Dendrimers block copolymers

Choi, J.S., Lee, E.J., Choi, Y.H., Jeong, Y.J. and Park, J.S. (1999) Poly(ethylene glycol)-block-poly(L-lysine) dendrimer novel linear polymer/dendrimer block copolymer forming a spherical water-soluble polyionic complex with DNA. Bioconjug. Chem., 10, 62-65. 

Star or dendrimer block copolymers based on acrylate and methacrylate units. [N. Niessner, F. Seitz, Eur. Pat. 545,184,1993] [ 376]. 

For the synthesis of linear hyperbranched block copolymers an analogy may be drawn to the linear dendrimer block copolymers. In a pioneering paper, the group of Kricheldorf suggested the use of terminally functional linear polymers as monoftmctional terminating agents or macro-cores for the synthesis of linear hyperbranched block copolymers. However, since a major side reaction is the well-known cydiza-tion of the focal A-group in the synthesis of hb polymers by polycondensation (see above), preparation of a block copolymer with narrow polydispersity cannot be achieved in this manner. 

NPs formed in different types of nanostractured polymers (dendrimers, block copolymers, layer-by-layer polyelectrolyte structures, etc) were studied in various catalytic reactions [9-11]. Amphiphilic block copolymers are largely studied for NP... 

Perrier RJ (2001) Direct Conversion of 5,6-Unsaturated Hexopyranosyl Compounds to Functionalized Glycohexanones. 215 277-291 Frey H, Schlenk C (2000) Silicon-Based Dendrimers. 210 69-129 Forster S (2003) Amphiphilic Block Copolymers for Templating Applications. 226 1-28 Frullano L, Rohovec J, Peters JA, Geraldes CFGC (2002) Structures of MRI Contrast Agents in Solution. 221 25-60... 

Meijer et al. [135] further studied aggregation phenomena of amphiphilic copolymers obtained by modifying the termini of the dendrimer units of the above series with carboxylic acid groups (49). TEM experiments indicated that all block copolymers formed large aggregates except third generation copolymer which formed worm-like micelles. 

Abstract This review highlights recent (2000-2004) advances and developments regarding the synthesis of block copolymers with both linear [AB diblocks, ABA and ABC triblocks, ABCD tetrablocks, (AB)n multiblocks etc.] and non-linear structures (star-block, graft, miktoarm star, H-shaped, dendrimer-like and cyclic copolymers). Attention is given only to those synthetic methodologies which lead to well-defined and well-characterized macromolecules. 

Nitroxide attached to macromolecules also induces the living radical polymerization of St. Yoshida and Sugita [252] prepared a polymeric stable radical by the reaction of the living end of the polytetrahydrofuran prepared by cationic polymerization with 4-hydroxy-TEMPO and studied the living radical polymerization of St with the nitroxide-bearing polytetrahydrofuran chain. The nitroxides attached to the dendrimer have been synthesized (Eq. 69) to yield block copolymers consisting of a dendrimer and a linear polymer [250,253]. 

As described in Sect. 7.1, novel hybrid block copolymers comprising on one hand a classical synthetic polymer and on the other hand a metal-containing polymer, a synthetic or natural (proteine, enzyme, etc.) polypeptide have recently been synthesized. Other hybrid block copolymers containing inorganic blocks, dendrimers, etc. will certainly be prepared and thoroughly investigated in the next few years. 

Several groups have engaged in the study of linear polymer-dendrimer conjugates (i.e. architectural copolymers). These structures combine block copolymer and dendrimer branching features within one molecular architecture [69-71],... 

The terminal groups of a dendrimer are large in number and can have functionalities capable of chemical reactions. If the terminal reactive terminal groups were near the periphery, they would be readily accessible for attachment to surfaces or to reagents. Block copolymers or networks with dendrimers as crosslink points would benefit from having them on the outside. 

In this section the emphasis will be on assemblies prepared from amphiphilic dendrimers. Amphiphilic dendrimers, carrying both hydrophobic and hydrophilic regions within one molecule, tend to self-assemble into a large variety of different aggregates depending on their structure. The dendritic amphiphiles investigated so far include unimolecular micelles, bolaamphiphiles, superam-phiphiles and various other AB and ABA block copolymers. 

Formation of a complex between DNA and polycationic compounds appears to be the initial and quite possibly a critical parameter for nonviral gene delivery. Several synthetic vector systems, which are generally cationic in nature, including poly(lysines), cationic liposomes or various types of block copolymers and recently dendrimers, have been shown to self-assemble with plasmid DNA [13-15] [16]. Specific physicochemical properties manifested by these DNA complexes depend on the type of cationic agent used however, interesting patterns for such interactions are beginning to evolve [17, 18]. Under certain conditions, the interaction of DNA with polyvalent cations results in... 

For some examples, see e.g. (a) Hogan CF, Harris AR, Bond AM et al (2006) Electrochemical studies of porphyrin-appended dendrimers. PhysChemChemPhys 8 2058-2065 (b) Jang W-D, Nishiyama N, Zhang G-D et al (2005) Supramolecular nanocarrier of anionic dendrimer porphyrins with cationic block copolymers modified with polyethylene glycol to enhance intracellular photodynamic efficacy. Angew Chem Int Ed 44 419 -23 (c) Loiseau F, Campagna S, Hameurlaine A et al (2005) Dendrimers made of porphyrin cores and carbazole chromophores as peripheral units. Absorption spectra, luminescence properties, and oxidation... 

Dendrimers, or arborols, or cascade, or cauliflower, or starburst polymers, were first synthesized in the early 1980s [3,4]. In 1985 Tomalia et al. [5] and Newkome et al. [6] presented the first papers dealing with dendrimers. A multitude of dendrimers have been presented in the literature ranging from polyami-doamine [7,8],poly(propylene imine) [9,10], aromatic polyethers [11-13] and polyesters [14, 15], aUphatic polyethers [16] and polyesters [17], polyalkane [18-19], polyphenylene [20], polysilane [21] to phosphorus [22] dendrimers. Combinations of different monomers as well as architectural modifications have also been presented. For example, chirality has been incorporated in dendrimers [23,24]. Copolymers of linear blocks with dendrimer segments (dendrons) [25-27] and block-copolymers of different dendrons have been described [28]. 

By covalent linkage of different types of molecules it is possible to obtain materials with novel properties that are different from those of the parent compounds. Examples of such materials are block-copolymers, soaps, or lipids which can self-assemble into periodic geometries with long-range order. Due to their amphiphilic character, these molecules tend to micellize and to phase-separate on the nanometer scale. By this self-assembly process the fabrication of new na-noscopic devices is possible, such as the micellization of diblock-co-polymers for the organization of nanometer-sized particles of metals or semiconductors [72 - 74]. The micelle formation is a dynamic process, which depends on a number of factors like solvent, temperature, and concentration. Synthesis of micelles which are independent of all of these factors via appropriately functionalized dendrimers which form unimolecular micelles is a straightforward strategy. In... 

Keywords. Dendrimers, Hyperbranched macromolecules. Block copolymers. Surface functionalization, Solvatochromism, Intrinsic viscosity... 

It is also possible to introduce polymerizable groups at the focal point of dendritic macromolecules and a number of authors have demonstrated the synthesis of novel hybrid dendritic-linear block copolymers by this methodology [69-73]. Initial experiments in the use of the dendritic macromonomers involved the preparation of a series of polyether dendrimers, such as the third generation derivative, 37, which contains a single styrene at its focal point [74]. Copolymerization of 37 with styrene then affords a hybrid block copolymer, 38, in which... 

The book consists of four articles reviewing the literature based on the authors own experiences over the last decade in this field. It does not claim to be exhaustive nor to provide complete coverage of the very extensive literature in this field. Instead, it focuses on the currently intense areas of research namely living polymerization, block copolymer synthesis, synthesis of dendrimers and finally macroporous thermosets. Hopefully, this volume will not only serve as a book on the design of macromolecular architectures but also as a source of inspiration to produce polymers combining several functional properties. 

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