Probing excited-state dynamics and intramolecular proton transfer in 1-acylaminoanthraquinones via the intermolecular solvent response

The dynamics of a series of 1-acylaminoanthraquinones with varying degrees of excited-state intramolecular proton transfer are studied in acetonitrile and dichloromethane. Events are followed via changes in the third-order intermolecular Raman response as a function of time after resonant excitation of the chromophore. Compared to electronically resonant probes of the solute, measuring the ultrafast dynamics using the nonresonant solvent response offers a new and complementary perspective on the events that accompany excitation and proton transfer. Experimentally observed changes in the nuclear polarizability of the solvent follow dynamic changes in the solvent-solute interactions. Reorganization of the solvent in response to the significant changes in the intermolecular interactions upon proton transfer is found to play an important role in the reaction dynamics. With transfer of the proton taking place rapidly, the solvent controls the dynamics via the time-dependent evolution of the free energy surface, even on subpicosecond time scales. In addition, the solvent response probes the effects of intermolecular energy transfer as energy released during the reactive event is rapidly transferred to the local solvent environment and then dissipates to the bulk solvent on about a 10 ps time scale. A brief initial account of a portion of this work has appeared previously, J. Am. Chem. Soc. 2004, 126, 8620-8621.     

New insight in the role of modifying ligands in the sol-gel processing of metal alkoxide precursors: A possibility to approach new classes of materials

This paper summarizes recent literature data and presents new experimental data on the mechanisms of chemical modification, hydrolysis and polycondensation of the alkoxides and demonstrates possibilities to approach new classes of materials, exploiting these mechanisms. Low reactivity of silicon alkoxides is improved by either basic catalysis exploiting an S_N2 mechanism or acidic catalysis facilitating a proton-assisted S_N1 mechanism as well as by modification with chelating ligands. Metal alkoxides are much stronger Lewis bases compared to silicon alkoxides and the acidity of water is strong enough to achieve their rapid hydrolysis via proton-assisted S_N1 pathway even in the absence of additional catalysts. Introduction of the modifying chelating ligands is leading generally to increased charge distribution in the precursor molecules. Modifying chelating ligands are also appreciably smaller than the alkoxide ligands they replace. The modification with chelating ligands is thus facilitating the kinetics of hydrolysis and polycondensation. The size and shape of the primary particles formed in sol-gel treatment of metal alkoxides are defined not by kinetic factors in their hydrolysis and polycondensation but by the interactions on the phase boundary, which is in its turn directed by the ligand properties. The products of the fast hydrolysis and condensation sequence consist of micelles templated by self-assembly of ligands (mainly oxo-species). This concept provides explanations for commonly observed material properties and allows for the development of new strategies for the preparation of materials. We discuss the formation of inverted micelles, obtained by the appropriate choice of solvents, which allows for the formation of hollow spheres. The modifying β-diketonate ligands act as the surfactant and form an interface between the hollow sphere and the solvent. Retention of ligands inside the gel particles is possible only if ligands possessing both chelating and bridging properties are applied. Application of such ligands, for example, diethanolamine, permits to prepare new transition metal oxide based microporous membranes.     

Photolithographic production of glass sample holders for improved sensitivity and resolution in ESR microscopy

Electron spin resonance microscopy (ESRM) is an imaging method aiming at the observation of stable free radicals in small samples with a spatial resolution of about 1 micrometer. One of the challenges associated with the useof ESRM in conjunction with small biological samples (e.g., single cells) is containing these samples in a manner that will minimize the effect on the quality factor of the resonator but yet enable easy handling and simultaneous optical and ESR observation. Here we present a new type of flat samples that provide an adequate answer to this challenge. The samples are made of thin glass coverslips, manufactured by photolithography techniques. Details of the manufacturing process as well as the expected improvements in sensitivity and resolution are provided.     

Refraction and ultra‐small‐angle scattering of X‐rays in a single‐crystal diamond compound refractive lens

In this work a double‐crystal setup is employed to study compound refractive lenses made of single‐crystal diamond. The point spread function of the lens is calculated taking into account the lens transmission, the wavefront aberrations, and the ultra‐small‐angle broadening of the X‐ray beam. It is shown that, similarly to the wavefront aberrations, the ultra‐small‐angle scattering effects can significantly reduce the intensity gain and increase the focal spot size. The suggested approach can be particularly useful for the characterization of refractive X‐ray lenses composed of many tens of unit lenses.     

Pulse acoustic microscopy characterization of the elastic properties of nanostructured metal-nanocarbon composites (Declercq/ICU'07)

New metal-nanocarbon composites were obtained by high-energy (ball milling) pre-treatment of the powder mixture followed by high-pressure/high-temperature treatment. Acoustic microscopy was used to study elastic properties and bulk irregularities of the samples.     

Studies with one- and two-proton drip line nuclei

In recent experiments at GANIL, we studied nuclei at the one- and two-proton drip line. The production rates allowed to search for direct 2p emission in the drip line nuclei ⁴²Cr, ⁴⁵Fe, and ⁴⁹Ni. No evidence for this decay mode was found in ⁴²Cr and ⁴⁹Ni, whereas the situation stays unclear for ⁴⁵Fe due to the limited statistics. In the medium-mass region ( A = 50-70), the half-life was measured for all proton-rich nuclei in the range T _z = 0 to T _z = - 1 between Z = 27 and Z = 36. First half-lives were determined for ⁶⁰Ga, ⁶²Ge, ⁶⁴As and ⁶⁶Se. Finally, β-decay studies of the 0⁺ → 0⁺ decay of ⁶²Ga have been performed at IGISOL in Jyv?skyl?. Non-analog transitions have been observed and are compared to theoretical predictions. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: blank@cenbg.in2p3.fr     

Surfaces of transport in non-Euclidean spaces

This paper is a survey of results on the generalized Lie problem of surfaces carrying more than one net of transport and its connections with kinematic geometry.Translated from Itogi Nauki i Tekhniki. Problemy Geometrii, Vol. 8, pp. 183–196, 1977.