Biomimetic alcohol oxidations by an iron(III) porphyrin complex: relevance to cytochrome P-450 catalytic oxidation and involvement of the two-state radical rebound mechanism

The systematic oxidation reactions of a wide range of alcohols have been carried out by using an iron porphyrin complex in order to understand their relation to cytochrome P-450 enzymes and to have a practical application to organic synthesis. The iron porphyrin complex catalyzed efficiently alcohol oxidation to the respective carbonyl compound via a high-valent iron-oxo porphyrin intermediate ((Porp)Fe=O+). Several mechanistic studies such as isotope 18O labeling, deuterium isotope effect, linear free energy relationship, and ring-opening of radical clock substrate, have suggested that the alcohol is oxidized by a sequence of reactions involving an alpha-hydroxyalkyl radical intermediate and oxygen rebound to form the gem-diol, dehydration of which yields the carbonyl compounds. Moreover, it has been proposed that a two-state reactivity mechanism can also be adopted for alcohol oxidation reactions in iron porphyrin model systems as exhibited by P-450 enzymes.     

Bioconversion of cellulose into ethanol by nonisothermal simultaneous saccharification and fermentation

The kinetic characteristics of cellulase and beta-glucosidase during hydrolysis were determined. The kinetic parameters were found to reproduce experimental data satisfactorily and could be used in a simultaneous saccharification and fermentation (SSF) system by coupling with a fermentation model. The effects of temperature on yeast growth and ethanol production were investigated in batch cultures. In the range of 35-45 degrees C, using a mathematical model and a computer simulation package, the kinetic parameters at each temperature were estimated. The appropriate forms of the model equation for the SSF considering the effects of temperature were developed, and the temperature profile for maximizing the ethanol production was also obtained. Briefly, the optimum temperature profile began at a low temperature of 35 degrees C, which allows the propagation of cells. Up to 10 h, the operating temperature increased rapidly to 39 degrees C, and then decreased slowly to 36 degrees C. In this nonisothermal SSF system with the above temperature profile, a maximum ethanol production of 14.87 g/L was obtained.     

Supramolecular conducting microfibers from amphiphilic tetrathiafulvalene-based organogelator

An amphiphilic tetrathiafulvalene molecule can gelate a variety of organic solvents in view of multiple intermolecular interactions, especially in polar solvent with the formation of highly-ordered columnar structures. The formation of mixed-valence states shows the semiconductive behaviors with the conductivity of 10^-4 S/cm, as promising candidates for organic electronics.     

Magnetic couplings in vanadium aromatic sandwich complexes and their crystals by using DFT methods

Using density functional theory, we have theoretically studied the origin of ferromagnetic coupling of spins in the long multiple deckers of vanadium sandwich complexes with benzene (Bz). This is done by calculating the band structure of their infinite one-dimensional (1D) crystals along the periodic (=Z) direction. We find that the magnetic coupling can be ascribed to spin polarization in the band (= those derived from d(z2)) whose k states are not involved in the formation of partial covalent bonds between vanadium atoms and benzene rings. We have also studied magnetic and electronic properties of multiple deckers of a naphthalene (Np)-vanadium complex. We find that there is a stronger covalent interaction as well as a stronger electrostatic interaction between V and Np rings than between V and Bz rings. This suggests that there is a possibility of longer multiple deckers of a Np-V complex. In addition, ferrimagnetic coupling of spins is expected, resulting in a magnetic moment 45% larger than that of the Bz-V complex at the same length. For their 1D crystals, band structure analysis also shows that the origin of magnetic coupling in long multiple deckers should be similar to that of Bz-V multiple deckers.     

Chiral attachment of styrene mediated by surface dimers on Ge100

We have investigated the chiral adsorption configurations of styrene on Ge(100) using scanning tunneling microscopy at 300 K. The chemisorbed styrene on a single Ge dimer reduces the symmetry of the molecule, which produces a chiral center, and leads to the (S) or (R) chiral on-top configuration. We have found that the dimeric adsorption of styrene induced by the Ge surface dimer structure forms the enantiomeric and diastereomeric paired end-bridge configurations. We determine the absolute chirality of adsorbed styrene on Ge(100) and demonstrate a novel method for the achiral molecule to produce dimeric enantiomers and diastereomers attached to the semiconductor surface.     

Tributyl phosphate degradation by immobilized cells of aCitrobacter sp.

Tributyl phosphate (TBP), a plasticizer and solvent, is used in nuclear fuel reprocessing, generating TBP wastes laden with residual uranium. ACitrobacter sp. accumulated heavy metals via a phosphohydrolase(s) that precipitated metals with inorganic phosphate liberated from an organic phosphate “donor” molecule (TBP). Mutant analysis suggested that TBP hydrolysis was not attributable to a previously documented acid phosphatase (monoesterase). Purified monoesterase had little activity against phospho di- and triesters, had no requirement for Mg²⁺ or Mn²⁺, and was EDTA-resistant. Conversely, TBP cleavage by immobilized cells was enhanced by Mg²⁺, and ininhibited by Mn²⁺ and EDTA. A separate phosphotri/diesterase was implicated.     

A new and convenient synthesis of N-substituted perhydroazepines from adipaldehyde and primary amines with tetracarbonylhydridoferrate,HFe(CO), as a selective reducing agent

Ethanolic tetracarbonylhydridoferrate combined with adipaldehyde is very efficient for the selective transformation of an amino group into perhydroazepine. A large variety of both aliphatic and aromatic amines react with adipaldehyde in the presence of tetracarbonylhydridoferrate at room temperature and carbon monoxide to give the corresponding N-alkyl- and N-arylperhydroazepines in good to excellent yields.     

Copolymerization of ethylene and 1-butene with highly active Ticl4/THF/Mgcl2, Ticl4/THF/Mgcl2/SiO2, and TiCl3.1/3AlCl3 catalysts

Highly active catalysts for copolymerization have been prepared by the precipitation of MgCl₂/ToCl₄ complex with or without high surface area silica. Copolymerization of ethylene and 1-butene has been tested by using the prepared catalysts at various concentrations of 1-butene. The catalytic activities are 20–80 kg/g Ti h. The rate of copolymerization is strongly affected by the addition of 1-butene. The decay rate of copolymerization is first order with respect to time. Analyses of copolymers with solvent extraction, DSC, IR, XRD, and NMR were performed. Ethylene reactivity ratio (k₁₁) for TiCl₄/MgCl₂/THF catalyst is calculated to be about 26 by NMR spectrum. © 1994 John Wiley & Sons, Inc.