Analyses of reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems using recently developed thermodynamic rate equations

This article presents reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems and regression analyses using recently developed thermodynamic rate equations that contain electrostatic and solvent-solute terms. The isomole fraction plots for these reaction systems are linear, and previous theoretical work has shown that the electrostatic term is negligible for such systems. On the other hand, the reaction rates are dependent upon the cosolvent mole fraction, indicating that the solvent-solute term, which is modeled empirically, is significant. The results of the analyses provide the foundation for a paradigm shift away from the emphasis on electrostatic effects to more tenable explanations of kinetic behavior in solvent systems.     

1,2-Diketones as photoinitiators of both cationic and free-radical photopolymerization under UV (392 nm) or Blue (455 nm) LEDs

The photoinitiation abilities of three 1,2-diketones [i.e., acenaphthenequinone ( ANPQ ), aceanthrenequinone ( AATQ ), and 9,10-phenanthrenequinone ( PANQ )]-based photoinitiating systems [PISs, with additives such as iodonium salt, N-vinylcarbazole (NVK), tertiary amine, and phenacyl bromide (R-Br)] for cationic photopolymerization and free-radical photopolymerization under the irradiation of ultraviolet (UV; 392 nm) or blue (455 nm) light-emitting diode (LED) bulb are investigated. All 1,2-diketones studied exhibit ground state absorption that match with the emission spectra of UV (392 nm) or blue LED (455 nm) better than that of the well-known blue-light-sensitive photoinitiator camphorquinone (CQ). In particular, AATQ /iodonium salt/NVK can show high photoinitiating ability (with epoxide conversion yield >70%) under the UV light irradiation due to the effect of NVK. In addition, 1,2-diketone/iodonium salt (and optional NVK) systems are capable of initiating free-radical photopolymerization of methacrylates, with conversions of 50–58%. Furthermore, some 1,2-diketone/tertiary amine (and optional R-Br) combinations are found to demonstrate high efficiency to initiate free-radical photopolymerization, and 71% of methacrylate conversion can be achieved with PANQ /tertiary amine/R-Br PIS. Some 1,2-ketone-based PISs can even exhibit higher efficiency than the CQ-based systems. The photochemical mechanism of the radical generation from the 1,2-diketone-based PISs is investigated and found to be consistent with the related photopolymerization efficiency. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 792–802     

计算代数方程组孤立奇异解的符号数值方法

求解代数方程组是计算代数几何的最基本问题之一,孤立奇异解的计算则是其中最具挑战性的课题之一,在科学与工程计算中有着广泛的应用,如机器人、计算机视觉、机器学习、人工智能、运筹学、密码学和控制论等.本文结合作者的研究成果,综述了符号数值方法在计算代数系统孤立奇异解、特别是近似奇异解精化与验证方面的研究进展,并对未来的研究方向提出了展望.     

具有复合幂函数和共存吸引子的新混沌系统的动力学分析与电路仿真

构造一个具有复合幂函数的三维连续自治混沌系统。系统的状态方程仅有5项，其中一项是指数小于1的复合幂函数。该系统具有结构简单、非双曲平衡点、吸引子共存的性质，展现出了复杂的动力学行为。首先，对系统的动力学行为进行分析，包括李雅普诺夫（Lyapunov）指数谱、分岔图以及庞加莱映射等，结果表明此系统具有混沌特性。然后进行混沌系统的电路设计，电路仿真结果验证了理论分析的正确性。     

Doxorubicin Encapsulation in Carbon Nanotubes Having Haeckelite or Stone–Wales Defects as Drug Carriers: A Molecular Dynamics Approach

Doxorubicin (DOX), a recognized anticancer drug, forms stable associations with carbon nanotubes (CNTs). CNTs when properly functionalized have the ability to anchor directly in cancerous tumors where the release of the drug occurs thanks to the tumor slightly acidic pH. Herein, we study the armchair and zigzag CNTs with Stone–Wales (SW) defects to rank their ability to encapsulate DOX by determining the DOX-CNT binding free energies using the MM/PBSA and MM/GBSA methods implemented in AMBER16. We investigate also the chiral CNTs with haeckelite defects. Each haeckelite defect consists of a pair of square and octagonal rings. The armchair and zigzag CNT with SW defects and chiral nanotubes with haeckelite defects predict DOX-CNT interactions that depend on the length of the nanotube, the number of present defects and nitrogen doping. Chiral nanotubes having two haeckelite defects reveal a clear dependence on the nitrogen content with DOX-CNT interaction forces decreasing in the order 0N > 4N > 8N. These results contribute to a further understanding of drug-nanotube interactions and to the design of new drug delivery systems based on CNTs.     

H2SO4-H2O中硝酸铜对脱硫石膏晶须生长的影响

以处理后的脱硫石膏为原料,在H₂SO₄-H₂O体系中以Cu(NO₃)₂为晶形控制剂采用水热法制备脱硫石膏晶须,探讨了Cu(NO₃)₂对脱硫石膏晶须生长的影响机理。结果表明:Cu(NO₃)₂对脱硫石膏有明显促溶作用,其中Cu²⁺可减小溶液中各离子的活度系数,使溶液中的Ca²⁺浓度增大。NO^-₃通过静电作用在Ca²⁺周围聚集并对SO^2-₄产生屏蔽作用,导致脱硫石膏继续溶解并使Ca²⁺和SO^2-₄的浓度处于相对稳定状态,有利于半水脱硫石膏晶体的形核与生长。此外,Cu²⁺还可在晶须的生长过程中选择性吸附在晶须表面,生成CuSO₄,促进了脱硫石膏的结晶生长,最终在Cu(NO₃)₂用量为2.0%(质量分数)时制备的脱硫石膏晶须长径比约为73。     

蛋白质-多糖复合体系在活性物质传递中的应用

蛋白质-多糖复合体系作为生物活性物质传递系统的壁材,有着人工合成聚合物或无机物等其他材料不可比拟的多重优势。本文就蛋白质和多糖之间的连接方式及蛋白质-多糖复合体系形成传递系统的多种形式进行了综述,以及对此领域的发展趋势进行了展望。结合蛋白质和多糖的结构特点,二者之间的链接方式分为非共价结合的物理共聚,和共价结合的美拉德偶联、化学交联、酶催化交联等方式,文中分别对各种连接方式的原理和机理,以及其影响因素做了深入阐述。以蛋白质-多糖复合体系为壁材对活性物质的传递形式大体上分成乳化系统、胶束、纳米凝胶、分子复合物以及壳核结构等系统。不同的活性物质的特征和传递需求,可针对性地选择合适结构的蛋白质和多糖种类以及二者的连接方式和传递系统的形式。并且,随着研究的逐步发展和推进,此领域的发展趋势朝着智能化和靶向性的方向进行。目前活性物质的蛋白质-多糖复合体系的传递系统,还依然面临着系统设计、评价和应用等多方面的挑战,这就要求我们在更全面更深入了解认识其对活性物质影响和功效的基础上,安全合理地设计和深入细致地评价活性成分的传递系统。