Alkenyl derivatives of the metals. Oxidative addition to intermediate tin(II) alkenyls; isolation, and crystal and molecular structure of n-butyltris(triphenylethenyl)tin(IV)

Reaction of tin(II) chloride with Li(CPhCPh2) at –78 °C in diethyl ether–hexane–tetrahydrofuran affords a deep red solution whose colour fades on warming, and which we believe contains the (unstable) first dialkenyltin(II) species. The latter survives long enough at low temperatures to undergo intermolecular oxidative addition, and one such adduct leads ultimately to the formation of Sn(CPhCPh2)3Bun, which has been fully characterised including a crystal and molecular structure study. The mechanism of formation of the final product has been examined and results are reported.

Heterogenisation of Os species on MCM-41 structure for epoxidation of trans-stilbene

Metal organic chemical vapour deposition technique (MOCVD) has been used to immobilise Os species onto the internal porous structure of MCM-41. Evidence suggests that volatile Os-3(CO)(12) cluster reacts with surface silanol groups of the MCM-41 via an oxidative addition reaction to yield a trinuclear HOs3(CO)(10)(OSi-) surface species. After heat treatment in air or at their very low surface coverage, these triangular sites break up to partially oxidised mononuclear surface species. In the presence of tert-butyl hydroperoxide (TBHP) as an oxidant, we demonstrate that the mononuclear species form extremely active species that catalyse the oxidation of trans-stilbene selectively to the corresponding epoxide. By carefully controlling the parameters of the MOCVD method (loading and calcination temperature), we report a new class of optimised MCM-41 porous heterogeneous catalysts carrying isolated but active Os sites for the selective oxidation of trans-stilbene in liquid phase. The reaction selectivity of the solid supported Os is apparently higher than the soluble homogeneous Os-3(CO)(12) cluster. It is envisaged that our solid supported catalysts not only facilitate separation from products but also offer an excellent utilisation of Os for catalysis. (C) 2003 Elsevier Science B.V. All rights reserved.

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.

The synthesis, structure, and reactions of some simple unsaturated σ-hydrocarbylplatinum(II) complexes

Trimethyltin compounds Me3SnR(R = CHCH2, CFCF2, or CCPh) are selective reagents for the synthesis of unsaturated hydrocarbyl derivatives such as trans-PtCl(R)(PPhEt2)2, by R/Cl exchange or oxidative addition (e.g., to Pt(PPh3)3); single crystal X-ray analyses of two such compounds (R = CHCH2 or CCPh) show that the trans-influence of R has only a low sensitivity to hybridisation at carbon, with sp3 > sp ⩾ sp2.

Enhancing the oxidative stability of rice crackers by addition of the ethanolic extract of phytochemicals from Cratoxylum formosum Dyer

Craloxylum formosum Dyer is consumed throughout the year as food and medicine in Thailand. It contains large amounts of chlorogenic acid and quinic acid derivatives. The antioxidative activity of the extract was studied in refined soybean oil coating on rice crackers without any seasoning. They were stored in accelerated oxidation conditions at 40 degrees C, 80% relative humidity (RH) in the dark for 18 days. The oxidative state of each sample was monitored by analyzing of the peroxide value (PV) and thiobarbituric acid reactive substances (TBARS) as well as by odor analysis by quantitative descriptive analysis (QDA). The C formosum extract was more effective than alpha-tocopherol due to metal ions present in the crackers, which resulted in alpha-tocopherol being less effective as an antioxidant. Sensory odor attributes of rice crackers were related more closely to TBARS than to PV values by linear regression analysis. The present study indicated that C. formosum extract was a promising source of a natural food antioxidant and was effective in inhibiting lipid oxidation in rice crackers.

Effects of oxidative stress on the cardiac myocyte proteome: modifications to peroxiredoxins and small heat shock proteins

Endogenous oxidative stress is a likely cause of cardiac myocyte death in vivo. We examined the early (0-2 h) changes in the proteome of isolated cardiac myocytes from neonatal rats exposed to H2O2 (0.1 mM), focussing on proteins with apparent molecular masses of between 20 and 30 kDa. Proteins were separated by two-dimensional gel electrophoresis (2DGE), located by silver-staining and identified by mass spectrometry. Incorporation of [35S]methionine or 32Pi was also studied. For selected proteins, transcript abundance was examined by reverse transcriptase-polymerase chain reaction. Of the 38 protein spots in the region, 23 were identified. Two families showed changes in 2DGE migration or abundance with H2O2 treatment: the peroxiredoxins and two small heat shock protein (Hsp) family members: heat shock 27 kDa protein 1 (Hsp25) and alphaB-crystallin. Peroxiredoxins shifted to lower pI values and this was probably attributable to 'over-oxidation' of active site Cys-residues. Hsp25 also shifted to lower pI values but this was attributable to phosphorylation. alphaB-crystallin migration was unchanged but its abundance decreased. Transcripts encoding peroxiredoxins 2 and 5 increased significantly. In addition, 10 further proteins were identified. For two (glutathione S-transferase pi, translationally-controlled tumour protein), we could not find any previous references indicating their occurrence in cardiac myocytes. We conclude that exposure of cardiac myocytes to oxidative stress causes post-translational modification in two protein families involved in cytoprotection. These changes may be potentially useful diagnostically. In the short term, oxidative stress causes few detectable changes in global protein abundance as assessed by silver-staining.

Enantioselective Intramolecular Michael Addition of Nitronates onto Conjugated Esters: Access to Cyclic γ-Amino Acids with up to Three Stereocenters

A highly stereoselective synthesis of conformationally constrained cyclic γ-amino acids has been devised. The key step involves an intramolecular cyclization of a nitronate onto a conjugated ester, promoted by a bifunctional thiourea catalyst. This methodology has been successfully applied to generate a variety of γ-amino acids, including some containing three contiguous stereocenters, with very high diastereoselectivity and excellent enantioselectivity. It is postulated that an interaction that is key to the success of the process is the simultaneous coordination of the thiourea functionality to both the conjugated ester and the nitronate. Finally, the synthetic utility of these compounds is demonstrated in the synthesis of two dipeptides derived from the C- and N-termini.

Effect of dietary supplementation with selenium-enriched yeast or sodium selenite on selenium tissue distribution and meat quality in beef cattle

The objective was to determine the concentration of total selenium (Se) and the proportion of total Se comprised as selenomethionine (SeMet) and selenocysteine (SeCys) in post mortem tissues of beef cattle offered diets containing graded additions of selenized enriched yeast (SY) [Saccharomyces cerevisae CNCM I-3060]), or sodium selenite (SS). Oxidative stability and tissue glutathione peroxidase (GSH-Px) activity of edible muscle tissue were assessed 10 d post-mortem. Thirty two beef cattle were offered, for a period of 112 d, a total mixed ration which had either been supplemented with SY (0, 0.15 or 0.35 mg Se/kg DM) or SS (0.15 mg Se/kg DM). At enrollment (0 d) and at 28, 56, 84 and 112 d following enrollment, blood samples were taken for Se and Se species determination, as well as whole blood GSH-Px activity. At the end of the study beef cattle were euthanized and samples of heart, liver, kidney, and skeletal muscle (LM and psoas major) were retained for Se and Se species determination. Tissue GSH-Px activity and thiobarbituric acid reactive substances (TBARS) were determined in skeletal muscle tissue (LM only). The incorporation into the diet of ascending concentrations of Se as SY increased whole blood total Se and the proportion of total Se comprised as SeMet, as well as GSH-Px activity. There was also a dose dependant response to the graded addition of SY on total Se and proportion of total Se as SeMet in all tissues and GSH-Px activity in skeletal muscle tissue. Furthermore, total Se concentration of whole blood and tissues was greater in those animals offered SY when compared with those receiving a comparable dose of SS, indicating an improvement in Se availability and tissue Se retention. Likewise, GSH-Px activity in whole blood and LM was greater in those animals offered SY when compared with those receiving a comparable dose of SS. However, these increases in tissue total Se and GSH-Px activity appeared to have little or no effect in meat oxidative stability.

Effects of chlorogenic acid and bovine serum albumin on the oxidative stability of low density lipoproteins in vitro

The ability of chlorogenic acid to inhibit oxidation of human low-density lipoprotein (LDL) was studied by in vitro copper-induced LDL oxidation. The effect of chlorogenic acid on the lag time before LDL oxidation increased in a dose dependent manner by up to 176% of the control value when added at concentrations of 0.25 -1.0 μM. Dose dependent increases in lag time of LDL oxidation were also observed, but at much higher concentrations, when chlorogenic acid was incubated with LDL (up to 29.7% increase in lag phase for 10 μM chlorogenic acid) or plasma (up to 16.6% increase in lag phase for 200 μM chlorogenic acid) prior to isolation of LDL, and this indicated that chlorogenic acid was able to bind, at least weakly, to LDL. Bovine serum albumin (BSA) increased the oxidative stability of LDL in the presence of chlorogenic acid. Fluorescence spectroscopy showed that chlorogenic acid binds to BSA with a binding constant of 3.88 x 104 M-1. BSA increased the antioxidant effect of chlorogenic acid, and this was attributed to copper ions binding to BSA, thereby reducing the amount of copper available for inducing lipid peroxidation.

Effects of stabiliser addition and in-container sterilisation on selected properties of milk related to casein micelle stability

Different stabilising salts and calcium chloride were added to raw milk to evaluate changes in pH, ionic calcium, ethanol stability, casein micelle size and zeta potential. These milk samples were then sterilised at 121 °C for 15 min and stored for 6 months to determine how these properties changed. Addition of tri-sodium citrate (TSC) and di-sodium hydrogen phosphate (DSHP) to milk reduced ionic calcium, increased pH and increased ethanol stability in a concentration-dependent fashion. There was relatively little change in casein micelle size and a slight decrease in zeta potential. Sodium hexametaphosphate (SHMP) also reduced ionic calcium considerably, but its effect on pH was less noticeable. In contrast, sodium dihydrogen phosphate (SDHP) reduced pH but had little effect on ionic calcium. In-container sterilisation of these samples reduced pH, increased ethanol stability and increased casein micelle size, but had variable effects on ionic calcium; for DSHP and SDHP, ionic calcium decreased after sterilisation but, for SHMP, it remained little changed or increased. Milk containing 3.2 mM SHMP and more than 4.5 mM CaCl2 coagulated upon sterilisation. All other samples were stable but there were differences in browning, which increased in intensity as milk pH increased. Heat-induced sediment was not directly related to ionic calcium concentration, so reducing ionic calcium was not the only consideration in terms of improving heat stability. After 6 months of storage, the most acceptable product, in appearance, was that containing SDHP, as this minimised browning during sterilisation and further development of browning during storage.

In vitro evaluation of fibrolytic enzymes as additives for maize (Zea mays L.) silage - I. Effects of ensiling temperature, enzyme source and addition level

A series of experiments was completed to investigate the impact of addition of enzymes at ensiling on in vitro rumen degradation of maize silage. Two commercial products, Depot 40 (D, Biocatalysts Ltd., Pontypridd, UK) and Liquicell 2500 (L, Specialty Enzymes and Biochemicals, Fresno, CA, USA), were used. In experiment 1, the pH optima over a pH range 4.0-6.8 and the stability of D and L under changing pH (4.0, 5.6, 6.8) and temperature (15 and 39 degreesC) conditions were determined. In experiment 2, D and L were applied at three levels to whole crop maize at ensiling, using triplicate 0.5 kg capacity laboratory minisilos. A completely randomized design with a factorial arrangement of treatments was used. One set of treatments was stored at room temperature, whereas another set was stored at 40 degreesC during the first 3 weeks of fermentation, and then stored at room temperature. Silages were opened after 120 days. Results from experiment I indicated that the xylanase activity of both products showed an optimal pH of about 5.6, but the response differed according to the enzyme, whereas the endoglucanase activity was inversely related to pH. Both products retained at least 70% of their xylanase activity after 48 h incubation at 15 or 39 degreesC. In experiment 2, enzymes reduced (P < 0.05) silage pH, regardless of storage temperature and enzyme level. Depol 40 reduced (P < 0.05) the starch contents of the silages, due to its high alpha-amylase activity. This effect was more noticeable in the silages stored at room temperature. Addition of L reduced (P < 0.05) neutral detergent fiber (NDF) and acid detergent fiber (ADF) contents. In vitro rumen degradation, assessed using the Reading Pressure Technique (RPT), showed that L increased (P < 0.05) the initial 6 h gas production (GP) and organic matter degradability (OMD), but did not affect (P > 0.05) the final extent of OMD, indicating that this preparation acted on the rumen degradable material. In contrast, silages treated with D had reduced (P < 0.05) rates of gas production and OMD. These enzymes, regardless of ensiling temperature, can be effective in improving the nutritive quality of maize silage when applied at ensiling. However, the biochemical properties of enzymes (i.e., enzymic activities, optimum pH) may have a crucial role in dictating the nature of the responses. (C) 2003 Elsevier B.V. All rights reserved.

Carbon addition alters vegetation composition on ex-arable fields

1. Recent changes in European agricultural policy have led to measures to reverse the loss of species-rich grasslands through the creation of new areas on ex-arable land. Ex-arable soils are often characterized by high inorganic nitrogen (N) levels, which lead to the rapid establishment of annual and fast-growing perennial species during the initial phase of habitat creation. The addition of carbon (C) to the soil has been suggested as a countermeasure to reduce plant-available N and alter competitive interactions among plant species. 2. To test the effect of C addition on habitat creation on ex-arable land, an experiment was set up on two recently abandoned fields in Switzerland and on two 6-year-old restoration sites in the UK. Carbon was added as a mixture of either sugar and sawdust or wood chips and sawdust during a period of 2 years. The effects of C addition on soil parameters and vegetation composition were assessed during the period of C additions and 1 year thereafter. 3. Soil nitrate concentrations were reduced at all sites within weeks of the first C addition, and remained low until cessation of the C additions. The overall effect of C addition on vegetation was a reduction in above-ground biomass and cover. At the Swiss sites, the addition of sugar and sawdust led to a relative increase in legume and forb cover and to a decrease in grass cover. The soil N availability, composition of soil micro-organisms and vegetation characteristics continued to be affected after cessation of C additions. 4. Synthesis and applications. The results suggest that C addition in grassland restoration is a useful management method to reduce N availability on ex-arable land. Carbon addition alters the vegetation composition by creating gaps in the vegetation that facilitates the establishment of late-seral plant species, and is most effective when started immediately after the abandonment of arable fields and applied over several years.

Multitrophic effects of nutrient addition in upland grassland

Although the effects of nutrient enhancement on aquatic systems are well documented, the consequences of nutritional supplements on soil food webs are poorly understood, and results of past research examining bottom-up effects are often conflicting. In addition, many studies have failed to separate the effects of nutrient enrichment and the physical effects of adding organic matter. In this field study, we hypothesised that the addition of nitrogen to soil would result in a trophic cascade, through detritivores (Collembola) to predators (spiders), increasing invertebrate numbers and diversity. Nitrogen and lime were added to plots in an upland grassland in a randomised block design. Populations of Collembola and spiders were sampled by means of pitfall traps and identified to species. Seventeen species of Collembola were identified from the nitrogen plus lime (N + L) and control plots. Species assemblage, diversity, richness, evenness and total number were not affected by nutrient additions. However, there was an increase in the number of Isotomidae juveniles and Parisotoma anglicana trapped in the N + L plots. Of the 44 spider species identified, over 80% were Linyphiidae. An effect on species assemblage from the addition of N + L to the plots was observed on two of the four sampling dates (July 2002 and June 2003). The linyphiid, Oedothorax retusus, was the only species significantly affected by the treatments and was more likely to be trapped in the control plots. The increased number of juvenile Collembola, and change in community composition of spiders, were consequences of the bottom-up effect caused by nutrient inputs. However, despite efforts to eliminate the indirect effects of nutrient inputs, a reduction in soil moisture in the N + L plots cannot be eliminated as a cause of the invertebrate population changes observed. Even so, this experiment was not confounded by the physical effects of habitat structure reported in most previous studies. It provides evidence of moderate bottom-up influences of epigeic soil invertebrate food webs and distinguishes between nutrient addition and plant physical structure effects. It also emphasises the importance Of understanding the effects of soil management practices on soil biodiversity, which is under increasing pressure from land development and food production.