GROUP TRANSFER POLYMERIZATION OF ETHYL ACRYLATE WITH LEWIS ACID CATALYST

This paper reports the kinetics of group transfer polymerization (GTP)of ethyl acrylate (EA)with zinc iodide catalyst in 1,2-dichloroethane using dimethyl ketene methyl trimethylsilyl acetal (MTS) as initiator at 0℃ and above 0℃. The amount of catalyst used was studied. When zinc iodide catalyst used is more than 10mol% relative to monomer, the rate of polymerization is proportional to the concentration of monomer, whereas zinc iodide catalyst used is less than 10 mol% of the monomer, the rate of polymerization is independent of the monomer concentration.In the GTP of EA an induction period was observed when the zinc iodide contents are less than l0mol%. If the reaction temperature is over 0℃, living species become unstable and diminish, leading to incomplete monomer conversion. The reaction curves equations are obtained. The polymers have narrow molecular weight distributions which are not changed as decreasing zinc iodide contents. The polydispersity is about 1.2.

THE CONTROL OF POLYMETHACRYLATE MOLECULAR STRUCTURE BY GROUP TRANSFER POLYMERIZATION

INTRODUCTION Group transfer polymerization (GTP) is a method for controlling the structure of acrylic polymers in which reactive chain ends are covalentiy bound to a trimethylsilyl group. In the presence of a catalyst, monomer inserts into these chain ends between the silyl group and the last monomer unit. The process is illustrated by equation (1) for methyl methacrylate. GTP is a living polymerization, i. e., there is little or no chain termination and no chain transfer. A significant advantage of GTP is that it

NON-ACETAL INITIATORS FOR GROUP TRANSFER POLYMERIZATION

It is reported that a variety of trimethylsilyl enol ethers of ketones and aldehydes can be used to initiate GTP of methacrylates and acryl- ates.The new initiators are easy to prepare from ketones or aldehydes.PMMA and PMA with controlled molecular weight and low polydispersity were obtained by using non-acetal initiators in the presence of bibenzoate,bifluo ide or Hgl_2,The living nature of polymerization is shown by the correspondence of theoretical and observed molecular weight and the preparation of A-B-A type triblock copolymer with methacrylate and acrylate segments can be prepared.

Quantum hydrogen tunneling promoting halogen-atom and group transfer chemistry

A quantum-hydrogen-tunneling-controlled halogen-atom and group transfer strategy has been successfully developed to generate carbon radicals by using the substituted cyclohexadiene as the abstractor under mild photochemical conditions,in which alkyl and aryl halides as well as numerous alcohol and thiol analogues can be activated.Mechanism investigation unveiled that this process is inhibited from thermodynamic and kinetic effects but is rendered successful through quantum tunneling.

A novel approach to authenticated group key transfer protocol based on AG codes

Group key management technique is a fundamental building block for secure and reliable group communication systems.In order to successfully achieve this goal, group session key needs to be generated and distributed to all group members in a secure and authenticated manner.The most commonly used method is based on Lagrange interpolating polynomial over the prime field F p={0,1,2,…, p-1}. A novel approach to group key transfer protocol based on a category of algebraic-geometry code is presented over the infinite field GF(2 m). The attractive advantages are obvious. Especially, the non-repeatability, confidentiality, and authentication of group key transfer protocols are obtained easily. Besides, a more generalized and simple mathematical construction model is proposed which also can be applied perfectly to related fields of information security.

The Transfer Ideal under the Action of a Nonmetacyclic Group in the Modular Case

Let Fq be a finite field of characteristic p (p ≠2) and V4 a four-dimensional Fq-vector space. In this paper, we mainly determine the structure of the transfer ideal for the ring of polynomials Fq[V4] under the action of a nonmetacyclic p-group P in the modular case. We prove that the height of the transfer ideal is 1 using the fixed point sets of the elements of order p in P and that the transfer ideal is a principal ideal.

Twisted Intramolecular Charge Transfer in Polydimethylsilylene Bearing Pyrenyl Groups

Polydimethylsilylenes bearing pyrenyl groups exhibit emissions fromtwisted intramolecular charge transfer state between the aromatic ring and thesilicon backbone both in polar and nonpolar solvents.

Lie group analysis for thermophoretic and radiative augmentation of heat and mass transfer in a Brinkman-Darcy flow over a flat surface with heat generation

A boundary layer analysis is presented to investigate numerically the effects of radiation, thermophoresis and the dimensionless heat generation or absorption on hydromagnetic flow with heat and mass transfer over a flat surface in a porous medium. The boundary layer equations are transformed to non-linear ordinary differential equations using scaling group of transformations and they are solved numerically by using the fourth order Runge-Kutta method with shooting technique for some values of physical parameters. Comparisons with previously published work are performed and the results are found to be in very good agreement. Many results are obtained and a representative set is displayed graphically to illustrate the influence of the various parameters on the dimensionless velocity, temperature and concentration profiles as well as the local skin-friction coefficient, wall heat transfer, particle deposition rate and wall thermophoretic deposition velocity. The results show that the magnetic field induces acceleration of the flow, rather than deceleration （as in classical magnetohydrodynamics （MHD） boundary layer flow） but to reduce temperature and increase concentration of particles in boundary layer. Also, there is a strong dependency of the concentration in the boundary layer on both the Schmidt number and mass transfer parameter.

Empirical Study on the Will of Farmland Transfer among Different Farmer Groups——A Sampling Survey on 42 Counties and Cities,64 Towns and 74 Villages in Jiangxi Province

Taking Jiangxi Province as an example,on the basis of the sampling survey on 42 counties and cities,64 towns and 74 villages in Jiangxi Province,the will of farmland transfer among different farmer groups with different income levels,different ages,and different educational backgrounds,is analyzed.The research indicates that as for middle-income or high-income groups,leaving home to seek jobs elsewhere is the most principal factor impacting farmland transfer,while as for low-income group,the price of agricultural products is an important factor impacting farmers’ land cultivation;permanent urban residence certificate is no longer the principal factor causing farmers’ land transfer,and it tends to be rational for farmers to abandon farmland.

基于高质量发展的学科备课组内部知识转移的路径分析

学科备课组是教学研究的战斗力基础,也是“三新”背景下教育高质量发展的有生力量,其内部知识的转移是中学高质量发展链条中的重要一环。重塑备课组团队精神、构建具有教师专业学习共同体表征的学科备课组、组织教研活动等,有利于促进学科备课组内部知识转移,为教师专业发展赋能,有效提升教学质量,进而促进教育高质量发展。

基于ISM-SD的地下洞室群施工进度风险传递路径研究

针对水电工程地下洞室群施工进度风险存在传递问题,提出了基于解释结构模型(ISM)和系统动力学(SD)的地下洞室群施工进度风险传递路径分析方法。根据地下洞室群的施工特点,建立了地下洞室群施工进度风险指标体系;结合风险传递机理,运用解释结构模型分析风险因素间传递关系,建立了风险因素传递矩阵,并总结归纳出风险因素关系对照表,通过系统动力学分析风险因素间传递路径,揭示了施工进度风险传递路径网络;集成ISM-SD构建了地下洞室群施工进度风险传递路径分析模型,并结合西南地区某大型水电站地下洞室群工程进行分析。结果表明,该方法可有效识别施工进度风险重要因素和关键传递路径,为地下洞室群施工进度风险管理提供了决策依据。

提升“专转本”计算机专业综合操作技能的探索与研究

探索在“专转本”计算机专业综合操作技能教学中,如何消除学生心理困扰,进行升学与就业的职业规划,寻找有效的学习方法,实践基于PBL的分组教学方法,既提升学生的计算机专业综合操作技能,也进一步提高学生“专转本”考试的升学率和职业专业技能与素养。

基于修正非线性薛定谔方程的三维聚焦波组波谱演化

为了研究深水三维聚焦波的定向演化,对4阶修正非线性薛定谔方程(MNLSE)、3阶非线性项薛定谔方程(NLSE)以及线性方程等3种演化模型进行数值求解,并对生成的波谱特征以及其演化过程中的能量转移、波陡变化、平均波数变化以及带宽变化等特征进行对比研究。研究结果表明:在2种非线性演化模型的演化过程中均存在能量向高波数和低波数的转移,导致波浪波形发生变化,且非线性还会影响聚焦波陡、聚焦波组达到聚焦所需时间以及带宽等参数的变化;上述特征在2种非线性演化模型中存在着显著差异,4阶MNLSE演化下的三维聚焦波组特征优于3阶NLSE的演化。

基于迁移学习和3D-WGMobileNet的青年抑郁症辅助诊断

提出一种基于3D-WGMobileNet和迁移学习的网络模型,实现对青年抑郁症不同阶段患者的正确分类。首先,对功能磁共振成像(fMRI)数据进行预处理,并通过局部一致性分析将4D fMRI数据转换为3D,进行降维处理。然后,使用迁移学习方法将阿尔茨海默症的特征迁移到提出的3D-WGMobileNet中。利用动态分组卷积构建卷积核的专家权重矩阵,提高模型的表达能力;利用滑窗分组卷积来压缩模型的参数量,增强模型的计算能力。最后,利用3D-WGMobileNet对抑郁症患者图像进行特征提取和分类。在人类连接组项目数据库上的实验结果表明结合迁移学习、动态分组卷积和滑窗分组卷积的3D-WGMobileNet获得较好的分类效果,其中,抑郁症和健康对照组、轻度抑郁症和健康对照组、轻度抑郁症和中度抑郁症的分类准确率分别达到89.00%、85.15%、87.90%,证明本文方法的可行性和有效性。

Density Functional Theory Study on the Histidine-assisted Mechanism of Arylamine N-Acetyltransferase Acetylation

Arylamine N-acetyltransferases （NATs, EC 2.3.1.5） catalyze the N-acetylation of primary arylamines, and play a key role in the biotransformation and metabolism of drugs, carcinogens, etc. In this paper, three possible reaction mechanisms are investigated and the results indicate that if the acetyl group directly transfers from the donor to the acceptor, the high activation energies will make it hard to obtain the target products. When using histidine to mediate the acetylation process, these energies will drop in the 15-45 kJ/mol range. If the histidine residue is protonated, the corresponding energies will be decreased by about 35-87 kJ/mol. The calculations predict an enzymatic acetylation mechanism that undergoes a thiolate-imidazolium pair, which agrees with the experimental results very well.

Molecular Dynamics and Combined QM/MM Studies on the Deactivation of anti-Tubercular Drug Isoniazid by Arylamine N-Acetyltransferases

Both a molecule dynamic study and a combined quantum mechanics and mole-cule mechanics（QM/MM） study on the acetylating deactivation mechanism of isoniazid were presented.This type of reaction was catalyzed by arylamine N-acetyltransferases（NATs） and the results strongly support a direct acetyl group transfer process rather than a stepwise one.The isoniazid was strictly restrained in proper relative position to accept the acetyl group by a Hydrogen-bond network formed by the residues at the active center.The residues,His110 and Cys70,would be functioned as ＇general base＇ rather than ＇general acid＇.If all the residues（including H2O molecules） were removed from the system,the activation energy will be increased from 145.1 to 243.3 kJ/mol.The calculations met the experimental data with good agreement.

Iron phthalocyanine-catalyzed radical phosphinoylazidation of alkenes:A facile synthesis of β-azido-phosphine oxide with a fast azido transfer step

Phosphinoylazidation of alkenes is a direct method to build nitrogen-and phosphorus-containing compounds from feed-stock chemicals.Notwithstanding the advances in other phosphinyl radical related difunctionalization of alkenes,catalytic phosphinoylazidation of alkenes has not yet been reported.Here,we describe the first iron-catalyzed intermolecular phosphinoylazidation of styrenes and unactivated alkenes.The method is practically useful and requires a relatively low loading of catalyst.Mechanistic studies confirmed the radical nature of the reaction and disclosed the unusually low activation energy 4.8 kcal/mol of radical azido group transfer from the azidyl iron(III)phthalocyanine species(PcFeulN3)to a benzylic radical.This work may help to clarify the mechanism of iron-catalyzed azidation,inspire other mechanism studies and spur further synthetic applications.

探析生物炭对Anammox工艺脱氮的影响及其机理

厌氧氨氧化(Anammox)因其高效率和低能耗的特点,被认为是当下最有前景的生物脱氮技术。但是,Anammox工艺在主流污水处理中的应用仍面临挑战,比如厌氧氨氧化菌倍增时间长、对生长环境要求苛刻、电子受体不易获得、生物质易随水流流失等。近年来,生物炭作为一种廉价易得、具有大比表面积、表面富含官能团的环境友好型载体,在促进Anammox脱氮工艺方面受到越来越多的关注。文中从制备方法对生物炭的影响出发,总结不同生物炭类型作为Anammox脱氮工艺生物载体的特点,并通过回顾前人的研究,尝试分析生物炭作为生物载体在Anammox脱氮工艺中缩短启动时间、提高脱氮性能和减轻污染物抑制方面的作用,以期为生物炭在Anammox脱氮工艺中的大规模应用提供参考。

基于格子Boltzmann方法的地埋管管群换热的模拟研究

土壤结构和地下水通常会影响地埋管换热器的传热,本文将利用随机四参数生成法建立双分布函数格子Boltzmann模型,对有渗流条件下地埋管管群换热器与饱和土壤多孔介质的换热情况进行了模拟,分析了影响埋管外土壤平均温度的主要因素。研究表明,土壤热传导特性主要受土壤孔隙度、地下水渗流速度和土壤骨架导热系数k s的影响。本文的研究结论对考虑土壤渗流的地下换热器的设计具有一定的指导意义。

含相变材料的充填体内置采热管群热压性能研究

通过将采热管群与充填采矿技术相结合可提取矿井中的地热能,有效缓解高地热带来的热害问题。本文以采热管群为研究对象,分析了充填体放热过程中传热流体的温度、速度和压力分布,讨论了雷诺数、管径、管间距和管排方式对采热管群性能的影响。结果表明:当雷诺数从100增加到5000时,换热量从2.24×10^(3)kJ增加到16.78×10^(3)kJ,综合评价因子从0.087增加到1.31。当管径从4 mm增加到6 mm时,换热量从15.07×10^(3)kJ增加到17.11×10^(3)kJ,综合评价因子从1.157增加到1.388。当管间距从130 mm增加到170 mm时,换热量从14.24×10^(3)kJ增加到16.25×10^(3)kJ,综合评价因子从1.013增加到1.263。此外,四路并联布置可以保证较高的换热量和较低的压降,从而获得较高的综合评价因子。该研究为充填体中采热管群的设计和优化提供了理论参考。