoisomerisation	p. 186
Bibliography and Notes for Chapter 5 "Photophysical properties of dendritic molecules"	p. 192
(Special) chemical reactions of dendritic molecules	p. 195
Covalent chemical reactions	p. 195
Metathesis	p. 195
Molecular imprinting	p. 201
Covalent introduction of functionalities in the interior of dendritic molecules	p. 203
Supramolecular (host/guest) interactions	p. 204
Non-covalent modification of a dendrimer periphery	p. 204
Self-assembly of dendrimers	p. 207
Inclusion of guest species in dendritic host molecules	p. 207
Dendrimers with multiple receptor units	p. 207
Guest inclusion by steric compression	p. 212
Guest inclusion by dynamic processes (diffusion)	p. 214
Self-assembly of dendrimers	p. 217
Dendritic stopper groups (in rotaxanes)	p. 220
Dendritic effects	p. 221
Dendritic effects in inclusion of guests	p. 223
Dendritic effects in catalysis	p. 224
Metal-containing dendritic catalysts	p. 224
Metal-free dendritic catalysts	p. 234
Dendritic effects on electrochemical properties	p. 240
Metal-free dendritic catalysts	p. 240
Redox gradients	p. 242
Redox sensors	p. 243
Redox potential and redox transfer kinetics	p. 244
Charge-separation processes	p. 244
Summary of the dendritic effect	p. 244
Bibliography and Notes for Chapter 6 "(Special) chemical reactions of dendritic molecules"	p. 246
Characterisation and analysis	p. 253
Chromatography	p. 253
Liquid chromatography	p. 253
Preparative liquid chromatography	p. 254
High-performance liquid chromatography	p. 254
Gel permeation chromatography	p. 257
Gel electrophoresis	p. 259
NMR spectroscopy	p. 260
(1D)-NMR spectroscopic studies	p. 261
Multidimensional NMR spectroscopy in dendrimer research	p. 261
Diffusion NMR spectroscopy	p. 262
Dynamic NMR spectroscopy	p. 263
Mass spectrometry	p. 263
Gentle ionisation methods: MALDI and ESI	p. 263
Study of dendrimers by MALDI and ESI-MS	p. 264
X-ray crystal structure analysis	p. 266
Small-angle scattering	p. 266
Principle of small-angle scattering	p. 267
Capability of small-angle scattering	p. 267
Structural analysis of dissolved dendrimers with SANS and SAXS	p. 268
Radial segment density distribution of flexible dendrimers	p. 268
Distribution of end groups	p. 269
Intermolecular interactions of flexible dendrimers in solution	p. 270
Scanning probe microscopy	p. 271
STM and AFM	p. 271
AFM images of dendrimers	p. 273
STM images of dendrimers	p. 274
Transmission electron microscopy	p. 274
TEM	p. 274
TEM images of dendrimers	p. 275
Chiroptical methods	p. 276
Optical rotatory dispersion and circular dichroism	p. 277
Chiroptical studies on chiral dendritic structures	p. 279
Summary	p. 280
Bibliography and Notes for Chapter 7 "Characterization and analysis"	p. 282
Special properties and potential applications	p. 289
Introduction	p. 289
Catalysis, membrane technology	p. 290
Dendrimers as catalyst supports	p. 291
Catalytic dendrimers for membrane reactors	p. 292
Dendrimers in enantioselective catalysis	p. 293
Dendrimers as phase transfer catalysts	p. 294
Pigments, adhesives, additives in chemical materials	p. 294
Dendrimers as additives	p. 294
Dendritic polymers for printing inks	p. 295
Dendritic polymers for paints	p. 295
Dendritic polymers as additives in foam formulation	p. 295
Network precursors for plastics	p. 296
Dendrimers as nanocapsules for dyes and for molecular imprinting	p. 296
Dendrimers for displays and (opto)electronics	p. 298
Liquid-crystalline dendrimers	p. 299
Biomimetics, sensor technology, diagnostics (fluorescence)	p. 300
Protein dendrimers	p. 300
Glycomimetics	p. 302
Dendrimers in sensor technology	p. 304
Quartz micro balance with dendritic sensor layers	p. 304
Luminescent dendrimers as sensor materials	p. 306
Fluorescing PET sensors	p. 308
Dendrimers in medical diagnostics	p. 311
Magnetic resonance imaging (MRI) processes	p. 311
DNA dendrimers as biosensors for DNA hybridisation	p. 313
Medical applications	p. 313
Dendrimers as carriers for cytostatic agents	p. 313
Gene therapy	p. 315
Photodynamic therapy	p. 316
Dendrimers in prevention against HIV	p. 317
Culture of organs and tissue	p. 318
Wound healing	p. 318
Boron neutron capture therapy	p. 319
Dendrimers in nanotechnology	p. 320
Photoswitchable dendrimers	p. 320
Dendrimers as impellers	p. 320
Dendrimers as nanotubes	p. 321
Dendritic polymers as templates	p. 324
Bibliography and Notes for Chapter 8 "Special properties and potential applications"	p. 324
Outlook	p. 331
Subject Index	p. 333
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