Migratory aptitudes of simple alkyl groups in the anionotropic rearrangement of quaternary chloromethyl borate species: a combined experimental and theoretical investigation

A combined experimental and theoretical investigation at the DFT and MP2 levels on the boron-to-carbon 1,2-shift in "ate species", coming from the quaternization of boranes (A) and boronate (B), is reported. To discuss the different migratory aptitudes of various alkyl groups, we have examined the migration of primary (R = Me, Et), secondary (R = i-Pr), and tertiary (R = t-Bu) alkyl groups. The effect of the counterion Li(+) and of the solvent (polarized continuous model (PCM) method) has been considered. The following results are relevant: (a) in all cases, the reaction proceeds via a concerted-type mechanism which explains the retention of configuration at the migrating group and the inversion at the migration terminus experimentally observed. (b) The trend of the migration barriers along the direction primary --> secondary --> tertiary alkyl group observed in "ate" species A is reversed in boronate species B, in agreement with the experimental evidences. (c) A simple theoretical model is proposed where the barrier trend is the result of a delicate interplay between two opposite factors: (1) a "steric effect", which favors the most sterically demanding migrating groups, and (2) a "charge effect" associated with the partial carbanionic nature of the migrating carbon atom and which favors the less substituted migrating carbons.     

The Specific-Force Performance Parameter for Electromagnetic Launchers

A new electromagnetic-launcher (EML) performance parameter called the specific force is presented and analyzed in this paper. The specific force is the second derivative of the EML's force equation with respect to current and represents the force generated by the EML per unit square ampere, i.e., the EML's current efficiency. The specific force is independent of operating current and is defined for EMLs utilizing linear and nonlinear magnetic materials. The second derivative is termed as the specific force, since it unifies the various EML geometries so that only one force equation is required. The specific force, together with the energy-conversion efficiency, can be used as criterion to evaluate and compare EML geometries for various applications. The specific force for conventional railguns, augmented railguns, conventional helical launchers, and high-efficiency helical launchers is derived in this paper. The experimental performance of conventional railguns, augmented railguns, and conventional helical launchers are also analyzed in terms of their specific-force parameters.      

Trade-offs between Error Exponents and Excess-Rate Exponents of Typical Slepian–Wolf Codes

Typical random codes (TRCs) in a communication scenario of source coding with side information in the decoder is the main subject of this work. We study the semi-deterministic code ensemble, which is a certain variant of the ordinary random binning code ensemble. In this code ensemble, the relatively small type classes of the source are deterministically partitioned into the available bins in a one-to-one manner. As a consequence, the error probability decreases dramatically. The random binning error exponent and the error exponent of the TRCs are derived and proved to be equal to one another in a few important special cases. We show that the performance under optimal decoding can be attained also by certain universal decoders, e.g., the stochastic likelihood decoder with an empirical entropy metric. Moreover, we discuss the trade-offs between the error exponent and the excess-rate exponent for the typical random semi-deterministic code and characterize its optimal rate function. We show that for any pair of correlated information sources, both error and excess-rate probabilities exponential vanish when the blocklength tends to infinity.     

Synthetic approaches to 5,7-disubstituted imidazo[5,1-f][1,2,4]triazin-4-amines

The preparation of 5,7-disubstituted imidazo[5,1-f][1,2,4]triazin-4-amines, exemplified by 5-[3-(benzyloxy)phenyl]-7-cyclobutylimidazo[5,1-f][1,2,4]triazin-4-amine, was developed through a linear and three convergent synthetic strategies, with the latter providing the greatest flexibility for diversification at the 5-position at the last step of the synthesis.     

Synthesis and Study of the Photophysical Properties of a New Eu<Superscript>3+</Superscript> Complex with 3-Hydroxypicolinamide

This work reports on the synthesis and characterization of a new complex of Eu³⁺ with the 3-hydroxypicolinamide ligand (Hhpa). Here we present an approach for obtaining bis[2-carbamoyl(κO)pyridin-3-olato(κO’)] lanthanide complexes, which were characterized through elemental analysis, thermal analysis, infrared and photoluminescence spectroscopies (emission, excitation, luminescence lifetimes, quantum efficiencies, Judd-Ofelt parameters and quantum yields). Although hpa can act as a bidentate ligand in different conformations, the results attest for the occurrence of a unique coordination site of low symmetry for the Eu³⁺ ions, in which two anionic hpa ligands coordinate the cations through an O/O chelating system. The phosphorescence of the synthesized gadolinium complex provides the energy of the triplet state, which is determined to be at 20,830 cm^-1 over the ground state. This makes the Hhpa ligand very adequate for sensitizing the Eu³⁺ luminescence, which leads to a very efficient antenna effect and opens a wide range of applications for the complex in light emitting organic-inorganic devices.     

Totally asymmetric simple exclusion process on networks

We study the totally asymmetric simple exclusion process (TASEP) on complex networks, as a paradigmatic model for transport subject to excluded volume interactions. Building on TASEP phenomenology on a single segment and borrowing ideas from random networks we investigate the effect of connectivity on transport. In particular, we argue that the presence of disorder in the topology of vertices crucially modifies the transport features of a network: irregular networks involve homogeneous segments and have a bimodal distribution of edge densities, whereas regular networks are dominated by shocks leading to a unimodal density distribution. The proposed numerical approach of solving for mean-field transport on networks provides a general framework for studying TASEP on large networks, and is expected to generalize to other transport processes.     

Noble metal nanoparticles produced by nanosecond laser ablation

Silver and gold thin films were deposited by pulsed laser ablation in a controlled Ar atmosphere at pressures between 10 and 100 Pa. Different morphologies, ranging from isolated nanoparticle arrays up to nanostructured thin films were observed. Fast imaging of the plasma allowed deducing the expansion dynamics of the ablated plume. Plasma velocity and volume were used together with the measured average ablated mass per pulse as input parameters in a model to estimate the average size of nanoparticles grown in the plume. The nanoparticle size is expected to decrease from 4 nm down to 1 nm with decreasing Ar pressure between 100 and 10 Pa: this was confirmed by transmission electron micrographs which indicate a reduced dispersion of particle size over narrow size ranges. The production of substrates for surface enhanced Raman scattering whose performances critically depend on nanoparticle size, shape, and structure is discussed.     

The application of Stille cross-coupling reactions with multiple nitrogen containing heterocycles

Substituted imidazoles and purine bioisosteres have been widely studied in the literature. We endeavored to combine these heterocyclic core structures into precursors, especially 7-azaindoles, of previously unknown pharmacologically relevant lead structures. A highly flexible synthetic procedure was developed, derived from investigations of the influence of the substrates, solvents, ligand systems, and side reactions.