Group IV M‐POSS (M=Zr,Hf) Coordination Polymers

The synthesis and characterization of Zr‐POSS and Hf‐POSS coordination polymers were reported. The IR data and the solid‐state ²⁹Si MAS NMR indicated the existence of Si? O? M linkage. The polarized optical microscopy images and the XRD data suggested their crystalline nature.     

Construction of dsDNA biosensor based on dendritic SiO2 nanoparticle and investigation on its interaction with benzo[a]pyrene

In this work, a new dsDNA biosensor was constructed to monitor the interaction of DNA and benzo[a]pyrene (BaP). Firstly, dendritic SiO₂ nanoparticles were synthesized by silanization of SiO₂ nanoparticles with (??-(methacryloyloxy)propyl) trimethoxysilane and polymerization with acrylic acid. Then, due to the rich carboxyl groups of these nanoparticles, they were associated with the amino groups of a self-assembly membrane formed on the gold electrode by a sulfur-containing compound, 5-amino-3-mercapto-1,2,4-triazole. Finally, dsDNA was immobilized on the electrode surface by static adsorption with the aid of metallic ion. The whole immobilization steps were characterized by cyclic voltammogram and electrochemical impedance spectrum. After that, using methylene blue as a probe, the interaction of BaP with dsDNA was investigated. A linear relationship between the percentages of current decrease with the logarithm of BaP concentrations was found in the range from 0.33 to 133???M.     

Post‐Synthetic Polymerization of UiO‐66‐NH2 Nanoparticles and Polyurethane Oligomer toward Stand‐Alone Membranes for Dye Removal and Separation

Metal–organic frameworks (MOFs) are widely used as porous materials in the fields of adsorption and separation. However, their practical application is largely hindered by limitations to their processability. Herein, new UiO‐66‐Urea‐based flexible membranes with MOF loadings of 50 ( 1 ), 60 ( 2 ), and 70 wt % ( 3 ) were designed and prepared by post‐synthetic polymerization of UiO‐66‐NH₂ nanoparticles and a polyurethane oligomer under mild conditions. The adsorption behavior of membrane 3 towards four hydrophilic dyes, namely, eosin Y (EY), rhodamine B (RB), malachite green (MG), and methylene blue (MB), in aqueous solution was studied in detail. It exhibits strong adsorption of EY and RB but weak adsorption of MG and MB in aqueous solution. Owing to the selective adsorption of these hydrophilic dyes, membrane 3 can remove EY and RB from aqueous solution and completely separate EY/MB, RB/MG, and RB/MB mixtures in aqueous solution. In addition, the membrane is uniformly textured, easily handled, and can be reused for dye adsorption and separation.     

Fluorinated star‐shaped block copolymers: Synthesis and optical properties

Tetrakis(4‐(1‐bromoethyl)phenyl)silane is synthesized and utilized to initiate the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) to generate bromo‐terminated four‐armed PMMA macroinitiators, which further initiate the ATRP of methylacryloyloxyl‐2‐hydroxypropyl perfluorooctanoate (FGOA) to create fluorinated star‐shaped block copolymers PMMA‐b‐poly(FGOA)s with fluorine content ranging from 0 to 31.7 wt %. The polymerizations are well controlled with the polydispersity indices <1.30. The polymers readily dissolve in common organic solvents and show good film‐formation. Compared with the nonfluorinated sample, the fluorinated films exhibit significantly increased water contact angles owing to the enrichment of fluorine on the surface. The enhanced hydrophobicity is advantageous for the optical stability when the devices work under a moist environment. Moreover, the films possess high thermo‐optic coefficients, tunable refractive indices, and extremely low birefringence coefficients because of the presence of bulky and rigid tetraphenylsilane core and star‐shaped topological structure, showing potential application in optical waveguide devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1969–1977     

Copolymerization of carbon dioxide and cyclohexene oxide catalyzed by chromium complexes bearing semirigid [ONSO]‐type ligands

Chromium complexes supported by tetradentate dianionic imine‐thioether‐bridged bis(phenol) ligands were prepared and employed in the synthesis of poly(cyclohexene carbonate) via the copolymerization of CO₂ and cyclohexene oxide. The catalytic activity, product selectivity, and kinetic behaviors of these [ONSO]Cr^III complexes have been systematically investigated. Results indicate the presence of electron‐withdrawing substituents on the ligands to enhance catalytic activity and polymer selectivity. A turnover frequency of 100 h^?1 is observed at a temperature of 110 °C, producing polycarbonate with >60% selectivity. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1938–1944