Rapid, energy-efficient synthesis of the layered carbide, Al₄C₃

The phase-pure binary aluminium carbide, Al4C3 can be synthesised in vacuo from the elements in 30 minutes via microwave heating in a multimode cavity reactor. The success of the reaction is dependent on the use of finely divided aluminium and graphite starting materials, both of which couple effectively to the microwave field. The yellow-brown powder product was characterised by powder X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy thermogravimetric-differential thermal analysis and Raman spectroscopy. Powders were composed of hexagonal single crystallites tens of microns in diameter (rhombohedral space group R[3 with combining macron]m; Z = 3; a = 3.33813(5) Å, c = 25.0021(4) Å) and were stable to 1000 °C in air, argon and nitrogen. Equivalent microwave reactions of the elements in air led to the formation of the oxycarbide phases Al2OC and Al4O4C

Fragmentation dynamics of the ethyl bromide and ethyl iodide cations: a velocity-map imaging study

The photodissociation dynamics of ethyl bromide and ethyl iodide cations (C2H5Br+ and C2H5I+) have been studied. Ethyl halide cations were formed through vacuum ultraviolet (VUV) photoionization of the respective neutral parent molecules at 118.2 nm, and were photolysed at a number of ultraviolet (UV) photolysis wavelengths, including 355 nm and wavelengths in the range from 236 to 266 nm. Time-of-flight mass spectra and velocity-map images have been acquired for all fragment ions and for ground (Br) and spin–orbit excited (Br*) bromine atom products, allowing multiple fragmentation pathways to be investigated. The experimental studies are complemented by spin–orbit resolved ab initio calculations of cuts through the potential energy surfaces (along the RC–Br/I stretch coordinate) for the ground and first few excited states of the respective cations. Analysis of the velocity-map images indicates that photoexcited C2H5Br+ cations undergo prompt C–Br bond fission to form predominantly C2H5+ + Br* products with a near-limiting ‘parallel’ recoil velocity distribution. The observed C2H3+ + H2 + Br product channel is thought to arise via unimolecular decay of highly internally excited C2H5+ products formed following radiationless transfer from the initial excited state populated by photon absorption. Broadly similar behaviour is observed in the case of C2H5I+, along with an additional energetically accessible C–I bond fission channel to form C2H5 + I+ products. HX (X = Br, I) elimination from the highly internally excited C2H5X+ cation is deemed the most probable route to forming the C2H4+ fragment ions observed from both cations. Finally, both ethyl halide cations also show evidence of a minor C–C bond fission process to form CH2X+ + CH3 products

Risk of myocardial infarction and stroke after acute infection or vaccination.

BACKGROUND: There is evidence that chronic inflammation may promote atherosclerotic disease. We tested the hypothesis that acute infection and vaccination increase the short-term risk of vascular events. METHODS: We undertook within-person comparisons, using the case-series method, to study the risks of myocardial infarction and stroke after common vaccinations and naturally occurring infections. The study was based on the United Kingdom General Practice Research Database, which contains computerized medical records of more than 5 million patients. RESULTS: A total of 20,486 persons with a first myocardial infarction and 19,063 persons with a first stroke who received influenza vaccine were included in the analysis. There was no increase in the risk of myocardial infarction or stroke in the period after influenza, tetanus, or pneumococcal vaccination. However, the risks of both events were substantially higher after a diagnosis of systemic respiratory tract infection and were highest during the first three days (incidence ratio for myocardial infarction, 4.95; 95 percent confidence interval, 4.43 to 5.53; incidence ratio for stroke, 3.19; 95 percent confidence interval, 2.81 to 3.62). The risks then gradually fell during the following weeks. The risks were raised significantly but to a lesser degree after a diagnosis of urinary tract infection. The findings for recurrent myocardial infarctions and stroke were similar to those for first events. CONCLUSIONS: Our findings provide support for the concept that acute infections are associated with a transient increase in the risk of vascular events. By contrast, influenza, tetanus, and pneumococcal vaccinations do not produce a detectable increase in the risk of vascular events

Moving boulders in flash floods and estimating flow conditions using boulders in ancient deposits

Boulders moving in flash floods cause considerable damage and casualties. More and bigger boulders move in flash floods than predicted from published theory. The interpretation of flow conditions from the size of large particles within flash flood deposits has, until now, generally assumed that the velocity (or discharge) is unchanging in time (i.e. flow is steady), or changes instantaneously between periods of constant conditions. Standard practice is to apply theories developed for steady flow conditions to flash floods, which are however inherently very unsteady flows. This is likely to lead to overestimates of peak flow velocity (or discharge). Flash floods are characterised by extremely rapid variations in flow that generate significant transient forces in addition to the mean-flow drag. These transient forces, generated by rapid velocity changes, are generally ignored in published theories, but they are briefly so large that they could initiate the motion of boulders. This paper develops a theory for the initiation of boulder movement due to the additional impulsive force generated by unsteady flow, and discusses the implications. Keywords

Competing in hot conditions at the Tokyo Olympic Games : Preparation strategies used by Australian race walkers

Introduction: The Tokyo 2021 Olympic Games was anticipated to expose athletes to the most challenging climatic conditions experienced in the history of the modern Olympic Games. This study documents strategies executed by Australian endurance athletes during the team holding camp and Olympic Games experiences, including (1) baseline physiological data, training data, and heat acclimation/acclimatization practices; (2) pre- and in-race cooling and nutritional strategies, and (3) Olympic Games race performance data. Methods: Six athletes (three males, three females; age 24 ± 4 years; VO2max 63.2 ± 8.7 mL⋅kg–1⋅min–1; sum of 7 skinfolds 53.1 ± 23.4 mm) were observed prior to and during the team holding camp held in Cairns, QLD, Australia. Athletes completed 6–7 weeks of intermittent heat acclimation training, utilizing a combination of 2–4 passive and active acclimation sessions per week. Active acclimation was systematically increased via exposure time, exercise intensity, temperature, and humidity. In the team holding camp, athletes undertook a further 23 heat acclimatization training sessions over 18 days in a continuous fashion. Hyperhydration (using sodium and glycerol osmolytes), and internal and external pre-and in-race cooling methods were also utilized. A low energy availability intervention was implemented with two athletes, as a strategy to periodize ideal race body composition. Race performance data and environmental conditions from the 2021 Olympic Games were also documented. Results: The highest values for aerobic capacity were 63.6 mL⋅kg–1⋅min–1 for female race walkers and 73.7 mL⋅kg–1⋅min–1 for males. Training volume for the six athletes was the highest in the second week of the team holding camp, and training intensity was lowest in the first week of the team holding camp. Performance outcomes included 6th place in the women’s 20 km event (1:30:39), which was within 2% of her 20 km personal best time, and 8th place in the men’s 50 km event (3:52:01), which was a personal best performance time. Conclusion: Periodized training, heat acclimation/acclimatization, cooling and nutritional strategies study may have contributed to the race outcomes in Olympic Games held hot, humid conditions, for the race walkers within this observational study

Photofragmentation dynamics of <i>N,N</i>-dimethylformamide following excitation at 193 nm

N,N-dimethylformamide, HCON(CH3)2, is a useful model compound for investigating peptide bond photofragmentation dynamics. We report data from a comprehensive experimental and theoretical study into the photofragmentation dynamics of N,N-dimethylformamide in the gas phase at 193 nm. Through a combination of velocity-map imaging and hydrogen atom Rydberg tagging photofragment translational spectroscopy, we have identified two primary fragmentation channels, namely fission of the NCO `peptide' bond, and NCH3 bond fission leading to loss of CH3. The possible fragmentation channels leading to the observed products are rationalised with recourse to CASPT2 calculations of the ground and first few excited-state potential energy curves along the relevant dissociation coordinates, and the results are compared with data from previous experimental and theoretical studies on the same system

Systematic literature review of determinants of sedentary behaviour in older adults:a DEDIPAC study

BACKGROUND: Older adults are the most sedentary segment of society and high sedentary time is associated with poor health and wellbeing outcomes in this population. Identifying determinants of sedentary behaviour is a necessary step to develop interventions to reduce sedentary time. METHODS: A systematic literature review was conducted to identify factors associated with sedentary behaviour in older adults. Pubmed, Embase, CINAHL, PsycINFO and Web of Science were searched for articles published between 2000 and May 2014. The search strategy was based on four key elements: (a) sedentary behaviour and its synonyms; (b) determinants and its synonyms (e.g. correlates, factors); (c) types of sedentary behaviour (e.g. TV viewing, sitting, gaming) and (d) types of determinants (e.g. environmental, behavioural). Articles were included in the review if specific information about sedentary behaviour in older adults was reported. Studies on samples identified by disease were excluded. Study quality was rated by means of QUALSYST. The full review protocol is available from PROSPERO (PROSPERO 2014: CRD42014009823). The analysis was guided by the socio-ecological model framework. RESULTS: Twenty-two original studies were identified out of 4472 returned by the systematic search. These included 19 cross-sectional, 2 longitudinal and 1 qualitative studies, all published after 2011. Half of the studies were European. The study quality was generally high with a median of 82 % (IQR 69-96 %) using Qualsyst tool. Personal factors were the most frequently investigated with consistent positive association for age, negative for retirement, obesity and health status. Only four studies considered environmental determinants suggesting possible association with mode of transport, type of housing, cultural opportunities and neighbourhood safety and availability of places to rest. Only two studies investigated mediating factors. Very limited information was available on contexts and sub-domains of sedentary behaviours. CONCLUSION: Few studies have investigated determinants of sedentary behaviour in older adults and these have to date mostly focussed on personal factors, and qualitative studies were mostly lacking. More longitudinal studies are needed as well as inclusion of a broader range of personal and contextual potential determinants towards a systems-based approach, and future studies should be more informed by qualitative work

Perfectionism and achievement goals in young Finnish ice-hockey players aspiring to make the Under-16 national team

Research on perfectionism suggests that is it useful to differentiate between perfectionistic strivings and perfectionistic concerns. Regarding the 2 x 2 achievement goal framework, the usefulness of this differentiation was recently demonstrated in a study with university student athletes (Stoeber, Stoll, Pescheck, & Otto, 2008, Study 2), in which it was found that perfectionistic strivings were associated with mastery-approach and performance-approach goals and perfectionistic concerns with mastery-avoidance, performance-approach, and performance-avoidance goals. Because the study was largely exploratory and only used non-elite athletes, the aim of the present research was to replicate and extend these findings by investigating a sample of 138 young, elite ice-hockey players, while adding further measures of perfectionism and using structural equation modelling (SEM) to confirm the relationships between perfectionistic strivings, perfectionistic concerns,and the 2 x 2 achievement goals. The SEM results showed that, in elite athletes also, perfectionistic strivings are associated with mastery-approach and performance-approach goals, whereas perfectionistic concerns are associated with masteryavoidance, performance-approach, and performance-avoidance goals. Our findings corroborate the importance of differentiating between perfectionistic strivings and perfectionistic concerns when studying perfectionism in sports, because only perfectionistic concerns (and not perfectionistic strivings) are associated with maladaptive patterns of achievement goals