（C5H7S2）3[Bi2Cl9）]的合成和晶体结构

标题化合物由ＢｉＣｌ３和乙酰丙酮在ＨＣｌ（气）／Ｃ２Ｈ５ＯＨ溶剂中通入Ｈ２Ｓ气体反应而得。晶体属四方晶系，Ｍｔ＝１１３０．７６，空间群Ｐ４１２１２。晶胞参数ａ＝ｂ＝８．８６７（２），ｃ＝４１．５１１（４）Ａ；Ｖ＝３２６４（１）Ａ＾３，Ｚ＝４，Ｄｃ＝２．３０ｇｃｍ＾－３，μ（ＭｏＫａ）＝１１８．６０７ｃｍ＾－１，Ｆ（０００）＝２１０４．晶结构由重原子法求得。最终偏离因子Ｒ＝０．０７２。晶体由分立的（     

（C_5H_7S_2）_3〔Bi_2Cl_9〕的合成和晶体结构

标题化合物由ＢｉＣｌ３和乙酰丙酮在ＨＣＩ（气）／Ｃ２Ｈ５ＯＨ溶剂中通入Ｈ２Ｓ气体反应而得。晶体属四方晶系，Ｍｒ＝１１３０．７６，空间群Ｐ４１２１２。晶胞参数ａ＝ｂ＝８．８６７（２），ｃ＝４１．５１１（４）Ａ；Ｖ＝３２６４（１）Ａ３，Ｚ＝４，Ｄｃ＝２．３０ｇｃｍ（－３），μ（ＭｏＫα）＝１１８．６０７ｃｍ（－１），Ｆ（０００）＝２１０４．晶体结构由重原子法求得。最终偏离因子Ｒ＝０．０７２。晶体由分立的（Ｃ５Ｈ７Ｓ２）＋阳离子和［Ｂｉ２Ｃｌ９］３－阴离子组成。每个Ｂｉ原子和６个Ｃｌ原子形成畸变的八面体配位。２个［ＢｉＣｌ６］八面体共面构成具有２次轴对称的［Ｂｉ２Ｃｌ９］（３－）配阴离子。还讨论了阳离子种类对Ｂｉ配阴离子结构类型的影响。     

钙—亚硫酰氯电池的研究

应用交流阻抗，恒电流，ＳＥＭ等方法，研究了Ｃａ－ＳＯＣｌ２电池中ＣａＣｌ２（ＳＥＩ）膜的性质，不同电解质和添加剂对电极性的影响，结果表明，ＣａＣｌ２ＳＥＩ膜在阳极反应电阻下降，ＣｕＣｌ２，ＣｕＢｒ２可改变ＣａＣｌ２沉积形态，提高阴极性能，组装的Ｃａ－ＳＯＣｌ２电池可高速率放电，在５０ｍＡ．ｃｍ＾－２的条件下，达到了１７．５ｍＡｈ．ｃｍ＾－２。     

大核镉硫簇合物的研究：（Ⅱ）两个八核镉在充簇合物的合成与晶体结构

利用ＣＳ２与镉硫化合物在溶剂中反应产生Ｓ＾２－来合成大核镉硫簇合物，得到了两个新的大核镉硫簇合物，并测定了其晶体结构，化合物（Ⅰ）为（Ｍｅ４Ｎ）２［ＳＣｄ８（ＳＰｈ）１２Ｃｌ４］，晶体属立方晶系，空间群Ｐａ３，ａ＝２６．７８２（３）Ａ，Ｖ＝１９２１１（４）Ａ＾３，Ｄｃ＝１．７５０ｇ／ｃｍ＾３，Ｚ＝８．１６３７个衍射点参与修正，Ｒ＝６．９６％，化合物（Ⅱ）为［Ｃｄ（Ｈ２Ｏ）６］［ＳＣｄ８（ＳＰｈ）１     

钇与丙氨酸配合物[Y（Ala）（H2O）6]Cl3的合成,表征及晶体结构

合成了钇人氨酸配合物的单晶，用Ｘ射线衍射法了配合物单晶的结构，化学式为「Ｙ（Ａｌａ）（Ｈ２Ｏ）６」Ｃｌ３。的晶体属单斜晶系，Ｐ２１／ｃ空间群，晶胞参数：ｄ＝０．８４４３（２）ｎｍ，ｂ＝１．５６５８（３）ｎｍ，ｃ＝１．１３５９（２）ｎｍ，β＝１０２．０９（２），Ｖ＝１．４６８４（５）ｎｍ＾３，Ｚ＝４，ＤＣ＝１．７７５ｇ／ｃｍ＾３，Ｙ＾３＋的配位数为８，其配位多面丛为三角十二面体。通过元素分析、红外光     

[NEt4][CoCl3(PPh3)]的合成和晶体结构

标题化合物是反应体系（ＮＨ４）３ＶＳ４／ＣｏＣ２（ＰＰｈ３）２／ＮＥｔ４Ｃｌ在ＣＨ２ＣＩ２中反应而得到的,单晶Ｘ射线结构分析表明其晶体地立方晶系,化学式为Ｃ２６Ｈ３５ＮＣｌ３ＣｏＰ,空间群为Ｐａ３,Ｍｒ＝５５７．８４,ａ＝１７．８０７（５）,Ａ,Ｖ＝５６４６．４Ａ＾３,Ｚ＝８,Ｄｃ＝１．３１ｇ／ｃｍ＾３,Ｆ（０００）＝２３２８,μ（ＭｏＫａ）＝９．６ｃｍ＾－１,Ｒ＝０．０６２,Ｒｗ＝０．０６７,标     

Eu^3＋,Bi^3＋Me2Y8（SiO4）6O2中的发光特性与取代格位

在紫外光激发下，Ｅｕ＾３＋和Ｂｉ＾３＋在Ｍｅ２Ｙ８（ＳｉＯ４）６Ｏ２基质（Ｍｅ＝Ｍｇ，Ｚｎ，Ｃａ，Ｓｒ）中分别发射红光（＾５Ｄ０－＾７Ｆ２）和蓝光（＾３Ｐ１－＾１Ｓ０）．Ｅｕ＾３＋发光的红橙比随着激发波长和Ｍｅ＾２＋的不同而变化。荧光拉曼光谱表明，Ｅｕ＾３＋在四种基质中同时占据了４ｆ格位和６ｈ格位。依据Ｂｉ＾３＋发光的Ｓｔｏｋｅｓ位移推断，当Ｍｅ＝Ｃａ，Ｚｎ时，Ｂｉ＾３＋主要占据４ｆ格位，而当Ｍｅ     

PTFE—乙醚柱反相萃取层析连续分离和测定镓（Ⅲ）铟（Ⅲ）的研究

研究了在抗坏血酸存在下的６ｍｏｌ／Ｌ ＨＢｒ介质作流动相，以ＰＴＦＥ（聚四氟乙烯）负载的乙醚作固定相，反相萃取层析使微量Ｇａ（Ⅲ），Ｉｎ（Ⅲ）与Ｆｅ＾３＋、Ｔｌ＾３＋、Ｍｏ＾６＋、Ａｕ＾３＋、Ｔｉ＾４＋、Ｂｉ＾３＋、Ａｌ＾３＋、Ｍｇ＾２＋、Ｃａ＾２＋、Ｎｉ＾２＋、Ｃｏ＾２＋、Ｃｄ＾２＋、Ｚｎ＾２＋、Ｐｂ＾２＋、Ｃｕ＾２＋等多种离子分离。留于柱上的铟、镓分别用ＨＣｌ（４ｍｏｌ／Ｌ）－Ｈ２Ｏ２（３％）     

（四甲基二硅撑）双（3—三甲硅基环戊二烯基）—四羰基二铁…

标题化合物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２〕２／（μ－ＣＯ）２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ２Ｃｌ、ＣｌＣＨ２ＣＯＯＣ２Ｈ５和Ｐｈ３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２Ｒ〕２（Ｒ：Ｍ     

平衡移动测定MmRn型配合物组成和稳定常数的研究

根据平衡移动原理推导出一种有判别单核或多核配合物并直接测定ＭｍＲｎ型配合物和稳定常娄的平衡移动法公式ｌｇ（Ａｉ／（Ａｍａｘ－Ａｉ）＾ｍ）＝ｎｌｇｃＲ＋ｌｇ（ｍ．β．（ＣＭ／Ａｍａｘ）＾（ｍ－１）。用ＳＣ３＋＝ＣＰＡⅢ和Ｆｅ＾３＋ＣＡＳ两个配合反应体系加以验证，结果令人满意。     

A confocal study of mechanism of 5-hydroxytryptamino induced intracellular calcium dynamics in cultured rat stomach fundus smooth muscle cells with a new Ca2+ indicator STDln-AM

A new fluorescent Ca²⁺ indicator STDln-AM for detecting [Ca²⁺], transients in cultured smooth muscle cells is presented. By making a comparison, the difference between STDln and fluo-3 is discussed in detail. Using the new Ca²⁺ indicator, the mechanism of 5-hydroxytryptamino (5-HT) induced intracellular calcium dynamics in stomach fundus smooth muscle cells (SFSMC) of rats is investigated. It is shown that in contrast with fluo-3, STDln is uniformly distributed in the cytosolic compartment but excluded from the nucleus, when it is transfected into cells. This feature makes it a real cytosol Ca²⁺ indicator and can reflect changes of cytosol [Ca²⁺] more accurately than that of fluo-3. In addition, STDln responds to the [Ca²⁺], transients more sensitive and faster than fluo-3. The results also show that, the L-type Ca²⁺ channel inhibitor Mn9202 and the PLC inhibitor Compound 48/80 can significantly inhibit the [Ca²⁺], elevation induced by 5-HT, while the PKC inhibitor D-Sphingosine can enhance the effect of 5-HT. The results suggest that 5-HT acts by the way of 5-HT₂ receptors on SFSMC, then through 5-HT₂ receptors coupled IP₃/Ca²⁺ and GC/PKC double signal transduction pathways to make Ca²⁺ release from intracellular Ca²⁺ stores and Ca²⁺ influx possibly through L-type calcium channels.     

八肋游仆虫中心蛋白N-端半分子与Tb3+，Ca2+的结合

用分子生物学方法表达、纯化了游仆虫中心蛋白及N-端半分子，用铽荧光探针法、离子竞争法研究了pH 7.4，0.01 mol· L^-1 Hepes条件下中心蛋白与铽、钙的结合性质。结果表明中心蛋白有4个铽结合部位，其中2个为高亲合结合部位、2个为低亲合结合部位。具有2个低亲合结合部位的中心蛋白半分子与铽结合的条件常数是(2.13±0.10)×10⁵ L·mol^-1，与钙结合的条件常数是(7.52±0.02)×10² L·mol^-1。     

Effects of BaCl<Subscript>2</Subscript> on slow vacuolar ion channels on radish by patch-clamp

The effects of BaCl₂ on slow vacuolar (SV) currents of radish are studied by using the whole-vacuolar patch-clamp recording mode. The Ca²⁺-dependent SV channel can be activated by cytosolic Ca²⁺. When 1 mmol/L BaCl₂ is added into pipette solution, SV currents are suppressed remarkably. Then adding BaCl₂ of different concentrations into the bath solution, SV currents reflect different effects. The results show that BaCl₂ with a lower concentration (<3 mmol/L) promotes the channel currents and the currents are saturated when BaCl₂ concentrations are between 1 μmol/L and 1 mmol/L, but BaCl₂ with higher concentration (≥ 3 mmol/L) inhibits SV currents.     

Ca2+-Mg2+-Zn2+体系在水溶性聚磷酸铵溶液中螯合规律的研究

近年来,水溶性聚磷酸铵在液体肥料和复合肥料的领域受到了广泛的关注,并在发达国家中得到了大面积的推广及应用。在pH值为5.5~8.0、温度为278.15 K~323.15 K的条件下,本文采用滴定法研究Ca_²⁺-Mg_²⁺-Zn_²⁺体系在聚磷酸铵溶液中的螯合规律。实验结果表明：相同质量分数的聚磷酸铵溶液对金属离子的螯合量会随着体系中Ca_²⁺、Mg_²⁺、Zn_²⁺的摩尔浓度的变化而变化;随着温度的升高而逐渐降低;随着pH的增加而逐渐增加;随着聚合度的升高而逐渐增加。采用傅里叶红外光谱对聚磷酸铵和A₁B₃C₃体系的螯合物进行表征。     

Comparison of Ca2+ and Mg2+ binding to calmodulin. An enthalpy,entropy, and gibbs free energy analysis

A consistent set of G _B , H _B , and S _B parameters have been determined from ion specific electrode, calorimetric, and spectrophotometric studies for the binding of Ca²⁺ and Mg²⁺ to bovine calmodulin at pH=7.0 and an ionic strength I of 0.113M. A non-linear least squares analysis of calcium specific ion electrode data yields, on a molar basis, four calcium dissociation constants: 10^–7 for the first site, 10^–5 for the fourth site, and two constants between these values. Both calorimetric experiments and an indicator method provide evidence that Mg²⁺ binds to calmodulin, probably at the same sites as Ca²⁺, but with affinities about 100 times smaller: 4×10^–5 for the first site and 2×10^–3 for the fourth. Calorimetric titrations on Ca²⁺ binding to calmodulin in three buffers are consistent with 0.46 protons released upon binding at all four sites and yield an average H _B per site of 5.6 and 7.9 kJ-mol^–1 for Ca²⁺ and Mg²⁺, respectively. The entropy of the system increases by 524 and 361 J-K^–1-mol^–1 when Ca²⁺ and Mg²⁺, respectively, bind to four sites on calmodulin, i.e., the selectivity of calmodulin for Ca²⁺ is primarily derived from entropy effects. Further analysis based on elimination of the entropy term for the metal ions demonstrates that calmodulin bound to Ca²⁺ has a larger entropy than the unbound calmodulin; the opposite is true for calmodulin bound to Mg²⁺. These analyses are consistent with the hypothesis that Ca²⁺ forms tight complexes at all sites on calmodulin and that release of waters of hydration upon binding is the source of the increase of entropy in the system.     

A Thermodynamic Study Between 18-Crown-6 with Mg2+, Ca2+, Sr2+and Ba2+ Cations in Water–Methanol and Water–Ethanol Binary Mixtures Using The Conductometric Method

The complexation reactions between Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ cations with the macrocyclic ligand, 18-Crown-6 (l8C6) in water–methanol (MeOH) binary systems as well as the complexation reactions between Ca²⁺ and Sr²⁺ cations with 18C6 in water–ethanol (EtOH) binary mixtures have been studied at different temperatures using conductometric method. The conductance data show that the stoichiometry of all the complexes is 1:1. It was found that the stability of 18C6 complexes with Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ cations is sensitive to solvent composition and in all cases, a non-linear behaviour was observed for the variation of log K _f of the complexes versus the composition of the mixed solvents. In some cases, the stability order is changed with changing the composition of the mixed solvents. The selectivity order of 18C6 for the metal cations in pure methanol is: Ba²⁺ > Sr²⁺ > Ca²⁺ > Mg²⁺. The values of thermodynamic parameters (Δ H _c ° and Δ S _c °) for formation of 18C6–Mg²⁺, 18C6–Ca²⁺, 18C6–Sr²⁺ and 18C6–Ba²⁺complexes were obtained from temperature dependence of the stability constants. The obtained results show that the values of (Δ H _c ° and Δ S _c °) for formation of these complexes are quite sensitive to the nature and composition of the mixed solvent, but they do not vary monotonically with the solvent composition.This revised version was published online in July 2005 with a corrected issue number.     

Study on the synthesis of novel fluorescent macrocyclic sensors and their sensitive properties for Cu2+ and Fe3+ in aqueous solution

In this work, we synthesised and characterised three novel fluorescence macrocyclic sensors containing optically active dansyl groups. The studies for the interaction of the synthesised compounds with various mental ions (Li⁺, Na⁺, K⁺, Ag⁺, Mg²⁺, Ca²⁺, Ba²⁺, Pb²⁺, Zn²⁺, Co²⁺, Cd²⁺, Hg²⁺, Ni²⁺, Cu²⁺, Mn²⁺, Cr³⁺, Al³⁺, Fe³⁺) were performed by fluorescence titration, Job’s plot, ESI-MS and DFT calculations. The results showed that the sensors 1a–1c displayed selective recognition for Cu²⁺ and Fe³⁺ ions and formed stoichiometry 1:1 complex through PET mechanism in DMSO/H₂O solution (1:1, v/v, pH 7.4 of HEPES). The binding constant (K) and detection limit were calculated.     

Study of Complex Formation Between Dicyclohexano-18-Crown-6 (DCH18C6) with Mg 2+, Ca2+, Sr 2+, and Ba2+ Cations in Methanol–Water Binary Mixtures Using Conductometric Method

The complexation reactions between Mg²⁺,Ca²⁺,Sr²⁺ and Ba²⁺ metal cations with macrocyclic ligand, dicyclohexano-18-crown-6 (DCH18C6) were studied in methanol (MeOH)–water (H₂O) binary mixtures at different temperatures using conductometric method . In all cases, DCH18C6 forms 1:1 complexes with these metal cations. The values of stability constants of complexes which were obtained from conductometric data show that the stability of complexes is affected by the nature and composition of the mixed solvents. While the variation of stability constants of DCH18C6-Sr ²⁺ and DCH18C6-Ba²⁺versus the composition of MeOH–H₂O mixed solvents is monotonic, an anomalous behavior was observed for variations of stability constants of DCH18C6-Mg²⁺ and DCH18C6-Ca²⁺ versus the composition of the mixed solvents. The values of thermodynamic parameters (ΔH_c°, ΔS_c°) for complexation reactions were obtained from temperature dependence of formation constants of complexes using the van’t Hoff plots. The results show that in most cases, the complexation reactions are enthalpy stabilized but entropy destabilized and the values of thermodynamic parameters are influenced by the nature and composition of the mixed solvents. The obtained results show that the order of selectivity of DCH18C6 ligand for metal cations in different concentrations of methanol in MeOH–H₂O binary system is: Ba²⁺>Sr²⁺>Ca²⁺> Mg²⁺.     

A novel red emitting phosphor Ca2SnO4: Eu

A novel red emitting phosphor, Eu³⁺-doped Ca₂SnO₄, was prepared by the solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the formation of Ca₂SnO₄: Eu³⁺. Field-emission scanning electron-microscopy (FE-SEM) observation indicated a narrow size-distribution of about 500 nm for the particles with spherical shape. Photoluminescence measurements indicated that the phosphor exhibits bright red emission at about 615 nm under UV excitation. The excellent luminescence properties make it possible as a good candidate for plasma display panels (PDP) application. Splitting of the ⁵D₀-⁷F_J transitions of Ca₂SnO₄: Eu³⁺ suggests that the Eu³⁺ ions occupied two nonequivalent sites in the crystallite. The luminescence lifetime measurement showed a bi-exponential decay, providing other evidence for the existence of two different environments for Eu³⁺ ions.     

Sol-Gel Processing of Sm2+-Doped Glass and Its Spectral Hole Burning at Room Temperature

The sol-gel process was applied to the preparation of Sm²⁺ ion-doped silicate glasses, which show persistent spectral hole burning at room temperature. The gels synthesized by the hydrolysis of metal alkoxides and SmCl₃·6H₂O were heated in air at 500°C, were then reacted with H₂ gas to form the Sm²⁺ ion. The Al₂O₃−SiO₂2 glasses are appropriate to reduce the Sm³⁺ ion with H₂ gas and show intense photoluminescence of Sm²⁺ ion. Persistent spectra hole burning was observed in the excitation spectrum for the⁷F₀→⁵D₀ transition of the Sm²⁺ ion by the irradiation of DCM dye laser. The hole width and depth were ∼16 cm⁻¹ and ∼10% of the total intensity, respectively, at 20°C.