Learning Interaction Kernels in Stochastic Systems of Interacting Particles from Multiple Trajectories

Foundations of Computational Mathematics - We consider stochastic systems of interacting particles or agents, with dynamics determined by an interaction kernel, which only depends on pairwise...     

1H NMR analysis of O‐methyl‐inositol isomers: a joint experimental and theoretical study

Density functional theory (DFT) calculations of ¹H NMR chemical shifts for l ‐quebrachitol isomers were performed using the B3LYP functional employing the 6‐31G(d,p) and 6‐311 + G(2d,p) basis sets. The effect of the solvent on the B3LYP‐calculated NMR spectrum was accounted for using the polarizable continuum model. Comparison is made with experimental ¹H NMR spectroscopic data, which shed light on the average uncertainty present in DFT calculations of chemical shifts and showed that the best match between experimental and theoretical B3LYP ¹H NMR profiles is a good strategy to assign the molecular structure present in the sample handled in the experimental measurements. Among four plausible O‐methyl‐inositol isomers, the l ‐quebrachitol 2a structure was unambiguously assigned based only on the comparative analysis of experimental and theoretical ¹H NMR chemical shift data. The B3LYP infrared (IR) spectrum was also calculated for the four isomers and compared with the experimental data, with analysis of the theoretical IR profiles corroborating assignment of the 2a structure. Therefore, it is confirmed in this study that a combined experimental/DFT spectroscopic investigation is a powerful tool in structural/conformational analysis studies. Copyright © 2012 John Wiley & Sons, Ltd.     

Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock

A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9 min of ultrasonic irradiation (20 kHz, 750 W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.     

Templated Synthesis of Copper(II) Azacyclam Complexes Using Urea as a Locking Fragment and Their Metal‐Enhanced Binding Tendencies towards Anions

Copper(II) azacyclam complexes 3 ²⁺ and 4 ²⁺ were obtained through a metal‐templated procedure involving the pertinent open‐chain tetramine, formaldehyde and a phenylurea derivative as a locking fragment. Both metal complexes can establish interactions with anions through the metal centre and the amide NH group. Equilibrium studies in DMSO by a spectrophotometric titration technique were carried out to assess the affinity of 3 ²⁺ and 4 ²⁺ towards anions. While the NH group of an amide model compound and the metal centre of the plain Cu^II(azacyclam)²⁺ complex do not interact at all with anions, 3 ²⁺ and 4 ²⁺ establish strong interactions with oxo anions, profiting from a pronounced cooperative effect. In particular, 1) they form stable 1:1 and 1:2 complexes with H₂PO₄^? ions in a stepwise mode with both hydrogen‐bonding and metal–ligand interactions, and 2) in the presence of CH₃COO^?, they undergo deprotonation of the amido NH group and thus profit from axial coordination of the partially negatively charged carbonyl oxygen atom in a scorpionate binding mode.     

A chemical view onto post-consumer poly(ethylene terephthalate) valorization through reactive blending with functionalized polyolefins

The recovery of poly(ethylene terephthalate) from post-consumer packaging products, such as beverage bottles, allowed to obtain flakes with a purity level suitable for reprocessing. Among many possibilities, the blending with polyolefins can provide toughened materials but, as poly(ethylene terephthalate) and polyolefins are immiscible, different methods of reactive compatibilization were followed to achieve a fine dispersion of polyolefln domains into a poly(ethylene terephthalate) matrix. In this meanwhile the use of a functionalized polyolefin, bearing reactive groups toward poly(ethylene terephthalate) terminals, is a promising route to obtain grafted copolymers acting as interface stabilizers. In particular, the use in the melt blending of ester or hydroxyl functionalized polyolefins in the presence of transesterification catalysts and/or anhydride functionalized polyolefins as compatibilizer precursors were both investigated by focusing onto chemical aspects. The prepared blends were analyzed through suitable fractionation methods, such as selective extractions, and spectroscopic analysis in order to identify the molecular architecture of the macromolecules resulting from the process and study their effectiveness at the interface region. Moreover the phase morphology and the thermo-mechanical properties were investigated and correlated to the structure of the macromolecular species in the system.     

Determination of antioxidant capacity of papaya fruit and papaya-based food and drug integrators, using a biosensor device and other analytical methods

Abstract  

Antioxidant and radical-scavenging properties are alleged to form the basis of the therapeutic properties attributed to the papaya and papaya-based food and drug integrators that have recently appeared on the market. In the present research a biosensor-based method was used to determine the antioxidant capacity of papaya fruit as is, that of several food and drug integrators, and lastly of pure papain alone. Results are compared using a reference spectrofluorimetric method and two other spectrophotometric methods. In addition pro-oxidant properties of the same samples were also checked using two colorimetric methods.     

Determination of antioxidant capacity of papaya fruit and papaya-based food and drug integrators,using a biosensor device and other analytical methods

Abstract  Antioxidant and radical-scavenging properties are alleged to form the basis of the therapeutic properties attributed to the papaya and papaya-based food and drug integrators that have recently appeared on the market. In the present research a biosensor-based method was used to determine the antioxidant capacity of papaya fruit as is, that of several food and drug integrators, and lastly of pure papain alone. Results are compared using a reference spectrofluorimetric method and two other spectrophotometric methods. In addition pro-oxidant properties of the same samples were also checked using two colorimetric methods. Graphical abstract