Theoretical Study of a Hybrid Organic–Inorganic Heteropolyoxometalate Compound

Crystallography Reports - Large study of theoretical calculations for the hybrid organic-inorganic heteropolyoxometalate (C6H8N)5[HAs2Mo6O26(H2O)]⋅3H2O (1) is reported. The results of...     

Parallel Versus Antiparallel β-Sheet Structure in Cyclic Peptide Hybrids Containing γ- or δ-Cyclic Amino Acids

Cyclic peptides with disc-shaped structures have emerged as potent building blocks for the preparation of new biomaterials in fields ranging from biological to material science. In this work, we analyze in depth the self-assembling properties of a new type of cyclic peptides based on the alternation of α-residues and cyclic δ-amino acids (α,δ-CPs). To examine the preferred stacking properties adopted by cyclic peptides bearing this type of amino acids, we carried out a synergistic in vitro/in silico approximation by using simple dimeric models and then extended to nanotubes. Although these new cyclic peptides (α,δ-CPs) can interact either in a parallel or antiparallel fashion, our results confirm that although the parallel β-sheet is more stable, it can be switched to the antiparallel stacking by choosing residues that can establish favorable cross-strand interactions. Moreover, the subsequent comparison by using the same methodology but applied to α,γ-CPs models, up to the moment assumed as antiparallel-like d,l -α-CPs, led to unforeseen conclusions that put into question preliminary conjectures about these systems. Surprisingly, they tend to adopt a parallel β-sheet directed by the skeleton interactions. These results imply a change of paradigm with respect to cyclic peptide designs that should be considered for dimers and nanotubes.     

A Nitrite Electrochemical Sensor Based on Boron‐Doped Diamond Planar Electrochemical Microcells Modified with a Monolacunary Silicotungstate Polyoxoanion

A new boron doped diamond microcells (BDD) was modified, for rapid, selective and highly sensitive determination of nitrite, using a coating film of polyoxometalates (POMs), formed by cyclic voltammetry on the molecular p‐phenylenediamine (PPD) functionalized BDD. The scanning electron microscopy (SEM) technique was used to examine the morphology of (PPD/SiW₁₁) modified (BDD) electrode. It was found that (SiW₁₁) layer was uniformly formed on the electrode surface. It was observed that (BDD/PPD/SiW₁₁) showed excellent electrocatalytic activities towards nitrite ion. Under the selected conditions, the anodic peak maximum at ?0.6 V was linear versus nitrite concentration in the 40 µM–4 mM range, and the detection limit obtained was 20 µM. The newly developed electrode has been successfully applied to the determination of nitrite content in real river water samples.     

New ion exchange membrane derived from sulfochlorated polyether sulfone for electrodialysis desalination of brackish water

The purpose of this work is to study the desalination of brackish water using a new ion exchange membrane, made from sulfochlorated polyethersulfone (Cl‐PES), and crosslinked using aminated polyethersulfone (NH2‐PES) as a crosslinking reagent. This membrane, named ClNH2 membrane, has been obtained by reaction between Cl‐PES with 1.3 SO₂Cl groups per monomer unit and 0.2 equivalent amount of NH2‐PES. ClNH2 membrane has been characterized in terms of contact angle, transport number, intrinsic conductivity, and water uptake (as a function of temperature). Electrodialysis performances of the newly synthetized membranes have been measured using an electrodialysis cell at a laboratory scale and compared to commercial membranes. All the experiments have been performed using synthetic brackish water solutions prepared from sodium chloride salts with different concentrations (varying from 0.5 to 5.0 g/L). The concentration of different water samples obtained has been found to be below the amount recommended by the World Health Organization (WHO) for drinking water.     

On von Neumann regular elements in <Emphasis Type="Italic">f</Emphasis>-rings

Let B be an Archimedean reduced f-ring. A positive element \({\omega}\) in B is said to satisfy the property \({(\ast)}\) if for every f-ring A with identity e and every \({\ell}\)-group homomorphism \({\gamma : A \rightarrow B}\) with \({\gamma(e) = \omega}\), there exists a unique \({\ell}\)-ring homomorphism \({\rho: B \rightarrow B}\) such that \({\gamma = \omega \rho}\) and \({\rho(e)^{\perp \perp} = \omega^{\perp \perp}}\). Boulabiar and Hager proved that any (positive) von Neumann regular element in B satisfies the property \({(\ast)}\) and proved that the converse holds in the C(X)-case. In this regard, they asked about this converse in the general case. Our main purpose in this note is to prove, via a counter-example, that the converse in question fails in general. In addition, we shall take the opportunity to extend the direct result obtained by Boulabiar and Hager, and to get the C(X)-case we were talking about in an easier way.     

Well‐posedness and regularity results for a 2m‐th order parabolic equation in symmetric conical domains of ℝN+1

In this paper, we use the domain decomposition method to prove well‐posedness and smoothness results in anisotropic weighted Sobolev spaces for a multidimensional high‐order parabolic equation set in conical time‐dependent domains of . Copyright © 2017 John Wiley & Sons, Ltd.     

Double Orthogonal Click Reactions for the Development of Antimicrobial Peptide Nanotubes

A new class of amphipathic cyclic peptides, which assemble in bacteria membranes to form polymeric supramolecular nanotubes giving them antimicrobial properties, is described. The method is based on the use of two orthogonal clickable transformations to incorporate different hydrophobic or hydrophilic moieties in a simple, regioselective, and divergent manner. The resulting cationic amphipathic cyclic peptides described in this article exhibit strong antimicrobial properties with a broad therapeutic window. Our studies suggest that the active form is the nanotube resulted from the parallel stacking of the cyclic peptide precursors. Several techniques, CD, FTIR, fluorescence, and STEM, among others, confirm the nanotube formation.     

Experimental and Computational Studies of the Molybdenum‐Flanking Arene Interaction in Quadruply Bonded Dimolybdenum Complexes with Terphenyl Ligands

To clarify the nature of the Mo?C_arene interaction in terphenyl complexes with quadruple Mo?Mo bonds, ether adducts of composition [Mo₂(Ar′)(I)(O₂CR)₂(OEt₂)] have been prepared and characterized (Ar′=Ar^Xyl₂, R=Me; Ar′=ArMes₂, R=Me; Ar′=Ar^Xyl2, R=CF₃) (Mes=mesityl; Xyl=2,6‐Me₂C₆H₃, from now on xylyl) and their reactivity toward different neutral Lewis bases investigated. PMe₃, P(OMe)₃ and PiPr₃ were chosen as P‐donors and the reactivity studies complemented with the use of the C‐donors CNXyl and CN₂C₂Me₄ (1,3,4,5‐tetramethylimidazol‐2‐ylidene). New compounds of general formula [Mo₂(Ar′)(I)(O₂CR)₂( L )] were obtained, except for the imidazol‐2‐ylidene ligand that yielded a salt‐like compound of composition [Mo₂(Ar^Xyl2)(O₂CMe)₂(CN₂C₂Me₄)₂]I. The Mo?C_arene interaction in these complexes has been analyzed with the aid of X‐ray data and computational studies. This interaction compensates the coordinative and electronic unsaturation of one of the Mo atoms in the above complexes, but it seems to be weak in terms of sharing of electron density between the Mo and C_arene atoms and appears to have no appreciable effect in the length of the Mo?Mo, Mo?X, and Mo? L bonds present in these molecules.     

A new distance measure including the weak preference relation: Application to the multiple criteria aggregation procedure for mixed evaluations

We introduce a new distance measure between two preorders that captures indifference, strict preference, weak preference and incomparability relations. This measure is the first to capture weak preference relations. We illustrate how this distance measure affords decision makers greater modeling power to capture their preferences, or uncertainty and ambiguity around them, by using our proposed distance measure in a multiple criteria aggregation procedure for mixed evaluations.     

Synthesis of aggregation pheromone components of cerambycid species through α-hydroxylation of alkylketones

The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media.