Sequence dependence and role of 5'-phosphate in the B to Z transition

Spectroscopic studies on pd(CG)3 and pd(GC)3 have been carried out to elucidate the sequence dependence and effect of free 5'-phosphate on the B to Z transition. Unlike d(CG)3, pd(CG)3 fails to undergo salt-induced B to Z transition at ambient temperature. Model building studies have been carried out to determine the inhibitory role of the 5'-phosphate group, but have been unsuccessful.

Glass transition. A new approach based on cluster model of glasses

The structure of real glasses has been considered to be microheterogeneous, composed of clusters and connective tissue. Particles in the cluster are assumed to be highly correlated in positions. The tissue is considered to have a truly amorphous structure with its particles vibrating in highly anharmonic potentials. Glass transition is recognized as corresponding to the melting of clusters. A simple mathematical model has been developed which accounts for various known features associated with glass transition, such as range of glass transition temperature,T g, variation ofT g with pressure, etc. Expressions for configurational thermodynamic properties and transport properties of glass forming systems are derived from the model. The relevence and limitations of the model are also discussed.

The Influence of Bilayer Composition on the Gel to Liquid Crystalline Transition

We report molecular dynamics simulations of bilayers using a united atom model with explicit solvent molecules. The bilayer consists of the single tail cationic surfactant behenyl trimethyl ammonium chloride (BTMAC) with stearyl alcohol (SA) as the cosurfactant. We study the gel to liquid crystalline transitions in the bilayer by varying the amount of water at fixed BTMAC to SA ratio as well as by varying the BTMAC to SA ratio at fixed water content. The bilayer is found to exist in the tilted, Lβ′ phase at low temperatures, and for the compositions investigated in this study, the Lβ′ to Lα melting transition occurred in the temperature range 330−338 K. For the highest BTMAC to SA composition (2:3 molar ratio), a diffuse headgroup−water interface is observed at lower temperatures, and an increase in the d-spacing occurs prior to the melting transition. This pretransition swelling is accompanied by a sharpening in the water density variation across the headgroup region of the bilayer. Signatures of this swelling effect which can be observed in the alkane density distributions, area per headgroup, and membrane thickness are attributed to the hydrophobic effect. At a fixed bilayer composition, the transition temperature (>338 K) from the Lβ′ to Lα transition obtained for the high water content bilayer (80 wt %) is similar to that obtained with low water content (54.3 wt %), confirming that the melting transition at these water contents is dominated by chain melting.

Boundary layer transition observations on a body of revolution with surface heating and cooling in water

Boundary layer flow visualization in water with surface heat transfer was carried out on a body of revolution which had the predicted possibility of laminar separation under isothermal conditions. Flow visualization was by in-line holographic technique. Boundary layer stabilization, including elimination of laminar separation, was observed to take place on surface heating. Conversely, boundary layer destabilization was observed on surface cooling. These findings are consistent with the theoretical predictions of Wazzan et al. in The stability and transition of heated and cooled incompressible laminar boundary layers, in Proceedings of the Fourth International Heat Transfer Conference, Vol. 2, FCI 4. Elsevier, Amsterdam (1970).

Electrophilic Addition of Phenylisocyanate at gamma-CH of Thio-beta-diketonates of Some Transition Metals

The quasi-aromatic property of metal chelates of thio-beta-diketones has been studied by reacting them with phenylisocyanate, where addition takes place at the gamma-CH in a stepwise manner. Mono-thiodiketonates of Ni(II), Pd(II), cu(II) and Co(III) and the dithio-acetylacetonate of Ni(II) react with phenylisocyanate to produce mono-, di- and triphenylamido [with cobalt (III) only] substituted derivatives. In the case of tris (ethylthioacetoacetato) cobalt (III), it is found that the reaction with phenylisocyanate gives two isomers, a chocolate coloured isomer in which the phenylamido carbonyl is not coordinated while the green coloured isomer has bonding through phenylemido carbonyl oxygen. The reactions of the thiodiketonates have been compared with those of beta-diketonates and beta-ketoiminates. The reaction products have been characterised by elemental analyses, magnetic moments, and electronic, IR and 1H NMR spectral studies.

Infrared and Mössbauer spectroscopic study of the metal-insulator transition in some oxides of perovskite structure

The IR spectra of some LaNi1−xBxO3 (B = Cr, Fe, and Co) compounds having perovskite structure have been studied in the range 1000−300 cm−1. An investigation of the changes in the metal-oxygen stretching frequency as x → xc from the insulating side has been carried out. An important feature is that as x → xc the vibrational features in the infrared spectra disappear when the resistivity is not, vert, similar10−1 Ω cm which is of two orders of magnitude more than the value of varrho0 at which the temperature coefficient of resistance changes sign. Mössbauer studies on Fe-containing samples with various conductivities show that the isomer shift decreases as conductivity increases which is indicative of larger Fe---O overlap.

A Novel Approach to the Study of Surface Oxidation States and Oxidation of Transition Metals by Auger Electron Spectroscopy

L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{45}$, L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ and L$_{23}$ M$_{23}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ Auger intensity ratios in transition metal oxides and sulphides are shown to be directly related to the number of valence electrons in the metal as well as to its oxidation state. The metal Auger intensity ratios provide a unique probe, independent of O (KLL) intensity, to study surface oxidation states of metals. These intensity ratios have been effectively employed to investigate surface oxidation of nickel, iron and copper. The oxidation studies have unravelled some interesting aspects of surface oxidation.

Photo-Electron Spectroscopic Studies Of The Adsorption Of Organic-Molecules With Lone Pair Orbitals On Transition-Metal Surfaces

Ultraviolet and x-ray photoelectron spectroscopy have been employed to investigate the adsorption of methanol, ethanol, diethylether, acetaldehyde, acetone, methyl acetate and methylamine on surfaces of Fe, Ni and Cu. All these molecules adsorb molecularly at low temperatures (≤100 K). Lone pair orbitals of these molecules are stabilized on these metal surfaces (by 0·4–1·0eV) due to molecular chemisorption. The molecules generally undergo transformations as the temperature is raised to 120 K or above. The new species produced seems to depend on the metal surface. Some of the product species identified are methoxy species, formaldehyde and carbon monoxide in the case of methanol and methyl acetate, ethoxy species in the case of ethanol and 2-propanol in the case of acetone.

Pressure-induced first-order transition in layered crystalline semiconductor GeSe to a metallic phase

The electrical resistivity of layerd crystalline GeSe has been investigated up to a pressure of 100 kbar and down to liquid-nitrogen temperature by use of a Bridgman anvil device. A pressure-induced first-order phase transition has been observed in single-crystal GeSe near 6 GPa. The high-pressure phase is found to be quenchable and an x-ray diffraction study of the quenched material reveals that it has the face-centered-cubic structure. Resistivity measurements as a function of pressure and temperature suggest that the high-pressure phase is metallic.

The neutron-antineutron transition amplitude in the MIT Bag Model

The neutron-antineutron transition amplitude caused by an effective six fermion interaction with strength λeff is calculated within the context of the MIT Bag Model. The transition mass δm is found to have the value λeff×3×10−4(GeV6).

Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.