Linear and star architecture methacrylate-functionalised PDMS

Methacrylate-terminated poly(dimethylsiloxane)s in both linear and star architectures have been produced through a time-efficient 1 pot, 2 stage reaction which involved hydrosilylation of small molecule silanes with allyl methacrylate and subsequent equilibration of the product with octamethylcyclotetrasiloxane (D4) in the presence of an acid catalyst. This synthetic route required only one work-up procedure and the products were comparable to those produced by 2 step processes typically reported in literature. All methacrylate-terminated products were approximately double the molar masses anticipated based on reagent loadings. This is thought to be due to redistribution of siloxane bonds in the presence of the platinum hydrosilylation catalyst accompanied by a loss of silicon from the reaction by evaporation of dimethylsilane. It is believed that this is the first report of such siloxane equilibration occurring at room temperature

When The News Was Sung: Ballads as News Media in Early Modern Europe

News songs differ in crucial ways to the other news media of the early modern period like newsletters, newspapers, or diplomatic correspondence – they differ even from the prose broadsheets and pamphlets that they so closely resemble. As historians of news we need to ask different kinds of questions of these multi-media artifacts. For example, how does the presentation in a performative genre affect the dissemination and reception of information about events? What part do orality and aurality play in how the news was sold and received? Here the activities and social status of street singers play an important role. We must consider the production, format and distribution of these songs in order to understand their impact. We also need to pay attention to the conjunction between text and melody, and the ways in which this affected the presentation of a news event. On a broader scale, what kind of information can ballads provide about specific news events that other documents cannot or will not provide? Can they offer us a new medium by which to interpret historical events? And lastly, how should historians deal with these profoundly emotive texts? The combination of sensationalist language and affecting music meant that songs had the potential to provoke a more powerful response than any other contemporary news source, and this emotional potency can at times be challenging for a modern historian to decipher and explain. This article will attempt to answer some of these questions and suggest some of the skills we as historians need to develop in order to appreciate the full meaning of songs as the most popular of news media in early modern Europe

Outreach:Impact on Skills and Future Careers of Postgraduate Practitioners Working with the Bristol ChemLabS Centre for Excellence in Teaching and Learning

Postgraduate engagement in delivering outreach activities is more commonplace than it once was. However, the impact on postgraduate students (typically studying for a Ph.D. degree) of participating in the delivery of these outreach activities has rarely, if ever, been recorded. The Bristol ChemLabS Outreach program has been running for ca. 17 years, and in that time, many postgraduate students have been involved (approximately 500), with around 250 typically for up to 3 years. We sought to investigate the impact of outreach engagement on postgraduate alumni who were involved in the program for over 3 years (32) and how the experiences and training of the outreach program had impacted on their careers postgraduation. Thirty of the 32 postgraduates engaged and ∼70% reported that their outreach experience had influenced their decision making on future careers. Many respondents reported that the skills and experiences gained through outreach participation had contributed to success in applying for and interviewing at their future employers. All respondents reported that outreach had helped them to develop key skills that were valued in the workplace, specifically, communication, teamwork, organizational skills, time planning, event planning, and event management. Rather than a pleasant distraction or an opportunity to supplement income, all participants noted that they felt there were many additional benefits and that this was time well spent. Outreach should not be viewed as a distraction to science research but rather an important enhancement to it provided that the program is well constructed and seeks to develop those delivering the outreach activities

Within-sibship genome-wide association analyses decrease bias in estimates of direct genetic effects

Estimates from genome-wide association studies (GWAS) of unrelated individuals capture effects of inherited variation (direct effects), demography (population stratification, assortative mating) and relatives (indirect genetic effects). Family-based GWAS designs can control for demographic and indirect genetic effects, but large-scale family datasets have been lacking. We combined data from 178,086 siblings from 19 cohorts to generate population (between-family) and within-sibship (within-family) GWAS estimates for 25 phenotypes. Within-sibship GWAS estimates were smaller than population estimates for height, educational attainment, age at first birth, number of children, cognitive ability, depressive symptoms and smoking. Some differences were observed in downstream SNP heritability, genetic correlations and Mendelian randomization analyses. For example, the within-sibship genetic correlation between educational attainment and body mass index attenuated towards zero. In contrast, analyses of most molecular phenotypes (for example, low-density lipoprotein-cholesterol) were generally consistent. We also found within-sibship evidence of polygenic adaptation on taller height. Here, we illustrate the importance of family-based GWAS data for phenotypes influenced by demographic and indirect genetic effects

Protein voltammetry and spectroscopy: integrating approaches

Cyclic voltammetry readily visualizes the redox properties of many proteins. Net electron exchange between the protein and an electrode produces an electrical current that simultaneously quantitates and characterizes the underlying redox event(s). However, no direct information regarding the molecular origin, or consequences, of electron transfer is available. Integrating voltammetric and spectroscopic methods is one route to a more ‘holistic’ description of protein electron transfer. Here, we illustrate this approach with spectroelectrochemical studies of Rhodovulum sulfidophilum cytochrome c 2 and Escherichia coli cytochrome bd that employ electronic absorbance, infra-red and magnetic circular dichroism spectroscopies

Structural basis for the oxidation of thiosulfate by a sulfur cycle enzyme

Reduced inorganic sulfur compounds are utilized by many bacteria as electron donors to photosynthetic or respiratory electron transport chains. This metabolism is a key component of the biogeochemical sulfur cycle. The SoxAX protein is a heterodimeric c-type cytochrome involved in thiosulfate oxidation. The crystal structures of SoxAX from the photosynthetic bacterium Rhodovulum sulfidophilum have been solved at 1.75 Ã… resolution in the oxidized state and at 1.5 Ã… resolution in the dithionite-reduced state, providing the first structural insights into the enzymatic oxidation of thiosulfate. The SoxAX active site contains a haem with unprecedented cysteine persulfide (cysteine sulfane) coordination. This unusual post-translational modification is also seen in sulfurtransferases such as rhodanese. Intriguingly, this enzyme shares further active site characteristics with SoxAX such as an adjacent conserved arginine residue and a strongly positive electrostatic potential. These similarities have allowed us to suggest a catalytic mechanism for enzymatic thiosulfate oxidation. The atomic coordinates and experimental structure factors have been deposited in the PDB with the accession codes 1H31, 1H32 and 1H33