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.     

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.