Tetrathiafulvalene hydrazone: efficient synthon for the synthesis of novel bidentate redox active ligands

The synthesis and the ability of TTF-hydrazone to act as a versatile precursor for the design of electroactive ligands are reported together with the chelating ability of these ligands through their M(CO)₄ complexes, (M = Mo, W).     

Genetic diversity and haplotype structure of 21 Y‐STRs,including nine noncore loci,in South Tunisian Population: Forensic relevance

Y chromosome STRs (Y‐STRs) are being used frequently in forensic laboratories. Previous studies of Y‐STR polymorphisms in different groups of the Tunisian population identified low levels of diversity and discrimination capacity (DC) using various commercial marker sets. This definitely limits the use of such systems for Y‐STRs genotyping in Tunisia. In our investigation on South Tunisia, 200 unrelated males were typed for the 12 conventional Y‐STRs included in the PowerPlex® Y System. Additional set of nine noncore Y‐STRs including DYS446, DYS456, DYS458, DYS388, DYS444, DYS445, DYS449, DYS710, and DYS464 markers were genotyped and evaluated for their potential in improving DC. Allele frequency, gene diversity, haplotype diversity (HD), and DC calculation revealed that DYS464 was the most diverse marker followed by DYS710 and DYS449 markers. The standard panel of 12 Y‐STRs (DC = 80.5%) and the nine markers were combined to obtain DC of 99%. Among the 198 different haplotypes observed, 196 haplotypes were unique (HD = 99.999). Out of the nine noncore set, six Y‐STRs (DYS458, DYS456, DYS449, DYS710, DYS444, and DYS464) had the greatest impact on enhancing DC. Our data provided putative Y‐STRs combination to be used for genetic and forensic applications.     

Simple synthesis of imidazo[1,2-A]pyridine derivatives bearing 2-aminonicotinonitrile or 2-aminochromene moiety

A simple and general method for the synthesis of new imidazopyridines bearing an aminopyridinyl, chromenyl, or quinolinyl moiety in the C2 position was developed. The Knoevenagel reaction between imidazo[1,2-a]pyridine-2-carbaldehyde 1 and malononitrile resulted in the formation of starting material 2. Subsequently, intramolecular cyclization between the cyano group of 2 and acetophenones, naphtols, hydroxyquinolines, or phenols, gave 3, 4, 5, and 6 compounds, respectively. This is a simple, reproducible, and environmentally friendly method of synthesizing substituted imidazopyridines using water as a solvent or under solvent-free conditions.     

An a posteriori error estimator based on shifts for positive Hermitian eigenvalue problems

This work deals with an a posteriori error estimator for Hermitian positive eigenvalue problems. The proposed estimator is based on the residual and the definition of suitable shifts in the matrix spectrum. The mathematical properties (certification and sharpness) are investigated and some numerical experiments are proposed.     

Synthesis of substituted 1,4-diazepines and 1,5-benzodiazepines using an efficient heteropolyacid-catalyzed procedure

An efficient and improved procedure for the synthesis of 1,4-diazepine and 1,5-benzodiazepine derivatives via the reaction of ketimine intermediates with aldehydes in the presence of Keggin-type heteropolyacids (HPAs) was developed. High yields and short reaction times were obtained for both electron-releasing and electron-withdrawing substituted 1,4-diazepine and 1,5-benzodiazepines derivatives.     

Finite element formulation for active functionally graded thin-walled structures

For the analysis and design process of smart structures with integrated piezoelectric patches, the finite element method provides an effective simulation approach. In this paper, an attempt on modeling and simulation of the behavior of hybrid active structures is carried out using developed Kirchhoff-type-four-node shell element.The finite element results are compared with reference solutions taking into account the electromechanical responses of smart structures with various geometries, and the results show very high agreement. The main aspect of the application of the proposed element is to predict the behavior of FGM shells containing piezoelectric layers. A set of numerical analyses is performed in order to highlight the applicability and effectiveness of the present finite element model, notably for smart FGM structures. A comprehensive parametric study is conducted to show the influence of material composition, the placement and the thickness of the piezoelectric layers on the deformation of the laminated structure.     

One-step Synthesis of PCL-Urethane Networks using a Crosslinking/de-crosslinking Agent

Thermally reversible cross-linked polycaprolactone-urethane (PCL-U) was prepared in one-step procedure. The PCL-U networks were synthesized from a di-isocyanate (4,4′-methylene bis(cyclohexylisocyanate) (HMDI) and hydroxyl bearing macromers and monomers: hydroxy-terminated PCL, glycerol and a di-alcohol Diels-Alder (DA) adduct. This adduct was used to introduce both diene and dienophile functions in the structure and also to protect the maleimide functions from polymerization. The thermoresponsive behavior of the material was characterized by commonly used methods such as solubility tests at different temperatures and differential scanning calorimetry analyses to highlight rDA reactions and also by rheological analysis. The effects of the cooling rate, the molar mass of polycaprolactone as well as the molar ratio [di-Isocyanate]/[PCL-diol] on the cross-linking/de-cross-linking temperatures were also analyzed. The reversible networks obtained have a self-healing behavior.     

Tetrathiafulvalene hydrazone an efficient precursor of various chelating electroactive ligands

Novel bidentate electroactive ligands containing one or two tetrathiafulvalene (TTF) cores as redox active unit have been synthesized thanks to the condensation of various carbonyl derivatives with TTF hydrazone. The electron donating ability of these redox active ligands determined by cyclic voltammetry is described together with the investigations of their molecular structures by X-ray diffraction studies. The chelating ability of these ligands has been exemplified through the coordination to molybdenum carbonyl fragment or the complexation to difluoroboron moiety.     

Synthesis,characterization, and solution behavior of mercury(II) chloride complexes with phosphine tellurides

The reaction of mercury(II) chloride with neutral phosphine telluride ligands (R₃PTe) produced new mercury(II) complexes, HgCl₂(R₃PTe)₂ [R = Me₂N (1), Et₂N (2), C₄H₈N (3), C₅H₁₀N (4) or ^n-Bu (5)]. Attempts to isolate the complex of HgCl₂ with the morpholinyl ligand, (OC₄H₈N)₃PTe, were unsuccessful. Complexes 1–5 have been characterized by elemental analyses, IR, and multinuclear (³¹P, ¹²⁵Te, and ¹⁹⁹Hg) NMR spectroscopy. The solution behavior of the complexes was investigated using variable temperature NMR spectroscopy in the presence of excess ligand and indicated fast ligand exchange on the NMR timescale at room temperature. The metal–ligand exchange barriers in these complexes were estimated to be in the range 8–11 kcal/mol. The results suggest that a slight change in the nature of the substituents on the phosphorus of the ligand can contribute considerably to the lability of the complex obtained. The NMR data are discussed and compared with those obtained for related phosphine chalcogenide systems.