Synthesis, crystal structures and protease activity of amino acid Schiff base iron(III) complexes

Iron(III) complexes, (NHEt3)[Fe(III)(sal-met)(2)] and (NHEt3)[Fe(III)(sal-phe)(2)], of amino acid Schiffbase ligands, viz., N-salicylidene-L-methionine and N-salicylidene L-phenylalanine, have been prepared and their binding to bovine serum albumin (BSA) and photo-induced BSA cleavage activity have been investigated. The complexes are structurally characterized by single crystal X-ray crystallography. The crystal Structures of the discrete mononuclear rnonoanionic complexes show FeN2O4 octahedral coordination geometry in which the tridentate dianionic amino acid Schiff base ligand binds through phenolate and carboxylate oxygen and imine nitrogen atoms. The imine nitrogen atoms are trans to each other. The Fe-O and Fe-N bond distances range between 1.9 and 2.1 angstrom. The sal-met complex has two pendant thiomethyl groups. The high-spin iron(III) complexes (mu(eff) similar to 5.9 mu(B)) exhibit quasi-reversible Fe(III)/Fe(II) redox process near -0.6 V vs. SCE in water. These complexes display a visible electronic hand near 480 nm in tris-HCl buffer assignable to the phenolate-to-iron(III) charge transfer transition. The water soluble complexes bind to BSA giving binding constant values of similar to 10(5) M-1. The Complexes show non-specific oxidative cleavage of BSA protein on photo-irradiation with UV-A light of 365 nm.

Dipolar reorientation and phase-transition in mixed alkali-halide crystals

We show that the results of Lüty and Ortiz-Lopez relating the cyanide reorientation rates to the high-temperature phase diagrams of alkali-halide-alkali-cyanide mixed crystals can be understood within simple mean-field theory.

Analysis of Raman bandwidths and bandshapes of glasses through their glass-transition temperatures

Raman bandwidths and bandshapes of some molecular and ionic glasses have been investigated through the glass-transition region. Widths of both polarised and depolarised bands exhibit step-like changes during the glass transition. Molecular and ionic glasses differ with respect to the magnitude and the nature of variations in bandwidths and reorientational times. An attempt has been made to understand the changes in bandwidths around the glass-transition temperature.

Relative Stabilities of Layered Perovskite and Pyrochlore Structures in Transition Metal-Oxides Containing Trivalent Bismuth

In order to investigate the factors determining the relative stabilities of layered perovskite and pyrochlore structures of transition metal oxides containing trivalent bismuth, several ternary and quaternary oxides have been investigated. While d0 cations stabilize the layered perovskite structure, cations containing partially-filled d orbitals (which suppress ferroelectric distortion of MO6 octahedra) seem to favor pyrochlore-related structures. Thus, the vanadium analogue of the layered perovskite Bi4Ti3O12 cannot be prepared; instead the composition consists of a mixture of pyrochlore-type Bi1.33V2O6, Bi2O3, and Bi metal. The distortion of Bi1.33V2O6 to orthorhombic symmetry is probably due to an ordering of anion vacancies in the pyrochlore structure. None of the other pyrochlores investigated, Bi2NbCrO7, Bi2NbFeO7, TlBiM2O7 (M = Nb, Ta), shows evidence for cation ordering in the X-Ray diffraction patterns, as indeed established by structure refinement of TlBiNb2O7.

Action of Transition Metal Oxides on Composite Solid Propellants

The catalytic effects of Fe2O3, Ni2O3, MnO2, and Co2O3 transition metal oxides (TMO) on the combustion of polystyrene and carboxyl-terminated polybutadiene were investigated. The order of activity of TMO's was explained by the presence of Co and absence of Fe and Ni in their lattice systems along with a reduced electron-transfer process; in systems which induce the metal ions to enter the lattice, the electron transfer process is much greater. The thermal decomposition of ammonium perchlorate propellants was enhanced to a greater extent by Co2O3 and MnO2 than by Fe2O3 and Ni2O3.

Critical Cation Balance In B-]Z Transition - Role Of Li+

The sodium salt of poly(dG-dC) is known to exhibit a B + Z transition in the presence of various cations and 60% alcohol. We here show that the lithium salt of poly(dG-dC) does not undergo B 4 Z transition in the presence of 60% alcohol since Li’ with its large hydration shell cannot stabilize the Z-form. On the other hand, high concentrations of Mg2* or micromolar concentrations of the cobalt hexamine complex which are known to stabilize the Z-form can compete with Li+ for charge neutraIization and hence bring about a B--t Z transition in the same polymer. From the model building studies the mode of action of the cobalt-hexamine complex in stabilizing the Z-form is postulated.

Cluster model of the glass transition

A cluster model of the glass transition has been developed, treating the relative size of the cluster as an order parameter. The model accounts for some of the features of the glass transition.

Improved estimation of size-transition matrices using tag-recapture data

We derive a new method for determining size-transition matrices (STMs) that eliminates probabilities of negative growth and accounts for individual variability. STMs are an important part of size-structured models, which are used in the stock assessment of aquatic species. The elements of STMs represent the probability of growth from one size class to another, given a time step. The growth increment over this time step can be modelled with a variety of methods, but when a population construct is assumed for the underlying growth model, the resulting STM may contain entries that predict negative growth. To solve this problem, we use a maximum likelihood method that incorporates individual variability in the asymptotic length, relative age at tagging, and measurement error to obtain von Bertalanffy growth model parameter estimates. The statistical moments for the future length given an individual's previous length measurement and time at liberty are then derived. We moment match the true conditional distributions with skewed-normal distributions and use these to accurately estimate the elements of the STMs. The method is investigated with simulated tag-recapture data and tag-recapture data gathered from the Australian eastern king prawn (Melicertus plebejus).

Characterisation and processing of amorphous binary mixtures with low glass transition temperature

The number of drug substances in formulation development in the pharmaceutical industry is increasing. Some of these are amorphous drugs and have glass transition below ambient temperature, and thus they are usually difficult to formulate and handle. One reason for this is the reduced viscosity, related to the stickiness of the drug, that makes them complicated to handle in unit operations. Thus, the aim in this thesis was to develop a new processing method for a sticky amorphous model material. Furthermore, model materials were characterised before and after formulation, using several characterisation methods, to understand more precisely the prerequisites for physical stability of amorphous state against crystallisation. The model materials used were monoclinic paracetamol and citric acid anhydrate. Amorphous materials were prepared by melt quenching or by ethanol evaporation methods. The melt blends were found to have slightly higher viscosity than the ethanol evaporated materials. However, melt produced materials crystallised more easily upon consecutive shearing than ethanol evaporated materials. The only material that did not crystallise during shearing was a 50/50 (w/w, %) blend regardless of the preparation method and it was physically stable at least two years in dry conditions. Shearing at varying temperatures was established to measure the physical stability of amorphous materials in processing and storage conditions. The actual physical stability of the blends was better than the pure amorphous materials at ambient temperature. Molecular mobility was not related to the physical stability of the amorphous blends, observed as crystallisation. Molecular mobility of the 50/50 blend derived from a spectral linewidth as a function of temperature using solid state NMR correlated better with the molecular mobility derived from a rheometer than that of differential scanning calorimetry data. Based on the results obtained, the effect of molecular interactions, thermodynamic driving force and miscibility of the blends are discussed as the key factors to stabilise the blends. The stickiness was found to be affected glass transition and viscosity. Ultrasound extrusion and cutting were successfully tested to increase the processability of sticky material. Furthermore, it was found to be possible to process the physically stable 50/50 blend in a supercooled liquid state instead of a glassy state. The method was not found to accelerate the crystallisation. This may open up new possibilities to process amorphous materials that are otherwise impossible to manufacture into solid dosage forms.

Composition-controlled metal-insulator transitions and minimum metallic conductivity in the oxide systems LaNi1-xMxO3 (M = Cr, Mn, Fe, or Co)

The composition-controlled metal-insulator transition in the perovskite systems LaNi1-xMxO3 (M = Cr, Mn, Fe, and Co) has been investigated by transport measurements over the temperature range 12-300 K. These systems, which have critical electron densities (nc) in the range (1-2) -1020 electrons cm-3, exhibit sharp metal-insulator transitions at the base temperature. The corresponding minimum metallic conductivity (Ï-min), separating the localized and itinerant electronic regimes, is of the order of 102 ohm-1 cm-1. Particular attention is paid to the idea of Ï-min scaling with nc, and our present results are compared with earlier studies of the metal-insulator transition in low (e.g., Ge:Sb) and high (e.g., metal-ammonia, supercritical Hg) electron-density systems. A link is established between the transport and magnetic properties of the title systems at the metal-insulator transition.

Electronic-structures of h2o.bf3 and related n-v addition-compounds - a combined eels-ups study in vapor-phase

The detailed electronic structure of the n-v addition compound H2O·BF3 has been investigated for the first time by a combined use of electron energy loss spectroscopy (EELS) and UV photoelectron spectroscopy (UPS) augmented by MO calculations. The calculated molecular orbital energies of H2O·BF3 agree well with the UPS results and have been used to assign the electronic transitions obtained from EELS and to construct an orbital correlation diagram. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.

A laser flash photolysis study of pivalothiophenone triplets: steric and electronic effects in thione photoreaction kinetics

Upon laser pulse excitation (Aex = 532 nm) into the lowest-lying '(n,a*) band system, pivalothiophenones in benzene solutions give rise to short-lived triplets (Ama: = 325-335 nm, em: = (1 1-15) X lo3 M-' cm-I) with quantitative intersystem crossing efficiencies. The triplet yields decrease slightly (by 10-30%) upon changing A, to 308 nm (Le., upon excitation into S2). Kinetic data are presented for intrinsic triplet lifetimes, self-quenching, and quenching by oxygen, di-tert-butylnitroxy radical, and various reagents capable of interacting with the triplets via energy, electron, or hydrogen-atom transfer and by biradical formation (possibly leading to cycloaddition). The mechanisms of the quenching processes are discussed. Relative to rigid aromatic thiones, namely, xanthione and thiocoumarin, the interaction of pivalothiophenone triplets with most of the quenchers are kinetically inefficient. This is interpreted primarily as a manifestation of the steric crowding at positions a to the thiocarbonyl group.

Low-temperature and high-pressure Raman and x-ray studies of pyrochlore Tb2Ti2O7: Phonon anomalies and possible phase transition

We have carried out temperature- and pressure-dependent Raman and x-ray measurements on single crystals of Tb2Ti2O7. We attribute the observed anomalous temperature dependence of phonons to phonon-phonon anharmonic interactions. The quasiharmonic and anharmonic contributions to the temperature-dependent changes in phonon frequencies are estimated quantitatively using mode Grüneisen parameters derived from pressure-dependent Raman experiments and bulk modulus from high-pressure x-ray measurements. Further, our Raman and x-ray data suggest a subtle structural deformation of the pyrochlore lattice at ~9 GPa. We discuss possible implications of our results on the spin-liquid behavior of Tb2Ti2O7.

A Combination of Hexagonal and 12-Sided Polygonal Voltage Space Vector PWM Control for IM Drives Using Cascaded Two-Level Inverters

This paper proposes a multilevel inverter configuration which produces a hexagonal voltage space vector structure in the lower modulation region and a 12-sided polygonal space vector structure in the overmodulation region. A conventional multilevel inverter produces 6n plusmn 1 (n = odd) harmonics in the phase voltage during overmodulation and in the extreme square-wave mode of operation. However, this inverter produces a 12-sided polygonal space vector location, leading to the elimination of 6n plusmn 1 (n = odd) harmonics in the overmodulation region extending to a final 12-step mode of operation with a smooth transition. The benefits of this arrangement are lower losses and reduced torque pulsation in an induction motor drive fed from this converter at higher modulation indexes. The inverter is fabricated by using three conventional cascaded two-level inverters with asymmetric dc-bus voltages. A comparative simulation study of the harmonic distortion in the phase voltage and associated losses in conventional multilevel inverters and that of the proposed inverter is presented in this paper. Experimental validation on a prototype shows that the proposed converter is suitable for high-power applications because of low harmonic distortion and low losses.

High-Pressure Studies Of SE100-XTEX Glasses

High pressure resistivity measurements on Se100-xTex, glasses for 0≤x≤30 are reported. Two composition regions, where the transport and transformation behaviour are different, are identified. For 0≤x≤6, there is a first-order-like transformation to metallic crystalline states, while for x>6 the transformation appears to be continuous. Glass-transition temperatures also show differences in trends as a function of composition around 6% Te. An attempt is made to explain the composition-dependent trends on the basis of known structural features of selenium glasses and of the nature of tellurium bonding. At concentrations with up to 6% tellurium, Te most likely enters selenium chain terminations, substituting for negatively charged Se1- defects, while at larger concentrations, tellurium probably enters chains and rings by a random substitution.