Crystallographic and NMR studies on sterols from green alga Chaetomorpha basiretorsa Setchell

Chemical investigation of the ethanol extract of the marine green alga Chaetomorpha basiretorsa Setchell led to the isolation of a new sterol stigmast-4,28-dien-3 alpha 6 beta-diol 1 in addition to the five known sterols of beta-lawsaritol 2, saringosterol 3, 24-hydroperoxy-24-vinyl - cholesterol 4, beta-stigmasterol 5, 29-hydroxystigmasta-5, 24(28) -dien-3 beta-ol 6. Compounds were isolated by normal phase silica gel and Sephadex LH - 20 gel colum chromatography, reverse phase HPLC and recrystalization. Their structures were elucidated by spectroscopic methods including MS, IR 1D/2D NMR and X-ray analysis. Cytotoxicity of compounds was screened by using the standard WIT method. All these compounds were isolated from the green alga Chaetomorpha basiretorsa Setchell for the first time and they were inactive (50% inhibitory concentration was greater than 10 mu g /cm(3)) against KB, Bel -7402, PC - 3M, Ketr 3 and MCF - 7 cell lines.

Synthesis and QSAR studies of novel triazole compounds containing thioamide as potential antifungal agents

Eighteen novel triazole compounds containing thioamide were designed and synthesized. Their structures were confirmed by elemental analysis, H-1 NMR, IR, and MS. The title compounds exhibited certain antifungal activity. And the geometry structures of the title compounds were optimized by means of the density functional theory (DFT) method at B3LYP/6-31G* level. The quantitative structure-activity relationship (QSAR) of the title compounds was systematically investigated. A correlative equation between FA and DELH, V was well established by using the multiple linear regression (MLR). (c) 2006 Elsevier Ltd. All rights reserved.

Crystal structure and DFT studies of a triazole derivative: 4-(2-hydrobenzylideneamino)-3-(1,2,4-triazol-4-yl-methyl) 1H-1,2,4-triazole-5 (4H)-thione

A novel triazole derivative 4-(2-hydrobenzylideneamino)-3-(1, 2, 4-triazol-4-ylmethyl)-1H-1, 2, 4-triazole-5 (4H)-thione(1) was synthesized and characterized using elemental analysis, MR, and H-1 NMR, and its crystal structure was determined via X-ray single crystal diffraction analysis. Crystal data: monoclinic, P2 (1)/c, a = 0.83335 (9) nm, b = 1. 49777 (16) run, c = 1. 14724 (12) nm, beta = 107. 990 (2)degrees, D = 1. 470 Mg/m(3), and Z = 4. The geometries and the vibrational frequencies were determined using the density functional theory(DFT) method at the B3LYP/6-31G* level. To demonstrate the accuracy of the reaction route of compound 1, one of the important intermediates was also tested using the same method. The structural parameters of the two compounds calculated using the DFT study are close to those of the crystals, and the harmonic vibrations of the two compounds computed via the DFT method are in good agreement with those in the observed IR spectral data. The thermodynamic properties of the title compound were calculated, and the compound shows a good structural stability at normal temperature. The test results of biological activities show that it has a certain bactericidal ability.

XPS and XRD studies of fresh and sulfided Mo2N

Mo surface species of molybdenum nitride and their changes under sulfiding conditions were investigated by XRD and XPS. Mo2N was synthesized by temperature-programmed reaction of MoO3, with NH3. The decomposition of the Mo3d spectra gave a Mo3d doubler which corresponded to Modelta+ (2 less than or equal to delta < 4), Mo4+ and Mo5+ Or Mo6+ species. The BE of the Mo species of passivated Mo2N shifted to higher energy level compared with the freshly prepared Mo2N due to the oxidation of Mo nitride during passivation. When Mo2N was contacted for 4 h with a 15% H2S-H-2 mixture at 400 degrees C, the XRD spectra did not reveal any new phase, which indicates a high stability of Mo2N against sulfidation, but XPS data showed the presence of sulfur, including S-0 and S2- species, and a decrease of the N/Mo atomic ratio revealed some changes in surface composition. More than one monolayer of Mo2N was transformed to sulfide. It is probable that the oxygen incorporated during passivation reacted with sulfur and formed a thin layer of molybdenum sulfide on the Mo2N surface. (C) 1998 Elsevier Science B.V. All rights reserved.

XRD and XPS studies on the ultra-uniform Raney-Ni catalyst prepared from the melt-quenching alloy

We present a novel method for preparing an ultra-uniform Raney-Ni catalyst, which includes melt-quenching, hydrogen treatment and leaching in an alkali solution. The resultant catalyst shows superior activity in the reaction of cyclohexanone hydrogenation. X-ray diffraction (XRD) and XPS have been employed to characterize the catalysts. As demonstrated, the pretreatment with hydrogen caused a distinct phase transfer of the Ni-Al alloys, forming more of the Ni2Al3 component. In the subsequent leaching process, the Ni2Al3 component shows high activity and the resultant catalyst exhibits high surface areas and small pores. Moreover, metallic Al in the hydrogen-pretreated alloy appeared to be leached more easily and thus the aluminium species remaining on the catalyst surface is aluminium oxide predominantly, which serves as a matrix to stabilize active Ni species on the surface. Copyright (C) 2001 John Wiley & Sons, Ltd.

Biomimetic emulators of high potential peroxygenases: Implications in bioremediation and metabolic studies

Nowadays, classical (bio)remediation processes are affected by some economical and environmental drawbacks. These approaches often seem to be inadequate, particularly in the perspective of sustainable green processes. Since immobilized metalloporphines can emulate the active site of peroxidases and peroxygenases, their use in several bioremediation processes has been analyzed in this work. The described catalytic reactions use bioinspired, homogenized or heterogenized, commercial porphines and showed a remarkable ability to catalyze substrates oxidation at the expenses of different oxidants such as Oxone and hydrogen peroxide. The biomimetic catalysts have been also investigated about their peroxidase- and peroxygenase-like catalysis and ability to emulate lignolytic peroxidases action and substrate specificity. The adducts showed a remarkable ability to catalyze veratryl alcohol (widely recognized as a simple model compound of lignin) oxidation at the expenses of H2O2. In the perspective of broadening industrial applications of the described catalysts, the oxidation of several pollutants such as durable textile dyes and inorganic sulfides, has been attempted with quite promising results, and some findings open the way toward industrial scaling-up. Accordingly, the inexpensiveness of the synthesis and the mild operational conditions allow these adducts to be proposed as applicable catalysts also for industrial large-scale processes. Besides, these synthetic models are helpful also to understand the behavior of pharmaceuticals, antifungal drugs in this case, in the environment, and to predict the drug metabolism by cytochromes P450. The biomimetic catalysts, for the studied cases, also proved to be much more efficient than the corresponding enzymes.

40 years of library and information studies education in Wales

Tedd, L.A. (2005). 40 years of library and information studies education in Wales. Education for Information, 23(1/2), 1-8.

Media History and Media Studies: aspects of the development of the study of media history in the UK 1945-2000

O'Malley, T. (2002). Media History and Media Studies: aspects of the development of the study of media history in the UK 1945-2000. Media History. 8 (2), 155-173. RAE2008

Studies on equine milk and comparative studies on equine and bovine milk systems

The composition of equine milk differs considerably from that of the milk of the principal dairying species, i.e., the cow, buffalo, goat and sheep. Because equine milk resembles human milk in many respects and is claimed to have special therapeutic properties, it is becoming increasingly popular in Western Europe, where it is produced on large farms in several countries. Equine milk is considered to be highly digestible, rich in essential nutrients and to possess an optimum whey protein:casein ratio, making it very suitable as a substitute for bovine milk in paediatric dietetics. There is some scientific basis for the special nutritional and health-giving properties of equine milk but this study provides a comprehensive analysis of the composition and physico-chemical properties of equine milk which is required to fully exploit its potential in human nutrition. Quantification and distribution of the nitrogenous components and principal salts of equine milk are reported. The effects of the high concentration of ionic calcium, large casein micelles (~ 260 nm), low protein, lack of a sulphydryl group in equine β-lactoglobulin and a very low level of κ-casein on the physico-chemical properties of equine milk are reported. This thesis provides an insight into the stability of equine casein micelles to heat, ethanol, high pressure, rennet or acid. Differences in rennet- and acid-induced coagulation between equine and bovine milk are attributed not only to the low casein content of equine milk but also to differences in the mechanism by which the respective micelles are stabilized. It has been reported that β-casein plays a role in the stabilization of equine casein micelles and proteomic techniques support this view. In this study, equine κ-casein appeared to be resistant to hydrolysis by calf chymosin but equine β-casein was readily hydrolysed. Resolution of equine milk proteins by urea-PAGE showed the multi-phosphorylated isoforms of equine αs- and β-caseins and capillary zone electrophoresis showed 3 to 7 phosphorylated residues in equine β-casein. In vitro digestion of equine β-casein by pepsin and Corolase PP™ did not produce casomorphins BCM-5 or BCM-7, believed to be harmful to human health. Electron microscopy provided very clear, detailed images of equine casein micelles in their native state and when renneted or acidified. Equine milk formed flocs rather then a gel when renneted or acidified which is supported by dynamic oscillatory analysis. The results presented in this thesis will assist in the development of new products from equine milk for human consumption which will retain some of its unique compositional and health-giving properties.

Fractionation and compositional studies of rabbit skeletal muscle membranes

The observations of Hooke (1665), Schleiden & Schwann (1839) and Virchow (1855) led to the identification of the cell as the basic structural unit of living material. In the intervening years, it has been firmly established that the chemical processes which underlie the proper functioning, development and reproduction of the organism are cellular activities. The development of the electron microscope has enabled cell structure to be studied in detail. A picture of the cell as an entity with a complex and highly organised internal structure has emerged from the work of Palade, Porter, Fernandez-Moran and many others. Although cells from different tissues and organisms differ in aspects of their structure and consequently in function, they have several features in common. A retentive membrane encloses a number of cell constituents, which include membrane-enclosed subcellular structures known as organelles. The cells of most tissues also contain a reticulum or system of branching tubules. The interplay of the biochemical activities of these structures enables the cell to function. Almost thirty years ago, Claude, Palade, Schneider, Hogeboom, de Duve and others set out to analytically fractionate the subcellular components obtained after the fragmentation of liver cells. This approach has become known as subcellular fractionation, and signalled a major conceptual breakthrough in biochemistry (reviewed by de Duve, 1964, 1967, 1971). The significance of this breakthrough has been underlined by the award of the 1974 Nobel Prize in Medicine to de Duve, Palade and Claude. This thesis is concerned with the application of subcellular fractionation techniques to the separation and characterisation of the membrane systems of the rabbit skeletal muscle cell.

Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: comparing laboratory and field studies

Numerous laboratory experiments have been performed in an attempt to mimic atmospheric secondary organic aerosol (SOA) formation. However, it is still unclear how close the aerosol particles generated in laboratory experiments resemble atmospheric SOA with respect to their detailed chemical composition. In this study, we generated SOA in a simulation chamber from the ozonolysis of α-pinene and a biogenic volatile organic compound (BVOC) mixture containing α- and β-pinene, Δ3-carene, and isoprene. The detailed molecular composition of laboratory-generated SOA was compared with that of background ambient aerosol collected at a boreal forest site (Hyytiälä, Finland) and an urban location (Cork, Ireland) using direct infusion nanoelectrospray ultrahigh resolution mass spectrometry. Kendrick Mass Defect and Van Krevelen approaches were used to identify and compare compound classes and distributions of the detected species. The laboratory-generated SOA contained a distinguishable group of dimers that was not observed in the ambient samples. The presence of dimers was found to be less pronounced in the SOA from the VOC mixtures when compared to the one component precursor system. The elemental composition of the compounds identified in the monomeric region from the ozonolysis of both α-pinene and VOC mixtures represented the ambient organic composition of particles collected at the boreal forest site reasonably well, with about 70% of common molecular formulae. In contrast, large differences were found between the laboratory-generated BVOC samples and the ambient urban sample. To our knowledge this is the first direct comparison of molecular composition of laboratory-generated SOA from BVOC mixtures and ambient samples.

Pyramidal quantum dots: single and entangled photon sources and correlation studies

Practical realisation of quantum information science is a challenge being addressed by researchers employing various technologies. One of them is based on quantum dots (QD), usually referred to as artificial atoms. Being capable to emit single and polarization entangled photons, they are attractive as sources of quantum bits (qubits) which can be relatively easily integrated into photonic circuits using conventional semiconductor technologies. However, the dominant self-assembled QD systems suffer from asymmetry related problems which modify the energetic structure. The main issue is the degeneracy lifting (the fine-structure splitting, FSS) of an optically allowed neutral exciton state which participates in a polarization-entanglement realisation scheme. The FSS complicates polarization-entanglement detection unless a particular FSS manipulation technique is utilized to reduce it to vanishing values, or a careful selection of intrinsically good candidates from the vast number of QDs is carried out, preventing the possibility of constructing vast arrays of emitters on the same sample. In this work, site-controlled InGaAs QDs grown on (111)B oriented GaAs substrates prepatterned with 7.5 μm pitch tetrahedrons were studied in order to overcome QD asymmetry related problems. By exploiting an intrinsically high rotational symmetry, pyramidal QDs were shown as polarization-entangled photon sources emitting photons with the fidelity of the expected maximally entangled state as high as 0.721. It is the first site-controlled QD system of entangled photon emitters. Moreover, the density of such emitters was found to be as high as 15% in some areas: the density much higher than in any other QD system. The associated physical phenomena (e.g., carrier dynamic, QD energetic structure) were studied, as well, by different techniques: photon correlation spectroscopy, polarization-resolved microphotoluminescence and magneto-photoluminescence.