钨的双氮配合物与碘代三甲基硅烷的反应——从配位氮分子形成N-Si键

本文首次报道了配位氮分子与碘代三甲基硅烷反应形成新的N-Si健的结果。钨的双氮配合物cis-CW (N₂)₂ (PMe₂ph) ₄〕与Me₃SiI在500℃反应可得到[WI(N₂SiMe₃)(PMe₂ph₄],又可续一步与HI反应而转化为[WI₂(N₂HSiMe₃)(PMe₂ph)₃]。用X-射线结构分析法确定了后一种配合物的分子结构。结果表明, Me₃Si-基团结合于金属的口一位氮原子上。     

Ba0.95Ce0.8Ho0.2O3-α的离子导电性

用高温固相反应法制备了Ba_0.95Ce_0.8Ho_0.2O_3-α，X–射线衍射表明，该材料为单相钙钛矿型斜方晶结构。以该材料为固体电解质，多孔性铂为电极，用气体浓差电池方法和交流阻抗谱方法分别测定了材料在600 ~ 1000℃温度范围，潮湿氢气、干燥和潮湿的空气中的离子迁移数和电导率，研究了该材料的离子导电性，并与BaCe_0.8Ho_0.2O_3-α作了比较。结果表明，在600 ~ 700 ℃、潮湿氢气中，Ba_0.95Ce_0.8Ho_0.2O_3-α是纯的质子导体，质子迁移数为1；在800 ~ 1000 ℃，是质子和电子的混合导体，质子迁移数为0.97 ~ 0.93。而BaCe_0.8Ho_0.2O_3-α在潮湿氢气中几乎是纯的质子导体，在600 ~ 900 ℃，质子迁移数为1；在1000 ℃，质子迁移数为为0.99。在600 ~ 1000℃温度范围内、干燥的空气中，它们都是氧离子和电子空穴的混合导体，氧离子迁移数分别为0.24 ~ 0.33和0.17 ~ 0.30；在潮湿的空气中，它们都是质子、氧离子和电子空穴的混合导体，质子迁移数分别为0.11 ~ 0.00 和0.09 ~ 0.01，氧离子迁移数分别为0.41 ~ 0.33和0.27 ~ 0.30。在潮湿的氢气和空气中，在600 ~ 800 ℃温度范围内，Ba_0.95Ce_0.8Ho_0.2O_3-α的质子电导率高于BaCe_0.8Ho_0.2O_3-α，但在800 ~ 1000 ℃温度范围内，Ba_0.95Ce_0.8Ho_0.2O_3-α的质子电导率则低于BaCe_0.8Ho_0.2O_3-α。在600 ~ 1000 ℃温度范围内、潮湿和干燥的空气中，氧离子电导率总是高于BaCe_0.8Ho_0.2O_3-α。     

L-半胱胺尾式卟啉铜(Ⅱ)修饰金电极检测苯酚

将制备的L-半胱胺卟啉铜(Ⅱ) (CuL) 配合物自组装在Au电极表面,获得电化学苯酚传感器(CuL/Au).在pH 7.0的磷酸盐缓冲液(PBS)中于-0.4 V～0.5 V (vs. SCE)电位范围内有一对氧化还原峰,峰电位分别为Epa = 0.09 V和Epc = - 0.06 V.实验结果表明CuL能够催化氧化苯酚,通过产物在电位0.1 V下的电化学响应对苯酚进行测定.该电极对苯酚表现出快速的响应(响应时间＜10 s).传感器对苯酚的测定具有较宽的线性范围(5.0×10-7 mol·L-1～2.5×10-4 mol·L-1),检出限为2.0×10-7 mol·L-1.该电极用于地表水中苯酚含量检测,并与标准方法4-氨基安替比林分光光度法作了对照,结果满意.     

铬蓝黑R-示波计时电位法快速测定天然水不同形态铝

报道了采用铬蓝黑R(EBBR)-示波计时电位法分别在酸性和碱性条件下直接检测天然水中的无机单核铝[Ali]和总单核铝[Ala]浓度.并用该法测定了酸消化水样中的总铝[AlT],由[Ala]-[Ali]间接得到有机单核[Alo],[AlT]-[Ala]得到酸溶态铝[Alr],从而实现了水中5种Al形态的电化学测定.实验条件和结果如下在碱性pH=8.0的0.5 mol*L-1 KCl+0.1 mol*L-1 Na2B4O7缓冲溶液中, EBBR切口为Ep1= -0.60 V,加入铝后出现新切口,Ep2=-1.05 V,检测线性范围为5×10-7～7×10-5 mol*L-1,检测下限为2×10-7 mol*L-1,在5× 10-6 mol*L-1 Al时相对标准偏差为4.6% (n=10).分别在酸性和碱性条件下测定了水样中的铝浓度,发现在酸性下测定的是无机单核铝,而在碱性下则是总单核铝(包括无机单核铝和有机单核铝两部分).据此实现了对铝形态的区分,测定了20多个实际水样,与Driscoll方法所获结果进行对照,结果基本一致.     

Ionic Conduction in Ba0.95Ce0.8Ho0.2O3-α

Ba0.95Ce0.8Ho0.2O3-a was prepared by high temperature solid-state reaction. X-ray diffraction （XRD） pattern showed that the material was of a single perovskite-type orthorhombic phase. Using the material as solid electrolyte and porous platinum as electrodes, the measurements of ionic transport number and conductivity of Ba0.95Ce0.8Ho0.2O3-a were performed by gas concentration cell and ac impedance spectroscopy methods in the temperature range of 600---1000 ℃in wet hydrogen, dry and wet air respectively. Ionic conduction of the material was investigated and compared with that of BaCe0.8Ho0.2O3-a. The results indicated that Ba0.95Ce0.8Ho0.2O3-a was a pure protonic conductor with the protonic transport number of 1 during 600---700℃ in wet hydrogen, a mixed conductor of protons and electrons with the protonic transport number of 0.97--0.93 in 800---1000 ℃. But BaCe0.8Ho0.2O3-a was almost a pure protonic conductor with the protonic transport number of 1 in 600---900 ℃ and 0.99 at 1000 ℃ in wet hydrogen. In dry air and in the temperature range of 600---1000 ℃, they were both mixed conductors of oxide ions and electronic holes, and the oxide-ionic transport numbers were 0.24--0.33 and 0.17--0.30 respectively. In wet air and in the temperature range of 600---1000 ℃, they were both mixed conductors of protons, oxide ions and electronic holes, the protonic transport numbers were 0.11--0.00 and 0.09--0.01 respectively, and the oxide-ionic transport numbers were 0.41--0.33 and 0.27--0.30 respectively. Protonic conductivity of Ba0.95Ce0.8Ho0.2O3-a in both wet hydrogen and wet air was higher than that of BaCe0.8Ho0.2O3-a in 600--- 800 ℃, but lower in 900--1000 ℃. Oxide-ionic conductivity of the material was higher than that of BaCe0.8Ho0.2O3-a in both dry air and wet air in 600---1000 ℃.     

S-(-)-α-苯乙胺分子印迹聚合物的制备及性能

以S-(-)-α-苯乙胺为模板,甲基丙烯酸为功能单体,分别以二甲基丙烯酸乙二醇酯、二乙烯基苯为交联剂,偶氮二异丁睛或二苯甲酮为引发剂,采用本体聚合法、悬浮聚合法合成了一系列S-(-)-α-苯乙胺印迹聚合物。利用紫外光谱、平衡结合实验、Scatchard模型等系统地探讨了影响聚合物性能的各种因素。结果表明:悬浮聚合法制备的聚合物性能略优于本体聚合的,其吸附量差别在10%~30%;印迹聚合物对于S-(-)-α-苯乙胺及其结构类似物苯乙酮的分离因子均大于1,最大达到2.86。将印迹聚合物用于α-苯乙胺外消旋体的拆分,分离度达到1.93。     

Heat Capacities and Thermodynamic Properties of Lanthanum/Holmium Perchlorate Complexes with Glycine

IntroductionSinceAnghilerietal.1reportedin 1975thatthecom plexoflanthanumchloridewithglycinehadanti canceref fect,complexesofrareearthwithaminoacidhavebeenex tensivelystudied .Inthepastdecades,about 2 0 0kindsofcomplexesofrare earthcompoundswithaminoacidshavebeensynthesizedandstudied .2 Theycanbeusedasantisepticandanticancerdrugsinmedicine,additivesofanimalforageandfertilizerinagriculture,andwooldyeintextileindus try .3,4 Complexesofrareearthwithaminoacidwerewidelyusedinmanyfields,however,the…     

环境与生物体系中铝形态分析技术的新进展

铝的形态分析是研究环境和生物体系中铝的毒性、生物有效性和传输机理的关键。从IUPAC2000，72，1453和Analyst2001，126(2)对元素形态概念的最新定义，在过去20年来，形态分析都是依据操作手段来进行“组形态”(group species)分析。然而，随着近5年来分析技术的发展，对铝的形态分析逐步达到了“单形态”(individual species)分析的水平。从以下两个方面对该领域的最新进展进行了评述，即：(1)组形态分析(fractionation)：离子交换、电化学分析和流动注射；(2)单形态分析(speciation)：联用技术、核磁共振和计算机拟合。