粗糙化银电极上氰基钴胺素的电化学行为

比较研究氰基钴胺素在光滑和粗糙化银电极上的电化学行为，发现在光滑银电极上氰基钴胺素的还原为一个二电子过程，而在粗糙化银电极上则为两个一电子过程，其原因是由于粗糙化银电极对氰根的强吸附作用。     

Silver nanoparticles dispersed within amphiphilic star-block copolymers as templates for plasmon band materials

Formation of silver nanoparticles has been developed based on a template technique. Amphiphilic star-block copolymers employed as single molecule template, utilizing the coordination of Ag⁺ ions with carboxyl groups in the core of the star-block copolymer. Silver nanoparticles have been prepared by the addition of chemical reductant, e.g., NaBH₄. The solution of the resultant nanosphere composites showed yellow due to the surface plasmon resonance. These composites were soluble in organic solvents, because hydrophobic corona of the star-block copolymer protected the fabricated silver nanoparticles from aggregation.     

Synthesis and characterisation of advanced UHMWPE/silver nanocomposites for biomedical applications

A supercritical fluid (SCF) route for facile and homogeneous introduction of silver nanoparticles into polymer hosts is described. Our focus is on ultra-high molecular weight polyethylene (UHMWPE). We demonstrate that the metallic nanoparticles have a substantial effect upon the wear and tribochemical properties of the polymer substrate.     

炭糊电极电位法测定痕量银

炭糊电位广泛应用于伏安法的测定,特别是修饰的炭糊电极,对于提高灵敏度和选择性具有极大的潜力,我们首次应用炭糊电极作为银离子的电位传感器,发现其具有制作方便、灵敏度高以及采用适当的掩蔽措施可得到较好的选择性等优点。 1 实验部分 1.1 仪器和试剂 pHS-10A数字酸度/离子计(萧山市科学仪器厂),pHS-2型酸度计(上海第二分析仪器厂).314 S~(2-)离子选择电极(江苏电分析仪器厂)。     

On the Reactivity of Silver Electrodes in a Chlorine Radiofrequency Plasma — Plasma Oxidation vs. Thermal Oxidation

The plasma‐electrochemical growth of an ion‐conducting film by the oxidation of a metal in an electronegative plasma is investigated and compared with results from thermal oxidation. As model system we studied the oxidation kinetics of silver electrodes in a Cl₂ rf plasma. The electrochemical control of the reaction by external currents through the product layer using the plasma as a fluid electrode was achieved. Both potentiostatic and galvanostatic control of the reaction was applied. The morphology of the product layer and its temporal evolution was investigated using SEM. A formation of silver chloride surface patterns in the oxidation process takes place if a simple stability criterion is not fulfilled. Specific surface morphologies were found under different experimental conditions. The morphology of the product layer is influenced by the external electric current and the substrate temperature. The influence of the plasma phase on the thermodynamics and kinetics of the oxidation process is discussed. The role of excited plasma species, the electrical charging of the surface and radiation from the plasma are taken into account.     

Pure Organic Phase Phenol Biosensor Based on Tyrosinase Entrapped in a Vapor Deposited Titania Sol‐Gel Membrane

A novel amperometric biosensor was constructed for the determination of phenols in pure organic phase. This biosensor was fabricated by immobilizing tyrosinase in a titania sol‐gel membrane which was obtained with a vapor deposition method. This method was facile and avoided the calcination step needed in conventional titania sol‐gel process. The titania sol‐gel membrane could effectively retain the essential water layer around the enzyme molecule needed for maintaining its activity in organic phase. The experimental parameters such as solvent and operating potential were optimized. At ?100 mV this biosensor showed a good amperometric response to phenols in pure chloroform without any mediator and rehydration of the enzyme. For catechol determination the sensor exhibited a fast response of less than 5 seconds. The sensitivity of different phenols was as follows: catechol > phenol > p‐cresol. Additionally, the apparent Michaelis‐Menten constants of the encapsulated tyrosinase to catechol, phenol and p‐cresol were found to be 0.15±0.003, 0.17±0.008 and 0.21±0.004 mM, respectively. The biosensor had also good reproducibility and stability. This work provided a promising platform for the construction of pure organic phase biosensors and the determination of substrates with poor water solubility.     

二硫代氨基甲酸螯合树脂化学修饰电极的制备及银离子的测定

将纯石墨电极经三氧化二铝抛光与浓硝酸和浓硫酸(1+1)混合酸使其极性化,之后于1 g·L-1聚氯乙烯(PVC)环己酮溶液10μL中浸渍片刻,取出,用红外灯照射烘干30 min,冷却后,将电极置于含有哌嗪、K3PO4及二甲基甲酰胺(DMF)(2:1:8)的混合液中使其反应;最后在氢氧化钠存在下与二硫化碳反应,用水洗至中性,即制成修饰有二硫代氨基甲酸螯合树脂的石墨电极,将其用于银的测定。与未修饰的电极相比此电极具有较高的灵敏度和较好的选择性,在1．0×10-8～1．0×10-5mol·L-1范围内,峰电流与浓度呈线性关系,检出限为5．0×10-9mol·L-1。     

Spectroscopic studies on 2,3,4,5-tetraphenylpyrylium salts with and without silver (I)-bridged structures

Two novel phenylated pyrylium compounds, silver (I)-bridged 2,3,4,5-tetraphenylpyrylium perchlorate (P1) and its silver (I)-free pyrylium ligand (P2) were prepared from 1,2,3,4-tetraphenylcyclopentadiene to examine their spectroscopic behaviors. The UV/vis absorption and fluorescent emission spectra of P1 and P2, measured in three solvents (acetonitrile, dichloromethane and toluene), reveal that the photophysical behaviors are closely related to silver (I) fragment, and strongly dependent on solvent polarity. In polar acetonitrile, P1 displays longer absorption wavelength and much lower fluorescent emission intensity than P2, although they exhibit much similarity in shape. In contrast, in nonpolar toluene, while P2 shows an apparent absorption band at 338 nm, P1 displays a tail-like line without absorption band observed. All the spectra obtained indicate a better coplanarity and a stronger intra-molecular charge transfer in P1 due to the effect of silver (I) fragment. Additionally, the 1H NMR spectra of P1 and P2, which were recorded under the same conditions, indicate that the silver (I) fragment reinforces pyrylium ring's capacity to localize the formal positive charge within the heterocyclic ring.     

偶氮染料在酸性介质中的电还原性质

研究了4个偶氮染料在酸性介质中的电还原性质。偶氮基在酸性介质中的还原均为不可逆四电子一步全还原。邻、对位上有吸电子基(如—CO_2Bu-n)的偶氮基较间位有吸电子基时更易被还原。分子中同时含有偶氮基和硝基时,偶氮基先被还原。