Protonation constant of salicylidene (N-benzoyl)glycyl hydrazone and its coordination behaviour towards some bivalent metal ions

Protonation constant of an unsymmetrical Schiff base, salicylidene(N-benzoyl)glycyl hydrazone (SalBzGH), and formation constants of its complexes have been determined potentiometrically at different temperatures in aqueous dioxane medium. Complexes of SalBzGH with VO(IV), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) have been prepared. Elemental analyses, pH-metric, molar conductance, magnetic susceptibility, electronic, IR, ESR, XRD (powder) and NMR studies have been carried out to study the coordination behaviour of SalBzGH toward these metal ions. pH-metric and 1H NMR studies show the presence of two dissociable protons in the ligand. IR and NMR spectra suggest the tridentate nature of the ligand, coordinating as a uninegative species in the Mn(II) complex and as a dinegative species in all the other complexes. Presence of two different conformers of the ligand at room temperature and stabilization of a single conformer upon complex formation have been established from¹H NMR spectra of the metal-free ligand, Zn(II) and Hg(II) complexes recorded at 296 K. Electronic and ESR spectra indicate highly distorted tetragonal geometry for VO(IV) and Cu(II) complexes. XRD powder patterns of the Zn(II) complexes are indexed for an orthorhombic crystal system.     

A new representation of permittivity versus temperature for alkanols of the same chain length

The alkanols of three carbon length have been studied by dielectric methods during many years and they do not obey any theoretical model. These substances have the same chain length and have one, two or three dipoles per molecule, so their ability to form hydrogen bridges changes from one substance to other, and one can obtain information by comparative studies. In previous works, we have measured the thermal dependence of permittivity of these substances and analysed the results with an empirical modification of the Onsager equation. Now we shall analyse and compare the results using a different representation. In this representation, the data shows straight lines, whose slopes depend on the quantity of dipoles of each molecule encouraging the high quality of the fittings obtained with the three substances, and also that they behave in the same dielectric way with the rise of temperature.     

Interaction of dipropyltin(IV) with amino acids,peptides, dicarboxylic acids and DNA constituents

Interaction of dipropyltin(IV) with selected amino acids, peptides, dicarboxylic acids or DNA constituents was investigated using potentiometric techniques. Amino acids form 1?:?1 and 1?:?2 complexes and, in some cases, protonated complexes. The amino acid is bound to dipropyltin(IV) by the amino and carboxylate groups. Serine is complexed to dipropyltin(IV) with ionization of the alcoholic group. A relationship exists between the acid dissociation constant of the amino acids and the formation constants of the corresponding complexes. Dicarboxylic acids form both 1?:?1 and 1?:?2 complexes. Diacids forming five- and six-membered chelate rings are the most stable. Peptides form complexes with stoichiometric coefficients 111(MLH), 110(ML) and 11-1(MLH_?1)(tin: peptide: H⁺). The mode of coordination is discussed based on existing data and previous investigations. DNA constituents inosine, adenosine, uracil, uridine, and thymine form 1?:?1 and 1?:?2 complexes and the binding sites are assigned. Inosine 5′-monophosphate, guanosine 5′-monophosphate, adenosine 5′-monophosphate and adenine form protonated species in addition to 1?:?1 and 1?:?2 complexes. The protonation sites and tin-binding sites were elucidated. Cytosine and cytidine do not form complexes with dipropyltin(IV) due to low basicity of the donor sites. The stepwise formation constants of the complexes formed in solution were calculated using the non-linear least-square program MINIQUAD-75. The concentration distribution of the various complex species was evaluated as a function of pH.     

Reaction of 1-benzoylethylpyridinium-4-aldoxime chloride with aquapentacyanoferrate(II)

The results of a spectrophotometric investigation of the reaction of the biologically active salt 1-benzoylethylpyridinium-4-aldoxime chloride with aquapentacyanoferrate(II) ion are presented. In spite of the presence of two donor sites, only the carbonyl group of the ligand coordinates to the iron centre. Reaction kinetics are consistent with a dissociative mechanism.     

Towards a naturally small cosmological constant from branes in 6D supergravity

We investigate the possibility of self-tuning of the effective 4D cosmological constant in 6D supergravity, to see whether it could naturally be of order 1/r⁴ when compactified on two dimensions having Kaluza–Klein masses of order 1/r. In the models we examine supersymmetry is broken by the presence of non-supersymmetric 3-branes (on one of which we live). If r were sub-millimeter in size, such a cosmological constant could describe the recently-discovered dark energy. A successful self-tuning mechanism would therefore predict a connection between the observed size of the cosmological constant, and potentially observable effects in sub-millimeter tests of gravity and at the Large Hadron Collider. We do find self-tuning inasmuch as 3-branes can quite generically remain classically flat regardless of the size of their tensions, due to an automatic cancellation with the curvature and dilaton of the transverse two dimensions. We argue that in some circumstances six-dimensional supersymmetry might help suppress quantum corrections to this cancellation down to the bulk supersymmetry-breaking scale, which is of order 1/r. We finally examine an explicit realization of the mechanism, in which 3-branes are inserted into an anomaly-free version of Salam–Sezgin gauged 6D supergravity compactified on a 2-sphere with nonzero magnetic flux. This realization is only partially successful due to a topological constraint which relates bulk couplings to the brane tension, although we give arguments why these relations may be stable against quantum corrections.     

Determination and analysis of dispersive optical constant of TiO2 and Ti2O3 thin films

Electron beam evaporation technique was used to prepare TiO₂ and Ti₂O₃ thin films onto glass substrates of thicknesses 50, 500 and 1000 nm for each sample. The structural investigations revealed that the as-deposited films are amorphous in nature. Transmittance measurements in the wavelength range (350-2000 nm) were used to calculate the refractive index n and the absorption index k using Swanepoel's method. The optical constants such as optical band gap , optical conductivity σ_opt, complex dielectric constant, relaxation time τ and dissipation factor tan δ were determined. The analysis of the optical absorption data revealed that the optical band gap E_g was indirect transitions. The optical dispersion parameters E_o and E_d were determined according to Wemple and Didomenico method.     

Molecular dynamics simulations of pure methane and carbon dioxide hydrates: lattice constants and derivative properties

ABSTRACT

We report extensive molecular dynamics simulation results of pure methane and carbon dioxide hydrates at pressure and temperature conditions that are of interest to various practical applications. We focus on the calculation of the lattice constants of the two pure hydrates and their dependence on pressure and temperature. The calculated lattice constants are correlated using second order polynomials which are functions of either temperature or pressure. Finally, the obtained correlations are used in order to calculate two derivative properties, namely the isothermal compressibility and the isobaric thermal expansion coefficient. The current simulation results are also compared against reported experimental measurements and other simulation studies and good agreement is found for the case of isothermal compressibility. On the other hand, for the case of isobaric thermal expansion coefficient good agreement is found only with other simulation studies, while the simulation studies are in disagreement with experiments, particularly at low temperatures.     

Determination of the in-plane anisotropy field in hexagonal systems via rotational magnetization: Theoretical model and Monte Carlo simulations

The magnetic anisotropy field in thin films with in-plane uniaxial anisotropy can be deduced from the VSM magnetization curves measured in magnetic fields of constant magnitudes. This offers a new possibility of applying rotational magnetization curves to determine the first- and second-order anisotropy constant in these films. In this paper we report a theoretical derivation of rotational magnetization curve in hexagonal crystal system with easy-plane anisotropy based on the principle of the minimum total energy. This model is applied to calculate and analyze the rotational magnetization process for magnetic spherical particles with hexagonal easy-plane anisotropy when rotating the external magnetic field in the basal plane. The theoretical calculations are consistent with Monte Carlo simulation results. It is found that to well reproduce experimental curves, the effect of coercive force on the magnetization reversal process should be fully considered when the intensity of the external field is much weaker than that of the anisotropy field. Our research proves that the rotational magnetization curve from VSM measurement provides an effective access to analyze the in-plane anisotropy constant K ₃ in hexagonal compounds, and the suitable experimental condition to measure K ₃ is met when the ratio of the magnitude of the external field to that of the anisotropy field is around 0.2. Supported by the National Natural Science Foundation of China (Grant Nos. 90505007 and 10774061) Recommended by LI FaShen