Tubular Morphology of Mesoporous Silica MCM‐41

We investigated detailed conditions for synthesizing the tubular form of MCM‐41 mesoporous aluminosilicate. The method is the delayed neutralization method in which the rate of neutralization is one of the controlling factors. Rapid neutralization results in the particulate form while gradual neutralization leads to tubules. It is found that the tubule morphology has several sub‐categories. There are thick‐walled, think‐walled hollow tubular MCM‐41 and solid core tubules. There are void structures in the channel framework that makes the nanochannels to be effectively interconnected.     

Bifunctional Ion‐Selective Electrode Based on C60‐Cryptand 22 for Silver and Iodine Ions

Fullerence C60‐cryptand 22 was prepared and successfully applied as the electric carrier in the PVC electrode membrane of a bifunctional ion‐selective electrode for cations, e.g., Ag⁺ ions as well as anions, e.g., I^? ions. The bifunctional ion‐selective electrode based on C60‐cryptand 22 can be applied as a Silver (Ag⁺) ion selective electrode with an internal electrode solution of 10^?3 M AgNO₃ in water (pH = 6.3), or as an Iodide (I^?) ion selective electrode with an acidic internal electrode solution of 10^?4 M KI_(aq) (pH = 2) in which the cryptand 22 is protonated, and the C60‐cryptand 22 is changed to C60‐Cryptand22–H⁺ and becomes an anionic electro‐carrier to absorb the I^? ion. The Ag⁺ ion selective electrode based on C60‐cryptand 22 gave a linear response with a near‐Nernstian slope (59.5 mV decade^?1) within the concentration range 10^?1‐10^?3 M Ag⁺_(aq). The Ag⁺ ion electrode exhibited comparatively good selectivity for silver ions, over other transition‐metal ions, alkali and alkaline earth metal ions. The Ag⁺ ion selective electrode with good stability and reproducibility was successfully used for the titration of Ag⁺_(aq) with Cl^? ions. The Iodide (I^?) Ion selective electrode based on protonated C60–cryptand22‐H⁺ also showed a linear response with a nearly Nernstian slope (58.5 mV decade^?1) within 10^?1 ‐ 10^?3 M I^? _(aq) and exhibited good selectivity for I^? ions and had small selectivity coefficients (10^?2–10^?3) for most of other anions, e.g., F^? , OH^?, CH₃COO^?, SO₄^2?, CO₃^2?, CrO₄^2?, Cr₂O₇^2? and PO₄^3? ions.     

Silver-Selective Electrode Based on a Direct Modified Electrode Silver Hexacyanoferrate(II) Film

ABSTRACT

A silver hexacyanoferrate(II) modified electrode is introduced as a silver-selective electrode. The electrode was prepared based on a new type of chemically modified electrodes by direct modification of the electrode surface. The electrode response characteristics were investigated by potentiometry. The calibration curve of the electrode shows a linear potentiometric response to Ag⁺ in the range of 10^-7 - 10^-2 M with detection limit of 5 × 10^-8. The modified electrode described in this paper is very simple, low cost and has linear response to Ag⁺ with a slope of 52-55 mV per decade.     

新型无机-有机杂化中孔发光材料(phen)_2Eu/MCM-41的合成与表征

合成出了担载稀土有机配合物的无机 -有机杂化中孔发光材料 ( phen) 2 Eu/MCM-4 1 ,用 X射线衍射、红外光谱、荧光光谱和紫外 -可见漫反射光谱对所得样品进行了表征 ,并与相应的纯稀土配合物进行了比较 .结果表明 ,所得杂化材料具有典型的中孔材料 MCM-4 1的结构 ,且经组装后孔结构保持不变 ,在紫外光照射下 ,发出稀土离子的特征谱线 ,但与纯稀土配合物相比 ,其激发光谱发生蓝移 ,稀土 Eu3 所处的格位对称性降低 ,荧光寿命延长 .另外 ,对光谱性质进行了讨论 .     

Characterization of a Silver Modified PVCAc Electrode and Its Application as a Ag(I)‐Selective Potentiometric Sensor

An all solid‐state Ag(I) ion‐selective electrode has been prepared by simply immersing a glassy carbon rod coated with PVCAc, which contained plasticizer and additive but no ionophore, into the AgNO₃ solution. The response of the electrode was linear with a Nernstian slope of 60.25 mV/decade within the concentration range from 1×10^?1 to 1×10^?5 M and with a detection limit of 4.25×10^?6 M. The stability as an effect of various cations was defined. The electrode is suitable for use in high acidic solutions (pH<1 to 7) and has successfully been applied for the determination of silver(I) concentrations in different samples.     

硫化银/凹凸棒的Ag+选择电极

以硝酸银、凹凸棒石和硫代乙酰胺为原料制得硫化银/凹凸棒-Ag₂S/ATT电极,并探讨了硫代乙酰胺配比、增塑剂用量、膜厚度以及溶液pH值等因素对电极性能的影响. 结果表明,新型银离子选择电极有较好的能斯特响应,其响应斜率48.0 mV·decade^-1,Ag⁺浓度线性响应范围1.0×10^-1 ~ 1.0×10^-6 mol·L^-1. 在pH = 2.0 ~ 8.0溶液中该电极电势可稳定72 h,对常见阳离子如Na⁺、Ca²⁺、Fe²⁺、Cu²⁺等呈现较强的抗干扰能力.     

The Environmental Effect of MCM-41 Mesoporous Silica on Solid Thermochromic N-(5-Chlorosalicylidene)aniline

Thermochromic N-(5-chlorosalicylidene)aniline was entrapped in a mesoporous silica designated as MCM-41 by grinding the twocomponents in the solid state. In the composite material the title compound lostits thermochromic properties and transformed to a photochromic tautomer with dramaticdifferences in the forward and backward ground state reactions with temperature.The observed change in colour with light is attributed to the cis-keto form ofthe title anil stabilized in the environment of the mesoporous MCM-41 material.     

Mesoporous Silica MCM‐41 Supported N‐Heterocyclic Carbene‐Pd Complex for Heck and Sonogashira Coupling Reactions

Heterocyclic carbene‐Pd complex was anchored onto the mesoporous silica MCM‐41 which exhibits high catalytic activity in Heck reaction under phosphine free reaction conditions for the reaction of iodo/bromoarenes with olefinic compounds such as butyl acrylate, isopropyl acrylate and styrene. This catalytic system also showed high activity for Sonogashira coupling reaction of various aryl halides under copper, phosphine and solvent‐free reaction conditions. The air and thermally stable catalyst were reused several times without significant loss of its activity. High efficiency of the catalyst along with its recycling ability and the rather low Pd‐loading demonstrated in both Heck and Sonogashira coupling reactions are the merits of the presented catalyst system.     

新型杯芳烃银离子选择电极的研究

报道了５,１１,１７,２３－四（１,１－二甲基乙基）－２５,２７－二羟基２６,２８－二「２－乙基硫）乙氧基」杯「４」芳烃为银离子载体的ＰＶＣ膜电极的研制。该银离子选择电极不仅对银离子有良好的灵敏度和高选择性,在１０＾－１－１０＾－５ｍｏｌ／Ｌ浓度范围内有良好的线性,能斯特响应为５６ｍＶ／ｐｅＡｇ．（２５℃）碱金属、碱土金属及过渡金属离子不干扰银的测定;而且对某些阴离子也表现出近似能斯特响应（５０ｍＶ／ｐｃｘ－）。用该电极对人工试样中银含量进行测定,结果与原子吸收光度法相符。     

硒功能化杯芳烃载体银离子选择性膜电极的研究

合成6个硒功能化杯芳烃为载体,采用双层夹心膜电位法直接测定了溶剂聚合物膜中载体与金属离子生成的络合物生成常数。制备并考察了以硒功能化杯芳烃为载体的银离子选择性电极的性能,发现以载体6为银离子选择性电子的载体,制成的膜电极,用作Ag^ 电位滴定Cl^-的指示电极,效果最佳。     

新型杯芳烃衍生物银离子选择电极的研究

以苯并噻唑、羟基硫醚的杯[4]芳烃衍生物为载体,制备了银离子选择电极（Ag^ -ISEs),研究了不同极性的膜增塑剂DBP、o-NPOE对电极性能的影响。研究结果表明,苯并噻唑取代的杯[4]芳烃作载体的Ag^ -ISEs对银离子有很好的能斯特响应和较宽的线性范围,低的检测限,对碱金属、碱土金属、过渡金属离子和铅离子有极高的选择性,汞离子对银离子的干扰很小,优于Ag2S固态商品电极。研制的Ag^ -ISEs可用于电位滴定的指示电极,结果令人满意。     

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。     

中性载体双(N-乙基-N-苯基氨基二硫代甲酸)1,4-丁二醇酯PVC膜银离子选择电极的研制

采用双层膜电位法直接测定了溶剂聚合物膜中载体双(N-乙基-N-苯基氨基二硫代甲酸)1,4-丁二醇酯与金属离子生成的络合物生成常数。制备并考察了以双(N-乙基-N-苯基氨基二硫代甲酸)1,4-丁二醇酯为载体的银离子选择性电极的性能。实验结果表明:该选择电极对银离子有良好的灵敏度和高选择性,在1×10-3~1×10-6mol/L的浓度范围内响应斜率为60.2 mV/paAg+,检出限为2.3×10-7mol/L,碱金属、碱土金属及过渡金属离子不干扰银的测定。该电极可作为Ag+准确滴定卤素阴离子的电位滴定指示电极,用于维生素B1药片中维生素B1含量的测定。     

Nitrite‐Selective Electrode Based On Cobalt(II) tert‐Butyl‐Salophen Ionophore

A series of polymeric nitrite‐selective electrodes containing a new lipophilic ionophore Co(II) tert‐butyl‐salophen is reported. The stability of Co(II) ionophores within a PVC‐based membrane was investigated by leaching experiments. Different membrane compositions were explored in order to reach the lowest possible limit of detection for a PVC‐based nitrite selective polymeric membrane electrode containing this ionophore. The optimal electrode showed a limit of detection of 2×10^?6 M and exhibited four orders of magnitude of discrimination over nitrate, chloride and bromide. The electrodes were evaluated in undiluted human urine and attest to the robustness of the ionophore.     

Low Potential Detection of NADH at Titanium‐Containing MCM‐41 Modified Glassy Carbon Electrode

Titanium‐containing MCM‐41 (Ti‐MCM‐41) modified glassy carbon electrode (GCE) can exhibit an excellent electrocatalytic activity towards the oxidation of β‐Nicotinamide adenine dinucleotide (NADH). A dramatic decrease in the over‐voltage of NADH oxidation reaction is observed at 0.28 V (vs. SCE). The modified electrode is found to be stable and reproducible. The electrode shows a linear response for a wide range of 10–1200 μM NADH and the detection limit is 8.0 μM. Ti‐MCM‐41 mesoporous molecular sieves provide an efficient matrix for development of NADH biosensors and the prepared electrode not only can be used to detect the concentration of NADH in biochemical reaction, but also as the potential matrix of the construction of dehydrogenases biosensor.     

Silver(I)‐Selective PVC Membrane Potentiometric Sensor Based on a Recently Synthesized Calix[4]arene

A new PVC membrane potentiometric sensor for Ag(I) ion based on a recently synthesized calix[4]arene compound of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐dihydroxy‐calix[4]arene‐thiacrown‐4 is developed. The electrode exhibits a Nernstian response for Ag(I) ions over a wide concentration range (1.0×10^?2?1.0×10^?6 M) with a slope of 53.8±1.6 mV per decade. It has a relatively fast response time (5–10 s) and can be used for at least 2 months without any considerable divergence in potentials. The proposed electrode shows high selectivity towards Ag⁺ ions over Pb²⁺, Cd²⁺, Co²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Sr²⁺, Mg²⁺, Ca²⁺, Li⁺, K⁺, Na⁺, NH₄⁺ ions and can be used in a pH range of 2–6. Only interference of Hg²⁺ is found. It is successfully used as an indicator electrode in potentiometric titration of a mixture of chloride, bromide and iodide ions.     

The complex (2,3;6,7;10,11;14,15-tetraphenyl-4,9,13,16-tetraoxo-1,5,8,12-tetraazacyclohexadecane) copper(II) as a carrier for a salicylate-sensitive poly(vinylchloride) membrane electrode

A new salicylate-selective electrode based on the complex (2,3;6,7;10,11;14,15-tetraphenyl-4,9,13,16-tetraoxo-1,5,8,12-tetraazacyclohexadecane) copper(II) [CuL] as the membrane carrier was developed. The electrode exhibits a good Nernstian slope of −60.9 ± 1.0 mV/decade and a linear range from 1.0 × 10⁻⁶ to 1.0 × 10⁻¹ M for salicylate. The detection limit is 5.0 × 10⁻⁷ M. The electrode has a fast response time (5–15 s) and can be used for more than three months. The selective coefficients were determined by the fixed interference method (FIM) and separate solution method (SSM). The salicylate-selective electrode could be used in the pH range 3.5–10.5. It was employed as an indicator electrode for direct determination of salicylate in pharmaceutical samples. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 9, pp. 1147–1154. The text was submitted by the authors in English.     

银纳米粒子修饰银电极法测定酪氨酸

通过NaBH₄还原AgNO₃得到胶体银纳米粒子,制作了以该纳米粒子修饰的银电极。研究了银纳米粒子修饰银电极在电催化中的应用,并对相关机理进行了探讨。该修饰电极对醋酸具有电催化活性,但酪氨酸却对该催化信号有明显的抑制作用,因此建立了用胶体银纳米粒子修饰银电极在NaAc-HAc缓冲溶液中检测酪氨酸的方法,并讨论了最佳工作条件。结果表明：在pH = 5.5时,峰电流与酪氨酸的浓度在1.0×10_-8～1.0×10_-3mol L_-1 范围内呈良好的线性关系,检出限为4.2×10_-9 mol L_-1,线性回归方程为Ip (μA) = 7.64 pC – 15.69 ( R = 99.73% )。用该方法检测氨基酸注射液中酪氨酸的含量,加标回收率在95.2%~107.8%之间。     

Vapor‐Phase Reaction of Citronellal over Mesoporous Molecular Sieves MCM‐41 and Zeolites

The vapor‐phase reaction of citronellal (CTN) at 220 °C and atmospheric pressure has been studied using mesoporous molecular sieves and zeolites in a fixed‐bed reactor. The primary products included isopulegol (IPG), menthone, and pulegol with subsequent reactions to form cyclic hydrocarbons. The CTN conversion and the product selectivity depend on the acidity and the textural property of catalysts. Lewis and/or Brönsted acid sites are essential for catalyzing this reaction. An increase of SiO₂/Al₂O₃ mol ratio diminishes the acid amount of all catalysts and enhances both the surface area and the structural order of MCM‐41. The catalytic activity follows the order of MCM‐41 > HZSM‐5 > Hβ > USY, in accordance with the relative total acid amount except that of MCM‐41. Despite its low acidity, Si‐MCM‐41 exhibits the best catalytic performance due to its uniform mesopores, large surface area and good stability; the CTN conversion and the IPG yield attain 91.9% and 58.6%, respectively, after at least 25 h time‐on‐stream.