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     

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.     

Recent Progress on Nickel-Based Oxide/(Oxy)Hydroxide Electrocatalysts for the Oxygen Evolution Reaction

Developing clean and sustainable energies as alternatives to fossil fuels is in strong demand within modern society. The oxygen evolution reaction (OER) is the efficiency-limiting process in plenty of key renewable energy systems, such as electrochemical water splitting and rechargeable metal–air batteries. In this regard, ongoing efforts have been devoted to seeking high-performance electrocatalysts for enhanced energy conversion efficiency. Apart from traditional precious-metal-based catalysts, nickel-based compounds are the most promising earth-abundant OER catalysts, attracting ever-increasing interest due to high activity and stability. In this review, the recent progress on nickel-based oxide and (oxy)hydroxide composites for water oxidation catalysis in terms of materials design/synthesis and electrochemical performance is summarized. Some underlying mechanisms to profoundly understand the catalytic active sites are also highlighted. In addition, the future research trends and perspectives on the development of Ni-based OER electrocatalysts are discussed.     

GDME-based methodology for the determination of free formaldehyde in cosmetics and hygiene products containing formaldehyde releasers

Analytical and Bioanalytical Chemistry - Formaldehyde is often applied in the industrial production of different products, such as textiles, insulation materials, or cosmetics, due to its...     

焊膏印刷工艺参数的选择与优化

表面贴装工艺流程的关键工序之一就是焊膏印刷,其工艺控制的好坏直接影响着装配的线路板的质量。通过对印刷工艺参数的分析,利用试验设计的方法来找出关键工艺参数,并加以优化设定,从而为控制工序参数奠定基础。     

Accurate estimation of capacities and cross-traffic of all links in a path using ICMP timestamps

The estimation of the link capacity and its available bandwidth in an end-to-end path is crucial for network management, admission control and flow control for adaptive applications. This paper introduces an estimation mechanism able to accurately estimate the available bandwidth of all links in an end-to-end path, through its capacity and cross-traffic estimation. The estimation procedures resort to the dispersions of packet pairs and trains using the concepts of ICMP Timestamp and Traceroute that, efficiently used together, enable the measurement of the dispersions in all links in the path. These mechanisms were evaluated through simulation experiments, where we analyzed the influence of the several network parameters on each estimation mechanism. The results show that these estimation methods are able to accurately estimate both the capacity and the cross-traffic of all links in a path with moderate length and with low overhead.     

基于规则的光学邻近矫正中规则的相关处理

讨论了如何选择适当的规则,如何建立简洁实用的规则库,如何应用规则库.提出了四种主要的光学邻近矫正规则,在实验结果中列举了规则库中的部分数据.利用规则矫正后的版图光刻得到的硅片图形有了明显的改善.规则库的自动建立部分 (OPCL)是基于规则的光学邻近矫正系统的重要组成部分.     

Modified gravity on the brane and dark energy

We analyze the dynamics of an AdS₅ braneworld with matter fields when gravity is allowed to deviate from the Einstein form on the brane. We consider exact five-dimensional warped solutions which are associated with conformal bulk fields of weight –4 and describe on the brane the following three dynamics: those of inhomogeneous dust, of generalized dark radiation, and of homogeneous polytropic dark energy. We show that, with modified gravity on the brane, the existence of such dynamical geometries requires the presence of non-conformal matter fields confined to the brane.     

Efficient computation of natural convection in a concentric annulus between an outer square cylinder and an inner circular cylinder

In this work, the natural convection in a concentric annulus between a cold outer square cylinder and a heated inner circular cylinder is simulated using the differential quadrature (DQ) method. The vorticity‐stream function formulation is used as the governing equation, and the coordinate transformation technique is introduced in the DQ computation. It is shown in this paper that the outer square boundary can be approximated by a super elliptic function. As a result, the coordinate transformation from the physical domain to the computational domain is set up by an analytical expression, and all the geometrical parameters can be computed exactly. Numerical results for Rayleigh numbers range from 104 to 106 and aspect ratios between 1.67 and 5.0 are presented, which are in a good agreement with available data in the literature. It is found that both the aspect ratio and the Rayleigh number are critical to the patterns of flow and thermal fields. The present study suggests that a critical aspect ratio may exist at high Rayleigh number to distinguish the flow and thermal patterns. Copyright © 2002 John Wiley & Sons, Ltd.