HR MAS 1H NMR and chemometrics as useful tool to assess the geographical origin of cocoa beans - Comparison with HR 1H NMR.

Chocolate and cocoa-based products are among the goods with higher added value. A current trend of the cocoa market is to offer to the consumers high quality cocoa products, namely mono-origin cocoa. However, a reliable analytical method able to trace the geographical origin of cocoa is lacking. In this work we tested the capability of HR MAS 1H NMR combined with chemometrics to assess the geographical origins of 60 fermented and dried cocoa beans of 23 different cocoa producing countries from the three major crop-growing areas (Africa, Central/South America, Asia/Oceania). Metabolic profiling was determined by HR MAS 1H NMR directly on cocoa powder after the method optimization. The same samples were also subjected to extraction and analysis with HR 1H NMR. HR MAS 1H NMR, as 1H NMR analysis, allowed the simultaneous detection of amino acids, polyalcohols, organic acids, sugars, methylxanthines, catechins. Moreover, HR MAS allows the detection of lipids, not present in the aqueous extract utilized for 1H NMR. The data set obtained is therefore representative of all classes of cocoa compounds. Untargeted HR MAS 1H NMR and 1H NMR datasets were utilized as fingerprint of the samples and elaborated with multivariate statistical methods. A targeted quantitative approach of selected metabolites was possible only with HR 1H NMR data, because HR MAS 1H NMR does not give reliable quantitative results. All the approaches adopted showed a discrimination of the cocoa origins. HR MAS presents the advantages to obtain a very rapid picture of the samples, comprising both lipophilic and hydrophilic components, avoiding any sample manipulation.

Concentration of DL-PCBs in fish from market of Parma city (north Italy): estimated human intake.

The concentrations of 12 congeners of non-ortho and mono-ortho dioxin-like polychlorinated biphenyls (ΣDL-PCB) were measured in 30 fish samples from Parma markets by GC/MS technique. The samples were randomly purchased, choosing the species commonly found in supermarkets. The concentration of DL-PCBs estimated remained under the fixed Italian limit of 4 pg g(-1)ww WHO-TEQ (World Health Organization-Toxic Equivalent) in the major part of the samples, so the situation seems to be not at a level sufficient to pose a risk to human health of the Parma population. The medium daily intake for DL-PCBs for Italian consumers (Parma) was also estimated. This value generally resulted minor than 2 pg g(-1) ww WHO-TEQ kg(-1) body weight, exceeding only in four cases: eel, smooth hound, starry smooth hound and tuna.

Identification and quantification of the main organic components of vinegars by high resolution 1H NMR spectroscopy.

A detailed analysis of the proton high-field NMR spectra of vinegars (in particular of Italian balsamic vinegars) is reported. A large number of organic substances belonging to different classes, such as carbohydrates, alcohols, organic acids, volatile compounds and amino acids, were assigned. The possibility of quantification of the substances identified in the whole vinegar sample, without extraction or pre-concentration steps, was also tested. The data validity was demonstrated in terms of precision, accuracy, repeatability and inter-day reproducibility. The effects of the most critical experimental parameters (sample concentration, water suppression and relaxation time) on the analysis response were also discussed. (1)H NMR results were compared with those obtained by traditional techniques (GC-MS, titrations), and good correlations were obtained. The results showed that (1)H NMR with water suppression allows a rapid, simultaneous determination of carbohydrates (glucose and fructose), organic acids (acetic, formic, lactic, malic, citric, succinic and tartaric acids), alcohols and polyols (ethanol, acetoin, 2,3-butanediol, hydroxymethylfurfural), and volatile substances (ethyl acetate) in vinegar samples. On the contrary, the amino acid determination without sample pre-concentration was critical. The (1)H NMR method proposed was applied to different samples of vinegars, allowing, in particular, the discrimination of vinegars and balsamic vinegars.