Thermally Crosslinkable and Chemically Modifiable Aromatic Polyesters Possessing Pendant Propargyloxy Groups

New aromatic (co)polyesters containing pendant propargyloxy groups were synthesized by phase transfer‐catalyzed interfacial polycondensation of 5‐(propargyloxy)isophthaloyl chloride (P‐IPC) and various compositions of P‐IPC and isophthaloyl chloride with bisphenol A. FTIR and NMR spectroscopic data, respectively, revealed successful incorporation of pendant propargyloxy groups into (co)polyesters and formation of (co)polyesters with desired compositions. (Co)polyesters exhibited good solubility in common organic solvents such as chloroform, dichloromethane, and tetrahydrofuran and could be cast into transparent, flexible, and tough films from chloroform solution. Inherent viscosities and number average molecular weights of (co)polyesters were in the range 0.77–1.33 dL/g and 43,600–118,000 g/mol, respectively, indicating the achievement of reasonably high‐molecular weights. The 10% weight loss temperatures of (co)polyesters were in the range 390–420 °C, demonstrating their good thermal stability. (Co)polyesters exhibited T_g in the range 146–170 °C and T_g values decreased with increase in mol % incorporation of P‐IPC. The study of non‐isothermal curing by DSC indicated thermal crosslinking of (co)polyesters via propargyloxy groups. The utility of pendant propargyloxy group was demonstrated by post‐modification of the selected copolyester with 1‐(4‐azidobutyl)pyrene, 9‐(azidomethyl)anthracene, and azido‐terminated poly(ethyleneglycol) monomethyl ether via copper(I)‐catalyzed Huisgen 1,3‐dipolar cycloaddition reaction. FTIR and ¹H NMR spectra confirmed that click reaction was quantitative. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 588–597     

Preparation and evaluation of uniform-sized molecularly imprinted polymer beads used for the separation of sulfamethazine

Uniform-sized molecularly imprinted polymer (MIP) beads were prepared using a one-step swelling and polymerization method. The obtained sulfamethazine (SMZ)-imprinted polymer showed high affinity and selectivity toward SMZ and other structurally related sulfonamides in acetonitrile or water-acetonitrile mobile phases, particularly in high aqueous systems. The column performance of the MIPs for SMZ and its analogues could be improved by elevating the column temperature and optimizing the flow rate. The hydrogen-bonding effect plays a significant role in the recognition process of SMZ-imprinted polymer systems in organic media, while the ion-exchange effect, as well as hydrophobic effect, dominates the retention mechanism in aqueous-rich media, in addition to shape recognition.     

Study of thermal aging effect on space charge in poly(methyl methacrylate)

Charges evolution in poly(methyl methacrylate) (PMMA) samples under thermal aging effect has been studied by means of two complementary techniques, thermal step method (TSM) and thermally stimulated depolarization current (TSDC). For the first method, measurements reveal that injected charges, whose quantity is found depending on the number of applied temperature cycles, remain close to the surface sample. TSDC measurements have been carried out for different temperatures ranging from 25 °C to 140 °C. Three distinguishable dipolar relaxations (β₁, β₂ and α) have been highlighted. In the same way, the presence of polarization and injected charges has been confirmed. In support of electric characterization, X-ray reflectometry has been used. The obtained results equally emphasized the thermal aging effect on the material.     

氧化物表面的侧表面原子成象——Ⅰ.Eu_2O_2晶体由位错滑移形成表面台阶的动态原位观察

通过高分辨电子显微术获得了Eu_2O_3晶体分子清洁的表面侧面原子成象,观察到了由表面附近位错滑移出表面而形成表面原子台阶的动态变化过程,同时还观察到了此种表面台阶的形核生长。     

碱性溶液中金电极上氧还原中间物研究

应用改进了的旋转全电极上的电势阶跃计时库仑法,分别测定了不同电极电势下氧还原过程中电极吸附中间物和溶解中间物氧化所需的电量,实验证明,在此过程中电极上确有吸附中间物存在,而且是电极电势的函数,但其分子属性尚需进一步鉴别。     

A reduced-restricted-quasi-Newton–Raphson method for locating and optimizing energy crossing points between two potential energy surfaces

We present a method for the location and optimization of an intersection energy point between two potential energy surfaces. The procedure directly optimizes the excited state energy using a quasi-Newton–Raphson method coupled with a restricted step algorithm. A linear transformation is also used for the solution of the quasi-Newton–Raphson equations. The efficiency of the algorithm is analyzed and demonstrated in some examples. © 1997 John Wiley & Sons, Inc. J Comput Chem 18 :992–1003, 1997     

One-step mild hydrothermal method to prepare low valent sodium vanadium(III) monohydrogenphosphate: NaV(HPO4)2

Green colored single crystals of a reduced sodium vanadium(III) monohydrogenphosphate, NaV(HPO₄)₂, were grown using a one-step mild hydrothermal method. The in situ reduction of V⁵⁺ to V³⁺ was performed using copper acetate as the reducing agent. The title compound crystalizes in the monoclinic space group Cc and exhibits a three-dimensional crystal structure that consists of distorted VO₆ octahedra connected to PO₃(OH) tetrahedra that are further connected via Na cations. The compound exhibits simple paramagnetic behavior at high temperatures and a discontinuity near 5 K is likely due to the onset of magnetic coupling. The compound was also characterized by TGA, IR and UV–vis spectroscopies.     

Monomer Protonation‐Dependent Surface Polymerization to Achieve One‐Step Grafting Cross‐Linked Poly(4‐Vinylpyridine) Onto Core–Shell Fe3O4@SiO2 Nanoparticles

Functional polymer‐grafting silica nanoparticles hold great promise in diverse applications such as molecule recognition, drug delivery, and heterogeneous catalysis due to high density and uniform distribution of functional groups and their tunable spatial distance. However, conventional grafting methods from monomers mainly consist of one or more extra surface modification steps and a subsequent surface polymerization step. A monomer protonation‐dependent surface polymerization strategy is proposed to achieve one‐step uniform surface grafting of cross‐linked poly(4‐vinylpyridine) (P4VP) onto core–shell Fe₃O₄@SiO₂ nanostructures. At an approximate pH, partially protonated 4VP sites in aqueous solution can be strongly adsorbed onto deprotonated silanol groups ( Si O⁻) onto Fe₃O₄@SiO₂ nanospheres to ensure prior polymerization of these protonated 4VP sites exclusively onto Fe₃O₄@SiO₂ nanoparticles and subsequent polymerization of other 4VP and divinylbenzene monomers harvested by these protonated 4VP monomers onto Fe₃O₄@SiO₂ nanoparticles, thereby achieving direct grafting of cross‐linked P4VP macromolecules onto Fe₃O₄@SiO₂ nanoparticles.     

多个时间常数线性体系暂态响应方程参数的代数求解法

从线性条件出发,推导了含n个时间常数体系恒电位阶跃时暂态响应方程,并提出一套解析形为ΔI=ΔI_∞+sum from i=1 to n k_iexp(-t/τ_i)暂态方程各未知参数的代数解法。该方法可对未知体系时间常数个数进行判定,比起一般曲线拟合更加快速简便,且抗干扰能力较强。     

轨道对称性匹配:MXene基体上的单原子催化以实现优异的氮还原反应

氨作为一种可被植物直接吸收用以合成其他有机物的重要成分,在化学化工及含氮化合物的生产当中起着至关重要的作用.传统工业生产氨气采用Haber-Bosch工艺,将空气中丰富的氮气转化为氨气,但该工艺需要较高的压强和温度来促进氮气分解,因此会消耗大量能源.近年来,电催化反应发展迅速.在电催化工艺中,通过控制操作电位及电解质便可提高生产效率,降低能源消耗.基于这种策略,各种针对能源环境的催化研究应运而生,如二氧化碳还原、水分解反应等.其中,对于氮还原的催化研究尤其是电催化设计领域研究相对较少.研究发现,在电催化剂中,异构掺杂及原子尺度的调控可以极大地影响催化剂的催化活性.其中,单原子催化(SAC)因其在催化活性和催化选择性上的优势受到广泛关注.MXene是一种二维过渡金属碳化物或氮化物,其优异的化学性能和稳定的表面构型可以对单原子起到良好的锚定与支撑作用,是一种更具潜力的单原子催化基体.本文基于上述思想,利用密度泛函第一性原理等模拟软件,设计并研究了以MXene为基体的28种过渡金属单原子催化体系,计算并分析了各SAC@MXene体系对氮还原反应的催化效果,从限制电势、催化路径、反应机制等方面探索了其催化性能.并对体系进行了态密度、晶体轨道哈密顿量、差分电荷密度等电子结构分析,找到了适用于MXene体系的单原子催化设计原则.通过对限制电势的计算表明,Ni@MXene和Co@MXene体系具有很低的限制电势(-0.13和-0.17 V),说明这些体系在较低的启动电压下即可发生氮还原反应.研究发现了一种新型适用于SAC@MXene氮催化体系的酶促-远端反应机制.电子结构分析得到SAC原子与MXene基体的Ti原子在催化过程中存在一种协同作用.态密度及晶体轨道哈密顿量也显示出SAC原子与MXene基体Ti之间的一种轨道对称性匹配关系,揭示了这种协同作用对催化反应的积极作用.计算的氢析出反应(HER)结果也显示,在相同化学环境下,SAC@MXene体系氮还原反应相对于氢析出反应更易发生.