Foreword .................................................... ix
1 Introduction ................................................. 1
1.1 Background/historical ................................... 1
1.2 Birth of a new macromolecular chemistry concept ......... 9
1.3 Dendritic polymer subclasses ........................... 11
1.4 International academic/commercial interest and
activity ............................................... 16
References .................................................. 20
2 The dendritic state ......................................... 25
2.1 Introduction ........................................... 25
2.2 Dendrons, dendrimers, and megamers ..................... 29
2.3 Advances in dendron and dendrimer internal complexity .. 64
2.4 Supramacromolecular assembly of dendrons ............... 88
2.5 Supramacromolecular self-assembly of dendrimers ........ 92
2.6 Dendritic supramolecular networks ...................... 96
2.7 Hierarchical Aufbau: picoscale to micron sized
dendritic lattices ..................................... 98
References .................................................. 99
3 Synthetic methodologies .................................... 113
3.1 Synthesis of dendritic polymers - a fourth major new
architectural class ................................... 113
3.2 Dendrons and dendrimers ............................... 118
3.3 Statistical, divergent growth ......................... 136
3.4 Controlled, convergent growth ......................... 142
3.5 Supramolecular self-assembly .......................... 149
References ................................................. 156
4 Characterization methodologies ............................. 162
4.1 The challenges of defining structures in a new,
unprecedented polymer architecture .................... 162
4.2 Determination of composition and chemical
functionality ......................................... 164
4.3 Characterization of dendritic architectural
structures ............................................ 168
4.4 Homogeneity and molecular weight ...................... 169
4.5 Determination of size/dimensions ...................... 174
4.6 Determination of thermal properties ................... 179
4.7 Determination of encapsulation properties ............. 179
References ................................................. 183
5 Nanomedical and advanced materials ......................... 187
5.1 Diagnostics ........................................... 187
5.2 Advanced imaging ...................................... 195
5.3 Dendrimers as vectors for genetic material delivery ... 203
5.4 Dendrimer-based nanopharmaceuticals ................... 215
5.5 Advanced materials .................................... 229
5.6 Summary ............................................... 245
References ................................................. 247
6 Toxicology of dendrimers and dendrons ...................... 255
6.1 Introduction .......................................... 255
6.2 Methods for measurement of toxicity in vitro and in
vivo .................................................. 257
6.3 Effects of charge and functionality ................... 259
6.4 Toxicity - effects of size, shape, and polarity ....... 263
6.5 Modulation of toxicity ................................ 266
6.6 Bio-permeability and biodistribution .................. 268
6.7 Immunogenicity of dendrimers .......................... 271
6.8 Summary ............................................... 272
References ................................................. 273
7 The dendritic effect ....................................... 276
7.1 Introduction/definitions .............................. 276
7.2 Architecture driven properties: dendritic versus
linear macromolecular architecture .................... 277
7.3 Architecture driven intrinsic dendrimer properties .... 279
7.4 Interdependence of critical nanoscale design
parameters (CNDPs) in a typical dendrimer family ...... 284
7.5 Relationship of CNDPs to dendritic effects ............ 285
7.6 Conservation of critical hierarchical design
parameters (CHDPs) .................................... 286
References ................................................. 288
8 A quantized building block concept leading to a new
nano-periodic system ....................................... 293
8.1 introduction .......................................... 293
8.2 First principles and central dogma for traditional
chemistry ............................................. 293
8.3 Heuristic atom mimicry of dendrimers .................. 298
8.4 Chemical bonding, valency and stoichiometric binding
ratios to form (dendrimer)n-type nano-compounds/
assemblies ............................................ 306
8.5 Proposed nano-periodic system for unifying and
defining nanoscience .................................. 307
8.6 Structural control in dendrimers: CNDPs ............... 315
8.7 Use of first principles to create a new nano-
periodic system ....................................... 330
8.8 Elemental periodic property patterns leading
to Mendeleev's periodic table ......................... 346
8.9 Nano-periodic physico-chemical property patterns ...... 347
8.10 Predictive nano-periodic property patterns of
importance to nano-medicine: discrete in vivo
excretion and permeability ............................ 352
8.11 First steps toward a "central dogma" for synthetic
nano-chemistry: dendrimer-based nano-chemistry ........ 354
8.12 First nano-periodic tables for predicting
amphiphilic dendron self-assembly to supramolecular
dendrimers based on the CNDPs: (a) size, (b) shape,
(c) surface chemistry, and (d) flexibility ............ 360
8.13 Overview of Aufbau intermediates involved in the
dimensional enhancement of soft nano-element; [S-1]
category complexity ................................... 364
8.14 Conclusions ........................................... 366
References ................................................. 369
9 The past, present, and future for dendrons and dendrimers .. 378
9.1 Historical overview of dendron/dendrimer structural
and process development ............................... 378
9.2 Dendrimer applications and products ................... 386
9.3 Summary ............................................... 389
9.4 Conclusion ............................................ 392
References ................................................. 393
Index ...................................................... 407
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