CD and NMR studies on the aggregation of amphotericin-B in solution

We report in this paper the aggregation properties of amphotericin-B (amp-B) in solution using CD and 1H-NMR techniques. Our results indicate that the preferred structure of amp-B in dimethylsulfoxide is a monomer at low concentrations (10−4M and below) and a stable dimer at higher concentrations (range 5 · 103 M to 10−2M). In a DMSO/ethanol mixture (1:1 (v/v)), the antibiotic is monomeric, irrespective of the concentration within the range studied. We propose a head-to-tail model based on NMR data. An understanding of the head-to-tail dimer, is, we believe important, particularly in view of the recent report wherein it is proposed that the drug inserts into bilayers as head-to-tail oligomers.

Interest in university studies : Its role and relation to other motivational variables

This dissertation empirically explored interest as a motivational force in university studies, including the role it currently plays and possible ways of enhancing this role as a student motivator. The general research questions were as follows: 1) What role does interest play in university studies? 2) What explains academic success if studying is not based on interest? 3) How do different learning environments support or impede interest-based studying? Four empirical studies addressed these questions. Study 1 (n=536) compared first-year students explanations of their disciplinary choices in three fields: veterinary medicine, humanities and law. Study 2 (n=28) focused on the role of individual interest in the humanities and veterinary medicine, fields which are very different from each other as regards their nature of studying. Study 3 (n=52) explored veterinary students motivation and study practices in relation to their study success. Study 4 (n=16) explored veterinary students interest experience in individual lectures on a daily basis. By comparing different fields and focusing on one study field in more detail, it was possible to obtain a many-sided picture of the role of interest in different learning environments. Questionnaires and quantitative methods have often been used to measure interest in academic learning. The present work is based mostly on qualitative data, and qualitative methods were applied to add to the previous research. Study 1 explored students open-ended answers, and these provided a basis for the interviews in Study 2. Study 3 explored veterinary students portfolios in a longitudinal setting. For Study 4, a diary including both qualitative and quantitative measures was designed to capture veterinary students interest experience. Qualitative content analysis was applied in all four studies, but quantitative analyses were also added. The thesis showed that university students often explain their disciplinary choices in terms of interest. Because interest is related to high-quality learning, the students seemed to have a good foundation for successful studies. However, the learning environments did not always support interest-based studying; Time-management and coping skills were found to be more important than interest in terms of study success. The results also indicated that interest is not the only motivational variable behind university studies. For example, future goals are needed in order to complete a degree. Even so, the results clearly indicated that it would be worth supporting interest-based studying both in professionally and generally oriented study fields. This support is important not only to promote high-quality learning but also meaningful studying, student well-being, and life-long learning.

Studies on the metabolism of a monoterpene ketone, R-(+)-pulegone-a hepatotoxin in rat: isolation and characterization of new metabolites

1. The metabolic disposition of R-(+)-pulegone (1) was examined in rats following four daily oral doses (250 mg/kg). 2. Six metabolites, namely pulegol (II), 2-hydroxy-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanone (III), 3,6-dimethyl-7a-hydroxy-5,6,7,7a-tetrahydro-2(4H)-benzofuranone (IV), menthofuran (V), 5-methyl-2-(1-methyl-1-carboxyethylidene)cyclohexanone (VI), and 5-methyl-5-hydroxy-2-(1-hydroxy-1-carboxyethyl)cyclohexanone (VII) have previously been isolated from rat urine, and identified (Moorthy et al. (1989a). Eight new metabolites have now been isolated from rat urine, namely, 5-hydroxy-pulegone (VIII), piperitone (IX), piperitenone (X), 7-hydroxy-piperitone (XI), 8-hydroxy piperitone (XII), p-cresol (XIII), geranic acid (XIV) and neronic acid (XV). These were identified by n.m.r., i.r. and mass spectrometry. 3. Based on these results, metabolic pathways for the biotransformation of R-(+)-pulegone in rat have been proposed.

Reaction of normal and pseudo 2-formylbenzenesulfonyl chlorides with amines:experimental and theoretical studies on the structure of 2-formyl benzenesulfonamides in solid, solution and gas phases

The reaction of 2-formylbenzenesulfonyl chloride 1 and its pseudo isomer 2 with primary amines give either the corresponding sulfonamido Schiff bases or the corresponding 2-formylbenzenesulfonamide depending on the concentration of the amine used. The derivatives exist as an equilibrium mixture of the corresponding sulfonamide and 2-alkyl-3-hydroxy(or 3-aminoalkyl)-benzisothiazole-1,1-dioxide. Spectroscopic studies suggest that 2-formylbenzenesulfonamides exist as benzisothiazole-1,1-dioxides in the solid state, as a mixture of 2-formylbenzenesulfonamide and the corresponding benzisothiazole-1,1-dioxide in solution and as 2-formyl-benzenesulfonamides in the gas phase.

Studies on molecular evolution and structural features of double-headed inhibitors of ?-amylase and trypsin in plants

Plant seeds usually have high concentrations of proteinase and amylase inhibitors. These inhibitors exhibit a wide range of specificity, stability and oligomeric structure. In this communication, we report analysis of sequences that show statistically significant similarity to the double-headed alpha-amylase/trypsin inhibitor of ragi (Eleusine coracana). Our aim is to understand their evolutionary and structural features. The 14 sequences of this family that are available in the SWISSPROT database form three evolutionarily distinct branches. The branches relate to enzyme specificities and also probably to the oligomeric state of the proteins and not to the botanical class of the plant from which the enzymes are derived. This suggests that the enzyme specificities of the inhibitors evolved before the divergence of commercially cultivated cereals. The inhibitor sequences have three regions that display periodicity in hydrophobicity. It is likely that this feature reflects extended secondary structure in these segments. One of the most variable regions of the polypeptide corresponds to a loop, which is most probably exposed in the native structure of the inhibitors and is responsible for the inhibitory property.

Molecular and serological studies on the recent seal virus epizootics in Europe and Siberia

The virus epizootics which occurred in seals in both Europe and Siberia during 1987/1988 were caused by two different morbillivirus, referred to as phocid distemper virus (PDV) 1 and 2, respectively. Molecular and serological studies have shown that the European virus is quite distinct from canine distemper virus (CDV), its closest relative in the morbillivirus group. Analysis of tissues obtained from infected seals from a wide geographical distrubution over Northern Europe showed that the infectious agent (PDV 1) was identical in all cases. Nucleotide sequence analysis of one of the virus genes suggested that this virus has evolved away from CDV over a long time period and is most probably an enzootic virus of marine mammals. In contrast, the virus (PDV 2) which caused the deaths of many Siberian seals was indistinguishable, both serologically and at the molecular level, from CDV and must have originated from a land source.

Further studies on Norrish type II reactions including a reaction in the first excited singlet state and cyclization of 1:4 biradicals

The Norrish type II processes of methyl-2,2-dimethyl- cyclopropyl ketone, alpha-alkoxy acetones and alkyl pyruvates have been examined using the AM1 semi-empirical molecular orbital method with complete geometry optimization at the partial configuration interaction level in the restricted Hartree-Fock (RHF) frame. The results reveal that the methyl-substituted cyclopropyl ketone has a constrained geometry favourable for hydrogen abstraction from the gamma-position relative to the carbonyl group in the excited singlet state. The presence of the ether oxygen atom in the beta-position relative to the carbonyl group in alkoxy acetones and alkyl pyruvates leads to increased reactivity relative to alkyl monoketones and diketones respectively. The cyclization of 1:4 biradicals has been studied in the unrestricted Hartree-Fock (UHF) frame, and the results reveal that the 1:4 biradical derived from alkoxy acetones readily cyclizes to form oxetanols. On the other hand, in the 1:4 biradicals derived from methyl-substituted cyclopropyl ketone, the three-membered ring breaks readily to form an enol intermediate. Delocalization of an odd electron in 1:4 biradicals derived from alkyl pyruvates is thought to make cyclization difficult.

Studies on age-hardening characteristics of ceramic particle/matrix interfaces in Al-Cu-SiCp composites using ultra low-load-dynamic microhardness measurements

Ultra low-load-dynamic microhardness testing facilitates the hardness measurements in a very low volume of the material and thus is suited for characterization of the interfaces in MMC's. This paper details the studies on age-hardening behavior of the interfaces in Al-Cu-5SiC(p) composites characterized using this technique. Results of hardness studies have been further substantiated by TEM observations. In the solution-treated condition, hardness is maximum at the particle/matrix interface and decreases with increasing distance from the interface. This could be attributed to the presence of maximum dislocation density at the interface which decreases with increasing distance from the interface. In the case of composites subjected to high temperature aging, hardening at the interface is found to be faster than the bulk matrix and the aging kinetics becomes progressively slower with increasing distance from the interface. This is attributed to the dislocation density gradient at the interface, leading to enhanced nucleation and growth of precipitates at the interface compared to the bulk matrix. TEM observations reveal that the sizes of the precipitates decrease with increasing distance from the interface and thus confirms the retardation in aging kinetics with increasing distance from the interface.

Studies on structural and electrical properties of barium strontium titanate thin films developed by metallo-organic decomposition

Thin films of barium strontium titanate (BST) including BaTiO3 and SrTiO3 end members were deposited using the metallo-organic decomposition (MOD) technique. Processing parameters such as nonstoichiometry, annealing temperature and time, film thickness and doping concentration were correlated with the structural and electrical properties of the films. A random polycrystalline structure was observed for all MOD films under the processing conditions in this study. The microstructures of the films showed multi-grains structure through the film thickness. A dielectric constant of 563 was observed for (Ba0.7Sr0.3)TiO3 films rapid thermal annealed at 750 degrees C for 60 s. The dielectric constant increased with annealing temperature and film thickness, while the dielectric constant could reach the bulk values for thicknesses as thin as similar to 0.3 mu m. Nonstoichiometry and doping in the films resulted in a lowering of the dielectric constant. For near-stoichiometric films, a small dielectric dispersion obeying the Curie-von Schweidler type dielectric response was observed. This behavior may be attributed to the presence of the high density of disordered grain boundaries. All MOD processed films showed trap-distributed space-charge limited conduction (SCLC) behavior with slope of similar to 7.5-10 regardless of the chemistry and processing parameter due to the presence of main boundaries through the film thickness. The grain boundaries masked the effect of donor-doping, so that all films showed distributed-trap SCLC behavior without discrete-traps. Donor-doping could significantly improve the time-dependent dielectric breakdown behavior of BST thin films, mostly likely due to the lower oxygen vacancy concentration resulted from donor-doping. From the results of charge storage density, leakage current and time-dependent dielectric breakdown behavior, BST thin films are found to be promising candidates for 64 and 256Mb ULSI DRAM applications. (C) 1997 Elsevier Science S.A.

The studies on micro-structural defects in deformed composite matrix of Al-Si-Mg and SiC

Detailed Fourier line shape analysis has been performed on three different compositions of the composite matrix of Al-Si-Mg and SiC. The alloy composition in wt% is Al-7%Si, 0.35%Mg, 0.14%Fe and traces of copper and titanium (similar to 0.01%) with SiC varying from 0 to 30wt% in three steps i.e., 0, 10 and 30wt%. The line shift analysis has been performed by considering 111, 200, 220, 311 and 222 reflections after estimating their relative shift. Peak asymmetry analysis has been performed considering neighbouring 111 and 200 reflections and Fourier line shape analysis has been performed after considering the multiple orders 111 and 222, 200 and 400 reflections. Combining all these three analyses it has been found that the deformation stacking faults both intrinsic alpha' and extrinsic alpha " are absent in this alloy system whereas the deformation twin beta has been found to be positive and increases with the increase of SiC concentration. So, like other Al-base alloys this ternary alloy also shows high stacking fault energy, and the addition of SiC introduces deformation twin which increases with its concentration in the deformed lattices.

Microstructural, dielectric, pyroelectric and ferroelectric studies on partially grain-oriented SrBi2Ta2O9 ceramics

Partially grain-oriented (48%) ceramics of strontium bismuth tantalate (SrBi2Ta2O9) have been fabricated via conventional sintering. The grain-orientation factor of the ceramics was determined, as a function of both the sintering temperature and duration of sintering using X-ray powder diffraction (XRD) techniques. Variations in microstructural features (from acircular to plate like morphology) as a function of sintering temperature of the pellets were monitored by Scanning Electron Microscopy (SEM). The dielectric constant and loss measurements as functions of both frequency and temperature have been carried out along the directions parallel and perpendicular to the pressing axis. The anisotropy (epsilon(rn)/epsilon(rp)) associated was found to be 2.21. The effective dielectric constant of the samples with varying porosity was predicted using different dielectric mixture formulae. The grain boundary and grain interior contributions to the dielectric properties were rationalized using the impedance spectroscopy. The pyroelectric coefficient for strontium bismuth tantalate ceramic was determined along the parallel and perpendicular directions to the pressing axis and found to be -23 muC/m(2)K and -71 muC/m(2)K, respectively at 300 K. The ferroelectric properties of these partially grain-oriented ceramics are superior in the direction perpendicular to the pressing axis to that in the parallel direction.

Structural and dielectric studies on poly(l-lithocholic acid)

In this paper, we report the results pretaining to the study of the structural, microstructural and the dielectric properties of poly(I-lithocholic acid) (PL), and the composite of PL dispersed in PMMA. The density of the composites was measured using Archimedes principle. The microstructural properties of the composities were studied using XRD and SEM techniques, which give an idea about the dispersion of the polymer PL in the PMMA matrix. The dielectric constants er of the composites were measured with a HP 4194A Impedance/Gain-Phase Analyzer in the frequency range 100 Hz-40 MHz at room temperature. The dielectric constants of the composites at different frequencies were predicted using Clasius-Mossotti and Maxwell's models.

Studies on the structural and ionic transport properties at elevated temperatures of La1-xMnO3 +/-delta synthesized by a wet chemical method

Structural transformation and ionic transport properties are investigated on wet-chemically synthesized La1-xMnO3 (X=0.0-0.18) compositions. Powders annealed in oxygen/air at 1000-1080 K exhibit cubic symmetry and transform to rhombohedral on annealing at 1173-1573 K in air/oxygen. Annealing above 1773 K in air or in argon/helium at 1473 K stabilized distorted rhombohedral or orthorhombic symmetry. Structural transformations are confirmed from XRD and TEM studies. The total conductivity of sintered disks, measured by four-probe technique, ranges from 5 S cm(-1) at 298 K to 105 S cm(-1) at 1273 K. The ionic conductivity measured by blocking electrode technique ranges from 1.0X10(-6) S cm(-1) at 700 K to 2.0X10(-3) S cm(-1) at 1273 K. The ionic transference number of these compositions ranges from 3.0X10(-5) to 5.0X10(-5) at 1273 K. The activation energy deduced from experimental data for ionic conduction and ionic migration is 1.03-1.10 and 0.80-1.00 eV, respectively. The activation energy of formation, association and migration of vacancies ranges from 1.07 to 1.44 eV. (C) 2002 Elsevier Science B.V. All rights reserved.