Voltammetric investigation of Tamsulosin

The electrooxidative behavior and determination of Tamsulosin HCl (TAM), one of the alpha(1)-adrenoceptor antagonist, on a glassy carbon disc electrode were investigated for the first time by using cyclic, linear sweep, differential pulse (DPV) and square wave voltammetry (SWV). TAM showed an irreversible oxidation behavior at all pH values and buffers studied. From the electrochemical response, the main oxidation step was found to be related to the methoxy group on the phenyl ring. DPV and SWV were used to generate peak current versus concentration curves for TAM. A linear response was obtained in the range comprised between 2x10(-6) and 4x10(-4) M for both techniques with detection limit of 3.34x10(-7) M for DPV and 2.45x10(-7) M for SWV. The methods were proposed for the determination of TAM in dosage forms adopting both DPV and SWV modes. The methods were extended to the in vitro determination of TAM in spiked serum samples.     

Voltammetric quantification and speciation of mercury compounds

The use of a carbon paste electrode modified with a thiolic resin for the determination of inorganic mercury and organomercury compounds, present simultaneously in a sample, is described. The compounds are first preconcentrated at the electrode surface by means of a purely chemical reaction with the modifier on the electrode surface. The high affinity of the modifier for the mercury compounds ensures low limits of detection and determination. Differentiation between several mercury species is possible by control of the reduction potential applied to the working electrode. This selective reduction results in the formation of atomic mercury at the electrode surface which can be determined with a very high sensitivity by means of its re-oxidation wave in cyclic voltammetry. Optimization of the instrumental parameters and evidence for the reduction processes are discussed. Analysis of inorganic mercury in the presence of methylmercury, with a detection limit of 4 μg Hg 1⁻¹, and of methylmercury in the presence of inorganic mercury, with a detection limit of 2 μg Hg 1⁻¹, is described in detail. In both cases the preconcentration time is 6 min. Other organomercury species can also be quantified. Application of the method to environmental aquatic samples is discussed.     

Voltammetric and chronoamperometric investigation of germanium amalgams: Part I. Properties of the homogenous amalgam

Using cyclic voltammetry and chronoamperometry with several anodic steps the deposition and particularly the oxidation of germanium from a HMDE was investigated within pH range 4–12 at Ge (IV) concentrations ranging from 4×10^?7M to 1×10^?4M in the absence of ligands capable to form the complex compounds with Ge(IV) in a solution. It was found that the initially formed product of electrodeposition is a homogeneous, usually supersaturated amalgam. Germanium from this amalgam oxidizes at about 1 V (vs. mercury sulphate reference electrode) or after some induction period, the length of which depends on concentration of Ge(0) in mercury, it begins to crystallize forming heterogenous germanium amalgam. Germanium from this heterogenous amalgam oxidizes in a separate voltammetric peak at more positive potentials. The solubility of germanium in mercury was evaluated on the basis of the oxidation current of homogenous amalgam and the value obtained is equal to (2±0.5)×10^?7M i.e. (1.1±0.3)×10^?7 wt. %. Applying the Stevens and Shain method the diffusion coefficient of germanium in mercury was found to be (1.32±0.1)×10^?5 cm² s^?1.     

Determination by gas chromatography/mass spectrometry of p-phenylenediamine in hair dyes after conversion to an imine derivative

In this paper we describe an analytical method for the determination of p-phenylenediamine (PPDA) in hair dyes. In the adopted methodology the analyte is transformed into the corresponding imine derivative by treatment with benzaldehyde, and then analyzed by gas chromatography (GC) combined to mass spectrometry (MS), operating in SIM conditions. The direct and simultaneous chemical derivatization of the two amino functions of the analyte with benzaldehyde enhances the instrumental responses enabling the use of a sensitive and accurate method. Concentrations of PPDA in a set of commercial hair coloring creams are determined making use of N-benzylidene-4-methylbenzene-amine as a very stable internal standard which is easily prepared by condensation of 4-methylbenzene-amine with benzaldehyde. The regression calibration curves for PPDA in hair dyes are linear within 0.1 +/- 25 mg/ml with 0.99 as a typical correlation coefficient.     

Raman spectroscopic quantification of milk powder constituents

Raman spectroscopy has significant potential for the quantification of food products. Milk powder is an important foodstuff and ingredient that is produced on large scale (over 20 million tonnes per annum). Raman spectroscopy, unlike near- and mid-infrared spectroscopies, has not been used extensively to quantify milk powder constituents. The effect of sample presentation on spectroscopic calibrations of protein and fat for 136 New Zealand milk powders was assessed using Raman spectroscopy. Prediction models were produced to quantify a protein concentration range of 32.19-37.65% w/w for skim milk powder, and a protein concentration range of 23.34-25.02% w/w and a fat concentration range of 26.26-29.68% w/w for whole milk powder (where ratios of prediction to deviation exceeded 2.6 with one exception). The resultant calibrations were not influenced by sample orientation; the sample temperature during data collection did affect the calibrations. Calcium fortification in the form of calcium carbonate was identified within a sub-set of samples, reinforcing the efficacy of Raman spectroscopy for identifying both crystalline and non-crystalline constituents within milk powder.     

HPLC quantification of dye flavonoids in Reseda luteola L. from Portugal

A HPLC method was developed for the simultaneous identification of Reseda luteola L. (weld) flavonoids and quantification of the main compounds responsible for the yellow color. This method was applied to a large number of wild Portuguese weld to evaluate its potential application as dyestuff for textile factories, as a substitute for the synthetic dyes currently used. Portuguese weld dyestuff content ranged between 1.04 and 5.87%, corresponding to a wide variation of the flavonoids amount (1.39–9.04%). Luteolin 4′‐O‐glucoside was found for the first time in R. luteola, but kaempferol, isorhamnetin, and their glycosides were not detected in the Portuguese specimens.     

Thermal analysis of hair treated with oxidative hair dye under influence of conditioners agents

This research aimed the effect on Caucasian hair tresses treated with oxidative hair dye, either incorporated or not with conditioners agents, analyzed by Differential Scanning Calorimetry (DSC) and Thermogravimetric analysis (TG). The formulations of hair dyes were emulsions oil-in-water with light blond color containing or not the conditioners agents: silanetriol and panthenol; PEG-12 dimethicone; hydrolyzed silk, hydrolyzed milk protein, and lactose. Each dye (1.5 g) was applied in the hair tress (2.0 g/20.0 cm of length of Caucasian light-brown), previously treated, more 1.5 g of hydrogen peroxide 20 vol during 40 min. Evaluation of mass loss of the different hair sample demonstrates that these chemical hair treatments impair the hair fibers, reduced their moisture content with respect to the untreated hair. The incorporation of conditioners agents (silanetriol and panthenol; PEG-12 dimethicone; hydrolyzed silk, hydrolyzed milk protein, and lactose) in oxidative hair dyes types did not decrease the damage caused on the tresses by the coloring process quantified by TG/DTG. However, the DSC curves demonstrated those conditioners agents (silanetriol and panthenol; PEG-12 dimethicone) dislocated the beginning of the third event in 20 °C and they inhibited the presence of the fourth event, having characterized thermal protection to the hair.     

Voltammetric measurement of reduced nicotinamide-adenine nucleotides and application to amperometric measurement of enzyme reactions.

The electrochemical oxidations of reduced nicotinamide-adenine dinucleotide and reduced nicotinamide-adenine dinucleotide phosphate on platinum and carbon electrodes are described. Well defined voltammetric anodic waves are observed on carbon electrodes, with a linear relationship between peak height and concentration for 0–0.5mM NADH and NADPH. Amperometric methods for NAD oxidoreductase analyses by direct electrochemical oxidation of the reduced nucleotide have been developed for lactic dehydrogenase and ethanol in serum.     

Voltammetric methods applied to identification, speciation, and quantification of analytes from works of art: an overview

Voltammetry of microparticles, an electrochemical methodology based on the record of the voltammetric response of sparingly soluble solids mechanically transferred to the surface of inert electrodes in contact with suitable electrolytes, is able to provide significant analytical information in the fields of conservation and restoration of cultural goods. Using this methodology, identification, speciation, and relative and absolute quantification of analytes from works of art samples can be achieved. Applications to the analysis of organic and inorganic pigments in paints, fibbers, ceramic materials as well as alteration compounds in paintings and metallic artifacts are reviewed.     

Multiple headspace-solid-phase microextraction: An application to quantification of mushroom volatiles

Multiple headspace-solid phase microextraction (MHS-SPME) followed by gas chromatography/mass spectrometry (GC–MS) and flame ionization detection (GC–FID) was applied to the identification and quantification of volatiles released by the mushroom Agaricus bisporus, also known as champignon. MHS-SPME allows to perform quantitative analysis of volatiles from solid matrices, free of matrix interferences. Samples analyzed were fresh mushrooms (chopped and homogenized) and mushroom-containing food dressings. 1-Octen-3-ol, 3-octanol, 3-octanone, 1-octen-3-one and benzaldehyde were common constituents of the samples analyzed. Method performance has been tested through the evaluation of limit of detection (LoD, range 0.033–0.078 ng), limit of quantification (LoQ, range 0.111–0.259 ng) and analyte recovery (92.3–108.5%). The results obtained showed quantitative differences among the samples, which can be attributed to critical factors, such as the degree of cell damage upon sample preparation, that are here discussed. Considerations on the mushrooms biochemistry and on the basic principles of MHS analysis are also presented.     

Simultaneous determination of p-phenylenediamines and aminophenols in hair dye products: interlaboratory study

An isocratic HPLC method routinely used in the National Laboratory for Food and Drug Analysis of Taiwan was validated for the simultaneous determination of six aminophenols and phenylenediamines in commercial hair dyes. After extraction of the commercial hair dye product, the dye intermediates were determined by HPLC. Recoveries from the extraction were between 91.6 and 96.5%. The method was then evaluated in an interlaboratory collaborative study according to AOAC guidelines. Five laboratories in Taiwan participated in the study that analyzed the test product, which was preanalyzed by two laboratories to ensure acceptable homogeneity. The RSD(r) and RSD(R) values of the measurements obtained for the dye intermediates in the product were < or = 3.75 and < or = 5.95%, respectively. The method demonstrated acceptable reproducibility, as evidenced by HorRat values of 0.82- 0.97. The applicability of the method to the determination of oxidative hair dye components was further demonstrated in analyses of two different products. The method is thus proposed to be used by manufacturers and laboratories to evaluate the quality of commercial hair dyes containing the six aminophenols and phenylenediamines.     

高效液相色谱法同时测定氧化型染发产品中33种染发剂

建立了高效液相色谱同时测定氧化型染发产品中33种禁限用染发剂含量的分析方法。采用Waters Atlantis^® T3 MV Kit色谱柱（250 mm×4.6 mm，5 μm），以磷酸盐缓冲液-乙腈为流动相，梯度洗脱，流速为1.0 mL/min，柱温为25℃；采用二极管阵列检测器（DAD），检测波长为235及280 nm，进样量为5 μL。结果表明，各成分在线性范围内线性关系良好，相关系数均高于0.999，各成分精密度实验相对标准偏差（RSDs）均小于2%；四氨基嘧啶硫酸盐和2，4-二氨基苯氧基乙醇盐酸盐在12 h内稳定性实验RSDs小于5%，其余31种成分在24 h内稳定性实验RSDs均小于5%；各成分在3个浓度水平下的加标回收率为77.6%~116.3%。该方法简便、快速、准确，适用于氧化型染发产品中多种染发剂的检测。     

Absorption spectroscopic investigation of rhodamine dye vapors

The dyes rhodamine 6G and rhodamine 19 are investigated. The dye stability versus temperature and time is studied. Bulk dye stuff is found to be less stable than dye adsorbed to the stainless steel cell walls and in the vapor phase. Rhodamine 6G converts to rhodamine 19 before evaporation. Adsorbed rhodamine 19 and rhodamine 19 vapor disintegrate most likely into 2,7-dimethylrhodamine 110 at elevated temperatures (> 320°C). For rhodamine 19 vapor the absorption spectrum, the saturated vapor density and the latent heat of evaporation are determined. The vapor absorption spectra of rhodamine 19 and 2,7-dimethylrhodamine 110 are compared with solution spectra.     

Synthesis of Ag NPs layer and its application as SERS substrate in the determination of p-phenylenediamine

Journal of Solid State Electrochemistry - An Ag nanoparticles (NPs) layer was synthesized on Ag sheet by alloying/electrochemical dealloying method: X-ray diffraction confirmed that the new Ag...     

Voltammetric,potentiometric and amperometric studies with a rotated aluminum wire electrode: Voltammetric behavior of the r.al.e.

A rotated aluminum wire electrode (R.Al.E.) is described for the determination of voltammograms and potentials. An aluminum electrode is highly polarizable both cathodically and anodically. Of all ions tested only hydroxyl and fluoride ions depolarize it anodically at highly negative potentials. In the absence of fluoride it is not a pH electrode, but it is a pOH electrode in the presence of an excess of hydroxyl ions. Fluoride in acid medium and hydroxyl ions yield well defined anodic diffusion currents. In the absence of fluoride or of an excess of hydroxyl ions the potential is ill defined. In acid medium a trace of fluoride (2.10^-5M or 0.4 p.p.m.) causes the potential to become approximately 600 mV more negative than in the absence of fluoride. At a pH greater than j l the potential varies 66 mV per unit change of pH.     

Primary constituents of blue cohosh: quantification in dietary supplements and potential for toxicity

Dietary supplements containing dried roots or extracts of the roots and/or rhizomes of blue cohosh (Caulophyllum thalictroides) are widely available. This botanical has a long history of use by Native Americans and its use continues to the present day. The primary constituents of blue cohosh are its alkaloids and saponins. The structures of the alkaloids magnoflorine, baptifoline, anagyrine, and N-methylcytisine have been known for many years. The last 10 years have seen a great increase in isolation and identification of the large number of saponins present in blue cohosh. Important developments in nuclear magnetic resonance techniques have contributed substantially to the increase in elucidation of the structures of the complex saponins. Several authors have described quantitative methods for both the alkaloids and saponins in blue cohosh. Such methods have made it possible to quantify these constituents in dietary supplements containing this botanical ingredient. Concentrations of both alkaloids and saponins vary substantially in dietary supplements of blue cohosh. The nicotinic alkaloid, N-methylcytisine, a potent toxicant, has been found in all dietary supplements of blue cohosh analyzed. The teratogenic alkaloid anagyrine has been found in some but not all dietary supplements.     

Voltammetric investigation of avidin-biotin complex formation using an electroactive bisbiotinyl compound

Formation of avidin-biotin complex was investigated using bisbiotinyl thionine (BBT) by means of voltammetric techniques. Thionine is an electroactive compound and has two amino groups that are necessary for the reaction with a biotinylation reagent. The biotinylation of thionine produces a new reagent with two biotin moieties at each end of thionine. Three BBTs of different lengths of the spacer that connects the biotin moiety to the thionine moiety were prepared. The avidin-biotin binding assay was achieved by measuring the electrode response of the thionine moiety in BBT. The binding affinity and the conformation of complex, which depended on the length of spacer, are discussed. BBT in which the spacer is shortest (BBT-S, distance between carbonyl group of the two biotin moieties: 11 Å) binds with only one avidin molecule. BBT with medium length of spacer (BBT-M, 28.8 Å) forms the complex with two avidin molecules. BBT with the longest spacer (BBT-L, 46.6 Å) allows binding with two avidin molecules as well as intramolecular binding within one avidin molecule. The affinity constants of BBT-S, BBT-M and BBT-L for avidin were estimated to be 7.0 × 10¹² M⁻¹, 3.2 × 10¹² M⁻¹ and 4.0 × 10¹² M⁻¹, respectively.