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).     

Nature of urea-fluoride interaction: incipient and definitive proton transfer

1,3-bis(4-nitrophenyl)urea (1) interacts through hydrogen bonding with a variety of oxoanions in an MeCN solution to give bright yellow 1:1 complexes, whose stability decreases with the decreasing basicity of the anion (CH3COO- > C6H5COO- > H2PO4- > NO2- > HSO4- > NO3-). The [Bu4N][1.CH3COO] complex salt has been isolated as a crystalline solid and its molecular structure determined, showing the formation of a discrete adduct held together by two N-H...O hydrogen bonds of moderate strength. On the other hand, the F- ion first establishes a hydrogen-bonding interaction with 1 to give the most stable 1:1 complex, and then on addition of a second equivalent, induces urea deprotonation, due to the formation of HF2-. The orange-red deprotonated urea solution uptakes carbon dioxide from air to give the tetrabutylammonium salt of the hydrogencarbonate H-bond complex, [Bu4N][1.HCO3], whose crystal and molecular structures have been determined.     

Models for biological trinuclear copper clusters. Characterization and enantioselective catalytic oxidation of catechols by the copper(II) complexes of a chiral ligand derived from (S)-(-)-1,1'-binaphthyl-2,2'-diamine

The dinuclear and trinuclear Cu(II) complexes of an octadentate ligand derived from (S)-1,1'-binaphthyl-2,2'-diamine have been prepared and characterized by UV/Vis, CD, EPR and NMR spectroscopy. The ligand contains two tridentate aminobis(benzimidazole) donor arms connected to a central bidentate diaminobinaphthyl linker, which hosts the chiral unit. In the dinuclear Cu complex the ligation occurs essentially within the tridentate arms of the ligand. The two Cu centers are EPR nonequivalent and noninteracting. The EPR data suggests that one of the Cu ions additionally interacts with one of the tertiary aminonaphthyl donors. In the trinuclear complex the two aminonaphthyl donors bind the third Cu ion. The EPR spectrum of this complex shows the signal for a mononuclear Cu(II) center bound to a tridentate arm, while the remaining two Cu(II) centers are coupled through hydroxo groups. The CD spectrum shows that in the free ligand a severe reduction of the dihedral angle between the naphthyl groups from the strain free range occurs. This conformation is stabilized by ring stacking interactions with the benzimidazole groups. On complex formation this interaction is removed because the benzimidazole groups are involved in metal binding. In the dinuclear Cu complex the conformation of the binaphthyl chromophore probably approaches the strain free range, while in the trinuclear Cu complex a marked flattening of the dihedral angle between the two naphthyl rings occurs. Both complexes are active catalysts in the oxidation of L-/D-Dopa derivatives to quinones. High enantioselectivity is observed in the oxidation of L-/D-Dopa methyl ester catalyzed by the dinuclear Cu complex, which exhibits strong preference for the d enantiomer. The enantioselectivity is largely lost for the trinuclear Cu complex.     

Oxygenation of calixarene phenol rings

[structure: see text] The first examples of epoxy-p-quinol and diepoxy-p-quinol calixarene derivatives have been obtained by base-promoted direct addition of O(2)(oxygenation) to calixarene phenol rings. The regio- and stereochemistry of these derivatives was determined by 2D NMR studies, in conjunction with MM3 calculations, and X-ray crystallography. Both the oxygenation and the subsequent carbonyl reduction occur with a preferential attack to the less hindered exo face of the calixarene rings.