Accessing novel fluorinated heterocycles with the hypervalent fluoroiodane reagent by solution and mechanochemical synthesis

A new and efficient strategy for the rapid formation of novel fluorinated tetrahydropyridazines and dihydrooxazines has been developed by fluorocylisation of β,γ-unsaturated hydrazones and oximes with the hypervalent fluoroiodane reagent. Mechanochemical synthesis delivered fluorinated tetrahydropyridazines in similar excellent yields to conventional solution synthesis, whereas fluorinated dihydro-oxazines were prepared in much better yields by ball-milling

Orientation cues for high-flying nocturnal insect migrants: do turbulence-induced temperature and velocity fluctuations indicate the mean wind flow?

Migratory insects flying at high altitude at night often show a degree of common alignment, sometimes with quite small angular dispersions around the mean. The observed orientation directions are often close to the downwind direction and this would seemingly be adaptive in that large insects could add their self-propelled speed to the wind speed, thus maximising their displacement in a given time. There are increasing indications that high-altitude orientation may be maintained by some intrinsic property of the wind rather than by visual perception of relative ground movement. Therefore, we first examined whether migrating insects could deduce the mean wind direction from the turbulent fluctuations in temperature. Within the atmospheric boundary-layer, temperature records show characteristic ramp-cliff structures, and insects flying downwind would move through these ramps whilst those flying crosswind would not. However, analysis of vertical-looking radar data on the common orientations of nocturnally migrating insects in the UK produced no evidence that the migrants actually use temperature ramps as orientation cues. This suggests that insects rely on turbulent velocity and acceleration cues, and refocuses attention on how these can be detected, especially as small-scale turbulence is usually held to be directionally invariant (isotropic). In the second part of the paper we present a theoretical analysis and simulations showing that velocity fluctuations and accelerations felt by an insect are predicted to be anisotropic even when the small-scale turbulence (measured at a fixed point or along the trajectory of a fluid-particle) is isotropic. Our results thus provide further evidence that insects do indeed use turbulent velocity and acceleration cues as indicators of the mean wind direction

Case Study: Extreme Weight Making Causes Relative Energy Deficiency, Dehydration and Acute Kidney Injury in a Male Mixed Martial Arts Athlete.

The aim of the present case study was to quantify the physiological and metabolic impact of extreme weight cutting by an elite male MMA athlete. Throughout an 8-week period, we obtained regular assessments of body composition, resting metabolic rate (RMR), VO2peak and blood clinical chemistry to assess endocrine status, lipid profiles, hydration and kidney function. The athlete adhered to a "phased" weight loss plan consisting of 7 weeks of reduced energy (ranging from 1300 - 1900 kcal.d-1) intake (phase 1), 5 days of water loading with 8 L per day for 4 days followed by 250 ml on day 5 (phase 2), 20 h fasting and dehydration (phase 3) and 32 h of rehydration and refuelling prior to competition (phase 4). Body mass declined by 18.1 % (80.2 to 65.7 kg) corresponding to changes of 4.4, 2.8 and 7.3 kg in phase 1, 2 and 3, respectively. We observed clear indices of relative energy deficiency, as evidenced by reduced RMR (-331 kcal), inability to complete performance tests, alterations to endocrine hormones (testosterone: 6 mmol.L-1). Moreover, severe dehydration (reducing body mass by 9.3%) in the final 24 hours prior to weigh-in induced hypernatremia (plasma sodium: 148 mmol.L-1) and acute kidney injury (serum creatinine: 177 μmol.L-1). These data therefore support publicised reports of the harmful (and potentially fatal) effects of extreme weight cutting in MMA athletes and represent a call for action to governing bodies to safeguard the welfare of MMA athletes

Vortical and Wave Modes in 3D Rotating Stratified Flows: Random Large Scale Forcing

Utilizing an eigenfunction decomposition, we study the growth and spectra of energy in the vortical and wave modes of a 3D rotating stratified fluid as a function of $\epsilon = f/N$. Working in regimes characterized by moderate Burger numbers, i.e. $Bu = 1/\epsilon^2 < 1$ or $Bu \ge 1$, our results indicate profound change in the character of vortical and wave mode interactions with respect to $Bu = 1$. As with the reference state of $\epsilon=1$, for $\epsilon < 1$ the wave mode energy saturates quite quickly and the ensuing forward cascade continues to act as an efficient means of dissipating ageostrophic energy. Further, these saturated spectra steepen as $\epsilon$ decreases: we see a shift from $k^{-1}$ to $k^{-5/3}$ scaling for $k_f < k < k_d$ (where $k_f$ and $k_d$ are the forcing and dissipation scales, respectively). On the other hand, when $\epsilon > 1$ the wave mode energy never saturates and comes to dominate the total energy in the system. In fact, in a sense the wave modes behave in an asymmetric manner about $\epsilon = 1$. With regard to the vortical modes, for $\epsilon \le 1$, the signatures of 3D quasigeostrophy are clearly evident. Specifically, we see a $k^{-3}$ scaling for $k_f < k < k_d$ and, in accord with an inverse transfer of energy, the vortical mode energy never saturates but rather increases for all $k < k_f$. In contrast, for $\epsilon > 1$ and increasing, the vortical modes contain a progressively smaller fraction of the total energy indicating that the 3D quasigeostrophic subsystem plays an energetically smaller role in the overall dynamics.Comment: 18 pages, 6 figs. (abbreviated abstract

Observation of inhibited electron-ion coupling in strongly heated graphite

Creating non-equilibrium states of matter with highly unequal electron and lattice temperatures (Tele≠Tion) allows unsurpassed insight into the dynamic coupling between electrons and ions through time-resolved energy relaxation measurements. Recent studies on low-temperature laser-heated graphite suggest a complex energy exchange when compared to other materials. To avoid problems related to surface preparation, crystal quality and poor understanding of the energy deposition and transport mechanisms, we apply a different energy deposition mechanism, via laser-accelerated protons, to isochorically and non-radiatively heat macroscopic graphite samples up to temperatures close to the melting threshold. Using time-resolved x ray diffraction, we show clear evidence of a very small electron-ion energy transfer, yielding approximately three times longer relaxation times than previously reported. This is indicative of the existence of an energy transfer bottleneck in non-equilibrium warm dense matter

PCA-induced respiratory depression simulating stroke following endoluminal repair of abdominal aortic aneurysm: a case report

<p>Abstract</p> <p>Aim</p> <p>To report a case of severe respiratory depression with PCA fentanyl use simulating stroke in a patient who underwent routine elective endoluminal graft repair for abdominal aortic aneurysm (AAA)</p> <p>Case presentation</p> <p>A 78-year-old obese lady underwent routine endoluminal graft repair for AAA that was progressively increasing in size. Following an uneventful operation postoperative analgesia was managed with a patient-controlled analgesia (PCA) device with fentanyl. On the morning following operation the patient was found to be unusually drowsy and unresponsive to stimuli. Her GCS level was 11 with plantars upgoing bilaterally. A provisional diagnosis of stroke was made. Urgent transfer to a high-dependency unit (HDU) was arranged and she was given ventilatory support with a BiPap device. CT was performed and found to be normal. Arterial blood gas (ABG) analysis showed respiratory acidosis with PaCO₂81 mmHg, PaO₂140 mmHg, pH 7.17 and base excess -2 mmol/l. A total dose of 600 mcg of fentanyl was self-administered in the 16 hours following emergence from general anaesthesia. Naloxone was given with good effect. There was an increase in the creatinine level from 90 μmol/L preoperatively to 167 μmol/L on the first postoperative day. The patient remained on BiPap for two days that resulted in marked improvement in gas exchange. Recovery was complete.</p

Sex differences in rheumatoid arthritis: more than meets the eye...

Sex differences in the prevalence of autoimmune diseases such as rheumatoid arthritis (RA) are well described, but the literature is not as clear about sex differences in RA disease course and prognosis. A recent study from a very large cross-sectional international cohort demonstrated slightly worse levels of disease activity and function in female patients with RA, compared with men. These findings are discussed in the context of our evolving knowledge of sex differences in the expression of this prototypic autoimmune disease, both in terms of the actual disease activity level, the effects that the disease has on physical function, and our ability accurately to measure these aspects

Towards interoperability in the european poetry community: the standardization of philological concepts

This paper stems from the Poetry Standardization and Linked Open Data project (POSTDATA). As its name reveals, one of the main aims of POSTDATA is to provide a means to publish European poetry (EP) data as Linked Open Data (LOD). Thus, developing a metadata application profile (MAP) as a common semantic model to be used by the EP community is a crucial step of this project. This MAP will enhance interoperability among the community members in particular, and among the EP community and other contexts in general (e.g. bibliographic records). This paper presents the methodology followed in the process of defining the concepts of the domain model of this MAP, as well as some issues that arise when labeling philological terms.info:eu-repo/semantics/publishedVersio

Direct observation of spin-polarised bulk bands in an inversion-symmetric semiconductor

Methods to generate spin-polarised electronic states in non-magnetic solids are strongly desired to enable all-electrical manipulation of electron spins for new quantum devices. This is generally accepted to require breaking global structural inversion symmetry. In contrast, here we present direct evidence from spin- and angle-resolved photoemission spectroscopy for a strong spin polarisation of bulk states in the centrosymmetric transition-metal dichalcogenide WSe$_2$. We show how this arises due to a lack of inversion symmetry in constituent structural units of the bulk crystal where the electronic states are localised, leading to enormous spin splittings up to $\sim\!0.5$ eV, with a spin texture that is strongly modulated in both real and momentum space. As well as providing the first experimental evidence for a recently-predicted `hidden' spin polarisation in inversion-symmetric materials, our study sheds new light on a putative spin-valley coupling in transition-metal dichalcogenides, of key importance for using these compounds in proposed valleytronic devices.Comment: 6 pages, 4 figure