Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate

Perceptions of the coach-athlete relationship predict the attainment of mastery achievement goals six months later : a two-wave longitudinal study among F.A. Premier League academy soccer players

All football teams that compete within the F. A. Premier League possess an academy, whose objective is to produce more and better home-grown players that are capable of playing professionally. These young players spend a large amount of time with their coach, but little is known about player’s perception of the coach-athlete relationship within F.A. Premier League Academies. The objectives of this study were to examine whether perceptions of the coach-athlete relationship changed over six months and if the coach-athlete relationship predicted self-reported goal achievement among F. A. Premier League academy players. This study included cross-sectional (n = 104) and longitudinal (n = 52) assessments, in which academy soccer players completed a measure of the coach-athlete relationship and goal achievement across either one or two time periods. The cross-sectional data were subjected to bivariate correlations, whereas the longitudinal data were analyzed using multiple regressions. Perceptions of the coach-athlete relationship remained stable over time. The coach-athlete relationship predicted the achievement of mastery goals six months later. Enhancing the quality of the coach-athlete relationship among elite adolescent athletes appears to be a suitable way of maximizing mastery achievement goals, particularly among developmental athletes who participate in team sports

"I'm Managing My Diabetes between Two Worlds": Beliefs and Experiences of Diabetes Management in British South Asians on Holiday in the East-A Qualitative Study.

Background. Diabetes is disproportionately high among British South Asians compared to the general UK population. Whilst the migrant British South Asians group has received most attention on research related to diabetes management, little consideration has been given to impact of travel back to the East. This study aimed to explore the role of social networks and beliefs about diabetes in British South Asians, to better understand their management behaviours whilst holidaying in the East. Methods. Semistructured interviews were conducted in Greater Manchester. Forty-four participants were recruited using random and purposive sampling techniques. Interviews were analysed thematically using a constant comparison approach. Results. Migrant British South Asians expressed a strong preference to be in a hot climate; they felt they had a healthier lifestyle in the East and often altered or abandoned their diabetes medication. Information acquisition on diabetes and availability of social networks in the East was valued. Conclusion. Social networks in the East are a valued source of information and support for diabetes. The lack of adherence to medication whilst abroad suggests that some migrant British South Asians have a poor understanding of diabetes. Future research needs to explore whether patients are seeking professional advice on diabetes management prior to their extended holiday

Structure and functional motifs of GCR1, the only plant protein with a GPCR fold?

Whether GPCRs exist in plants is a fundamental biological question. Interest in deorphanizing new G protein coupled receptors (GPCRs), arises because of their importance in signaling. Within plants, this is controversial as genome analysis has identified 56 putative GPCRs, including GCR1 which is reportedly a remote homologue to class A, B and E GPCRs. Of these, GCR2, is not a GPCR; more recently it has been proposed that none are, not even GCR1. We have addressed this disparity between genome analysis and biological evidence through a structural bioinformatics study, involving fold recognition methods, from which only GCR1 emerges as a strong candidate. To further probe GCR1, we have developed a novel helix alignment method, which has been benchmarked against the the class A – class B - class F GPCR alignments. In addition, we have presented a mutually consistent set of alignments of GCR1 homologues to class A, class B and class F GPCRs, and shown that GCR1 is closer to class A and /or class B GPCRs than class A, class B or class F GPCRs are to each other. To further probe GCR1, we have aligned transmembrane helix 3 of GCR1 to each of the 6 GPCR classes. Variability comparisons provide additional evidence that GCR1 homologues have the GPCR fold. From the alignments and a GCR1 comparative model we have identified motifs that are common to GCR1, class A, B and E GPCRs. We discuss the possibilities that emerge from this controversial evidence that GCR1 has a GPCR fol

Innovative Technologies for Human Exploration: Opportunities for Partnerships and Leveraging Novel Technologies External to NASA

Human spaceflight organizations have ambitious goals for expanding human presence throughout the solar system. To meet these goals, spaceflight organizations have to overcome complex technical challenges for human missions to Mars, Near Earth Asteroids, and other distant celestial bodies. Resolving these challenges requires considerable resources and technological innovations, such as advancements in human health and countermeasures for space environments; self-sustaining habitats; advanced power and propulsion systems; and information technologies. Today, government space agencies seek cooperative endeavors to reduce cost burdens, improve human exploration capabilities, and foster knowledge sharing among human spaceflight organizations. This paper looks at potential opportunities for partnerships and spin-ins from economic sectors outside the space industry. It highlights innovative technologies and breakthrough concepts that could have significant impacts on space exploration and identifies organizations throughout the broader economy that specialize in these technologies

Assessing the effect of dynamics on the closed-loop protein-folding hypothesis

The closed-loop (loop-n-lock) hypothesis of protein folding suggests that loops of about 25 residues, closed through interactions between the loop ends (locks), play an important role in protein structure. Coarse-grain elastic network simulations, and examination of loop lengths in a diverse set of proteins, each supports a bias towards loops of close to 25 residues in length between residues of high stability. Previous studies have established a correlation between total contact distance (TCD), a metric of sequence distances between contacting residues (cf. contact order), and the log-folding rate of a protein. In a set of 43 proteins, we identify an improved correlation ( r 2 = 0.76), when the metric is restricted to residues contacting the locks, compared to the equivalent result when all residues are considered ( r 2 = 0.65). This provides qualified support for the hypothesis, albeit with an increased emphasis upon the importance of a much larger set of residues surrounding the locks. Evidence of a similar-sized protein core/extended nucleus (with significant overlap) was obtained from TCD calculations in which residues were successively eliminated according to their hydrophobicity and connectivity, and from molecular dynamics simulations. Our results suggest that while folding is determined by a subset of residues that can be predicted by application of the closed-loop hypothesis, the original hypothesis is too simplistic; efficient protein folding is dependent on a considerably larger subset of residues than those involved in lock formation. </jats:p

Measurement of isoprene nitrates by GCMS

According to atmospheric chemistry models, isoprene nitrates play an important role in determining the ozone production efficiency of isoprene; however this is very poorly constrained through observations as isoprene nitrates have not been widely measured. Measurements have been severely restricted largely due to a limited ability to measure individual isoprene nitrate isomers. An instrument based on gas chromatography/mass spectrometry (GCMS) and the associated calibration methods are described for the speciated measurements of individual isoprene nitrate isomers. Five of the primary isoprene nitrates which formed in the presence of NOx by reaction of isoprene with the hydroxyl radical (OH) in the Master Chemical Mechanism are identified using known isomers on two column phases and are fully separated on the Rtx-200 column. Three primary isoprene nitrates from the reaction of isoprene with the nitrate radical (NO3) are identified after synthesis from the already identified analogous hydroxy nitrate. A Tenax adsorbent-based trapping system allows the analysis of the majority of the known hydroxy and carbonyl primary isoprene nitrates, although not the (1,2)-IN isomer, under field-like levels of humidity and showed no impact from typical ambient concentrations of NOx and ozone

Innovative Technologies for Global Space Exploration

Under the direction of NASA's Exploration Systems Mission Directorate (ESMD), Directorate Integration Office (DIO), The Tauri Group with NASA's Technology Assessment and Integration Team (TAIT) completed several studies and white papers that identify novel technologies for human exploration. These studies provide technical inputs to space exploration roadmaps, identify potential organizations for exploration partnerships, and detail crosscutting technologies that may meet some of NASA's critical needs. These studies are supported by a relational database of more than 400 externally funded technologies relevant to current exploration challenges. The identified technologies can be integrated into existing and developing roadmaps to leverage external resources, thereby reducing the cost of space exploration. This approach to identifying potential spin-in technologies and partnerships could apply to other national space programs, as well as international and multi-government activities. This paper highlights innovative technologies and potential partnerships from economic sectors that historically are less connected to space exploration. It includes breakthrough concepts that could have a significant impact on space exploration and discusses the role of breakthrough concepts in technology planning. Technologies and partnerships are from NASA's Technology Horizons and Technology Frontiers game-changing and breakthrough technology reports as well as the External Government Technology Dataset, briefly described in the paper. The paper highlights example novel technologies that could be spun-in from government and commercial sources, including virtual worlds, synthetic biology, and human augmentation. It will consider how these technologies can impact space exploration and will discuss ongoing activities for planning and preparing them

Social networks, work and network-based resources for the management of long-term conditions: a framework and study protocol for developing self-care support

Background: increasing the effective targeting and promotion of self-care support for long-term conditions requires more of a focus on patient contexts and networks. The aim of this paper is to describe how within a programme of research and implementation, social networks are viewed as being centrally involved in the mobilisation and deployment of resources in the management of a chronic condition. This forms the basis of a novel approach to understanding, designing, and implementing new forms of self-management support.Methods: drawing on evidence syntheses about social networks and capital and the role of information in self-management, we build on four conceptual approaches to inform the design of our research on the implementation of self-care support for people with long-term conditions. Our approach takes into consideration the form and content of social networks, notions of chronic illness work, normalisation process theory (NPT), and the whole systems informing self-management engagement (WISE) approach to self-care support.Discussion: the translation and implementation of a self-care agenda in contemporary health and social context needs to acknowledge and incorporate the resources and networks operating in patients' domestic and social environments and everyday lives. The latter compliments the focus on healthcare settings for developing and delivering self-care support by viewing communities and networks, as well as people suffering from long-term conditions, as a key means of support for managing long-term conditions. By focusing on patient work and social-network provision, our aim is to open up a second frontier in implementation research, to translate knowledge into better chronic illness management, and to shift the emphasis towards support that takes place outside formal health services.<br/