Synthesis of Block Copolymers Modified with Phosphonate Ester Groups Using Nitroxide‐Mediated Radical Polymerization

Abstract

Fluorescent gold nanoparticles are important biological labels, in particular for combined optical and electron microscopy. It is reported that density and type of surface ligands have key influence on the dominant UV‐vis fluorescence band in positively and negatively charged gold nanoparticles capped with citrate, gold oxide, and cetyltrimethyl ammonium bromide (CTAB). The peak excitation and emission energies and fluorescence intensities vary with nanoparticle size, reflecting changes in surface charge and surface potential as well as a varying density of surface adsorbates. The fluorescence peak shifts, the evolution of zeta potentials, and fluorescence intensity trends are explained by a model of the principal fluorescence transitions that takes into account the nanoparticle surface conditions, such as the adhesion of ligands. Varying surface ligands is a simple strategy to optimize fluorescence intensity and to design spectral properties of gold nanoparticles.

Nitroxides: Applications in Synthesis and in Polymer Chemistry

“…The great functional group compatibility of NMP has enabled various interesting monomers to be prepared that bear functional groups that can readily be further modified chemically, and these monomers have been used for the synthesis of block copolymers. Useful functional groups such as epoxides, [257] silyloxysilylphenyl, [258] aryl sulfonates, [259] alkynes, [260] olefins, [261] perylene bisimide, [262] terpyridyl, [263] and dialkyl phosphonates [264] are tolerated as subunits on the monomer in NMP.…”

Phosphonic acid‐based amphiphilic diblock copolymers derived from ROMP

“…[15][16][17] Phosphorus-containing polymers have broad application areas; besides their flameretardant properties, 18 they are also used in biomaterials for their adhesive properties to metals, bone, and dentin. [19][20][21][22] The incorporation of phosphonic acid into acrylic monomers used in the dental industry can promote both biocompatibility and adhesion to the teeth, because of the formation of calcium phosphonates and phosphonate complexes. 21,[23][24][25] Phosphonates, corresponding anions of phosphonic acid, have strong interactions with and adsorb very powerfully onto mineral surfaces.…”

Nitroxide: Anwendungen in der Synthese und in der Polymerchemie

“…Zu diesen Gruppen zählen beispielsweise Epoxy-, [257] Silyloxysilylphenyl-, [258] Arylsulfonyl-, [259] Alkinyl-, [260] Alkenyl-, [261] Perylendiimid-, [262] Terpyridyl- [263] und Dialkylphosphonat-Einheiten. [264] Die in Blockcopolymerisationen als Initiatoren eingesetzten Makroalkoxyamine können neben den genannten [265] Mit dem PEGylierten Alkoxyamin 136 gelang die NMP des phosphorylierten Polymers 137 (Schema 50). [266] Dieses Produkt wurde seinerseits chemisch weiter zum Polymer 138 modifiziert, das Phosphorsäureeinheiten trägt.…”