[Co(3,3-tri)(men)Cl][ZnCl_4]和[Co(3,3-tri)(cmen)Cl][ZnCl_4]两体系配合物的合成及两经式异构体的晶体结构

分别合成了 [Co(3, 3-tri)(men)Cl][ZnCl4]、[Co(3, 3-tri)(cmen)Cl][ZnCl4] (3, 3-tri = N-(3-胺基丙基)-1, 3-丙二胺,men = N-甲基乙二胺,cmen = 1, 2-二胺基-丙烷) 2体系的部分配合物异构体,用单晶 X-射线衍射分析方法解析了2异构体的晶体结构。其中 [Co(3, 3-tri)(men)Cl][ZnCl4] 体系的一异构体Ⅰ的化学简式为 CoCl(C9H27N5)ZnCl4,晶体属正交晶系,空间群 Pca21,a = 16.788(2),b = 7.964(1),c = 14.416(2) 牛琕 =1927.3(4) ?,Dc = 1.747 g/cm3,Z = 4,F(000) = 1032,Mr = 506.91,R = 0.0352,wR =0.0935;[Co(3, 3-tri)(cmen)Cl]2+ 体系的一异构体Ⅱ的化学简式为 CoCl(C9H27N5)ZnCl4稨2O, 晶体属三斜晶系,空间群 P ,a = 9.511(3), b = 9.972(3),c = 11.694(3) 牛琣 = 68.367(5),b = 85.196(6),?= 86.580(5),V = 1026.9(5)?3,Dc = 1.698 g/cm3,Z = 2,F(000) = 536,Mr = 524.92,R = 0.0494,wR = 0.1180。两异构体中 Co3+ 为六配位,晶胞中对映体比例均为1:1。在配合物异构体Ⅰ和Ⅱ中,三元胺以经式排布,三元胺配体(3, 3-tri)仲胺上的氢相对于Cl分别处于顺位(syn-)和反位(anti-);二元胺配体氮(或邻位碳)取代的胺基氮原子(N*)与三元胺配体中的仲氮原子分别处于对位(trans(N*))和邻位(cis(N*))。     

New Temperature Integral Approximate Formula for Non-isothermal Kinetic Analysis

A new approximate formula for temperature integral is proposed. The linear dependence of the new fomula on x has been established. Combining this linear dependence and integration-by-parts, new equation for the evaluation of kinetic parameters has been obtained from the above dependence. The validity of this equation has been tested with data from numerical calculating. And its deviation from the values calculated by Simpson's numerical integrating was discussed. Compared with several published approximate formulae, this new one is much superior to all other approximations and is the most suitable solution for the evaluation of kinetic parameters from TG experiments. This revised version was published online in August 2006 with corrections to the Cover Date.     

Approximate formulae for calculation of the integral òT0Tmexp(-E/RT)dT

Summary In this paper two approximate formulae have been developed for calculation of the integral ò^T₀T^mexp(-E/RT)dT by using integration-by-parts approaches. They are in the following forms: I(m,T) = (RT^m+2)/(E+(m+2)RT)exp(-E/RT) I(m,T) = (RT^m+2)/(E+(m+2)(0.00099441E+0.93695599RT)exp(-E/RT) The validity of the two formulae has been confirmed and their accuracies have been tested with data from numerical calculating. In contrast to existing other integral methods, both the present approaches are simply used, accurate, and can be used for arbitrary values of m.     

液相色谱-串联质谱法检测雄蜂蛹粉中50种抗生素残留

建立了液相色谱-串联质谱检测雄蜂蛹粉中50种抗生素残留（大环内酯类、喹诺酮类、磺胺类、四环素类、硝基咪唑类、林可霉素和氯霉素）的方法。样品经高氯酸溶液和醋酸铅溶液提取沉淀蛋白质，清液用磷酸氢二钾溶液调节pH值至8，经固相萃取净化后进行仪器分析。采用多反应监测正离子或负离子模式检测，可以一次完成对雄蜂蛹粉中50种目标化合物的定性和定量测定。50种抗生素的加标回收率为70.2%~118.3%，相对标准偏差（RSD）为1.8%~13.6%。该方法操作简便，灵敏度高，适用于雄蜂蛹粉中多种兽药残留的分析确证。     

Characterization of proteins separated by displacement chromatography using low angle laser light scattering photometry

Summary -Lactoglobulin A and B (-LACT) were separated by displacement chromatography (DSC) on an ionexchange column using dextran sulfate as the displacer. A LALLS photometer and a UV detector, in series, were used to determine the molecular weight (MW) of the proteins, on-line. The results indicate that both, -LACT A and B, were present as dimers in the buffer used for the mobile phase. The MWs of the proteins were about 6–8% higher than the theoretical MW of a dimer (37,000). Additional control studies have shown the presence of a high molecular weight species in both the proteins, which could possibly be an aggregate. This species was observed in the LALLS signal but was nearly absent in the UV signal. Our work has demonstrated the feasibility of interfacing LALLS with displacement chromatography for detecting impurities or aggregates which may be difficult to detect by conventional detectors used for chromatography.     

流动注射微柱预分离富集荧光光度法测定肥料中的铈

用抗坏血酸将Ce(Ⅳ)还原为Ce(Ⅲ),以多聚磷酸钠作为增强剂,建立了铈的流动注射荧光分析法,考查了各种因素对测定Ce的影响.此方法线性范围为2.0×10-9～1.2×10-8 g·ml-1.采用流动注射微柱预分离富集测定了GBW07602标样和氨基酸微肥中的铈含量.测定结果与推荐值有良好的一致性.     

锂离子筛的制备及其交换性能研究

用浓度为0.5mol/L的盐酸对高温固相合成的前体LiMn2O4进行酸洗脱锂,制得锂离子筛HMn2O4,并在不同pH值和温度下进行了Li 交换性能的研究,同时运用XRD和TEM进行了相应表征。结果表明,锂离子筛吸附交换前后晶体结构只发生了细微变化,但都仍为尖晶石型结构;交换反应在前10min速率最快,约20min就趋于平衡;Li 交换总量随pH值增大而升高,其中pH=7时交换容量为18.5526mg/g;Li 交换量和交换选择性随温度的升高而显著增强。     

5C + 1S] annulation: a facile and efficient synthetic route toward functionalized 2,3-dihydrothiopyran-4-ones

[reaction: see text] A facile and efficient synthetic route toward highly substituted 2,3-dihydrothiopyran-4-ones 2 has been developed via a formal [5C + 1S] annulation of readily available alpha-alkenoyl ketene-(S,S)-acetals 1 with sodium sulfide nonahydrated salt (Na2S x 9H2O) and utilized in the synthesis of 2-(4-chlorophenyl)-6-(morpholin-4-yl)-4H-thiopyran-4-one 5l, an inhibitor of DNA-dependent protein kinase (DNA-PK).     

Valence Bond Study of Dissociation Behavior and Spectroscopic Constants for the Ground States of LiF and NaF

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端羟丁腈聚氨酯/聚甲基丙烯酸甲酯互穿网络高聚物的T_g和形态研究——Ⅰ.组分比和交联程度的影响

用同步法合成了端羟丁腈聚氨酯/聚甲基丙烯酸甲酯互穿网络高聚物[PU(HTBN)/PMMA-IPN]。用动态力学方法和透射电镜研究了它们的T_(?)转变行为和形态。理论计算和实验结果表明,样品具有两个明显相互分离但又各自连续的相结构,呈现出分属于组分聚合物的两个Tg转变(Tg_1,Tg_2)。在全IPN中,PMMA相区的尺寸(1000—2000?),比在接枝共聚物(3000—6000?)和半IPN(—3000?)中的明显变小。适当的交联程度可使相区进一步变小,变均匀,相连续性增加。这是网络互穿造成的“强迫互容”所致。部分丁腈羟(HTBN)分子同PMMA的反应,使一些样品出现了Tg_2升高的现象。