Novel canonical coding method for representation of three-dimensional structures

A new canonical coding method for representation of three-dimensional structures, CAST (CAnonical representation of STereochemistry), is described. CAST canonically codes stereochemistry around an atom in a molecule. The same CAST notations are given for atoms of molecules in the same conformation. The CAST code is based on the dihedral angles of four atoms that are uniquely defined by a molecular tree structure. CAST has successfully represented similarities and differences between several conformers.     

Significant differences in site of protonation and extent of fragmentations in chemical ionization and fast atom bombardment mass spectrometry of simple bifunctional compounds. A mechanistic implication for formation of protonated molecules

Chemical ionization (CI) and fast atom bombardment (FAB) mass spectra of simple bifunctional aromatic compounds were compared. Some significant differences were revealed with respect to the site of protonation and extent of fragmentations. Unlike conventional CI ionization, the protonated molecule formation by FAB could not be accounted for by ordinary proton transfer reactions in the gas phase. The observed ions under FAB conditions appear to be regulated by proton exchange reactions through frequent collisions in some particular region between the matrix and the gas phase.     

Effect of compression on interaction between 1,4-dihydropyridine compounds and lactose monohydrate

Manidipine dihydrochloride or benidipine hydrochloride will change to hydrate form in part, when differential scanning calorimetric (DSC) measurement is carried out together with lactose monohydrate. This interaction was accelerated by compressing their mixture. It can be suggested that the interaction may cause by the disruption of crystal structure of lactose monohydrate due to compression to set free of water molecules. A new DSC peak at 170 degrees C, which was not observed in each component, appeared in DSC measurement of a mixture. This will be based on hydrate formed by the interaction, i.e., movement of water molecules. The profile of the plotting of the DSC peak area ratio before and after compression against the compression force changed by the molar ratio of lactose monohydrate in a mixture. In the case of low molar ratio of lactose monohydrate, profiles for manidipine dihydrochloride and benidipine hydrochloride differed from each other. This will be because manidipine dihydrochloride is stickier than benidipine hydrochloride. The profile for manidipine dihydrochloride became more gradual and showed lag compression force region when the amount of addition of the lubricant, magnesium stearate in a mixture increased. The endothermic peak area at 170 degrees C for manidipine dihydrochloride was larger than that for benidipine hydrochloride. It should be suggested that benidipine hydrochloride is easier to be transformed to its hydrate than manidipine dihydrochloride.     

Structural studies of the carbon monoxide complex of [NiFe]hydrogenase from Desulfovibrio vulgaris Miyazaki F: suggestion for the initial activation site for dihydrogen

The carbon monoxide complex of [NiFe]hydrogenase from Desulfovibrio vulgaris Miyazaki F has been characterized by X-ray crystallography and absorption and resonance Raman spectroscopy. Nine crystal structures of the [NiFe]hydrogenase in the CO-bound and CO-liberated forms were determined at 1.2-1.4 A resolution. The exogenously added CO was assigned to be bound to the Ni atom at the Ni-Fe active site. The CO was not replaced with H(2) in the dark at 100 K, but was liberated by illumination with a strong white light. The Ni-C distances and Ni-C-O angles were about 1.77 A and 160 degrees, respectively, except for one case (1.72 A and 135 degrees ), in which an additional electron density peak between the CO and Sgamma(Cys546) was recognized. Distinct changes were observed in the electron density distribution of the Ni and Sgamma(Cys546) atoms between the CO-bound and CO-liberated structures for all the crystals tested. The novel structural features found near the Ni and Sgamma(Cys546) atoms suggest that these two atoms at the Ni-Fe active site play a role during the initial H(2)-binding process. Anaerobic addition of CO to dithionite-reduced [NiFe]hydrogenase led to a new absorption band at about 470 nm ( approximately 3000 M(-1)cm(-1)). Resonance Raman spectra (excitation at 476.5 nm) of the CO complex revealed CO-isotope-sensitive bands at 375/393 and 430 cm(-1) (368 and 413 cm(-1) for (13)C(18)O). The frequencies and relative intensities of the CO-related Raman bands indicated that the exogenous CO is bound to the Ni atom with a bent Ni-C-O structure in solution, in agreement with the refined structure determined by X-ray crystallography.     

Spatial distribution of YO molecules ejected from laser-ablated YBa2 Cu3 O7−x

One-dimensional imaging laser-induced fluorescence spectroscopy has been used for in-situ measurements of spatial distributions of YO molecules produced during the ArF-laser ablation of YBa₂ Cu₃ O _7–x in vacuum and oxygen gas environment. The time-integrated angular distribution of particles ejected in vacuum has a cos ⁿ form, where 11 <n < 13. When oxygen gas was introduced, YO molecules were confined in a smaller volume, and temporal changes of their spatial distribution were interpreted in terms of blast-wave formation.     

Synthesis of poly(diallyl phthalate) and silica gel polymer hybrids utilizing π–π interactions

We report here the synthesis of homogeneous polymer hybrids of poly(diallyl phthalate) (PDAP) and silica by utilizing π–π interactions. Use of arylalkoxysilanes such as phenyltrimethoxysilane (PhTMOS), phenethyltrimethoxysilane (PhenethylTMOS) and mesityltrimethoxysilane (MesTMOS) as sources for inorganic phases resulted in optically transparent PDAP-silica polymer hybrids in a wide range of organic and inorganic content ratios. On the other hand, alkoxysilanes such as tetramethoxysilane (TMOS), methyltrimethoxysilane (MTMOS) and i-butyltrimethoxysilane (iBuTMOS) resulted in phase separated, turbid solids. A mixture of tetramethoxysilane (TMOS) and PhTMOS was also studied for the synthesis of PDAP-silica gel polymer hybrids to control the cross-linking density in the inorganic phase. Homogeneity was found to be improved with an increase in PhTMOS content. These homogeneous PDAP polymer hybrids were found to have high thermal stability which wasachieved by nano-scale dispersion of PDAP in silica through extensiveinterface interactions. The homogeneity of the polymer hybrids was confirmed by SEM and TEM, which demonstrate a nanometer level integration of the organic polymer and the inorganic phase.