Controllable synthesis of poly(N-vinylpyrrolidone) and its block copolymers by atom transfer radical polymerization

At room temperature atom transfer radical polymerization (ATRP) of N-vinylpyrrolidone (NVP) was carried out using 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra-azacyclo-tetradecane (Me₆Cyclam) as ligand in 1,4-dioxane/isopropanol mixture. Methyl 2-chloropropionate (MCP) and copper(I) chloride were used as initiator and catalyst, respectively. The polymerization of NVP via ATRP could be mediated by the addition of CuCl₂. The resultant poly(N-vinylpyrrolidone) (PNVP) has high conversion of up to 65% in 3 h, a controlled molecular weight close to the theoretical values and narrow molecular weight distribution between 1.2 and 1.3. The living nature of the ATRP for NVP was confirmed by the experiments of PNVP chain extension. With PNVP-Cl as macroinitiator and N-methacryloyl-N′-(α-naphthyl)thiourea (MANTU) as a hydrophobic monomer, novel fluorescent amphiphilic copolymers poly(N-vinylpyrrolidone)-b-poly(N-methacryloyl-N′-(α-naphthyl)thiourea) (PNVP-b-PMANTU) were synthesized by ATRP. PNVP-b-PMANTU copolymers were characterized by ¹H NMR, GPC-MALLS and fluorescence measurements. The results revealed that PNVP-b-PMANTU presented a blocky architecture.     

双羟基吡喃酮化合物的合成及清除自由基性能

以麦芽酚或乙基麦芽酚为起始原料，经乙酰化、钯碳氢化、羰基α位乙酰氧化和脱乙酰基等4步反应，合成了两种双羟基吡喃酮化合物。利用核磁共振氢谱、碳谱和高分辨质谱对每一步反应产物进了结构表征，优化了合成反应工艺，并通过清除自由基反应对化合物的抗氧化活性进行了测试。结果表明，双羟基吡喃酮化合物对ABTS+?、DPPH?和galvinoxyl?三种自由基清除率分别达到88.9%、83.8%和68.4%，明显高于维生素E和2,6-二叔丁基对甲酚的自由基清除率，表现出优异的抗氧化活性。构效关系研究表明，在吡喃酮结构中引入羟基或增强侧链取代基的给电子能力均能提高化合物清除自由基的能力，为新型抗氧化剂的合成开发提供了参考。     

Kinetics modelling of Fischer-Tropsch synthesis over an industrial Fe-Cu-K catalyst

The kinetic experiments of Fischer-Tropsch synthesis (FTS) over an industrial Fe-Cu-K catalyst are carried out in a micro-fixed-bed reactor under the conditions as follows: temperature of 493-542 K, pressure of 10.9-30.9 bar, H₂/CO feed ratio of 0.98-2.99, and space velocity of 4000-10?000 h⁻¹. The effects of secondary reactions of olefins are investigated by co-feeding C₂H₄ and C₃H₆. A detailed kinetics model taking into account the increasingly proven evidence of the olefin re-adsorption mechanism is then proposed. In this model, different sites are assumed for FTS reactions and water gas shift (WGS) reaction, respectively. Rate expressions for FTS reactions are based on the carbide polymerisation mechanism, in which olefin re-adsorption is considered to be a reverse step of olefin desorption reaction. Rate expression for WGS reaction is based on the formate mechanism. An integral reactor model considering both FTS and WGS kinetics is used to describe the reaction system, and the simultaneous estimation of kinetic parameters is conducted with non-linear regression procedure. The optimal model shows that the rate determining steps in FTS reactions proceed via the desorption of hydrocarbon products and the adsorption of CO and the slowest step in WGS reaction is the desorption of gaseous carbon dioxide via formate intermediate species. The activation energies of FTS reactions and WGS reaction are in good agreement with literature values.     

关于木素生物降解酶类活力测定问题的讨论

由于木素结构和生物降解过程复杂多样，全面测定一个菌株的木素降解活力也比较困难，目前已发现三类主要参与木素降解的酶类（LIP、MnP、漆酶），但至今很少有国际上公认的酶活力测定方法，也未见到能把某一菌株木素降解酶类的活力与其在木质纤维材料中降解木素的能力定量关联的报导。本文综合评述了几类主要的木素降解酶类活力测定方法的作用机制和存在的问题，指出一个菌株的木素降解活力是由它的生理特性和总体代谢能力共同决定的，仅由一类或几类酶活力的表现水平难以对其作出确切的评价，从这个角度出发进行研究才能更客现他认识菌株的木素降解活力．     

A Novel Inorganic Polymer as Cathode Material for Secondary Lithium Batteries

Summary: This paper introduces a new inorganic poly(phosphazene disulfide) material. With unique element composition and molecular structure, the polymer has noncombustible safety and preferable conductivity. When used as cathode material for rechargeable lithium batteries, the polymer's first discharge capacity is as high as 467.9 mAh · g^?1, which can be retained at 409.9 mAh · g^?1 after 60 repeated cycles. Therefore, it has a great application potential in the field of lithium batteries.

Replacement of the Cl atoms by S? S groups by refluxing Na₂S₂ and linear poly(dichloro‐phosphazene).     

Kinetics of Thermal Dehydroxylation and Carbonation of Magnesium Hydroxide

The kinetics of simultaneous dehydroxylation and carbonation of precipitated Mg(OH)₂ were studied using isothermal and nonisothermal thermogravimetric analyses. Specimens were analyzed using X-ray diffraction, transmission electron microscopy, and through measurements of the volume of carbon dioxide evolved in a subsequent reaction with hydrochloric acid. From 275° to 475°C, the kinetics of isothermal dehydroxylation in helium were best fit to a contracting-sphere model, yielding an activation energy of 146 kJ/mol, which was greater than values reported in the literature for isothermal dehydroxylation under vacuum (53–126 kJ/mol). The carbonation kinetics were complicated by the fact that dehydroxylation occurred simultaneously. The overall kinetics also could be fit to a contracting-sphere model, yielding a net activation energy of 304 kJ/mol. The most rapid carbonation kinetics occurred near 375°C. At this temperature, Mg(OH)₂ underwent rapid dehydroxylation and subsequent phase transformation, whereas thermodynamics favored the formation of carbonate. During carbonation, MgCO₃ precipitated on the surface of disrupted Mg(OH)₂ crystals acting as a kinetic barrier to both the outward diffusion of H₂O and the inward diffusion of CO₂.     

P_2O_5和V_2O_5对CaO－Al_2O_3－SiO_2系统玻璃分相与析

Ｐ＿２Ｏ＿５和Ｖ＿２Ｏ＿５对ＣａＯ－Ａｌ＿２Ｏ＿３－ＳｉＯ＿２系统玻璃分相与析晶行为的影响膝立东，陆德明，甘朝亢（山东轻工业学院２５０１００）ＴｈｅＥｆｆｅｃｔｓｏｆＰ＿２Ｏ＿５ａｎｄＶ＿２Ｏ＿５ｏｎｔｈｅＰｈａｓｅｓｅｐａｒａｔｉｏｎａｎｄＣｒｙｓ...     

醋酸-水二元系25——75℃恒温汽液平衡的研究

建立了利用静态法测定溶液蒸气压的装置,它包括平衡器、零压计、水银压差计、脱气室以及高真空设备。在此装置中测定了醋酸-水二元系在25—75℃范围内的蒸气压。为了得到完整的恒温汽液数据,利用我们先前发展的一个直接热力学方法来计算平衡汽相组成,计算时考虑了汽相缔合。本文中用表格形式发表了所得的计算结果。 为了拟合实验数据,用了一个由热力学推导得到的关联活度系数与温度的多项式,多项式参数由最小二乘法求得。利用这些参数,并外推至常压,预测所得泡点和汽相组成与文献报导的恒压实验数据,具有良好地一致。这些参数,可在低压至常压的广阔范围内的实际汽液平衡计算中使用。     

三容系统的解耦神经网络PID控制

三容水箱是常见的非线性强耦合系统,利用一种非线性动态解耦的方法对其进行解耦(其特点是能利用非线性补偿的方式将该类系统各回路输入与输出之间完全解耦),然后采用基于BP神经网络的PID控制策略对其进行控制,并利用MATLAB进行仿真。仿真结果证明解耦的有效性,表明了BP神经网络的PID算法比传统的数字PID具有更强的抗扰动性。     

2000—2020年中国地下水开采时空演变特征EI北大核心CSCD

采用Mann-Kendall趋势检验法、重心模型和标准差椭圆法研究了2000—2020年我国地下水开采时间变化特征、空间分布特征和重心迁移过程。结果表明:2000—2020年我国地下水开采量呈现波动性减少趋势,年均递减率为0.83%;华北地区在严格的地下水开采管理、地下水超采综合治理和南水北调工程共同作用下,地下水开采量得以压减,东北地区和西北地区由于黑龙江、新疆农业经济发展,地下水开采量明显增加;我国地下水开采重心主要分布在河北、山西和内蒙古交界处,有向西北方向偏移的趋势,地下水开采空间分布格局由东北—西南方向逐渐偏转为东—西方向,方向性趋势也更为明显。