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Poly(glycidyl methacrylate) (PGMA) was synthesized by Fe(0)-mediated living radical polymerization followed with post-modification by PhSeZnCl. A series of selenide functionalized PGMAs with different selenium concentrations and molecular weights were obtained. The introduction of selenide groups into PGMA resulted in a polymer with high refractive index. The relationships between the concentration of selenium, degree of polymerization and refractive index were investigated. Results showed that the refractive index of the final polymer could be adjusted by the concentration of selenium and degree of polymerization, which provided a useful way to fabricate polymeric materials with adjustable refractive index. [ABSTRACT FROM AUTHOR]

Stimulus-responsive materials containing selenide under oxidizing conditions have wide application prospects, especially in biomedicine. Due to the intricate preparation process, the scarcity of studies on the structure–activity relationship of regulatory factors in the oxidative stimulus response poses challenges to material design. Herein, based on selenol-ene chemistry, a diverse library of unsymmetric selenides is synthesized, enabling systematic investigation into the regulation of selenide oxidative elimination with variable substituent groups and positions. The α/β-positions of β-carbonyl unsymmetric selenides are efficiently modified with electron-donating or electron-withdrawing groups through a one-pot, two-step reaction involving ammonolysis of γ-selenobutyrolactone (SBL), followed by nucleophilic addition with unsaturated acrylate. In situ NMR tracking shows that the oxidative elimination of selenide had a distinct substituent effect. Both the electron and steric effects of the substituent influence the induction period of the selenide oxidative and elimination reactions. With the optimal substituent and position, the selenides would exhibit a timebomb-type response upon oxidation stimulus. Finally, a novel amphiphilic polymer comprising selenide-linked polyethylene glycol (PEG) and cholesterol moieties is synthesized as a representative ROS-sensitive material and exhibits a time-dependent reduction in micelle size. [ABSTRACT FROM AUTHOR]

Diselenide-containing polymers are facilely synthesized from polymers prepared by atom transfer radical polymerization (ATRP). Benefiting from the ATRP technology, this protocol provides a flexible route for controlling the polymer structure, which allows for a great variety of architectures of selenium-containing polymer materials for applications in various fields. The oxidative and reductive responsive behavior of the obtained diselenide-containing polymers is also investigated. [ABSTRACT FROM AUTHOR]

Pendant selenium‐containing maleimide polymers with different selenium contents are synthesized via a radical copolymerization of styrene and N‐butylmaleimide phenyl selenide. The polymer structures are characterized by nuclear magnetic resonance, gel permeation chromatography, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, and scanning electron microscopy with an energy‐dispersive spectrometer, which results in the desired structures and selenium contents. The refractive indices of the polymers, which change as a function of different contents of selenium and oxidative stimuli by H2O2 or O3, are investigated. Finally, a photonic crystal (PC) is prepared based on the selenium‐containing polymer. The visible color changes of the PC are investigated as a function of different concentrations and contact times of O3. [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]

Diselenide-containing polymers have attracted more and more attention due to their redox sensitivity and bioapplication. In this work, a bifunctional diselenocarbonate is prepared and used to mediate the reversible addition-fragmentation chain transfer (RAFT) polymerization, producing α,ω-selenocarbonate-labeled telechelic polystyrene. Based on effective aminolysis of the terminal selenocarbonates and the followed spontaneous oxidation coupling reaction of diselenols, monoblock cyclic polystyrene linked by one diselenide bond and multiblock cyclic copolymer linked by several diselenide bonds are prepared by manipulating the concentration of α,ω-telechelic polystyrene in solution. The progress of aminolysis and the subsequent spontaneous oxidation of selenols to diselenides are monitored by UV-vis, gel permeation chromatography (GPC), and NMR characterizations, confirming the cyclic topologies of the resultant polymers (monocyclic or multiblock cyclic polymer). The monoblock cyclic or multiblock polymers show redox sensitivity, which can be converted to linear polymer by reducing or oxidizing agent. Moreover, the obtained monoblock cyclic polymer or multiblock cyclic copolymer can be transformed to each other under UV irradiation by adjusting the concentration of the cyclic polystyrene. For the first time, this work provides an alternative and promising approach to realize the topological transformation of polymers by installing multiresponsive diselenide moities into the backbone of cyclic polymer. [ABSTRACT FROM AUTHOR]