A QM/MM study of a nucleophilic aromatic substitution reaction catalyzed by 4-chlorobenzoyl-CoA dehalogenase

Calculated using a QM/MM method, the free energy profile for the conversion of 4-chlorobenzoate to 4-hydroxybenzoate catalyzed by 4-chlorobenzoyl-CoA dehalogenase indicates the existence of a stable Meisenheimer complex.     

喷水室典型空气处理过程中空气流速的实验研究

针对纺织厂空调系统的核心-喷水室,研究喷水室内处理空气的冷却减湿和等焓加湿两个典型热湿交换过程。提出Re准数对传热传质有显著作用,而Re数的大小取决于流体速度。通过实验研究当空气流速从3m/s提高到5m/s时对喷水室热湿交换性能的影响,从而确定空气流动速度因素对两个热湿交换效率的影响趋势。根据拟合的数学曲线,总结出当空气的流动速度提高后,热湿交换效率相应提高。从而推动高速喷水室在实际工程中的应用。     

Target Syntheses of Two New Bivanadyl Capped Keggin Polyoxometalate Derivatives

Two new bivanadyl capped Keggin polyoxometalate-based inorganic–organic hybrid compounds, [M(2,2′-bipy)₂(H₂O)]₂[AsMo₁₂O₄₀(VO)₂]}(M = Co 1, Zn 2; bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Li₃[AsMo₁₂O₄₀] · nH₂O as starting materials. Single crystal X-ray analysis revealed that compounds 1 and 2 were isostructural, consisting of a neutral bivanadyl capped Keggin POMs bigrafted by [M(2,2′-bipy)₂(H₂O)]²⁺ fragments. Other characterizations by elemental analysis, IR spectra, XPS spectra, power X-ray diffraction and TG analysis were also described in the paper. The study of the electrochemical properties of compounds 1 and 2 exhibit similar redox behaviors, undergoing three two-electron reversible redox processes, and the electrocatalysis of 1 has also been studied in detail. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Solubility and Solution Thermodynamic Properties of 4-(4-Hydroxyphenyl)-2-butanone (Raspberry Ketone) in Different Pure Solvents

The solubility of 4-(4-hydroxyphenyl)-2-butanone (raspberry ketone) in six pure solvents was experimentally determined at temperatures ranging from 283.15 to 313.15 K under the pressure 0.10 MPa by employing a gravimetrical method. The experimental results indicate that the solubility of raspberry ketone in all studied solvents is temperature dependent, a rise in temperature brings about an increase in solubility. The experimental solubility data of raspberry ketone in six pure solvents (acetone, ethanol, ethyl acetate, n-propyl alcohol, n-butyl alcohol, and distilled water) was correlated by using several commonly used thermodynamic models, including the Apelblat, van’t Hoff and λh equations. The results of the error analysis indicate that the van’t Hoff equation was able to give more accurate and reliable predictions of solubility with root-mean-square deviation less than 0.56%. Furthermore, the changes of dissolution enthalpies (Δ_diss H°), dissolution entropies (Δ_diss S°) and dissolution Gibbs energies (Δ_diss G°) of raspberry ketone in the solvents studied were estimated by the van’t Hoff equation. The positive value of Δ_diss H°, Δ_diss S°, and Δ_diss G° indicated that these dissolution processes of raspberry ketone in the solvents studied were all endothermic and enthalpy-driven.     

Enhanced Enzymatic Synthesis of a Cephalosporin,Cefadroclor, in the Presence of Organic Co-solvents

In this study, we investigated the enzymatic synthesis of a semi-synthetic cephalosporin, cefadroclor, from 7-aminodesacetoxymethyl-3-chlorocephalosporanic acid (7-ACCA) and p-OH-phenylglycine methyl ester (D-HPGM) using immobilized penicillin G acylase (IPA) in organic co-solvents. Ethylene glycol (EG) was employed as a component of the reaction mixture to improve the yield of cefadroclor. EG was found to increase the yield of cefadroclor by 15–45%. An investigation of altered reaction parameters including type and concentration of organic solvents, pH of reaction media, reaction temperature, molar ratio of substrates, enzyme loading, and IPA recycling was carried out in the buffer mixture. The best result was a 76.5% conversion of 7-ACCA, which was obtained from the reaction containing 20% EG (v/v), D-HPGM to 7-ACCA molar ratio of 4:1 and pH 6.2, catalyzed by 16 IU mL^?1 IPA at 20 °C for 10 h. Under the optimum conditions, no significant loss of IPA activity was found after seven repeated reaction cycles. In addition, cefadroclor exhibited strong inhibitory activity against yeast, Bacillus subtilis NX-2, and Escherichia coli and weaker activity against Staphylococcus aureus and Pseudomonas aeruginosa. Cefadroclor is a potential antibiotic with activity against common pathogenic microorganisms.     

DYNAMICS MODELING,SIMULATION, AND CONTROL OF ROBOTS WITH FLEXIBLE JOINTS AND FLEXIBLE LINKS$^{\bf 1)}$

本文探究了铰柔性对机器人动力学响应和动力学控制的影响. 首先, 建立由$n$个柔性铰和$n$个柔性杆组成的空间机器人模型, 运用递推拉格朗日动力学方法, 得到柔性机器人系统的刚柔耦合动力学方程. 在动力学建模过程中, 除了考虑杆件的拉伸变形、弯曲变形、扭转变形以及非线性耦合变形对机器人系统动力学行为的影响, 还考虑了铰的柔性对机器人动力学响应和控制的影响. 其中, 柔性铰模型是基于Spong的柔性关节简化模型, 将柔性铰看成线性扭转弹簧, 不仅考虑了铰阻尼的存在, 还考虑了柔性铰的质量效应. 其次, 编写了空间柔性铰柔性杆机器人仿真程序, 研究铰的刚度系数和阻尼系数对系统动力学响应的影响. 研究表明: 随着柔性铰刚度系数的增大, 柔性机器人的动态响应幅值减小, 振动频率变大. 随着柔性铰阻尼系数的增大, 柔性机器人的动态响应幅值减小, 振动幅值的衰减速度变快. 可通过调节柔性铰的刚度和阻尼来减小柔性铰柔性杆机器人的振动, 因此铰阻尼的研究具有重要工程意义. 最后, 研究了铰柔性在机器人系统动力学控制中的影响. 在刚性铰机械臂和柔性铰机械臂完成相同圆周运动时, 通过逆动力学方法求解得到两种情况下的关节驱动力矩. 研究表明: 引入柔性铰会使控制所需的驱动力矩变小, 对机器人控制的影响显著.     

Photochemistry of benzene and quinoxaline fused Δ-1,2,3-triazolines and their trapping products

The benzene and quinoxaline fused Δ²-1,2,3-triazolines 1a and 1b were synthesized in good yields using Knoevenagel condensation and intramolecular 1,3-dipolar cycloaddition as two of the key reactions. Photolysis (254 nm) of Δ²-1,2,3-triazoline 1a or 1b in acetonitrile led to the homolytic cleavage of nitrogen that generated diethyl diazomalonate 7, highly reactive intermediates aziridines 8a,b, and isoindoles B. The latter two species subsequently underwent rearrangement to give the nitrogen extrusion products 9a,b, and polymers. Furthermore, the reactive intermediates were trapped by dienophiles to give the corresponding cycloadducts. Subsequent rearrangement of the N-bridged cycloadducts gave N-substituted pyrrolo[3,4-b]quinoxalines 12b and 15b in 6% and 9% yields, respectively. Irradiation of 1a in the presence of fumaronitrile led to the isolation of cycloadduct 16a with retention of stereochemistry. Thermal reaction of 1b gave more nitrogen extruded product 9b (58-63% yield) than that by photolysis (5-23% yield), which implied that zwitterionic intermediate might be involved in the former.