Synthesis and NMR spectroscopic analysis of 3-nitro-pyranoside, 3-nitro-septanoside and 4-nitro-septanoside derivatives by condensation of the anion of nitromethane with glycoside

The utility of the nitroaldol reaction for accessing 3-nitro-pyranoside, 3-nitro-septanoside or 4-nitro-septanoside derivatives, by reaction of the anion of nitromethane with glycoside dialdehydes is demonstrated. Initially, the feasibility of using unprotected glucoside dialdehydes was probed for the synthesis of the septanoside products, but this affoided pyranoside rather than septanoside targets. Subsequent studies utilised protected glycoside dialdehydes within the methodology, which allowed entry into a range of 3-nitro or 4-nitro-septanosides in good yield NMR spectroscopic analysis allowed determination of the stereochemistry of each of the products thus afforded.

Tyrosinase activated melanoma prodrugs

Metastatic malignant melanoma remains a highly aggressive form of skin cancer for which no reliable methods for treatment exist. Given the increasing incidence of this cancer, considerable attention has focused on the development of new and improved methods for tackling this disease. Within this article, methods for treating melanoma are reviewed and discussed with particular attention focusing on prodrugs that are activated by the tyrosinase enzyme. This enzyme is up-regulated and is of elevated activity within malignant melanomas compared with healthy melanocytes, providing an ideal in-situ tool for the activation of melanoma prodrugs. By way of background to the prodrug strategies discussed within this review, the causes of melanoma, the enzymology of tyrosinase, and the chemistry of the biosynthetic pathways associated with melanogenesis are presented. Aspects of the design, mode of action, and biological profiles of key prodrugs that are activated by tyrosinase, and that show potential for the treatment of melanoma, are then presented and compared.

Characterisation of soils containing naturally occurring radioactive material (NORM) using in situ and rapid laboratory techniques. Case study: South Terras, Cornwall

In situ analysis has become increasingly important for contaminated land investigation and remediation. At present, portable techniques are used mainly as scanning tools to assess the spread and magnitude of the contamination, and are an adjunct to conventional laboratory analyses. A site in Cornwall, containing naturally occurring radioactive material (NORM), provided an opportunity for Reading University PhD student Anna Kutner to compare analytical data collected in situ with data generated by laboratory-based methods. The preliminary results in this paper extend the author‟s poster presentation at last September‟s GeoSpec2010 conference held in Lancaster.

Analysis of wall plasters and natural sediments from the Neolithic town of Çatalhöyük (Turkey) by a range of analytical techniques

Wall plaster sequences from the Neolithic town of Çatalhöyük have been analysed and compared to three types of natural sediment found in the vicinity of the site, using a range of analytical techniques. Block samples containing the plaster sequences were removed from the walls of several different buildings on the East Mound. Sub-samples were examined by IR spectroscopy, X-ray diffraction and X-ray fluorescence to determine the overall mineralogical and elemental composition, whilst thin sections were studied using optical polarising microscopy, IR Microscopy and Environmental Scanning Electron Microscopy with Energy Dispersive X-ray analysis. The results of this study have shown that there are two types of wall plaster found in the sequences and that the sediments used to produce these were obtained from at least two distinct sources. In particular, the presence of clay, calcite and magnesian calcite in the foundation plasters suggested that these were prepared predominantly from a marl source. On the other hand, the finishing plasters were found to contain dolomite with a small amount of clay and no calcite, revealing that softlime was used in their preparation. Whilst marl is located directly below and around Çatalhöyük, the nearest source of softlime is 6.5 km away, an indication that the latter was important to the Neolithic people, possibly due to the whiter colour (5Y 8/1) of this sediment. Furthermore, the same two plaster types were found on each wall of Building 49, the main building studied in this research, and in all five buildings investigated, suggesting that the use of these sources was an established practice for the inhabitants of several different households across the site.

The use of earth observation techniques to improve catchment-scale pollution predictions

Remote sensing can potentially provide information useful in improving pollution transport modelling in agricultural catchments. Realisation of this potential will depend on the availability of the raw data, development of information extraction techniques, and the impact of the assimilation of the derived information into models. High spatial resolution hyperspectral imagery of a farm near Hereford, UK is analysed. A technique is described to automatically identify the soil and vegetation endmembers within a field, enabling vegetation fractional cover estimation. The aerially-acquired laser altimetry is used to produce digital elevation models of the site. At the subfield scale the hypothesis that higher resolution topography will make a substantial difference to contaminant transport is tested using the AGricultural Non-Point Source (AGNPS) model. Slope aspect and direction information are extracted from the topography at different resolutions to study the effects on soil erosion, deposition, runoff and nutrient losses. Field-scale models are often used to model drainage water, nitrate and runoff/sediment loss, but the demanding input data requirements make scaling up to catchment level difficult. By determining the input range of spatial variables gathered from EO data, and comparing the response of models to the range of variation measured, the critical model inputs can be identified. Response surfaces to variation in these inputs constrain uncertainty in model predictions and are presented. Although optical earth observation analysis can provide fractional vegetation cover, cloud cover and semi-random weather patterns can hinder data acquisition in Northern Europe. A Spring and Autumn cloud cover analysis is carried out over seven UK sites close to agricultural districts, using historic satellite image metadata, climate modelling and historic ground weather observations. Results are assessed in terms of probability of acquisition probability and implications for future earth observation missions. (C) 2003 Elsevier Ltd. All rights reserved.

Novel charge transfer supramolecular assemblies with Keggin anions and 2-amino-5-nitropyridine

Several novel compounds with the non-linear optical chromophore 2-amino-5-nitropyridine (2A5NP) and Keggin polyoxoanions (alpha-isomers), having the general formula (2A5NP)(m)H-n[XM12O40]center dot xH(2)O, M = Mo, W, were synthesised. Compounds were obtained with X = P, n = 3, m = 3 and 4 and X = Si, n = m = 4 ( x = 2 - 6). Thus, for each of the anions [PMo12O40](3-) and [PW12O40](3-) two different compounds were obtained, with the same anion and organic counterpart but with a different stoichiometric ratio. These presented different charge transfer properties and thermal stability. All compounds were characterised by spectroscopic and analytical techniques. The single crystal X-ray diffraction structure of (2A5NP)(4)H-3[PMo12O40]center dot 2.5H(2)O center dot 0.5C(2)H(5)OH showed that the water solvent molecules and the organic chromophores are assembled via infinite one-dimensional chains of hydrogen bonds with formation of open channels, which accommodate [ PMo12O40] 3- and ethanol solvent molecules.

The chemistry of intrinsically chiral surfaces

Intrinsically chiral metal and mineral surfaces show enantioselective behaviour without modifiers. Examples are artificial high-Miller-index surfaces of metal single crystals with cubic bulk lattice symmetry, which have no mirror planes and are therefore chiral, or surfaces of naturally occurring crystallites of some common minerals, such as alpha-quartz or calcite. Recent findings with regards to the surface geometry, reactivity and thermal stability of intrinsically chiral surfaces are discussed. A number of enantioselective effects have been reported in connection with the adsorption of small chiral molecules (e.g. alanine, cysteine) on intrinsically chiral surfaces under well-defined conditions. From a combination of experimental surface science techniques and theoretical ab initio model calculations it emerges that these effects are due to a combination of attractive and repulsive adsorbate-substrate and inter-adsorbate interactions.

Simple general method of generating non-oxo, non-amavadine model octacoordinated vanadium(IV) complexes of some tetradentate ONNO chelating ligands from various oxovanadium(IV/V) compounds and structural characterization of one of them

A simple general route of obtaining very stable octacoordinated non-oxovanadium( IV) complexes of the general formula VL2 (where H2L is a tetradentate ONNO donor) is presented. Six such complexes (1-6) are adequately characterized by elemental analysis, mass spectrometry, and various spectroscopic techniques. One of these compounds (1) has been structurally characterized. The molecule has crystallographic 4 symmetry and has a dodecahedral structure existing in a tetragonal space group P4n2. The non-oxo character and VL2 stoichiometry for all of the complexes are established from analytical and mass spectrometric data. In addition, the non-oxo character is clearly indicated by the complete absence of the strong nu(v=o) band in the 925-1025 cm(-1) region, which is a signature of all oxovanadium species. The complexes are quite stable in open air in the solid state and in solution, a phenomenon rarely observed in non-oxovanadium(IV) or bare vanadium(IV) complexes.

Analytical and compositional aspects of isoflavones in food and their biological effects

This paper provides an overview of analytical techniques used to determine isoflavones (IFs) in foods and biological fluids with main emphasis on sample preparation methods. Factors influencing the content of IFs in food including processing and natural variability are summarized and an insight into IF databases is given. Comparisons of dietary intake of IFs in Asian and Western populations, in special subgroups like vegetarians, vegans, and infants are made and our knowledge on their absorption, distribution, metabolism, and excretion by the human body is presented. The influences of the gut microflora, age, gender, background diet, food matrix, and the chemical nature of the IFs on the metabolism of IFs are described. Potential mechanisms by which IFs may exert their actions are reviewed, and genetic polymorphism as determinants of biological response to soy IFs is discussed. The effects of IFs on a range of health outcomes including atherosclerosis, breast, intestinal, and prostate cancers, menopausal symptoms, bone health, and cognition are reviewed on the basis of the available in vitro, in vivo animal and human data.

Volatile flavour profile of goat meat extracted by three widely used techniques

Three procedures for the isolation of volatiles from grilled goat meat were compared: dynamic headspace entrainment on Tenax TA, simultaneous steam distillation-extraction, and solid-phase microextraction. Headspace entrainment on Tenax TA extracted the highest number of Maillard-derived volatile compounds. Two hundred and three volatile components were identified: 159 are reported for the first time in goat meat. Most of the volatiles detected (155) were lipid oxidation products, such as hydrocarbons, aldehydes, alcohols, ketones, carboxylic acids and esters. Forty-eight Maillard-derived compounds were identified. comprising pyrazines, pyrroles, thiophenes, furanthiol derivatives, alkyl and alicyclic sulphides, pyridines, and thiazoles. Some reported character impact compounds of cooked meat, e.g., 12-methyltridecanal, (EE)-2,4-decadienal, methional, and dimethyl trisulphide were identified in the volatile profile of goat meat, together with a series of C-2 to C-5 alkylformylcyclopentenes, which have been reported in cooked chicken, pork, beef and lamb, as being important for the characteristic flavour impression of different animal species. (C) 2009 Published by Elsevier Ltd.

Computational chemistry for elucidating protein function: energetics and dynamics of myoglobin-ligand systems

State-of-the-art computational methodologies are used to investigate the energetics and dynamics of photodissociated CO and NO in myoglobin (Mb···CO and Mb···NO). This includes the combination of molecular dynamics, ab initio MD, free energy sampling, and effective dynamics methods to compare the results with studies using X-ray crystallography and ultrafast spectroscopy metho ds. It is shown that modern simulation techniques along with careful description of the intermolecular interactions can give quantitative agreement with experiments on complex molecular systems. Based on this agreement predictions for as yet uncharacterized species can be made.