Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

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     

Voltammetric study of the behaviour of N-acetyl-p-aminophenol in aqueous solutions at a platinum electrode

The electrochemical oxidation of N-acetyl-p-aminophenol (PAR) was investigated at a Pt electrode with the application of cyclic (CV) and differential pulse (DPV) voltammetry methods. An effect of scan rate, substrate concentration and pH on electrode reactions was determined. The parameters of substrate electro-oxidation, i.e. heterogeneous rate constant, charge transfer coefficient, and diffusion coefficient, were calculated. Our investigation's results prove the exchange of two electrons and one proton in the first step, followed by a chemical reaction. PAR electro-oxidation occurs according to an EC mechanism.     

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.     

新一代IP QoS的实现

文章介绍了新一代IP骨干网上的IP QoS实现技术，论述了集成业务(IntServ)与差分业务(DiffServ)解决方案的特点，详细介绍了相关的队列管理与排队机制。并结合多协议标签交换（MPLS)技术的最新发展，阐述了综合多协议标签交换流量工程与DiffServ技术体系端到端IP QoS的实现。     

Fast handoff with reducing waste rate approach for wireless resources management in UMTS mobile networks

3G Wideband CDMA systems adopt the Orthogonal Variable Spreading Factor code tree as the channelization codes management for achieving high data rate transmission in personal multimedia communications. It assigns a single channelization code for each accepted connection. Nevertheless, it wastes the system capacity when the required rate is not powers of two of the basic rate. One good solution is to assign multiple codes for each accepted connection but it causes two inevitable drawbacks: long handoff delay and new call setup delay due to high complexity of processing with multiple channelization codes, and high cost of using more number of rake combiners. Especially, long handoff delay may result in more call dropping probability and higher Grade of Service, which will degrade significantly the utilization and revenue of the 3G cellular systems. Therefore, we propose herein an adaptive efficient codes determination algorithm based on the Markov Decision Process analysis approach to reduce the waste rate and reassignments significantly while providing fast handoff. Numerical results demonstrate that the proposed approach yields several advantages, including the lowest GOS, the least waste rate, and the least number of reassignments. Meanwhile, the optimal number of rake combiners is also analyzed in this paper. This research was supported in part by the National Science Council of Taiwan, ROC, under contract NSC-93-2213-E-324-018.     

数字电视的条件接收系统

数字电视的兴起使人们能够欣赏到高质量的电视节目,伴随数字电视的成熟,条件接收系统(CAS)得到很好的发展。主要介绍数字电视条件接收系统相关技术的发展、基本功能、安全机制、工作原理及其安全性要求。     

用于高频谐振器的PbTiO_3基压电陶瓷

传统的PZT压电陶瓷的相对介电常数较大,一般为1 000以上,用于高频谐振器不易与线路匹配;而PbTiO3基压电陶瓷的相对介电常数较小,一般仅为200左右,对于10 MHz以上频率的谐振器,用PbTiO3基压电陶瓷作为压电振子是最佳的选择。本文主要研究用于高频谐振器的MnO2和Nd2O3改性PbTiO3基压电陶瓷的性质。PbTiO3基压电陶瓷的性质的改善是与此种陶瓷的制备工艺,显微结构和电导机制紧密相关的。     

Comparative studies on the mechanism of uridine phosphorolysis

We have used quantum mechanical method to study the transition states(TSs) of uridine phosphorolysis reaction. Comparing the four different reaction pathways and the five transition states obtained, we conclude that enzymatic uridine phosphorolysis takes place mainly according to acid-catalyzed SN2 mechanism. The proposed reaction pathway is consistent with many experimental results.