Temporal evolution of Raman intensities on surface-enhanced Raman scattering active copper and gold electrodes at negative potentials

The effect of a roughening procedure on surface-enhanced Raman scattering (SERS) intensity of pyridine at copper and gold electrodes subjected to negative potential has been investigated. Among four procedures tested for a copper electrode the one consisting of electrochemical activation in a solution of LiCl and CuCl₂ resulted in the most stable and effective surface. It was proved that the presence of pyridine during the pretreatment procedure caused a very fast, irreversible decay of SERS intensity for both copper and gold electrodes. Quite stable, at least at room temperatures, gold surfaces were obtained by oxidation-reduction cycles activation in KCl solution.     

Influence of Some Aggressive Media on Corrosion Resistance of Mortars With Spent Cracking Catalyst

The influence of spent catalyst from catalytic cracking in fluidized bed on the hydration process of cement and the properties of cement mortars were studied. The spent catalyst was used as an additive to cement in the mortars (10 and 20% of cement). The samples of mortars kept in water for28 days, then they were placed in sulfate and chloride media for 2 months (the control samples were kept in water for 3 months). After this time they were subjected to bending strength and compressive strength determinations. Thermogravimetric and infrared absorption studies were performed and capillary elevation, capability of binding heavy metals, and changes in mass and apparent density were determined too. The studies disclosed the pozzolana nature of spent catalyst and its influence on cement mortars being in contact with corrosive media. This revised version was published online in August 2006 with corrections to the Cover Date.     

Infrared study on electrolyte solutions in acetone part III. reactivity of acetone in aldolic condensation

Infrared spectra of perchlorate, halide and nitrate solutions in acetone are studied. The CO and CCC band frequency changes are discussed in terms of the electronic structure of acetone molecules complexed with cation and anion. The correlation between the shift of the CO and CCC bands and the reactivity of acetone molecules in aldolic condensation reaction is given. An explanation of the anion effect in aldolic condensation is proposed.     

Intermolecular coupling of the NH stretching and bending vibrations in the amide - electrolyte solutions

The polarized Raman scattering by the amide - electrolyte solutions have been investigated in the NH stretching and NH₂ bending vibration regions. The differences between the frequencies of the isotropic and anisotropic components are interpreted in terms of hydrogen bonding and intermolecular coupling of the NH vibrators.     

Immobilization of laccase on gold, silver and indium tin oxide by zirconium-phosphonate-carboxylate (ZPC) coordination chemistry

In this paper we present a simple method allowing for stable laccase immobilization on various conducting surfaces that retains the activity of the enzyme. The strategy for laccase immobilization presented in this paper relies on Zr(4+) ion coordination chemistry that involves -COO- terminal groups present on the protein. Using a host of techniques, including surface plasmon resonance (SPR), quartz crystal microbalance (QCM) gravimetry, atomic force microscopy (AFM), surface enhanced Raman scattering (SERS), resonance Raman scattering (RR) and electrochemical techniques, we show that laccase bound to a surface coordinatively through zirconium phosphonate/carboxylate (ZPC) functionalities forms a stable enzymatic layer with the enzyme retaining its activity to a significant extent.     

Bis(μ‐succinato‐O,O′:O′′,O′′′)bis[bis(2‐amino‐1,3‐benzothiazole‐N3)copper(II)]

In the title dimeric complex, [Cu₂(C₄H₄O₄)₂(C₇H₆N₂S)₄], which possesses a centre of symmetry, the Cu atoms are enclosed in a 14‐membered ring. They adopt a distorted square‐bipyramidal (4+2) coordination. The four closest donor atoms are two N atoms of 2‐amino­benzo­thiazole ligands and two O atoms of the succinate carboxylate groups. They form a square‐planar cis arrangement, with an average Cu—N distance of 2.003 (3) Å and Cu—O distances of 1.949 (3) and 1.965 (3) Å. Two longer Cu—O bonds of 2.709 (3) and 2.613 (3) Å involving the remaining O atoms of the carboxylate groups complete the sixfold coordination of the Cu atoms. The H atoms of each amino group of the 2‐amino­benzo­thiazole molecules form intra‐ and inter­molecular N—H?O hydrogen bonds. A nearly perpendicular inter­molecular C—H?Cg interaction (Cg is the centroid of the imidazole ring) is observed. The intramolecular Cu?Cu distance is 6.384 (2) Å.     

A 1:1 cocrystal of di‐μ‐chloro‐bis{[N‐(1‐hydroxy­but‐2‐yl)­salicyl­idene­iminato‐N,O,O′]copper(II)} monohydrate and its methanol solvate

The structure consists of two crystallographically independent and differently solvated binuclear complexes, {[Cu₂Cl₂(C₁₁H₁₄NO₂)₂]·CH₄O}·{[Cu₂Cl₂(C₁₁H₁₄NO₂)₂]·H₂O}. The water and methanol solvate mol­ecules are similarly connected with the complex mol­ecules by two hydrogen bonds. The asymmetrical system of hydrogen bonds breaks up the potential centrosymmetricity of both chelate mol­ecules. All copper(II) centres are in a square‐pyramidal environment, with four short bonds in the basal plane formed by two trans O atoms and one N atom of the tridentate ligand, and a bridge chloride ion. The fifth axial long bond is formed by a chloride ligand which lies in the basal plane of the neighbouring copper(II) ion.     

Ma?analytische Bestimmung von Lanthan mit Natriumwolframat in Anwesenheit von Adsorptionsindicatoren

Zusammenfassung Zur genauen und schnellen Bestimmung von Lanthan wird die Titration mit Natrium-wolframat unter Verwendung der Adsorptionsindicatoren Chlorphenolrot, o-Kresolrot und Methylrot, sowie der Gemische Methylrot + Bromkresolgrün und Chlorphenolrot + Anilinblau empfohlen. Der Fehler der Bestimmung beträgt höchstens 0,5%. Die Methode eignet sich zur Bestimmung von La³⁺ in reinen Salzen und zur Bestimmung der Summe von Seltenen Erdmetallen nach vorhergehender Abtrennung von anderen Schwermetallen, die mit Natriumwolframat einen schwerlöslichen Niederschlag bilden.

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Volumetric determination of lanthanum using sodium tungstate in presence of adsorption indicators

The accurate and rapid method described employs the following indicators: chlorophenol red, o-cresol red, methyl red, and the mixtures methyl red + bromocresol green and chlorophenol red + aniline blue. In all instances the error is smaller than 0.5%. The method is suitable for La³⁺ determination in lanthanum salts and also for the determination of the total amount of rare earths after separation from other heavy metals forming with sodium tungstate difficultly soluble precipitates.

     

Electro-oxidation of o-aminophenol studied by cyclic voltammetry and surface enhanced Raman scattering (SERS)

Cyclic voltammetry and surface enhanced Raman scattering (SERS) spectra were used over a wide pH range to examine the products of o-aminophenol oxidation on a roughened silver electrode. The results of the study indicated that at least two oxidation products are formed at the stationary potential of the electrode. The major product in alkaline and neutral media was identified as 2,2′-dihydroxyazobenzene, a linear dimer formed by N---N coupling of o-aminophenol cation radicals. In acidic solutions the cyclic dimer 3-aminophenoxazone formed by C---N coupling of o-aminophenol cation radicals dominates on the silver electrode.     

Surface‐enhanced resonance Raman spectroscopic characterization of cytochrome c immobilized on 2‐mercaptoethanesulfonate monolayers on silver

Single‐component self‐assembled monolayers (SAMs) of mercaptoethanesulfonate (MES) on Ag surfaces were studied with surface‐enhanced resonance Raman scattering (SERRS) spectroscopy with a view to their application to immobilize (ferro)cytochrome c (cyt c). SERS studies revealed that MES molecules adopt primarily trans (T) conformation even at early stages of the SAM growth and over wide range of pH values. High accessibility of the negatively charged groups for (bio)molecules in solution makes single‐component MES SAMs suitable linkage monolayers for electrostatic attachment of cyt c, which was verified with SERRS. Cyt c was successfully anchored to MES‐coated Ag at natural (∼5), neutral, and isoelectric point (10.6) pH. At pH = 7.0 and 10.6, SERRS bands characteristic of native six‐coordinated low‐spin (6cLS) heme iron configuration were detected. Lack of buffering resulted in additional appearance of five‐coordinated high‐spin (5cHS) SERRS markers and the presence of bands indicating ferric ion. An electrostatic attraction between protein and SAM was confirmed to exclude the hydrophobic interactions involved in cyt c binding. Cyt c attached to MES SAM on Ag was found to be electroactive at neutral pH, and protein oxidation was assisted with reversible conversion of 6cLS to the non‐native 5cHS state. Alteration of heme orientation deduced from SERRS spectra upon change of redox state allowed us to propose the protein dynamics as the electron transfer rate‐limiting step. Copyright © 2010 John Wiley & Sons, Ltd.