The photophysical properties of singlet and triplet metal-to-ligand charge transfer (MLCT) states of [Cu(I)(diimine)(2)](+), where diimine is 2,9-dimethyl-1,10-phenanthroline (dmphen), 2,9-dibutyl-1,10-phenanthroline (dbphen), or 6,6'-dimethyl-2,2'-bipyridine (dmbpy), were studied. On 400 nm laser excitation of [Cu(dmphen)(2)](+) in CH(2)Cl(2) solution, prompt (1)MLCT fluorescence with a quantum yield of (2.8 +/- 0.8) x 10(-5) was observed using a picosecond time-correlated single photon counting technique. The quantum yield was dependent on the excitation wavelength, suggesting that relaxation of the Franck-Condon state to the lowest (1)MLCT competes with rapid intersystem crossing (ISC). The fluorescence lifetime of the copper(I) compound was 13-16 ps, unexpectedly long despite a large spin-orbit coupling constant of 3d electrons in copper (829 cm(-1) ). Quantum chemical calculations using a density functional theory revealed that the structure of the lowest (1)MLCT in [Cu(dmphen)(2)](+) (1(1)B(1)) was flattened due to the Jahn-Teller effect in 3d(9) electronic configuration, and the dihedral angle between the two phenanthroline planes (dha) was about 75 degrees with the dha around 90 degrees in the ground state. Intramolecular reorganization energy for the radiative transition of 1(1)B(1) was calculated as 2.1 x 10(3) cm(-1), which is responsible for the large Stokes shift of the fluorescence observed (5.4 x 10(3) cm(-1)). To understand the sluggishness of the intersystem crossing (ISC) of (1)MLCT of the copper(I) compounds, the strength of the spin-orbit interaction between the lowest (1)MLCT (1(1)B(1)) and all (3)MLCT states was calculated. The ISC channels induced by strong spin-orbit interactions (ca. 300 cm(-1)) between the metal-centered HOMO and HOMO - 1 were shown to be energetically unfavorable in the copper(I) compounds because the flattening distortion caused large splitting (6.9 x 10(3) cm(-1)) between these orbitals. The possible ISC is therefore induced by weak spin-orbit interactions (ca. 30 cm(-1)) between ligand-centered molecular orbitals. Further quantum mechanical study on the spin-orbit interaction between the lowest (3)MLCT (1(3)A) and all (1)MLCT states indicated that the phosphorescence borrows intensity from 2(1)B(1). The radiative rate of the phosphorescence was also structure-sensitive. The flattening distortion reduced the transition dipole moment of 2(1)B(1) --> the ground state, and decreased the extent of mixing between 1(3)A and 2(1)B(1), thereby considerably reducing the phosphorescence radiative rate at the MLCT geometry compared to that at the ground state geometry. The theoretical calculation satisfactorily reproduced the radiative rate of ca. 10(3) s(-1) and accounted for the structure-sensitive phosphorescence intensities of copper(I) bis(diimine) compounds recently demonstrated by Felder et al. (Felder, D.; Nierengarten, J. F.; Barigelletti, F.; Ventura, B.; Armaroli, N. J. Am. Chem. Soc. 2001, 123, 6291).

Self-assembled monolayers of alkanethiols CnH2, §(n = 6 ---18) adsorbed on the surface of a polycrystalline bulk Cu were constructed and characterized by x-ray photoelectron (XPS) and surface-enhanced Raman scattering (SERS) spectroscopy and contact angle and impedance measurements. The protection ability of the alkanethiol monolayers against Cu corrosion in an aerated 0.5M Na2SO4 solution was examined by impedance and polarization techniques. Results of XPS, SERS, and contact angle measurements showed that alkanethiols were chemisorbed on the Cu surface by the formation of strong bonds between Cu and S atoms following cleavage of a S-H bond and formed densely packed, water-repellent monolayers on the surface. The advancing contact angle of these monolayer films was comparable to that of alkanethiolate monolayers adsorbed at a vapor-deposited Cu on a Si wafer. However, sufficiently high protection abilities of the films against Cu corrosion were not obtained in 0.5M Na2SO4. A preliminary experiment demonstrated the formation of a promising protective film which was prepared on the Cu surface by modification of self-assembled ll-mercapto-l-undecanol monolayer with octyltrichlorosilane to form cross-linkages between the thiol molecules with siloxane bonds.

Calculations of the electronic structure and X-ray spectra of the MO{'-(M = Ti, V, Mn, Fe, CO, Ni) clusters, modeling the respective solid-state monoxides, have been performed by the X,-DV method. The main purpose of the present work was to investigate an influence of the resonant emission processes on the X-ray emission spectra of the monoxides. It has been shown, that resonant emission can appreciably affect the shape of the ML,, ,and, to an even greater degree, the MM,, ,-X-ray emission spectra of the 1.h.s. transition 3d-metal monoxides.

Crystallization of amorphous titania prepared by hydrolysis of ethoxide was accelerated even by a small amount of water in the vapor phase. The existence of water promoted the change of localized structure of the amorphous titania to anatase structure, which resulted in acceleration of anatase nucleation. The anatase crystals grew in steam by solid-state epitaxial growth, but stopped growing in a short time. The growth of anatase crystals under hydrothermal conditions could be divided into the following two stages: the first stage with fast growth rate by the solid-state epitaxial growth and the second stage with slow growth rate by the dissolution and deposition process.

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Esophagitis dissecans superficialis (EDS) is a rare and severe endoscopic finding characterized by sloughing of large fragments of esophageal mucosal lining. Although EDS has been reported in association with serious illnesses and certain medications, the pathophysiological association of autoimmune bullous dermatoses with EDS has gained remarkable attention. Among these dermatoses, pemphigus vulgaris and pemphigoid frequently present with various types of esophageal involvement including EDS. We review the pathophysiology and clinical features of this involvement with the presentation of our experiences. The importance of endoscopic evaluation of this entity is discussed.

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