胶束增敏荧光光度法测血液中锌

应用表面活性剂对荧光配合物的增敏作用测定微量金属元素,是近代分析化学的一个新领域。但关于表面活性剂应用于血液中锌的测定尚未见有文献报道。本文选用表面活性剂CTMAB对Zn-H_2QS体系的荧光增敏作用进行血液中锌的测定。     

胶束增敏荧光光谱法测定吡哌酸

采用不同表面活性剂对吡哌酸在胶束体系中的荧光性质进行了研究，发现在酸性介质中十二烷基硫酸钠(SDS)对吡哌酸有较强的增敏作用，据此建立了胶束增敏荧光光谱法测定吡哌酸的新方法。方法线性范围为0．07-0．36μg／mL，检出限为0.04μg／mL，平均回收率为98．6％-101．3％，相对标准偏差为1．1％-1．2％。样品测定结果令人满意。     

胶束介质对2，3－氨基吩嗪光谱性质的影响及其荧光增敏机理研究

本文研究了胶束介质对邻苯二胺的酶催化氧化产物２，３－二氨基吩嗪的光谱性质的影响，发现胶束介质对其吸收光谱影响很小，非离子表面活性剂对其荧光具有强烈的增敏作用，荧光量子效率可提高近十倍。进一步研究表明，非离子表面活性剂对２，３－二氨基吩嗪的增敏原因在于其增溶作用及给电子效应。     

显色反应中表面活性剂增溶及增敏机理的现状及分析(续)

(四)光度分析中胶束增敏机理研究的现状自从表面活性剂在光度分析中得到应用以来,关于表面活性剂的增敏机理曾经进行了广泛的研究。但是,表面活性剂究竟以什么形式参与增敏作用这一基本问题至今尚未取得比较一致的看法。目前,主要流行以下三种观点:(1)以胶束形式参与增敏作用,但与染料分子相互作用的是胶束中的表面活性剂分子,(2)以表面活性剂的单分子形式参与增敏作用,而极性端的电荷起着决定性的作用,(3)CMC值以前,表面活性剂以单分子形式增敏,而在CMC值以后则以胶束形式增敏,即单分子和胶束均有增敏作用。     

表面活性剂对金属-桑色素荧光反应的增敏作用

研究了表面活性剂对Zr⁴⁺、Hf⁴⁺、Al³⁺、Ga³⁺、In³⁺、及Sb(Ⅴ)与桑色素荧光反应的增敏作用。在阴离子表面活性剂十二烷基磺酸钠存在下,三元体系的灵敏度成倍增加。利用这种增敏作用,渴望建立这些元素的高灵敏度荧光分析方法。     

杜仲叶中绿原酸的协同增敏荧光光谱法测定

研究了四硼酸钠-阳离子表面活性剂十六烷基三甲基溴化铵(CTMAB)微乳液混合体系对绿原酸的协同荧光增敏作用.结果表明,单独存在的四硼酸钠和CTMAB对绿原酸的荧光强度无显著增敏作用,但四硼酸钠-CTMAB混合体系对绿原酸具有较好的协同荧光强度增敏作用.在优化条件下,绿原酸浓度在0.13～1.32μg·mL<-1>范围内...     

表面活性剂对金属荧光反应的增敏作用

研究了各种类型的表面活性剂对铪-栎精、锆-栎精、锡-桑色素、镁-8-羟基喹啉-5-磺酸(镁-H_QS)、锌-H_2QS、镉-H_2QS、铽-EDTA-磺基水杨酸体系荧光光谱的影响.结果表明:在适当的表面活性剂存在下,各种配合物的荧光强度均大大增强.确定了在有表面活性剂参与下三元配合物的最佳形成条件;以荧光法测定了这些荧光配合物的组成.用相对法测定了有表面活性剂和没有表面活性剂存在时荧光配合物的量子效率,并计算了在激发波长下各自的摩尔吸光系数.发现在有表面活性剂存在时,由于生成了有固定组成的三元离子缔合物,荧光配合物的量子效率和摩尔吸光系数都有不同程度的提高,从而大大增强了它们的荧光强度.讨论了表面活性剂胶束的作用以及表面活性剂的分子结构对荧光反应的影响.指出只有那些分子中带电荷基团与共轭大π键不相邻的表面活性剂才能对荧光反应起增敏作用.利用表面活性剂的增敏作用有可能建立一些高灵敏度的金属荧光分析法.     

表面活性剂增敏催化动力学荧光法测定蔬菜中的色氨酸

在PH=4.8的HAc-NaAc缓冲溶液中,基于表面活性剂十六烷基三甲基溴化胺对色氨酸催化高碘酸钾氧化罗丹明B的褪色反应有较强的增敏作用,建立了测定色氨酸的表面活性剂增敏催化动力学荧光新方法.研究了反应的适宜条件及动力学参数.在优化实验条件下,色氨酸浓度在3.0-25.0 mg/L范围内与荧光强度呈良好线性关系,回归方...     

司帕沙星金属络合物在胶束体系中的荧光特性研究及应用

研究了在金属离子存在下司帕沙星在胶束体系中的荧光特性,首次发现锌（Ⅱ）和阴离子表面活性剂十二烷基硫酸钠对司帕沙星的荧光有显著的协同增敏作用,据引建立了测定人体尿液中司帕沙星含量的同步－导数荧光光谱法,定量线性范围为０．０４～４．０ｍｇ／Ｌ,检测限为０．０４ｍｇ／Ｌ。相对标准偏差为１．６％～３．９％。探讨了锌（Ⅱ）和十二烷基硫酸钠对司帕沙星荧光的增敏机理。     

阳极溶出伏安法中表面活性剂增敏机理探讨

本文探讨了表面活性剂在镉的阳极溶出伏安法中的增敏机理，认为表面活性剂可使训金属的水合子或其它络离子发生部分解离，既增加了溶液中电活性络离子的深度，又使离子的扩散速度加快，从而产生增敏作用。     

Gels from a semifluorinated n-alkane in fluorinated solvents as a probe for intermolecular interactions

Diblock semifluorinated n-alkanes can form aggregates and gels in fluorinated solvents. We have investigated the thermal behavior of binary mixtures comprising F(CF₂)₈(CH₂)₁₆H and fluorinated solvents. The solvents were perfluorohexane, perfluoroheptane, perfluorooctane, perfluorooctyl bromide, perfluorodecalin, and perfluorotributylamine. The phase diagrams were used to calculate the activity coefficients of the two components and the main excess thermodynamic functions. The solubility and self-assembly behavior of F₈H₁₆ in the fluorinated solvents are related to the different solute–solvent dispersion interactions that depend on the polarizabilities and ionization potentials of the interacting species, and on the structural properties of the solvent.     

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性;均苯四甲酸二酐;联苯四羧酸二酐;二羟基联苯胺;聚酰亚胺;聚苯并噁唑;耐热性     

HCOO在Cu(110)、Ag(110)和Au(110)表面的吸附

采用密度泛函理论(DFT)以及广义梯度近似方法(GGA)计算了甲酸根(HCOO)在Cu(110)、Ag(110)和Au(110)表面的吸附. 计算结果表明, 短桥位是最稳定的吸附位置, 计算的几何参数与以前的实验和计算结果吻合. 吸附热顺序为Cu(110)(-116 kJ·mol-1)>Ag(110)(-57 kJ·mol-1)>Au(110)(-27 kJ·mol-1), 与实验上甲酸根的分解温度相一致. 电子态密度分析表明, 吸附热顺序可以用吸附分子与金属d-带之间的Pauli 排斥来关联, 即排斥作用越大, 吸附越弱. 另外还从计算的吸附热数据以及实验上HCOO的分解温度估算了反应CO2+1/2H2→HCOO的活化能, 其大小顺序为Au(110)>Ag(110)>Cu(110).     

Studies on the Formation of Catalytically Active PGM Nanoparticles from Model Solutions as a Basis for the Recycling of Spent Catalysts

The paper presents basic studies on the precipitation of platinum, palladium, rhodium, and ruthenium nanoparticles from model acidic solutions using sodium borohydride, ascorbic acid, and sodium formate as reducing agents and polyvinylpyrrolidone as a stabilizing agent. The size of the obtained PGM particles after precipitation with NaBH₄ solution does not exceed 55 nm. NaBH₄ is an efficient reducer; the precipitation yields for Pt, Pd, Ru, Rh are 75, 90, 65 and 85%, respectively. By precipitation with ascorbic acid, it is possible to efficiently separate Pt, Rh, and Ru from Pd from the two-component mixtures. The obtained Pt, Pd, and Rh precipitates have the catalytic ability of the catalytic reaction of p-nitrophenol to p-aminophenol. The morphological characteristic of the PGM precipitates was analyzed by AFM, SEM-EDS, and TEM.     

Transition metal complexes of the tripodal ligand 4-(2′-pyridylmethyl)-4-azaheptane-1,7-diamine. Crystal structures of [CuLCl]ClO4 and [NiL(MeCN)2](ClO4)2

The tripodal ligand 4-(2′-pyridylmthyl)-4-azaheptane-1,7-diamine has been prepared by reaction of 2-aminemethyl pyridine with acrylonitrile, followed by the reduction of the nitrile groups. Copper(II), nickel(II), zinc(II), cobalt(III) and chromium(III) complexes of the ligand have been prepared and characterized and the crystal structures of the complexes [CuLCl]ClO₄ and [NiL(MeCN)₂](ClO₄)₂ determined. The copper complex is five coordinate with approximate square pyramidal stereochemistry with the apical position occupied by a primary amine donor. The nickel complex is octahedral with the pyridine nitrogen donor lying trans to an acetonitrile ligand.     

SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES WITH AMPICILLIN

Abstract

The reaction, in water, of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with sodium ampicillinate at room temperature has allowed isolation of dimers with the following general formula [M(amp)Cl]₂ × nH₂O (n = 1.5?3.2). The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibilities and spectroscopic methods (IR, Raman, EPR and UV-Visible). A dinuclear structure based on octahedrally coordinated metal ions is proposed.     

Magnetism of metal-nitroxide compounds involving bis-chelating imidazole and benzimidazole substituted nitronyl nitroxide free radicals

Coordination compounds based on imidazole and benzimidazole substituted nitronyl nitroxide radicals with transition metal ions and trivalent lanthanide ions are described from the perspective of their magnetic properties.For the transition metal compounds the crystal structures show various metal-nitroxide dimensionalities including mononuclear (0D), one-dimensional (1D) and two-dimensional (2D) complexes. The mononuclear complexes were isolated with most metal ions of the first transition series. One copper(II) complex shows a copper(II)-radical ferromagnetic coupling (J = +75 cm⁻¹) while for the other mononuclear compounds, mainly with manganese(II), the metal-radical interactions are antiferromagnetic. The one-dimensional and two-dimensional complexes are manganese(II) compounds which show canting effects leading to weak ferromagnetism.For the trivalent lanthanide ions [La(III), Gd(III) and Eu(III)], three series of mononuclear complexes were obtained in which the metal center is bound to four, two or one nitroxide radicals depending on the counter ions and ancillary ligands. Unexpectedly, in most gadolinium(III) complexes, the Gd(III)-radical interactions were found to be antiferromagnetic in contradiction with other foundings and previous theoretical models. In support to the magnetic studies, the optical properties of the lantanide complexes have also been investigated and are briefly described.     

New Complexes of Ditopic Ligands with “d” and/or “s” Metal Ions

Abstract

The asymmetric compartmental macrocycles containing one N₂O₂ or N₃O₂ Schiff base and one O₂O₃ or O₂O₄ crown-ether like chamber, have been obtained by condensation reaction of the formyl precursors 3,3′-(3-oxapentane-1, 5-diyldioxy) bis (2-hydroxybenzaldehyde) or 3,3′-(3,6-dioxaoctane-1,8-diyldioxy)-bis(2-hydroxybenzaldehyde) with ethyl ethylenediamine (H₂L_A, H₂L_C), 1,5-diamino-3-azamethylpentane(H₂L_B, H₂L_D), also in the presence of metal ions as templating agents. These ditopic ligands, with dissimilar coordination sites, have been designed and used for the selective complexation of “d” and/or “s” metal ions, respectively into the Schiff base and the crown ether chamber. The selectivity of these processes strongly depends on the size and on the donor atom sets of the sites. The possibility to obtain mononuclear M(L)·nH₂O (M = Ni²⁺, Cu²⁺, Co²⁺), Mn(L)(CH₃COO)·nH₂O or Na(L) and hetero-dinuclear MNa(L)(CH₃COO) (M = Ni²⁺, Cu²⁺, Co²⁺) and MnNa(L)(CH₃COO)₂·nH₂O complexes has been successfully tested. The ligands and complexes have been characterized by ir, nmr, mass spectrometry and magnetic susceptibility measurements.

Two of the ligands used for the preparation of the solid samples, i.e., to H₂L_A and H₂L_B, have been employed to study complexation reactions of Co(II) and Na(I) in solution. In order to obtain information on the ligand preorganization effect toward the complex stabilities, a simpler open chain parent compound of H₂L_B (H₂L_E) has been also prepared and studied. FT-IR spectra show that H₂L_A is unable to complex Na⁺ in DMSO while the complexation reactions of Na⁺ by H₂L_B and of Co²⁺ by H₂L_A take place with slow kinetics. Therefore, thermodynamic data have been obtained only for the systems Co²⁺/H₂L_B and Co²⁺/H₂L_E. The thermodynamic parameters obtained for the complexation reactions show that the pre-organization of the donor atoms in H₂L_B does not add a significant contribution to the stabilities of the complexes. Both H₂L_B and H₂L_E form in DMSO 1:1, 1:2 and 1:3 = M:L complexes with very similar stabilities and almost equal enthalpies of formation. Physico-chemical studies suggest besides that the slow reaction of Na⁺ with H₂L_B is probably due to the formation of a 1:1 complex where the metal cation, initially occupying the O₃ cage of the ligand, slowly binds also the oxygens of the phenolic moieties. Spectral and calorimetric data on solutions containing H₂L_B and different Co²⁺: Na⁺ ratios evidence that in DMSO no stable heterodinuclear complexes form when the neutral ligand is considered.     

具有聚集诱导发光性质的近红外荧光染料

聚集诱导发光(AIE)现象的发现为解决传统有机荧光分子在高浓度和聚集形态下存在的荧光猝灭问题提供了最佳方案,并实现了在光电器件、化学传感、生物成像和靶向治疗等众多领域的广泛应用.随着对AIE 发光机理研究的不断深入,AIE 分子体系得到了极大的扩展.其中,一类具有给体-受体结构的AIE分子能够显著降低分子能隙,使发光分...     

Simple,Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel（Ⅱ）, Copper （Ⅱ）, Cobalt （Ⅱ）, and Iron （Ⅲ） with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.