ℙmax variations related to slaloms

We prove the iteration lemmata, which are the key lemmata to show that extensions by Pmax variations satisfy absoluteness for Π₂-statements in the structure 〈H (ω ₂), ∈, NS_{ω 1}, R 〉 for some set R of reals in L (ℝ), for the following statements: (1) The cofinality of the null ideal is ℵ₁. (2) There exists a good basis of the strong measure zero ideal. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photopolymerization of methyl methacrylate in the presence of tertiary amines

The sensitization effect of tertiary amines on the photopolymerization of methyl methacrylate was studied. N,N-Dimethylbenzylamine, triethylamine, and N,N-dimethylaniline increased the rate of polymerization in this order, but pyridine did not show any effect. A free-radical mechanism was confirmed by the tacticity of polymer, the retarding effect of hydroquinone, and the copolymer composition with styrene. On the basis of the detailed kinetics of the sensitized polymerization and the ultraviolet spectra of the reaction mixtures, a sensitization mechanism is proposed, in which the excited monomer and the amine form a complex and generate an initiating radical.     

Rapid ruthenium-catalyzed synthesis of pyranopyrandiones by reconstructive carbonylation of cyclopropenones involving C[bond]C bond cleavage

Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions.     

Characterization of the non-stoichiometric and isomorphic hydration and solvation in FK041 clathrate

FK041 crystallizes as a non-stoichiometric hydrate or as solvated hydrates which were characterized as isomorphic clathrates by powder X-ray diffractometry. Moisture and organic solvent vapor sorption studies, differential scanning calorimetry and thermogravimetric analysis revealed that FK041 monohydrate forms a physically stable host crystal, which has lattice channels for guest water and/or organic solvent molecules. The hydration state varies non-stoichiometrically between dihydrate and tetrahydrate depending on the relative humidity and the mol content of the co-existing organic solvent, that is 2-propanol, ethanol, or acetone. These organic solvents are thought to replace a part of originally present water with a mol ratio of 1:3. 2-Propanol exhibited the most stable solvation, indicating that the size and shape of 2-propanol are the most preferable to the lattice channels.     

Reaction of 2-dialkylamino-5-phenyl-1,3-oxathiolium cation with sulphur ylides

The reaction of 2-dialkylamino-5-phenyl-1,3-oxathiolium cation 1 with sulphur ylides 2 was investigated. The behavior of 1 was solvent-dependent. In CH₂Cl₂, carbamate ester 3 was obtained: in CH₃CN, the intermediate sulphonium salt 5, which on hydrolysis gave 3, was isolated. On the other hand, reaction in MeOH gave the diphenacyl derivative 6. The reaction mechanism is discussed.     

Synthesis of 2-alkylidenetetrahydrofurans by Ru-catalyzed regio- and stereoselective codimerization of dihydrofurans with alpha,beta-unsaturated esters

2-(1-Alkoxycarbonyl)alkylidenetetrahydrofurans were readily synthesized by the codimerization of 2,3- or 2,5-dihydrofurans with alpha,beta-unsaturated esters using a zerovalent Ru catalyst, Ru(cod)(cot), with high regio- and stereoselectivity.     

Meso-tetrakis[o-(N-methyl)pyridinium]porphyrin ensembles with axially coordinated cyclodextrin-penetrating phenethylimidazole: reversible dioxygen-binding in aqueous DMF solution

alpha-Cyclodextrin (alpha CD)-penetrating 2-methyl-1-phenethylimidazole coordinates to the zinc(II) and iron(II) complexes of meso-tetrakis[o-(N-methyl)pyridinium] porphyrinate, giving non-covalently linked alpha CD-porphyrin ensembles; the iron(II) complex can reversibly bind and release dioxygen in aqueous DMF solution.     

Recent developments on creation of artificial metalloenzymes

Organic synthesis using biocatalysts has been developed over many years and is still a prominent area of research. In this context, various hybrid biocatalysts composed of a synthetic metal complex catalyst and a protein scaffold (i.e. “artificial metalloenzymes”) have been constructed. One of the most recent research areas in biocatalysts-mediated synthesis is CC bond/cleavage, the most important type of reaction in organic chemistry. Some of the artificial enzymes were applied to in-cell reactions as well as in vitro systems. The effects of the structural fluctuation in biomacromolecules on their functions have also been realized. This review article includes recent research examples of artificial metalloenzymes used to CC bond formation/cleavage. As a perspective, we also focus on how we apply protein dynamics factor for the creation of new generation artificial metalloenzymes.     

Experimental determination of ionization potentials of tetraphenylporphine and metallotetraphenylporphines

Gas-phase ionization potentials of tetraphenylporphine and some metallotetraphenylporphines have been determined by the method of photocurrent measurements in nonpolar solvents reported previously [1]. The values obtained range from 5.9 to 6.3 eV, depending on the central metal ion, correlating well with the reported polarographic oxidation potentials. It has been concluded that photoelectron ejection from these complexes in isooctane occurs from the porphyrin π-system in all cases including Co(II) tetraphenylporphine, in which the electron is thought to be removed from the metal in polar solvents.