High-Temperature Fluorocarbon Chemistry Revisited.

The thermal dissociation reactions of C2F4 and C2F6 were studied in shock waves over the temperature range 1000-4000 K using UV absorption spectroscopy. Absorption cross sections of C2F4, CF2, CF, and C2 were derived and related to quantum-chemically modeled oscillator strengths. After confirming earlier results for the dissociation rates of C2F4, CF3, and CF2, the kinetics of secondary reactions were investigated. For example, the reaction CF2 + CF2 → CF + CF3 was identified. Its rate constant of 1010 cm3 mol-1 s-1 near 2400 K is markedly larger than the limiting high-pressure rate constant of the dimerization CF2 + CF2 → C2F4, suggesting that the reaction follows a different path. When the measurements of the thermal dissociation CF2 (+Ar) → CF + F (+Ar) are extended to temperatures above 2500 K, the formation of C2 radicals was shown to involve the reaction CF + CF → C2F + F (modeled rate constant 8.0 × 1012 (T/3500 K)1.0 exp(-4400 K/T) cm3 mol-1 s-1) and the subsequent dissociation C2F (+Ar) → C2 + F + (Ar) (modeled limiting low-pressure rate constant 3.0 × 1016 (T/3500 K)-4.0 exp(-56880 K/T) cm3 mol-1 s-1). This mechanism was validated by monitoring the dissociation of C2 at temperatures close to 4000 K. Temperature- and pressure-dependences of rate constants of reactions involved in the system were modeled by quantum-chemistry based rate theory.

Orthostatic hypotension as a risk factor for longitudinal deterioration of cognitive function in the elderly.

BACKGROUND AND PURPOSE: Orthostatic hypotension is frequent with aging with a prevalence of 20%-30% in people aged 65 or older and is considered to increase the risk for coronary events, strokes and dementia. Our objective was to characterize the association of orthostatic hypotension and cognitive function longitudinally over 6 years in a large cohort of the elderly aged over 50 years. METHODS: In all, 495 participants were assessed longitudinally with the Schellong test and comprehensive cognitive testing using the extended CERAD neuropsychological test battery at baseline and after 6 years. In a subgroup of 92 participants, cerebral magnetic resonance imaging was evaluated for white matter changes using a modified version of the Fazekas score. RESULTS: The prevalence of orthostatic hypotension increases with aging reaching up to 30% in participants aged >70 years. Participants with orthostatic hypotension presented with a higher vascular burden index (1.03 vs. 0.69, P ≤ 0.001), tended to have a higher prevalence of cerebral white matter hyperintensities (91.7% vs. 68.8%, P = 0.091) and showed a faster deterioration in executive and memory function (Trail Making Test B 95 vs. 87 s, P ≤ 0.001; word list learning sum -0.53 vs. 0.38, P = 0.002) compared to participants without orthostatic hypotension. CONCLUSION: Orthostatic hypotension seems to be associated with cognitive decline longitudinally.

Shock wave and modelling study of the dissociation pathways of (C2F5)3N.

The thermal decomposition of perfluorotriethylamine, (C2F5)3N, was investigated in shock waves by monitoring the formation of CF2. Experiments were performed over the temperature range of 1120-1450 K with reactant concentrations between 100 and 1000 ppm of (C2F5)3N in the bath gas Ar and with [Ar] in the range of (0.7-5.5) × 10-5 mol cm-3. The experiments were accompanied by quantum-chemical calculations of the energies of various dissociation paths and by rate calculations, in particular for the dissociation of C2F5via C2F5 → CF3 + CF2. The overall reaction can proceed in different ways, either by a sequence of successive C-N bond ruptures followed by fast C2F5 decompositions, or by a sequence of alternating C-C and C-N bond ruptures. A cross-over between the two pathways can also take place. At temperatures below about 1300 K, yields of less than one CF2 per (C2F5)3N decomposed were observed. On the other hand, at temperatures around 2000 K, when besides the parent molecule, CF3 also dissociates, yields of six CF2 per (C2F5)3N decomposed were measured. The rate-delaying steps of the dissociation mechanism at intermediate temperatures were suggested to be the processes (C2F5)NCF2 → (C2F5)N + CF2 and (CF2)N → N + CF2. The reduction of the CF2 yields at low temperatures was tentatively attributed to a branching of the mechanism at the level of (C2F5)2NCF2, from where the cyclic final product perfluoro-N-methylpyrrolidine, (C4F8)NCF3, is formed which was identified in earlier work from the literature.

Multi-band effects in in-plane resistivity anisotropy of strain-detwinned disordered Ba(Fe1-xRux)2As2.

In-plane resistivity anisotropy was measured in strain-detwinned as-grown and partially annealed samples of isovalently-substituted [Formula: see text] ([Formula: see text]) and the results were contrasted with previous reports on anneal samples with low residual resistivity. In samples with high residual resistivity, detwinned with application of strain, the difference of the two components of in-plane resistivity in the orthorhombic phase, [Formula: see text], was found to obey Matthiessen rule irrespective of sample composition, which is in stark contrast with observations on annealed samples. Our findings are consistent with two-band transport model in which contribution from high mobility carriers of small pockets of the Fermi surface has negligible anisotropy of residual resistivity and is eliminated by disorder. Our finding suggests that magnetic/nematic order has dramatically different effect on different parts of the Fermi surface. It predominantly affects inelastic scattering for small pocket high mobility carriers and elastic impurity scattering for larger sheets of the Fermi surface.

Assessing body image in anorexia nervosa using biometric self-avatars in virtual reality: Attitudinal components rather than visual body size estimation are distorted.

BACKGROUND: Body image disturbance (BID) is a core symptom of anorexia nervosa (AN), but as yet distinctive features of BID are unknown. The present study aimed at disentangling perceptual and attitudinal components of BID in AN. METHODS: We investigated n = 24 women with AN and n = 24 controls. Based on a three-dimensional (3D) body scan, we created realistic virtual 3D bodies (avatars) for each participant that were varied through a range of ±20% of the participants' weights. Avatars were presented in a virtual reality mirror scenario. Using different psychophysical tasks, participants identified and adjusted their actual and their desired body weight. To test for general perceptual biases in estimating body weight, a second experiment investigated perception of weight and shape matched avatars with another identity. RESULTS: Women with AN and controls underestimated their weight, with a trend that women with AN underestimated more. The average desired body of controls had normal weight while the average desired weight of women with AN corresponded to extreme AN (DSM-5). Correlation analyses revealed that desired body weight, but not accuracy of weight estimation, was associated with eating disorder symptoms. In the second experiment, both groups estimated accurately while the most attractive body was similar to Experiment 1. CONCLUSIONS: Our results contradict the widespread assumption that patients with AN overestimate their body weight due to visual distortions. Rather, they illustrate that BID might be driven by distorted attitudes with regard to the desired body. Clinical interventions should aim at helping patients with AN to change their desired weight.

Shock Wave and Theoretical Modeling Study of the Dissociation of CH2F2. I. Primary Processes.

The unimolecular dissociation of CH2F2 leading to CF2 + H2, CHF + HF, or CHF2 + H is investigated by quantum-chemical calculations and unimolecular rate theory. Modeling of the rate constants is accompanied by shock wave experiments over the range of 1400-1800 K, monitoring the formation of CF2. It is shown that the energetically most favorable dissociation channel leading to CF2 + H2 has a higher threshold energy than the energetically less favorable one leading to CHF + HF. Falloff curves of the dissociations are modeled. Under the conditions of the described experiments, the primary dissociation CH2F2 → CHF + HF is followed by the reaction CHF + HF → CF2 + H2. The experimental value of the rate constant for the latter reaction indicates that it does not proceed by an addition-elimination process involving CH2F2* intermediates, as assumed before.

Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF.

The thermal decomposition of hexafluoropropylene oxide, C3F6O, to perfluoroacetyl fluoride, CF3COF, and CF2 has been studied in shock waves highly diluted in Ar between 630 and 1000 K. The measured rate constant k1 = 1.1 × 1014 exp(-162(±4) kJ mol-1/RT) s-1 agrees well with literature data and modelling results. Using the reaction as a precursor, equimolar mixtures of CF3COF and CF2 were further heated. Combining experimental observations with theoretical modelling (on the CBS-QB3 and G4MP2 ab initio composite levels), CF3COF is shown to dissociate on two channels, either leading to CF2 + COF2 or to CF3 + FCO. By monitoring the CF2 signals, the branching ratio was determined between 1400 and 1900 K. The high pressure rate constants for the two channels were obtained from theoretical modelling as k5,∞(CF3COF → CF2 + COF2) = 7.1 × 1014 exp(-320 kJ mol-1/RT) s-1 and k6,∞(CF3COF → CF3 + FCO) = 3.9 × 1015 exp(-355 kJ mol-1/RT) s-1. The experimental results obtained at [Ar] ≈ 5 × 10-6 mol cm-3 were consistent with modelling results, showing that the reaction is in the falloff range of the unimolecular dissociation. The mechanism of secondary reactions following CF3COF dissociation has been analysed as well.

Shock wave studies of the pyrolysis of fluorocarbon oxygenates. II. The thermal dissociation of C4F8O.

The thermal decomposition of octafluorooxalane, C4F8O, to C2F4 + CF2 + COF2 has been studied in shock waves highly diluted in Ar between 1300 and 2200 K. The primary dissociation was shown to be followed by secondary dissociation of C2F4 and dimerization of CF2. The primary dissociation was found to be in its falloff range and falloff curves were constructed. The limiting low and high pressure rate constants were estimated and compared with modelling results. Quantum-chemical calculations identified possible reaction pathways, either leading directly to the final products of the reaction or passing through an open-chain CF2CF2CF2 intermediate which dissociates in a second step.

A mechanical rotator for neutron scattering measurements.

We have designed and built a mechanical rotation system for use in single crystal neutron scattering experiments at low temperatures. The main motivation for this device is to facilitate the application of magnetic fields transverse to a primary training axis, using only a vertical cryomagnet. Development was done in the context of a triple-axis neutron spectrometer, but the design is such that it can be generalized to a number of different instruments or measurement techniques. Here, we discuss some of the experimental constraints motivating the design, followed by design specifics, preliminary experimental results, and a discussion of potential uses and future extension possibilities.

Shock wave study and theoretical modeling of the thermal decomposition of c-C4F8.

The thermal dissociation of octafluorocyclobutane, c-C4F8, was studied in shock waves over the range 1150-2300 K by recording UV absorption signals of CF2. It was found that the primary reaction nearly exclusively produces 2 C2F4 which afterwards decomposes to 4 CF2. A primary reaction leading to CF2 + C3F6 is not detected (an upper limit to the yield of the latter channel was found to be about 10 percent). The temperature range of earlier single pulse shock wave experiments was extended. The reaction was shown to be close to its high pressure limit. Combining high and low temperature results leads to a rate constant for the primary dissociation of k1 = 10(15.97) exp(-310.5 kJ mol(-1)/RT) s(-1) in the range 630-1330 K, over which k1 varies over nearly 14 orders of magnitude. Calculations of the energetics of the reaction pathway and the rate constants support the conclusions from the experiments. Also they shed light on the role of the 1,4-biradical CF2CF2CF2CF2 as an intermediate of the reaction.

Surface Collective Modes in the Topological Insulators Bi_{2}Se_{3} and Bi_{0.5}Sb_{1.5}Te_{3-x}Se_{x}.

We used low-energy, momentum-resolved inelastic electron scattering to study surface collective modes of the three-dimensional topological insulators Bi_{2}Se_{3} and Bi_{0.5}Sb_{1.5}Te_{3-x}Se_{x}. Our goal was to identify the "spin plasmon" predicted by Raghu and co-workers [Phys. Rev. Lett. 104, 116401 (2010)]. Instead, we found that the primary collective mode is a surface plasmon arising from the bulk, free carriers in these materials. This excitation dominates the spectral weight in the bosonic function of the surface χ^{"}(q,ω) at THz energy scales, and is the most likely origin of a quasiparticle dispersion kink observed in previous photoemission experiments. Our study suggests that the spin plasmon may mix with this other surface mode, calling for a more nuanced understanding of optical experiments in which the spin plasmon is reported to play a role.

Effects of a 10-week conventional strength training program on lower leg muscle performance in adolescent boys compared to adults.

AIM: The use of resistance training by adolescents has been an area of controversy. The aim of the present work was therefore to evaluate the degree of strength trainability in adolescents compared to adults. METHODS: Thirteen healthy male adolescents (AL) and eight adults (AD) volunteered to participate in a 10-week training program. Subjects performed supervised exercises for the legs, calf raise, leg curl and leg extension three times a week. Maximal strength, explosive power and anaerobic power were assessed prior and after the 10-week training program. RESULTS: Significant interaction effects (time * age group) were found only for explosive strength as improvements of squat jump and counter movement jump performance (P<0.05) in favor of the AL group. No between-group changes were found for maximal strength and anaerobic power. However, significant time effects were observed for these parameters within both groups. CONCLUSION: Taken together, adolescents show distinct muscular adaptations by a higher gain in explosive power in response to resistance training when compared to adults. This might be related to peak height velocity (PHV) which is a "sensitive" period of trainability and accelerated adaptation to resistance training in adolescents.

Postoperative adiponectin levels in pediatric patients undergoing open heart surgery.

BACKGROUND: Adipose tissue is an important endocrine organ that secretes cytokines, including adiponectin, levels of which are negatively correlated with the severity of the inflammatory process. Aim. To assess the time course of adiponectin levels following open heart surgery with cardiopulmonary bypass and its correlation with early postoperative outcomes. MATERIALS AND METHODS: Blood samples were obtained from 24 children undergoing cardiac surgery and analyzed for adiponectin, C-reactive protein, and other inflammatory markers. RESULTS: Baseline adiponectin levels were negatively correlated with patients' preoperative weight and age. Postoperative adiponectin levels decreased compared to baseline (P = 0.01) and correlated negatively with duration of cardiopulmonary bypass (r = -0.438, P = 0.037), length of stay in the pediatric intensive care unit (r = -0.457, P = 0.025), and the inotropic score (r = -0.471, P = 0.02). Adiponectin levels were positively correlated with sVCAM 1 levels; however, there was no correlation between adiponectin levels and sP selectin, tPA, MCP1, and sCD40. CONCLUSIONS: The inflammatory response after open heart surgery with cardiopulmonary bypass is associated with a reduction in adiponectin levels. Prolonged or more complicated surgery induced a more substantial inflammatory process characterized by a significant reduction in adiponectin levels over time and a delayed return to baseline levels.

Magnonlike dispersion of spin resonance in Ni-doped BaFe2As2.

Inelastic neutron scattering measurements on Ba(Fe0.963Ni0.037)2As2 manifest a neutron spin resonance in the superconducting state with anisotropic dispersion within the Fe layer. Whereas the resonance is sharply peaked at the antiferromagnetic (AFM) wave vector Q(AFM) along the orthorhombic a axis, the resonance disperses upwards away from Q(AFM) along the b axis. In contrast to the downward dispersing resonance and hourglass shape of the spin excitations in superconducting cuprates, the resonance in electron-doped BaFe2As2 compounds possesses a magnonlike upwards dispersion.

Interlayer coherence and superconducting condensate in the c-axis response of optimally doped Ba(Fe(1-x)Co(x))2As2 high-T(c) superconductor using infrared spectroscopy.

We report on the infrared studies of the interlayer charge dynamics of a prototypical pnictide superconductor Ba(Fe(0.926)Co(0.074))(2)As(2). We succeeded in probing the intrinsic interlayer response by performing infrared experiments on the crystals with a cleaved ac surface. Our experiments identify the coexistence of the suppression of the electronic spectral weight and the development of a coherent Drude-like response in the normal state. The formation of the interlayer condensate is clearly observed in the superconducting state and appears to be linked to coherent contribution to the normal-state conductivity.

Unusual temperature dependence of band dispersion in Ba(Fe(1-x)Ru(x))2As2 and its consequences for antiferromagnetic ordering.

We have performed detailed studies of the temperature evolution of the electronic structure in Ba(Fe(1-x)Ru(x))(2)As(2) using angle resolved photoemission spectroscopy. Surprisingly, we find that the binding energy of both hole and electron bands changes significantly with temperature in both pure and Ru substituted samples. The hole and electron pockets are well nested at low temperature in unsubstituted (BaFe(2)As(2)) samples, which likely drives the spin density wave and resulting antiferromagnetic order. Upon warming, this nesting is degraded as the hole pocket shrinks and the electron pocket expands. Our results demonstrate that the temperature dependent nesting may play an important role in driving the antiferromagnetic-paramagnetic phase transition.

Effects of transition metal substitutions on the incommensurability and spin fluctuations in BaFe2As2 by elastic and inelastic neutron scattering.

The spin fluctuation spectra from nonsuperconducting Cu-substituted, and superconducting Co-substituted, BaFe(2)As(2) are compared quantitatively by inelastic neutron scattering measurements and are found to be indistinguishable. Whereas diffraction studies show the appearance of incommensurate spin-density wave order in Co and Ni substituted samples, the magnetic phase diagram for Cu substitution does not display incommensurate order, demonstrating that simple electron counting based on rigid-band concepts is invalid. These results, supported by theoretical calculations, suggest that substitutional impurity effects in the Fe plane play a significant role in controlling magnetism and the appearance of superconductivity, with Cu distinguished by enhanced impurity scattering and split-band behavior.

Infrared measurement of the pseudogap of P-doped and Co-doped high-temperature BaFe2As2 superconductors.

We report on infrared studies of charge dynamics in a prototypical pnictide system: the BaFe2As2 family. Our experiments have identified hallmarks of the pseudogap state in the BaFe2As2 system that mirror the spectroscopic manifestations of the pseudogap in the cuprates. The magnitude of the infrared pseudogap is in accord with that of the spin-density-wave gap of the parent compound. By monitoring the superconducting gap of both P- and Co-doped compounds, we find that the infrared pseudogap is unrelated to superconductivity. The appearance of the pseudogap is found to correlate with the evolution of the antiferromagnetic fluctuations associated with the spin-density-wave instability. The strong-coupling analysis of infrared data further reveals the interdependence between the magnetism and the pseudogap in the iron pnictides.

Effect of 3d doping on the electronic structure of BaFe2As2.

The electronic structure of BaFe(2)As(2) doped with Co, Ni and Cu has been studied by a variety of experimental and theoretical methods, but a clear picture of the dopant 3d states has not yet emerged. Herein we provide experimental evidence of the distribution of Co, Ni and Cu 3d states in the valence band. We conclude that the Co and Ni 3d states provide additional free carriers to the Fermi level, while the Cu 3d states are found at the bottom of the valence band in a localized 3d(10) shell. These findings help shed light on why superconductivity can occur in BaFe(2)As(2) doped with Co and Ni but not Cu.

Incommensurate spin-density wave order in electron-doped BaFe2 As2 superconductors.

Neutron diffraction studies of Ba(Fe(1-x)Co(x))(2)As)(2) reveal that commensurate antiferromagnetic order gives way to incommensurate magnetic order for Co compositions between 0.056 < x < 0.06. The incommensurability has the form of a small transverse splitting (0, ± ε, 0) from the commensurate antiferromagnetic propagation vector Q(AFM) = (1,0,1) (in orthorhombic notation) where ε ≈ 0.02-0.03 and is composition dependent. The results are consistent with the formation of a spin-density wave driven by Fermi surface nesting of electron and hole pockets and confirm the itinerant nature of magnetism in the iron arsenide superconductors.