氧化铁和羟基氧化铁光催化还原银离子

在波长λ≥320 nm的紫外灯照射下, 水溶液中的银离子能在氧化铁和羟基氧化铁催化剂表面发生还原反应而生成颗粒银. 在这些催化剂上, Ag(I)的等温吸附线都符合Langmuir吸附方程; Ag(I)的初始还原速率均随其初始吸附量的增加而线性增大, 并且增大的幅度依α-Fe2O3>α-FeOOH>γ-Fe2O3>γ-FeOOH>δ-FeOOH的顺序降低. 但是, 在前三种催化剂上, 只有当Ag(I)的吸附量达到其饱和吸附量的一半时, Ag(I)的还原才能发生, 并且几乎不受氮气的影响. 在δ-FeOOH和TiO2体系中通入氮气, 能显著加快Ag(I)的光催化还原. 这说明O2与Ag(I)竞争催化剂上的吸附位点和还原物种, 且与催化剂的性质有关. XRD分析表明, α-Fe2O3和δ-FeOOH分别具有较好和较差的结晶度. 这说明氧化铁和羟基氧化铁的结晶度越高, 越有利于光生载流子的分离及其与表面目标物种发生氧化还原反应.     

电解银表面氧物种转化的原位拉曼光谱表征

 首次采用原位共焦显微激光拉曼光谱研究了经纯氧预处理后电解银表面吸附的不同氧物种在升温过程中相互转化的情况. 结果发现,当温度低于423 K时, Ag-O2物种缓慢转化为超氧物种 Ag［O-O］-; 温度升高至423 K时, Ag［O-O］-物种将随着时间的延长转化为 Ag-O(α) 物种; 继续升高温度, Ag-O(α) 物种首先转化为 Ag-O-O-Ag 物种,再进一步转化为电解银表面最稳定的 Ag-O(γ) 次表层氧物种并保持至973 K以上. 结合实际反应体系,低温下电解银表面吸附的氧物种主要是分子氧,在类似乙烯环氧化反应的条件下这些分子氧将转化成 Ag-O(α) 物种,而在类似甲醇选择氧化制甲醛的反应条件下又转化为在高温下较稳定的 Ag-O(γ) 物种,根据具体的转化细节推测了可能的机理.     

Ag/BiOX (X=Cl,Br, I)复合光催化剂的制备、表征及其光催化性能

采用光化学沉积法制备了一系列不同Ag含量的新型Ag/BiOX(X=Cl,Br,I)复合光催化剂,应用X射线粉末衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)、光致发光(PL)谱、紫外-可见(UV-Vis)光谱和N2物理吸附等手段对催化剂进行表征,并以420nm<λ<660nm的可见光为光源,评价了该催化剂光催化降解酸性橙II的活性,考察了不同含量的Ag沉积对BiOX样品光催化性能的影响.N2物理吸附测试结果表明,沉积银在一定程度降低了催化剂的比表面积.UV-Vis测试结果表明,Ag能产生表面等离子共振吸收,有效增强BiOCl和BiOBr对可见光的吸收能力.PL测试结果则表明,Ag能显著抑制光生电子(e-)和空穴(h+)的复合.Ag的存在大幅度提高了BiOX对染料的光催化降解活性.当负载Ag的质量分数(w)为1%-2%时,可使BiOCl、BiOBr和BiOI光催化活性分别提高了10、13和2倍.Ag/BiOX复合光催化剂具有更高催化活性的原因是复合光催化剂对可见光有很强的吸收能力,同时产生了银等离子体光催化作用和银抑制了Ag/BiOX(X=Cl,Br,I)的光生电子-空穴的复合.     

CTAB对四-(4-N-甲基吡啶)卟啉SERS谱的影响

研究了阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)对四-(4-N-甲基吡啶)卟啉(H2TMPyP)及其银配合物(AgTMPyP)在Ag胶中的表面增强拉曼散射(SERS)谱的影响.SERS光谱表明,吸附于Ag胶粒的H2TMPyP与衬底银原子结合形成AgTMPyP,加入CTAB后,部分AgTMPyP表面络合物还原为H2TMPyP.相似的去金属化反应也出现在AgTMPyP/Ag胶/CTAB体系中.CTAB的加入使SERS谱带强度明显增加.AgTMPyP的去金属化被认为是由于CTAB的存在使Ag胶颗粒表面附近微环境发生改变.     

一种新型的长光程薄层光谱电化学池

1 前言光谱电化学是近年来发展起来的一门新兴学科,是把光谱方法和电化学方法结合起来,可进行现场分析的技术.作者曾用夹心式薄层电解池研究过超常价态Ag(Ⅲ)、Cu(Ⅲ),大分子冠醚配合物电还原反应的机理.对于一般的薄层电解池,由于从薄层正面透光,主要有三点不足:(1)由薄层溶液厚度决定的短光程,使得溶液粒子的检测灵敏度较低;(2)光透电极既需要透光     

1,2-二(2-胺基苯氧基)乙烷银配合物的合成与晶体结构

本文采用配体1, 2-二(邻氨基苯氧基)乙烷(L)分别与AgPF6, AgCF3SO3, AgNO3和AgSbF6 进行配位反应,依次得到了四个配合物1 [Ag2(L)2(PF6)]、2 [Ag2(L)2(CF3SO3)2]、3 [Ag(L)NO3]n 和4 [Ag(L)2SbF6]n,并通过FTIR、元素分析、以及X射线单晶衍射等对配合物的结构与组成进行了表征。单晶衍射结果表明,配合物1和2为双核银(I)配合物,3和4为银(I)的配位聚合物。配合物1具有穴状结构,2经Ag?Ag键桥连两个配体形成扭曲的非平面结构。聚合物3的结构为一维(1D)“之”字链,4具有三维(3D)多孔的结构框架。在四个配合物结构中,相应的抗衡阴离子均未参与Ag(I)进行配位作用。     

基于纳米Ag粒子的表面等离子体共振光谱测定CN-的研究

利用UV-辐照光化学还原法制备了平均直径为20 nm的黄色胶体银溶液,银粒子的表面等离子体共振(SPR)光谱的最大吸收波长位于399 nm处,摩尔吸光系数为1.3×104 L·mol-1·cm-1.利用Ag粒子与CN-反应的动力学特性,研究了SPR光谱的λMAX吸光与CN-浓度的关系及其影响因素,拟定了检测环境水样中隐色、有毒CN-离子的方法.标准工作曲线的线性相关系数0.9995,测定下限0.05 μg/mL, 相对标准偏差RSD(%)≤6.1 (n=5).对Ag粒子与CN-反应的机理进行了探讨.     

在阴离子表面活性剂存在下以2-(5'-氯-2'-吡啶偶氮)-5-二甲氨基苯胺分光光度测定银

本文提出了一个简便、灵敏而有选择性的测定银的分光光度法.方法基于银(I)在阴离子表面活性剂十二烷基硫酸钠存在下与2-(5'-氯-2'-吡啶偶氮)-5-二甲氨基苯胺(简称5-Cl-PADMA,1)的颜色反应.银络合物的吸收峰位于500nm,在530nm以显色剂参比摩尔吸光系数6.7×10~4.在pH6～10.5之间吸光值恒定.银浓度在0～1.2ppm时服从Beer定律.用等摩尔连续变化法和摩尔比例法测得络合物中Ag(I)与5-Cl-PADMA的比例为1∶2.在掩蔽剂柠檬酸盐和Ca-CyDTA存在下,该反应对银的测定是选择性的.方法已用于铀和铝试样中银的测定.     

银纳米线与BSA相互作用的光谱学研究

主要研究了粒径为60 nm的银纳米线与牛血清白蛋白(BSA)之间的相互作用.利用紫外可见吸收光谱法和荧光光谱法对反应体系进行了光谱学实验研究.实验结果表明,随着银纳米线溶液浓度的增加,反应体系的紫外吸收峰强度增大.但是,荧光强度却明显猝灭.由荧光结果可以得知银纳米线和BSA的相互作用过程是静态猝灭;同步荧光光谱结果表明,银纳米线对蛋白质周围的环境产生了影响.由变温荧光实验结果还可获得银纳米线与BSA相互作用的结合常数、结合位点数以及吉布斯自由能变.由热力学数据可知银纳米与牛血清白蛋白可以自发结合发生反应,且主要结合力为范德华力和氢键.     

基于纳米Ag粒子的表面等离子体共振光谱测定CN-的研究

利用UV-辐照光化学还原法制备了平均直径为20 nm的黄色胶体银溶液,银粒子的表面等离子体共振(SPR)光谱的最大吸收波长位于399 nm处,摩尔吸光系数为1.3×104 L·mol-1·cm-1.利用Ag粒子与CN-反应的动力学特性,研究了SPR光谱的λMAX吸光与CN-浓度的关系及其影响因素,拟定了检测环境水样中隐色、有毒CN-离子的方法.标准工作曲线的线性相关系数0.9995,测定下限0.05 μg/mL, 相对标准偏差RSD(%)≤6.1 (n=5).对Ag粒子与CN-反应的机理进行了探讨.     

Relative silver(I) ion binding energies of α-amino acids: A determination by means of the kinetic method

The relative silver(I) ion binding energies of 19 α-amino acids have been measured by means of the kinetic method. In general, they are similar to the relative copper(I) ion binding energies of corresponding amino acids although there are differences that can be accounted for by differences in silver(I) and copper(I) chemistry. The correlation with proton basicities is comparatively poorer. Again, the differences between silver(I) and proton binding can be attributed to differences in silver(I) and proton chemistry. The relative silver(I) binding energies measured are best described as relative basicities or ΔΔG _Ag ^° ’s. The observed internal consistency during construction of a silver(I) ion basicity ladder implies that ΔΔS _Ag ^° is approximately zero except when histidine and lysine are involved. For 16 α-amino acids, their relative silver(I) ion basicities ≈ relative silver(I) ion affinities or ΔΔG° _Ag ≈ ΔΔH _Ag ^° .     

人血清蛋白-丙酮(乙醇)体系的荧光光谱及共振散射光谱特性

人血清蛋白-丙酮(乙醇)体系的荧光光谱及共振散射光谱特性     

X=Y-ZH systems as potential 1,3-dipoles. Part 61: Metal exchanged zeolites, silver(I) oxide, Ni(II) and Cu(I) complexes as catalysts for 1,3-dipolar cycloaddition reactions of imines generating proline derivatives

A range of regio- and stereo-selective 1,3-dipolar reactions of imines of α-amino esters, generating polysubstituted prolines, catalysed by silver(I) exchanged zeolites or silver(I) supported on titania, both in combination with DBU, are described. The use of a catalytic amount of silver(I) oxide, Ni(II) complexes and cuprous iodide as catalysts for the cycloaddition reactions are also disclosed.     

Reaktionsmechanismen des Oxoniumions von neuen Gesichtspunkten der Säure—Basen-Katalyse

Hydroxide ion is shown to react with α-glucose in two ways. Firstly, it catalyses mutarotation of α-glucose in conjunction with the hydrate sheath, and secondly, it reacts extremely rapidly as partially dehydrated hydroxide ion with formation of α-glucosate ion without mutarotation of α-glucose. This knowledge, combined with the author's determination of the hydrogen bond entropy of the hydrated oxonium ion leads to new views on the mechanism of very rapid oxonium ion reactions. The hydrogen bond entropy of the hydrated oxonium ion ΔS was determined by the author from the coefficients of the water catalysisk _W and oxonium ion catalysiskH₃O⁺ of the mutarotation of α-glucose $$\Delta S = R ln {{k_w } \mathord{\left/ {\vphantom {{k_w } {k_{H_3 O^ + } }}} \right. \kern-\nulldelimiterspace} {k_{H_3 O^ + } }},$$ As the proton of the hydrated oxonium ion is attracted by both oxygen atoms with the same intensity, (ΔS)/2 is the hydrogen bond entropy of the single hydrated proton, which is to be considered as the activated oxonium ion of the reactions between the oxonium ion and the anions. While only the activation of the oxonium ion is necessary for the reaction of the oxonium ion with hydroxide ion, the reaction of the oxonium ion with acetate ion needs furthermore the activation of this anion, which consists of rupture of the internal hydrogen bond of this anion. The enthalpy of activation of the acetate ion is determined by the author from the acetate ion catalysis and the water catalysis of the α-glucose mutarotation. The activation enthalpy of the reaction of the oxonium ion with acetate is therefore the sum of the activation enthalpies of the oxonium ion and of the anion. Furthermore it is shown that the high migration velocity of the hydrogen ion in aqueous solution is due to the proton exchange between the water molecules, initiated by the single hydrated proton.     

Synthesen der Nonactinsäure

Two stereoselective syntheses of nonactic acid I, the building block of the macrotetrolide antibiotic nonactin are described. The characteristic cis-configuration of the 2,5-substituents on the tetrahydrofuran ring of I is obtained in the first synthesis by catalytic hydrogenation of the furan derivative X. This key intermediate possesses the carbon skeleton and correct distribution of oxygen functions for conversin into nonactic acid. It is synthesized by an electrophilic substitution of 2-acetonylfuran (VI) with the N-cyclohexyl-N-propenyl nitrosonium ion (V) generated from the corresponding α-chloronitrone (VII) and silver fluoroborate, followed by hydrolysis and oxidation of the aldehyde group. The second synthesis starts with a diol already having the correct configuration of the side chain that contains the hydroxyl group. For this purpose threo-1-octen-5,7-diol (XV) is synthesized from acetylacetone in two steps. Oxidative cleavage of the terminal double bond of this threo-diol yields an aldehyde which is converted by a Wittig reaction, with the carbanion, obtained from diethyl α-methoxycarbonylethyl phosphonate, into the open chain intermediate, 2-methyl-6,8-dihydroxy-2-nonenoic acid methylester (XVIII). Base-catalyzed cyclisation of this α,β-unsaturated dihydroxy ester yields the methyl ester of nonactic acid (I) as the main product.     

The determination of copper ions based on sensitized chemiluminescence of silver nanoclusters

We report on the first application of novel, water-soluble and fluorescent silver nanoclusters (Ag NCs) in a chemiluminescent (CL) detection system. A method has been developed for the determination of copper(II) ion that is based on the fact that the weak CL resulting from the redox reaction between Ce(IV) ion and sulfite ion is strongly enhanced by the Ag NCs and that the main CL signals now originate from Ag NCs. UV-visible spectra, CL spectra and fluorescent (FL) spectra were acquired to investigate the enhanced CL mechanism. It is proposed that the electronic energy of the excited state intermediate SO₂* that originates from the CL reaction is transferred to Ag NCs to form an electronically excited NC whose emission is observed. In addition, it is found that copper(II) is capable of inhibiting the CL of the nanoclusters system, but not if other common metal ions are present. The detection of copper(II) is achieved indirectly by measuring the CL intensity of Ag NCs. Under the optimized experimental conditions, a linear relationship does exist between the intensity of CL and the concentrations of copper(II) in the range of 0.2?nM to 0.1?m??. The detection limit is 0.12?nM. The method is applied to the determination of copper(II) ion in tap water with satisfactory results.

离子选择性电极动力学分析法测定银

光度法测定某些金属离子催化K_4Fe(CN)_6与水的取代反应的动力学分析已有报道,但干扰较多,灵敏度低。用氰离子选择电极的电位动力学法测定Hg~(2+)、Au~(3+)已有研究。本文探讨了对银离子的测定,发现在一定条件下银离子浓度与电位值的变化有线性关系,线性范围在2.5×10~(19)～8.0×10~(-8)mol/L。此法干扰较少,灵敏度高。同时对该反应的机理也进行了初步探讨。     

Permanganate oxidation of α-amino acids: kinetic correlations for the nonautocatalytic and autocatalytic reaction pathways

The reactions of permanganate ion with seven α-amino acids in aqueous KH(2)PO(4)/K(2)HPO(4) buffers have been followed spectrophotometrically at two different wavelengths: 526 nm (decay of MnO(4)(-)) and 418 nm (formation of colloidal MnO(2)). All of the reactions studied were autocatalyzed by colloidal MnO(2), with the contribution of the autocatalytic reaction pathway decreasing in the order glycine > l-threonine > l-alanine > l-glutamic acid > l-leucine > l-isoleucine > l-valine. The rate constants corresponding to the nonautocatalytic and autocatalytic pathways were obtained by means of either a differential rate law or an integrated one, the latter requiring the use of an iterative method for its implementation. The activation parameters for the two pathways were determined and analyzed to obtain statistically significant correlations for the series of reactions studied. The activation enthalpy of the nonautocatalytic pathway showed a strong, positive dependence on the standard Gibbs energy for the dissociation of the protonated amino group of the α-amino acid. Linear enthalpy-entropy correlations were found for both pathways, leading to isokinetic temperatures of 370 ± 21 K (nonautocatalytic) and 364 ± 28 K (autocatalytic). Mechanisms in agreement with the experimental data are proposed for the two reaction pathways.     

Dimeric and polymeric silver(I) saccharinato complexes of two bis(pyridine) ligands: Synthesis,structural, spectroscopic,fluorescent and thermal properties

The reaction of silver(I) with 1,2-bis[1-(pyridin-2-yl)ethylidene]hydrazine (bpeh) and N,N-bis(pyridin-2-ylmethyl)amine (bpma) in the presence of Na(sac) (sac = saccharinate) yielded [Ag₂(sac)₂(bpeh)] (1) and [Ag(sac)(bpma)]_n (2) with conformational chirality. Both complexes have been characterized by elemental analysis, IR, thermal analysis and X-ray single crystal diffraction. Complex 1 displays a binuclear composition, in which each silver(I) ion is bound to one monodentate sac ligand and one of the bidentate pyridylimino groups of the bpeh ligand in a distorted trigonal coordination geometry. Complex 2 is a one-dimensional helical polymer, in which silver(I) centers are bridged by tridentate bpma ligands, and each silver(I) ion is coordinated in a distorted tetrahedral geometry by one monodentate sac ligand, a bidentate pyridylamine group of one bpma ligand, and a py group of another bpma ligand. Weak intermolecular C–H?O hydrogen bonds and C–H?π interactions lead to assembly of 1 and 2 into three-dimensional supramolecular frameworks. Spectral and thermal analysis data for 1 and 2 are in agreement with the crystal structures. In addition, both complexes in the solid state display intraligand π–π∗ fluorescence.