金属簇合物[(n-Bu)4N]3[WS4Ag3X3Br](X=Cl,Br,I)的热行为和热分解反应动力学

用TG-DTG-DTA联用技术研究了金属簇合物[(n-Bu)₄N]₃[WS₄Ag₃X₃Br](X=Cl,Br,I)在动态氮气气氛中的热行为和热性质,通过对热分解过程中各步反应中间体的元素分析跟踪,判断了相应的分解组分;并结合其物质结构进行了讨论。对各步反应进行了动力学分析,并通过活化能和反应进程的依赖关系探讨了反应的复杂性。     

基于聚硫堇膜对DNA杂交的直接电化学检测

In this work, the application of a conducting polymer, poly（thionine）, modified electrode as matrix to DNA immobilization as well as transducer to label-free DNA hybridization detection was introduced. The electropolymerization of thionine onto electrode surface was carried out by a simple two-step method, which involved a preanodization of glassy carbon electrode at a constant positive potential in thionine solution following cyclic voltammetry scans in the solution. Electrochemical detection was performed by differential pulse voltammetry in the electroactivity potential domain of poly（thionine）. The resulting poly（thionine） modified electrode showed a good stability and electroactivity in aqueous media during a near neutral pH range. Additionally, the pendant amino groups on the poly（thionine） chains enabled poly（thionine） modified electrode to immobilize phosphate group terminated DNA probe via covalent linkage. Hybridization process induced a clear decrease in poly（thionine） redox current, which was corresponding to the decrease in poly（thionine） electroactivity after double stranded DNA was formed on the polymer film. The detection limit of this electrochemical DNA hybridization sensor was 1.0 × 10^-10mol/L. Compared with complementary sequence, the hybridization signal values of 1-base mismatched and 3-base mismatched samples were 63.9% and 9.2%, respectively.     

多孔线性控制套筒致裂效果影响因素分析

针对坚硬难垮落顶板弱化问题,在分析多孔线性控制套筒致裂机理的基础上,建立700mm×300mm×400mm试块。通过套筒致裂压力及钻孔孔壁周围应变变化情况,分析孔壁周围应力大小、分布及应力集中现象,研究钻孔直径、孔间距、套筒致裂压力对应力集中现象的影响,同时分析这三者对裂纹扩展方向的影响,得出套筒致裂最优法。试验结果表明:(1)套筒致裂效果受钻孔直径、孔间距和套筒压力等综合因素影响,采用大直径、大间距的布孔方式可获得较好的致裂效果;(2)多孔线性控制致裂试验的张性裂缝扩展方向主要沿着各钻孔中心连线方向;(3)钻孔直径30mm、间距300mm的试块致裂压力为18.6MPa,远大于顶板岩体抗拉强度,将套筒致裂法应用于顶板弱化是可行的。本研究对解决采空区坚硬顶板大面积悬顶具有理论意义和应用价值。     

高效阴离子交换色谱-脉冲安培检测法同时测定生物转化样品中的海藻糖、葡萄糖和麦芽糖

建立了高效阴离子交换色谱-脉冲安培电化学检测法同时测定生物转化样品中海藻糖、葡萄糖和麦芽糖的分析方法。选用CarboPac^TM10色谱柱(250 mm×2 mm)对分离条件进行优化,使用标准样品测定了线性范围和工作曲线,柱温为30 ℃,流速为0.30 mL/min,以氢氧化钠溶液和醋酸钠溶液为流动相进行梯度洗脱,脉冲安培法进行检测。研究结果表明,该方法可在15 min内实现海藻糖生物转化液中3种糖的快速定量分析。海藻糖、葡萄糖和麦芽糖峰面积与质量浓度的线性关系良好,检出限为0.010~0.100 mg/L。将此方法用于酶法制备海藻糖的检测,加标回收率为89.40%~103.2%。在生物转化样品中检测到海藻糖浓度为101.084 g/L,转化率达到了50.5%。该方法灵敏度高,简便快速,可应用于海藻糖制备样品中各种成分的分离和定量检测。