The influence of the molecular system on the performance of heteronuclear decoupling in solid-state NMR

The intensity of the carbon signal in a CPMAS experiment has been measured for two CH and three CH(2) moieties in four test molecules under different phase-modulated proton decoupling conditions and as a function of the spinning rate. The proton decoupling schemes investigated were the golden standard TPPM and three of the GTn family. Aim of this analysis was to better describe experimentally the impact and limitations of phase-modulated decoupling. Sizeable differences in the response to decoupling were observed in otherwise chemically identical molecular fragments, such as the CHCH(2) found in tyrosine, phenyl-succinic acid or 9-Anthrylmethyl-malonate, probably due to differences in spin-diffusion rates. In keeping with known facts, the efficiency of the decoupling was observed to decrease with the MAS rate, but with somewhat different trends for the tested systems.     

Improved extraction of vegetable oils under high-intensity ultrasound and/or microwaves

Ultrasound-assisted extraction (UAE) and microwave-assisted extraction (MAE) techniques have been employed as complementary techniques to extract oils from vegetable sources, viz, soybean germ and a cultivated marine microalga rich in docosahexaenoic acid (DHA). Ultrasound (US) devices developed by ourselves, working at several frequencies (19, 25, 40 and 300 kHz), were used for US-based protocols, while a multimode microwave (MW) oven (operating with both open and closed vessels) was used for MAE. Combined treatments were also studied, such as simultaneous double sonication (at 19 and 25 kHz) and simultaneous US/MW irradiation, achieved by inserting a non-metallic horn in a MW oven. Extraction times and yields were compared with those resulting from conventional procedures. With soybean germ the best yield was obtained with a ‘cavitating tube’ prototype (19 kHz, 80 W), featuring a thin titanium cylinder instead of a conventional horn. Double sonication, carried out by inserting an immersion horn (25 kHz) in the same tube, improved the yield only slightly but halved the extraction time. Almost comparable yields were achieved by closed-vessel MAE and simultaneous US/MW irradiation. Compared with conventional methods, extraction times were reduced by up to 10-fold and yields increased by 50–500%. In the case of marine microalgae, UAE worked best, as the disruption by US of the tough algal cell wall considerably improved the extraction yield from 4.8% in soxhlet to 25.9%. Our results indicate that US and MW, either alone or combined, can greatly improve the extraction of bioactive substances, achieving higher efficiency and shorter reaction times at low or moderate costs, with minimal added toxicity.     

A neutral gas model for electron swarms

A BGK-type Boltzmann equation for a neutral gas is considered as a model for electron swarms, because the gas and the electron Boltzmann equation have a common diffusion approximation. Both full- and half-range theory are developed using orthogonality methods of solution. Preliminary comparisons with diffusion theory are presented.     

Symmetric and asymmetric fission of charged sodium clusters

A deformed-jellium model is used to calculate the fission barrier height of Na ₂₄ ²⁺ → Na ₂₁ ⁺ +Na ₃ ⁺ and Na ₄₂ ²⁺ → 2Na ₂₁ ⁺ within the Kohn—Sham Density Functional Theory (i.e., including shell effects). Although the shape of the barrier obviously depends on the parametrization of the fission path, we have found that the barrier maximum corresponds to a configuration in which the emerging fragments are already formed and rather well apart. The two examples chosen serve to illustrate the influence of the electronic shell effects.     

A ketogenic diet increases succinic dehydrogenase (SDH) activity and recovers age-related decrease in numeric density of SDH-positive mitochondria in cerebellar Purkinje cells of late-adult rats

Ketogenic diets (KDs) have been applied in the therapy of paediatric epilepsy for nearly a century. Recently, beneficial results have also been reported on metabolic disorders and neurodegeneration, designating aged individuals as possible recipients. However, KDs efficacy decrease after the suckling period, and very little is known about their impact on the aging brain. In the present study, the effect on the neuronal energetic supply of a KD containing 20% of medium chain triglycerides (MCT) was investigated in Purkinje cells of the cerebellar vermis of late-adult (19-month-old) rats. The animals were fed with the KD for 8 weeks, and succinic dehydrogenase (SDH) activity was cytochemically determined. The following parameters of SDH-positive mitochondria were evaluated by the use of a computer-assisted image analysis system connected to a transmission electron microscope: numeric density (Nv), average volume (V), volume density (Vv), and cytochemical precipitate area/mitochondrial area (R). Young, age-matched, and old animals fed with a standard chow were used as controls. We found significantly higher Nv in MCT-KD-fed rats vs. all the control groups, in young vs. late-adult and old controls, and in late-adult vs. old controls. V and Vv showed no significant differences among the groups. R was significantly higher in MCT-KD-fed rats vs. all the control animals, and in old vs. young and late-adult controls. Present data indicate that the ketogenic treatment counteracted age-related decrease in numeric density of SDH-positive mitochondria, and enhanced their metabolic efficiency. Given the central role of mitochondrial impairment in age-related physio-pathological changes of the brain, these findings may represent a starting point to examine novel potentialities for KDs.     

Ergodicity of a Single Particle Confined in a Nanopore

We analyze the dynamics of a gas particle moving through a nanopore of adjustable width with particular emphasis on ergodicity. We give a measure of the portion of phase space that is characterized by quasiperiodic trajectories which break ergodicity. The interactions between particle and wall atoms are mediated by a Lennard-Jones potential, so that an analytical treatment of the dynamics is not feasible, but making the system more physically realistic. In view of recent studies, which proved non-ergodicity for systems with scatterers interacting via smooth potentials, we find that the non-ergodic component of the phase space for energy levels typical of experiments, is surprisingly small, i.e. we conclude that the ergodic hypothesis is a reasonable approximation even for a single particle trapped in a nanopore. Due to the numerical scope of this work, our focus will be the onset of ergodic behavior which is evident on time scales accessible to simulations and experimental observations rather than ergodicity in the infinite time limit.     

Passively Q-switched Tm:YLF laser

Stable passive Q-switching of a Tm: LiYF4 laser is obtained using polycrystalline Cr2+: ZnS as a saturable absorber. The achieved maximum pulse energy of 0.9 mJ and peak power of 65 kW for a pulse duration of ～14 ns represent substantial improvement and highest values for a passively Q-switched diode-pumped Tm laser operating at ～1.9 μm.     

Shear banding in biphasic liquid-liquid systems

In this Letter, we present the first systematic report of shear-induced banding in microconfined biphasic liquid-liquid systems, i.e., formation of alternating regions of high and low volume fraction of dispersed-phase droplets in a parallel plate flow cell. Such a flow-driven, gap-dependent phenomenon is only observed at low values of the viscosity ratio between the dispersed and the continuous phase, and in a given range of the applied shear rate. Based on rheological measurements, band formation is found to be associated with a viscosity decrease as compared to the homogeneous, structureless case, thus showing that system microstructure is somehow evolving towards reduced viscous dissipation under shear flow.     

Entropy Production in Stochastic Systems with Fast and Slow Time-Scales

The behavior of stochastic systems with interacting fast and slow degrees of freedom is investigated both for discrete and continuous processes. Effective equations that govern the process on the slow timescale are derived by asymptotic methods, both for the propagator and the entropy production of the systems. It is found that in general the result of the limiting procedure for entropy does not coincide with the one defined for the effective slow process and features an additional contribution. The specific conditions under which such a correction does or does not arise are stated and the general explicit form of this remnant entropy production is offered. Finally, the fluctuation theorems that are satisfied by this additional term are given.     

Polarization splitter based on a square-lattice photonic-crystal fiber

A three-core polarization splitter based on a square-lattice photonic-crystal fiber is presented. The component separates the input field into two orthogonally polarized beams that are coupled to the horizontal and vertical output ports. The splitter has been designed through modal and beam propagation analysis by employing high-performance codes based on the finite-element method. Results obtained for a device length of 20 mm show extinction ratios as low as -23 dB with bandwidths as great as 90 nm.