Facile synthesis of graft copolymers containing rigid poly(dialkyl fumarate) branches by macromonomer method

Graft copolymers show microphase separated structure as seen in block copolymers and have lower intrinsic viscosity than block copolymers because of a branching structure. Therefore, considering molding processability, especially for polymers containing rigid segments, graft copolymers are useful architectures. In this work, graft copolymers containing rigid poly(diisopropyl fumarate) (PDiPF) branches were synthesized by full free‐radical polymerization process. First, synthesis of PDiPF macromonomers by addition‐fragmentation chain transfer (AFCT) was investigated. 2,2‐Dimethyl‐4‐methylene‐pentanedioic acid dimethyl ester was found to be an efficient AFCT agent for diisopropyl fumarate (DiPF) polymerization because of the suppression of undesired primary radical termination, which significantly took place when common AFCT agent, methyl 2‐(bromomethyl)acrylate, was used. Copolymerization of PDiPF macromonomer with ethyl acrylate accomplished the generation of the graft copolymer having flexible poly(ethyl acrylate) backbone and rigid PDiPF branches. The graft copolymer showed a microphase separated structure, high transparency, and characteristic thermal properties to PDiPF and poly(ethyl acrylate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2474–2480     

Dynamic Interactions in Synthetic Receptors: A Guest Exchange Saturation Transfer Study

The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF₄⁻ are mediated by the side chains on the receptor (100 s⁻¹<k_ex<5000 s⁻¹), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method.     

A new endocytic model based on the co-rotational grid method

Endocytosis plays important roles in many cellular physiological processes, such as metabolism and immune. Many theoretical models have been proposed to study the endocytic process, but little has considered the tensile deformation of the membrane and the actin forces. In this paper, a new endocytic model is proposed based on the co-rotational grid method. Our model gives a direct estimation of the in-plane strain of the plasma membrane and provides a basis for the calculation of further scission process of the vesicle. The results fit well with experimental data in the literature. Moreover, it is suggested that the active forces of actin at the endocytic site is the main mechanism driving the invagination of the plasma membrane.     

QEPAS系统中石英音叉模态仿真计算与研究

对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算，获得石英音叉前6阶振型与模态频率，认知了第4阶对称摆动振型为有效振动，利用单因素法分析了石英音叉的音臂长度l₁、音臂宽度w₁、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响，敏感度依次为： l₁> w₁>d>θ>t>h，考虑实际设计情形，筛选出了l₁，w₁，d与h四个石英音叉设计变量，采用Box-Behnken实验设计方案与RSM(response surface methodology)方法，以Fre为函数目标，建立l₁，w₁，d与h的二次回归响应面模型，得到了参数之间的交互作用，利用Design-Expert软件对响应面模型进行设计参数反求，结果表明，在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小，基本满足QEPAS系统的计算需求，所提出的研究与设计方法具有一定通用性，可为QEPAS系统中石英音叉结构参数设计提供参考。     

“蜡烛火焰划分”实验的局限成因分析及改进研究

人教版初中化学首个探究性实验"蜡烛及其燃烧"明确指出火焰的划分方法，但在实际教学中肉眼观察法和火柴梗燃烧法对蜡烛火焰的划分存在一定的局限性。采用文献研究法和实验验证法分析其局限性的成因——燃料的析炭能力强弱、材料结构的不同等，并提出相应的改进建议。     

Multiple positive solutions for Schrödinger‐Poisson system involving singularity and critical exponent

In this paper, the existence and multiplicity of positive solutions is established for Schrödinger‐Poisson system of the form where 0 ∈ Ω is a smooth bounded domain in , , and λ > 0 is a real parameter. Combining with the variational method and Nehari manifold method, two positive solutions of the system are obtained.     

求解矩阵方程AXB+CXD=F参数迭代法的最优参数分析

本文针对求矩阵方程AXB+CXD=F唯一解的参数迭代法，分析当矩阵A，B，C，D均是Hermite正（负）定矩阵时，迭代矩阵的特征值表达式，给出了最优参数的确定方法，并提出了相应的加速算法.     

Electrochemical Characteristics of a Triphenylamine Derivative by Microelectrode Voltammetry

With the objective of understanding the kinetic redox properties of triphenylamine derivatives in association with chemical reactions, for their future application in functional organic semiconductor devices, the electrochemical characteristics of 4‐(2,2‐diphenylethenyl)‐N,N‐bis(4‐methylphenyl)‐benzenamine (TPA) were evaluated. Based on cyclic voltammograms of TPA on Pt disk electrodes with diameters of 300 μm and 10 μm at slow and fast scan rates in an acetonitrile solution, the TPA^.+ is stable, while the TPA²⁺ is unstable. Importantly, the unstable TPA²⁺ appears to break down by a subsequent chemical reaction. A Cottrell plot analysis from chronoamperometry of a solution containing TPA reveals that both the first and second oxidations are one‐electron reactions. Concerning the stabilization mechanism of the first oxidation state of TPA, the results of molecular orbital calculations indicate that the electrons of the HOMO level are distributed in the triphenylamine group, which induces a resonance‐stabilized TPA^.+. Based on these results, TPA/TPA^.+ is suggested to have a sufficient stability for further application in organic semiconductor devices.     

Poisson discretizations of Wiener functionals and Malliavin operators with Wasserstein estimates

This article proposes a global, chaos-based procedure for the discretization of functionals of Brownian motion into functionals of a Poisson process with intensity $\lambda >0$. Under this discretization we study the weak convergence, as the intensity of the underlying Poisson process goes to infinity, of Poisson functionals and their corresponding Malliavin-type derivatives to their Wiener counterparts. In addition, we derive a convergence rate of $O\left({\lambda }^{?1∕4}\right)$ for the Poisson discretization of Wiener functionals by combining the multivariate Chen–Stein method with the Malliavin calculus. Our proposed sufficient condition for establishing the mentioned convergence rate involves the kernel functions in the Wiener chaos, yet we provide examples, especially the discretization of some common path dependent Wiener functionals, to which our results apply without committing the explicit computations of such kernels. To the best our knowledge, these are the first results in the literature on the universal convergence rate of a global discretization of general Wiener functionals.