Parahydrogen-Induced Polarization in Heterogeneous Hydrogenations over Silica-Immobilized Rh Complexes

The use of heterogeneous catalysts for parahydrogen-induced polarization (PHIP) of nuclear spins opens new horizons for production of hyperpolarized substances. Immobilization of homogeneous hydrogenation catalysts is a promising approach for designing the efficient heterogeneous catalytic systems capable of PHIP generation. Herein, we study the formation of PHIP in the gas-phase and in the liquid-phase hydrogenations of propyne and propylene catalyzed by silica-immobilized Rh complexes synthesized by the ligand-exchange anchoring of the Wilkinson’s complex RhCl(PPh₃)₃, the binuclear complex Rh₂Cl₂(C₈H₁₂)₂ and the cationic complex [Rh(C₈H₁₂)₂]⁺[BF₄]^? to the phosphine-modified silica gel. We consider the stability and the mechanistic aspects of the hydrogenation over the immobilized Wilkinson’s catalyst in terms of PHIP observation. Using a PASADENA (parahydrogen and synthesis allow dramatically enhanced nuclear alignment) effect, it is found, in particular, that liquid-phase propyne hydrogenation over the immobilized Wilkinsons’s catalyst at 70°C proceeds in a stable regime with a stereoselective cis addition of a hydrogen molecule, while in the gas phase at the same temperature the hydrogenation stereoselectivity is observed only for a short time after the reaction is started, and then the catalyst rapidly loses its activity. The reasons of the catalyst deactivation are discussed based on the literature data, the results of infrared spectroscopy study, and the comparison to the behavior of the immobilized binuclear and cationic Rh complexes. In addition, it is shown that the immobilized Wilkinson’s catalyst is reduced as temperature increases in the range of 90–130°C, as confirmed by X-ray photoelectron spectroscopy.     

Mesoscale and clusters of synchrony in networks of bursting neurons

We study the role of network architecture in the formation of synchronous clusters in synaptically coupled networks of bursting neurons. We give a simple combinatorial algorithm that finds the largest synchronous clusters from the network topology. We demonstrate that networks with a certain degree of internal symmetries are likely to have cluster decompositions with relatively large clusters, leading potentially to cluster synchronization at the mesoscale network level. We also address the asymptotic stability of cluster synchronization in excitatory networks of Hindmarsh-Rose bursting neurons and derive explicit thresholds for the coupling strength that guarantees stable cluster synchronization.     

Continuous monitoring of dough fermentation and bread baking by magnetic resonance microscopy

The consumer quality of baked products is closely related with dough structure properties. These are developed during dough fermentation and finalized during its baking. In this study, magnetic resonance microscopy (MRM) was employed in a study of dough fermentation and baking. A small hot air oven was installed inside a 2.35-T horizontal bore superconducting magnet. Four different samples of commercial bread mixes for home baking were used to prepare small samples of dough that were inserted in the oven and allowed to rise at 33°C for 112 min; this was followed by baking at 180°C for 49 min. The entire process was followed by dynamic T₁-weighted 3D magnetic resonance imaging with 7 min of temporal resolution and 0.23×0.23×1.5 mm³ of spatial resolution. Acquired images were analyzed to determine time courses of dough pore distribution, dough volume and bread crust thickness. Image analysis showed that both the number of dough pores and the normalized dough volume increased in a sigmoid-like fashion during fermentation and decreased during baking due to the bread crust formation. The presented magnetic resonance method was found to be efficient in analysis of dough structure properties and in discrimination between different dough types.     

The system Na2CO3–CaCO3–MgCO3 at 6 GPa and 900–1250°C and its relation to the partial melting of carbonated mantle

In order to constrain the Na₂CO₃–CaCO₃–MgCO₃ T–X diagram at 6?GPa in addition to the binary and pseudo-binary systems we conducted experiments along the Na₂CO₃–Ca_0.5Mg_0.5CO₃ join. At 900–1000°C, melting does not occur and isothermal sections are presented by one-, two- and three-phase regions containing Ca-bearing magnesite, aragonite, Na₂CO₃ (Na₂) and Na₂(Ca_1–0.9Mg_0-0.1)_3-4(CO₃)_4-5 (Na₂Ca_3-4), Na₄(Ca_1–0.6Mg_0–0.4)(CO₃)₃ (Na₄Ca), Na₂(Ca_0-0.08Mg_1–0.92)(CO₃)₂ (Na₂Mg) phases with intermediate compositions. The minimum melting point locates between 1000°C and 1100°C. This point would resemble that of three eutectics: Mgs–Na₂Ca₃–Na₂Mg, Na₂Mg–Na₂Ca₃–Na₄Ca or Na₂Mg–Na₄Ca–Na₂, in the compositional interval of [45Na₂CO₃·55(Ca_0.6Mg_0.4)CO₃]–[60Na₂CO₃·40Ca_0.6Mg_0.4CO₃]. The liquidus projection has seven primary solidification phase regions for Mgs, Dol, Arg, Na₂Ca₃, Na₄Ca, Na₂ and Na₂Mg. The results suggest that extraction of Na and Ca from silicate to carbonate components has to decrease minimum melting temperature of carbonated mantle rocks to 1000–1100°C at 6?GPa and yields Na-rich dolomitic melt with a Na# (Na₂O/(Na₂O?+?CaO?+?MgO))?≥?28?mol%.     

Pair creation in QED-strong pulsed laser fields interacting with electron beams

QED effects are known to occur in a strong laser pulse interaction with a counterpropagating electron beam, among these effects being electron-positron pair creation. We discuss the range of laser pulse intensities of J≥5×10(22) W/cm2 combined with electron beam energies of tens of GeV. In this regime multiple pairs may be generated from a single beam electron, some of the newborn particles being capable of further pair production. Radiation backreaction prevents avalanche development and limits pair creation. The system of integro-differential kinetic equations for electrons, positrons and γ photons is derived and solved numerically.     

Monte Carlo方法模拟光在生物组织中传播的新进展

Monte Carlo方法已被广泛用于模拟复杂的随机介质如生物组织中光的辐射传输.在生物光子应用中,早期的Monte Carlo模拟模型忽略了光在组织中传输的波动性,而用中性粒子光子包来模拟其传播过程.然而,许多光学诊断技术是基于光在组织中的偏振效应和多重散射的相干性来揭示组织的生理和病理信息,这就要涉及光辐射的波动性.本文阐述了用Monte Carlo方法模拟光在生物组织中传播的最新进展.     

Distortion-free single point imaging of multi-layered composite sandwich panel structures

The results of a magnetic resonance imaging (MRI) investigation concerning the effects of an aluminum honeycomb sandwich panel on the B1 and B0 fields and on subsequent image quality are presented. Although the sandwich panel structure, representative of an aircraft composite material, distorts B0 and attenuates B1, distortion-free imaging is possible using single point (constant time) imaging techniques. A new expression is derived for the error caused by gradient field distortion due to the heterogeneous magnetic susceptibility within a sample and this error is shown not to cause geometric distortion in the image. The origin of the B0 distortion in the sample under investigation was also examined. The graphite-epoxy 'skin' of the panel is the principal source of the B0 distortion. Successful imaging of these structures sets the stage for the development of methods for detecting moisture ingress and degradation within composite sandwich structures.     

Polarization control of optical transmission of a periodic array of elliptical nanoholes in a metal film

The spectral dependences of polarized optical transmission of a metal film with a periodic array of elliptical nanoholes have been studied. Such nanostructured metal films exhibit enhanced broadband optical transmission that one can control by selecting the polarization of incident and (or) transmitted light.     

Phase analysis of quantum oscillations in graphite

The quantum de Haas-van Alphen (dHvA) and Shubnikov-de Haas oscillations measured in graphite were decomposed by pass-band filtering onto contributions from three different groups of carriers. Generalizing the theory of dHvA oscillations for 2D carriers with an arbitrary spectrum and by detecting the oscillation frequencies using a method of two-dimensional phase-frequency analysis which we developed, we identified these carriers as (i) minority holes having a 2D parabolic massive spectrum p(2)(perpendicular)/2m(perpendicular), (ii) massive majority electrons with a 3D spectrum and (iii) majority holes with a 2D Dirac-like spectrum +/-vp(perpendicular) which seems to be responsible for the unusual strongly-correlated electronic phenomena in graphite.