A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

The mechanisms of CO₂ coupling with the propargylic alcohol using alkali carbonates M₂CO₃ (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs₂CO₃-mediated carboxylative cyclization of the propargylic alcohol with CO₂, and (b) the conversion of the αACC intermediate with Cs₂CO₃ to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO₃ together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO₂ with the propargylic alcohol. Compared to other alkali carbonates M₂CO₃ (M = Li, Na, K), the stronger basicity of Cs₂CO₃ and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield.     

Nanocomposite hydrogel consisting of Na‐montmorillonite with enhanced mechanical properties

A new kind of nanocomposite (NC) hydrogel with Na‐montmorillonite (MMT) is presented in this article. The NC hydrogels were synthesized by free radical copolymerization of acrylamide and (3‐acrylamidopropyl) trimethylammonium chloride (ATC) in the presence of MMT and N,N′‐methylene‐bis‐acrylamide used as chemical cross‐linker. Due to the cation‐exchange reaction between MMT and ATC (cationic monomer) during the synthesis of NC hydrogels, MMT platelets were considered chemical “plane” cross‐linkers, different from “point” cross‐linkers. With increasing amount of MMT, the crosslinking degree enhanced, causing a decrease of the swelling degree at equilibrium. Investigations of mechanical properties indicated that NC hydrogels exhibited enhanced strength and toughness, which resulted from chemical interaction between exfoliated MMT platelets and polymer chains in hydrogels. Dynamic shear measurements showed that both storage modulus and loss modulus increased with increasing MMT content. The idea described here provided a new route to prepare hydrogels with high mechanical properties by using alternative natural Na‐MMT. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1020–1026     

Lipase‐Supported Metal–Organic Framework Bioreactor Catalyzes Warfarin Synthesis

A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase‐supported metal–organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors.     

XY(H,Li,Na)分子基态的结构与势能函数

运用群论及原子分子反应静力学方法,推导了XY(H,Li,Na)分子基态的电子态及相应的离解极限.并采用密度泛函方法(B3LYP)和二次组态相互作用方法(QCISD)优化计算了XY(H,Li,Na)分子基态的平衡结构、振动频率和离解能.使用QCISD/6-311++G(3df,3pd)方法,对XY(H,Li,Na)分子基态进行了单点能扫描计算,采用最小二乘法拟合Murrell-Sorbie函数得到了相应的势能函数和与该基态相对应的光谱常数(Be,αe,ωe和ωexe),计算结果与实验数据符合得相当好.     

提高微晶硅薄膜太阳电池效率的研究

采用甚高频等离子体增强化学气相沉积技术制备了系列微晶硅薄膜太阳电池，指出了气体总流量和背反射电极的类型对电池性能参数的影响.电池的I-V测试结果表明：随反应气体总流量的增加，对应电池的短路电流密度、开路电压和填充因子都有很大程度的提高，结果使得电池的光电转换效率得以提高.另外，ZnO/Ag/Al背反射电极能明显提高电池的短路电流密度，进而也提高了电池的光电转换效率.对气体总流量和背反射电极类型影响电池效率的原因进行了分析. 关键词： 微晶硅薄膜太阳电池 气体流量 ZnO/Ag/Al背反射电极     

从诺贝尔物理学奖看光学的发展

从一个新的角度分析、讨论了光学的发展过程.并对光学今后的发展做了展望.     

生长温度对碳纳米管阴极场发射性能的影响

碳纳米管(Carbon Nanotubes,CNTs)场发射平面显示器(Field Emission Display,FED)与其他显示器比较显示了其独特优点,被认为是未来理想的平面显示器之一。碳纳米管阴极作为器件的核心部分,其性能的好坏直接影响显示器的性能。针对30~60英寸(76.2~152.4cm)大屏幕显示器所用的厚膜工艺,即采用丝网印刷法制备了碳纳米管阴极阵列,研究了化学气相沉积法在不同温度下生长的CNTs的场发射电流-电压特性,找到了适合FED用碳纳米管的最佳生长温度。结果表明生长温度越高(750℃),CNTs场发射性能越好。并用荧光粉阳极测试这些CNTs的场发射发光显示效果,验证了上述结论。     

用于机械振动实时监测的光纤光栅有源传感装置

把一对中心反射波长分别为1562.11nm和1562.71nm的光纤光栅粘贴在均质、等厚、等腰三角形悬臂梁上下表面作为环形腔光纤激光器端镜，当机械振动激励自由端时，通过观测激光输出脉冲，地施加于自由端的机械振动的频率进行了实时监测；观察两光栅波长漂移量差值的变化，可在0～6.1mm的范围内判断所测振动的振幅。低于100Hz时，实验结果与实际值基本吻合。     

Optimal Control of Non-well-posed Heat Equations

This work is concerned with Pontryagin＇s maximum principle of optimal control problems governed by some non-well-posed semilinear heat equations. A type of approach to the non-well-posed optimal control problem is given.     

浮栅ROM器件辐射效应机理分析

分析了浮栅ROM器件的辐射效应机理，合理地解释了实验中观察到的现象.指出辐射产生的电子空穴对在器件中形成的氧化物陷阱电荷和界面陷阱电荷是导致存储单元及其外围电路出现错误的原因.浮栅ROM器件的中子、质子和⁶⁰Co γ辐射效应都是总剂量效应 . 关键词： FLASH ROM EEPROM 中子 质子 60Co γ')" href="#">⁶⁰Co γ 总剂量效应