Synthesis and luminescence behaviour of novel heterodecanuclear silver(I)-rhenium(I) alkynyl complexes. X-ray crystal structures of [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Me2bpy)(CO)3]4](PF6)2 and [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Br2phen)(CO)3]4](PF6)2

A novel series of luminescent heterodecanuclear mixed-metal alkynyl complexes, [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(N--N)(CO)3]4](PF6)2, (N--N = tBu2bpy, Me2bpy, phen, Br2phen), have been successfully synthesized; the X-ray crystal structures of [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Me2bpy)(CO)3]4](PF6)2 and [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Br2phen)(CO)3]4](PF6)2 have also been determined.     

A novel histidine assay using tetraphenylporphyrin manganese (III) chloride as a molecular recognition probe by resonance light scattering technique

A novel histidine-selective method has been developed for the determination of histidine in aqueous solutions by resonance light scattering (RLS) technique. At pH 8.0, the weak RLS intensity of tetraphenylporphyrin manganese (III) chloride [MnTPPCl] was greatly enhanced by the addition of histidine with the maximum peak located at 483 nm. Under the optimum conditions, it was found that the enhanced RLS intensity was in proportion to the concentration of histidine in the range 7.8 × 10⁻⁷-2.4 × 10⁻⁵ mol l⁻¹. Low detection limit of 9.2 × 10^-8 mol l⁻¹ has been achieved. The histidine concentrations in synthetic samples and real samples were determined with satisfactory results. The sensitivity and selectivity of this method are high enough to permit the determination of trace amounts of histidine without any significant interference from high levels of other components such as common anions and especially, other amino acids.     

Fabrication of beta-Ni(OH)2 and NiO hollow spheres by a facile template-free process

Ni(OH)2 hollow microspheres with beta-Ni(OH)2 nanosheets as the in situ formed building units were fabricated via a novel template-free approach in a strong alkaline solution of glycine, and can be converted into NiO hollow microspheres by a thermal decomposition process.     

Non-Born-Oppenheimer trajectories with self-consistent decay of mixing

A semiclassical trajectory method, called the self-consistent decay of mixing (SCDM) method, is presented for the treatment of electronically nonadiabatic dynamics. The SCDM method is a modification of the semiclassical Ehrenfest (SE) method (also called the semiclassical time-dependent self-consistent-field method) that solves the problem of unphysical mixed final states by including decay-of-mixing terms in the equations for the evolution of the electronic state populations. These terms generate a force, called the decoherent force (or dephasing force), that drives the electronic component of each trajectory toward a pure state. Results for several mixed quantum-classical methods, in particular the SCDM, SE, and natural-decay-of-mixing methods and several trajectory surface hopping methods, are compared to the results of accurate quantum mechanical calculations for 12 cases involving five different fully dimensional triatomic model systems. The SCDM method is found to be the most accurate of the methods tested. The method should be useful for the simulation of photochemical reactions.     

Theoretical study of nitric oxide adsorption on Au clusters

The adsorption properties of NO molecule on anionic, cationic, and neutral Au(n) clusters (n=1-6) are studied using the density functional theory with the generalized gradient approximation, and with the hybrid functional. For anionic and cationic clusters, the charge transfer between the Au clusters and NO molecule and the corresponding weakening and elongation of the N-O bond are essential factors of the adsorption. The neutral Au clusters have also remarkable adsorption ability to NO molecule. The adsorption energies of NO on the cationic clusters are generally greater than those on the neutral and anionic clusters.     

Enhancement of Photocurrent Generation of a Novel Stilbazolium Dye Dimer in LB Monolayer Films

A novel dye dimer,bis-{[1-(N-hexadecyl-4-pyridinium)-2-(4-N,N-dimethylaminopheyl)] ethenyl} methane diiodide (C16BP) was synthesized,and the photoelectrochemistry of the dye Langmuir-Blodgett monolayer modified ITO electrode was investigated.For comparison,the photoelectrochemistry of the monomer (E)-N-hexadexyl-4-[2-(4-N,N-dimethylaminophenyl) ethenyl] pyridinium iodide (C16P) was also measured.The results show that the photocurrent generation property of the dimer is enhanced.The photocurrent generation quantum yield is 0.38% for C16BP,while that for C16P is 0.23%.     

A chemical inhibitor reveals the role of Raf kinase inhibitor protein in cell migration

Raf kinase inhibitor protein (RKIP) is a modulator of cell signaling that functions as an endogenous inhibitor of multiple kinases. We demonstrate here a positive role for RKIP in the regulation of cell locomotion. We discovered that RKIP is the relevant cellular target of locostatin, a cell migration inhibitor. Locostatin abrogates RKIP's ability to bind and inhibit Raf-1 kinase, and it acts by disrupting a protein-protein interaction, an uncommon mode of action for a small molecule. Small interfering RNA-mediated silencing of RKIP expression also reduces cell migration rate. Overexpression of RKIP converts epithelial cells to a highly migratory fibroblast-like phenotype, with dramatic reduction in the sensitivity of cells to locostatin. RKIP is therefore the compound's valid target and a key regulator of cell motility.     

A Novel Dinuclear Nickel(II) Complex with Three Bridges of Cl–, OAc– and (‐OCH2CH2O‐) Group of N,N, N′, N′‐Tetrakis(2‐benzimidazolyl methyl‐1, 4‐di‐ethylene amino) Glycol Ether

The novel dinuclear Ni²⁺ complex [Ni₂(μ‐Cl)(μ‐OAc) (EGTB)]·Cl·ClO₄·2CH₃OH, where EGTB is N, N, N′, N′‐tetrakis (2‐benzimidazolyl methyl‐1, 4‐di‐ethylene amino)glycol ether, crystallizes in the orthorhombic space group Pnma with a = 15.272(2), b = 14.768(2), c = 22.486(3) Å, V = 5071.4(12) ų, Z = 4, D_calc = 1.414 g cm^?3, and is bridged by triply bridging agents of a chloride ion, an acetate and an intra‐ligand (‐OCH₂CH₂O‐) group. The nickel coordination geometry is that of a slightly distorted octahedron with a NiN₃O₂Cl arrangement of the ligand donor atoms. The Ni–Cl distance is 2.361(2) Å, and two Ni–O distances are 1.996(5) and 2.279(6) Å. The three Ni–N distances are 2.033(7), 2.060(6), and 2.166(6) Å with the Ni–N bond trans to an ether oxygen the shortest, the Ni–N bond trans to an acetate oxygen the middle and the Ni–N bond trans to Cl the longest.     

Two novel procedures of preparation for [Tc(CO)<Subscript>2</Subscript>(NO)]<Superscript>2+</Superscript>labeled by EHIDA and its biodistribution

To develop potential new Tc radiopharmaceuticals, a novel compound [^99mTc(CO)₂(NO)(EHIDA)]⁰ (EHIDA: 2,6-diethylphenylcarbamoylmethyliminodiacetic acid) has been prepared by reacting [^99mTc(CO)₃)(EHIDA)]⁻ with NOBF₄ both in water and acetonitrile. The conversion of [^99mTc(CO)₃)(EHIDA)]⁻ to [^99mTc(CO)₂(NO)(EHIDA)]⁰ was supported by TLC, HPLC and eletrophoresis. The radiochemical purity (more than 99%) was proved by TLC and HPLC. The biodistribution in mice demonstrated that [Tc(CO)₂(NO)(EHIDA)]⁰ showed higher uptake in blood, kidney and lung (15 min, blood: 19.24±2.95; kidney: 13.61±3.49; lung: 10.81±1.09.) but a lower uptake in liver (15 min, 5.73±0.74). The slower clearances (120 min, blood: 12.75±1.34; kidney: 13.61±3.49) from blood and kidney were also found. This research describes two methods for the conversion of [^99mTc(CO)₃]⁺ into [^99mTc(CO)₂)(NO)]²⁺ by using NOBF₄ as the source of NO⁺ both in organic solvent and water. The latter method offers the possibility to introduce the NO-group in high yield in water.