Adduct formation between alkali metal ions and anionic LV(V)O(2)(-) (L(2-) = tridentate ONS ligands) species: syntheses, structural investigation, and photochemical studies

Syntheses of alkali metal adducts [LVO(2)M(H(2)O)(n)] (1-7) (M = Na(+), K(+), Rb(+), and Cs(+); L = L(1)(-)L(3)) of anionic cis-dioxovanadium(V) species (LVO(2)(-)) of tridentate dithiocarbazate-based Schiff base ligands H(2)L (S-methyl-3-((5-(R-2-hydroxyphenyl))methyl)dithiocarbazate, R = H, L = L(1); R = NO(2), L = L(2); R = Br, L = L(3)) have been reported. The LVO(2)(-) moieties here behave like an analogue of carboxylate group and have displayed interesting variations in their binding pattern with the change in size of the alkali metal ions as revealed in the solid state from the X-ray crystallographic analysis of 1, 3, 6, and 7. The compounds have extended chain structures, forming ion channels, and are stabilized by strong Coulombic and hydrogen-bonded interactions. The number of coordinated water molecules in [LVO(2)M(H(2)O)(n)] decreases as the charge density on the alkali metal ion decreases (n = 3.5 for Na(+) and 1 for K(+) and Rb(+), while, for Cs(+), no coordinated water molecule is present). In solution, compounds 1-7 are stable in water and methanol, while in aprotic solvents of higher donor strengths, viz. CH(3)CN, DMF and DMSO, they undergo photoinduced reduction when exposed to visible light, yielding green solutions from their initial yellow color. The putative product is a mixed-oxidation (mu-oxo)divanadium(IV/V) species as revealed from EPR, electronic spectroscopy, dynamic (1)H NMR, and redox studies.     

Monoamine oxidase and succinate dehydrogenase inhibitory properties of substituted mercaptoquinazolones

Twelve 6-substituted-2-(1′-mercaptoacetyl-3′-arylurea)-3-phenyl-4-quinazolones were synthesized by condensation of 6-substituted anthranilic acids and aryl isothiocyanates followed by reaction with chloroacetyl arylurea. These compounds were characterized by their sharp melting points and elemental analyses. All compounds were evaluated for their enzyme inhibitory activity. It was found that all substituted quinazolones at a final concentration of 2 × 10^?4 M inhibited in vitro monoamine oxidase and succinate dehydrogenase activity of rat brain homogenates and the degree of inhibition ranged from 11–77% and 25–53%, respectively.     

\bar K K and\bar p p off-shell annihilations fromK − +p → Λ + pions at 4.2 GeV/c

We have investigated the properties of off-shell \(\bar K\) K and \(\bar p\) p annihilations into pions by using the interactionsK ^? p → Λ + pions at 4.2 GeV/c. The properties considered are multiplicities, hadronic temperatures and angular distributions. These properties appear more akin to those of \(\bar p\) p annihilations in flight than to that of \(\bar p\) p annihilation at rest despite the fact that the annihilation energy is small.     

Equilibrium studies in solution involving nickel(II) complexes of flexidentate Schiff base ligands: isolation and structural characterization of the planar red and octahedral green species involved in the equilibrium

Three new flexidentate 5-substituted salicylaldimino Schiff base ligands (L1-OH-L3-OH) based on 1-(2-aminoethyl)piperazine (X=H, L1-OH; X=NO2, L2-OH; and X=Br, L3-OH) and their nickel(II) complexes (1a, 1b, 2, and 3) have been reported. The piperazinyl arm of these ligands can in principle have both boat and chair conformations that allow the ligands to bind the Ni(II) center in an ambidentate manner, forming square-planar and/or octahedral complexes. The nature of substitution in the salicylaldehyde aromatic ring and the type of associated anion in the complexes have profound influences on the coordination geometry of the isolated products. With the parent ligand L1-OH, the product obtained is either a planar red compound [Ni(L1-O)]+, isolated as tetraphenylborate salt (1a), or an octahedral green compound [Ni(L1-NH)(H2O)3](2+), isolated with sulfate anion (1b); both have been crystallographically characterized. In aqueous solution, both these planar (S=0) and octahedral (S=1) forms are in equilibrium that has been followed in the temperature range 298-338 K by 1H NMR technique using the protocol of Evans's method. The large exothermicity of the equilibrium process [Ni(L1-O)]+ + 3H2O + H+<=>[Ni(L1-NH)(H2O)3](2+) (DeltaH degrees=-46 +/- 0.2 kJ mol(-1) and DeltaS degrees=-133 +/- 5 J K(-1) mol(-1)) reflects formation of three new Ni-OH2 bonds in going from planar to the octahedral species. With the 5-nitro derivative ligand L2-OH, the sole product is an octahedral compound 2, isolated as a sulfate salt while with the bromo derivative ligand L3-OH, the exclusive product is a planar molecule 3 with associated tetraphenylborate anion. Both 2 and 3 have been structurally characterized by X-ray diffraction analysis.     

Role of a Surface Active Agent in the Sol-Emulsion-Gel Synthesis of Spherical Alumina Powders

Spheroidal alumina particles of tailor-made size were prepared by the sol-emulsion-gel method under simultaneous mechanical agitation and sonication and by systematic variation of the concentration of a non-ionic surfactant in the organic solvent (oil phase) above or below the critical micelle concentration (CMC). The CMC of the surfactant in the organic solvent of low dielectric constant was determined from discernible breaks in surface tension, viscosity, optical absorption and dye fluorescence vs. concentration curves. The CMC of the surfactant played an important role in controlling the sol droplet size and accordingly, the size of the alumina particles obtained therefrom. Transmission electron microscopy (TEM) revealed that near (but below) CMC the nanospheroids (10–50 m) were in the state of chain-like agglomerates. Beyond CMC, spheroidal particles of larger dimensions were obtained. Particle size analysis showed a sharp decrease in mean size with increasing concentration of the surfactant up to CMC, above which a gentle upward trend was noticed.     

A novel imido-transfer reaction of aldehydes with Ph3PNTs using RuCl2(PPh3)3 as catalyst

(N-Tosylimino)triphenylphosphorane (Ph₃PNTs) was found to be an efficient imido-transfer reagent for the imidation of a variety of aldehydes using RuCl₂(PPh₃)₃ as the catalyst.     

Thermoplastic modification of monomeric and partially polymerized Bisphenol A dicyanate ester

Bisphenol A dicyanate ester (BADCy) was modified with different amounts of an engineering thermoplastic, polysulfone (PS) to improve impact strength of the parent resin. Differential scanning calorimetry of the blends suggested that addition of PS widens the curing exotherm of the BADCy considerably. FTIR of cured neat resins indicated total conversion of cyanate functional groups into triazine rings by cyclotrimerization. The cured neat resins showed phase separated morphology with cyanate ester as the continuous phase. The modified resins were shown to have better thermal, hygrothermal and impact strength properties. However, when glass fiber reinforced composites were made using partially polymerized BADCy and PS, very little or no phase separation in the resin was noticed. Flexural and impact strength measurement of composites showed that PS modification has compromised the flexural properties and only retained the impact strength of the parent resin containing composite. This study thus suggests that improvements realized in thermoplastic modification of monomeric BADCy are not directly transferable to composites using a partially prepolymerized BADCy.     

Recombination emission in hydrogen-fluorine systems

Visible emission which is generated when H₂ is added to partially dissociated F₂ is found to be due to Δυ = 4, 5, and 6 transitions of HF(X). The temporal and stoichiometric dependence of this emission strongly suggests that it results from direct combination of hydrogen and fluorine atoms and/or from recombination of hydrogen atoms with subsequent transfer of vibrational energy from H₂ to HF.     

Human FEN-1 can process the 5'-flap DNA of CTG/CAG triplet repeat derived from human genetic diseases by length and sequence dependent manner

Trinucleotide repeat (TNR) instability can cause a variety of human genetic diseases including myotonic dystrophy and Huntington's disease. Recent genetic data show that instability of the CAG/CTG repeat DNA is dependent on its length and replication origin. In yeast, the RAD27 (human FEN-1 homologue) null mutant has a high expansion frequency at the TNR loci. We demonstrate here that FEN-1 processes the 5'-flap DNA of CTG/CAG repeats, which is dependent on the length in vitro. FEN-1 protein can cleave the 5'-flap DNA containing triplet repeating sequence up to 21 repeats, but the activity decreases with increasing size of flap above 11 repeats. In addition, FEN-1 processing of 5'-flap DNA depends on sequence, which play a role in the replication origin-dependent TNR instability. Interestingly, FEN-1 can cleave the 5'-flap DNA of CTG repeats better than CAG repeats possibly through the flap-structure. Our biochemical data of FEN-1's activity with triplet repeat DNA clearly shows length dependence, and aids our understanding on the mechanism of TNR instability.