Voltammetric determination of tartaric acid in wines by electrocatalytic oxidation on a cobalt(II)-phthalocyanine-modified electrode associated with multiway calibration.

The electrocatalytic oxidation of tartaric acid on a carbon paste electrode modified with cobalt (II)-phthalocyanine was demonstrated and applied to the development of a highly sensitive, simple, fast and inexpensive voltammetric sensor to determine tartaric acid. The electrochemical behavior of the modified electrode was investigated by cyclic and square wave voltammetry, and the effect of experimental variables, such as dispersion and loading of cobalt (II)-phthalocyanine, together with optimum conditions for sensing the analyte by square wave voltammetry were assessed. In addition, the absence of a significant memory effect combined with the ease of electrode preparation led to the development of a sensitive and direct method to determine tartaric acid in wines. Interferences from other low molecular weight organic acids commonly present in wines were circumvented by using a multiway calibration technique, successfully obtaining the second order advantage by modeling voltammetric data with unfolded partial least square with residual bilinearization (U-PLS/RBL). A linear response range between 10 and 100 µmol L-1 (r = 0.9991), a relative prediction error of 4.55% and a recovery range from 96.41 to 102.43% were obtained. The proposed method is non-laborious, since it does not use sample pretreatment such as filtration, extraction, pre-concentration or cleanup procedures.

In-line electrochemical reagent generation coupled to a flow injection biamperometric system for the determination of sulfite in beverage samples.

This work reports an in-line electrochemical reagent generation coupled to a flow injection biamperometric procedure for the determination of SO3(2-). The method was based on a redox reaction between the I3(-) and SO3(2-) ions, after the diffusion of SO2 through a gas diffusion chamber. Under optimum experimental conditions, a linear response ranging from 1.0 to 12.0 mg L(-1) (R=0.9999 and n=7), a detection and quantification limit estimated at 0.26 and 0.86 mg L(-1), respectively, a standard deviation relative of 0.4% (n=10) for a reference solution of 4.0 mg L(-1) SO3(2-) and sampling throughput for 40 determinations per hour were achieved. Addition and recovery tests with juice and wine samples were performed resulting in a range between 92% and 110%. There were no significant differences at a 95% confidence level in the analysis of eight samples when comparing the new method with a reference procedure.

Electrochemical study of ricin at glassy carbon electrode.

Ricin, Ricinus communis agglutinin 60 - RCA 60, is a deadly phytotoxic protein which inhibits ribosomes (class II), and there is no known effective antidote in living organisms. Ricin is composed of two polypeptide chains, A and B, linked covalently by a single disulfide bond. The analytical methods for the detection of RCA 60 are commonly laborious, expensive, require skilled labor, and involve sophisticated equipment. Aimed at the development of electroanalytical methods for RCA 60 detection, here we studied the electrochemical oxidation of RCA 60 on a glassy carbon (GC) electrode over a wide pH range, using cyclic voltammetry, differential pulse voltammetry (DPV) and square wave voltammetry (SWV). Two quasi-reversible electrochemical RCA 60 oxidation peaks were identified on the GC electrode by SWV. For values of 2.2 ≤ pH ≤ 10.2, DPV studies revealed that the peak potentials, EP1 and EP2, display a linear dependence with pH and the reaction mechanism involves the transfer of 2H⁺/2e⁻ (peak 1) and 1H⁺/1e⁻ (peak 2). The first and second RCA 60 oxidation steps may correspond to the oxidation of cysteine and tyrosine-tryptophan residues, respectively. The oxidation product of the second RCA 60 oxidation step appears at 7.0 ≤ pH ≤ 11.8. For pH ≥ 10.2, both processes are pH independent, resulting in a pKa of ca. 10.2. A third RCA 60 oxidation peak only appears at acidic pH. RCA 60 samples extracted from different castor seed cultivars showed similar electrochemical behavior, enabling the implementation of an analytical voltammetric method.

Automatic determination of chlorine without standard solutions using a biamperometric flow-batch analysis system.

This study presents an automatic analysis system that does not require the use of standard solutions. The system uses an electrochemical flow cell for in line generation of the standards, and operates under the standard addition technique. The versatility of this system was demonstrated by the development of a one key touch fully automatic method for the determination of total available chlorine in real samples. The extremely simple, accurate and inexpensive method was based simply on the biamperometric monitoring of the well known redox reaction of chlorine with iodide ions in a flow-batch system, where the produced iodine (triiodide ions) generates an electrical current proportional to the chlorine concentration in the sample. The flow-batch parameters were optimized to maximize the sensitivity without losses on the precision of the analysis. An excellent linear dependence between the biamperometric signal and the chlorine concentration for the standard additions and a good agreement between the proposed approach and a reference method were obtained. The method was successfully applied to determine chlorine in several different bleach and chlorinated water samples (r=0.9995, LOD=8.261 x 10(-7) mol L(-1)) and could be easily extended to other oxidants and samples. Comparison to a reference method and recoveries close to 100% demonstrated the reliability of the proposed method. In addition, low residue disposal and reagent consumption, allied with high accuracy and precision, make it very promising for routine applications.

The Application of DNA-Biosensors and Differential Scanning Calorimetry to the Study of the DNA-Binding Agent Berenil.

The in situ DNA-damaging capacity of berenil (1) has been investigated usingan electrochemical approach employing double stranded (ds) DNA-modified glassy carbonelectrode biosensors. Electrochemical voltammetric sensing of damage caused by 1 todsDNA was monitored by the appearance of peaks diagnostic of the oxidation of guanineand adenine. When 1 was incorporated directly onto the biosensor surface, DNA damagecould be observed at concentrations of additive as low as 10 µM. In contrast, when thedsDNA-modified biosensor was exposed to 1, in acetate buffer solution, the method wasmuch less sensitive and DNA damage could be detected only in the presence of 100 µMberenil. When mixed solutions of 1 and single stranded (ss) DNA, polyguanylic acid orpolyadenylic acid were submitted to voltammetric study, the oxidation signals of therespective bases decreased in a concentration-dependent manner and the major variation ofthe adenine current peak indicated preferential binding of 1 to adenine. The electrochemical results were in close agreement with those deriving from a differentialscanning calorimetric study of the DNA-berenil complex.