Electroless preparation and electrochemical behavior of a platinum-doped nickel hexacyanoferrate film–zinc modified electrode: catalytic ability of the electrode for electrooxidation of methanol

The use of a zinc substrate as an electrode and the modification of its surface by means of a thin film of platinum-doped nickel hexacyanoferrate (Pt-NiHCF) were developed. The modification conditions of the zinc surface including the electroless deposition of metallic nickel on the electrode surface from NiCl₂ solution, chemical derivatization of the deposited nickel to the NiHCF film in 0.5 M K₃[Fe(CN)₆] solution, and electrochemical penetration of metallic platinum into the modified film are described. The modified zinc electrodes prepared under optimum conditions show a well-defined redox couple due to the [Ni^IIFe^III/II(CN)₆]^1–/2– system. The effects of pH, the alkali metal cation, and the anion of the supporting electrolyte on the electrochemical characteristics of the modified electrode were studied in detail. The diffusion coefficients of hydrated alkali metal cations in the film (D), the transfer coefficient (), and the transfer rate constant for the electron (k_s) were calculated in the presence of some alkali metal cations. The electrocatalytic activity of the modified electrode for methanol oxidation was demonstrated. The stability of the modified electrode under various experimental conditions was investigated.     

Conformational changes of the amyloid beta-peptide (1-40) adsorbed on solid surfaces

The conformational change of the 39-43 residues of the amyloid beta-peptide (Abeta) toward a beta-sheet enriched state promotes self-aggregation of the peptide molecules and constitutes the major peptide component of the amyloid plaques in Alzheimer patients. The crucial question behind the self-aggregation of Abeta is related to the different pathways the peptide may take after cleavage from the amyloid precursor proteins at cellular membranes. This work is aiming at determining the conformation of the Abeta (1-40) adsorbed on hydrophobic Teflon and hydrophilic silica particles, as model sorbent surfaces mimicking the apolar transmembrane environment and the polar, charged membrane surface, respectively. The mechanism by which the Abeta interacts with solid surfaces strongly depends on the hydrophobic/hydrophilic character of the particles. Hydrophobic and electrostatic interactions contribute differently in each case, causing a completely different conformational change of the adsorbed molecules on the two surfaces. When hydrophobic interactions between the peptide and the sorbent prevail, the adsorbed Abeta (1-40) mainly adopts an alpha-helix conformation due to H-bonding in the apolar part of the peptide that is oriented towards the surface. On the other hand, when the peptide adsorbs by electrostatic interactions beta-sheet formation is promoted due to intermolecular association between the apolar parts of the adsorbed peptide. Irrespective of the characteristics of the solid sorbent, crowding the surface results in intermolecular association between adsorbed molecules leading to a strong aggregation tendency of the Abeta (1-40). [Diagram: see text] CD spectra of Abeta (1-40) at pH 7: A) in solution ([Abeta]=0.2 mg.ml(-1)) freshly prepared (line) and after overnight incubation (symbols);B) on Teflon (Gamma=0.5 mg.m(-2)).     

Electropolymerized Pyrrole‐Substituted Manganese Phthalocyanine Films for the Electroassisted Biomimetic Catalytic Reduction of Molecular Oxygen

We report for the first time on the electroassisted biomimetic activation of molecular oxygen by a newly prepared electropolymerized polypyrrole‐manganese phthalocyanine film. The prepared films and their intervention in the electroassisted catalytic reduction of molecular oxygen were analyzed by cyclic voltammetry and UV‐visible spectrophotometry on optically transparent electrodes. The obtained results demonstrate the probable existence of the key‐steps responsible for the suggested formation of the highly reactive manganese oxo intermediate.     

Monolayer adsorption isotherms and a disordered medium model

A model of disordered medium is proposed to describe the monolayer adsorption isotherm on heterogeneous surfaces. The model is based on the premise that adsorption medium consists of separate regions in each of which there is a permanent local equilibrium constant, the character of the changes of which is determined by the disorder parameter of the medium. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 189–193, May–June, 2006.     

Sorption of binary liquid mixtures on polymer networks Part I. Determination of surface excess isotherms and free energy functions

Two groups of polymer networks (polymer resins) are investigated by selective liquid sorption fromn-propanol-water mixtures. Group 1 consists of gel polymerized polar (hydrophilic) ion exchangers which swell in the binary liquid mixture. Group 2 consists of non-polar, non-swelling, macroporous resins. The free energy isotherms accompanying the sorption processes are calculated from the excess isotherms and the bulk activities. The adsorption excess free energies reveal the differences in polarity of the polymer network.     

The Studies of the Heterogeneous Properties of Solid Surfaces by Means of the Derivatograph Q-1500 D

A simple method has been adopted to obtain an important information on the heterogeneous properties of materials studied, adsorbed liquid films and liquid-solid interactions. The method utilizes Q-TG mass loss and the first derivative Q-DTG mass loss curves with respect to temperature and time obtained during programmed liquid thermodesorption in quasi-isothermal conditions. The values of the adsorption capacity, total porosity of material, the value of active centers, desorption energy distribution and mesopore-size distribution functions obtained by this method are in good agreement with those estimated on the basis of independent methods. The theoretical and experimental results provided novel and unique data on the heterogeneity of solid surfaces, properties of liquid adsorbed films and thermal stability of the liquid/solid interfaces. This paper presents the more important results obtained so far in the studies the liquid/solid systems by means of the Paulik's classical and quasi-isothermal techniques. This revised version was published online in July 2006 with corrections to the Cover Date.     

新型含氮螯合树脂的制备及其吸附性能

以三甘醇和苯磺酰氯为原料,二乙烯三胺为交联剂合成了新型含氮螯合树脂(5),其结构经IR表征.讨论了Ni2 浓度和pH对5吸附容量的影响.动力学研究表明,5对Ni2 的吸附速率符合鲛岛公式.     

Cu3N薄膜及其研究现状

Cu3N薄膜是近10年来研究的热点材料之一.Cu3N是立方反ReO3结构,理想立方反ReO3结构的一个晶胞中Cu原子占据立方边的中心位置而N原子占据立方晶胞的八个顶点,此结构的体心位置有一较大间隙,Cu原子以及其他原子如Pd、碱金属原子等很有可能进入此位置导致Cu3N的电学性能、光学性能等发生很大的变化,这使得该材料具有很大的潜在应用价值.Cu3N的晶格常数为0.3815nm,密度5.84g/cm3,分子量204.63,颜色呈黑绿色或红褐色,空间点群Pm3m.Cu3N薄膜在室温下相当稳定并且热分解温度较低(300℃左右),热分解前后薄膜的光学反射率有较大差别,这可使Cu3N薄膜用作一次性光记录材料.此外,Cu3N薄膜还可用作在Si片上沉积金属Cu线的缓冲层、低磁阻隧道结的阻挡层、自组装材料的模板等.     

Influence of the e-beam irradiation and photo-oxidation aging on the structure and properties of LDPE-OMMT nanocomposite films

In this paper two systems, polyethylene (LDPE) and polyethylene/commercial organo-modified montmorillonite (LDPE/OMMT) nanocomposite, were subjected to e-beam irradiation at different doses and both the molecular modifications and mechanical properties have been investigated through solubility, FT-IR, calorimetric and tensile tests. Moreover, in some of the irradiated systems photo-oxidation aging was performed and its effects were studied. The results show an enhancement with irradiation of the positive effect of the nano-filler loading, related to the increase of the mechanical properties, due to the increase of the nano-filler polymer interaction.Nevertheless calorimetric and FT-IR data indicate that the well known reduction of LDPE/OMMT nanocomposite resistance to photo-oxidation ageing, with respect to LDPE, is amplified by ionizing radiation.