Time-resolved gas-phase kinetic, quantum chemical, and RRKM studies of reactions of silylene with alcohols

Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of 1-silacyclopent-3-ene and phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with methanol, ethanol, 1-propanol, 1-butanol and 2-methyl-1-butanol. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at room temperature. In the study with methanol several buffer gases were used. All five reactions showed pressure dependences characteristic of third body assisted association reactions. The rate constant pressure dependences were modelled using RRKM theory, based on Eo values of the association complexes obtained by ab initio calculation (G3 level). Transition state models were adjusted to fit experimental fall-off curves and extrapolated to obtain k∞ values in the range 1.9 to 4.5 × 10-10 cm3 molecule-1 s-1. These numbers, corresponding to the true bimolecular rate constants, indicate efficiencies of between 16 and 67% of the collision rates for these reactions. In the reaction of SiH2 + MeOH there is a small kinetic component to the rate which is second order in MeOH (at low total pressures). This suggests an additional catalysed reaction pathway, which is supported by the ab initio calculations. These calculations have been used to define specific MeOH-for-H2O substitution effects on this catalytic pathway. Where possible our experimental and theoretical results are compared with those of previous studies.

The effect of the magnetic field of the secondary star in dwarf novae

We investigate the effect of a secondary star magnetic field on the accretion disc dynamics of dwarf novae. Simulations have been carried out with a particle code and a dipolar magnetic field structure. The magnetic field acts to remove angular momentum from the disc material, increasing the inward mass flow. This makes the accretion disc more centrally condensed, causing a reduction in the recurrence time for dwarf nova outbursts. We have produced Doppler tomograms and light curves which may be compared with observations. These tomograms are significantly different from those produced in the absence of a magnetic field on the secondary. We derive an upper limit to the magnetic moment of the secondary star in UGem of mu_2<2x10^32 A m^2. The magnetic truncation of the accretion disc produces resonance phenomena similar to those seen in the superoutbursts of SUUMa systems. While these have not been observed for systems like UGem, observations of the SUUMa systems provide us with a useful diagnostic of the disc-field interaction. We are able to place an upper limit on the magnetic moment of the secondary in ZCha of mu_2<1x10^30 A m^2.

Characterisation of secondary metabolites associated with neutrophil apoptosis

We studied changes in secondary metabolites in human neutrophils undergoing constitutive or tumour necrosis factor (TNFalpha) stimulated apoptosis by a combination of high-performance liquid chromatography (HPLC) and NMR spectroscopy. Our results show that in contrast to freshly isolated neutrophils, neutrophil cells aged for 20 h in vitro had marked differences in the levels of a number of endogenous metabolites including lactate, amino acids and phosphocholine (PCho). There was no change in the concentration of taurine or glutamate and the ATP/ADP ratio was not affected. Levels of glutamine and lactate actually decreased. Identical changes were also observed in neutrophils stimulated to undergo apoptosis over a shorter time period (6 h) in the presence of TNFalpha and the phosphatidylinositol-3-kinase inhibitor wortmannin (WM). The changes in the concentration of PCho suggest possible activation of phospholipase associated with apoptosis or a selective failure of phosphatidycholine synthesis. The increased levels of apoptosis obtained with WM+TNFalpha, compared to TNFalpha by itself, suggest a synergistic effect by these compounds. The acceleration in rate of apoptosis probably arises from suppression by WM of pathway(s) that normally delay the onset of apoptosis. Changes in PCho and other endogenous metabolites, if proven to be characteristic of apoptosis in other cell systems, may permit non-invasive quantification of apoptosis. '

Secondary structure analysis of the dissimilatory sulphite reductase in Desulfovibrio desulfuricans

The complete sequences of the dsrA and dsrB genes coding for the α− and β−subunits, respectively, of the sulphite reductase enzyme in Desulfovibrio desulfuricans were determined. Analyses of the amino acid sequences indicated a number of serohaem/Fe4S4 binding consensus sequences whilst predictive secondary structure analysis revealed a similar pattern of α−helix and β−strand structures between the two subunits which was indicative of gene duplication.

Teacher stance as reflected in feedback on student writing: An empirical study of secondary school teachers in five countries

This study examines the feedback practices of 110 EFL teachers from five different countries (Cyprus, France, Korea, Spain, and Thailand), working in secondary school contexts. All provided feedback on the same student essay. The coding scheme developed to analyse the feedback operates on two axes: the stance the teachers assumed when providing feedback, and the focus of their feedback. Most teachers reacted as language teachers, rather than as readers of communication. The teachers overwhelmingly focused on grammar in their feedback and assumed what we called a Provider role, providing the correct forms for the student. A second role, Initiator, was also present, in which teachers indicate errors or issues to the learner but expect the learner to pick this up and work on it. This role was associated with a more even spread of feedback focus, where teachers also provided feedback on other areas, such as lexis, style and discourse.

Writing in French in secondary schools in England and Germany: are the British really 'bad language learners’?

It is widely assumed that the British are poorer modern foreign language (MFL) learners than their fellow Europeans. Motivation has often been seen as the main cause of this perceived disparity in language learning success. However, there have also been suggestions that curricular and pedagogical factors may play a part. This article reports a research project investigating how German and English 14- to 16-year-old learners of French as a first foreign language compare to one another in their vocabulary knowledge and in the lexical diversity, accuracy and syntactic complexity of their writing. Students from comparable schools in Germany and England were set two writing tasks which were marked by three French native speakers using standardised criteria aligned to the Common European Framework of Reference (CEF). Receptive vocabulary size and lexical diversity were established by the X_lex test and a verb types measure respectively. Syntactic complexity and formal accuracy were respectively assessed using the mean length of T-units (MLTU) and words/error metrics. Students' and teachers' questionnaires and semi-structured interviews were used to provide information and participants' views on classroom practices, while typical textbooks and feedback samples were analysed to establish differences in materials-related input and feedback in the two countries. The German groups were found to be superior in vocabulary size, and in the accuracy, lexical diversity and overall quality – but not the syntactic complexity – of their writing. The differences in performance outcomes are analysed and discussed with regard to variables related to the educational contexts (e.g. curriculum design and methodology).

Bile salt composition is secondary to bile salt concentration in determining hydrocortisone and progesterone solubility in intestinal mimetic fluids.

Simulated intestinal fluids (SIFs) used to assay the solubility of orally administered drugs are typically based on a single bile salt; sodium taurocholate (STC). The aim of this study was to develop mimetic intestinal fluids with a closer similarity to physiological fluids than those reported to date by developing a mixed bile salt (MBS) system (STC, sodium glycodeoxycholate, sodium deoxycholate; 60:39:1) with different concentrations of lecithin, the preponderant intestinal phospholipid. Hydrocortisone and progesterone were used as model drugs to evaluate systematically the influence of SIF composition on solubility. Increasing total bile salt concentration from 0 to 30 mM increased hydrocortisone and progesterone solubility by 2- and ∼25-fold, respectively. Accordingly, higher solubilities were measured in the fed-state compared to the fasted-state SIFs. Progesterone showed the greatest increases in solubility in STC and MBS systems (2-7-fold) compared to hydrocortisone (no significant change; P>0.05) as lecithin concentration was increased. Overall, MBS systems gave similar solubility profiles to STC. In conclusion, the addenda of MBS and lecithin were found to be secondary to the influence of BS concentration. These data provide a foundation for the design of more bio-similar media for pivotal decision-guiding assays in drug development and quality control settings.

Secondary school teachers' perspectives on teaching about topics that bridge science and religion

The question of where to locate teaching about the relationships between science and religion has produced a long-running debate. Currently, Science and Religious Education (RE) are statutory subjects in England and are taught in secondary schools by different teachers. This paper reports on an interview study in which 16 teachers gave their perceptions of their roles and responsibilities when teaching topics that bridge science and religion and the extent to which they collaborated with teachers in the other subject area. We found that in this sample, teachers reported very little collaboration between the curriculum areas. Although the science curriculum makes no mention of religion, all the science teachers said that their approaches to such topics were affected by their recognition that some pupils hold religious beliefs. All the RE teachers reported struggling to ensure students know of a range of views about how science and religion relate. The paper concludes with a discussion about implications for curriculum design and teacher training.

Secondary cyclogenesis along an occluded front leading to damaging wind gusts: windstorm Kyrill, January 2007

Windstorm Kyrill affected large parts of Europe in January 2007 and caused widespread havoc and loss of life. In this study the formation of a secondary cyclone, Kyill II, along the occluded front of the mature cyclone Kyrill and the occurrence of severe wind gusts as Kyrill II passed over Germany are investigated with the help of high-resolution regional climate model simulations. Kyrill underwent an explosive cyclogenesis south of Greenland as the storm crossed polewards of an intense upper-level jet stream. Later in its life cycle secondary cyclogenesis occurred just west of the British Isles. The formation of Kyrill II along the occluded front was associated (a) with frontolytic strain and (b) with strong diabatic heating in combination with a developing upper-level shortwave trough. Sensitivity studies with reduced latent heat release feature a similar development but a weaker secondary cyclone, revealing the importance of diabatic processes during the formation of Kyrill II. Kyrill II moved further towards Europe and its development was favored by a split jet structure aloft, which maintained the cyclone’s exceptionally deep core pressure (below 965 hPa) for at least 36 hours. The occurrence of hurricane force winds related to the strong cold front over North and Central Germany is analyzed using convection-permitting simulations. The lower troposphere exhibits conditional instability, a turbulent flow and evaporative cooling. Simulation at high spatio-temporal resolution suggests that the downward mixing of high momentum (the wind speed at 875 hPa widely exceeded 45 m s-1) accounts for widespread severe surface wind gusts, which is in agreement with observed widespread losses.

The impact of secondary pests on Bacillus thuringiensis (Bt) crops

The intensification of agriculture and the development of synthetic insecticides enabled worldwide grain production to more than double in the last third of the 20th century. However, the heavy dependence and, in some cases, overuse of insecticides has been responsible for negative environmental and ecological impacts across the globe, such as a reduction in biodiversity, insect resistance to pesticides, negative effects on nontarget species (e.g. natural enemies) and the development of secondary pests. The use of recombinant DNA technology to develop genetically engineered (GE) insect resistant crops could mitigate many of the negative side effects of pesticides. One such genetic alteration enables crops to express toxic crystalline (Cry) proteins from the soil bacteria Bacillus thuringiensis (Bt). Despite the widespread adoption of Bt crops, there are still a range of unanswered questions concerning longer term agro-ecosystem interactions. For instance, insect species that are not susceptible to the expressed toxin can develop into secondary pests and cause significant damage to the crop. Here we review the main causes surrounding secondary pest dynamics in Bt crops and the impact of such outbreaks. Regardless of the causes, if non-susceptible secondary pest populations exceed economic thresholds, insecticide spraying could become the immediate solution at farmers’ disposal, and the sustainable use of this genetic modification technology may be in jeopardy. Based on the literature, recommendations for future research are outlined that will help to improve the knowledge of the possible longterm ecological trophic interactions of employing this technology.

Phosphorylation of CLEC-2 is dependent on lipid rafts, actin polymerization, secondary mediators, and Rac

The C-type lectin-like receptor 2 (CLEC-2) activates platelets through Src and Syk tyrosine kinases via a single cytoplasmic YxxL motif known as a hem immunoreceptor tyrosine-based activation motif (hemITAM). Here, we demonstrate using sucrose gradient ultracentrifugation and methyl-beta-cyclodextrin treatment that CLEC-2 translocates to lipid rafts upon ligand engagement and that translocation is essential for hemITAM phosphorylation and signal initiation. HemITAM phosphorylation, but not translocation, is also critically dependent on actin polymerization, Rac1 activation, and release of ADP and thromboxane A(2) (TxA(2)). The role of ADP and TxA(2) in mediating phosphorylation is dependent on ligand engagement and rac activation but is independent of platelet aggregation. In contrast, tyrosine phosphorylation of the GPVI-FcRgamma-chain ITAM, which has 2 YxxL motifs, is independent of actin polymerization and secondary mediators. These results reveal a unique series of proximal events in CLEC-2 phosphorylation involving actin polymerization, secondary mediators, and Rac activation.

Departmental differences in attitudes to special educational needs in the secondary school

As trends in favour of inclusion continue, questions arise concerning the extent to which teachers in mainstream schools feel prepared for the task of meeting pupils' special educational needs. Little previous research has considered how the subject taught impacts upon the attitudes of mainstream teachers towards pupils with special educational needs. In this article, Jean Ellins, research fellow at the University of Birmingham, and Jill Porter, senior lecturer at the University of Bath, report on their research into the attitudes of teachers in one mainstream secondary school. Building a detailed case study using documents, records of pupil progress, an interview and a questionnaire using a Likert-type attitude scale and open-ended questions, these researchers set out to explore distinctions between the attitudes of teachers working in different departments. Their findings suggest that the teachers of the core subjects, English, mathematics and science, had less positive attitudes than their colleagues. Further, pupils with special educational needs made least progress in science where teacher attitudes were the least positive. Jean Ellins and Jill Porter review the implications of these findings and make recommendations for future practice and further enquiry.

A brief cognitive-behavioural intervention for pain reduces secondary hyperalgesia

Repeated exposure to pain can result in sensitization of the central nervous system, enhancing subsequent pain and potentially leading to chronicity. The ability to reverse this sensitization in a top-down manner would be of tremendous clinical benefit, but the degree that this can be accomplished volitionally remains unknown. Here we investigated whether a brief (~5 min) cognitive-behavioural intervention could modify pain perception and reduce central sensitization (as reflected by secondary hyperalgesia). In each of 8 sessions, 2 groups of healthy human subjects received a series of painful thermal stimuli that resulted in secondary hyperalgesia. One group (regulate) was given brief pain-focused cognitive training at each session, while the other group (control) received a non-pain-focused intervention. The intervention selectively reduced pain unpleasantness but not pain intensity in the regulate group. Furthermore, secondary hyperalgesia was significantly reduced in the regulate group compared with the control group. Reduction in secondary hyperalgesia was associated with reduced pain catastrophizing, suggesting that changes in central sensitization are related to changes in pain-related cognitions. Thus, we demonstrate that central sensitization can be modified volitionally by altering pain-related thoughts.

Motivational trajectories for early language learning across the primary-secondary school transition

The transition from primary to secondary school is an area of concern across a range of curriculum subjects, and this is no less so for foreign language learning. Indeed problems with transition have been identified in England as an important barrier to the introduction of language learning to the primary school curriculum, with implications for learners’ longer-term motivation for the subject. This longitudinal study investigated, through a questionnaire, the development of 233 learners’ motivation for learning French in England, during the transition from primary to secondary schooling. It also explored whether levels and patterns of motivation differed according to the type of language teaching experienced, comparing a largely oracy-focused approach with one with greater emphasis on literacy activities. Learners showed high and increasing levels of motivation across transition, placing particular value on learning French for travel. Being taught through an oracy or a literacy-focused approach had less impact on learners’ motivation than broader classroom experiences, with the development of a sense of progress and feeling that instruction met their learning needs being especially important. A growing disjuncture emerged between valuing the learning of French for travel/communication and learners’ low levels of self-efficacy for communication with native speakers, together with a desire for more communication-based activities. By the end of the first year of secondary school less positive attitudes towards learning French and less optimism about the possibility of future progress were beginning to emerge. The paper concludes by outlining the implications of the study for classroom practice in language learning.