N-Chloroacetyl-N-hydroxy- β-Phe-NHMe and N-chloroacetyl-N-hydroxy-α-Phe-OMe were designed, synthe-sized and evaluated as irreversible inhibitors of thermolysin, a representative zinc protease. Analysis of kinetic data of the enzymic activity of thermolysin in the presence of these inhibitors revealed that they are indeed potent inactivators of thermolysin having the k(inact)/K(I ) values of 3.06 and 0.05 M (-1) s(-1) , respectively. We have established that the inhibitory activity of N-chloroacetyl-N-hydroxy-β-Phe-NHMe stems mainly from the (R)-enantiomer that belongs to the "L" series. The (R)-enantiomer is also responsible for the inactivation in the case of N-chloroacetyl-N-hydroxy-α-Phe-OMe, but this enantiomer belongs to the "D"-series.

Ferrisilicates with MFI type structure were hydrothermally synthesized. The structural environments of iron in the ferrisilicates were characterized by XRD, SEM, IR, EPR, and ammonia-TPD. It has been shown that pH of the final gel mixture during the synthesis affects the crystal size, morphology, chemical composition and catalyticactivity. The results of the lattice parameters, IR, and EPR indicate the existence of a framework iron and the content of framework iron depends on pH of the synthesis gel. Finally, the catalytic activity of these zeolites was examined for the cyclohexane oxidation to cyclohexanol and cyclohexanone in the liquid phase. The conversion of this reaction was increased with increasing iron content of the framework lattice positions.

Relatively inert surface of microcrystalline MgO was modified into chemically active one by carrying out controlled hydration followed by dehydration at elevated temperature under dynamic vacuum. Even though the treatment by the first cycle of hydration-dehydration did not alter the porosity of MgO, it largely enhanced surface reactivity of the MgO toward adsorbed water, turning its outer layer into brucite upon rehydration. Treatment by the second cycle of hydration-dehydration generated micropores, and slit-shaped mesopores, raising the porosity of the MgO. The overlayer of Fe2O3 of the core/shell type composite magnesium oxide enhanced this surface modification, turning its surface into more porous and more active one than that of uncoated MgO, after the treatment by the hydration-dehydration.

The crystal structure of a cyclopropane sorption complex of dehydrated fully Ca (2+) -exchanged zeolite X, Ca46Si100Al92O384· 30C3H6 (a = 24.988(4) Å), has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at 21(1)℃. The crystal was prepared by ion exchange in a flowing stream of 0.05M aqueous Ca(NO3)2 for four days, followed by dehydration at 460℃ and 2×10 (-6) Torr for two days, and exposure to 100 Torr of cyclopropane gas at 21(1)℃. The structure was determined in this atmosphere and refined to the final error indices R1 = 0.068 and R2 = 0.082, with 373 reflections for which I > 3σ (I). In this structure, Ca 2+ ions are located at two crystallographic sites. Sixteen Ca 2+ ions fill the octahedral sites I at the centers of the hexagonal prisms (Ca-O = 2.412(9)Å). The remaining 30 Ca 2+ ions are at sites Ⅱ; each extends 0.46Å into the supercage (an increase of 0.16Å upon C3H6 sorption) where it coordinates to three trigonally arranged framework oxygens at 2.311(8)Å. Each of the 30 cyclopropane molecules was found to complex to Ca 2+ ions at site II by the induced dipole interaction (Ca-C = 2.99(4)Å). All carbon atoms in each cyclopropane molecule are equivalent and equidistant from Ca 2+ ions at site II with which they are associated.

Three anthrylazacrown ethers in which the anthracene fluorophore π system is separated from the electron donor atoms by one methylene group were synthesized, and their photophysical study was accomplished. These fluorescent compounds showed a maximum fluorescence intensity at pH=5 in aqueous solutions and a decrease in fluorescence intensity upon binding of paramagnetic metal cations (Mn 2+ (d 5 ), Co 2+ (d 7 ), Cu 2+ (d 9 )). The decrease in fluorescence intensity may be attributed to the paramagnetic effect of metal cations to deactivate the excited state by the nonradiative quenching process. The benzylic nitrogen was found to play an important role in changing fluorescence intensity. From the observed linear Stern-Volmer plot and the fluorescence lifetime independence of the presence of metal ions, it was inferred that the chelation enhanced fluorescence quenching (CHEQ) mechanism in the system is a ground state static quenching process. Enhanced fluorescence was also observed when an excess Na + ion was added to the quenched aqueous solution, and it was attributed to cation displacement of a complexed fluorescence quencher.

Thermal and photoinduced silylallylation reactions of organic halides with 3-stannyl-2-(silylmethyl)propene are explored. Silylallylations occur in moderate to high yields, producing various functionalized allylsilane products in which halide carbon is bonded to the terminal alkenic carbon of allylsilane with the removal of tributyltin group. The reactions, which tolerate functional groups such as carbonyl, ester, nitrile, acetal, and ketal, hold synthetic potential for the construction of functionalized allylsilanes.

Second-order-rate constants (kN) have been measured spectrophotometrically for the reactions of 4-nitrophenyl 2-furoate (1) with a series of secondary alicyclic amines in H2O containing 20 mole % DMSO at 25.0℃. 1 is about 5-8 times more reactive than 4-nitrophenyl benzoate (2), although 1 is expected to be less reactive than 2 based on MO calculations and 13 C NMR study. The Brфnsted-type plots for the aminolysis reactions of 1 and 2 are linear with βnuc values of 0.78 and 0.85, respectively. The replacement of the CH=CH group by an O atom in the acyl moiety (2->1) does not cause any mechanism change. The reaction of piperidine with a series of substituted phenyl 2-furoates gives a linear Hammett plot with a large ρ- value (ρ- = 2.88) when σ- constants are used. The linear Brфnsted and Hammett plots with a large ρ- value suggest that the aminolysis reaction of 1 proceeds via rate-determining break-down of the addition intermediate to the porducts.

Computations are reported for the very floppy cumulenones H2CnO (n = 3-7). The structures, harmonic frequencies and dipole moments are computed using the DFT and MP2 methods. H2C6O and H2C7O are treated for the first time. The carbon skeletons in ground states of these molecules with smaller number of carbon atoms are found to be bent, but very floppy. Those of the cumulenones with higher number of carbon atoms are predicted to be nearly linear. All the molecules are predicted to be of Cs symmetry by the present results. Good agreement with the available experimental observations is obtained.

The method of calculating the excess Helmholtz free energy from the averaged effective acceptance ratio for the Lennard-Jones fluid and the inverse twelve fluid has been slightly modified and applied to the two-center-Lennard-Jones liquid. The excess Helmholtz free energy is calculated directly from the average of the modified effective acceptance ratio through a single Metropolis Monte Carlo simulation. Therefore this method does not need any reference system. The results of the present method were satisfactory compared with those of the perturbation theories and the overlap ratio method.

Antioxidant activities of various mushroom fruiting bodies were investigated in vitro. Among the mushroom extracts examined, Armillariella mellea, Daedalea dickinsi, Fomitella fraxinea and Pleurotus cornusopiae markedly exhibited inhibition on lipid peroxidaton of rat liver microsomes. Ergosterol peroxide (5,8-epidioxy-5α,8α-ergosta-6,22E-dien-3β-ol), antioxidant from A. mellea, was isolated by solvent extraction, silica gel column chromatography and recrystallization. The structure of the compound was determined by NMR, GC/MS and X-ray crystallography. Ergosterol peroxide showed potent inhibition on lipid peroxidation and exhibited higher antioxidant activity than well-known antioxidants, α-tocopherol and thiourea.

Binaphthol-derived chiral ketones 1a-c were synthesized and were shown to serve as active catalysts for asymmetric epoxidation of olefins using Oxone, although their enantioselectivities were not high. However, very interestingly, the stereochemical outcome of the resulting epoxides implicates that in the epoxidation using 1a-c, the planar transition state may be more favorable than the spiro transition state.