Conformational analysis of hydrazones. 1H dynamic nuclear magnetic resonance and solvent effects in aryl- and 2-furylaldehyde ethylaminoacetylhydrazones

Aryl- and 2-furylaldehyde ethylaminoacetylhydrazones were examined in different solvents and over a wide temperature range with ¹H NMR in order to study their conformational properties. Nearly equal amounts of the E/Z isomers, relative to the C?N bond, are present, even when the solvents and the substituents on the aldimino carbon produce small changes in the isomeric mixture. The activation parameters of the thermal isomerization process were measured, and the results are in the line with a lateral-shift type mechanism, also supported by theoretical calculations on a model compound. No other internal process was noted from the low-temperature spectral behaviour, and this was interpreted in terms of a highly biased equilibrium concerning the rotation around the C(O)? N bond. Chemical shifts obtained in different solvents also enable the most stable arrangement of the whole molecule of these compounds to be postulated.     

Space tensors in general relativity II: Physical applications

The general theory of space tensors is applied to the study of a space-time manifoldsV ₄ carrying a distinguished time-like congruence Γ. The problem is to determine a physically relevant spatial tensor analysis over (V ₄, Γ), in order to proceed to a correct formulation of Relative Kinematics and Dynamics. This is achieved by showing that each choice of gives rise to a corresponding notion of ‘frame of reference’ associated with the congruence Γ. In particular, the frame of reference (Γ, ∇*) determined by the standard spatial tensor analysis is shown to provide the most natural generalization of the concept of frame of reference in Classical Physics. The previous arguments are finally applied to the study of geodesic motion inV ₄. As a result, the general structure of the gravitational fields in the frame of reference (Γ, ∇*) is established. This work was assisted by funds from the C.N.R. under the aegis of the activity of the National Group for Mathematical Physics.     

On the renormalization method: a different outlook,and the energy-momentum tensor in the gφ4 theory

An alternate method of renormalizing a quartic self-interacting boson theory has been developed. We find that one can obtain finite renormalized expressions for the perturbation theory contributions to the Green's function without carrying out limiting procedures. As a consequence of the analysis, one is able to renormalize explicitly the field energy-momentum tensor to all orders. There exists a one-parameter family of renormalized tensors. The method will allow for a simple determination of the asymptotic “zero-mass” theory.     

Research on heterocyclic compounds. XIII. Synthesis of 4,5-dihydro-5-oxo-3-isoxazoleacetic acid and related compounds

Some new 4,5-dihydro-5-oxoisoxazole derivatives were synthesized as part of a study to prepare potential antiinflammatory agents. The reaction of the diethyl ester of 3-oxopentanedioic acid with hydroxylamine afforded the 3-hydroxyimino derivative, which was then cyclized to the title compound. This reacted with diazomethane to give a couple of isomeric methyl derivatives, namely methyl 2,5-dihydro-2-methyl-5-oxo-3-isoxazoleacetate and methyl 5-methoxy-3-isoxazoleacetate. Reaction of these compounds with ammonia gave the corresponding acetamides. All compounds were characterized by elemental analysis, uv, ir, and ¹H-nmr spectra.     

Thermal conductivities of molecular liquids by reverse nonequilibrium molecular dynamics

The reverse nonequilibrium molecular dynamics method for thermal conductivities is adapted to the investigation of molecular fluids. The method generates a heat flux through the system by suitably exchanging velocities of particles located in different regions. From the resulting temperature gradient, the thermal conductivity is then calculated. Different variants of the algorithm and their combinations with other system parameters are tested: exchange of atomic velocities versus exchange of molecular center-of-mass velocities, different exchange frequencies, molecular models with bond constraints versus models with flexible bonds, united-atom versus all-atom models, and presence versus absence of a thermostat. To help establish the range of applicability, the algorithm is tested on different models of benzene, cyclohexane, water, and n-hexane. We find that the algorithm is robust and that the calculated thermal conductivities are insensitive to variations in its control parameters. The force field, in contrast, has a major influence on the value of the thermal conductivity. While calculated and experimental thermal conductivities fall into the same order of magnitude, in most cases the calculated values are systematically larger. United-atom force fields seem to do better than all-atom force fields, possibly because they remove high-frequency degrees of freedom from the simulation, which, in nature, are quantum-mechanical oscillators in their ground state and do not contribute to heat conduction.     

Optical characterization of ultrasmall Si nanoparticles prepared through electrochemical dispersion of bulk Si

Studying the properties and stability of silicon nanoparticles (Si-np) in aqueous environments may lead to novel applications in biological systems. In this work, we use absorption and photoluminescence (PL) spectroscopy to characterize ultrasmall Si-np prepared through anodic etching and ultrasonic fractionation of a crystalline Si wafer. Their behavior is studied over time in 2-propanol and during treatments with water, NaOH, HCl, and H(2)O(2). The observed population is divided into two types of material: bright species consisting of well-etched Si-np, approximately 1 nm in diameter, and dark species derived from partially etched or aggregated Si structures. The dark material is seen by its scattering in the 2-propanol and water solutions and is largely removed via precipitation with the NaOH or HCl treatment. The bright material includes three distinct species with their respective emissions in the UV-B, UV-A, and hard-blue regions of the spectrum. The hard-blue PL is shown to have a simple pH dependence with a pK(a) approximately 3, providing an important insight into its chemical origin and signaling for possible application of Si-np as environmental probes. Our results offer some potential for tailoring the PL properties of ultrasmall Si-np through control of their surface chemistry.     

Enhancement of a 24.77-nm line emitted by the plasma of a boron nitride capillary discharge irradiated by a high-intensity ultrashort laser pulse

Investigations of plasma produced by a boron nitride capillary discharge irradiated with a guided 20-TW Ti: sapphire laser pulse at a peak intensity of 4 x 10(18) W/cm2 are presented. The guided laser radiation in the plasma channel generated He-like ions that, subject to suitable plasma temperature, recombined into Li-like nitrogen ions. Intense radiation at a wavelength of 24.77 nm was observed, indicating possible lasing at the 3d(5/2) - 2p(3/2) transition in Li-like nitrogen.     

Osculating spaces to secant varieties

We generalize the classical Terracini’s Lemma to higher order osculating spaces to secant varieties. As an application, we address with the so-called Horace method the case of thed-Veronese embedding of the projective 3-space. This research is part of the T.A.S.C.A. project of I.N.d.A.M., supported by P.A.T. (Trento) and M.I.U.R. (Italy).