From mononuclear to multinuclear complexes of palladium containing unsaturated hydrocarbon ligands

This review summarizes the author’s contributions to the field of chemistry of group 10 metal complexes containing unsaturated hydrocarbon ligands, with a brief introduction showing how his research subject has shifted from mononuclear type to multinuclear type complexes. New structure and reactivity trends in the multipalladium complexes with bridging allyl and allenyl/propargyl ligands, as well as bridging conjugated polyene molecules are discussed in terms of some unique bonding features of these complexes.     

Redox features of β-VOPO4 catalyst using tracer and laser Raman spectroscopy

The oxygen ions of the β-VOPO₄ catalyst were exchanged with an tracer by a reduction–oxidation method and by a catalytic oxidation of but-1-ene using ₂. The bands at 992 and 900 cm⁻¹ were more shifted to lower frequencies than those at 1076 and 1002 cm⁻¹. Applying the correlation between the Raman bands and stretching vibrations in the literature, the exchanged oxygen species were estimated. The results suggest that the P–O–V vacancies corresponding to 992 and 900 cm⁻¹ were responsible for reoxidation and the V=O oxygen corresponding to the 1002 cm⁻¹ band of β-VOPO₄ was not. The (VO)₂P₂O₇ was oxidized to β-VOPO₄ by O₂ above 823 K. The insertion position of oxygen was determined at the bands at 992 and 900 cm⁻¹ of β-VOPO₄ using ₂, which is the same as the exchanged position.     

Kinetics of catalytic combustion in air over Pt/Al2O3/Al catalyst

Summary Catalytic combustion of toluene, propylene and CO over Pt/Al₂O₃ /Al catalyst was investigated. Strong inhibition effects are observed when the mixture of toluene, propylene and CO is oxidized. A reaction mechanism of catalytic combustion over Pt/Al₂O/Al is proposed. The results from kinetic models are in good agreement with the experimental data.     

Volumetric study on the inclusion complex formation of α- and β-cyclodextrin with 1-alkanols at different temperatures

The partial molar volumes (V_a) of 1-alkanols (carbon number, m=5, 6, 7) in - and -cyclodextrin (CD) solutions at 5.00 mmol kg^–1 have been determined as a function of alkanol concentration (C_a) between 293.2 and 308.2 K by using a dilatometer. It has been observed that with an increase in C_a, V_a increased in -CD solution but decreased in -CD solution, asymptotically to a value of V_a in CD-free water. The dependence of V_a on C_a provided the binding constant (K) of 1:1 complex, the volume change in complex formation, and the partial molar volume of complex itself. The complex formation mechanism has been discussed on the basis of these values and their carbon number dependences in the respect of geometric behavior, hydrophobic interaction, and van der Waals interaction. It is concluded that the CD cavity in water is not rigid but flexible for fitting in nicely with guest molecule.     

Concise and highly stereocontrolled synthesis of 1-deoxygalactonojirimycin and its congeners using dioxanylpiperidene,a promising chiral building block

[reaction: see text] A concise and stereoselective synthesis of the chiral building block, dioxanylpiperidene 4 as a precursor for deoxyazasugars, starting from the Garner aldehyde 5 using catalytic ring-closing metathesis (RCM) for the construction of the piperidine ring is described. The asymmetric synthesis of 1-deoxygalactonojirimycin and its congeners 1-3 was carried out via the use of 4 in a highly stereocontrolled mode.     

Cloning and characterization of an active fragment of luciferase from a luminescent marine alga, Pyrocystis lunula

Two marine dinoflagellates, Lingulodinium polyedrum and Pyrocystis lunula, emit light in a reaction involving the enzymatic oxidation of its tetrapyrrole luciferin by molecular oxygen. The characteristic properties of P. lunula luciferase have not been clarified, whereas L. polyedrum luciferase, which has three active domains, has been characterized. A cloned partial cDNA of the P. lunula luciferase encodes an active fragment corresponding to part of domain 2 and all of domain 3 of L. polyedrum luciferase. The homology of the amino acid sequence between the two luciferases in domain 3 is about 84.3%. A recombinant His-tagged luciferase fragment containing domain 3 (Mr = 46 kDa) catalyzed the light-emitting oxidation of luciferin (lambdamax = 474 nm). This protein was purified by a single affinity-chromatography procedure. The pH-activity profile and the bioluminescence spectrum of the recombinant enzyme having a third domain are almost identical to those of an extract from P. lunula cultured in vitro. The recombinant enzyme is active at pH 8.0, although the recombinant enzyme derived from the second domain of L. polyedrum luciferase is inactive at pH 8.0. Substitution of Glu-201 by histidine in the third domain of P. lunula luciferase showed a decrease of activity above pH 7.0, suggesting that histidine residues could be responsible for pH-sensitivity in dinoflagellate luciferase.     

Regioselective oxidation of internal olefins bearing neighboring oxygen functions by means of palladium catalysts. Preparation of β-alkoxy or acetoxy ketones from allyl and homoallyl ethers or esters

A new preparative method of β- and γ-alkoxy (acetoxy) ketones, which are important precursors of vinyl ketones and 1,4-diketones, respectively, is presented. With PdCl₂/CuCl/O₂ or PdCl₂/p-benzoquinone catalyst system, internal olefins bearing allylic alkoxy or acetoxy group underwent regioselective oxidation to form the corresponding β-alkoxy or β-acetoxy ketones. Similarly, γ-acetoxy ketones were obtained from homoallyl acetates having internal olefins with high regioselectivity.     

Molecular mobility of lyophilized poly(vinylpyrrolidone) and methylcellulose as determined by the laboratory and rotating frame spin-lattice relaxation times of 1H and 13C

Laboratory- and rotating- frame spin-lattice relaxation times (T(1) and T(1rho)) of (1)H and (13)C in lyophilized poly(vinylpyrrolidone) (PVP) and methylcellulose (MC) are determined to examine feasibility of using T(1) and T(1rho) as a measure of molecular motions on large time scales related to the storage stability of lyophilized formulations. The T(1rho) of proton and carbon was found to reflect the mobility of PVP and MC backbones, indicating that it is useful as a measure of large-time-scale molecular motions. In contrast to the T(1rho), the T(1) of proton measured in the same temperature range reflected the mobility of PVP and MC side chains. The T(1) of proton may be useful as a measure of local molecular motions on a smaller-time-scale, although the measurement is interfered by moisture under some conditions. The temperature dependence of T(1) and T(1rho) indicated that methylene in the MC molecule had much higher mobility than that in the dextran molecule, also indicated that methylene in the PVP side chain had a higher mobility than that in the MC side chain.