Syntheses, Structures and Properties of Two Mn(Ⅱ) Clusters Based on 1,10-Phenanthroline-2,9-dicarbaldehyde Dioxime Ligand

Two novel clusters [Mn~Ⅲ_3（μ_3-O）（phendox）3]X·13H_2O（X = Cl（1）, Br（2]） have been obtained from the solvothermal reactions of 1,10-phenanthroline-2,9-dicarbaldehyde dioxime（H_2phendox） with MnCl_2·4H_2O or anhydrous MnBr_2, and their structures were characterized by elemental analysis, FT-IR, XRD, TGA, MS and single-crystal X-ray diffraction. It crystallizes in trigonal, space group P3_1/c. X-ray analysis reveals that the neighbouring [Mn_3（μ_3-O）（phendox）_3]＋ cores are linked by C–H···Cl hydrogen bonds and form an infinite supramolecular chain along the c-axis. Neighbouring chains are packed with each other by off-set p-p interactions of the aromatic rings on phenox2-. A 3D supramolecular architecture in a honeycomb topology is formed with 1D hexagonal channel in the dimensions of 13？ × 13？ along the c-axis. The gas adsorption studies show that compound 1·13H_2O is stable upon the removal of guest molecules and the desolvated compound absorbed considerable amount of CO_2.

Synthesis and Crystal Structure of the First Example of a Tris-Chelated Co(II) Complex Based on Oxamide Dioxime Ligand

A new cobalt(II) complex, [Co(H2 oxado)3 ]C2 O4 H2 oxado·2H2 O (H2 oxado = oxamide dioxime), has been synthesized in aqueous solution and characterized by elemental analysis and single crystal X-ray structure determination. The complex crystallizes in the triclinic space group P-1, with the parameters a = 9.46(4), b = 11.84(5), c = 12. 81(5)?&Aring, α = 104.94(6), β = 99.29(5), γ = 106.73(5), V = 1284(9) &Aring3, Z = 2. The central cobalt(II) cation is pseudo-octahedrally coordinated by six imino N atoms of the neutral oxamide dioxime ligand. In the solid state, each of the following bricks, namely the cationic complexes, the oxalate dianions as well as the oxamide dioxime crystallization molecules, pile up parallel to the a axis. The bulk structure is consolidated by an extended three-dimensional network of hydrogen bridgings—that link the ionic partners, oxamide dioxime and water molecules to one another—and by coulombic interactions.

Synthesis, Spectroscopic and Electrochemical Investigations of Two vic-Dioximes and Their Mononuclear Ni（Ⅱ）, Cu（Ⅱ） and Co（Ⅱ） Metal Complexes Containing Morpholine Group

Two vic-dioxime ligands （LxH2） containing morpholine group have been synthesized from 4-[2-（dimethylaminoethyl）] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at -15 ℃. Reaction of two vic-dioxime ligands with MCl2·nH2O （M： Ni, Cu or Co and n=2 or 6） salts in 1 ： 2 molar ratio afforded metal complexes of type [M（LxH）2] or [M（LxH）2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities （Am） in DMF （dimethyl formamide） at 10^-3 mol·L^-1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, ^1H NMR and ^13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.

Synthesis and Characterization of Complexes of Copper（Ⅱ）, Nickel（Ⅱ） and Cobalt（Ⅱ） with vic-Dioximes Bearing N＇p-Aminobenzoyl Benzaldehyde Hydrazone

Six different arylhydrazone derivatives of p-aminobenzoic hydrazide of vic-dioximes were synthesized by reaction of chloroglyoxime and dichloroglyoxime with N＇-p-aminobenzoyl benzaldehyde, 4-hydroxybenzaldehyde and 4-methoxybenzaldehyde hydrazones, respectively. Metal-ligand （1 ： 2） complexes of vic-dioxime derivatives with Cu（Ⅱ）, Ni（Ⅱ） and Co（Ⅱ） were prepared from corresponding metal acetates. The ligands and their complexes were characterized on the basis of elemental analyses and spectral data. The complexing abilities of these new vic-dioximes toward transition metals of Co（Ⅱ）, Cu（Ⅱ）, Ni（Ⅱ）, Zn（Ⅱ）, Cd（Ⅱ）, Mn（Ⅱ） and Cr（Ⅲ） were determined by solid-liquid extraction studies.

Dynamic changes in cerebral microcirculation and hypoxia in the early stages of diffuse axonal injury

This study demonstrated that damage to the cerebral microvasculature, the formation of microthrombi and swelling of vascular endothelial cells occur early and peak 12 hours after injury in a rat model of diffuse axonal injury. Moreover, these pathological changes were most evident in the cerebral cortex. Cerebral microcirculatory dysfunction peaked later and had a shorter duration than axonal injury. In addition, the radioactive imaging agent, 99Tcm-4, 9-diaza-2, 3, 10, 10- tetramethyldodecan-2, 11 -dione dioxime, was used to visualize the dynamic changes that occur in tissue with cerebral hypoxia. The results demonstrated that cerebral hypoxia occurs at an early stage in diffuse axonal injury. Cerebral hypoxia was evident 12 hours after injury and declined slightly 24 hours after injury, but was significantly higher than in the control group. The pathological changes that underpin microcirculatory dysfunction did not occur at the same time as axonal injury, but did occur simultaneously with neuronal injury. Cerebral hypoxia plays a key role in promoting the secondary brain injury that occurs after diffuse axonal injury.

Supertough spontaneously self-healing polymer based on septuple dynamic bonds integrated in one chemical group

The development of spontaneously self-healing materials with excellent mechanical properties remains a formidable challenge despite the extensive interest in such materials. This is because the self-healing and mechanical properties of a material are usually optimized via contradictory routes. The present study demonstrated a supertough spontaneously self-healing polymer,Fe-(2,6-diacetylpyridine dioxime)-urethane-based polyurethane(Fe-PPOU) based on septuple dynamic bonds integrated in one chemical group. A synergistic effect was induced by the presence of multiple dynamic crosslinking points, which comprised the integrated dynamic interactions, and the hidden lengths of the folded polymeric chains in Fe-PPOU. Thus, the mechanical and self-healing properties of the polymer were simultaneously optimized. Fe-PPOU demonstrated the highest reported toughness(139.8 MJ m^(-3)) among all the room-temperature spontaneously self-healing polymers with a nearly 100% healing rate. Fe-PPOU exhibited instant(30 s) self-healing to reach a strength of 1.6 MPa that was higher than the original strength of numerous recently reported self-healing polymers.

A Linear Ce^(Ⅲ) Complex Based on in-situ Generated N-hydroxy-1,8-naphthalenedicarboximide

A Ce^(Ⅲ) linear complex of N-hydroxy-1,8-naphthalenedicarboximide(HL)has been synthesized with acenaphthoquinone dioxime(acndH_(2))under solvothermal conditions,in which L is generated by a series of in-situ reactions starting from acndH2.X-ray crystallography reveals the coordination chains of Ce^(Ⅲ) ions are assembled into a 3D supramolecular framework viaπ···πinteractions.The title complex has been characterized by IR and UV-Vis spectra and thermogravimetric analysis(TGA).Furthermore,the fluorescent properties study demonstrated a ligand-based emission of the Ce^(Ⅲ) complex with~6 nm blue-shift compared with the emisision of the HL ligand.