Second-order electrochemical data generation to quantify carvacrol in oregano essential oils.

A novel analytical method using voltammetric second-order modeling based on multivariate curve resolution-alternating least-square (MCR-ALS) is presented for the first time for the quantitation of carvacrol (CAR) in oregano essential oils (OEO). The second-order cyclic voltammetry data were generated on the basis that CAR shows a diffusional system. Thus, the scan rate (v) was used as a second instrumental mode and cyclic voltammograms at different v were acquired for a single sample, generating the second-order data. CAR determination was performed in presence of thymol, included as a potential interferent. Results demonstrated that MCR-ALS successfully exploited the second-order advantage and the recoveries were not statistically different than 100%. The limits of detection and quantitation were estimated using the MCR-ALS which were 6.27 × 10-5°mol°L-1°and 1.90 × 10-4°mol L-1, respectively. Finally, the developed methodology was implemented to quantify of CAR in OEO samples.

Electrochemical magneto immunosensor based on endogenous ß-galactosidase enzyme to determine enterotoxicogenic Escherichia coli F4 (K88) in swine feces using square wave voltammetry.

Diseases caused by enterotoxicogenic Escherichia coli F4 (K88) (ETEC F4) are a problem in swine production establishments. Due to the high rate of mortality and morbidity of E. coli infections, a rapid and accurate diagnosis is important in order to choose an appropriate treatment to reduce the economic impact. Therefore, an electrochemical magneto-immunosensor (EMI) was developed to detect and quantify ETEC F4 in swine feces samples through a direct non-competitive immunoassay. ETEC F4 was selectively captured by immunomagnetic separation. The detection principle was based on the activity of ß-galactosidase endogenous enzyme (ß-gal), which hydrolyses the p-aminophenyl-ß-D-galactopyranoside (p-APG) producing p-aminophenol (p-AP), which was oxidized on a carbon screen printed electrode (CSPE) using square wave voltammetry (SWV). All parameters related to construction and electrochemical responses were optimized. The total analysis time to quantify ETEC F4 using the EMI was less than 2h and the limit of detection (LOD) was 33CFUmL-1. The perceptual relative error (%Er) was 20%. The magneto-immunosensor was validated versus conventional method of culture and plate count, obtaining a very good agreement. The EMI is simple, fast and economical to detect and quantify ETEC F4 in swine feces samples, being thus a valuable tool in swine production.

Eletrochemical reduction of patulin and 5-hydroxymethylfurfural in both neutral and acid non-aqueous media. Their electroanalytical determination in apple juices.

The electro-reduction of patulin mycotoxin and 5-hydroxymethylfurfural at glassy carbon electrodes in acetonitrile +0.1 mol L(-1) tetrabutylammonium perchlorate, in both the absence and the presence of different aliquots of trifluoroacetic acid is reported. 5-hydroxymethylfurfural is the most common interference in the determination of patulin in products derived from apples. The electrochemical techniques were cyclic and square wave voltammetries, and controlled potential bulk electrolysis. The number of electrons exchanged in the patulin electro-reduction of n=1 could be inferred from controlled potential bulk electrolysis measurements. Ultraviolet-visible and infrared spectroscopies were used to identify patulin electro-reduction product/s. A value of (2.1±0.1)×10(-5) cm(2) s(-1) for the patulin diffusion coefficient was calculated from convoluted cyclic voltammograms. A method based on square wave voltammetry was developed for the quantitative determination of patulin in both fresh, and commercial apple juices in the presence of 5-hydroxymethylfurfural. Calibration curves obtained from solutions of the commercial reagent, and commercial apple juices were linear in the range from 3.0×10(-7) to 2.2×10(-5) mol L(-1). The lowest concentration measured experimentally for a signal to noise ratio of 3:1 was 3×10(-7) mol L(-1) (45 ppb) and a recovery percent of 84% was determined for commercial apple juices. This electroanalytical methodology appears as a good screening method for the determination of patulin in apple juices.

Qualitative and quantitative electroanalysis of synthetic phenolic antioxidant mixtures in edible oils based on their acid-base properties.

A simple electroanalytical method using square wave voltammetry at a Pt band ultramicroelectrode to perform a qualitative and quantitative analysis of different synthetic antioxidant mixtures permitted by official regulations in edible oils is proposed. The methodology was based on the comparison of voltammetric signals obtained in acetonitrile+0.1M (C4H9)4NF6P with those recorded in the same reaction medium when different aliquots of (C4H9)4NOH were added to allow a qualitative differentiation between antioxidants. Firstly, studies on solutions prepared from commercial reagents were carried out. Then, the results obtained were transferred to the analysis of a real matrix, i.e., an edible olive oil. From real samples spiked with a known amount of different synthetic antioxidant mixtures, we could deduce the presence of these antioxidants by comparing results obtained in the neutral medium with those obtained after the successive addition of base. The standard addition method was used to quantify the individually spiked synthetic antioxidants in the real sample. Recovery percentages were between 88% and 118%. The reproducibility was 1.5%, 3.1%, 4.1% and 4.1% in ACN+0.1M TBAHFP and 1.5%, 4.6%, 6.6% and 2.5% in Bz/EtOH (1:2)+0.1M H2SO4 for TBHQ, BHA, BHT and PG, respectively. The repeatability was 1% for PG in both media. These parameters show a good system performance.