Unsaturated σ-hydrocarbyl transition-metal complexes. Part 2. Synthesis and reactions of vinylplatinum complexes and a comparison with analogous fluorovinyl and alkynyl complexes

Alkenyl (CHCH2 or CFCF2) or alkynyl (CCPh) derivatives of trimethyltin are shown to be superior to lithium or magnesium reagents for the synthesis of corresponding mono-organoplatinum(II) species by metathesis (L = SnMe3R +cis-[PtCl2L2]→trans-[PtRClL2]+ SnMe3Cl tertiary phosphine). The reactivity order for SnMe3R is R = CCPh > CFCF2 > CHCH2. This order is also found for oxidative addition of SnMe3R to Pt0 to give cis-[PtRL2(SnMe3)]. When the latter complex (R = CHCH2) reacts with X2 or MeX further oxidative addition occurs exclusively at the platinum centre. Aromatic isonitriles (R′NC)co-ordinate to the platinum and give insertion products trans-[Pt{C(CHCH2)= NR′}ClL2] on heating or carbene complexes with NBunH2. The alkynyl trans-[Pt(CCPh)ClL2] also forms 1 :1 adducts with R′NC and carbene complexes therefrom, but no insertion products. Spectroscopic data for the new complexes are presented.

Mechanism of the Escherichia coli DNA T:G-mismatch endonuclease (Vsr protein) probed with thiophosphate-containing oligodeoxynucleotides

The mechanism of the Escherichia coli DNA T:G mismatch endonuclease (Vsr) has been investigated using oligodeoxynucleotides substituted, at the scissile phosphate, with isomeric phosphorothioates and a 3'-phosphorothiolate. Binding and kinetic data with the phosphorothioates/phosphorothiolate indicate that the two magnesium ions, which constitute essential co-factors, are required to stabilise the extra negative charge developed on the phosphate as the transition state is formed. Additionally one of the magnesium ions serves to activate the leaving group (the non-bridging 3'-oxygen atom of the scissile phosphate) during the hydrolysis reaction. Stereochemical analysis, using the R-p phosphorothioate isomer, indicates that Vsr carries out a hydrolytic reaction with inversion of stereochemistry at phosphorus, compatible with an in-line attack of water and a pentacovalent transition state with trigonal bipyramidal geometry. In conjunction with structures of Vsr bound to its products, these data allow the reconstruction of the enzyme-substrate complex and a comprehensive description of the hydrolysis mechanism. (c) 2005 Elsevier Ltd. All rights reserved.

Using the significant dust deposition event on the glaciers of Mt. Elbrus, Caucasus Mountains, Russia on 5 May 2009 to develop a method for dating and provenancing of desert dust events recorded in snow pack.

A significant desert dust deposition event occurred on Mt. Elbrus, Caucasus Mountains, Russia on 5 May 2009, where the deposited dust later appeared as a brown layer in the snow pack. An examination of dust transportation history and analysis of chemical and physical properties of the deposited dust were used to develop a new approach for high-resolution provenancing of dust deposition events recorded in snow pack using multiple independent techniques. A combination of SEVIRI red-green-blue composite imagery, MODIS atmospheric optical depth fields derived using the Deep Blue algorithm, air mass trajectories derived with HYSPLIT model and analysis of meteorological data enabled identification of dust source regions with high temporal (hours) and spatial (ca. 100 km) resolution. Dust, deposited on 5 May 2009, originated in the foothills of the Djebel Akhdar in eastern Libya where dust sources were activated by the intrusion of cold air from the Mediterranean Sea and Saharan low pressure system and transported to the Caucasus along the eastern Mediterranean coast, Syria and Turkey. Particles with an average diameter below 8 μm accounted for 90% of the measured particles in the sample with a mean of 3.58 μm, median 2.48 μm and the dominant mode of 0.60 μm. The chemical signature of this long-travelled dust was significantly different from the locally-produced dust and close to that of soils collected in a palaeolake in the source region, in concentrations of hematite and oxides of aluminium, manganese, and magnesium. Potential addition of dust from a secondary source in northern Mesopotamia introduced uncertainty in the provenancing of dust from this event. Nevertheless, the approach adopted here enables other dust horizons in the snowpack to be linked to specific dust transport events recorded in remote sensing and meteorological data archives.

Effects of phytate and minerals on the bioavailability of oxalate from food

Phytate and mineral cations are both considered as important dietary factors for inhibiting the crystallisation of calcium oxalate kidney stones in susceptible individuals. In this paper, the phytate and mineral composition of whole bran cereals (wheat, barley and oat) and legumes were determined together with their soluble and insoluble oxalate concentrations in order to investigate the effects on oxalate solubility. The oat bran sample had the highest soluble oxalate concentration at 79 ± 1.3 mg/100 g, while total and soluble oxalate concentrations in the food samples studied range from 33 to 199 mg/100 g and 14 to 79 mg/100 g, respectively. The phytate concentration was in the range from 227 to 4393 mg/100 g and the concentrations of cations were in the range 54–70 mg/100 g for calcium, 75–398 mg/100 g for magnesium, 244–1529 mg/100 g for potassium and 4–11 mg/100 g for iron. Soluble oxalate concentration did not increase in proportion to total oxalate, and the phytate concentration in all foods was sufficient to contribute to an increase in soluble oxalate concentration by binding calcium.

Phylogenetic variation in the shoot mineral concentration of angiosperms

The calcium (Ca) concentration of plant shoot tissues varies systematically between angiosperm orders. The phylogenetic variation in the shoot concentration of other mineral nutrients has not yet been described at an ordinal level. The aims of this study were (1) to quantify the shoot mineral concentration of different angiosperm orders, (2) to partition the phylogenetic variation in shoot mineral concentration between and within orders, (3) to determine if the shoot concentration of different minerals are correlated across angiosperm species, and (4) to compare experimental data with published ecological survey data on 81 species sampled from their natural habitats. Species, selected pro rata from different angiosperm orders, were grown in a hydroponic system under a constant external nutrient regime. Shoots of 117 species were sampled during vegetative growth. Significant variation in shoot carbon (C), calcium (Ca), potassium (K), and magnesium (Mg) concentration occurred between angiosperm orders. There was no evidence for systematic differences in shoot phosphorus (P) or organic-nitrogen (N) concentration between orders. At a species level, there were strong positive correlations between shoot Ca and Mg concentration, between shoot P and organic-N concentration, and between shoot K concentration and shoot fresh weight:dry weight ratio. Shoot C and cation concentration correlated negatively at a species level. Species within the Poales and the Caryophyllales had distinct shoot mineralogies in both the designed experiment and in the ecological survey.

How do plants respond to nutrient shortage by biomass allocation?

Plants constantly sense the changes in their environment; when mineral elements are scarce, they often allocate a greater proportion of their biomass to the root system. This acclimatory response is a consequence of metabolic changes in the shoot and an adjustment of carbohydrate transport to the root. It has long been known that deficiencies of essential macronutrients (nitrogen, phosphorus, potassium and magnesium) result in an accumulation of carbohydrates in leaves and roots, and modify the shoot-to-root biomass ratio. Here, we present an update on the effects of mineral deficiencies on the expression of genes involved in primary metabolism in the shoot, the evidence for increased carbohydrate concentrations and altered biomass allocation between shoot and root, and the consequences of these changes on the growth and morphology of the plant root system.

Milk and dairy products: dietary partners for life?

The importance of milk in the human diet as a supplier of energy, high quality protein and other key nutrients, including calcium, is broadly accepted yet in the mind of many there remains uncertainty about whether or not these foods contribute to increased risk of cardiovascular and other chronic diseases. The evidence from long term prospective cohort studies that high milk consumption does not increase cardiovascular disease risk and indeed may provide benefit is now pretty unequivocal, although the effects of butter and cheese and benefits of fat reduced milk and saturated fat reduced milk are less certain. Milk is a crucial supplier of calcium, phosphorus and magnesium for bone growth and development in children and it is concerning that due to reduced milk consumption intake of these nutrients is often sub-optimal, particularly for female children. In addition, specific health issues in pregnant women and the elderly can be alleviated by milk or components of milk and these effects are not all explained by traditional nutrition.

The effect of nutrient fortification of sauces on product stability, sensory properties and subsequent liking by older adults

There are potential nutritional and sensory benefits of adding sauces to hospital meals. The aim of this study was to develop nutrient fortified sauces with acceptable sensory properties suitable for older people at risk of under-nutrition. Tomato, gravy and white sauce were fortified with macro and micro-nutrients using food ingredients rich in energy and protein as well as vitamin and mineral premixes. Sensory profile was assessed by a trained panel. Hedonic liking of fortified compared with standard sauces was evaluated by healthy older volunteers. The fortified sauces had higher nutritional value than the conventional ones, for example the energy content of the fortified tomato, white sauce and gravy formulations were increased between 2.5 and 4 fold compared to their control formulations. Healthy older consumers preferred the fortified tomato sauce compared with unfortified. There were no significant differences in liking between the fortified and standard option for gravy. There were limitations in the extent of fortification with protein, potassium and magnesium, as excessive inclusion resulted in bitterness, undesired flavours or textural issues. This was particularly marked in the white sauce to the extent that their sensory characteristics were not sufficiently optimised for hedonic testing. It is proposed that the development of fortified sauces is a simple approach to improving energy intake for hospitalised older people, both through the nutrient composition of the sauce itself and due to the benefits of increasing sensorial taste and lubrication in the mouth.