Preparation of luminescent Si nanoparticles by tailoring the size,crystallinity and surface composition

The preparation of sizeable quantities of luminescent Si nanoparticles (Si-np) with controlled morphology is a challenging task. Here, we describe two strategies aiming at size reduction of the Si-np produced in a laser-assisted silane pyrolysis reactor without detrimental effects on the process yield and on the nanoparticle structural and compositional properties. The first method is based on the addition of a sensitizer gas to dilute silane and consequently reduce the nucleation centres density without decreasing the reaction temperature. The second consists in the introduction of a collector at a variable distance from the irradiated region to freeze the particle growth and decrease the inter-particle sintering probability. We report on the characterization of the produced Si-np, and we show that by combining the two methods, we are able to prepare 4 nm crystalline core size nanoparticles with a productivity of 1 g per hour. We also describe the enhancement effect of the wet-chemical oxidation processes on the luminescence emission intensity of the Si-np.     

Dense plasma diagnostics with an amplitude-division soft-x-ray laser interferometer based on diffraction gratings

We report the demonstration of an amplitude-division soft-x-ray interferometer that can be used to generate high-contrast interferograms at the wavelength of any of the saturated soft-x-ray lasers (5.6-46.9 nm) that are available at present. The interferometer, which utilizes grazing-incidence diffraction gratings as beam splitters in a modified Mach-Zehnder configuration, was used in combination with a tabletop 46.9-nm laser to probe a large-scale (~2.7-mm-long) laser-created plasma.     

Renormalization group for Markov chains and application to metastability

In this paper we introduce a new renormalization group method for the study of the long-time behavior of Markov chains with finite state space and with transition probabilities exponentially small in an external parameter. A general approach of metastability problems emerges from this analysis and is discussed in detail in the case of a two-dimensional Ising system at low temperature,     

Saturated high-repetition-rate 18.9-nm tabletop laser in nickellike molybdenum

We report saturated operation of an 18.9-nm laser at 5-Hz repetition rate. An amplification with a gain-length product GL of 15.5 is obtained in the 4d 1S0-4p 1P1 laser line of Ni-like Mo in plasmas heated at grazing incidence with approximately 1-J pulses of 8.1-ps duration from a tabletop laser system. Lasing is obtained over a broad range of time delays and pumping conditions. We also measure a GL of 13.5 in the 22.6-nm transition of the same ion. The results are of interest for numerous applications requiring high-repetition-rate lasers at wavelengths below 20 nm.     

Therapeutic Potential of Highly Selective A3 Adenosine Receptor Ligands in the Central and Peripheral Nervous System

Ligands of the G_i protein-coupled adenosine A₃ receptor (A₃R) are receiving increasing interest as attractive therapeutic tools for the treatment of a number of pathological conditions of the central and peripheral nervous systems (CNS and PNS, respectively). Their safe pharmacological profiles emerging from clinical trials on different pathologies (e.g., rheumatoid arthritis, psoriasis and fatty liver diseases) confer a realistic translational potential to these compounds, thus encouraging the investigation of highly selective agonists and antagonists of A₃R. The present review summarizes information on the effect of latest-generation A₃R ligands, not yet available in commerce, obtained by using different in vitro and in vivo models of various PNS- or CNS-related disorders. This review places particular focus on brain ischemia insults and colitis, where the prototypical A₃R agonist, Cl-IB-MECA, and antagonist, MRS1523, have been used in research studies as reference compounds to explore the effects of latest-generation ligands on this receptor. The advantages and weaknesses of these compounds in terms of therapeutic potential are discussed.     

Divergent and solvent dependent reactions of 4-ethoxycarbonyl-3-methyl-1-tert-butoxycarbonyl-1,2-diaza-1,3-diene with enamines

Starting from 1-tert-butyloxycarbonyl-3-methyl-4-ethoxycarbonyl-1,2-diaza-1,3-diene and β,β,β and α,β-substituted enamines a careful choice of solvents and temperatures allows the divergent synthesis of 5,6-dihydro-4H-pyridazines, 2-(1-N-boc-hydrazono-ethyl)-4-pyrrolidin-1-yl-but-3-enoic acid ethyl ester, and 1-amino-pyrroles. Moreover, some interesting conclusions about the mechanism(s) of the reaction have been drawn by careful analysis of products' structure and distribution. Thus, the reaction may proceed through a stereospecific [4+2] cycloaddition mechanism giving rise to 5,6-dihydro-4H-pyridazines or by simple addition or domino addition/cyclization pathways affording, respectively, 2-(1-N-boc-hydrazono-ethyl)-4-pyrrolidin-1-yl-but-3-enoic acid ethyl ester and 1-amino-pyrroles (formally the [3+2] cycloaddition product).     

Captured at last: a catalyst-substrate adduct and a Rh-dihydride solvate in the asymmetric hydrogenation by a Rh-monophosphine catalyst

The mechanism of asymmetric hydrogenation catalyzed by [Rh(NBD)((R)-PhenylBinepine)(2)]SbF(6)1 has been studied by NMR experiments and DFT computations. Either the low-temperature hydrogenation of the catalyst-substrate adduct 4 or the reaction of solvate dihydride 6 with MAC produced the hydrogenation product with over 99% ee (S).     

Multicomponent diffusion in nanosystems

We present the detailed analysis of the diffusive transport of spatially inhomogeneous fluid mixtures and the interplay between structural and dynamical properties varying on the atomic scale. The present treatment is based on different areas of liquid state theory, namely, kinetic and density functional theory and their implementation as an effective numerical method via the lattice Boltzmann approach. By combining the first two methods, it is possible to obtain a closed set of kinetic equations for the singlet phase space distribution functions of each species. The interactions among particles are considered within a self-consistent approximation and the resulting effective molecular fields are analyzed. We focus on multispecies diffusion in systems with short-range hard-core repulsion between particles of unequal sizes and weak attractive long-range interactions. As a result, the attractive part of the potential does not contribute explicitly to viscosity but to diffusivity and the thermodynamic properties. Finally, we obtain a practical scheme to solve the kinetic equations by employing a discretization procedure derived from the lattice Boltzmann approach. Within this framework, we present numerical data concerning the mutual diffusion properties both in the case of a quiescent bulk fluid and shear flow inducing Taylor dispersion.     

An Alternate Solution of Fluorescence Recovery Kinetics after Spot-Bleaching for Measuring Diffusion Coefficients. 2. Diffusion of Fluorescein in Aqueous Sucrose Solutions

The traditional analysis of the fluorescence recovery kinetics after spot bleaching yields expressions for the diffusion coefficient of the probe that are not suitable for linear fittings. In a previous work we developed an improved recovery function that is a better alternative for data analysis. To illustrate its application to real cases and compare it with the previous data treatment, we measured the time response of fluorescein in aqueous sucrose solutions, covering the unsaturated and the supercooled region, where decoupling between diffusion and viscosity is observed. The results are compared with the mobility of different types of solutes in aqueous sucrose solutions and are discussed in terms of the classical hydrodynamic model.     

Measurement of long-range cross-correlation rates using a combination of single- and multiple-quantum NMR spectroscopy in one experiment

A method is described to determine long-range cross-correlations between the modulations of an anisotropic chemical shift (e.g., of a C' carbonyl carbon in a protein) and the fluctuations of a weak long-range dipolar interaction (e.g., in cross-correlation between the same C' carbonyl and the H(N) proton of the neighboring amide group). Such long-range correlations are difficult to measure because the corresponding long-range scalar couplings are so small that Redfield's secular approximation is often violated. The method, which combines features of single- and double-quantum NMR spectroscopy, allows one to cancel the effects of dominant short-range dipolar interactions (e.g., between the CSA of the amide nitrogen N and the dipolar coupling to its attached proton H(N)) and is designed so that the secular approximation is rescued even if the scalar coupling between the long-range dipolar coupling partners is very small. The cross-correlation rates thus determined in ubiquitin cover a wide range because of local motions and variations of the CSA tensors.