Crosslinked poly(ethylene oxide) containing siloxanes fabricated through thiol‐ene photochemistry

Homogenous amphiphilic crosslinked polymer films comprising of poly(ethylene oxide) and polysiloxane were synthesized utilizing thiol‐ene “ click ” photochemistry. A systematic variation in polymer composition was Carried out to obtain high quality films with varied amount of siloxane and poly(ethylene oxide). These films showed improved gas separation performance with high gas permeabilities with good CO₂/N₂ selectivity. Furthermore, the resulting films were also tested for its biocompatibility, as a carrier media which allow human adult mesenchymal stem cells to retain their capacity for osteoblastic differentiation after transplantation. The obtained crosslinked films were characterized using differential scanning calorimetry, dynamic mechanical analysis, thermogravimetric analysis, FTIR, Raman‐IR , and small angle X‐ray scattering. The synthesis ease and commercial availability of the starting materials suggests that these new crosslinked polymer networks could find applications in wide range of applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1548–1557     

Thermally induced solid-state transformation of cimetidine. A multi-spectroscopic/chemometrics determination of the kinetics of the process and structural elucidation of one of the products as a stable N3-enamino tautomer

Exposure of cimetidine (CIM) to dry heat (160–180 °C) afforded, upon cooling, a glassy solid containing new and hitherto unknown products. The kinetics of this process was studied by a second order chemometrics-assisted multi-spectroscopic approach. Proton and carbon-13 nuclear magnetic resonance (NMR), as well as ultraviolet and infrared spectroscopic data were jointly used, whereas multivariate curve resolution with alternating least squares (MCR-ALS) was employed as the chemometrics method to extract process information. It was established that drug degradation follows a first order kinetics.     

DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585     

Sonochemical approach for synthesis of zinc oxide-poly methyl methacrylate hybrid nanoparticles and its application in corrosion inhibition

Hybrid nanoparticles (HNPs) with zinc oxide and polymethyl metha acrylate (inorganic/ polymer) were synthesized through the exploitation of ultrasound approach. The synthesized HNPs were further characterized employing transmission electron microscopy and x-ray diffraction. ZnO-PMMA based HNPs exhibit excellent protection properties to mild steel from corrosion when gets exposed to acidic condition. Electrochemical impendence spectroscopy (EIS) analysis was accomplished to evaluate the corrosion inhibition performance of MS panel coated with 2 wt% or 4 wt% of HNPs and its comparison with bare panel and that of loaded with only standard epoxy coating., Tafel plot and Nyquist plot analysis depicted that the corrosion current density (I_corr) decreases from 16.7 A/m² for bare material to 0.103 A/m² for 4% coating of HNPs. Applied potential (E_corr) values shifted from negative to positive side. These results were further supported by qualitative analysis. The images taken over a period of time indicated the increase in lifetime of MS panel from 2 to 3 days for bare panel to 10 days for HNPs coated panel, showing that ZnO-PMMA HNPs have potential application in metal protection from corrosion by forming a passive layer.     

Naphthalimide‐phthalimide derivative based photoinitiating systems for polymerization reactions under blue lights

Naphthalimide‐phthalimide derivatives (NDPDs) have been synthesized and combined with an iodonium salt, N‐vinylcarbazole, amine or 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine to produce reactive species (i.e., radicals and cations). These generated reactive species are capable of initiating the cationic polymerization of epoxides and/or the radical polymerization of acrylates upon exposure to very soft polychromatic visible lights or blue lights. Compared with the well‐known camphorquinone based systems used as references, the novel NDPD based combinations employed here demonstrate clearly higher efficiencies for the cationic polymerization of epoxides under air as well as the radical polymerization of acrylates. Remarkably, one of the NDPDs (i.e., NDPD2) based systems is characterized by an outstanding reactivity. The structure/reactivity/efficiency relationships of the investigated NDPDs were studied by fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques. The key parameters for their reactivity are provided. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 665–674     

Monte Carlo simulation of electric conductivity for pure and doping fullerene (C60)

In this paper, we have used Monte Carlo (MC) method to simulate and study the temperature and doping effects on the electric conductivity of fullerene (C60). The results show that the band gap has reduced by the doping and the charge carrier transport is facilitated from valence band to conduction band by the temperature where is touched a 300 K. In this case, the conductivity reached a value of $4\times {10}^{-7}\text{S}{\text{cm}}^{-1}$. The electric conductivity of C60 can increase by the triphenylmethane dye crystal violet (CV) alkali metal to reach $4\times {10}^{-3}\text{S}{\text{cm}}^{-1}$ at 303 K. Our results of MC simulation have a good agreement with those extracted from literature [10], [33].     

Convergence of solutions for the fractional Cahn–Hilliard system

This paper deals with the Cauchy–Dirichlet problem for the fractional Cahn–Hilliard equation. The main results consist of global (in time) existence of weak solutions, characterization of parabolic smoothing effects (implying under proper condition eventual boundedness of trajectories), and convergence of each solution to a (single) equilibrium. In particular, to prove the convergence result, a variant of the so-called ?ojasiewicz–Simon inequality is provided for the fractional Dirichlet Laplacian and (possibly) non-analytic (but $C^1$) nonlinearities.     

超强频率梳激光场驱动下多光子共振谐波辐射的相位突变研究

本文从理论上研究了在双色频率梳激光场驱动下多光子谐波辐射光谱中的相位突变现象。我们利用Floquet理论非微扰地模拟了频率梳激光场与原子分子等量子系统的相互作用过程。谐波辐射信号是多光子偶极跃迁相干叠加的结果,通过调节频率梳激光场间的相对相位,可以相干地控制谐波辐射信号的强度。通过对谐波信号进行傅里叶变换,可以提取不同跃迁路径的相对相位信息。我们通过改变频率梳组激光场的强度和频率组分实现多光子跃迁频率,让其跨越共振跃迁频率时,谐波相位会发生突变。从而可以观测超强激光场驱动下量子系统共振跃迁频率的斯塔克能移。     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).