Charge Transfer Transitions from Cyclohexadienyl-Type Radicals to Host Molecules in Anthracene Single Crystals

The optical absorption spectra of 1-, 2- and 9-dibenzo-cyclohexadienyl radical in anthracene crystals have been obtained and analyzed. It is shown that the absorption lines consist of vibrational progression and charge-transfer lines for 2- and 9-DBCR. Each line belonging to the former has the same polarization as the most intense 0–0 vibrational line and the latter show polarization character depending on the direction of charge transfer and the transition energy was found to have a coulombic dependence on the distance of charge transfer. It is pointed out that only charge transfer lines were observed for 1-DBCR. The splitting of lines were observed and ascribed either to the resonance transfer interaction between two neighboring molecules situated at an equal distance from the radical or to the site symmetry. It is suggested that the intensity of the charge-transfer lines are borrowed from the intra-radical transition. The result that the charge transfer lines are more intense than the intra-radical lines for 1-DBCR was discussed.     

Manganese centers with various valency in alkali halides

Abstract

Optical absorption bands and epr spectra of NaCl: Mn⁺⁺ X-irradiated at liquid nitrogen and room temperature are studied. Manganese epr spectra are divided into three classes, based on the value of hyperfme splitting constants. It is shown that the epr spectra with the hyperhe splitting constants of around 250 × 10-⁴, 80 × 10^?4 and 20 × 10^?4 cm^?1 are caused by Mn⁺, Mn⁺⁺ and Mn⁹, respectively. Formation of several manganese centers by X-irradiation is discussed. It is suggested that optical absorption bands at 410 and 440 nm are caused by Mn^O at the lattice site and that the Mn^O center which gives an epr spectrum with A = 15. 5 × 10^?4 cm^?1 is associated with a Mn⁰ center which is not at a substitutional site.     

Empirical determination of the random fraction in disordered channel

A new method of deriving the random fraction in a disordered channel : rom dechanneling experiments is described. In this method backscattering spectra obtained at two different doses are employed, with an assumption on the dose dependence of the defect concentration. The method is applied to the experimental data for B-implanted Si and it is found that the obtained random fraction is similar to the result of the diffusion calculation made by the present authors. The depth profiles of defects are also obtained and compared with the result of theoretical calculations.     

Soot formation characteristics in a lab-scale turbulent pulverized coal flame with simultaneous planar measurements of laser induced incandescence of soot and Mie scattering of pulverized coal

Soot formation characteristics of a lab-scale pulverized coal flame were investigated by performing carefully controlled laser diagnostics. The spatial distributions of soot volume fraction and the pulverized coal particles were measured simultaneously by laser induced incandescence (LII) and Mie scattering imaging, respectively. In addition, the radial distributions of the soot volume fraction were compared with the OH radical fluorescence, gas temperature and oxygen concentration obtained in our previous studies [1], [2]. The results indicated that the laser pulse fluence used for LII measurement should be carefully controlled to measure the soot volume fraction in pulverized coal flames. To precisely measure the soot volume fraction in pulverized coal flames using LII, it is necessary to adjust the laser pulse fluence so that it is sufficiently high to heat up all the soot particles to the sublimation temperature but also sufficiently low to avoid including a too large of a change in the morphology of the soot particles and the superposition of the LII signal from the pulverized coal particles on that from the soot particles. It was also found that the radial position of the peak LII signal intensity was located between the positions of the peak Mie scattering signal intensity and peak OH radical signal intensity. The region, in which LII signal, OH radical fluorescence and Mie scattering coexisted, expanded with increasing height above the burner port. It was also found that the soot formation in pulverized coal flames was enhanced at locations where the conditions of high temperature, low oxygen concentration and the existence of pulverized coal particles were satisfied simultaneously.     

Representations of (α, β, γ) triple system

We introduce a notion of (α, β, γ) triple system which generalizes the familiar generalized Jordan triple system. We then discuss its realization by some bilinear algebras and vice versa. We also give a characterization of the structurable algebra of Allison in terms of (?1, 1) Freudenthal–Kantor triple system by imposing some additional triple product constraints.     

Time operators for quantum walks

Letters in Mathematical Physics - We study time operators for discrete-time quantum systems. Quantum walks are typical examples. We construct time operators for one-dimensional homogeneous quantum...     

Regioselective protection of sugars catalyzed by dimethyltin dichloride

The first catalytic process for protection of hydroxyl groups in sugars has been developed. Highly regioselective protection was accomplished along with high chemical yield. The regioselectivity of the benzoylation was realized as an intrinsic character of sugars based on a stereorelationship among their hydroxyl groups. Furthermore, complete protection of alpha-methyl glucoside and beta-methyl xyloside was accomplished.     

ASEDock-docking based on alpha spheres and excluded volumes

ASEDock is a novel docking program based on a shape similarity assessment between a concave portion (i.e., concavity) on a protein and the ligand. We have introduced two novel concepts into ASEDock. One is an ASE model, which is defined by the combination of alpha spheres generated at a concavity in a protein and the excluded volumes around the concavity. The other is an ASE score, which evaluates the shape similarity between the ligand and the ASE model. The ASE score selects and refines the initial pose by maximizing the overlap between the alpha spheres and the ligand, and minimizing the overlap between the excluded volume and the ligand. Because the ASE score makes good use of the Gaussian-type function for evaluating and optimizing the overlap between the ligand and the site model, it can pose a ligand onto the docking site relatively faster and more effectively than using potential energy functions. The posing stage through the use of the ASE score is followed by full atomistic energy minimization. Because the posing algorithm of ASEDock is free from any bias except for shape, it is a very robust docking method. A validation study using 59 high-quality X-ray structures of the complexes between drug-like molecules and the target proteins has demonstrated that ASEDock can faithfully reproduce experimentally determined docking modes of various druglike molecules in their target proteins. Almost 80% of the structures were reconstructed within the estimated experimental error. The success rate of approximately 98% was attained based on the docking criterion of the root-mean-square deviation (RMSD) of non-hydrogen atoms (< or = 2.0 A). The markedly high success of ASEDock in redocking experiments clearly indicates that the most important factor governing the docking process is shape complementarity.     

Chemocavity: specific concavity in protein reserved for the binding of biologically functional small molecules

The idea that there should be a specific site on a protein for a particular functional small molecule is widespread. It is, however, usually not so easy to understand what characteristics of the site determine the binding ability of the functional small molecule. We have focused on the concurrence rate of the 20 standard amino acids at such binding sites. In order to correlate the concurrence rate and the specific binding site, we have analyzed high-quality X-ray structures of complexes between proteins and small molecules. A novel index characterizing the binding site based on the concurrency rate has been introduced. Using this index we have identified that there is a specific concavity designated as a chemocavity where a specific group of small molecules, i.e., canonical molecular group, is highly inclined to be bound. This study has demonstrated that a chemocavity is reserved for a specific canonical molecular group, and the prevalent idea has been confirmed.     

Syntheses, structures, and coordination chemistry of phosphole-containing hybrid calixphyrins: promising macrocyclic P,N2,X-mixed donor ligands for designing reactive transition-metal complexes

The syntheses, structures, and coordination chemistry of phosphole-containing hybrid calixphyrins (P,N2,X-hybrid calixphyrins) and the catalytic activities of their transition-metal complexes are reported. The 5,10-porphodimethene type 14pi-P,(NH)2,X- and 16pi-P,N2,X-hybrid calixphyrins (X = O, S, NH) are prepared via acid-promoted dehydrative condensation between a sigma4-phosphatripyrrane and the corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by DDQ oxidation. Both spectroscopic and crystallographic data of the hybrid calixphyrins have revealed that the conformation and size of the macrocyclic platforms as well as the oxidation state of the -conjugated pyrrole-heterole-pyrrole (N-X-N) units vary considerably depending on the combination of heteroles. The sigma3-P,(NH)2,S- and sigma3-P,N2,S-hybrids react with Pd(OAc)2 and Pd(dba)2, respectively, to afford the same Pd(II)-P,N2,S-hybrid complex, in which the calixphyrin platform is regarded as a dianionic ligand. In the complexation with [RhCl(CO)2]2 in dichloromethane, the sigma3-P,N2,S-hybrid behaves as a neutral ligand to afford an ionic Rh(I)-P,N2,S-hybrid complex, whereas the sigma3-P,N2,NH-hybrid behaves as an anionic ligand to produce Rh(III)-P,N3-hybrid complexes. In the latter reaction, it is likely that a neutral Rh(I)-P,N3-hybrid complex, generated as a highly nucleophilic intermediate, undergoes C-Cl bond activation of the solvent. The complexation of AuCl(SMe2) with the sigma3-P,N2,X-hybrids (X = S, NH) leads to the formation of the corresponding Au(I)-monophosphine complexes. The spectral data and crystal structures of these metal complexes exhibit the hemilabile nature of the phosphole-containing hybrid calixphyrin platforms derived from the flexible phosphole unit and the redox active N-X-N units. The hybrid calixphyrin-palladium and -rhodium complexes catalyze the Heck reaction and hydrosilylations, respectively, implying that the metal center in the core is capable of activating the substrates under appropriate reaction conditions. The present results demonstrate the potential utility of the phosphole-containing hybrid calixphyrins as a new class of macrocyclic P,N2,X-mixed donor ligands for designing highly reactive transition-metal complexes.