Giant Dielectric Permittivity of Electron-Doped Manganite Thin Films, Ca(1-x)La(x)MnO(3) ($0<= x<= 0.03)

A giant low-frequency, in-plane dielectric constant, eps~10^6, for epitaxial thin films of Ca(1-x)La(x)MnO(3) (x<=0.03) was observed over a broad temperature range, 4K <= T 300K. This phenomenon is attributed to an internal barrier-layer capacitor (IBLC) structure, with insulating boundaries between semiconducting grains. The room-temperature eps increases substantially with electron (La) doping. The measured values of eps exceed those of conventional two-phase IBLC materials based on (Ba,Sr)TiO(3) as well as recently discovered CaCu(3)Ti(4)O(12) and (Li,Ti) doped NiO.Comment: 5 pages, 4 fig.s, J. Appl. Phys., Jan. 15, 2005 (in press

Low-Temperature Permittivity of Insulating Perovskite Manganites

Measurements of the low-frequency (f<=100 kHz) permittivity and conductivity at T<= 150 K are reported for La(1-x)Ca(x)MnO(3) (0<=x<=1) and Ca(1-y)Sr(y)MnO(3) (0<=y<=0.75) having antiferromagnetic, insulating ground states covering a broad range of Mn valencies from Mn(3+) to Mn(4+). Static dielectric constants are determined from the low-T limiting behavior. With increasing T, relaxation peaks associated with charge-carrier hopping are observed in the real part of the permittivities and analyzed to determine dopant binding energies. The data are consistent with a simple model of hydrogenic impurity levels and imply effective masses m*/m_e~3 for the Mn(4+) compounds. Particularly interesting is a large dielectric constant (~100) associated with the C-type antiferromagnetic state near the composition La(0.2)Ca(0.8)MnO(3).Comment: 6 pages, 8 figures, PRB in pres

The effect of carbohydrate dose and timing on timed effort and time to exhaustion within a simulated cycle race in male professional cyclists

A key performance limitation affecting professional endurance cycling is carbohydrate storage and utilisation (Pöchmüller, Schwingshack, Colombani & Hoffmann, 2016, Journal of the International Society of Sports Nutrition, 13). Muscle glycogen stores alone are inefficient at maintaining optimal blood glucose levels beyond two hours of exercise; consequently, exogenous CHO is commonly used to counteract this (Jeukendrup, 2011, Journal of Sports Sciences, 21, 91-99). High concentrations of CHO can cause drops in blood glucose, excessive glycogen utilisation and gastrointestinal discomfort (GID) (Jeukendrup, 2011). Therefore, the aim of this study was to determine if frequent, smaller CHO feedings would be preferable to large, bolus CHO feedings on time trial cycling performance. With institutional ethics approval, 5 professional cyclists completed a 4h simulated cycle ride with 3 timed efforts in a randomised, cross-over, double blind design study. Each timed effort occurred in the last 10 min of each hour (TE1, TE2, TE3); participants were asked to cycle with maximum effort for this time. There was also a final effort at the end of the 4th hour to replicate a sprint finish. This was measured as time to exhaustion (TTE). Two interventions were used; a frequent feed (F) where participants drank 20g maltodextrin in 300ml flavoured water solution 3 times per hour and a bolus feed (B) where participants drank 60g maltodextrin solution once per hour. Heart rate, power output, GID, perceived exertion (RPE), blood lactate and blood glucose were recorded before and after TE1, TE2, TE3 and TTE. Wilcoxen signed rank test and Cohen’s D was performed to study differences between interventions and effect sizes.In the F intervention, average watts were significantly higher at TE2 (P<0.05 d=0.75) and TE3 (P<0.05 d=1.21) and the RPE was lower TE1 (P≥0.05 d=1.12), TE2 (P<0.05, d=1.12) and TTE (P≥0.05 d=1.12) compared to B. There was no significant difference between any other variables. The results suggest that despite power output being higher, RPE was lower in the F intervention. Gut absorption of CHO is limited to 1g/h (Jeukendrup, 2011), which may help explain these findings. This is one of the first studies to look at concentration and timing of CHO consumption in endurance cycling. Regular feeds of 20g CHO may be more beneficial on power output and RPE in endurance cycling compared to hourly 60g feeds

Increasing 3D Supramolecular Order by Decreasing Molecular Order. A Comparative Study of Helical Assemblies of Dendronized Nonchlorinated and Tetrachlorinated Perylene Bisimides

A nonplanar, twisted, and flexible tetrachlorinated perylene bisimide (Cl4PBI) was functionalized with two AB3 minidendrons containing hydrogenated or semifluorinated dodecyl groups. The hydrogenated dendron was attached to the imide groups of Cl4PBI via m = 0, 1, and 2 methylenic units, whereas the dendron containing semifluorinated groups was attached via m = 3 or a di(ethylene oxide) linker (m = 2EO). The supramolecular structures of these compounds, determined by a combination of differential scanning calorimetry, X-ray diffraction, and solid-state NMR, were compared with those of nonchlorinated planar and rigid PBI reported previously, which demonstrated the thermodynamically controlled formation of 2D periodic arrays at high temperatures and 3D arrays at low temperatures. The molecularly less ordered Cl4PBI containing hydrogenated dendrons self-organize into exclusively 3D crystalline periodic arrays under thermodynamic control for m = 0 and 2, while the more highly molecularly ordered PBI produced less stable and ordered 3D crystals and also 2D assemblies. This induction of a higher degree of 3D order in supramolecular assemblies of the less well-ordered molecular building blocks was unanticipated. The semifluorinated dendronized Cl4PBI with m = 3 formed a 2D columnar hexagonal array under kinetic control, whereas the compound with m = 2EO formed an unusual 2D honeycomb-like hexagonal phase under thermodynamic control. These Cl4PBI compounds provide a new route to stable crystalline assemblies via thermodynamic control at lower temperatures than previously obtained with PBI, thus generating 3D order in an accessible range of temperature of interest for structural analysis and for technological applications

Why Do Membranes of Some Unhealthy Cells Adopt a Cubic Architecture?

Nonlamellar lipid arrangements, including cubosomes, appear in unhealthy cells, e.g., when they are subject to stress, starvation, or viral infection. The bioactivity of cubosomes-nanoscale particles exhibiting bicontinuous cubic structures-versus more common vesicles is an unexplored area due to lack of suitable model systems. Here, glycodendrimercubosomes (GDCs)-sugar-presenting cubosomes assembled from Janus glycodendrimers by simple injection into buffer-are proposed as mimics of biological cubic membranes. The bicontinuous cubic GDC architecture has been demonstrated by electron tomography. The stability of these GDCs in buffer enabled studies on lectin-dependent agglutination, revealing significant differences compared with the vesicular glycodendrimersome (GDS) counterpart. In particular, GDCs showed an increased activity toward concanavalin A, as well as an increased sensitivity and selectivity toward two variants of banana lectins, a wild-type and a genetically modified variant, which is not exhibited by GDSs. These results suggest that cells may adapt under unhealthy conditions by undergoing a transformation from lamellar to cubic membranes as a method of defense

Self-organization of rectangular bipyramidal helical columns by supramolecular orientational memory epitaxially nucleated from a Frank-Kasper σ phase

Programming living and soft complex matter via primary structure and self-organization represents the key methodology employed to design functions in biological and synthetic nanoscience. Memory effects have been used to create commercial technologies including liquid crystal displays and biomedical applications based on shape memory polymers. Supramolecular orientational memory (SOM), induced by an epitaxial nucleation mediated by the close contact spheres of cubic phases, emerged as a pathway to engineer complex nanoscale soft matter of helical columnar hexagonal arrays. SOM preserves the crystallographic directions of close contact supramolecular spheres from the 3D phase upon cooling to the columnar hexagonal periodic array. Despite the diversity of 3D periodic and quasiperiodic nanoarrays of supramolecular dendrimers, including Frank-Kasper and quasicrystal, all examples of SOM to date were mediated by Im3m (body-centered cubic, BCC) and Pm3n (Frank-Kasper A15) cubic phases. Expanding the scope of SOM to non-cubic arrays is expected to generate additional morphologies that were not yet available by any other methods. Here we demonstrate the SOM of a dendronized triphenylene that self-organizes into helical columnar hexagonal and tetragonal P42/mnm (Frank-Kasper σ) phases. Structural analysis of oriented fibers by X-ray diffraction reveals that helical columnar hexagonal domains self-organize an unusual rectangular bipyramidal morphology upon cooling from the σ phase. The discovery of SOM in a non-cubic Frank-Kasper phase indicates that this methodology may be expanded to other periodic and quasiperiodic nanoarrays organized from self-assembling dendrimers and, most probably, to other soft and living complex matter

A supramolecular helix that disregards chirality

The functions of complex crystalline systems derived from supramolecular biological and non-biological assemblies typically emerge from homochiral programmed primary structures via first principles involving secondary, tertiary and quaternary structures. In contrast, heterochiral and racemic compounds yield disordered crystals, amorphous solids or liquids. Here, we report the self-assembly of perylene bisimide derivatives in a supramolecular helix that in turn self-organizes in columnar hexagonal crystalline domains regardless of the enantiomeric purity of the perylene bisimide. We show that both homochiral and racemic perylene bisimide compounds, including a mixture of 21 diastereomers that cannot be deracemized at the molecular level, self-organize to form single-handed helical assemblies with identical single-crystal-like order. We propose that this high crystalline order is generated via a cogwheel mechanism that disregards the chirality of the self-assembling building blocks. We anticipate that this mechanism will facilitate access to previously inaccessible complex crystalline systems from racemic and homochiral building blocks

Self-organisation of dodeca-dendronized fullerene into supramolecular discs and helical columns containing a nanowire-like core

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