Adatom Hypothesis as a Predominant Mechanism of Surface Enhanced Raman Scattering: A Review of Experimental Argumentation

A contemporary review of research concerning the mechanism of surface enhanced Raman scattering (SERS) is presented and it is stated that this problem is yet to be solved. The necessity to yet once again analyze some of the familiar experimental observations and the deep-rooted beliefs and revise quantitative evaluations of SERS enhancement via major mechanisms (electromagnetic and chemical) with allowance made for most important experimental characteristics of SERS is substantiated. The characteristics are enumerated and the role they play in the above evaluations is sketched. Attention is focused mainly on electrochemical aspects of SERS problem, which to a large extent define the content and salient features of SERS and provide basic experimental justification for the so-called adatom hypothesis.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 899–935.Original Russian Text Copyright © 2005 by Lazorenko-Manevich.In memory of Vladislav Vladimirovich Marinyuk     

铁氰化镧修饰电极的制备及表征

An electroactive polynuclear inorganic compound of rare earth metal hexacyanoferrate, lanthanum hexacyanoferrate (LaHCF), was prepared by electrochemical deposition on the surface of a glassy carbon electrode with a potential cycling procedure. The cyclic voltammogram of LaHCF exhibits a pair of well-defined redox peaks with the formal potential of 208 mV (vs. SCE) at a scan rate of 100 mV/s in 0.2 mol/L NaCl solution and the redox peak currents increase linearly with the square root of the scan rate up to 1000 mV/s. The effects of the concentration of supporting electrolyte on the electrochemical characteristics of LaHCF were studied by voltammetry. LaHCF was also characterizated by scanning electron microscope (SEM), FTIR and XPS techniques.     

Modification of Glassy Carbon Electrodes with a Poly‐L‐Lysine/Glutaraldehyde Film

A film of poly‐L ‐lysine (PLL) adheres better to the surface of a glassy carbon electrode when the PLL is partially cross‐linked by means of glutaraldehyde. A film composition of 97.5% PLL/2.5% glutaraldehyde gives good adhesion and retains the anionic exchange capability of the PLL. The performance of the film was tested with hexacyanoferrate(III) using electrochemical and nonelectrochemical accumulation.     

Electrochemical hydrogenation of citral

The conditions for preparative electrocatalytic hydrogenation of citral to citronellol were found. Changes in the electrocatalytic properties of the nickel cathode depend on the method of pretreatment of the electrode (mechanical surface cleaning, thermal treatment, cathode-anode activation, and electrodeposition). The use of the nickel cathode with the surface covered with dispersed nickel in electrocatalytic hydrogenation was recommended. For Part 4, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1531–1534, August, 1998.     

Dielectric relaxation spectroscopy in poly(hydroxyethyl acrylates)/water hydrogels

The electrical and dielectric properties of poly(hydroxyethyl acrylate), PHEA, hydrogels were studied by means of dielectric relaxation spectroscopy in wide ranges of frequencies (5–2 × 10⁹ Hz), temperatures (173–363 K) and water contents (0.065–0.46, g of water per gram of dry material). The secondary dipolar mechanisms (γ and β_sw) and the dc conductivity mechanism were studied in detail by analyzing the dielectric susceptibility data within the complex permittivity formalism, the modulus formalism, and the complex impedance formalism. For both mechanisms molecular mobility was found to increase with increasing temperature or increasing water content (T-f-h superposition principle). The energy parameters and the shape parameters of the response were determined for both mechanisms at several water contents and temperatures. The temperature dependence of dc conductivity was found to change from Vogel-Tamman-Fulcher (VTF) type to Arrhenius type at water contents of ca. 0.30. At water contents lower than about 0.30 the hydrogels are homogeneous whereas at higher water contents a separate water phase appears. In terms of the strong/fragile classification scheme our results suggest that the PHEA hydrogels are fragile systems. ©1995 John Wiley & Sons, Inc.     

A Novel Micro—hole Electrode Used to Investigate Electron Transfer Reactions at ITIES

A novel micro-hole electrode was fabricated to investigate the electron transfer reaction at the interface between two immiscible electrolyte solutions (ITIES). The electron transfer reaction between feero/ferricyanide in aqueous phase(W) and ferrocene in 1,2-dichloroethane (O) phase was studied as a test experiment. The results showed that the diffusion coefficient obtained from the micro-hole electrode was consistent with that obtained at macro-interface. Due to its simplicity and the very small IR drop it will be a useful tool for the study of ITIES systems.     

用光谱学方法研究不同放电等离子体粒子约束

本文用光谱学方法研究在ＨＬ－１装置上ＬＨＣＤ及ＥＣＲＨ等离子体，弹丸注入等离子体，偏压电极与偏压孔栏等离子体粒子约束特性。结果表明：在弹丸注入使用正向偏压电极与偏压孔栏期间，等离子体粒子约束行到改善，较低密度下（＾ｎｅ＜２．０×１０＾１＾３ｃｍ＾－＾３），ＬＨＣＤ脉冲期间粒子约束得到改善；而当密度＾－ｎｅ大于２．０×１０＾１＾３ｃｍ＾－＾３时，等离子体约束变坏。ＥＣＲＨ脉冲期间粒子约束得不到改善。     

聚吡咯碳糊电极的研制及应用

研制了聚吡咯电极，探讨了该电极的性能和实用性，实验结果表明，该电极可用于伏安法快速测定Ｌ－抗坏血酸，在０．１ｍｏｌ／ＬＫＮＯ３底液中，线性范围为１．０×１０＾－１１～９．０×１０＾－９ｍｏｌ／Ｌ检测限为５．０×１０＾－１２ｍｏｌ／Ｌ，电极具有具有良好的重现性和高选择性，响应迅速，使用寿命３个月以上。     

The electrochemical behavior of commercial clarithromycin and spectroscopic detection of its structural changes

The aim of the present study was to examine the behavior of commercial clarithromycin, Clathrocyn®, comparing to the results previously obtained using pure clarithromycin under the same experimental conditions. The study was performed by cyclic linear sweep voltammetry and the bulk of electrolyte was analyzed by FTIR spectroscopy and HPLC. At gold electrode, in the range of ?1.2 V to 1.0 V vs. SCE in 0.05 M NaHCO₃, the electrochemical determination of pure clarithromycin was previously defined by four anodic and one cathodic reproductive peaks, and commercial clarithromycin is defined by reproductive one anodic peak which appears from 0.60 to 0.80 V vs. SCE. Previously, FTIR analysis of the bulk electrolyte showed the apparent changes in pure clarithromycin molecule structure: in the ester bond of the lactone and in ethers and acetal bonds. FTIR analysis of the bulk electrolyte also showed changes in the molecule structure in commercial-tablets form of clarithromycin: indicating disappearance of lactone structure and changes of carbonyl group at position 9.     

Fabrication of the slanted electrode matrix on tilting 4.5° (1 1 1) silicon

The slanted low electrode matrix is designed and fabricated on one tilting 4.5° (1 1 1) silicon wafer to reduce the actuating voltage of 8×8 micro-electromechanical systems (MEMS) optical switch matrix. Due to compact size of the upper electrode chip and (1 1 1) silicon anisotropic etching in KOH solution, photomask is designed which is to fabricate the slanted low electrode matrix that can be matched with the upper electrode chip and every slanted low electrode has enough space for actuating cantilever. The experimental results show that all of the applied voltages for the full range of actuating micromirrors of 8×8 MEMS optical switch matrix are in the range of 67.2±0.5 V. It is demonstrated that the fabricated slanted low electrode matrix has good consistency and every slanted low electrode can be precisely aligned with one-to-one corresponding upper electrodes.