Chromone-3-carboxylic acid as a potential electron scavenger: a surface-enhanced Raman scattering study

A SERS study of chromone 3-carboxylic acid adsorbed on silver colloids was undertaken, in order to assess the ability of this compound to accept electrons in charge transfer (CT) processes. Theoretical SERS intensities under photoinduced CT resonant conditions have been carried out for both the neutral and the deprotonated species allowing to conclude, by comparison with the experimental data, that the recorded SER corresponds to the anionic form of the acid linked to the metal. It was shown that the SERS-CT mechanism predominates for this particular compound, thus explaining the strong enhancement of the band at ca. 1600 cm(-1) assigned to the 8a ring stretching mode. The identification of CT processes is of the utmost importance for understanding the mechanism through which these benzopyranes may act as antioxidants.     

Deformations of the hemisphere that increase scalar curvature

Consider a compact Riemannian manifold M of dimension n whose boundary ?M is totally geodesic and is isometric to the standard sphere S ^n?1. A natural conjecture of Min-Oo asserts that if the scalar curvature of M is at least n(n?1), then M is isometric to the hemisphere $S_{+}^{n}$ equipped with its standard metric. This conjecture is inspired by the positive mass theorem in general relativity, and has been verified in many special cases. In this paper, we construct counterexamples to Min-Oo??s Conjecture in dimension n??3.     

Series representations for densities functions of a family of distributions—Application to sums of independent random variables

Series representations for several density functions are obtained as mixtures of generalized gamma distributions with discrete mass probability weights, by using the exponential expansion and the binomial theorem. Based on these results, approximations based on mixtures of generalized gamma distributions are proposed to approximate the distribution of the sum of independent random variables, which may not be identically distributed. The applicability of the proposed approximations are illustrated for the sum of independent Rayleigh random variables, the sum of independent gamma random variables, and the sum of independent Weibull random variables. Numerical studies are presented to assess the precision of these approximations.     

Unified approach to superposition states of the quantized radiation field

Summary In the recent years various and interesting superposition states of the quantized radiation field were investigated in the literature, such as that involving two number states by Wodkiewiczet al.; that involving two coherent states by Hillery and Gerryet al.; that involving two squeezed states by Xinet al., etc. Here we study a general one-parameter superposition state which unifies those states and others in the literature, all becoming a particularization of ours. General expressions characterizing the physical properties of the field are obtained. The role played by the present superposition state as an alternative interpolating state is also discussed. The authors of this paper have agreed to not receive the proofs for correction.     

Monadic dynamic algebras

The main purpose of this work is to introduce the class of the monadic dynamic algebras (dynamic algebras with one quantifier). Similarly to a theorem of Kozen we establish that every separable monadic dynamic algebra is isomorphic to a monadic (possibly non‐standard) Kripke structure. We also classify the simple (monadic) dynamic algebras. Moreover, in the dynamic duality theory, we analyze the conditions under which a hemimorphism of a dynamic algebra into itself defines a quantifier. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic and theoretical studies on solid 1,2-ethylenediamine dihydrochloride salt.

A structural study of [H3N(CH2)2NH3)]2+.2Cl-, the smallest element of the homologous series of the alpha,omega-diamine dihydrochlorides, was carried out by means of Raman and FTIR spectroscopy coupled to ab initio molecular orbital (MO) calculations. As a primary concern, an adequate molecular model for the representation of these solid amine salts was chosen. Thus, several models, varying in the number and position of the counterions as well as in the number of diamine units, were considered. It was found that the best molecular system (i.e., that yielding the best compromise between accuracy and computational requirements) consists of one ethylenediamine cation surrounded by six chloride ions in an arrangement based on the crystal structure reported in the literature for [H3N(CH2)2NH3)]2+.2Cl-. This conclusion will hopefully allow for a better understanding of the conformational preferences, in the solid state, of these biologically relevant linear polyamines.     

Properties of C60 polymerized under high pressure and temperature

60 polymers. Pure and mixed phase polymeric samples were synthesized by simultaneously subjecting microcrystalline C₆₀ powder or pellets to various pressures () and temperatures (). The optical spectra of the orthorhombic, tetragonal, and rhombohedral C₆₀ polymer phases are observed to be quite distinct and rich. These spectra exhibit numerous lines and an overall downshift in frequency relative to C₆₀ is observed, consistent with a loss of double bonds from the fullerene cage. The LDMS spectra of a sample synthesized at under hydrostatic conditions and , exhibited a succession of clear peaks at mass numbers corresponding to , similar to the LDMS data on the C₆₀ photopolymer. This is taken as further evidence for interfullerene bonds in these high-pressure polymers. The XRD pattern of this sample indicates the presence of a strong texture in the sample. Received: 14 November 1996/Accepted: 8 January 1997     

Formation of an intermediate phase in the ball milling synthesis of the sillenite phase of BSO and BTO

High-energy ball milling is a relatively new process for the synthesis of technologically useful compounds that require high temperatures in the conventional solid-state reaction method. It is thought that high-impact energy transferred to microscopic amounts of powder momentarily trapped between two colliding balls leads to a local transient of high pressure and temperature that drives the reaction at the surface of the trapped particles. The technique of ball milling has been successfully used to produce nanocrystals of the sillenite phase of bismuth silicate (BSO), and its titanate (BTO) and germanate (BGO) homologues. Our aim in this paper is to see, experimentally, whether passage through an intermediate phase occurs en route to the final product. The results of our study using various analytical techniques show that indeed, in the case of BSO and BTO, an intermediate phase is formed temporarily along the grinding route. The SEM pictures of the powders in the various stages of the grinding process also indicate that a process of phase transformation takes place at the surface of the crystals. We have not been able to identify the precise structure of the intermediate phase, but show that it is an unstable phase that transforms with heat treatment preferentially into the desired sillenite phase in the case of BTO and to the reactants in the case of BSO. PACS 81.20.Ev     

Nature of potential barrier in (Ca1/4,Cu3/4)TiO3 polycrystalline perovskite

The nonohmic electrical features of (Ca_1/4,Cu_3/4)TiO₃ perovskite ceramics, which have very strong gigantic dielectric is believed originate from potential barriers at the grain boundaries. In the present study, we used the admittance and impedance spectroscopy technique to investigate (Ca_1/4,Cu_3/4)TiO₃ perovskite ceramics with low nonohmic electrical properties. The study was conducted under two different conditions: on as-sintered ceramics and on ceramics thermally treated in an oxygen-rich atmosphere. The results confirm that thermal treatment in oxygen-rich atmospheres influence the nonohmic properties. Annealing at oxygen-rich atmospheres improve the nonohmic behavior and annealing at oxygen-poor atmospheres decrease the nonohmic properties, a behavior already reported for common metal oxide nonohmic devices and here firstly evidenced for the (Ca_1/4,Cu_3/4)TiO₃ perovskite related materials. The results show that oxygen also influences the capacitance values at low frequencies, a behavior that is indicative of the Schottky-type nature of the potential barrier.