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.     

A Pseudo-Random Frequency Modulation Continuous Wave Coherent Lidar Using an Optical Field Correlation Detection Method

We propose a new detection method for a pseudo-random frequency modulation continuous wave (RM-CW) coherent lidar. The feature of this method is modulation of local beam with a time delayed pseudo-random sequence. Heterodyne detection and correlation detection between the received beam and the local beam are simultaneously carried out in an optical field. In the RM-CW coherent lidar using the optical field correlation detection method, the received equipment is greatly simplified. We carried out preliminary experiments and demonstrated that the new method is effective for detection of a CW coherent lidar.     

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     

镁掺杂对In2O3电导和气敏性能的影响

用共沉淀法制备了Mg2 + 掺杂的In2 O3 纳米粉 ,研究了镁掺杂对In2 O3 电导和气敏性能的影响 .结果表明 :MgO和In2 O3 间可形成有限固溶体In2 -xMgxO3 (0≤x≤ 0 .40 ) ;MgIn× 电离的空穴对材料导带电子的湮灭 ,使掺镁纳米粉的电导变得很小 ;n(Mg2 + )∶n(In3 + ) =1∶2共沉淀物于 90 0℃下热处理 4h ,用所得的纳米粉制作的传感器在 32 0～ 370℃下 ,对 45 μmol/LC2 H5OH的灵敏度达 10 2 .5 ,为相同浓度干扰气体Petrol的 12倍多 .     

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.     

Overview: The Potential of silanes for chromate replacement in metal finishing industries

Trialkoxysilanes (or silanes) have emerged as a very promising alternative for chromates in metal finishing industries. Compared to the conventional chromating processes, the major merits of silane-based surface treatments include: eco-compliance, easy-control processing, comparable corrosion protection of metals as well as paint adhesion to a variety of topcoats. In this overview paper, we report the recent status of silane studies including results of corrosion performance tests, the mechanism of corrosion protection of metals by silanes and the themal stabilities of silane films. We also address the new fields that we are beginning to explore such as nano-structured silane films, “self-healing” silane films, and “super-primers”.     

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。