Fractionation of Raw and Parboiled Rice Husks with Deep Eutectic Solvents and Characterization of the Extracted Lignins towards a Circular Economy Perspective

In the present work, rice husks (RHs), which, worldwide, represent one of the most abundant agricultural wastes in terms of their quantity, have been treated and fractionated in order to allow for their complete valorization. RHs coming from the raw and parboiled rice production have been submitted at first to a hydrothermal pretreatment followed by a deep eutectic solvent fractionation, allowing for the separation of the different components by means of an environmentally friendly process. The lignins obtained from raw and parboiled RHs have been thoroughly characterized and showed similar physico-chemical characteristics, indicating that the parboiling process does not introduce obvious lignin alterations. In addition, a preliminary evaluation of the potentiality of such lignin fractions as precursors of cement water reducers has provided encouraging results. A fermentation-based optional preprocess has also been investigated. However, both raw and parboiled RHs demonstrated a poor performance as a microbiological growth substrate, even in submerged fermentation using cellulose-degrading fungi. The described methodology appears to be a promising strategy for the valorization of these important waste biomasses coming from the rice industry towards a circular economy perspective.     

Assessment of quantum‐chemical methods for electronic properties and geometry of signaling biomolecules

A reasonable balance between accuracy and feasibility of quantum‐chemical methods depends on the complexity of the molecular system and the scientific goals. Six series of indole‐, naphthalene‐, phenol‐, benzoic‐, phenoxy‐, other auxin‐derivatives, and a test set of similar organic molecules have been chosen for an assessment of 13 density functional and semi‐empirical molecular orbital methods with respect to electronic and structural properties. The accuracy and precision of HOMO/LUMO calculations are determined by comparison with experimental ionization potentials and electron affinities. Further comparison was performed at atomic level by covariance analysis. The methods KMLYP, MSINDO, and PM3 are precise and accurate for the whole set of molecules. The method AM1 offers comparable accuracy with the exception of electron affinities of indole derivatives, where significant deviations from experiment were observed. Geometrical properties were best reproduced with the semi‐empirical method MSINDO. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Sulfonated RAFT Copolymers as Heparin Mimetics: Synthesis,Reactivity Ratios,and Anticoagulant Activity

The glycosaminoglycan heparin is a clinically important anticoagulant drug, primarily used to reduce the risk of blood clots (thrombosis) during surgery. Despite its importance in medicine and its continuous use over many decades, heparin suffers from several limitations associated with its heterogeneity and its extraction from animal tissues. In order to address these limitations, reversible addition‐fragmentation chain transfer polymerization is utilized to prepare a library of heparin mimetic copolymers from the sulfonated monomers sodium 4‐styrene sulfonate, potassium‐3‐sulfopropyl acrylate, potassium‐3‐sulfopropyl methacrylate, and sodium‐2‐acrylamido‐2‐methyl‐1‐propane sulfonate. Copolymers are prepared using combinations of two different monomers in various ratios. Monomer reactivity ratios are also determined for some representative monomer combinations, and all polymers are characterized by ¹H NMR spectroscopy and gel permeation chromatography. The anticoagulant activities of the copolymers are determined by activated partial thromboplastin time and thrombin clotting time assays and structure–activity relationships are explored.     

Heterogeneous electron-transfer rate constants for fe(h(2)o)(6)(3+/2+) at metal oxide electrodes

The title redox couple, in noncoordinating perchlorate medium, has been used to probe the electrochemical behavior of different IrO2-based electrodes; pure oxide electrodes, as well as IrO2-SnO2 mixtures, have been investigated. The obtained results show that the electrode material strongly affects the electrochemical response. A tentative explanation, based on the different point of zero charge of the considered oxides, is presented.     

Electron solvation by polar molecules: the interaction of Na atoms with solid methanol films studied with MIES and density functional theory calculations

The interaction of Na atoms with CH(3)OH films was studied with metastable impact electron spectroscopy (MIES) under UHV conditions. The films were grown at 90(+/-10) K on tungsten substrates and exposed to Na. Na-induced formation of methoxy (CH(3)O) species takes place, and Na atoms become ionized. At small Na exposures the outermost solvent layer remains largely intact as concluded from the absence of MIES signals caused by the reaction products. However, emission from CH(3)O, located at the film surface, occurs at larger exposures. In the same exposure range also Na species can be detected at the surface. The spectral feature from 3s Na ionization occurs at an energetic position different from that found for metals or semiconductors. The results are compared with density functional theory calculations [see Y. Ferro, A. Allouche, and V. Kempter, J. Chem. Phys. 120, 8683 (2004), preceding paper]. Experiment and theory agree in the energetic positions of the main spectral features from the methanol and sodium ionization. The calculations suggest that the 3s Na emission observed experimentally originates from solvated 3s electrons which are located far from the Na core and become stabilized by solvent molecules. The simultaneous emergence of emission from CH(3)O and from solvated 3s electrons suggests that the delocalization and, consequently, the solvation play an important role in the Na-induced formation of CH(3)O from CH(3)OH.     

Differences between predicted and observed sequences in Saccharomyces cerevisiae

We recently studied the protein composition of a Saccharomyces cerevisiae wine yeast strain (K310) of enological interest. About 2,500 spots of 8-250 kDa observed molecular mass were resolved by two-dimensional gel electrophoresis. Experimental molecular masses and isoelectric points were calculated for most of them. Twenty-seven proteins were subjected to Edman microsequencing. N-terminal sequences of 12/27 proteins were determined, whereas internal sequences of 6/27 proteins were obtained following in situ proteolysis. Comparison between the experimental data and those reported in the SWISS-PROT database revealed some differences between genotypic and phenotypic sequences. These are indicative of the changes a protein can undergo with respect to the primary structure coded by the genomic DNA. Our results highlight the need to complement genomic analysis with detailed proteomics in order to refine the vast amount of information provided by DNA sequencing and to find an exact correlation between genome and proteome.     

A Contribution to the Study of the Alloying Behaviour of the Rare Earths with Tin

The general alloying behaviour of tin with the rare earths was summarized on the base of the available literature data. A re-examination of the La? Sn alloys has been performed using x-ray and metallographic analyses. The existence of the following phases has been observed or confirmed: . The formation heats of the La? Sn alloys have been measured using a direct isoperibol calorimeter. The values of ΔH_form (solid alloys, room temperature, K cal/g atom) are the following: . A re-examination of the Y? Sn alloys has been also carried out confirming the existence and the crystal structures of the following phases: Y₅Sn₃, Y₅Sn₄, Y₁₁Sn₁₀, YSn₂ and YSn₃. A few calorimetric measurements performed on selected Sn-rich alloys have given the following values of the ΔH_form: YSn₂ (?15.5 ± 1.0 Kcal/g atom), YSn₃ (?12.5 ± 0.5 Kcal/g atom). The results obtained are discussed briefly and are compared with the data available for other rare earth-tin alloys.     

An improved force field for conformational analysis of sulfated polysaccharides

A force field to be used in molecular mechanics studies of sulfated polysaccharides with explicit account of water and counterion interactions was derived from the analysis of six crystal structures of sulfated monosaccharide salts. The force field is based on Allinger's MM2, and was developed starting from the parameters used in previous studies of heparin and related oligosaccharides. While the novel parameters have been derived empirically, use of the atomic charge distribution obtained from ab initio quantum-mechanical computations, at the 6–31 + G^** level, improves the quality of structural fitting significantly. The overall discrepancy between the positions of the nonhydrogen atoms determined by X-ray diffractometry and those corresponding to the minimum-energy structure is 0.21 Å. While most geometrical features of both carbohydrate and sulfate moieties are reproduced satisfactorily, in some cases (particularly in the case of the Na⁺ salt of α-methyl-4-O-sulfogalactopyranoside) the hydrogen bond pattern is altered by energy minimization, probably due to errors in the balance of the strong electrostatic forces. © 1997 by John Wiley & Sons, Inc.