Applications purement semi-affines et tressages

In this Note, we show essentially two results which complete the article by Ait Mokhtar et al., 2008. The first one, having defined the maps purement semi-affines, consists in looking the writing clarify of the compound of these maps. The second result, having defined the tressage, consists in showing that the compound of two tressages is also a tressage.     

New Numerical Approach for Fractional Variational Problems Using Shifted Legendre Orthonormal Polynomials

This paper reports a new numerical approach for numerically solving types of fractional variational problems. In our approach, we use the fractional integrals operational matrix, described in the sense of Riemann–Liouville, with the help of the Lagrange multiplier technique for converting the fractional variational problem into an easier problem that consisting of solving an algebraic equations system in the unknown coefficients. Several numerical examples are introduced, combined with their approximate solutions and comparisons with other numerical approaches, for confirming the accuracy and applicability of the proposed approach.     

Prescriptive analytics for FIFA World Cup lodging capacity planning

The FIFA World Cup, comprising sixty-four matches spanning an entire month, has, in recent years, been attended by about three million spectators of which over half a million are visitors requiring lodging. Planning lodging capacity for an event of this magnitude is necessary for host nations where pre-existing infrastructures are either inadequate or lacking. This paper develops an optimization analytics framework that sequentially employs two integer programming models for foreign spectator analysis and the consequent lodging requirements. The framework is applied to assess the preparedness of lodging infrastructure in Qatar for FIFA 2022.     

Synthesis,structural, spectroscopic,and thermal studies of some transition-metal complexes of a ligand containing the amino mercapto triazole moiety

A new series of transition-metal complexes of Schiff base ligand containing the amino mercapto triazole moiety ( HL ) was prepared. The Schiff base and its metal complexes were elucidated by different spectroscopic techniques (infrared [IR], ¹H nuclear magnetic resonance, UV–Visible, mass, and electron spin resonance [ESR]), and magnetic moment and thermal studies. Quantum chemical calculations have been carried out to study the structure of the ligand and some of its complexes. The IR spectra showed that the ligand is chelated with the metal ion in a neutral, tridentate, and bidentate manner using NOS and NO donors in complexes 1 – 6 , 10–12 , and 7 and 8 , respectively, whereas it behaves in a monobasic tridentate fashion using NOS donor sites in copper(II) nitrate complex ( 9 ). The magnetic moment and electronic spectra data revealed octahedral and square pyramidal geometries for complexes 2 , 11 , 12 , and 5 – 8 and 10 , respectively. However, the other complexes were found to have tetrahedral ( 4 ), trigonal bipyramidal ( 1 and 3 ), and square planar ( 9 ) structures. Thermal studies revealed that the chelates with different crystallized solvents undergo different types of interactions and the decomposition pathway ended with the formation of metal oxygen (MO) and metal sulfur (MS) as final products. The ESR spectrum of copper(II) complex 10 is axial in nature with hyperfine splitting with ²B_1g as a ground state. By contrast, complexes 7 and 8 undergo distortion around the Cu(II) center, affording rhombic ESR spectra. The HL ligand and some of its complexes were screened against two bacterial species. Data showed that complex 12 demonstrated a better antibacterial activity than HL ligand and other chelates.     

Anticancer activity of lanthanum (III) and europium (III) 5-fluorouracil complexes on Caco-2 cell line

Lanthanide complexes are of increasing importance in cancer diagnosis and therapy. In the present study 1:1 and 1:3 solid complexes of La (III)–5-FU (5-fluorouracil) were prepared and characterized. In solution, the formation of 1:1 La (III) and Eu (III) complexes enabled the enhancement of 5-FU's effectiveness. Binding constants of the 1:1 complexes of both metals were estimated using spectrophotometry and HPLC with fluorescence detection methods. The thermodynamic parameters ΔG ^° , ΔH ^° and ΔS ^° were calculated using differential scanning calorimetry. Evaluation of the cytotoxic activity of the 1:1 La (III)- and Eu (III)–5-FU complexes was performed through two methodologies, trypan blue for cell viability where La (III)- and Eu (III)–5-FU complexes were found to have 52,000 and 80,000 dead cells, respectively, and via flow cytometric analysis to measure the apoptotic values, which were found to be 59.87 and 86.86% respectively.     

Structural characterization,thermal, DFT,cytotoxicity, and antimetastatic properties of cocaine complexes with La(III), Er(III), and Yb(III)

Research on Chemical Intermediates - Reaction of cocaine (Cn) with Ln(III) chloride salts [where Ln?=?La(III), Er(III), and Yb(III)] afforded complexes of the [Ln(Cn)Cl(OH2)3].2Cl type...     

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO₂ electroreduction (CO₂R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO₂ reduction (CO₂R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO₂R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.     

One-Pot Synthesis of Chiral N-Arylamines by Combining Biocatalytic Aminations with Buchwald–Hartwig N-Arylation

The combination of biocatalysis and chemo-catalysis increasingly offers chemists access to more diverse chemical architectures. Here, we describe the combination of a toolbox of chiral-amine-producing biocatalysts with a Buchwald–Hartwig cross-coupling reaction, affording a variety of α-chiral aniline derivatives. The use of a surfactant allowed reactions to be performed sequentially in the same flask, preventing the palladium catalyst from being inhibited by the high concentrations of ammonia, salts, or buffers present in the aqueous media in most cases. The methodology was further extended by combining with a dual-enzyme biocatalytic hydrogen-borrowing cascade in one pot to allow for the conversion of a racemic alcohol to a chiral aniline.     

A switchable ionic liquid with polarity swing-assisted regeneration properties used for the preconcentration of cadmium in biological samples

In the present study the cadmium (Cd) was determined in serum samples of psoriatic patients. The severity of psoriasis was evaluated according to criteria based on standard clinical diagnosis using Psoriasis Area Severity Index (PASI) score. In present study, an innovative tunable green solvent system based microextraction (TSS-ME) was applied for the enrichment of Cd in acid digested serum samples prior to determination with flame atomic absorption spectrometry. The hydrophobic complex of Cd-ammonium pyrrolidine thiocarbamate was extracted in a tunable solvent system which was prepared from a polybasic amine (N, N, N′, N′-tetramethyl-1, 4-diaminobutane), decanol and water system. The tunable green solvent system (TSS) which has zero ionic strength was converted to homogeneous monophasic polar hydrophilic phase via exposure to CO₂ at different pressure and time duration. Then hydrophobic enriched Cd- ammonium pyrrolidine thiocarbamate was back extracted, using HNO₃ (0.1 to 0.5 mol L⁻¹) then the second round of TSS-ME was applied. The acidic aqueous phase enrich with analyte was separated from tunable solvent. The separated TSS was easily reused for up to 10 time for preconcentration purposes without loss of its enrichment character. The smoker and nonsmoker psoriatic patients at PASI >10, have two to three folds higher Cd levels in serum samples than healthy persons.     

Racemisation in Chemistry and Biology

The two enantiomers of a compound often have profoundly different biological properties and thus their liability to racemisation in aqueous solutions is an important piece of information. The authors reviewed the available data concerning the process of racemisation in vivo, in the presence of biological molecules (e.g., racemase enzymes, serum albumin, cofactors and derivatives) and under purely chemical but aqueous conditions (acid, base and other aqueous systems). Mechanistic studies are described critically in light of reported kinetic data. The types of experimental measurement that can be used to effectively determine rate constants of racemisation in various conditions are discussed and the data they provide is summarised. The proposed origins of enzymatic racemisation are presented and suggest ways to promote the process that are different from processes taking place in bulk water. Experimental and computational studies that provide understanding and quantitative predictions of racemisation risk are also presented.