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Selenium-containing polystyrene (DSe-PS) microspheres were synthesized by soap-free emulsion polymerization using 1,2-bis(2,3,5,6-tetrafluoro-4-vinylphenyl)diselane (FVPDSe) and divinylbenzene (DVB) as crosslinking agents. The particle size of the obtained DSe-PS was characterized by a scanning electron microscope and dynamic light scattering. The results showed that the diameter of the obtained DSe-PS microspheres could be adjusted by changing the ratio of the monomer and crosslinker/water. The diselenide moiety in the obtained DSe-PS microspheres could be oxidized to seleninic acid by H2O2 which can catalyze the oxidation of acrolein. The oxidized DSe-PS microspheres exhibited higher catalytic activity and selectivity to methyl acrylate in a model oxidation of acrolein. [ABSTRACT FROM AUTHOR]

Stimuli-responsive functional gels have shown significant potential for application in biosensing and drug release systems. In this study, aggregation-induced emission luminogen (AIEgen)-functionalized, diselenide-crosslinked polymer gels were synthesized via free radical copolymerization. A series of polymer gels with different crosslink densities or tetraphenylethylene (TPE) contents were synthesized. The diselenide crosslinker in the gels could be fragmented in the presence of H2O2 or dithiothreitol (DTT) due to its redox-responsive property. Thus, the TPE-containing polymer chains were released into the aqueous solution. As a result, the aqueous solution exhibited enhanced fluorescence emission due to the strong hydrophobicity of TPE. The degradation of polymer gels and fluorescence enhancement in an aqueous solution under different H2O2 or DTT concentrations were studied. Furthermore, the polymer gels could be used as drug carriers, suggesting a visual drug release process under the action of external redox agents. The AIEgen-functionalized, diselenide-crosslinked polymer gels hold great potential in the biomedical area for biosensing and controlled drug delivery. [ABSTRACT FROM AUTHOR]

Hyperbranched polycaprolactone with controlled structure was synthesized by reversible addition-fragmentation chain transfer radical ring-opening polymerization along with self-condensed vinyl polymerization (SCVP) of 2-methylene-1,3-dioxepane (MDO). Vinyl 2-[(ethoxycarbonothioyl) sulfanyl] propanoate (ECTVP) was used as polymerizable chain transfer agent. Living polymerization behavior was proved via pseudo linear kinetics, the molecular weight of polymers increasing with conversion and successful chain extension. The structure of polymers was characterized by 1H NMR spectroscopy, tripe detection gel permeation chromatography, and differential scanning calorimetry. The polymer composition was shown to be able to tune to vary the amount of ester repeat units in the polymer backbone, and hence determine the degree of branching. As expected, the degree of crystallinity was lower and the rate of degradation was faster in cases of increasing the number of branches. [ABSTRACT FROM AUTHOR]

This work developed novel selenium-containing polyimides with a high intrinsic refractive index. Four polyimides with different selenium contents and repeat unit structures were designed and synthesized via amine-dianhydride polycondensation of one of two diamines, i.e., 4,4′-oxydianiline or bis(4-aminophenyl)selanide, with one of two dianhydrides, i.e., bis(4-(3,4-dicarboxylbenzoyloxy)phenyl) ester dianhydride or 1,1′-bis(4-(3,4-dicarboxylbenzoyloxy)phenyl) selenide dianhydride. Various techniques, e.g., nuclear magnetic resonance, Fourier transformed infrared spectroscopy, and wide-angle X-ray diffraction, were used to characterize the polymers’ structures. Differential scanning calorimetry, thermogravimetric analysis, ultraviolet-visible spectroscopy, and spectroscopic ellipsometry were used to characterize the properties of the polymers. The selenium contents showed a positive effect on the refractive index of the final polymer. In addition, the refractive index can reach up to 1.968 at 633 nm, which was the highest intrinsic refractive index of a polyimide ever reported. Because of the high intrinsic refractive index, the reflective ratio of visible light on the surface of a silicon wafer was significantly reduced, indicating the potentially utility of the polymer in an anti-reflection coating. [ABSTRACT FROM AUTHOR]

Selenium-containing monomer monophenyl maleimide selenide (MSM) was synthesized and copolymerized with styrene (St) using reversible addition-fragmentation chain transfer (RAFT) polymerization. Copolymers with controlled molecular weight and narrow molecular weight distribution were obtained. The structure of the copolymer was characterized by nuclear magnetic resonance, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrum, Fourier transform infrared spectroscopy (FT-IR) and Ultraviolet-visible spectroscopy (UV-vis) spectroscopy. The copolymer can be oxidized byH2O2 to form carbon-carbon double bonds within the main chain due to the unique sensitivity of selenide groups in the presence of oxidants. Such structure changing resulted in an interesting concentration-related photoluminescence emission enhancement. [ABSTRACT FROM AUTHOR]

Ring-opening copolymerization (ROCOP) is an effective means to prepare functionalized polyester. In this work, a type of selenide-containing polyesters with controllable structure, molecular weight, and molecular weight distribution was successfully prepared by ROCOP of γ-selenobutyrolactone and epoxy compounds. The influence of the catalyst, solvent, and reaction temperature on the reaction efficiency was examined. Then, kinetic study was investigated under an optimized condition. The structure of the copolymers was carefully characterized by nuclear magnetic resonance (NMR), 1H NMR, 13C NMR, and 77Se NMR, Matrix-assisted laser-desorption-ionization time-of-flight mass spectrometry (MALDI-TOF-MS), and size exclusion chromatography (SEC). The resulting polymers showed a linear structure with a sequence regulated backbone repeating unit of ester-selenide. On this basis, some typical epoxides were investigated to verify the scope of the polymerization system. Due to the "living"/controlled characteristics of this ROCOP, multiblock, amphiphilic, and stereotactic copolymers could be prepared with a pre-designed structure. As expected, the selenide-containing amphiphilic copolymer could self-assemble to micelles and showed an oxidative response. [ABSTRACT FROM AUTHOR]

Selenide-containing amphiphilic copolymers have shown significant potential for application in drug release systems. Herein, we present a methodology for the design of a reactive oxygen species-responsive amphiphilic diblock selenide-labeled copolymer. This copolymer with controlled molecular weight and narrow molecular weight distribution was prepared by sequential organoselenium-mediated reversible addition fragmentation chain transfer (Se-RAFT) polymerization and selenol-based nucleophilic reaction. Nuclear magnetic resonance (NMR) and matrix-assisted laser desorption/ionization time-to-flight (MALDI-TOF) techniques were used to characterize its structure. Its corresponding nanomicelles successfully formed through self-assembly from the copolymer itself. Such nanomicelles could rapidly disassemble under oxidative conditions due to the fragmentation of the Se–C bond. Therefore, this type of nanomicelle based on selenide-labeled amphiphilic copolymers potentially provides a new platform for drug delivery. [ABSTRACT FROM AUTHOR]

Dynamic structures containing polymers can behave as thermosets at room temperature while maintaining good mechanical properties, showing good reprocessability, repairability, and recyclability. In this work, alkyl diselenide is effectively used as a dynamic cross-linker for the design of self-healing poly(urea–urethane) elastomers, which show quantitative healing efficiency at room temperature, without the need for any catalysts or external interventions. Due to the combined action of the urea bond and amide bond, the material has better mechanical properties. We also compared the self-healing effect of alkyl diselenide-based polyurethanes and alkyl disulfide-based polyurethanes. The alkyl diselenide has been incorporated into polyurethane networks using a para-substituted amine diphenyl alkyl diselenide. The resulting materials not only exhibit faster self-healing properties than the corresponding disulfide-based materials, but also show the ability to be processed at temperatures as low as 60 °C. [ABSTRACT FROM AUTHOR]