Hybrid Organic-Inorganic Nanostructures Fabricated from Layer-by-Layer Self-Assembled Multilayers of Hyperbranched Polyglycerols and Phosphorus Dendrimers

Multilayer thin films of cationic phosphorous dendrimers and anionic hyperbranched polyglycerols were fabricated by electrostatic layer-by-layer (LbL) self-assembly (SA). The film formation was monitored by surface plasmon resonance (SPR) spectroscopy and UV-visible spectroscopy, and it was found that the stepwise, alternating deposition results in a linear growth up to four bilayers. Hybrid organic-TiO2 nanostructures were generated by exposing the supramolecular multilayers to TiCl4 precursors. The amounts of TiO2 incorporated inside the scaffolds could be tuned by controlling the porosity of the multilayers with the addition of a small amount of salts. The resulting hybrid films exhibit …

Cover Picture: Macromol. Rapid Commun. 11/2005

Multi-Arm Star Polyglycerol-block-poly(tert-butyl acrylate) and the Respective Multi-Arm Poly(acrylic acid) Stars

Well-defined multi-arm star block copolymers, polyglycerol-block-poly(tert-butyl acrylate) (PG-b-PtBA), with average arm-numbers of 17, 27, 36, 66 and 90 arms, respectively, have been prepared by atom transfer radical polymerization (ATRP) of tBA in acetone, using a core-first strategy. After hydrolysis with excess concentrated HCl in refluxing dioxane, full hydrolysis of the tert-butyl ester groups was achieved, resulting in multi-arm star polyelectrolytes, polyglycerol-block-poly(acrylic acid) (PG-b-PAA). The hyperbranched macroinitiators employed were prepared on the basis of hyperbranched polyglycerols via esterification with 2-bromoisobutyryl bromide. Both CuBr/PMDETA and CuBr/Me 6 TRE…

Photocatalysis within Hyperbranched Polyethers with a Benzophenone Core

Quenching and product studies have been performed to demonstrate the suitability of hyperbranched polyethers with a tetrafunctionalized benzophenone core as photocatalysts. The triplet photosensitized transformation of an unsaturated diazo compound has been used as the model reaction. The polymer with highest molecular weight led to a similar product distribution even after several catalytic cycles, which evidences its excellent photostability under prolonged irradiation time. We attribute this to the stabilizing effect of the hyperbranched polymer shell.

Novel Multifunctional Polymeric Photoinitiators and Photo-Coinitiators Derived from Hyperbranched Polyglycerol

A new class of hyperbranched PPIs and PPCs have been prepared. The introduction of compatibilizing groups such as MEEA or trimethylacetate enhanced their solubility in radiation-curable formulations and led to an improved photoactivity compared with the corresponding MPI and MPC. Although the molecular weights of the subject PPIs and PPCs exceeded 800 g mol -1 , the viscosities of the radiation-curable formulations were still suitable for inkjet application. The combination of high photoactivity, low viscosity, and low extract-ability after curing rendered the resulting hyperbranched PPIs and PPCs attractive as components in the inkjet ink for inkjet printing, e.g., in food packaging.

Linear-Hyperbranched Amphiphilic AB Diblock Copolymers Based on Polystyrene and Hyperbranched Polyglycerol

A convenient three-step strategy has been developed for the preparation of well-defined amphiphilic, linear hyperbranched block copolymers by hypergrafting. The synthetic procedure is based on a combination of carbanionic polymerization with the alkoxide-based controlled ring-opening multibranching polymerization of glycidol. A linear AB diblock copolymer polystyrene-block-polybutadiene (PS-b-PB) with narrow polydispersity was obtained by anionic copolymerization. Subsequent hydroxylation by hydroboration led to PS 508 -b-(PB-OH) 56 , used as macro--initiator for the polymerization of glycidol under slow monomer addition conditions.

Systematic investigation of functional core variation within hyperbranched polyglycerols

A novel series of hyperbranched polyether polyols with various n-alkyl amine cores (mono- and bifunctional) and photoactive cores (benzylamine and 1-naphthylmethylamine) have been prepared. Polymerization of glycidol was carried out in two ways, starting directly from primary amine initiators and from bisglycidolized amine initiators. NMR spectroscopy and size exclusion chromatography (SEC) showed good control over the molecular weights only, when bisglycidolized amines were used. Molecular weights and polydispersity of the hyperbranched polyglycerols prepared with these initiator-cores were in the range of 1600 to 8400 g/mol and of 1.5 to 2.5, respectively. MALDI-ToF mass spectrometry conf…

Controlled Crystallization of CaCO3on Hyperbranched Polyglycerol Adsorbed to Self-Assembled Monolayers

The formation of biominerals by living organisms is governed by the cooperation of soluble and insoluble macromolecules with peculiar interfacial properties. To date, most of the studies on mineralization processes involve model systems that only account for the existence of one organic matrix and thus disregard the interaction between the soluble and insoluble organic components that is crucial for a better understanding of the processes taking place at the inorganic-organic interface. We have set up a model system composed of a matrix surface, namely, a self-assembled monolayer (SAM), and a soluble component, hyperbranched polyglycerol. The model mineral calcium carbonate displays diverse…

Synthesis of multiarm star poly(glycerol)-block-poly(2-hydroxyethyl methacrylate).

Well-defined multiarm star block copolymers poly(glycerol)-b-poly(2-hydroxyethyl methacrylate) (PG-b-PHEMA) with an average of 56, 66, and 90 PHEMA arms, respectively, have been prepared by atom transfer radical polymerization (ATRP) of HEMA in methanol by a core-first strategy. The hyperbranched macroinitiators employed were prepared on the basis of well-defined hyperbranched polyglycerol by esterification with 2-bromoisobutyryl bromide. Polydispersites M(w)/M(n) of the new multiarm stars were in the range of 1.11-1.82. Unexpectedly, with the combination of CuCl/CuBr(2)/2,2'-bipyridyl as catalyst, the polymerization conversion can be driven to maximum values of 79%. The control of CuCl cat…