Enzymatic polymerization: A new method of polymer synthesis

Enzymatic polymerization denotes an in vitro polymerization via nonbiosynthetic pathways catalyzed by an isolated enzyme. This article describes the recent progress of this polymerization technique, developed mainly during this decade. The polymerization utilizes enzymes of hydrolases and oxidoreductases as catalysts. This new method of polymer synthesis provided natural polysaccharides like cellulose, amylose, xylan, and chitin, and unnatural polysaccharides catalyzed by a glycosidase from well-designed monomers, various functionalized polyesters catalyzed by lipase from a variety of monomers, and polyaromatics materials catalyzed by an oxidoreductase and an enzyme model complex from phenols and anilines. An oxidoreductase also initiated vinyl polymerizations. Characteristic features of enzymatic polymerizations are discussed, including the importance of the combination of substrate monomer and enzyme. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3041–3056, 1999     

Synthesis and characterization of chitosan‐modified polymethyl methacrylate latex particles

Stable chitosan‐modified polymethyl methacrylate (PMMA) latex particles were prepared by using 2,2′‐azobis(2‐amidinopropane) dihydrochloride (V‐50) as the cationic initiator. The polymerization rate (R_p) is controlled by the V‐50 concentration ([V‐50]) and R_p is less sensitive to the chitosan concentration ([C]) used in the synthesis work. The reaction system follows Smith–Ewart Case III kinetics due to the relatively large particles produced. The zeta potential data show that the isoelectric point (pI) of the latex particles is 10.7. The amounts of V‐50 (C_V‐50) and chitosan (C_c) ultimately incorporated into the particles correlate reasonably well with [V‐50] and [C], respectively. At pH 7, the quantity of the negatively charged bovine serum albumin (BSA, pI = 4.8) adsorbed on the positively charged chitosan‐free particles (Q) via the electrostatic interaction increases with increasing C_V‐50. However, Q is relatively insensitive to changes in C_c. This result implies that only the outermost region of the hairy chitosan‐modified particles is available for adsorption of the relatively large protein species. Colloidal stability shows a significant influence on the BSA adsorption process. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1489–1499, 1999     

Mo纳米薄膜热力学性质的分子动力学模拟

采用改进嵌入原子法(MAEAM),通过经典的分子动力学(MD)模拟计算了高熔点过渡金属体心立方(bcc) Mo块体Gibbs自由能和表面能. 对于纳米薄膜的热力学数据,比如Gibbs自由能等,可以看成是薄膜内部原子和表面原子两部分数据之和,然后根据薄膜的体表原子之比就可以直接计算出总的自由能,并由此可以得到热力学性质与薄膜尺寸及温度的定量关系式. 分别计算了bcc Mo块体及其纳米尺寸薄膜的自由能和热容,结果表明,Mo纳米薄膜的热力学性质具有尺寸效应,并且在薄膜尺寸小于15—20nm时,这种效应变得非常明 关键词： 改进嵌入原子法 Mo纳米薄膜 表面自由能 热容     

新型铜配合物修饰热解石墨电极上的氧电催化还原

 采用新型单核铜配合物高氯酸咪唑N-2-羟基乙基二乙烯三胺合铜(Ⅱ)(Cu［L(ImH)］(ClO4)2)修饰热解石墨(PG)电极表面制得了Cu［L(ImH)］/PG电极,并采用循环伏安法和电位阶跃实验研究了该电极对氧的催化还原作用. 结果表明,该电极在中性和碱性条件下对氧气的催化还原具有良好的稳定性,还原峰电流随电位扫描速度的增大而增强,Ip～v1/2呈线性关系. 根据电位阶跃实验的I～t-1/2曲线,计算出电极反应的电子转移数约为4, 推断氧气在该电极上的还原是经历了4电子过程还原为水,催化机理属于混合控制的ECE (E电极反应, C化学反应)过程.     

洛仑兹破缺标量场的霍金隧穿辐射

把洛仑兹破缺的标量场方程推广到弯曲时空中,并通过Aether-like项对标量场方程进行修正,该项所产生的效应也会影响到黑洞时空视界附近处的物理效应.接着,进一步在半经典近似下得到了修正的Hamilton-Jacobi方程,然后用这一修正的Hamilton-Jacobi方程研究了史瓦西黑洞的隧穿辐射特征,并讨论了洛仑兹破缺对黑洞霍金辐射和黑洞熵的影响.结果表明,u~α=δ_t~αu~t,δ_r~αu~r形式的Aether-like项的效应可能使黑洞温度增加,而黑洞熵降低.该工作可以帮助我们更深刻地理解弯曲时空中的洛仑兹破缺效应的物理性质.     

Laccase Encapsulation in ZIF-8 Metal-Organic Framework Shows Stability Enhancement and Substrate Selectivity

CgL1 laccase from Corynebacterium glutamicum was encapsulated into the metal-organic framework (MOF) ZIF-8 which was synthesized in a rapid enzyme friendly aqueous synthesis, the fastest in situ encapsulation of laccases reported to date. The obtained enzyme/MOF, i. e. laccase@ZIF-8 composite showed enhanced thermal (up to 70 °C) and chemical (N,N-dimethylformamide) stability, resulting in a stable heterogenous catalyst, suitable for high temperature reactions in organic solvents. Furthermore, the defined structure of ZIF-8 produced a size selective substrate specificity, so that substrates larger than the pore size were not accepted. Thereby, 2’-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) was used to verify that the enzyme is immobilized inside the MOF versus the outside surface. The enzyme@MOF composite was analyzed by atomic absorption spectroscopy (ASS) to precisely determine the enzyme loading to 2.1 wt%.     

碳纳米管增强型复合材料功能梯度板的自由振动模型与尺度效应

基于一种新的各向异性修正偶应力理论,建立了碳纳米管增强复合材料功能梯度板的自由振动模型。该模型能够描述尺度效应,且仅包含一个尺度参数。基于一阶剪切变形理论和哈密顿原理推演了板的运动微分方程,并以四边简支板为例给出了自振频率的解析解。讨论了板的几何尺寸、碳纳米管体分比含量和分布方式等因素对板的自振频率的影响。结果表明,本文模型所预测的板的自振基频总是高于经典弹性理论的Mindlin板模型的预测结果,两者间的差异在板的几何尺寸接近尺度参数的值时非常明显,且会随着板的几何尺寸的增大而逐渐消失。     

基于精化锯齿理论的功能梯度夹心微板静弯曲模型

基于精化锯齿理论和新修正偶应力理论,建立了能够准确预测功能梯度夹心微板挠度、位移和应力的静弯曲模型。为了描述微板不同方向上的尺度效应,将两个正交材料尺度参数引入本文模型。以受双向正弦载荷作用的简支板为例,探究了夹心微板弯曲行为中尺度效应对结构刚度的影响。算例结果表明,当微板几何参数与材料尺度参数接近时,基于本文模型所测微板的最大弯曲挠度、局部位移和应力均小于传统精化锯齿理论给出的结果,捕捉到了尺度效应;尺度效应随着微板几何尺寸的增大而逐渐减弱,当微板几何尺寸远大于材料尺度参数时,尺度效应消失。此外,板的跨厚比和功能梯度变化指数也会对尺度效应产生一定影响。     

内埋武器高速风洞弹射投放模型试验关键技术研究

针对新一代战斗机超声速内埋武器弹射投放分离安全性问题,采用高速风洞投放实验技术研究内埋武器从开式武器舱弹射投放分离动态运动过程,风洞投放模型试验过程中采用除垂直加速度不足外,其余全部运动严格相似的轻模型相似设计方法,并针对轻模型法垂直加速度不足所导致的投放垂直位移偏离实物位移问题,采用一种简单易行的公式修正法进行补偿,试验给出了不同初始弹射投放分离条件下,内埋武器从载机投放分离后运动轨迹与姿态角随分离时间的变化规律,试验马赫数$Ma = 1.5$.研究结果表明:初始投放分离角速度对内埋武器投放分离后的运动轨迹及姿态角有较大的影响,当初始投放分离角速度$\omega _{z0}^s = 0^\circ/{\rm s}$时,内埋导弹出舱后先向下运动远离载机的流场干扰区,之后逐渐向载机方向抬升靠近并最终碰撞载机,高速风洞投放试验结果是不安全的,但经过公式修正后投放试验结果比较乐观,垂直方向运动仍然一直下降远离载机,这说明采用高速风洞投放试验得出的导弹不安全投放分离对真实载机来说不一定会出现,高速风洞投放试验结果比较保守. 当初始投放分离角速度$\omega _{z0}^s= 15^\circ/{\rm s}$和$\omega _{z0}^s = 30^\circ/{\rm s}$时,内埋导弹投放分离后运动趋势几乎一致, 均没出现向载机靠近的现象,内埋导弹具有一定的初始投放分离角速度有利于内埋武器的安全分离.