This article gives an overview of a recently developed channel system, frit-inlet asymmetrical flow field-flow fractionation (FI-AFlFFF), which can be applied for the separation of nanoparticles, proteins, and water soluble polymers. A conventiona l asymmetrical flow FFF channel has been modified into a frit-inlet asymmetrical type by introducing a small inlet frit near the injection point and the system operation of the FI-AFlFFF channel can be made with a great convenience. Since sample components injected into the FI-AFlFFF channel are hydrodynamically relaxed, sample injection and separation processes proceed without interruption of the migration flow. Therefore in FI-AFlFFF, there is no requirement for a valve operation to switch the direction of the migration flow that is normally achieved during the focusing/relaxation process in a conventional asymmetrical channel. In this report, principles of the hydrodynamic relaxation in FI-AFlFFF channel are described with equations to predict the retention time and to calculate the complicated flow variations in the developed channel. The retention and resolving power of FI-AFlFFF system are demonstrated with standard nanospheres and protreins. An attempt to elucidate the capability of FI-AFlFFF system for the separation and size characterization of nanoparticles is made with a fumed silica particle sample. In FI-AFlFFF, field programming can be easily applied to improve separation speed and resolution for a highly retaining component (very large MW) by using flow circulation method. Programmed FI-AFlFFF separations are demonstrated with polystyrene sulfonate standards and pululans and the dynamic separation range of molecular weight is successfully expanded.

This article gives an overview of a recently developed channel system, frit-inlet asymmetrical flow field-flow fractionation (FI-AFlFFF), which can be applied for the separation of nanoparticles, proteins, and water soluble polymers. A conventiona l asymmetrical flow FFF channel has been modified into a frit-inlet asymmetrical type by introducing a small inlet frit near the injection point and the system operation of the FI-AFlFFF channel can be made with a great convenience. Since sample components injected into the FI-AFlFFF channel are hydrodynamically relaxed, sample injection and separation processes proceed without interruption of the migration flow. Therefore in FI-AFlFFF, there is no requirement for a valve operation to switch the direction of the migration flow that is normally achieved during the focusing/relaxation process in a conventional asymmetrical channel. In this report, principles of the hydrodynamic relaxation in FI-AFlFFF channel are described with equations to predict the retention time and to calculate the complicated flow variations in the developed channel. The retention and resolving power of FI-AFlFFF system are demonstrated with standard nanospheres and protreins. An attempt to elucidate the capability of FI-AFlFFF system for the separation and size characterization of nanoparticles is made with a fumed silica particle sample. In FI-AFlFFF, field programming can be easily applied to improve separation speed and resolution for a highly retaining component (very large MW) by using flow circulation method. Programmed FI-AFlFFF separations are demonstrated with polystyrene sulfonate standards and pululans and the dynamic separation range of molecular weight is successfully expanded.

Frequency spectra of the complex permittivity of 2-methoxyethanol (2-ME) with water, ethanol, dimethylsulphoxide (DMSO), N,N-dimethylformamide (DMF) and N,N-dimethylacatamide (DMA) have been determined over the frequency range of 10 MHz to 20 GHz at 25 $^{\circ}C$, using the Time domain reflectometry method, for 11 concentrations for each system. The static dielectric constant, dielectric constant at microwave frequency, relaxation time, excess dielectric parameters, and Kirkwood correlation factor have been determined. The relaxation in these systems within the frequency range can be described by a single relaxation time constant, using the Debye model. The parameters show a systematic change with the concentration.

To show the effects of metallothionein (MT) on the activity of enzymes involved in the removal of reactive oxygen species, MT has been added to the assay systems of superoxide dismutase (SOD), catalase and peroxidase. We have used assay systems of SOD based on NADPH oxidation and nitrite formation from hydroxylammonium chloride as an assay of superoxide breakdown rate. The two assay systems showed different results at the high concentration of MT. MT showed the scavenging of superoxide in the SOD assay system in the presence and absence of SOD. MT added to the SOD assay system behaved as an activator of SOD, but apo-MT behaved as an inhibitor. When MT was added to the assay system in the presence of a fixed amount of SOD, the breakdown rate of superoxide increased. The effects of MT on the decomposition of hydrogen peroxide and the activity of catalase and peroxidase decomposing hydrogen peroxide were evaluated. MT decreased the activities of catalase and peroxidase. We have concluded that the function of MT as an antioxidant might effect the level of superoxide scavenging and not the level of hydrogen peroxide.

Lithium inserted into artificial carbon has been synthesized as a function of the Li concentration. The characteristics of these prepared compounds were determined from the studies using X-ray diffraction(XRD), solid nuclear magnetic resonance (NM R) spectrophotometric and differential scanning calorimeter(DSC) analysis. X-ray diffraction showed that lower stage intercalation compounds were formed with increasing Li concentration. In the case of the AG3, most compounds formed were of the stage 1 structure. Pure stage 1 structural defects of artificial graphite were not observed. 7Li-NMR data showed that bands are shifted toward higher frequencies with increasing lithium concentration; this is because non-occupied electron shells of Li increased in charge carrier density. Line widths of the Li inserted carbon compounds decreased slowly because of nonhomogeneous local magnetic order and the random electron spin direction for located Li between graphene layers. The enthalpy and entropy changes of the compounds can be obtained from the differential scanning calorimetric analysis results. From these results, it was found that exothermic and endothermic reactions of lithium inserted into artificial carbon are related to the thermal stability of lithium between artificial carbon graphene layers.

Three simple carboxamides incorporating the phenethylamine moiety have been isolated from strain XR-NC of a symbiotic bacterium Xenorhabdus nematophilus. Their structures were identified by spectroscopic data and synthesis. The compounds exhibited significant cytotoxicities against human cancer-cell line, viz. the gastric adenocarcinoma, colon adenocarcinoma and lung adenocarcinoma.

The palladium catalyzed dehalogenative homocoupling of haloarylsulfonates under reductive conditions has proceeded selectively depending on the type of the halogen. Thus, an iodo or a bromo leaving group of haloarylsulfonates was homocoupled to gi ve symmetrical biaryls in good yields with the sulfonate group intact, whereas a chloro leaving group gave no reaction under the conditions used. When the more reactive nickel catalyst was employed instead of the palladium catalyst in the reaction, both dehalogenative and desulfonative homocouplings of haloarylsulfonates occurred regardless of the type of the halogen used.

A new ligand containing the long aliphatic hydrocarbon chain, dipyridylstearylamine (dps) and its copper(Ⅱ) complex, Cu(dps)(NO3)2 have been prepared. The copper complex was characterized structurally and spectroscopically. The XRD crystal structure of the copper complex reveals that copper is octahedrally coordinated by dps and two nitrato ligands. The nitrato groups ligate asymmetrically to the copper. Crystal data are P1bar, a=8.249(2), b=10.416(3), $c=20.915(4)\AA$, $\alpha=86.54(2)$, $\beta=84.026(2)$, $\gamma=72.32(2)^{\circ}$, V=1702.7(7) $\AA3$ , Z=2, ${\lambda}$(Mo $K\alpha)=0.71073\AA$, $\mu=0.689$ mm-1 , T=293(2) K, R=0.0560 for 3529 reflections. The dps and the copper complex are stable in the air and the copper complex exhibits features of typical of other copper(Ⅱ) complexes containing dipyridylamine-based ligand.

The kinetics and mechanism of the reactions of thiophenyl dimethylacetates (TDA) and trimethylacetates (TTA) with benzylamines in acetonitrile are studied. The reactions are first order in both the amine and the substrate. Relatively large values of ${\beta}X(\betanuc$ = 1.1-1.5; TDA and 1.1-1.5; TTA) and ${\beta}Z({\beta}lg$ = -1.8~-2.0; DTA and -1.3~-1.6; TTA) for benzylamines, significantly large kH/kD values (=1.2-1.5; DTA and 1.2-1.5; TTA) involving deuterated benzylamines, and large ${\rho}XZ$ (=0.82; TDA and 1.05; TTA) values are interpreted to indicate stepwise acyl transfer mechanism, but with the hydrogen bonded four center type transition state for benzylamine. The relatively greater magnitudes of ${\rho}XZ$ and the secondary kinetic isotope effects involving deuterated nucleophiles are in line with the proposed mechanism.

Quantitative Structure-Activity Relationship (QSAR) have been established of 57 fluorovinyloxyacetamides compounds to correlate and predict EC50 values. Genetic algorithm (GA) and multiple linear regression analysis were used to select the descriptors and to generate the equations that relate the structural features to the biological activities. This equation consists of three descriptors calculated from the molecular structures with molecular mechanics and quantum-chemical methods. The results of MLR and GA show that dipole moment of z-axis, radius of gyration and logP play an important role in growth inhibition of barnyard grass.

The effects of ortho- (R = H and CH3) and Y-substituents (Y = OCH3, CH3H and CN), which are directly attached to the carbonyl carbon, on the protonation equilibria of the para-X-substituted benzoyl derivatives, 4-X -2, 6-di-R-C6H2-C(=O)-Y, are investigated theoretically using the B3LYP method with 6-31+G* basis set. Structurally, both of the (B) and (BH+ ) forms in the species with R = H are nearly coplanar regardless of the Y-substituents implying that the steric repulsion between Y-substituent and R = H is relatively small. In the species with R = CH3 , the tortional angle (Θ) between the carbonyl moiety and aryl ring varies from zero to near right angle depending on the degree of steric repulsion between Y and R = CH3 and the resonance demand. However the reaction energies, ΔG°, for the protonation processes are more favorable for R = CH3 than for R = H due to stronger electron donating effect of R = CH3 , although the species with R = CH3 are unfavorable sterically. On the other hand, the Hammett type plots are progressively better correlated with б+ than with б values on going from Y = OCH3 to Y = CN for both species with R = H and CH3 indicating that the degree of resonance delocalization between carbonyl moiety and X-substituent is increased for a more electron accepting Y-substituent. Nevertheless the effects of R = CH3 on the magnitude of Hammett type reaction constants ( б or б+ ) are not much different from those of R = H.

A new chiral stationary phase (CSP) based on (1R,2S)-2-amino-1-indanol, which is expected to be conformationally rigid because of its cyclic nature, was prepared. The new CSP was applied in resolving various $N-acyl-\alpha-arylalkylamines$. The chromatographic resolution results on the new CSP were compared with those on the other CSP based on (1S,2R)-norephedrine, which is believed to be conformationally flexible. Comparison of the chromatographic resolution results on the two CSPs demonstrated that conformationally flexible analytes are resolved better on the conformationally rigid CSP while conformationally rigid analytes are resolved better on the conformationally flexible CSP. From these results it was concluded that conformational rigidity or flexibility of CSPs is the important factor for the chiral recognition.

New lipophilic triesters of calix[4]arene and calix[4]quinone are investigated as sodium ion-selective ionophores in poly(vinyl chloride) membrane electrodes. For an ion selective electrode based on calix[4]arene triester I, the linear response is 1 ${\times}$10-3.5 to 1 ${\times}$ 10-1 M of Na+ concentrations. The selectivity coefficients for sodium ion over alkali metal and ammonium ions are determined. The detection limit (logaNa+ = -4.50) and the selectivity coefficient (logKNa+,K+pot = -1.86) are obtained for polymeric membrane electrode containing calix[4]arene triester I.

Poly(p-tert-butyltrimethoxymonopropyloxycalix[4]arene-methylsiloxane) (TBCX-MS) has been prepared and used as a stationary phase in isothermal capillary gas chromatographic separation of some positional isomers. Retention factors (k) and separatio n factors $(\alpha)$ for the isomers were measured and compared with those on poly(p-tert-butyl-dimethoxydipropyloxycalix[4]arene-tetramethyldisiloxane) (TBCX-TMDS), poly(dimethoxydipropyloxycalix[4]arenetetramethyl-disiloxane) (CX-TMDS). Most of the isomers investigated are well resolved on TBCX-MS. Retention of all the compounds decreases on the three phases in the order, TBCX-TMDS ${\geq}$ TBCX-MS > CX-TMDS. Similar retention values on TBCX-TMDS and TBCX-MS seem to indicate that retention property of the two phases is not significantly affected by the spatial position of the calixarene moiety.