Novel synthesis of heterocyclic spirans by tandem cycloaddition to sulfur-containing heterocumulenes

Novel Ni(C0)₄-promoted tandem cycloadditions of diphenylcyclo- propenone to isothiocyanates and to CS₂ were found to provide new heterocyclic spirans, pyrroline-2-one-5-spiro-5′-thiolene-4′-ones and a thiolene-2-one-5-spiro-5′-thiolene-4′-one, respectively, in moderate yields.     

Guest shape-responsive fitting of porous coordination polymer with shrinkable framework

In situ synchrotron X-ray powder diffraction patterns of porous coordination polymers [[Cu(2)(pzdc)(2)(bpy)].G] have been measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine) (where G = H(2)O for CPL-2 superset H(2)()O, G = benzene for CPL-2 superset benzene, and G = void for the apohost). The structures of apohost and CPL-2 superset benzene were determined from Rietveld analysis. Adsorption of benzene in the channels induced a remarkable contraction in the crystal (b axis; 6.8%, volume; 4.9%), although the channels were occupied by the benzene molecules. This crystal transformation provides a new pore structure that is well suited for benzene molecules, and we denote it as a "shape-responsive fitting" transformation. This type of pore gives rise to a new guideline: frameworks can be composed of flexible motifs that are linked via strong bond and/or stiff motifs that are connected via weaker bonds.     

Biomimetic oxidation of alcohols by coenzyme PQQ-trimethyl ester

Oxidation of alcohols to corresponding carbonyl compounds by coenzyme PQQ-trimethyl ester was performed in the presence of aluminum t-butoxide or aluminum chloride under anaerobic conditions. Reduced PQQTME (PQQTMEH₂) was obtained by acidification of an aluminum complex of reduced PQQTME which was isolated in the reaction.     

Inclusion of Nonopiate Analgesic Drugs in Cyclodextrins. I. X-Ray Structure of a 1 : 1 β-Cyclodextrin-p-bromoacetanilide Complex

The preparation and X-ray crystal structure of a 1 : 1 complex between -cyclodextrin (-CD) and the analgesic p-bromoacetanilide are reported. Thermogravimetric and UV spectrophotometric analyses of single crystals grown from an aqueous solution containing host and guest in 1 : 1 molar ratio yielded the composition -CD p-bromoacetanilide $ 13.5H2O. Crystals of the complex are triclinic, space group P1, with a = 15.197(3), b = 15.613(2), c = 15.743(4) Å, = 87.16(2), = 98.29(2), = 103.39(1)° and Z = 2 crystallographically independent complex units per unit cell. The -CD molecules form head-to-head dimers which pack in the channel-mode. Each dimer contains two guest molecules whose acetylamino substituents are located at the dimer interface while the bromine atoms protrude from the -CD primary faces. The acetyl residues of both guest molecules were found to be disordered but the X-ray data permitted     

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.