High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.     

Selective quenching of tryptophanyl fluorescence in bovine serum albumin by the iodide ion

Modified Stern-Volmer equation is obeyed by bovine serum albumin (BSA)-iodide system showing selective quenching of tryptophanyl fluorescence of BSA. The fraction of accessible protein fluorescence is 0.56 and the effective Stern-Volmer constant is 290 M^-1 at pH 7.4 in 0.005 M phosphate buffer at 25°C. Collisional quenching is operative both in the BSA -I⁻¹ system and the model system, tryptophan-I⁻¹. It is supported by the observed relationship between the ratio of quenching rate constants (k _q ) and diffusion coefficients and alsok _q with bulk viscosity.     

Structural,magnetic and Mössbauer spectral studies of nanosize aluminum substituted nickel zinc ferrites

Nanosize aluminum substituted nickel zinc ferrites were prepared through aerosol route and characterized using TEM, XRD, magnetic measurements and Mössbauer spectroscopy. The particle size of as obtained samples was found to be ∼10 nm which increases up to ∼85 nm upon annealing at 1200 °C. The unit cell parameter ‘a’ decreases linearly with concentration of aluminum due to the small ionic radius of aluminum. The saturation magnetization for all the samples after annealing at 1200 °C lies in the range 12.9–72.6 emu/g and decreases linearly with concentration of aluminum. Room temperature Mössbauer spectra of all as obtained samples of ferrite compositions exhibited a broad doublet suggesting super paramagnetic nature. This doublet is further resolved into two doublets and assigned to the surface region and internal region atoms of the particles. The samples annealed at 1200 °C show broad sextets, which were fitted with five sextets, indicating different local environment of both tetrahedrally and octahedrally coordinated Fe cation.     

On algebras of Toeplitz fuzzy matrices

In this paper, necessary and sufficient conditions are given for a product of Toeplitz fuzzy matrices to be Toeplitz. As an application, a criterion for normality of Toeplitz fuzzy matrices is derived and conditions are deduced for symmetric idempotency of Toeplitz fuzzy matrices. We discuss similar results for Hankel fuzzy matrices. Keywords: Fuzzy matrix, Toeplitz and Hankel matrices.     

Bounds on charged lepton mixing with exotic charged leptons

We examine the effects of mixing induced light heavy charged lepton neutral currents on the partial wave amplitude for the process l⁺l⁻ →ZZ (withl = e,μ or τ). By imposing the constraints that the amplitude should not exceed the perturbative unitarity limit at high energy (√s = Λ), we obtain bounds on light heavy charged lepton mixing parameter sin²(2θ _L ^a ) where θ _L ^a is the mixing angle of the ordinary charged lepton with its exotic partner. For Λ = 1 TeV, no bound is obtained on sin² (2θ _L ^a ) form _E < 0.69 TeV. However, sin² (2θ _L ^a ) ≤ 1.52×10⁻⁵ form _E = 5 TeV, sin² (2θ _L ^a ) ≤ 2.41 ×10⁻⁷ form _E = 10 TeV. Similarity for Λ = ∞ no bound is obtained on sin² (2θ _L ^a ) for m_E < 1.97 TeV and sin² (2θ _L ^a ) ≤ 0.15 form _E = 5 TeV and sin² (2θ _L ^a ) ≤ 3.88×10^-2 form _E = 10 TeV.     

Amine-templated metal squarates

Two layered amine-templated cobalt squarates, [C₆N₂H₁₄]₂[Co₂(C₄O₄)₃(H₂O)₄], I, and [C₃N₂H₅]₂[Co₂(C₄O₄)₃(H₂O)₄], II, have been prepared under hydrothermal conditions. Both I and II contain chains formed by dimers comprising two cobalt atoms bound to the squarate units, the chains being connected through hydrogen bond interactions. An amine-templated cobalt squarate of the formula [C₄N₂H₁₂][Co(C₄O₄)₂(H₂O)₄][H₂O]₂, III, as well as its Ni, Zn and Cd analogues have been prepared by room temperature reactions. III has a layered architecture wherein the cobalt-squarate monomers are linked by the amine molecules. Co and Zn analogues of [Ni(C₄O₄)(H₂O)₂(C₃N₂H₄)] with ligating imidazole units have also been prepared and characterized.     

Substituent electronic effects on the persistence and absorption spectra of (Z)-o-xylylenols. A nanosecond laser flash photolysis study

[reaction: see text] A systematic investigation on a broad set of aldehydes reveals that the lifetimes of (Z)-photoenols can be modulated by variation of the substituents. We have found that the lifetimes of (Z)-enols (in benzene) can be varied by more than 1 order of magnitude with a judicious choice of the substituents that exert mesomeric and inductive effects as, for example, in the case of pentamethylbenzaldehyde (tau = 35 ns) and dicyanomesitaldehyde (tau = 760 ns). This study thus points to the fact that the electronic factors in conjunction with hydrogen bonding stabilization can considerably broaden the uni- as well as bimolecular chemistry based on photoenolization. Further, we have shown that the photoenols exhibit dramatic shifts in their absorption properties with variation of the substituents; although the photoenols have long been considered to be colored, their absorption properties have not been heretofore comprehensively examined.     

Separation of dideoxyribonucleosides in trace amounts by automated liquid chromatography and capillary electrophoresis.

No satisfactory high-performance liquid chromatographic (HPLC) method is currently available for the separation of the major dideoxyribonucleosides (ddNs) and their derivatives. A method involving HPLC has been developed for the separation of five major ddNs [ddA, ddC, ddI, azT and 2',3'-dideoxy-2',3'-didehydrothymidine (d4T)]. Elution of the common and modified components of DNA was also examined under the selected separation conditions of HPLC. The elution characteristics of these compounds were studied using serum plasma samples spiked with ddN derivatives. In addition, capillary electrophoresis (CE) was investigated for the separation of ddNs and their derivatives. Picomolar amounts of the five major ddNs and the metabolic product of azT [5'-O-glucuronide-3'-azido-3'-deoxythymidine (Glo-azT)] were satisfactorily resolved in 10 min by using a modification of CE. The spectral properties of the ddNs were characterized under different pH conditions and compared with those of their parent deoxyribonucleosides (dNs) because these compounds are commonly measured in HPLC by their spectral properties. The spectra of ddC and ddT derivatives resemble very closely those of dC and dT, but those of ddA and ddI differ to some extent from their parent dNs. The HPLC method was extensively examined for satisfactory resolutions of these compounds. For example, an isocratic elution method, although simple, failed to resolve these compounds and ion-pair chromatography did not offer any advantage. Gradient elution involving buffered solutions and increasing amounts of an organic modifier yielded satisfactory results. Methanol appeared to be the organic modifier of choice. A reversed-phase matrix with smaller than octadecyl alkyl chains did not produce the necessary interactions. Uniform spherical beads of smaller diameter produced superior resolutions. The separation of these compounds on three commercially available columns is discussed. The separation of human plasma samples spiked with dideoxynucleoside derivatives by HPLC was accomplished in ca. 16 min. The presence of the dNs did not interfere in their separations.     

Oxidations with IBX: benzyl halides to carbonyl compounds, and the one-pot conversion of olefins to 1,2-diketones

A variety of benzyl halides were converted to the corresponding aldehydes/ketones in respectable yields by IBX in DMSO at 65 °C. The bromohydrin reaction of olefins using NBS-H₂O in DMSO can be nicely adapted to IBX-mediated oxidation of benzyl halides in such a way that olefins are converted to the corresponding 1,2-diketones in good isolated yields in one-pot.