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Tacle is a citrus variety which recently gained further interest due to its antioxidant and biological properties. This study suggests using Nuclear Magnetic Resonance (NMR) imaging to characterize Tacle juice's metabolic composition as it is intimately linked to its quality. First, polar and apolar solvent systems were used to identify a significant fraction of the Tacle metabolome. Furthermore, the antioxidant capacity and the total content of flavonoids, polyphenols and β-carotene in the juice were investigated with UV—Visible spectroscopy. Tacle juice was clarified and fractionated by ultrafiltration (UF) and nanofiltration (NF) membranes in order to recover and purify its bioactive principles. Finally, the second part of this work sheds light on the spectrophotometric assays and 1H-NMR spectra of fractions coming from membrane operations coupled with a multivariate data analysis technique, PCA, to explore the impact of UF and NF processes on the metabolic profile of the juice. [ABSTRACT FROM AUTHOR]

Aqueous solutions of F127 pluronic systems exhibit an interesting thermal gelation above a certain concentration. This phenomenon concerns the transition from a liquid-like behavior at low temperatures to a solid-like behavior at high temperatures, and it is due to different temperature responses from the different polymer segments, polypropylene oxide (PPO) and polyethylene oxide (PEO). Such property leads to a structural change in the self assembled macromolecule upon heating, from an isotropic micellar structure to an ordered cubic structure. These two types of assembly are clearly distinct with respect to their rheological behavior. This contribution emphasizes the rheological properties of the pluronic system in micellar and cubic phase, in combination with NMR, Dynamic Light Scattering and DSC information. The results emphasize the gelation process upon heating and a cubic phase characterized by higher storage modulus and higher A and z Weak Gel Model exponents than the micellar phase. Micellar growth upon heating was found within micellar phase. The presented data support the hypothesis that each polymer segment actively participates in the formation of the different phases: while PPO is responsible for micelle formation, PEO plays a dominating role in cubic phase formation. Finally, different stiffness between the core and the corona of the aggregates in the two phases is observed.

The use of high-resolution magic angle spinning (HR-MAS) 13C NMR spectroscopy is proposed here as an innovative and non-destructive approach to investigate the chemical composition of the organic fraction of municipal solid waste (OFMSW) and for monitoring the evolution of their composition during the oxidative iron-based Fenton treatment to which the initial matrix is subjected. The high quality and the good resolution of the 13C HR-MAS NMR spectra allowed an accurate assignment and quantification of the various types of carbon present in the analyzed organic matrix. Moreover, the HR-MAS has also shown its effectiveness in monitoring the different oxidative processes to which the same initially organic matrix has been subjected. The results obtained from the HR-MAS spectra on the collected samples during the different oxidative experiments, indicate that Fenton treatment is able to modify the percentage of the different types of carbons as a function of the concentrations of both Fenton reactants, H2O2 and Fe2+ salt, and of the oxidative process time. [ABSTRACT FROM AUTHOR]

A model carried out the ordering of apolar molecules dissolved in uniaxial mesophases where the interactions between the solute and the local medium were described on a molecular scale. The proposed model proved to be highly reliable and very effective tool for the description of orientational order when short-range interactions totally control the solute ordering.

Bitumen has unique chemo-mechanical properties, and for this reason, it is today one of the main constituents of many industrial products beside its common use in highway pavements construction. While the excellent rheological properties of bitumens have been investigated by means of different techniques, much remains to be known about the intrinsic properties of this complex material. It is therefore important to investigate its structure and properties from a closer point of view, towards possible useful modifications of the neat material. The present research developed a technique to investigate the composition of bitumens using Thin Layer Chromatography (TLC) to separate the different fractions, and Nuclear Magnetic Resonance (NMR) spectroscopy to assess and quantify the aliphatic hydrogen part with respect to the aromatic part. To achieve a comprehensive understanding of the chemical composition of the materials, Proton Nuclear Magnetic Resonance (¹H-NMR) analysis was conducted in solution, using CCl4 as solvent, on three different neat bitumens and on their asphaltene and maltene fractions. The combined application of TLC and ¹H-NMR spectroscopy enables the advanced characterization of bitumens supplied from different sources or obtained from different processes. This further allows addressing the use of specific modifications according to the bitumen final applications. [ABSTRACT FROM AUTHOR]

Despite the potential versatility of Vitamin C as a ligand, only for few metal complexes does full characterization exist. Vitamin C metal complexes, indeed, are difficult to study experimentally because the ligand has multiple protonation and oxidation states, and the metal-ligand complexes are in general not as tight as one might expect and frequently resistant to crystallographic characterization. In most cases, coordination via one of the hypothesized modes is invoked, characterized by monodentate or bidentate coordination via the most acidic oxygen atoms, with the ligand singly or doubly deprotonated. In this study the ability of l-ascorbic acid to form complexes with Al 3+ and Ni 2+ ions under physiological conditions was investigated by using a combination of potentiometric measurements, 1 H NMR spectroscopy, and DFT computations in order to recognize the structural properties of the resulting complexes in aqueous solution. The comparison between the values of the free energies of complexation obtained by using DFT quantum chemical calculations and estimated from experimental stability constants according to the mass action law and by considering the involved equilibria allows to select structure and preferred coordination modes of formed complexes. The protonation constant of the free ligand was also determined using potentiometric data and its reproduction by using computational approaches was critically commented.

We have obtained a very large data set of spectral parameters from the analysis of (1)H NMR and (13)C satellite spectra of 2,2'-bithiophene dissolved in anisotropic, partially orienting mesophases. In particular, this parameter set includes 33 dipolar couplings, which are directly related to the interatomic distances, the dihedral angle phi between the two thiophenic rings, and the anisotropic solute-solvent interaction potential. This allows an exhaustive investigation of the conformational equilibrium of 2,2'-bithiophene in a liquidlike phase. Comparison with the predictions of high-level theoretical calculations for the isolated molecule provides evidence of a strong flattening as well as the sharpening effect of the medium on the conformer population. The approximations needed to apply vibrational corrections to flexible molecules are discussed in detail and some general conclusions concerning their effect on structure and conformational equilibria are proposed.