The temperature dependence of the kinetic parameters of the aspartase-catalyzed reaction has been examined in the direction of deamination. The pK1values at 37$^{\circ}C$, 25$^{\circ}C$, 16$^{\circ}C$ and 7$^{\circ}C$ were 6.2 $\pm$ 0.1, 6.3 $\pm$ 0.1, $6.7{\pm}0.3$ and 6.9 $\pm$ 0.3, respectively. On the other hand, the pK2 values at 37$^{\circ}C$,25$^{\circ}C$, 16$^{\circ}C$ and 7$^{\circ}C$ were 8.1 $\pm0.2$, 8.3 $\pm$ 0.2, 8.2 $\pm$ 0.3 and 8.0 $\pm$ 0.2,respectively. The enthalpy of ionization, DHion, calculated from the slope of pK1, are 6.0 $\pm$ 0.3 kcal/mol. These results validate the prediction that aspartase requires a histidine residue for a general base, and a cysteine (or having a carboxyl functional group) for a general acid.

Multiblock copolymers consisting of poly( g-benzyl L-glutamate) (PBLG) as the hydrophobic part and poly(ethylene oxide) (PEO) as the hydrophilic part (GEG) were synthesized and characterized. GEG polymeric micelles were prepared by the dialysis technique. Particle size distributions based on intensity,volume, and number-average were 22.6 $\pm$ 11.9 nm, 23.5 $\pm$ 4.6 nm, and 23.7 $\pm$ 37 nm, respectively. It was observed that par-ticle size and size distribution of GEG polymeric micelles changed significantly with the choice of initial sol-vent. Transmission electron micrographs (TEM) showed the polymeric micelles to be spherically shaped, with sizes ranging from 20 nm to 40 nm in diameter. Fluorescence spectroscopy measurements suggested that GEG block copolymers wereassociated in water to form polymeric micelles, and the critical micelle concentrations (CMC) value of the block copolymers was 0.0094 g/L. Further evidenceof micelle formation of GEG block copolymers and limited mobility of the PBLG chain in the core ohe micelle was obtained with 1 H NMR in D2O.

A simple and inexpensive colorimetric spectrometer for determining total cholesterol has been developed,comprising a diode laser as the light sourcoptical fibers for the light guide and a photodiode as the detector.The stabilty and performance of the new system was investigated by obtaining the calibration curve for stan-dard cholesterol solutions. The total cholesterol in humanserum was also measured by the analyzer and com-pared with the value obtained by a conventional spectrometer. The results showed that the developed spectrometer was useful for the determination of cholesterol levels. The visible diodelaser used in the study exhibited good spectroscopic and operational properties for colorimetric absorption spectrometry and could be a key component for the development of a simple and economical analyzer.

2,2￠-Dihydroxyazobenzene (DHAB) was attached to poly(ethylenimine) (PEI) to obtain DHAB-PEI. Spectral titration revealed that uranyl, Fe(III), Cu(II), and Zn(II) ion form 1 : 1-type complexes with DHAB attached to PEI. Formation constants for the metal complexes formed by the DHAB moieties of DHAB-PEI were mea-sured by using various competing ligands. The results indicated thatthe concentrations of uranyl, Fe(III), and Cu(II) ions can be reduced to 10 -16 -10 -23 M at p 8 with DHAB-PEI when the concentration of the DHAB moiety is 1 residue M. By using cyanuric chloride as the coupling reagent, DHAB-PEI was immobilized on Sephadex G-25 resin to obtain DHAB-PEI-Seph. Binding of uranyl,Fe(III), Cu(II), and Zn(II) ion by DHAB-PEI-Seph was characterized by using competing ligands. A new method has been developed for characteriza-tion of metal sequestering ability of a chelating resin. Formation constants and metal-binding capacity of two sets of binding sites on the resin were estimated for each metal ion. DHAB-PI-Seph was applied to recovery of metals such as uranium,Fe, Cu, Zn, Pb, V, Mn, and W from seawater. The uranium recovery from seawaterby DHAB-PEI-Seph does not meet the criterion for economical feasibility partlydue to interference by Fe and Zn ions. The seawater used in the experiment was contaminated by Fe and Zn and, therefore, the efficiency of uranium extractionfrom seawater with DHAB-PEI-Seph could be improved if the experiment is carried out in a cleaner sea.

Matrix/Surface-assisted laser desorption/ionization (M/SALDI) mass spectrometry of polypropylene glycol and polystyrene, directly deposited on graphite plate, is demonstrated. Graphite plate is effective both as an en-ergy transfer medium and robu st sampling support for LDI of polymers. Mass spectra ofpolymers can be easily obtained due to homogeneous distribution on graphite surface and their ion signals are long-lived by large ef-fective desorption volume enough to investigate M/SALDI process.

Electrochemical and spectroelectrochemical studies of cobalt-Schiff (Co-SB) base complexes, Co(salen) [N-N'-bis(salicylaldehyde)-ethylenediimino cobalt(II)] and Co(salophen) [N-N'-bis(salicylaldehyde)-1,2-pheny-lenediimino cobalt(II)], have been c arried out to test them as oxygen reduction catalysts. Both compounds were found to form an adduct with oxygen and exhibit catalytic activities for oxygen reduction. Comparison of spec-tra obtained from electrooxidized complexes with those from Co-SB complexes equilibrated with oxygen in-dicates that the latter are consistent with the postulated complex formed with oxygen occupying the coaxial ligand position, namely, Co(III)-SB·O2 - .The catalysis of oxygen reduction is thus achieved by reducing Co(III) in the oxygen-Co-SB adduct, releasing the oxygen reduction product, e.g., O2 - ., from the Co(II)-SB complex.

Association of cytochrome c with anionic membranes involved both electrostatic and hydrophobic interactions and their relative contributions depended on the physical state of the membrane and the redox state of cyto-chromec.Hydrophobic interaction was favored by the membranes in gel phase, by the membranes with a large curvature, and by the membranes with a high surface charge density. Ferrocytochrome c was less dissociable by NaCl than ferricytochrome c suggesting that a lower protein stability is beneficial for hydrophobic interac-tion.Hydrophobic interaction induced larger structural perturbations on cytochrome c as monitored by the loss of the Fe-Met bond and by the increase in the distance between heme and Trp-59. When bound to anionic mem-branes,spin-labeled cytochrome c showed an electron paramagnetic resonance spectrum with two or more components, providing a direct evidence for multiple conformations of bound cytochrome c.

In this study we have investigated the determination of proper time step in molecular dynamics simulation.Since the molecular dynamics is mathematically related to nonlinear dynamics, the analysis of eigenvalues isused to explain the relationship between the time step and dynamics. The tracings of H2 and CO2 molecular dynamics simulation agrees very well with the analytical solutions. For H2, the time step less than 1.823 fs pro-vides stable dynamics. ForCO2, 3.808 fs might be the maximum time step for proper molecular dynamics. Al-though this results were derived for most simple cases of hydrogen and carbon dioxide, we could quantitatively explain why improperly large time step destroyed the molecular dynamics. From this study we could set the guide line of the proper time step for stable dynamics simulation in molecular modeling software.

Arenealdehyde 2-benzothiazolylhydrazone in thianthrene cation radicalafforded triazolo[3,4-b]benzothiazoles and 1,2,4-triazoles as major and minor product, respectively. On the contrary the similar reaction in tris(2,4-dibromophenyl)aminium hexachloroantimonate gave 1,2,4-triazoles and triazolo[3,4-b]benzothiazoles as ma-jor and minor product, respectively.

Corroles and oxacorroles were synthesized by acid-catalyzed, 2+2 condensation. The condensation afforded different corroles bearing core-heteroatoms at the predesignated locations. Regioselective a- a’ linkage be-tween pyrrole and furan or betwee n pyrrole and pyrrole was achieved by keeping the linking carbon at different position of starting dipyrromethanes. The condensation was only fruitful when furan-containing dipyrromethanes were condensed.

We present the results of computer simulation for the steady shear flows of rodlike molecules using nonequi-librium molecular dynamics simulation (NEMD) method. The model particle is a rigid rod composed of lin-early connected 6-sites and the Lennard-Jones 12-6 potential governs interactions between sites in different molecules. The system of rodlike molecules exhibits the change of orientational structure, that is, isotropic-nematic transition at high shear rates. We elucidate the nature of the ordered system developed from an isotro-pic phase by steady shear through an analysis of various quantities: orientational order parameters, orientational pair correlation functions, orientational distribution function, and snapshots of configurations. The effects of temperature and density on the shear rate dependence of orientational structure are described.

A new series of three ring type liquid crystalline compounds containing partially fluorinated alkenyl or alkyl side chains together with fluorine substituted cyclohexylbiphenyls were designed and synthesized in this study. The structures of synthe sized compounds were established by 1 H, 13 C and 19 F NMR spectroscopy. The phase transition temperatures of fluorinated liquid crystalline compounds were determined by cross-polarizing mi-croscopy equipped withhot stage. All compounds were found to have nematic liquid crystalline phase with rel-atively low phase transition temperature and wide liquid crystalline temperature range. The dependence of phase transition temperatures on the chainlength falls into three categories; (a) decreasing transition tempera-tures for 4-fluoro-4'-[4-fluoro-4-(1-fluoroalkyl)cyclohexyl]biphenyl (15) series, (b) higher transition tempera-tures for odd numbered chains for 4-fluoro-4'-[4-fluoro-4-(1-fluoroalk-1-enyl)cyclohexyl]biphenyl (14) series, (c) higher transition temperatures for even numbered chains for 4-[4-(1,2-difluoroalk-1-enyl)-4-fluorocyclo-hexyl]-4'-fluorobiphenyl (16) series.