Mean distance of closest approach of ions: Lithium salts in aqueous solutions

Numerical values for the mean distance of closest approach of ions, “a”, for lithium salts in aqueous solutions are presented and discussed. These values were obtained from both experimental activity and diffusion coefficients, and estimated by using different theoretical approaches.     

Specialized Pro-Resolving Mediators in Neuroinflammation: Overview of Studies and Perspectives of Clinical Applications

Specialized pro-resolving mediators (SPMs) are lipid mediators derived from poly-unsaturated fatty acids (PUFAs) which have been demonstrated to have an important role in the inflammation environment, preventing an overreaction of the organism and promoting the resolution of inflammation. Our purpose was to point out the current evidence for specialized pro-resolving mediators, focusing on their role in neuroinflammation and in major neurological diseases.     

Radio-tracer methods for studying speciation in natural waters

Radio-tracer experiments have shown that antimony, mercury and zinc interact to form complexes with humic and/or fulvic acids, whose molar masses can be estimated by gel chromatography. Sb(III) and (V) humates are stable in the pH range 7–11, but are largely dissociated below pH 4; humic acid does not reduce Sb(V) to Sb(III) in solution. Mercury forms a strong complex with humic+fulvic acids. Zinc forms complexes with both humic acids and glycine, and the humic acid complex has similar elution behaviour on dextran gel to a fraction from river water equilibrated with⁶⁵Zn. At least one other form of zinc, in addition to Zn²⁺, occurs in this river.     

3-D QSAR studies on histone deacetylase inhibitors. A GOLPE/GRID approach on different series of compounds

Docking simulation and three-dimensional quantitative structure-activity relationships (3D-QSARs) analyses were conducted on four series of HDAC inhibitors. The studies were performed using the GRID/GOLPE combination using structure-based alignment. Twelve 3-D QSAR models were derived and discussed. Compared to previous studies on similar inhibitors, the present 3-D QSAR investigation proved to be of higher statistical value, displaying for the best global model r2, q2, and cross-validated SDEP values of 0.94, 0.83, and 0.41, respectively. A comparison of the 3-D QSAR maps with the structural features of the binding site showed good correlation. The results of 3D-QSAR and docking studies validated each other and provided insight into the structural requirements for anti-HDAC activity. To our knowledge this is the first 3-D QSAR application on a broad molecular diversity training set of HDACIs.     

Beam search heuristics for quadratic earliness and tardiness scheduling

In this paper, we present beam search heuristics for the single machine scheduling problem with quadratic earliness and tardiness costs, and no machine idle time. These heuristics include classic beam search procedures, as well as filtered and recovering algorithms. We consider three dispatching heuristics as evaluation functions, in order to analyse the effect of different rules on the performance of the beam search procedures. The computational results show that using better dispatching heuristics improves the effectiveness of the beam search algorithms. The performance of the several heuristics is similar for instances with low variability. For high variability instances, however, the detailed, filtered and recovering beam search (RBS) procedures clearly outperform the best existing heuristic. The detailed beam search algorithm performs quite well, and is recommended for small- to medium-sized instances. For larger instances, however, this procedure requires excessive computation times, and the RBS algorithm then becomes the heuristic of choice.     

Metallacrown ethers with a symmetric bis(phosphite) ligand derived from 1,2-bis-(2-hydroxyethoxy)benzene: Synthesis, characterization and hydroformylation of styrene

To better understand the effects of ligand configuration on hydroformylation reactions carried out in the presence of LiBPh₄·3dme (dme = 1,2-dimethoxyethane), a conformationally restrained bis(phosphite) ligand derived from 1,2-bis-(2-hydroxyethoxy)benzene, {[(2,2′-O₂C₁₂H₈)P(C₂H₄O₂)]₂C₆H₄}, 1, has been prepared and its Rh(I) metallacrown ether complex has been evaluated as a catalyst for the hydroformylation of styrene. Both the activity and regioselectivity of the catalyst are sensitive to the amount of the LiBPh₄·3dme added with the activity decreasing by 16% and the regioselectivity for the iso increasing by 9% at a 8:1 LiBPh₄:Rh ratio.Model complexes for the octahedral, cis-Mo(CO)₄(1), 2, and square planar, cis-PtCl₂(1), 3, and cis-PdCl₂(1), 4, complexes in the catalytic cycle has been have been studied using multinuclear NMR spectroscopy and X-ray crystallography. Although the X-ray crystal structure of 2 suggests that the metallacrown ether ring could adopt a configuration capable of binding alkali metal cations, this does not appear to occur in a dichloromethane-d₂ solution of 2 because no shift in the ³¹P NMR resonance 2 is observed upon the addition of an excess of LiBPh₄·3dme. The ³¹P{¹H} NMR spectra of chloroform-d solutions of 2 (in the presence of a catalytic amount of HgCl₂) and of 4 and the X-ray crystal structures of the complexes indicate that the bis(phosphite) ligands are cis coordinated in these complexes in both the solution and in the solid state. This is particularly surprising for 4 because related PdCl₂{Ph₂P(CH₂CH₂O)_nCH₂CH₂PPh₂} (n = 3-5) complexes exhibit both cis-trans and monomer-oligomer equilibria in solution.     

Synthesis of silicalite-1 from organo-silicic gels

Well crystallized silicalite-1 has been obtained from three sources of amorphous silica, namely, rice hull ashes, commercial Davisil, and a fume silica from Aldrich. The silicas were first dissolved in glycerol according to a recently described reaction. This reaction transforms rapidly and efficiently large surface area silicates into poly-alkoxide gels. It can be schematized as an etherification of an alcohol function of glycerol by the weakly acid surface silanol groups. The facile hydrolysis of the alkoxide permits the preparation of relatively pure and reactive silica, keeping the mesoporous character of the parent starting material. We insist on the mesoporous character of the solids obtained upon hydrolyzing the organo-silicic gel because we believe the gel plays a role of template in the secondary synthesis of mesoporous structures. The hydrolysis is carried out in presence of a structure directing agent, namely tetra-propylammonium hydroxide, TPAOH. After aging, the residue is dried and calcined. The first advantage of using the organo-silicic gel is probably related to the high degree of depolymerization of silica, witness by the C/Si ratio. The second one, more subtle to define, is to provide an intermediate silica with hydrophilic a hydrophobic regions, interfering differently with the surfactant. After calcination at 500 degrees C, well crystallized silicalite-1 is obtained. The texture of the starting silica influences the textural characteristics of the final silicalite-1.     

Auslander–Buchweitz Approximation Theory for Triangulated Categories

We introduce and develop an analogous of the Auslander–Buchweitz approximation theory (see Auslander and Buchweitz, Societe Mathematique de France 38:5–37, 1989) in the context of triangulated categories, by using a version of relative homology in this setting. We also prove several results concerning relative homological algebra in a triangulated category $\mathcal{T},$ which are based on the behavior of certain subcategories under finiteness of resolutions and vanishing of Hom-spaces. For example: we establish the existence of preenvelopes (and precovers) in certain triangulated subcategories of $\mathcal{T}.$ The results resemble various constructions and results of Auslander and Buchweitz, and are concentrated in exploring the structure of a triangulated category $\mathcal{T}$ equipped with a pair $(\mathcal{X},\omega),$ where $\mathcal{X}$ is closed under extensions and ω is a weak-cogenerator in $\mathcal{X},$ usually under additional conditions. This reduces, among other things, to the existence of distinguished triangles enjoying special properties, and the behavior of (suitably defined) (co)resolutions, projective or injective dimension of objects of $\mathcal{T}$ and the formation of orthogonal subcategories. Finally, some relationships with the Rouquier’s dimension in triangulated categories is discussed.     

Thermo- and pH-Responsive Gelatin/Polyphenolic Tannin/Graphene Oxide Hydrogels for Efficient Methylene Blue Delivery

Gelatin (GE), amino-functionalized polyphenolic tannin derivative (TN), and graphene oxide (GO) were associated to yield thermo- and pH-responsive hydrogels for the first time. Durable hydrogel assemblies for drug delivery purposes were developed using the photosensitizer methylene blue (MB) as a drug model. The cooling GE/TN blends provide brittle physical assemblies. To overcome this disadvantage, different GO contents (between 0.31% and 1.02% wt/wt) were added to the GE/TN blend at 89.7/10.3 wt/wt. FTIR and RAMAN spectroscopy analyses characterized the materials, indicating GO presence in the hydrogels. Incorporation studies revealed a total MB (0.50 mg/mL) incorporation into the GE/TN-GO hydrogel matrices. Additionally, the proposed systems present a mechanical behavior similar to gel. The GO presence in the hydrogel matrices increased the elastic modulus from 516 to 1650 Pa. SEM revealed that hydrogels containing MB present higher porosity with interconnected pores. Dissolution and swelling degree studies revealed less stability of the GE/TN-GO-MB hydrogels in SGF medium (pH 1.2) than SIF (pH 6.8). The degradation increased in SIF with the GO content, making the polymeric matrices more hydrophilic. MB release studies revealed a process controlled by Fickian diffusion. Our results point out the pH-responsible behavior of mechanically reinforced GE/TN-GO-MB hydrogels for drug delivery systems purposes.