XANES and EXAFS of copper compounds: Studies of copper carboxylates with metal-metal bonds and of the complex formed byPseudomonas aeruginosa

X-ray absorpion near edge structure (xanes) of copper compounds with copper in 1+, 2+ and 3+ states has been studied. Extended x-ray absorption fine structure (exafs) has been employed to determine bond distances and coordination numbers in several model copper compounds. Employing bothxanes andexafs, the structure of the copper complex formed by the micro-organismPseudomonas aeruginosa has been shown to be square-planar with the Cu-O distance close to that in cupric glucuronates and cupric acetylacetonate.exafs has been shown to be useful for studying metal-metal bonds in copper carboxylates.

NMR (1H, 13C) and MO (ab initio, CNDO/2, EHT) studies on basic and N-protonated hydrazinecarbothioamide

The conformational preferences of hydrazinecarbothioamide (HCTA, H2NNHCSNH2) in its basic and N-protonated (PHCTA, H3NNNHCSNH2) forms have been studied by 1H and 13C NMR spectroscopy and by theoretical LCAO-MO methods (ab initio, CNDO/2 and EHT). The hindered rotation around the C---N bond has been investigated by a total line shape analysis for the thioamide protons and by the three MO methods. Changes in the molecular conformation and electronic structure on protonation are briefly discussed.

Chemical Modification Studies of Gelonin - Involvement of Arginine Residues in Biological-Activity

Gelonin inhibits protein synthesis by inactivating the eukaryotic 60 S ribosomal subunit by an unknown mechanism. The protein was purified in high yield by a new method using Cibacron blue F3GA-Sepharose. Chemical modification studies reveal that arginine residues are essential for biological activity.

Studies in terpenoids. Part 42. Synthesis of 3-(2-hydroxyisopropyl)5,8-dimethyl-1,2-naphthoquinone (emmotin-H)

Emmotin-H, a naturally occurring sesquiterpenoid 1,2-naphthoquinone pigment (1) has been synthesised in a four step sequence starting from the known 5,8-dimethyl-4-oxotetralin-2-carboxylic acid (3a). Selenium dioxide oxidation of its methyl ester (3b) gives 3-methoxycarbonyl-5,8-dimethyl-1,2-naphthoquinone (4) which on reductive acetylation affords the corresponding diacetoxynaphthalene ester (5). Its reaction with excess of methylmagnesium iodide is accompanied by aerial oxidation during work-up and furnishes emmotin-H (1).

DSC studies on the phase transformation of hydrazonium sulfate

The high temperature phase transformation of hydrazonium sulfate, N2H6SO4 has been studied using DSC. The enthalpy of phase transition is found to be 3.63 ± 0.1 kJ mole−1. The phase transition temperature is found to decrease with the increase of particle size. It appears that the strain energy and not surface energy, is responsible for the phase transformation. The molar volume of the salt increases during the transformation as found by the dilatometric experiment involving percentage of linear thermal expansion. On cooling, the transformation from the high temperature modification to orthorhombic form is incomplete and extends over a wide range of temperature.

Singlet emission studies on porphyrins appended with heterocyclic bases

Porphyrins appended in the meso positions with 1,2-diazole, indole and quinoline are shown to exhibit enhanced fluorescence quantum yields relative to meso tetraphenyl porphyrin. The singlet emission yields decrease with the number of appended heterocyclic bases. An intramolecular charge transfer resonance mechanism has been advanced to interpret these results.

LIII absorption edge studies of mixed valent cerium intermetallics and related systems

LIII absorption edge measurements clearly delineate 3+ and 4+ states of Ce. Absorption edges of 3+ compounds show a single peak, while those of 4+ compounds show two peaks, both appearing at higher energies than the characteristic peaks of 3+ compounds. In systems where there is interconfigurational fluctuation, features due to both 3+ and 4+ states are distinctly seen.

x-ray studies on crystalline complexes involving amino-acids and peptides .10. head-to-tail sequences in the crystal-structure of l-lysine acetate

l-Lysine acetate crystallises in the monoclinic space group P21 with a = 5.411 (1), b = 7.562(1), c= l2.635(2) Å and β = 91.7(1). The crystal structure was solved by direct methods and refined to an R value of 0.049 using the full matrix least squares method. The conformation and the aggregation of lysine molecules in the structure are similar to those found in the crystal structure of l-lysine l-aspartate. A conspicuous similarity between the crystal structures of l-arginine acetate and l-lysine acetate is that in both cases the strongly basic side chain, although having the largest pK value, interacts with the weakly acidic acetate group leaving the α-amino and the α-carboxylate groups to take part in head-to-tail sequences. These structures thus indicate that electrostatic effects are strongly modulated by other factors so as to give rise to head-to-tail sequences which have earlier been shown to be an almost universal feature of amino acid aggregation in the solid state.

Studies in metal-ammonia reduction-5: Reduction and reductive methylation of some naphthoic acids

Birch reductio and reductive methylations of some substituted naphtholic acids have been examined. The factors influencing the mechanism of reduction process have been discussed. Some of the reduced naphthoic acids are useful synthons for synthesis.

Statistical power calculation and sample size determination for environmental studies with data below detection limits

Power calculation and sample size determination are critical in designing environmental monitoring programs. The traditional approach based on comparing the mean values may become statistically inappropriate and even invalid when substantial proportions of the response values are below the detection limits or censored because strong distributional assumptions have to be made on the censored observations when implementing the traditional procedures. In this paper, we propose a quantile methodology that is robust to outliers and can also handle data with a substantial proportion of below-detection-limit observations without the need of imputing the censored values. As a demonstration, we applied the methods to a nutrient monitoring project, which is a part of the Perth Long-Term Ocean Outlet Monitoring Program. In this example, the sample size required by our quantile methodology is, in fact, smaller than that by the traditional t-test, illustrating the merit of our method.

Characterization of Ion-Exchange Fibers for Controlled Drug Delivery

Increasing attention has been focused on methods that deliver pharmacologically active compounds (e.g. drugs, peptides and proteins) in a controlled fashion, so that constant, sustained, site-specific or pulsatile action can be attained. Ion-exchange resins have been widely studied in medical and pharmaceutical applications, including controlled drug delivery, leading to commercialisation of some resin based formulations. Ion-exchangers provide an efficient means to adjust and control drug delivery, as the electrostatic interactions enable precise control of the ion-exchange process and, thus, a more uniform and accurate control of drug release compared to systems that are based only on physical interactions. Unlike the resins, only few studies have been reported on ion-exchange fibers in drug delivery. However, the ion-exchange fibers have many advantageous properties compared to the conventional ion-exchange resins, such as more efficient compound loading into and release from the ion-exchanger, easier incorporation of drug-sized compounds, enhanced control of the ion-exchange process, better mechanical, chemical and thermal stability, and good formulation properties, which make the fibers attractive materials for controlled drug delivery systems. In this study, the factors affecting the nature and strength of the binding/loading of drug-sized model compounds into the ion-exchange fibers was evaluated comprehensively and, moreover, the controllability of subsequent drug release/delivery from the fibers was assessed by modifying the conditions of external solutions. Also the feasibility of ion-exchange fibers for simultaneous delivery of two drugs in combination was studied by dual loading. Donnan theory and theoretical modelling were applied to gain mechanistic understanding on these factors. The experimental results imply that incorporation of model compounds into the ion-exchange fibers was attained mainly as a result of ionic bonding, with additional contribution of non-specific interactions. Increasing the ion-exchange capacity of the fiber or decreasing the valence of loaded compounds increased the molar loading, while more efficient release of the compounds was observed consistently at conditions where the valence or concentration of the extracting counter-ion was increased. Donnan theory was capable of fully interpreting the ion-exchange equilibria and the theoretical modelling supported precisely the experimental observations. The physico-chemical characteristics (lipophilicity, hydrogen bonding ability) of the model compounds and the framework of the fibrous ion-exchanger influenced the affinity of the drugs towards the fibers and may, thus, affect both drug loading and release. It was concluded that precisely controlled drug delivery may be tailored for each compound, in particularly, by choosing a suitable ion-exchange fiber and optimizing the delivery system to take into account the external conditions, also when delivering two drugs simultaneously.

Studies of phosphazenes. Part 15. Chloro(phenoxy)cyclotetraphosphazenes, N4P4Cl8-n(OPh)n

The reaction of N4P4Cl8(1) with sodium phenoxide (or phenol in the presence of triethylamine) has been studied under a variety of experimental conditions. The chloro(phenoxy)-derivatives, N4P4Cl8-n(OPh)n[n= 1 or 2 (mixture of four non-geminal isomers), 3(mixture of non-geminal isomers), 4(mixture of isomers), 5(mixture of isomers), 6(mixture of four non-geminal isomers), or 8], have been isolated by column chromatography over silica gel. Attempts to separate geometric isomers were unsuccessful. Structural elucidation of the products is based on the 31P n.m.r. data for the chloro-precursors and 1H and 31P n.m.r. spectra of the dimethylamino- and/or methoxy-derivatives. The chlorine-replacement pattern is discussed.