Difarma

a b s t r a c t 1 H NMR spectroscopy was employed to investigate the molecular quality of Aglianico red wines from the Campania region of Italy. The wines were obtained from three different Aglianico vineyards characterized by different microclimatic and pedological properties. In order to reach an objective evaluation of "terroir" influence on wine quality, grapes were subjected to the same winemaking procedures. The careful subtraction of water and ethanol signals from NMR spectra allowed to statistically recognize the metabolites to be employed in multivariate statistical methods: Principal Component Analysis (PCA), Discriminant Analysis (DA) and Hierarchical Clustering Analysis (HCA). The three wines were differentiated from each other by six metabolites: ␣-hydroxyisobutyrate, lactic acid, succinic acid, glycerol, ␣-fructose and ␤-d-glucuronic acid. All multivariate analyses confirmed that the differentiation among the wines were related to micro-climate, and carbonate, clay, and organic matter content of soils. Additionally, the wine discrimination ability of NMR spectroscopy combined with chemometric methods, was proved when commercial Aglianico wines, deriving from different soils, were shown to be statistically different from the studied wines. Our findings indicate that multivariate statistical elaboration of NMR spectra of wines is a fast and accurate method to evaluate the molecular quality of wines, underlining the objective relation with terroir.

Manure products fermented underground in cow horns and commonly used as field spray (preparation 500) in the biodynamic farming system, were characterized for molecular composition by solid-state nuclear magnetic resonance [ 13 C cross-polarization magic-angle-spinning NMR ( 13 C-CPMAS-NMR)] spectroscopy and offline tetramethylammonium hydroxide thermochemolysis gas chromatography-mass spectrometry. Both thermochemolysis and NMR spectroscopy revealed a complex molecular structure, with lignin aromatic derivatives, polysaccharides, and alkyl compounds as the predominant components. CPMAS-NMR spectra of biodynamic preparations showed a carbon distribution with an overall low hydrophobic character and significant contribution of lignocellulosic derivatives. The results of thermochemolysis confirmed the characteristic highlighted by NMR spectroscopy, revealing a molecular composition based on alkyl components of plant and microbial origin and the stable incorporation of lignin derivatives. The presence of biolabile components and of undecomposed lignin compounds in the preparation 500 should be accounted to its particularly slow maturation process, as compared to common composting procedures. Our results provide, for the first time, a scientific characterization of an essential product in biodynamic agriculture, and show that biodynamic products appear to be enriched of biolabile components and, therefore, potentially conducive to plant growth stimulation.

Interactions of glyphosate (N-phosphonomethylglycine) herbicide (GLY) with soluble fulvic acids (FAs) and humic acids (HAs) at pH 5.2 and 7 were studied by (1)H and (31)P NMR spectroscopy. Increasing concentrations of soluble humic matter determined broadening and chemical shift drifts of proton and phosphorus GLY signals, thereby indicating the occurrence of weak interactions between GLY and humic superstructures. Binding was larger for FAs and pH 5.2 than for HAs and pH 7, thus suggesting formation of hydrogen bonds between GLY carboxyl and phosphonate groups and protonated oxygen functions in humic matter. Changes in relaxation and correlation times of (1)H and (31)P signals and saturation transfer difference NMR experiments confirmed the noncovalent nature of GLY-humic interactions. Diffusion-ordered NMR spectra allowed calculation of the glyphosate fraction bound to humic superstructures and association constants (K(a)) and Gibbs free energies of transfer for GLY-humic complex formation at both pH values. These values showed that noncovalent interactions occurred most effectively with FAs and at pH 5.2. Our findings indicated that glyphosate may spontaneously and significantly bind to soluble humic matter by noncovalent interactions at slightly acidic pH and, thus, potentially pollute natural water bodies by moving through soil profiles in complexes with dissolved humus.

Interactions between fulvic acids (FAs) and a β-glucosidase (GLU) enzyme and consequent modifications of enzymatic activity were investigated at pH 5.0 and 7.2 by 1 H nuclear magnetic resonance (NMR) spectroscopy. With increasing FA content, the enzyme proton signals were progressively broadened, while the relaxation (T 1 and T 2 ) and correlation (τ c ) times of GLU decreased and increased, respectively. Regardless of pH, these effects were greater for the hydroxy-alkylic and aromatic protons of GLU, suggesting that the FAenzyme associations, which progressively limited GLU tumbling rate, resulted from weak interactions, such as H-bonds and dispersive hydrophobic bonds. The catalytic activity of β-D-glucosidase, when in weakly bound complexes with FA, was studied by following the change of NMR signals of two different substrates, p-nitrophenyl-β-D-glucopyranoside (pNPG) and salicin, and their hydrolysis products. Spectral evidence suggests that enzyme activity was substantially reduced with increasing FA concentration and the rate reduction was more pronounced for salicin than for pNPG. The enzyme inhibition may be explained by either a partial cover of GLU active sites by fulvic molecules or modification of the enzyme conformational structure during formation of humic-enzyme complexes. Our results indicate that even weak interactions of FA with GLU are sufficient to inhibit partially its catalytic activity, and that the environmental role of extracellular enzymes may be significantly reduced when coming into contact with organic matter in the soil.

We employed 1 H NMR spectroscopy to examine the molecular profile of a white "Fiano di Avellino" wine obtained through fermentation by either a commercial or a selected autochthonous Saccharomyces cerevisiae yeast starter. The latter was isolated from the same grape variety used in the wine-making process in order to strengthen the relationship between wine molecular quality and its geographical origin. 1 H NMR spectra, where water and ethanol signals were suppressed by a presaturated T 1 -edited NMR pulse sequence, allowed for definition of the metabolic content of the two differently treated wines. Elaboration of NMR spectral data by multivariate statistical analyses showed that the two different yeasts led to significant diversity in the wine metabolomes. Our results indicate that metabolomics by 1 H NMR spectroscopy combined with multivariate statistical analysis enables wine differentiation as a function of yeast species and other wine-making factors, thereby contributing to objectively relate wine quality to the terroir.

We followed the reactivity of acetone with 3-aminopropyltrimethoxysilane, a potential organosilane coupling agent, by (1)H, (13)C and (29)Si NMR spectroscopy. Selective 1D and 2D-edited NMR experiments significantly contributed to simplify the spectral complexity of reaction solution and elucidated molecular structures within progressive reaction phases. The course of the 3-aminopropyltrimethoxysilane reaction with acetone was shown by a progressive decrease of both reactants, and a concomitant appearance of water and methanol, due to formation of imine and hydrolysis of alkoxysilane groups, respectively. The occurrence of multiple siloxane linkages in a progressively larger cross-linked macromolecular structure was revealed by DOSY-NMR experiments and new signals in (29)Si-NMR spectra at different reaction times. The NMR approach described here may be applied to investigate the reactivity of other γ-aminopropylalkoxysilanes and contribute to define procedures for the preparation of silica-based materials.

High-resolution magic-angle-spinning (HRMAS) one-and two-dimensional 1 H and 13 C NMR spectroscopy was used to study intact healthy (myometrium) and benign (leiomyoma) uterine tissues of 10 patients. Twenty-eight metabolites were detected and assigned in both types of tissue. Principal component analysis (PCA) was applied to a conventional water-suppressed 1 H HRMAS NMR spectrum, and two NMR spectral editing methods, namely Carr-Purcell-Meiboom-Gill (CPMG) spin-echo and diffusion-edited techniques, were used. Only the PCA of CPMG spectra resulted in a good differentiation between the two tissue types. The CPMG spin-echo spectra were also useful in indicating depleted levels of taurine in uterine leiomyomas, which were well correlated with the histopathological determination. In addition, statistical analysis revealed that most leiomyomas contained elevated concentrations of glutamate and glutamine. Our results suggest that HRMAS represents a valuable adjunct to histopathology to improve the diagnostic accuracy of uterine leiomyomas, whilst concomitantly reducing the diagnosis time.

We followed the reactivity of acetone with 3-aminopropyltrimethoxysilane, a potential organosilane coupling agent, by (1)H, (13)C and (29)Si NMR spectroscopy. Selective 1D and 2D-edited NMR experiments significantly contributed to simplify the spectral complexity of reaction solution and elucidated molecular structures within progressive reaction phases. The course of the 3-aminopropyltrimethoxysilane reaction with acetone was shown by a progressive decrease of both reactants, and a concomitant appearance of water and methanol, due to formation of imine and hydrolysis of alkoxysilane groups, respectively. The occurrence of multiple siloxane linkages in a progressively larger cross-linked macromolecular structure was revealed by DOSY-NMR experiments and new signals in (29)Si-NMR spectra at different reaction times. The NMR approach described here may be applied to investigate the reactivity of other γ-aminopropylalkoxysilanes and contribute to define procedures for the preparation of...

Background: The influence of pH on the formation of host-guest complexes between the cucurbit[7]uril (CB[7]) macrocyclic host and three auxin plant hormones, namely indole-3-acetic acid (IAA), 2-naphthalene acetic acid (2-NAA), and 2,4-dichlorophenoxyacetic acid (2,4-D), was studied by 1 H NMR and relaxation experiments. Results: Only protonated auxins formed inclusion complexes with CB[7], exhibiting preferential encapsulation of the aromatic part inside the host cavity, and orientation of the carboxyl group towards the carbonyl-laced portals of CB[7]. At pH values above the auxin pK a values, the guest molecules were negatively ionized and were no longer retained within the macrocyclic host, suggesting that a pH-controlled release of auxin guests from the CB[7] host is possible. Conclusions: The development of a technology based on the use of cucurbit[n]urils for the pH-controlled release of auxin molecules in plant systems represents an opportunity to exploit these macrocyclic compounds in a variety of agricultural applications.

Natural organic matter (NOM) plays a critical role in regulating the transport and the fate of organic contaminants in the environment. NMR spectroscopy is a powerful technique for the investigation of the sorption and binding mechanisms between NOM and pollutants, as well as their mutual chemical transformations. Despite NMR relatively low sensibility but due to its wide versatility to investigating samples in the liquid, gel, and solid phases, NMR application to environmental NOM-pollutants relations enables the achievement of specific and complementary molecular information. This report is a brief outline of the potentialities of the different NMR techniques and pulse sequences to elucidate the interactions between NOM and organic pollutants, with and without their labeling with nuclei that enhance NMR sensitivity. Copyright © 2015 John Wiley & Sons, Ltd.