Combining a sequential, one-pot RAFT polymerization with the polymerization-induced self-assembly process results in a versatile oxidation-responsive carrier system.

Polymer–metal hybrids are interesting materials in general and serve as precursors for a wide range of possible applications. Herein, we present the controlled radical polymerization of 2-acrylamidoglycolic acid (AGA), a polyelectrolyte capable of chelating various metals, using reversible addition–fragmentation chain transfer (RAFT) polymerization. Polymerization kinetics and behavior in aqueous solution were investigated for PAGA homopolymers, and we further show that double hydrophilic poly­(N-acryloyl­morpholine)-block-PAGA (PNAM-b-PAGA) or poly­(ethylene oxide)-block-PAGA (PEO-b-PAGA) block copolymers with varying weight fractions of PAGA can be prepared. Upon addition of different metal cations, these block copolymers form wormlike and spherical hybrid assemblies in aqueous media. The aggregates react reversibly to changes in pH, and their size and shape are influenced by the PAGA/metal ratio, the overall PAGA weight fraction, the type of metal cation, and the block copolymer concentration.

Reactive polymersomes represent av ersatile artificial cargo carrier system that can facilitate an immediate release in response to aspecific stimulus.The herein presented oxidation-sensitive polymersomes feature at ime-delayed release mechanism in an oxidative environment, whichc an be precisely adjusted by either tuning the membrane thickness or partial pre-oxidation. These polymeric vesicles are conveniently prepared by PISA allowing the straightforwarda nd effective in situ encapsulation of cargo molecules,asshown for dyes and enzymes.Kinetic studies revealed acritical degree of oxidation causing the destabilization of the membrane,w hile no release of the cargo is observed beforehand. The encapsulation of glucose oxidase directly transforms these polymersomes into glucose-sensitive vesicles,a ss mall molecules including sugars can passively penetrate their membrane. Considering the ease of preparation, these polymersomes represent av ersatile platform for the confinement and burst release of cargo molecules after ap recisely adjustable time span in the presence of specific triggers,s uch as H 2 O 2 or glucose.

This study investigates the correlation between photocytotoxicity and the prolonged excited state lifetimes exhibited by certain Ru(II) polypyridyl photosensitizers comprised of π-expansive ligands. The eight metal complexes selected for this study differ markedly in their triplet state configurations and lifetimes. Human melanoma SKMEL28 and human leukemia HL60 cells were used as in vitro models to test photocytotoxicity induced by the compounds when activated by either broadband visible or monochromatic red light. The photocytotoxicities of the metal complexes investigated varied over two orders of magnitude and were positively correlated with their excited state lifetimes. The complexes with the longest excited state lifetimes, contributed by low-lying 3 IL states, were the most phototoxic toward cancer cells under all conditions.

Upon extending a hydrophobic polymer chain from the end of a preceding hydrophilic chain in aqueous solutions, the resultant block copolymers may eventually undergo self-assembly.