新型杂多配合物K3H2[GeW8Mo3VO40]·4H2O的合成与晶体结构

用分步酸化、分步加料法合成出新型杂多配合物K3H2[GeW8Mo3VO40]·4H2O,并用X射线单晶衍射法测定其晶体结构,该晶体属单斜晶系,C2空间群,a＝1.894 4(4)nm,b＝3.292 0(7)nm,c＝1.249 4(2)nm,β＝90.25(3)°,V＝7.792(4)nm3,Z＝6.最终偏差因子R＝0.063.RW＝0.067.     

Synthesis of Poly(isosorbide carbonate) <Emphasis Type="Italic">via</Emphasis> Melt Polycondensation Catalyzed by Ca/SBA-15 Solid Base

Ca/SBA-15 solid bases with different Ca/Si atomic ratios were prepared by a one-pot route and employed as catalysts for the production of poly(isosorbide carbonate) (PIC) from diphenyl carbonate and isosorbide via a transesterification polymerization process. The relationship between physicochemical properties and catalytic performance for Ca/SBA-15 in this melt process was investigated by means of various characterization techniques. It was found that basic site amount and strength were responsible for this transesterification process; the weak and medium basic sites inclined to promote polycondensation reaction. It was worth noting that strong basic sites could favor the decomposition of the resultant PIC, resulting in the decrease of weight-average molecular weight (M_w) and yield, and the sample with Ca/Si atomic ratio of 0.4 exhibited the best catalytic performance, giving PIC with M_w of 4.88 × 10⁴ g/mol and T_g of 169 °C at the optimal conditions. This excellent activity can be ascribed to the presence of rich basic sites and specific basic strength on the surface of 0.4Ca/SBA-15.     

Truxene-based Conjugated Microporous Polymers via Different Synthetic Methods

Four truxene-based conjugated microporous polymers(Tr-CMPs)were prepared via different synthetic methods and their structure-property relationships were studied.The polymer networks have high Brunauer-Emmett-Teller(BET)specific surface areas ranging from 554 m^2·g^–1to 1024 m^2·g^–1.Pore sizes of the CMPs with different linkers are mainly located between 0.60 and 1.96 nm.Among all the Tr-CMPs,TrCMP4 has the highest BET surface area of 1024 m^2·g^–1and exhibits the highest H2 uptake of 0.88 wt%.Tr-CMP2 prepared by Suzuki-Miyaura coupling reaction has the highest photoluminescence quantum yields(PLQYs)of 13.06% and CO2 uptake of 6.25 wt%.     

有机锡催化苯氨基甲酸甲酯分解的研究

对几种锡化合物催化苯氨基甲酸甲酯(MPC)热分解制苯基异氰酸酯(PI)反应进行了研究, 发现二丁基氧化锡具有较高的催化活性. 用HPLC-MS确定了分解的未知副产物为二苯基碳化二亚胺(DPCD). 分析认为生成N,N'-二苯基脲(DPU)和DPCD的反应为合成PI的主要竞争反应. 常压下以Bu₂SnO为催化剂时的适宜反应条件为以邻二氯苯(ODCB)为溶剂, 溶剂用量为MPC用量的15倍(质量比), Bu₂SnO用量为MPC用量的0.075 (摩尔比), 反应时间1 h. 此条件下MPC转化率为85.17%, PI收率为67.65%.     

Synthesis of Poly(isosorbide carbonate) via Melt Polycondensation Catalyzed by Ca/SBA-15 Solid Base

Ca/SBA-15 solid bases with different Ca/Si atomic ratios were prepared by a one-pot route and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a transesterification polymerization process.The relationship between physicochemical properties and catalytic performance for Ca/SBA-15 in this melt process was investigated by means of various characterization techniques.It was found that basic site amount and strength were responsible for this transesterification process;the weak and medium basic sites inclined to promote polycondensation reaction.It was worth noting that strong basic sites could favor the decomposition of the resultant PIC,resulting in the decrease of weight-average molecular weight(Mw)and yield,and the sample with Ca/Si atomic ratio of 0.4 exhibited the best catalytic performance,giving PIC with Mw of 4.88×104 g/mol and Tg of 169°C at the optimal conditions.This excellent activity can be ascribed to the presence of rich basic sites and specific basic strength on the surface of0.4Ca/SBA-15.     

Thermodynamics of the System HNO3-UO2(NO3)2-H2O at 298.15 K

The sorption of ⁶⁰Co, ⁶⁵Zn, ⁷⁵Se, ¹⁰³Pd, ¹¹⁰Ag and ²⁰³Hg radionuclides by polyurethane foam (PUF) was investigated and optimized with respect to the selection of appropriate sorptive medium, metal, thiocyanate ions (except for ¹¹⁰Ag) and PUF concentration and equilibration time. The influence of common anions and cations on the sorption of each metal was examined. The sorption data subjected to different sorption isotherms have shown that the sorption of all the radionuclides followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The sorption capacity intensity and energy were evaluated for each element studied. The variation of sorption with temperature was monitored for all radionuclides except zinc and selenium. The values of H, S and G were estimated and found to be negative indicating exothermic and spontaneous nature of sorption. It was found that PUF is an effective and economical sorbent for traces of metal ions which can be used for the separation/preconcentration of these ions from their very dilute solutions and has useful applications in radioanalytical and environmental chemistry and in radioactive and industrial liquid waste management.     

对生蒴蛤谷胱甘肽转移酶的光谱研究

为深入了解海洋软体生物谷胱甘肽转移酶(GSTs)的性质和特点,以对生蒴蛤肝肠为材料,经GSH亲和层析与反向HPLC分离得到纯化蛋白(adGST),经SDS-PAGE、凝胶过滤与飞行时间质谱分析确定该酶为双亚基组成,全酶分子量50000,亚基为25000.紫外光谱分析表明,该酶在280nm有最大吸收峰;荧光光谱分析表明,该酶的最大激发波长为280nm,在350nm有最大发射峰;用圆二色谱与傅里叶变换红外光谱对该酶进行二级结构测定,结果表明,该酶含有约35%左右的α-螺旋,30%左右的β-折叠,表明该酶属于典型的球状蛋白.