Differentiation between Ripening Stages of Iberian Dry-Cured Ham According to the Free Amino Acids Content.

In this paper, the differentiation of three ripening stages, postsalting, drying, and cellar, of Iberian dry-cured ham has been carried out according to their free amino acids contents. Eighteen L-amino acids, alanine, 2-aminobutanoic acid, aspartic acid, cysteine, glutamine, glycine, histidine, hydroxyproline, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tyrosine, and valine have been determined by gas chromatography with derivatization with N,O-bis(trimethylsilyl)-trifluoroacetamide. Gas chromatography-mass spectrometry was used to confirm the presence of the eighteen amino acids in the ham samples, and gas chromatography using a DB-17HT column and flame ionization detector was used for quantitative determination. Extraction with a mixture methanol-acetonitrile has been carried out, achieving recoveries in the range 52-164%. Methimazole was used as internal standard. Limits of detection ranged between 7.0 and 611.7 mg·kg-1. Free amino acids have been used as chemical descriptors to differentiate between the ripening stages. Principal component analysis and linear discriminant analysis have been used as chemometric techniques, achieving complete differentiation between the ripening stages. Alanine, tyrosine, glutamine, proline, 2-aminobutanoic acid, cysteine, and valine were the most differentiating amino acids.

A uniform nonlinearity criterion for rational functions applied to calibration curve and standard addition methods.

Rational functions of the Padé type are used for the calibration curve (CCM), and standard addition (SAM) methods purposes. In this paper, the related functions were applied to results obtained from the analyses of (a) nickel with use of FAAS method, (b) potassium according to FAES method, and (c) salicylic acid according to HPLC-MS/MS method. A uniform, integral criterion of nonlinearity of the curves, obtained according to CCM and SAM, is suggested. This uniformity is based on normalization of the approximating functions within the frames of a unit area.

Geographical characterization of Spanish PDO paprika by multivariate analysis of multielemental content.

A multielemental analytical method has been proposed to determine the contents of Al, B, Ca, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Sr and Zn in paprika samples from the two Protected Designations of Origin recognized in Spain, such as Murcia and La Vera (Extremadura). The samples are mineralized by acid wet digestion using a mixture of perchloric and nitric acids and analyzed by means of inductively coupled plasma atomic emission spectroscopy. The method performance has been checked studying the absence of matrix effect, trueness, precision, linearity, limit of detection and limit of quantification. The proposed method has been applied to analyze samples of sweet, hot and hot/sweet paprika from the considered production areas. Differences between paprika samples from Murcia and Extremadura were found and pattern recognition methods, such as linear discriminant analysis, linear support vector machines, soft independent modeling of class analogy and multilayer perceptrons artificial neural networks, has been used to obtain classification models. Sweet and hot/sweet paprika types were differentiated by means of linear models and hot paprika was differentiated by using artificial neural networks. A model based on artificial neural networks is proposed to differentiate the geographical origin of paprika, with independence of the type, leading to an overall classification performance of 99%.

Characterisation of tequila according to their major volatile composition using multilayer perceptron neural networks.

Differentiation of silver, gold, aged and extra-aged tequila using 1-propanol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanol and 2-methyl-1-butanol and furan derivatives like 5-(hydroxymethyl)-2-furaldehyde and 2-furaldehyde has been carried out. The content of 1-propanol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanol and 2-methyl-1-butanol was determined by means of head space solid phase microextraction gas chromatography mass-spectrometry. 5-(Hydroxymethyl)-2-furaldehyde and 2-furaldehyde were determined by high performance liquid chromatography with diode array detection. Kruskal-Wallis test was used to highlight significant differences between types of tequila. Principal component analysis was applied as visualisation technique. Linear discriminant analysis and multilayer perceptron artificial neural networks were used to construct classification models. The best classification performance was obtained when multilayer perceptron model was applied.

Differentiation of tea varieties using UV-Vis spectra and pattern recognition techniques.

Tea, one of the most consumed beverages all over the world, is of great importance in the economies of a number of countries. Several methods have been developed to classify tea varieties or origins based in pattern recognition techniques applied to chemical data, such as metal profile, amino acids, catechins and volatile compounds. Some of these analytical methods become tedious and expensive to be applied in routine works. The use of UV-Vis spectral data as discriminant variables, highly influenced by the chemical composition, can be an alternative to these methods. UV-Vis spectra of methanol-water extracts of tea have been obtained in the interval 250-800 nm. Absorbances have been used as input variables. Principal component analysis was used to reduce the number of variables and several pattern recognition methods, such as linear discriminant analysis, support vector machines and artificial neural networks, have been applied in order to differentiate the most common tea varieties. A successful classification model was built by combining principal component analysis and multilayer perceptron artificial neural networks, allowing the differentiation between tea varieties. This rapid and simple methodology can be applied to solve classification problems in food industry saving economic resources.

Classification of Spanish DO white wines according to their elemental profile by means of support vector machines.

Spanish white wines from four production areas protected by Appellation Control laws have been analysed by inductively coupled plasma optical emission spectrometry to determine the contents of aluminium, barium, boron, calcium, chromium, copper, iron, magnesium, manganese, nickel, phosphorous, potassium, silicon, sodium, strontium, sulphur and zinc. These elements were used as chemical descriptors in order to differentiate wines from different brands certified of origin. Kruskal-Wallis test was applied to highlight significant differences between the four considered classes and pattern recognition methods were applied to construct classification models. In this way, principal component analysis was used to visualise data trends and backward stepwise linear discriminant analysis was applied in order to reduce the number of input variables. The concentrations of chromium, manganese, silicon, sodium and strontium were used to construct a support vector machine classification model, obtaining a 100% of classification performance.

Reorientation of thiols during 2D self-assembly: interplay between steric and energetic factors.

Reorientation of thiols during their 2D self-assembly is well established; however, little is known about its energetics and the factors that control its onset. We have developed a new strategy to determine the critical reorientational surface concentration (crsc) of thiols at the substrate/solution interface, which makes use of a cathodic stripping protocol. Its application to distinct homologous series of alkylthiols shows that the magnitude of the crsc and its variation with the molecular size is strongly dependent on the nature of the terminal group. Methyl-terminated alkylthiols reorient close to the saturation coverage of the lying-down phase, thus following their molecular size trend; whereas reorientation of alkylthiols bearing a negatively charged end group starts well below the monolayer coverage of the lying-down phase, with its onset being almost independent of the molecular size. Hydroxy-terminated alkylthiols show an intermediate behavior. A theoretical approach is developed to determine the reorientation equilibrium constant from the crsc value. The standard free energy of reorientation has been found to vary linearly with the alkyl chain length, and to increase upon replacing the terminal methyl group by a negatively charged one. A quantitative correlation between the reorientation equilibrium constant and the hydrophobicity of the molecule has been established. Overall, these findings have allowed us to disentangle the role of steric and energetic factors in the onset of the reorientation process of alkylthiols, demonstrating that their interplay can be finely tuned by varying either the alkyl chain length or the nature of the terminal group.

Quantitation of twelve metals in tequila and mezcal spirits as authenticity parameters.

In this paper the differentiation of silver, gold, aged and extra-aged tequila and mezcal has been carried out according to their metal content. Aluminum, barium, calcium, copper, iron, magnesium, manganese, potassium, sodium, strontium, zinc, and sulfur were determined by inductively coupled plasma optical emission spectrometry. The concentrations found for each element in the samples were used as chemical descriptors for characterization purposes. Principal component analysis, linear discriminant analysis and artificial neural networks were applied to differentiate types of tequila and mezcal. Using probabilistic neural networks 100% of success in the classification was obtained for silver, gold, extra-aged tequila and mezcal. In the case of aged tequila 90% of samples were successfully classified. Sodium, potassium, calcium, sulfur, magnesium, iron, strontium, copper and zinc were the most discriminant elements.