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Uso del QPCS con matricole universitarie (PLS–Chimica Unibo) dall’a.a. 2018-19, con ipotesi di partenza: lo sviluppo dell’autodirezione nell’apprendimento favorisce la continuità negli studi. Il percorso è in tre fasi: a) somministrazione del QPCS a matricole chimiche (N=436); b) restituzione in presenza dei risultati; c) tutorato a 44 studenti. Riflessioni: modalità di restituzione, uso dei risultati QPCS, reazioni degli studenti. Obiettivo: costruire un quadro concettuale per futura ricerca., Dirigere se stessi nello studio e nel lavoro. Competenzestrategiche.it: strumenti e applicazioni

The present review proposes an exhaustive focus on what are the metals of interest, and what is the state of the art about analytical methodologies suitable to detect these toxic metals in herbal medicines. This review would also be a stimulus to solicit International Organizations to fill the gap of the lack of strict and comprehensive laws regulating the maximum allowable concentrations for an increasing number of contaminants in these matrices, especially considering their enormous consumption. Herbal medicines are more and more worldwide used. This fact certainly presents serious problems for the potential human health risks. This is due to the fact that the laws in force generally do not provide for strict quality controls of herbal medicines to certify the concentration of compounds and elements that may be hazardous for human health, and sometimes very severe or even lethal. Heavy metals have a decidedly substantial part of the contaminants in herbal medicines.

Yeasts are widely used in several areas of food industry, e.g. baking, beer brewing, and wine production. Interest in new analytical methods for quality control and characterization of yeast cells is thus increasing. The biophysical properties of yeast cells, among which cell size, are related to yeast cell capabilities to produce primary and secondary metabolites during the fermentation process. Biophysical properties of winemaking yeast strains can be screened by field-flow fractionation (FFF). In this work we present the use of flow FFF (FlFFF) with turbidimetric multi-wavelength detection for the number–size distribution analysis of different commercial winemaking yeast varieties. The use of a diode-array detector allows to apply to dispersed samples like yeast cells the recently developed method for number–size (or mass–size) analysis in flow-assisted separation techniques. Results for six commercial winemaking yeast strains are compared with data obtained by a standard method for cell sizing (Coulter counter). The method here proposed gives, at short analysis time, accurate information on the number of cells of a given size, and information on the total number of cells.

An authenticity study on Italian grape marc spirit was carried out by gas chromatography (GC) and chemometrics. A grape marc spirit produced in Italy takes the particular name of “grappa”, a product which has peculiar tradition and production in its country of origin. Therefore, the evaluation of its authenticity plays an important role for its consumption in Italy, as well as for its exportation all around the world. For the present work, 123 samples of grappa and several kinds of spirits were analyzed in their alcohol content by electronic densimetry, and in their volatile fraction by gas-chromatography with a flame-ionization detector. Part of these samples (94) was employed as a training set to compute a chemometric model (by linear discriminant analysis, LDA) and the other part (29 samples) was used as a test set to validate it. Finally, two grappa samples seized from the market by the Italian Customs and Monopolies Agency and considered suspicious due to their aroma reported as non-compliant were projected onto the LDA model to evaluate the compliance with the “grappa” class. A further one-class classification method by principal component analysis (PCA) was carried out to evaluate the compliance with other classes. Results showed that the suspicious samples were not recognized as belonging to any of the analyzed spirit classes, confirming the starting hypothesis that they could be grappa samples adulterated in some way.

Accomplishing the Italian law to verify honey quality is onerous, because it requires measuring many chemical and physical parameters. On the contrary, bioluminescence-based analytical methods allow for rapid and inexpensive analysis. Bioluminescence has never been applied before to verify honey adulteration. The application of chemometrics to analytical methods based on bioluminescence has been here explored for this scope. Several honey samples were prepared, in which sugar syrup was added without exceeding legal limits: in this case, univariate analysis prescribed by the law cannot reveal the fraud. All samples were subjected to measurements of parameters prescribed by the law and also to bioluminescence analysis, executed using the Vibrio fischeri bacterium, one of the most common bioluminescent bacteria. Principal components analysis, linear discriminant analysis, and partial least square regression were applied to discriminate sugar-added honeys with respect to natural honeys, both by regulated physicochemical parameters and by bioluminescence ones. The feasibility of combining bioluminescence and multivariate analysis for a rapid screening of honey authenticity was demonstrated.

The direct quantification of Active Pharmaceutical Ingredients in solid formulations is a challenging open issue. A consolidated analytical technique based on X-ray Powder Diffraction is available, being the definitive test for the identification of polymorphs and crystal phases. However, its application for quantitative analysis is hindered by matrix effects: refinement methods (e.g. Rietveld method) require a complete knowledge of samples' composition, while univariate calibration methods require the matrix effect to be studied and severely suffer from the co-presence of crystalline and amorphous phases in the sample. Multivariate analysis is the only way to bypass problems affecting refinements procedures and univariate calibration. In particular, the multivariate standard addition method (SAM) is promising; however, it is straightforward only when the analytical blank (matrix devoid of analyte) is available: in that case SAM is applied by simply extrapolating the SAM model to the matrix experimental signal. In this work, the quantitative analysis of polymorphic forms of Active Pharmaceutical Ingredients based on X-ray Powder Diffraction is performed for the first time by a method based on multivariate standard addition method combined with net analyte signal procedure; it allows for reliable quantification of polymorphs of active principles in solid formulations, which are rapidly analyzed without any sample pre-treatment. Two test cases are presented: quantification of two polymorphs of piracetam in binary mixtures (forms II and III), and quantification of paracetamol (form I) in Tachifludec®.

The production of wine grapes in upstate New York (USA) is limited by diseases that are promoted by the cool and sometimes rainy climate. A breeding program has been introducing disease resistance from related species into the cultivated stock. Previous work has indicated that such resistance may be based on biochemical reactions rather than on a hypersensitive reaction. We therefore undertook metabolic profiling of amino acids and phenolic compounds in berries from collections of susceptible and resistant hybrids over the course of berry development to determine whether any of these compounds could be causal in disease resistance. The most abundant amino acids were GLN, ARG, PRO and THR. The amount of amino acids in ripe berries was from 3 to 4.7-fold higher compared to earlier stages. The concentrations of total phenolics were variable through the season with no consistent trend between susceptible and resistant fruits. Notable changes in phenolic compounds, especially anthocyanins, were recorded, especially during the ripening phase, when phenolics and anthocyanins increased following veraison. The most abundant phenolic compounds were catechin and epi-catechin; the most abundant anthocyanin was delphinidin-3-glucoside, which had a slightly greater concentration in resistant fruit at harvest, followed by malvidin-3-glucoside and petunidin-3-glucoside. The content of both amino acids and phenolic compounds in white-fruited parent cv. Horizon was equal to several-fold lower than the progeny plants, whether susceptible or resistant, depending on the harvest time. While no major differences between susceptible and resistant lines were found, multivariate analyses showed that it is possible to discriminate the susceptibility or resistance of grapes by analyzing their combined concentrations of amino acids, polyphenols and anthocyanins. Therefore, these compounds are influenced by the resistance capacity of grapes and could be used as a chemical fingerprint of this ability. However, it is likely that these are associations with disease resistance rather than their cause as no major consistent differences were noted.

A liquid chromatography-tandem mass spectrometry method for the determination of four Alternaria toxins, i.e. alternariol, alternariol monomethyl ether, tentoxin, and tenuazonic acid in tomato-based and fruit-based products was developed using a QuEChERs approach for the extraction of the mycotoxins. To optimise the QuEChERs extraction, several parameters were tested: types of QuEChERs pouches, sample weights, quantities of added water, use of dispersive SPE as a purification step, types of solvent and conditions of shaking. The method showed good linearity (R2> 0.997) and precision (RSD% < 10) for all analytes. Tenuazonic acid showed very good recovery (98.8%–108.9%) for tomato-based products, as well as for fruit-based products. The method was successfully applied to 57 samples collected from the Italian market. Tenuazonic acid was found in appreciable concentrations in some products. The highest value was found in a tomato sauce sample (814 μg/kg).

The direct chemical analysis allows investigating samples without altering them, keeping the sample available for further analysis. For the qualitative investigation, analytical procedures like gas-chromatography, Raman microscopy, and Infra Red spectroscopy are available; however, the univariate approach is not exhaustive in the case of very complex matrices. The quantitative approach is still an open issue, due to the strong matrix effect hindering the creation of univariate calibration methods in interpolation mode. The multivariate analysis may be the solution. Three-way Principal Components Analysis (PCA) allows for comprehension of variables influencing classification. The Partial Least Squares regression (PLS) combined with Discriminant Analysis (DA) allows classifying. Multivariate standard addition calibration based on PLS coupled with Net Analyte Signal (NAS) calculation allows bypassing the matrix effect in quantitative analysis. This Chapter is focused on the issues mentioned above. Three sections will be presented: SECTION 1: three-way PCA is applied to the discrimination among bacterial species in samples analyzed as such by pyrolysis gas chromatography-mass spectrometry. Applications to timely analysis of pathogenic microbes are foreseen. SECTION 2: PLS-DA is applied to Raman spectra to discriminate adulterated beeswaxes from natural ones. This procedure may be implemented to prevent possible adulteration of bees’ products. SECTION 3: PLS-NAS is applied to ATR spectra to quantify biogenic silica in marine sediments. The new method allows to accurately study the time evolution of primary productivity in the Antarctic basins.

A quick and widespread diffusion of heavy metals as contaminants in all the environmental systems has called the attention to their determination. Indeed, heavy metals, together with pesticides, are very dangerous pollutants owing to their bioaccumulation and toxicity. It is, therefore, necessary to determine these metals at trace and ultra-trace level especially in aquatic ecosystems to establish reasonable water quality criteria. Certain marine species, in particular mussels, clams, but also oysters accumulate toxic metals, being filtering organisms. It was verified that an adult organism is able to filter several liters per hours (also up to 4-5 L h-1), depending on its weight. This prerogative involves two important facts and consequences: 1. The ability to accumulate all harmful substances for humans, toxic metals, in particular, requires particular attention and inspections before being sold on the market. 2. In addition to this important and fundamental aspect of public health, the determination of toxic metals in mussels, clams and also oysters, that are not only filtering organisms but also sessile species, can be usefully employed for bio-monitoring campaigns, that evaluate the long-term trend of the pollution load of an aquatic ecosystem, information that evidently cannot be provided by punctual determinations. For completely mapping environmental pollution, the sampling duration and cadence are very important. However, it should be emphasized that the use of bio-monitors, just proposed by several authors, but certainly not scientifically supported, is possible only in the case of a long sampling plan. In any case, the metal determination in mussels and bivalve mollusks evidently must be accurate, reproducible and especially it must show very low limits of detection. The present work reports and discusses the different analytical methodologies for the determination of emerging metals pollutants, together with all toxic metals, in mussels, clams, and oysters.