Metal complexation of crosslinked polyacrylamide-supported dithiocarbamates: Effect of the molecular character and extent of crosslinking on complexation

Dithiocarbamate functions were incorporated into different polyacrylamide matrices crosslinked with a flexible and hydrophilic crosslinking agent, tetraethyleneglycol diacrylate (TEGDA), and their complexation behaviours were investigated. Crosslinked polyacrylamides with varying extents of the tetrafunctional TEGDA crosslinks were prepared by free radical solution polymerization at 60°C using potassium persulphate as initiator in ethanol. The dithiocarbamate functionality was incorporated into these polyacrylamides by a two-step polymer-analogous reaction involving (i)trans-amidation with ethylenediamine and (ii) dithiocarbamylation of the aminopolyacrylamide with carbon disulphide and alkali. The complexations of dithiocarbamate with Cu(II), Ni(II), Zn(II), Co(II) and Hg(II) ions were followed under different conditions. The metal ion intake varied with the extent of the crosslinking agent and the observed trend in complexation is Hg(II) > Cu(II)> Zn(II)> Co(II)> Ni (II). The time-course of complexation, the possibility of recycling, swelling characteristics, and spectral and thermal analyses were carried out. The thermal stability increases upon complexation with metal ions.     

环丙沙星在胶束体系中的荧光特性研究及应用

研究了环丙沙星在胶束体系中的荧光性质，发现十二烷基硫基酸对环丙沙星有较强的增敏作用。据此建立了胶束增敏荧光光谱法测定痕量环丙沙星的新方法，经样品测定，其线性范围为0．033－0．60μg.mL^-1，检出限为0．033μg.mL^-1，回收率为94．0％－98．1％相对标准偏差为1．5％－2．8％。     

A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007     

A New Flow Instrument for Conductance Measurements at Elevated Temperatures and Pressures: Measurements on NaCl(aq) to 458 K and 1.4 MPa

A new flow electrical conductance instrument was constructed and tested on dilute NaCl solutions up to 458 K, and on more concentrated solutions (maximum 0.436 mol⋅kg⁻¹) at 373 K. The results of the new instrument agreed with those of previous authors within the estimated experimental errors. The model of Bernard et al. (J. Phys. Chem. 96, 3833–3840 (1992), MSA) was found to represent the high-temperature results without introducing an ion-pairing equilibrium constant. The Fuoss–Hsia conductance equation as given by Fernandez-Prini was found to represent the dilute concentrations with Λ° (NaCl) as the only adjustable parameter. It was found that Λ° (NaCl) could be expressed as a function of solvent viscosity and density by using three parameters found by regression of literature results between 278.15 and 523 K. This equation along with the FHFP theory permits the equivalent conductivity of dilute sodium chloride solutions to be calculated within the accuracy of the existing experimental measurements.     

气相色谱-质谱联用法测定维生素C泡腾片中的甜蜜素

采用气相色谱-质谱(GC-MS)选择离子监测法(SIM),建立了准确可靠、灵敏度高、快速简便的测定维生素C泡腾片中甜蜜素含量的新方法.样品中的甜蜜素衍生后用有机试剂提取,在选择离子模式下进行测定,以保留时间和特征离子比例进行定性,单离子定量.甜蜜素的线性范围为0.05-10mg/L,检出限为0.6mg/kg,回收率为90.5%-96.9%,相对标准偏差小于4.4%.方法分析所用时间短,结果准确可靠,选择性好,适用于维生素C泡腾片中甜蜜素含量的检验.     

Phase diagram of Na2S2O3 + ethanol + water at ambient pressure and temperature

In the present communication, we report the studies concerning liquid–liquid–solid equilibria for the ternary system sodium thiosulphate (Na₂S₂O₃) + ethanol + water at ambient pressure and at room temperature (303 ± 2 K). The solubility data of Na₂S₂O₃ are reported for solutions in water, ethanol and solutions of varying concentrations of ethanol in water. The phase diagram for the said system is developed, described and compared with similar system K₂CO₃ + methanol + water. These results have been explained in terms of structural properties of aqueous ethanol solutions and further discussed in terms of the effect of ions to cause phase separation.     

韧性金属裂纹尖端损伤区内应变场测量——数字散斑相关法应用

本文用数字散斑相关方法测量了五种不同幂硬化指数韧性金属材料(铝和铜),双边裂纹尖端细观区域内应变场.对所得结果用韧性损伤模型进行了分析.在此法中以金属自然表面结构为散斑场,不同加载状态的散斑场进行比较,得到相对变形与应变.图象之间相关性 C 是变形参数或是位移及其导数的泛函.使其相关性 C 取最大值的试凑变形即为其真实变形场.这一方法在细观测量中应用得到满意的结果.     

Potentiometric studies on the complexation equilibria between some trivalent lanthanide metal ions and biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS)

Summary The chelation behaviour of some trivalent lanthanide and yttrium metal ion with biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS) has been investigated by potentiomotric measurements at 20±0.5°C in 75% (v/v) dioxane-water medium at various ionic strengths of sodium perchlorate. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of (average number of ligand bound per metal ion) andpL (free ligand exponent). The formation constants of metal chelates have been computed on a PC-XT computer, using a program patterned after that of Sullivan et al. to give _n values using weighted least squares method. TheS _min values (S _min =²) have been calculated. The order of formation constants of chelates was found to be: La³⁺3+3+3+3+3+3+3+3+3+. The formation constants of the chelates formed have been correlated to size and ionization potentials of the metal ions.

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Potentiometrische Untersuchungen der Komplexierungsgleichgewichte zwischen einigen trivalenten Metallionen und biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS)

Zusammenfassung Es wurde das Chelierungsverhalten einiger trivalenter Lanthanidenionen mit biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS) mittels potentiometrischer Messungen bei 20±0.5°C in 75% (v/v) Dioxan-Wasser bei verschiedener Ionenstärke an Natriumperchlorat untersucht. Die Methode nach Bjerrum und Calvin in der Modifikation nach Irving und Rossotti wurde zur Ermittlung der Werte (mittlere Anzahl an Liganden pro Metallion) undpL (Exponent an freiem Liganden) verwendet. Die Komplexbildungskonstanten wurden in Anlehnung an Sullivan et al. an einem PC-XT Computer errechnet. DieS _min-Werte (S _min=²) wurden ebenfalls bestimmt. Die Reihung der Chelatbildungskonstanten war: La³⁺3+3+3+3+3+3+3+3+3+. Die Bildungskonstanten sind mit der Größe und dem Ionisierungspotential der Metallionen zu korrelieren.

     

金属表面在反射方向产生光学二次谐波的研究(Ⅰ)

用Rudnick和Stern引入的唯象参数“a”和“b”来描述表面电流,本文推导了金属表面在反射方向产生的光学二次谐波的表达式.由此证明了:从谐波信号随入射光偏振态的变化可以直接得到关于参数“a”的信息.和过去的实验相比,这种方法能更加精确、可靠地测定“a”的数值.     

纳米二氧化钛粒子分散性能的研究

以四氯化钛为原料，采用溶胶-凝胶法技术合成路线，获得了平均粒径为63nm的二氧化钛粉末。采用分散技术，不仅可以改善粒子的分散性能，而且对粒子的生长也起到一定的抑制作用。研究表明：(1)采用SDS作为分散剂时，其极性基团和非极性基团分别与水和纳米TiO2粒子相结合，从而阻隔了TiO2粒子的团聚，起到分散作用。(2)以稀土元素La作为分散剂，其独特的轨道结构，不仅扩大了能量吸收的范围，更重要的是它与TiO2形成的络合物，使其成为相对独立的小团体，而它本身很小的固溶度使其难于形成合金化组元，结果被释放出来，从而形成更小的纳米TiO2粒子，起到分散纳米TiO2粒子的作用，并同时抑制纳米TiO2粒子的生长。