Synthesis of the μ-PH hexaosmium clusters [Os6H2(CO)20L(μ3-PH)](L = CO or MeCN) and their reactions with base: X-ray crystal structures of [Os6H2(CO)20(MeCN)(μ3-PH)] and [Os6H3(CO)19(CO2Me)(μ3-PH)]

Mild heating of the phosphidotriosmium cluster [Os3H(CO)10(µ2-PH2)](1) with [Os3(CO)12 –n(MeCN)n](n= 1 or 2) gives high yields of the (µ3-PH) bridged hexaosmium clusters (2) and (3); reactions of (2) and (3) with bases and X-ray structure analyses of (3) and of (6), which was obtained from (3) and MeO– followed by acid treatment are described.

Stepwise construction of [Os6(CO)18(μ6-P)]-, a hexanuclear osmium cluster monoanion with trigonal-prismatic co-ordination for phosphorus: X-ray crystal structures of [Os6(μ-H)2(CO)20(MeCN)(μ3-PH)] and [PPh3Me][Os6(CO)18(μ6-P)]

Treatment of the labile cluster [Os3(CO)11(MeCN)] with PH3 affords the substituted product [Os3(CO)11(PH3)](1) in high yield. Subsequent reaction of (1) with Na2CO3 in MeOH, followed by acidification, gives the hydrido phosphido cluster [Os3(µ-H)(CO)10(µ-PH2)](2). When (2) is heated to 45–60 °C in the presence of [Os3(CO)11(MeCN)] a hexanuclear complex with the formulation [Os6(µ-H)2(CO)21(µ3-PH)](3) is obtained. If this reaction is repeated using [Os3(CO)10(MeCN)2] instead of [Os3(CO)11(MeCN)], an acetonitrile-containing product, [Os6(µ-H)2(CO)20(MeCN)(µ3-PH)](4), is obtained. An X-ray analysis of (4) shows that two Os3 triangular units are linked by a µ3-phosphinidene ligand, which symmetrically bridges an Os–Os edge of one triangle and is terminally co-ordinated to one Os atom of the second triangle. When (3) is treated with a weak base, such as [N(PPh3)2]Cl or [PPh3Me] Br, deprotonation to the corresponding cluster monoanion [Os6(µ-H)(CO)21(µ3-PH)]–(5) occurs. Treatment of (5) with a weak acid regenerates (3) in quantitative yield. Thermolysis of (3) leads to a closing up of the metal framework, affording the cluster [Os6(µ-H)(CO)18(µ6-P)], which readily deprotonates to give the anion [Os6(CO)18(µ6-P)]–(7) in the presence of [N(PPh3)2] Cl or [PPh3Me]Br. The same anion (7) may also be obtained by direct thermolysis of (5). An X-ray analysis of the [PPh3Me]+ salt of (7) confirms that the phosphorus occupies an interstitial site in a trigonal-prismatic hexaosmium framework, and co-ordinates to all six metal atoms with an average Os–P distance of 2.31 (1)Å. Proton and 31P n.m.r. data on all the new clusters are presented, and the position of the phosphorus resonance in the 31P n.m.r. spectrum is related to the changes in the environment of the phosphorus atom.

Multimodel estimate of the global terrestrial water balance: setup and first results

Six land surface models and five global hydrological models participate in a model intercomparison project (WaterMIP), which for the first time compares simulation results of these different classes of models in a consistent way. In this paper the simulation setup is described and aspects of the multi-model global terrestrial water balance are presented. All models were run at 0.5 degree spatial resolution for the global land areas for a 15-year period (1985-1999) using a newly-developed global meteorological dataset. Simulated global terrestrial evapotranspiration, excluding Greenland and Antarctica, ranges from 415 to 586 mm year-1 (60,000 to 85,000 km3 year-1) and simulated runoff ranges from 290 to 457 mm year-1 (42,000 to 66,000 km3 year-1). Both the mean and median runoff fractions for the land surface models are lower than those of the global hydrological models, although the range is wider. Significant simulation differences between land surface and global hydrological models are found to be caused by the snow scheme employed. The physically-based energy balance approach used by land surface models generally results in lower snow water equivalent values than the conceptual degree-day approach used by global hydrological models. Some differences in simulated runoff and evapotranspiration are explained by model parameterizations, although the processes included and parameterizations used are not distinct to either land surface models or global hydrological models. The results show that differences between model are major sources of uncertainty. Climate change impact studies thus need to use not only multiple climate models, but also some other measure of uncertainty, (e.g. multiple impact models).

Linking energy and maintenance management for sustainability through three American case studies

Purpose – The purpose of this paper is to present the findings and lessons learned from three case studies conducted for facilities located in California, North America. The findings aim to focus on energy and maintenance management practices and the interdependent link between energy and maintenance. Design/methodology/approach – The research is based on a positivist epistemological philosophical approach informed by action research. The research cycle was completed for each case study. A case study report was provided to each facility management team to foster collaboration with the researcher and to document case study process and results. Findings – Composite findings of the case studies include: there is an interdependent link between energy and maintenance management; reactive maintenance and energy management methods are commonly used; and more proactively operated and managed buildings require the interdependent link between energy maintenance management to be better understood. Research limitations/implications – The three case studies were located in California. Although the case study results can be generalized, determination of how to generalize and apply the results to commercial buildings outside of the USA is beyond the scope of this paper. Practical implications – Detailed discussion of the needs of the three facility management teams are discussed by identifying a current challenge, developing a solution and documenting lessons learned using the research cycle. Originality/value – The paper seeks to demonstrate the interdependencies of energy and maintenance management, two topics which are often researched interdependently. Additionally, the paper provides insight about maintenance management, a topic often cited as being under researched.

Plant and invertebrate resources for farmland birds in pastoral landscapes

On 16 UK livestock holdings within pastoral landscapes, we investigated the provision of plant and invertebrate resources for farmland birds in spring barley and winter wheat cereal-based whole crop silages as alternatives to maize and grass silages. The benefits of low input barley systems were also investigated; barley fields were subjected to two separate herbicide sub-treatments on a split-field design (high input broad-spectrum or low input narrow spectrum herbicides). The abundance of plant resources and invertebrates was assessed for three growing seasons during summer and winter for each crop type. The study clearly demonstrated the value of spring barley for the provision of plant resources when compared to the other silage cropping systems, whilst invertebrate responses were variable. No differences in plant and invertebrate resources were found between the barley treatments. Throughout the year, forage maize afforded the lowest provision of resources for farmland birds, and because it is likely that maize will continue to be grown in pastoral areas, the value of this habitat needs to be improved if farmland birds are to benefit. To provide plant and invertebrate resources for farmland birds in pastoral landscapes we strongly advocate the growing of spring sown barley whole-crop silage followed by over-wintering stubbles. © 2011 Elsevier B.V. All rights reserved.

Comparison of heat stability of goat milk subjected to ultra-high temperature and in-container sterilisation

Goatmilk with and without stabilizing salt was subjected to in-container and UHTsterilization. Heatstability was assessed by measuring the amount of sediment in the milk. Without stabilizing salts, goatmilk usually produced less sediment when subjected to in-containersterilization compared with UHT processing. Addition of stabilizing salts up to 12.8 mM resulted in a progressive increase in sediment for in-containersterilization. In contrast, adding stabilizing salts at 6.4 mM initially reduced sediment formation in UHT-treated milk but addition of stabilizing salts at 12.8 mM increased sediment formation. Adding stabilizing salts to goatmilk increased pH, decreased ionic calcium, and increased ethanol stability. Adding up to 2 mM calcium chloride increased sediment formation more after UHT treatment than after in-containersterilization. These results suggest that no single mechanism or set of reactions causes milk to produce sediment during heating and that the favored pathway is different for UHT and in-containersterilization processes. Poor heatstability could be induced both by increasing ionic calcium and by decreasing it. Ethanol stability is not a good indicator of heatstability for in-containersterilization, but it may be for UHTsterilization, if milk does not enter the region of poor heatstability found at low concentrations of ionic calcium.

Feasibility of using dialysis for determining calcium ion concentration and pH in calcium-fortified soymilk at high temperature

Dialysis was performed to examine some of the properties of the soluble phase of calcium (Ca) fortified soymilk at high temperatures. Dialysates were obtained while heating soymilk at temperatures of 80 and 100 °C for 1 h and 121 °C for 15 min. It was found that the pH, total Ca, and ionic Ca of dialysates obtained at high temperature were all lower than in their corresponding nonheated Ca-fortified soymilk. Increasing temperature from 80 to 100 °C hardly affected Ca ion concentration ([Ca2+]) of dialysate obtained from Ca chloride-fortified soymilk, but it increased [Ca2+] in dialysates of Ca gluconate-fortified soymilk and Ca lactate-fortified soymilk fortified with 5 to 6 mM Ca. Dialysates obtained at 100 °C had lower pH than dialysate prepared at 80 °C. Higher Ca additions to soymilk caused a significant (P≤ 0.05) reduction in pH and an increase in [Ca2+] of these dialysates. When soymilk was dialyzed at 121 °C, pH, total Ca, and ionic Ca were further reduced. Freezing point depression (FPD) of dialysates increased as temperature increased but were lower than corresponding soymilk samples. This approach provides a means of estimating pH and ionic Ca in soymilks at high temperatures, in order to better understand their combined role on soymilk coagulation.

Mineral partitioning in milk and milk permeates at high temperature

The soluble phase of milk was separated at 20 and 80°C using ultrafiltration. The resulting permeates were then subjected to further ultrafiltration and dialysis at close to these two temperatures. It was found that pH, Ca2+ and soluble Ca decreased as the separation temperature increased both in original UF permeates and in dialysates obtained from these permeates, but P decreased only slightly. The major reason for these changes was due to the precipitation of calcium phosphate/citrate complexes onto the casein micelle with concomitant release of H+. The pH of both permeates and dialysates from milk at 20°C were slightly higher than for milk. When UF permeates collected at 20 and 80°C, were each dialysed at both these temperatures, the dialysate collected at 80°C showed much less temperature dependence for pH and ionic calcium compared with that collected at 20°C. This is in contrast to milk, which shows considerable temperature dependence for pH and ionic calcium. Further experiments revealed that the pH and Ca2+ concentration of permeates showed high temperature dependence above the temperature at which they were separated, but a much lower temperature dependence below that temperature. These findings suggest that dialysis and UF of milk at high temperature provide the best means yet for estimating the pH and ionic calcium of milk at that temperature.

Therapygenetics: the 5HTTLPR and response to psychological therapy

Although pharmacogenetic research thrives,1 genetic determinants of response to purely psychotherapeutic treatments remain unexplored. In a sample of children undergoing cognitive behaviour therapy (CBT) for an anxiety disorder, we tested whether treatment response is associated with the serotonin transporter gene promoter region (5HTTLPR), previously shown to moderate environmental influences on depression.

A comparison of reverse osmosis, nanofiltration and ultrafiltration as concentration processes for skim milk prior to drying

Skim milk was concentrated by reverse osmosis (RO), nanofiltration (NF) and ultrafiltration (UF) and the retentates were spray-dried. The resulting powders were reconstituted to 25% TS and sterilised to evaluate their heat stability. Reverse osmosis led to maximum retention of calcium, a fall in pH for its retentate and its reconstituted powder. All RO powders produced a weak gel on heating. Some calcium was lost during NF and a greater amount during UF. Their resulting reconstituted powders had a higher pH than those produced by RO. Powders produced by UF showed poor heat stability. Only one powder produced by NF showed good heat stability. This could be improved by addition of stabilisers at appropriate addition rates.