Revision of structural properties of GdBO3 nanopowders doped with Eu3+ ions through spectroscopic studies

Monoclinic Gd(1-x)Eu(x)BO(3) nanopowders were successfully synthesized using a modified Pechini method. The crystal structure of the prepared materials was revised and confirmed using several techniques such as: IR, XRD, TEM, Raman spectroscopy and EDX analysis. The obtained material was comprised of particles, consisting of parts with the average size 350 nm. The luminescence properties of the prepared phosphors with different concentrations of Eu(3+) ions were characterized by excitation and emission spectra and its kinetic decay. The Judd-Ofelt parameters (Ω(2), Ω(4)), quantum efficiency, η, and chromaticity coordinates were also calculated.     

Crystal and electronic structure, lattice dynamics and thermal properties of Ag(I)(SO3)R (R = F, CF3) Lewis acids in the solid state

Trifluoromethansulfonate of silver(I), AgSO(3)CF(3) (abbreviated AgOTf), extensively used in organic chemistry, and its fluorosulfate homologue, AgSO(3)F, have been structurally characterized for the first time. The crystal structures of both homologues differ substantially from each other. AgOTf crystallizes in a hexagonal system (R3 space group, No.148) with a = b = 5.312(3) ? and c = 32.66(2) ?, while AgSO(3)F crystallizes in a monoclinic system in the centrosymmetric P2(1)/m space group (No.11) with a = 5.4128(10) ?, b = 8.1739(14) ?, c = 7.5436(17) ?, and β = 94.599(18)°, adopting a unique structure type (100 K data). There are two types of fluorosulfate anions in the structure; in one type the F atom is engaged in chemical bonding to Ag(I) and in the other type the F atom is terminal; accordingly, two resonances are seen in the (19)F NMR spectrum of AgSO(3)F. Theoretical analysis of the electronic band structure and electronic density of states, as well as assignment of the mid- and far-infrared absorption and Raman scattering spectra for both compounds, have been performed based on the periodic DFT calculations. AgSO(3)F exhibits an unusually low melting temperature of 156 °C and anomalously low value of melting heat (ca. 1 kJ mol(-1)), which we associate with (i) disorder of its anionic sublattice and (ii) the presence of 2D sheets in the crystal structure, which are weakly bonded with each other via long Ag-O(F) contacts. AgSO(3)F decomposes thermally above 250 °C, yielding mostly Ag(2)SO(4) and liberating SO(2)F(2). AgOTf is much more thermally stable than AgSO(3)F; it undergoes two consecutive crystallographic phase transitions at 284 °C and 326 °C followed by melting at 383 °C; its thermal decomposition commences above 400 °C leading at 500 °C to crystalline Ag(2)SO(4) and an unidentified phase as major products of decomposition in the solid state.     

Biosynthesis of the polyene antifungal antibiotic nystatin in Streptomyces noursei ATCC 11455: analysis of the gene cluster and deduction of the biosynthetic pathway

BACKGROUND: The polyene macrolide antibiotic nystatin produced by Streptomyces noursei ATCC 11455 is an important antifungal agent. The nystatin molecule contains a polyketide moiety represented by a 38-membered macrolactone ring to which the deoxysugar mycosamine is attached. Molecular cloning and characterization of the genes governing the nystatin biosynthesis is of considerable interest because this information can be used for the generation of new antifungal antibiotics. RESULTS: A DNA region of 123,580 base pairs from the S. noursei ATCC 11455 genome was isolated, sequenced and shown by gene disruption to be involved in nystatin biosynthesis. Analysis of the DNA sequence resulted in identification of six genes encoding a modular polyketide synthase (PKS), genes for thioesterase, deoxysugar biosynthesis, modification, transport and regulatory proteins. One of the PKS-encoding genes, nysC, was found to encode the largest (11,096 amino acids long) modular PKS described to date. Analysis of the deduced gene products allowed us to propose a model for the nystatin biosynthetic pathway in S. noursei. CONCLUSIONS: A complete set of genes responsible for the biosynthesis of the antifungal polyene antibiotic nystatin in S. noursei ATCC 11455 has been cloned and analyzed. This represents the first example of the complete DNA sequence analysis of a polyene antibiotic biosynthetic gene cluster. Manipulation of the genes identified within the cluster may potentially lead to the generation of novel polyketides and yield improvements in the production strains.     

Characterization of a Transformation Function of a Photochromic Adaptive Filter

Simple, fast and accurate procedure is developed for measuring a Transformation Function (TF) of a Photochromic Adaptive Filter (PAF). Photochromic filters, whose spectral transmittance depends on previous and immediate radiant exposure and other environmental conditions, require special methods of spectro-photometry to determine their properties. This article describes methodology of characterizing the luminous transmittance as a function of light intensity using easy to implement method. Transformation functions of sample filters for different sources of radiation and varied light intensity are evaluated. The measuring system can also be used for fast determination of spatially and spectrally uniform light sources with UV spectral component.     

Fluorine Determination and Matrix Effects in DC and HF Hollow Cathode Discharges

Abstract

The InF bands excited in a hollow cathode discharge have been used for fluorine determination in solid samples (containing from 10^?6 to 10^?1% F) and solutions (at the F^? concentrations from 1 μg/ml to 1 mg/ml). The discharge operated at direct current (dc) or high frequency current (hf). A dependence of the InF band intensities on the fluorine concentration has been investigated. Matrix effects caused by some metals and halides have been studied and discussed.     

Application of the density functional method to study phase transitions in an associating Lennard-Jones fluid adsorbed in energetically heterogeneous slit-Like pores

A density functional approach is used to study the adsorption of the four-bonding-site model associating Lennard-Jones fluid in slit-Like pores with energetically heterogeneous walls. The fluid-wall potential is qualitatively similar to that invoked by Röcken, P., Somoza, A., Tarazona, P., and Findenegg, G. H., 1999, J. chem. Phys., 108, 8089, i.e. it consists of a homogeneous part that varies in the direction perpendicular to the wall and a periodic part, varying also in one direction parallel to the wall. Both parts are modelled by Lennard-Jones 9,3-type functions. The structure of the adsorbed film is characterized by the local densities of all particles and the densities of the monomers. The phase diagrams are evaluated for several systems characterized by different corrugation of the adsorbing potential. The adsorbing field is strong enough to allow for the layering transition. As well as the formation of the so-called bridge phase that fills the pore space over the most energetic parts of the wall and of capillary condensation, the layering transition is observed within the first layer adjacent to the pore walls. If the adsorbing potential due to each pore wall is shifted in phase by π/2, the bridge phase is not formed.     

Phase coexistence and interface structure of a two-component Lennard-Jones fluid in porous media: application of Born—Green—Yvon equation

The Born-Green-Yvon equation with smoothed density approximation is used to calculate the liquid-liquid density profiles of a symmetric Lennard-Jones fluid in a hard sphere disordered matrix. The phase diagrams are evaluated for model systems characterized by different matrix densities and compared with the results of theoretical predictions and the Monte Carlo simulations of Gordon, P. A., and Glandt, E. D., 1996, J. chem. Phys., 105, 4257. It was found that increasing the matrix packing fraction reduces the magnitude of the miscibility gap and smooths the density profiles between two coexisting phases.     

Molecular dynamics study of the formation of small crystallites of Lennard-Jones particles in slit-like pores with (100) fcc walls

Canonical ensemble molecular dynamics is used to investigate the formation of small crystallites in slit-like pores with crystalline walls of (100) fcc symmetry. We study the influence of the pore width and the energetic parameters of the fluid particle-pore wall potential on the structure of the frozen droplets. We analyse the density profiles, in-plane radial distribution functions, in-plane diffusion coefficients, the distributions of Voronoi polygons, as well as the snapshots of consecutive configurations.     

Polydisperse fluid in contact with a semipermeable membrane

Using density functional theory developed by Rosefeld, a model polydisperse fluid has been studied in contact with a membrane permeable to some components of the fluid. Calculations were carried out for three kinds of polydisperse fluid, each characterized by a different distribution of particle sizes. The structure of fluid has been evaluated on both sides of the membrane, plus the distribution of the particles in bulk fluid and in the surface layers. The adsorption and osmotic pressure in the system have been calculated.     

The influence of random changes in the adsorbing potential on phase transitions in a Lennard-Jones fluid confined to energetically heterogeneous slit-like pores

A density functional approach is used to study the adsorption and phase behaviour of a Lennard-Jones (LJ) fluid in slit-like pores with energetically heterogeneous walls, investigating how the randomly varying part of the fluid-solid potential imposed on a periodic ‘back-ground’ potential modifies the phase behaviour of the confined fluid. Non-local density functional theory is employed to describe the system. To study the system with a random external field, the method used is based on investigations of several replicas of the system and on averaging the final thermodynamic results over the replicas.