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.

Synthesis, characterisation, Mössbauer spectra, and structures of some trinuclear iron-tin clusters

Reactions of [Fe3(CO)12] with diaryltin species SnR2(R1= 2,4,6-triisopropylphenyl, R2= 2,6-diethylphenyl, R3= pentamethylphenyl) and with Sn[CH(PPh2)2]2 have been investigated. The tin reagents SnR2(R = R1 or R2) reacted under mild conditions to give in moderate yields the trinuclear species [Fe2(CO)8(µ-SnR12)]1 or [Fe2(CO)8(µ-SnR22)]2, as orange-red crystalline solids, which decompose in air on prolonged exposure. The compound [Fe2(CO)8(µ-SnR42)]3(R4= 2,4,6-triphenylphenyl) can be similarly obtained. Prolonged treatment of the carbonyl with the novel tin reagent SnR32, by contrast, afforded the known compound spiro-[(OC)8Fe2SnFe2(CO)8]4 for which data are briefly reported. Reactions with tin or lead reagents M[CH(PPh2)2]2(M = Sn or Pb) afforded [Fe2(CO)6(µ-CO)(µ-dppm)][dppm = 1,2-bis(diphenylphosphino)methane] rapidly and almost quantitatively. Full crystal and molecular structural data are reported for [Fe2(CO)8(µ-SnR12)] and [Fe2(CO)8(µ-SnR22)]. Mössbauer data are also presented for compounds 1–3, and interpreted in terms of the structural data for these and other systems.

Visible-near infrared spectroscopy sensor for predicting curd and whey composition during cheese processing

The potential of visible-near infrared spectra, obtained using a light backscatter sensor, in conjunction with chemometrics, to predict curd moisture and whey fat content in a cheese vat was examined. A three-factor (renneting temperature, calcium chloride, cutting time), central composite design was carried out in triplicate. Spectra (300–1,100 nm) of the product in the cheese vat were captured during syneresis using a prototype light backscatter sensor. Stirring followed upon cutting the gel, and samples of curd and whey were removed at 10 min intervals and analyzed for curd moisture and whey fat content. Spectral data were used to develop models for predicting curd moisture and whey fat contents using partial least squares regression. Subjecting the spectral data set to Jack-knifing improved the accuracy of the models. The whey fat models (R = 0.91, 0.95) and curd moisture model (R = 0.86, 0.89) provided good and approximate predictions, respectively. Visible-near infrared spectroscopy was found to have potential for the prediction of important syneresis indices in stirred cheese vats.

Oxygen/Glucose deprivation induces a reduction in synaptic AMPA receptors on hippocampal CA3 neurons mediated by mGluR1 and adenosine A3 receptors

Hippocampal CA1 pyramidal neurons are highly sensitive to ischemic damage, whereas neighboring CA3 pyramidal neurons are less susceptible. It is proposed that switching of AMPA receptor (AMPAR) subunits on CA1 neurons during an in vitro model of ischemia, oxygen/glucose deprivation (OGD), leads to an enhanced permeability of AMPARs to Ca2+, resulting in delayed cell death. However, it is unclear whether the same mechanisms exist in CA3 neurons and whether this underlies the differential sensitivity to ischemia. Here, we investigated the consequences of OGD for AMPAR function in CA3 neurons using electrophysiological recordings in rat hippocampal slices. Following a 15 min OGD protocol, a substantial depression of AMPAR-mediated synaptic transmission was observed at CA3 associational/commissural and mossy fiber synapses but not CA1 Schaffer collateral synapses. The depression of synaptic transmission following OGD was prevented by metabotropic glutamate receptor 1 (mGluR1) or A3 receptor antagonists, indicating a role for both glutamate and adenosine release. Inhibition of PLC, PKC, or chelation of intracellular Ca2+ also prevented the depression of synaptic transmission. Inclusion of peptides to interrupt the interaction between GluA2 and PICK1 or dynamin and amphiphysin prevented the depression of transmission, suggesting a dynamin and PICK1-dependent internalization of AMPARs after OGD. We also show that a reduction in surface and total AMPAR protein levels after OGD was prevented by mGluR1 or A3 receptor antagonists, indicating that AMPARs are degraded following internalization. Thus, we describe a novel mechanism for the removal of AMPARs in CA3 pyramidal neurons following OGD that has the potential to reduce excitotoxicity and promote neuroprotection

The impact of a seasonally ice free Arctic Ocean on the temperature, precipitation and surface mass balance of Svalbard

The observed decline in summer sea ice extent since the 1970s is predicted to continue until the Arctic Ocean is seasonally ice free during the 21st Century. This will lead to a much perturbed Arctic climate with large changes in ocean surface energy flux. Svalbard, located on the present day sea ice edge, contains many low lying ice caps and glaciers and is expected to experience rapid warming over the 21st Century. The total sea level rise if all the land ice on Svalbard were to melt completely is 0.02 m. The purpose of this study is to quantify the impact of climate change on Svalbard’s surface mass balance (SMB) and to determine, in particular, what proportion of the projected changes in precipitation and SMB are a result of changes to the Arctic sea ice cover. To investigate this a regional climate model was forced with monthly mean climatologies of sea surface temperature (SST) and sea ice concentration for the periods 1961–1990 and 2061–2090 under two emission scenarios. In a novel forcing experiment, 20th Century SSTs and 21st Century sea ice were used to force one simulation to investigate the role of sea ice forcing. This experiment results in a 3.5 m water equivalent increase in Svalbard’s SMB compared to the present day. This is because over 50 % of the projected increase in winter precipitation over Svalbard under the A1B emissions scenario is due to an increase in lower atmosphere moisture content associated with evaporation from the ice free ocean. These results indicate that increases in precipitation due to sea ice decline may act to moderate mass loss from Svalbard’s glaciers due to future Arctic warming.

Mental contamination in obsessive–compulsive disorder

It was recently proposed that feelings of contamination can arise in the absence of physical contact with a contaminant. Currently, there are limited data regarding this construct of ‘mental contamination’ although it is hypothesised to be relevant to obsessive compulsive disorder(OCD) where compulsive washing in response to contamination fear is a common presentation (Rachman,2006). This research examined the presence of mental contamination in OCD. Participants (N=177) with obsessive compulsive symptoms completed questionnaires to assess mental contamination, OCD symptoms and thought-action fusion (TAF). Findings indicated that 46% of participants experienced mental contamination, and severity was associated with severity of OCD symptoms and TAF. Mental contamination in the absence of contact contamination was reported by 10.2% of participants. Similar findings were reported in a sub-sample of participants who had received a formal diagnosis of OCD (N=54). These findings suggest that mental contamination is a distinct construct that overlaps with, but is separate from, contact contamination, and provide preliminary empirical support for the construct.

The UK's Electoral Reform Referendum of May 2011

The UK’s second nationwide referendum, held in May 2011, offers rich opportunities for analysing the dynamics of a referendum campaign. The articles gathered together in this symposium address three themes. The first concerns the determinants and dynamics of public opinion during a referendum campaign, the second relates to the potential for interaction between the referendum and simultaneous elections, and the third focuses on coverage of the referendum in the media. Following a brief outline of the background to the referendum, this paper introduces the contribution that each article makes to these themes.

Six new loci associated with body mass index highlight a neuronal influence on body weight regulation

Common variants at only two loci, FTO and MC4R, have been reproducibly associated with body mass index (BMI) in humans. To identify additional loci, we conducted meta-analysis of 15 genome-wide association studies for BMI (n > 32,000) and followed up top signals in 14 additional cohorts (n > 59,000). We strongly confirm FTO and MC4R and identify six additional loci (P < 5 x 10(-8)): TMEM18, KCTD15, GNPDA2, SH2B1, MTCH2 and NEGR1 (where a 45-kb deletion polymorphism is a candidate causal variant). Several of the likely causal genes are highly expressed or known to act in the central nervous system (CNS), emphasizing, as in rare monogenic forms of obesity, the role of the CNS in predisposition to obesity.

Tripodal molecules for the promotion of phosphoester hydrolysis

A series of low molecular weight tripodal amide/histidine-containing compounds (1–2) have been synthesised and shown to increase the rate of bis-(p-nitrophenyl) phosphate (BNPP) and soman (GD) breakdown in buffered aqueous solution.

Variation in the use of chemotherapy in lung cancer

Factors influencing the use of chemotherapy for the initial (6 months) treatment of lung cancer in South East England were investigated. The variables explored as possibly influencing the use of chemotherapy were sex, age, the year of diagnosis, the type of lung cancer, the stage, the index of multiple deprivation and the cancer network of residence. Chi2 analysis and multivariate logistic regression models were used to examine the effect of each of the variables on the use of chemotherapy. The results showed a highly significant trend in use of chemotherapy over time; the adjusted proportion of patients receiving chemotherapy increasing from 13.6% in 1994 to 29.3% in 2003. However, age, cancer network and type of lung cancer had the strongest influence on the use of chemotherapy. This finding is important when we consider that the NHS Cancer Plan aims at improving inequalities in cancer care in the UK.

Factors influencing the use of antitumoral chemotherapy in the South East of England

Influences on the use of chemotherapy for the treatment of cancer within the South East region of England for patients diagnosed with colorectal, lung, breast and prostate cancer were investigated. The variables investigated as possibly influencing the selection of chemotherapy were the sex of the patients, their age, the year of diagnosis, the cancer site, the cancer stage, the index of multiple deprivation (IMD) and the cancer network of residence. Logistic regression used to adjust the proportion receiving chemotherapy in relation to other variables considered showed significant differences in the proportion of patients receiving chemotherapy between different cancer sites and different networks. There was also a highly significant trend seen in use of chemotherapy over time; the adjusted proportion of patients receiving chemotherapy increasing from 10.6% in 1993 to 24.3% in 2002. Age, stage and cancer site seemed to have the most influence on the use of chemotherapy.

Poetry of social conscience, poetry of transition: Ann Hawkshaw's 'Introductory Stanzas' and 'The Mother to her Starving Child'

Through close readings of Ann Hawkshaw's poetry in the context of industrial Manchester in the 1840s, this article highlights the interaction of form and content in poetry that makes use of the idea of the past to question or complicate the politics of the present.

Secret history

A survey of the genre, secret history, during the eighteenth century.