DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585     

安徽省地区专业化的度量

利用樊福卓构造的地区专业化综合指数,结合1998—2012年度安徽省17个主要城市15个产业对安徽省地区近年来的专业化程度进行度量,分析安徽省的地区专业化特征,为安徽省产业布局提供新的理论思路。     

一种新型的烟片复烤机加湿方法

传统KG型烟片复烤机加湿效果差,加湿喷嘴容易堵塞与损坏,回潮效率低,回潮区温度超标,严重浪费蒸汽与水.采用新型气水二流体雾化喷嘴,在喷孔外端加装调节帽,实现二次雾化.回潮效果明显提高(达到4%以上),回潮区温度可控制在70℃左右,节约蒸汽30%以上.     

两种改进的非线性方程组四阶迭代求解法

文章基于两点Gauss型求积公式,分别结合梯形积分公式和Adomian分解法构造了两种牛顿型迭代格式.借助泰勒展开式,文章证明了这两种迭代格式都具有四阶收敛,并通过数值实验例子验证这两种迭代格式的有效性.     

基于Dempster-Shafer证据理论的矿山遥感分类

本文分析了矿山用地的特点,利用Dempster-Shafter证据理论用信任区间表示判决结果的特点,计算地类不确定性分布图,以CBV为最大划分像元归属类别原则对遥感图像上的矿山用地进行分类.实验结果表明,D-S证据理论用于矿山用地分类的精度高于最大似然方法的精度.     

Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

Gravitational wave imprint of new symmetry breaking

It is believed that there are more fundamental gauge symmetries beyond those described by the Standard Model of particle physics. The scales of these new gauge symmetries are usually too high to be reachable by particle colliders. Considering that the phase transition (PT) relating to the spontaneous breaking of new gauge symmetries to the electroweak symmetry might be strongly first order, we propose considering the stochastic gravitational waves (GW) arising from this phase transition as an indirect way of detecting these new fundamental gauge symmetries. As an illustration, we explore the possibility of detecting the stochastic GW generated from the PT of \begin{document}$ {\bf{B}}-{\bf{L}}$\end{document} in the space-based interferometer detectors. Our study demonstrates that the GW energy spectrum is reachable by the LISA, Tianqin, Taiji, BBO, and DECIGO experiments only for the case where the spontaneous breaking of \begin{document}$ {\bf{B}}-{\bf{L}}$\end{document} is triggered by at least two electroweak singlet scalars.     

“零被引专利”就没有价值吗?——“零被引专利”在科学论文中的应用分析

 分析前人对零被引的研究成果发现，"零被引"的定义可能存在一定的局限，即只考察同类数据库中的引用情况。分析CSTPCD 2009-2012年的科技论文与引文发现，期刊论文引用了大量的技术专利。存在专利数据库中的"零被引专利"在科技论文中却有较高的引用次数。以其中1件"零被引专利"CN 01134280.3为例，从技术内容解读、10篇施引文献及其内容分析，展示了该项技术发明影响的研究主题，并通过文献调研解析了该项研究成果的工业化应用。基于钱学森的"基础科学-技术科学-工程科学"理论，探讨了使用较高科技论文引用次数的"零被引专利"及较高专利引用次数的"零被引论文"定量分析技术科学的可能性。     

国家层面创新能力的评价

 综述了创新、创新监测与评价的研究进展，辨析了国家创新能力、创新型国家和科技强国的内涵特征，分析了中国创新能力在世界上的相对位置，探讨了建设科技强国的经验及启示。     

锡苯和铅苯二聚反应的理论研究

采用密度泛函理论B3LYP方法,研究了锡苯和铅苯的[2+2],[4+2]及[4+4]二聚反应的微观机理和势能剖面,考察了Sn(Pb)原子上的2,4,6-三甲基苯基(Mes)取代基对反应势能剖面的影响.研究结果表明,所有反应均为协同过程,且大多数情况下,2个C—Sn(Pb)键同步形成.[2+2]和[4+2]反应在热力学和动力学上均比相应的[4+4]反应容易进行,而[4+2]反应在动力学上比相应的[2+2]反应有利.Sn(Pb)原子上的Mes取代基在热力学和动力学上均不利于反应的进行.铅苯的动力学稳定性与锡苯相当,但其热力学稳定性高于锡苯.