Photophysics of (1-butyl-4-(1H-inden-1-ylidene)-1,4-dihydropyridine (BIDP): an experimental test for conical intersections

Fluorescence experiments on (1-butyl-4-(1H-inden-1-ylidene)-1,4-dihydropyridine (BIDP) are reported in liquid and glassy solutions. The data indicate a fast decay in the fluid nonpolar, nonprotic solutions (decay times approximately 10(-12) s) and rapid but considerably slower decay in polar ones. In frozen solutions (polar and nonpolar), the fluorescence quantum yield is much higher (near 0.5 and around 0.1 in polar and nonpolar glasses, respectively). The rapid nonradiative transitions in fluid solutions are assigned to internal conversion in both solvent classes, as intersystem crossing is much slower and no net reaction is observed. These results are in agreement with predictions made for the closely related (in terms of electronic structure) but simpler molecule cyclopentadienyl-1,4-dihydropyridine (CPDHP) for which an S1/S0 conical intersection was recently proposed [Int. J. Quant. Chem. 2005, 102, 961]. The crossing of the two lowest singlet states is calculated to vanish in polar solvents such as methyl cyanide, leading to longer lifetime of S1 of CPDHP. As BIDP has a very similar electronic structure, the model predicts a corresponding change in this larger molecule. The strong fluorescence observed in the glassy environments is rationalized by the hindering of the internal torsion required to reach the geometry of the conical intersection.     

Axiplyns A-E, new sesquiterpene isothiocyanates from the marine sponge Axinyssa aplysinoides

Five new isothiocyanate sesquiterpenes, designated axiplyns A-E (1-5) have been isolated, together with two known isothiocyanate sesquiterpenes (6, 7), from the sponge Axinyssa aplysinoides collected at Misali Island, Tanzania. Axiplyns 4 and 5 embody a new indane sesquiterpene skeleton, and compounds 1, 2, and 5 contain unprecedented ring systems, namely a 6,8-dioxabicyclo[3.2.1]octane and a 2-oxabicyclo[2.2.1]heptane. Axiplyns A, B, and C are potent brine shrimp toxins with LD₅₀ values between 1.5 and 1.8 μg/mL.     

Large time behavior of the heat kernel

In this paper we study the large time behavior of the (minimal) heat kernel k_P^M(x,y,t) of a general time-independent parabolic operator Lu=u_t+P(x,∂_x)u which is defined on a noncompact manifold M. More precisely, we prove that

     

Radial vibrations of composite piezoelectric ceramic disks

A theory is developed for the radial vibrations of thin disks composed of several piezoelectric ceramic materials bonded at their cylindrical interfaces. Closed type solutions are obtained for the resonant and antiresonant frequency equations, and numerical results are presented for various steel/PZT-4 composite disks. The frequency spectrums and corresponding electromechanical coupling factors are found to be quite sensitive to the heterogeneity of the considered piezoelectric systems.     

Hadamard products of product operators and the design of gradient-diffusion experiments for simulating decoherence by NMR spectroscopy

An extension of the product operator formalism of NMR is introduced, which uses the Hadamard matrix product to describe many simple spin 1/2 relaxation processes. The utility of this formalism is illustrated by deriving NMR gradient-diffusion experiments to simulate several decoherence models of interest in quantum information processing, along with their Lindblad and Kraus representations.     

Macroscopic modelling of transport phenomena in porous media. 1: The continuum approach

This is the first of two papers presenting a systematic development of a continuum model of a porous medium and of transport processes occurring in it. The concept of a Representative Elementary Volume (REV) as opposed to any arbitrary volume of averaging quantities at the micro-scale, is quantified. A universal criterion for selecting the size of an REV as a function of measurable characteristics of a porous medium and selected tolerance levels of estimation errors, is developed. The rules of spatial averaging are extended by including the effects of both the configuration of the solid matrix and of interphase transfer phenomena within an REV.     

Blue fluorescent dye-protein complexes based on fluorogenic cyanine dyes and single chain antibody fragments

Fluoromodules are complexes formed upon the noncovalent binding of a fluorogenic dye to its cognate biomolecular partner, which significantly enhances the fluorescence quantum yield of the dye. Previously, several single-chain, variable fragment (scFv) antibodies were selected from a yeast cell surface-displayed library that activated fluorescence from a family of unsymmetrical cyanine dyes covering much of the visible and near-IR spectrum. The current work expands our repertoire of genetically encodable scFv-dye pairs by selecting and characterizing a group of scFvs that activate fluorogenic violet-absorbing, blue-fluorescing cyanine dyes, based on oxazole and thiazole heterocycles. The dye binds to both yeast cell surface-displayed and soluble scFvs with low nanomolar K(d) values. These dye-protein fluoromodules exhibit high quantum yields, approaching unity for the brightest system. The promiscuity of these scFvs with other fluorogenic cyanine dyes was also examined. Fluorescence microscopy demonstrates that the yeast cell surface-displayed scFvs can be used for multicolor imaging. The prevalence of 405 nm lasers on confocal imaging and flow cytometry systems make these new reagents potentially valuable for cell biological studies.     

Complementary mild-slope equations in a two-layer fluid

Mild-slope (MS) type equations are depth-integrated models, which predict under appropriate conditions refraction and diffraction of linear time-harmonic water waves. By using a streamfunction formulation instead of a velocity potential one, the complementary mild-slope equation (CMSE) was shown to give better agreement with exact linear theory compared to other MS-type equations. The main goal of this work is to extend the CMSE model for solving two-layer flow with a free-surface. In order to allow for an exact reference, an analytical solution for a two-layer fluid over a sloping plane beach is derived. This analytical solution is used for validating the results of the approximated MS-type models. It is found that the two-layer CMSE model performs better than the potential based one. In addition, the new model is used for investigating the scattering of linear surface water waves and interfacial ones over variable bathymetry.     

Correlation of finite strain measures

A numerical scheme for correlating any two finite strain measures is given, and situations in which such a scheme might be used are introduced. A check is established by comparison with the Reiner-Hanin solution of the Almansi-to-Hencky conversion. A numerical example is provided.     

Effect of Substituents and of Wavelength of Irradiation on the Photo-Fries-Rearrangement of Enol-Esters Preliminary Communication

Enol-esters 1a-1e undergo clean Photo-Fries-rearrangements without side reactions. With anthroyl derivatives the reaction is observed only at 254 nm, not at 366 nm.