Miguel A. Cantarelli

Classification of Argentinean Sauvignon Blanc Wines by UV Spectroscopy and Chemometric Methods

UNLABELLED Argentina is an important worldwide wine producer. In this country, there are several recognizable provinces that produce Sauvignon blanc wines: Neuquén, Río Negro, Mendoza, and San Juan. The analysis of the provenance of these white wines is complex and requires the use of expensive and time-consuming techniques. For this reason, this work discusses the determination of the provenance of Argentinean Sauvignon blanc wines by the use of UV spectroscopy and chemometric methods, such as principal component analysis (PCA), cluster analysis (CA), linear discriminant analysis (LDA), and partial least square discriminant analysis (PLS-DA). The proposed method requires low-cost equipment and short-time analysis in comparison with other techniques. The results are in very good agreement with results based on the geographical origin of Sauvignon blanc wines. PRACTICAL APPLICATION This manuscript describes a method to determine the geographical origin of Sauvignon wines from Argentina. The main advantage of this method is the use of nonexpensive techniques, such as UV-Vis spectroscopy.

Determination of oleic acid in sunflower seeds by infrared spectroscopy and multivariate calibration method.

A method for the determination of oleic acid in sunflower seeds is proposed. One hundred samples of sunflower seeds were analyzed by near-infrared diffuse reflectance spectroscopy (NIRDRS). The direct measures were realized in ground and sifted seeds. The PLS multivariate calibration model was obtained using first derivate absorbance values as response matrix, while the oleic acid concentration matrix was obtained analyzing the seed samples by gas chromatography with a flame ionization detector (GC-FID). The NIRDRS-PLS model was validated externally using unknown samples of sunflower seeds. The accuracy and precision of the method was evaluated using GC as reference method. The following figures of merit (FOM) were obtained: LOD=3.4% (w/w); LOQ=11.3% (w/w); SEN=8x10(-5); SEL=0.15; analytical sensibility (gamma)=1.5 and linear range (LR)=18.1-89.2% (w/w). This method is useful for the fast determination of oleic acid in sunflower seeds and for quality control of raw materials.

Multielemental Analysis and Classification of Amaranth Seeds According to Their Botanical Origin

The characterization of amaranth seeds (Amaranthus spp.) was developed for Amaranthus hypochondriacus, Amaranthus cruentus, and Amaranthus dubius. The elemental concentrations were determined by inductively coupled plasma optic atomic spectroscopy. Pattern recognition methods were used for the characterization of seed samples: nonsupervised methods included principal components analysis and cluster analysis; supervised methods were linear discriminant analysis and partial least squares discriminant analysis (PLS-DA). Informed are the concentrations of the following elements: Ag, Al, Ba, Ca, Co, Cr, Cu, Fe, K, La, Li, Mg, Mn, Mo, Na, Ni, P, S, Sr, V, Zn, and Zr. The lowest mineral content was found in A. hypochondriacus, and the highest one was found in A. dubius. For the classification, selected variables for all multivariate methods were Ba, Cr, Li, Mn, Ni, S, and Sr. Nonsupervised methods allowed us to distinguish between the three species of amaranth; however, PLS-DA supervised methods showed the best prediction ability.

Chemometric tools for the characterisation of honey produced in La Pampa, Argentina, from their elemental content, using inductively coupled plasma optical emission spectrometry (ICP-OES)

Summary Thirty two samples of natural honey produced in the province of La Pampa (Argentina) were characterised on the basis of their phosphorous, aluminium, iron, calcium, magnesium and sodium contents. Analytical determinations were carried out using inductive coupled plasma optical emission spectrometry (ICP-OES). For characterisation, chemometric methods used were Principal Components Analysis (PCA) and Cluster Analysis (CA), while for classification, Linear Discriminant Analysis (LDA) was used. The results show that samples obtained within 50 km from the centre of the province (around Santa Rosa, the capital city), were different from those coming from the rest of the province, generating a classification based on geographical origin. Phosphorous content was the most significant variable in the classification of the PCA model.

Simultaneous determination of saccharin and aspartame in commercial noncaloric sweeteners using the PLS-2 multivariate calibration method and validation by capillary electrophoresis.

A new method to determine a mixture for sweetener sodium saccharin and aspartame in commercial noncaloric sweeteners is proposed. A classical full factorial design for standards was used in the calibration step to build the partial least-squares (PLS-2) model. Instrumental data were obtained by means of UV-visible spectrophotometry. Salicylic acid was used as an internal standard to evaluate the adjustment of the real samples to the PLS model. The concentration of analytes in the commercial samples was evaluated using the obtained model by UV spectral data. The PLS-2 method was validated by capillary zone electrophoresis (CZE), finding in all cases a relative error of less than 11% between the PLS-2 and the CZE methods. The proposed procedure was applied successfully to the determination of saccharin and aspartame in noncaloric commercial sweeteners.

Chemometric Characterization of Sunflower Seeds

The spectroscopic characterization of different varieties of sunflower seeds based on their oleic acid content is proposed. One hundred fifty samples of sunflower seeds from different places of Argentina were analyzed by near-infrared diffuse reflectance spectroscopy (NIRDRS). Seed samples were grounded and sieved without chemical treatment previous to the analysis. For the characterization, the used multivariate methods were: principal component analysis (PCA), cluster analysis (CA), linear discriminant analysis (LDA), and partial least square discriminant analysis (PLS-DA). By using PCA, CA, and LDA, and from the point of view of varieties of sunflower seeds, 2 groups were differentiated, based on the concentration of oleic acid: a low oleic group, which ranged from 15% to 25% w/w oleic acid; and the other one (mid-high oleic varieties) which ranged from 26% to 90% w/w oleic acid. However, by using the PLS-DA, 3 groups were correctly differentiated based on the concentration of oleic acid: low oleic (from 15% to 25% w/w oleic acid); mid oleic (26% to 76% w/w oleic acid); and high oleic (≥ than 77% w/w oleic acid), demonstrating the high classification ability of this method. This multivariate characterization of sunflower seed varieties did not require chromatographic analysis to generate the matrix of concentrations, and only direct measures of NIRDRS spectra were required. This characterization can be useful to quickly know the variety of sunflower seed in the grain market. Practical Applications: This manuscript describes a method to determine 3 varieties of sunflower seeds (high, mid, and low oleic) The advantage of this method is to avoid the use of techniques that require long-time analysis.

Study and Determination of As, Cr, and Pb in Amaranth Seeds

The concentration of As, Cr, and Pb toxic elements was determined in three species of amaranth seeds: A. hypochondriacus, A. cruentus, and A. dubius. The determinations were carried out by inductively coupled plasma optical atomic spectroscopy (ICP-OES). The result shows that Cr and As were found in minor concentrations than allowed by the World Health Organization (WHO; 120 and 4 mg kg−1 resp.); As (mg kg−1): A. dubius (0.76) A. cruentus (<0.50) and A. hypochondriacus (<0.50); Cr (mg kg−1): A. dubius (8.19) A. cruentus (1.15) and A. hypochondriacus (1.20). However, the concentration of Pb was high: A. dubius (19.04) A. cruentus (30.20) and A. hypochondriacus (35.56) more than the maximum of WHO (10 mg kg−1). To avoid systematic error, recovery and validation studies were performed: recovery test: 102.3%; validation (by standard addition): 96.0–103.1%. Due to the fact that amaranth had been proposed as new food due to its nutraceutical properties, the high concentration of Pb found in this study indicates that Pb should be evaluated in these amaranth species to avoid the intake of toxic element by human beings.

Changes in Amino Acid Profile in Roots of Glyphosate Resistant and Susceptible Soybean (Glycine max) Induced by Foliar Glyphosate Application

Amino acid profiles are useful to analyze the responses to glyphosate in susceptible and resistant soybean lines. Comparisons of profiles for 10 amino acids (Asp, Asn, Glu, Gln, Ser, His, Gly, Thr, Tyr, Leu) by HPLC in soybean roots were performed in two near isogenic pairs (four varieties). Foliar application of glyphosate was made to soybean plants after 5 weeks of seeding. Roots of four varieties were collected at 0 and 72 h after glyphosate application (AGA) for amino acid analysis by HPLC. Univariate analysis showed a significant increase of several amino acids in susceptible as well as resistant soybean lines; however, amino acids from the major pathways of carbon (C) and nitrogen (N) metabolism, such as Asp, Asn, Glu and Gln, and Ser, increased significantly in susceptible varieties at 72 h AGA. Multivariate analysis using principal component analysis (2D PCA and 3D PCA) allowed different groups to be identified and discriminated based on the soybean genetic origin, showing the amino acid responses on susceptible and resistant varieties. Based on the results, it is possible to infer that the increase of Asn, Asp, Glu, Gln, and Ser in susceptible varieties would be related to the deregulation of C and N metabolism, as well as changes in the growth mechanisms regulated by Ser.