M.L. Rodriguez-Mendez

Carbon Paste Electrodes Made from Different Carbonaceous Materials: Application in the Study of Antioxidants

This work describes the sensing properties of carbon paste electrodes (CPEs) prepared from three different types of carbonaceous materials: graphite, carbon microspheres and carbon nanotubes. The electrochemical responses towards antioxidants including vanillic acid, catechol, gallic acid, l-ascorbic acid and l-glutathione have been analyzed and compared. It has been demonstrated that the electrodes based on carbon microspheres show the best performances in terms of kinetics and stability, whereas G-CPEs presented the smallest detection limit for all the antioxidants analyzed. An array of electrodes has been constructed using the three types of electrodes. As demonstrated by means of Principal Component Analysis, the system is able to discriminate among antioxidants as a function of their chemical structure and reactivity.

Biomimetic biosensor based on lipidic layers containing tyrosinase and lutetium bisphthalocyanine for the detection of antioxidants

This paper describes the preparation of a biomimetic Langmuir-Blodgett film of tyrosinase incorporated in a lipidic layer and the use of lutetium bisphthalocyanine as an electron mediator for the voltammetric detection of phenol derivatives, which include one monophenol (vanillic acid), two diphenols (catechol and caffeic acid) and two triphenols (gallic acid and pyrogallol). The first redox process of the voltammetric responses is associated with the reduction of the enzymatically formed o-quinone and is favoured by the lutetium bisphthalocyanine because significant signal amplification is observed, while the second is associated with the electrochemical oxidation of the antioxidant and occurs at lower potentials in the presence of an electron mediator. The biosensor shows low detection limit (1.98×10(-6)-27.49×10(-6) M), good reproducibility, and high affinity to antioxidants (K(M) in the range of 62.31-144.87 μM). The excellent functionality of the enzyme obtained using a biomimetic immobilisation method, the selectivity afforded by enzyme catalysis, the signal enhancement caused by the lutetium bisphthalocyanine mediator and the increased selectivity of the curves due to the occurrence of two redox processes make these sensors exceptionally suitable for the detection of phenolic compounds.

Screening analysis of beer ageing using near infrared spectroscopy and the Successive Projections Algorithm for variable selection

This work proposes a method for monitoring the ageing of beer using near-infrared (NIR) spectroscopy and chemometrics classification tools. For this purpose, the Successive Projections Algorithm (SPA) is used to select spectral variables for construction of Linear Discriminant Analysis (LDA) classification models. A total of 83 alcoholic and non-alcoholic beer samples packaged in bottles and cans were examined. To simulate a long storage period, some of the samples were stored in an oven at 40°C, in the dark, during intervals of 10 and 20 days. The NIR spectrum of these samples in the range 12,500-5405 cm(-1) was then compared against those of the fresh samples. The results of a Principal Component Analysis (PCA) indicated that the alcoholic beer samples could be clearly discriminated with respect to ageing stage (fresh, 10-day or 20-day forced ageing). However, such discrimination was not apparent for the non-alcoholic samples. These findings were corroborated by a classification study using Soft Independent Modelling of Class Analogy (SIMCA). In contrast, the use of SPA-LDA provided good results for both types of beer (only one misclassified sample) by using a single wavenumber in each case, namely 5550 cm(-1) for non-alcoholic samples and 7228 cm(-1) for alcoholic samples.

Evaluation of oxygen exposure levels and polyphenolic content of red wines using an electronic panel formed by an electronic nose and an electronic tongue

An electronic panel formed by an electronic nose and an electronic tongue has been used to analyse red wines showing high and low phenolic contents, obtained by flash release and traditional soaking, respectively, and processed with or without micro-oxygenation. Four oxygen transfer rate conditions (0.8, 1.9, 8.0, and 11.9 μl oxygen/bottle/day) were ensured by using synthetic closures with controlled oxygen permeability and storage under controlled atmosphere. Twenty-five chemical parameters associated with the polyphenolic composition, the colour indices and the levels of oxygen were measured in triplicate and correlated with the signals registered (seven replicas) by means of the electronic nose and the electronic tongue using partial least squares regression analysis. The electronic nose and the electronic tongue showed particularly good correlations with those parameters associated with the oxygen levels and, in particular, with the influence of the porosity of the closure to oxygen exposure. In turn, the electronic tongue was particularly sensitive to redox species including oxygen and phenolic compounds. It has been demonstrated that a combined system formed from the electronic nose and the electronic tongue provides information about the chemical composition of both the gas and the liquid phase of red wines. This complementary information improves the capacity to predict values of oxygen-related parameters, phenolic content and colour parameters.

Optimized architecture for Tyrosinase-containing Langmuir–Blodgett films to detect pyrogallol

The control of molecular architectures has been a key factor for the use of Langmuir–Blodgett (LB) films in biosensors, especially because biomolecules can be immobilized with preserved activity. In this paper we investigated the incorporation of tyrosinase (Tyr) in mixed Langmuir films of arachidic acid (AA) and a lutetium bisphthalocyanine (LuPc2), which is confirmed by a large expansion in the surface pressure isotherm. These mixed films of AA–LuPc2 + Tyr could be transferred onto ITO and Pt electrodes as indicated by FTIR and electrochemical measurements, and there was no need for crosslinking of the enzyme molecules to preserve their activity. Significantly, the activity of the immobilised Tyr was considerably higher than in previous work in the literature, which allowed Tyr-containing LB films to be used as highly sensitive voltammetric sensors to detect pyrogallol. Linear responses have been found up to 400 μM, with a detection limit of 4.87 × 10−2 μM (n = 4) and a sensitivity of 1.54 μA μM−1 cm−2. In addition, the Hill coefficient (h = 1.27) indicates cooperation with LuPc2 that also acts as a catalyst. The enhanced performance of the LB-based biosensor resulted therefore from a preserved activity of Tyr combined with the catalytic activity of LuPc2, in a strategy that can be extended to other enzymes and analytes upon varying the LB film architecture.

Bioelectronic tongue based on lipidic nanostructured layers containing phenol oxidases and lutetium bisphthalocyanine for the analysis of grapes

In this work, a multisensor system formed by nanostructured voltammetric biosensors based on phenol oxidases (tyrosinase and laccase) has been developed. The enzymes have been incorporated into a biomimetic environment provided by a Langmuir-Blodgett (LB) film of arachidic acid (AA). Lutetium bisphthalocyanine (LuPc2) has also been introduced in the films to act as electron mediator. The incorporation of the enzymes to the floating layers to form Tyr/AA/LuPc2 and Lac/AA/LuPc2 films has been confirmed by the expansion in the surface pressure isotherms and by the AFM images. The voltammetric response towards six phenolic compounds demonstrates the enhanced performance of the biosensors that resulted from a preserved activity of the tyrosinase and laccase combined with the electron transfer activity of LuPc2. Biosensors show improved detection limits in the range of 10(-7)-10(-8) mol L(-1). An array formed by three sensors AA/LuPc2, Tyr/AA/LuPc2 and Lac/AA/LuPc2 has been employed to discriminate phenolic antioxidants of interest in the food industry. The Principal Component Analysis scores plot has demonstrated that the multisensor system is able to discriminate phenols according to the number of phenolic groups attached to the structure. The system has also been able to discriminate grapes of different varieties according to their phenolic content. This good performance is due to the combination of four factors: the high functionality of the enzyme obtained using a biomimetic immobilization, the signal enhancement caused by the LuPc2 mediator, the improvement in the selectivity induced by the enzymes and the complementary activity of the enzymatic sensors demonstrated in the loading plots.

Analysis of the influence of the type of closure in the organoleptic characteristics of a red wine by using an electronic panel

An electronic panel formed by an electronic nose, an electronic tongue and an electronic eye has been successfully used to evaluate the organoleptic characteristics of red wines vinified using different extraction techniques and micro-oxygenation methods and bottled using closures of different oxygen transmission rates (OTR). The three systems have demonstrated a good capability of discrimination by means of Principal Component Analysis (PCA). Partial Least Squares Discriminant Analysis (PLS-DA) has permitted to establish prediction models based on the type of closure, the polyphenol content or the effect of micro-oxygenation. The best correlations found using the e-eye and the e-nose are related to the OTR of the closure. In contrast, the electronic tongue is more sensitive to the polyphenol content. The discrimination and prediction capabilities of the system are significantly improved when signals from each module are combined. The electronic panel can be a useful tool for the characterisation and control of oxygen and antioxidant capability of red wines.

Immobilization of lutetium bisphthalocyanine in nanostructured biomimetic sensors using the LbL technique for phenol detection

This study describes the development of amperometric sensors based on poly(allylamine hydrochloride) (PAH) and lutetium bisphthalocyanine (LuPc(2)) films assembled using the Layer-by-Layer (LbL) technique. The films have been used as modified electrodes for catechol quantification. Electrochemical measurements have been employed to investigate the catalytic properties of the LuPc(2) immobilized in the LbL films. By chronoamperometry, the sensors present excellent sensitivity (20 nA μM(-1)) in a wide linear range (R(2)=0.994) up to 900 μM and limit of detection (s/n=3) of 37.5 × 10(-8)M for catechol. The sensors have good reproducibility and can be used at least for ten times. The work potential is +0.3 V vs. saturated calomel electrode (SCE). In voltammetry measurements, the calibration curve shows a good linearity (R(2)=0.992) in the range of catechol up to 500 μM with a sensitivity of 90 nA μM(-1) and LD of 8 μM.

Classification of non-alcoholic beer based on aftertaste sensory evaluation by chemometric tools

Sensory evaluation is the application of knowledge and skills derived from several different scientific and technical disciplines, physiology, chemistry, mathematics and statistics, human behavior, and knowledge about product preparation practices. This research was aimed to evaluate aftertaste sensory attributes of commercial non-alcoholic beer brands (P1, P2, P3, P4, P5, P6, P7) by several chemometric tools. These attributes were bitter, sour, sweet, fruity, liquorice, artificial, body, intensity and duration. The results showed that the data are in a good consistency. Therefore, the brands were statistically classified in several categories. Linear techniques as Principal Component Analysis (PCA) and Linear Discriminant Analysis (LDA) were performed over the data that revealed all types of beer are well separated except a partial overlapping between zones corresponding to P4, P6 and P7. In this research, for the confirmation of the groups observed in PCA and in order to calculate the errors in calibration and in validation, PLS-DA technique was used. Based on the quantitative data of PLS-DA, the classification accuracy values were ranked within 49-86%. Moreover, it was found that the classification accuracy of LDA was much better than PCA. It shows that this trained sensory panel can discriminate among the samples except an overlapping between two types of beer. Also, two types of artificial networks were used: Probabilistic Neural Networks (PNN) with Radial Basis Functions (RBF) and FeedForward Networks with Back Propagation (BP) learning method. The highest classification success rate (correct predicted number over total number of measurements) of about 97% was obtained for RBF followed by 94% for BP. The results obtained in this study could be used as a reference for electronic nose and electronic tongue in beer quality control.

Analysis of organic acids and phenols of interest in the wine industry using Langmuir-Blodgett films based on functionalized nanoparticles.

A chemically modified electrode consisting of Langmuir-Blodgett (LB) films of n-dodecanethiol functionalized gold nanoparticles (SDODAuNP-LB), was investigated as a voltammetric sensor of organic and phenolic acids of interest in the wine industry. The nanostructured films demonstrated interfacial properties being able to detect the main organic acids present in grapes and wines (tartaric, malic, lactic and citric). Compared to a bare ITO electrode, the modified electrodes exhibited a shift of the reduction potential in the less positive direction and a marked enhancement in the current response. Moreover, the increased electrocatalytic properties made it possible to distinguish between the different dissociable protons of polyprotic acids. The SDODAuNP-LB sensor was also able to provide enhanced responses toward aqueous solutions of phenolic acids commonly found in wines (caffeic and gallic acids). The presence of nanoparticles increased drastically the sensitivity toward organic acids and phenolic compounds. Limits of detection as low as 10(-6) mol L(-1) were achieved. Efficient catalytic activity was also observed in mixtures of phenolic acid/tartaric in the range of pHs typically found in wines. In such mixtures, the electrode was able to provide simultaneous information about the acid and the phenol concentrations with a complete absence of interferences. The excellent sensing properties shown by these sensors could be attributed to the electrocatalytic properties of the nanoparticles combined with the high surface to volume ratio and homogeneity provided by the LB technique used for the immobilization. Moreover, the LB technique also provided an accurate method to immobilize the gold nanoparticles giving rise to stable and reproducible sensors showing repeatability lower than 2% and reproducibility lower than 4% for all the compounds analyzed.