The ${alpha}$-amylase gene of Bacillus licheniformis has been cloned and two mutant ${alpha}$-amylase genes of which histidine 235 was changed to glutamine (H235Q) and aspartic acid 328 to glutamic acid (D328E) have been produced by site-directed mutagenesis. The kinetic parameters, optimum pH and thermostability of wild type(WT) and these two mutant amylases expressed in E. coli MC1061 have been compared after purification. The $K_m$ values of WT, H235Q and D328E ${alpha}$-amylases were 0.22%, 0.73%, and 0.80% respectively, when using starch as the substrate. The $V_max$ values of wild type ${alpha}$ -amylase and mutant ${alpha}$-amylases were 0.6-0.7%/minute, and did not show any significant differences among them. The optimum pH of D328E ${alpha}$-amylase was shifted to more acidic pH. Also, the thermostability of H235Q ${alpha}$-amylase was increased compared to the wild type ${alpha}$-amylase.

The polymer matrix effect on the selectivity, response rate and reproducibility for coextraction type anion-selective optode membranes were investigated with DOA-plasticized PVC, PVC/hydroxylated PVC, PU/hydroxylated PVC and DOS-plasticized CTA matrices. Optode membranes were prepared with TDMACl and ETH2412 dissolved in one of the four solvent polymeric matrices. The PU/hydroxylated PVC and PVC-based membranes have almost the same selectivity coefficients, while the CTA-based membrane is more selective toward lipophilic anions. The membrane with PU/hydroxylated PVC adhered strongly to a glass surface, and showed highly reproducible and relatively rapid response. Very poor adhesion of PVC/hydroxylated PVC and CTA-based membranes limited the usability of those membranes as sensor components. Based on these results, and considering the biocompatibility for clinical samples, the optode made with PU/hydroxylated PVC was applied to determine the thiocyanate ion in human saliva. The results obtained with this simple device were comparable to those with rather complicated ISE methods.

Iodine-induced lactonization of ${\alpha}$-Phenylsulfonyl-${\gamma},{\delta}$-Unsaturated Amides provided 2,4-trans-substitued ${\gamma}$-butyrolactones in high selectivity. NBS-or NCS-induced lactonization of N,N-dimethyl-2-(phenylsulfonyl)-4-pentenamide in DME-$H-2O(2:1 vol)$ gave 2-halo-4-(halomethyl)-2-(phenylsulfonyl)-${\gamma}$-butyrolactone.

Tetracarbonylhydridoferrate, $HFe(CO)^-_4$, generated by the reaction of $Fe(CO)_5$ with alkaline solution, is a good reducing agent for mono-dehalogenation of gem-dihalocyclopropanes. It also acts as a good reducing catalyst under phase transfer reaction conditions. 1,1-Dibromo-2-phenylcyclopropane and 1,1-dichloro-2-phenylcyclopropane were reduced to the corresponding mono-dehalogenated products in excellent yields. Thermodynamically stable trans-l-bromo-2-phenyl cyclopropane was formed as the major product over the cis-isomer, trans/cis=3/2. The 1-bromo-2-phenyl cyclopropane radical intermediate was formed by single electron transfer from $HFe(CO)^-_4$. Dissociation of bromide anion, followed abstraction of hydrogen radical from alcoholic solvent would lead to the formation of the stable trans-isomer. The further mechanistic aspects were discussed.

The ${\alpha},{\beta}$-enoyl chiral iron complexes, ${\alpha},{\beta}-enoyl-{\eta}^5-(C_5H_5)Fe(CO)(PPh_3)$ (1) were prepared from ${\alpha},{\beta}-enoyl-{\eta}^5-(C_5H_5)Fe(CO)_2$(2) and triphenylphosphine through a photochemical ligand substitution followed by carbonylation.

A series of aliphatic hydrocarbons, methane to hexane in the liquid state, are modeled with the molecular mechanical potential parameters treating all hydrogen degrees of freedom explicitly. Thermodynamic properties (heat capacities and heats of vaporization) are calculated from relatively short (20ps) molecular dynamics trajectories. The liquid state structures are also examined through various radial distribution functions. Molecular dynamics simulations reproduce experimentally measured properties within a few percent errors, thus indicate that the present set of all-hydrogen parameters is suitable for simulating macromolecular systems in bulk.

We have calculated the ${\pi}$-electron density, atom self-polarizability, and free valence on each atom of N-(2-chlorobenzyl)-pyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-2-chloropyridinium salts using a simple Huckel method in order to discuss their intramolecular photocyclization reaction in a qualitative method. Our calculation qualitatively predicts that photocyclization occurs through forming radicals as a reaction intermediate by breaking a C-Cl bond after photoexcitation into a triplet state via intersystem crossing from an initially excited singlet state. We noticed that this C-Cl bond breaking is aided by ${\pi}$-complex formation between a chlorine atom and the ${\pi}$ -electrons of the neighboring ring in the triplet state and a stronger ${\pi}$-complex bond makes C-Cl bond breaking, i.e., radical formation, much easier. A chlorine atom will form a stronger ${\pi}$ -complex bond to a benzyl ring of N-(benzyl)-2-chloropyridinium than a pyridinium ring of N-(2-chlorobenzyl)-pyridinium because the former can donate its ${\pi}$-electron more easily than the latter. The chlorine at position 15 of N-(2-chlorobenzyl)-2-chloropyridinium salt in the excited state also provides its ${\pi}$-electron to the benzyl ring. So this ${\pi}$-electron can increase the bond strength of the $\pi-complex.$ Therefore, the strength of ${\pi}$-complex follows the order of N-(2-chlorobenzyl)-2-chloropyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-pyridinium salts and thus the radical formation rate. This provides us with an intramolecular photocyclization reaction rate of the same order as given above.

2nd-order rate constants have been measured spectrophotometrically for the reactions of 4-nitrophenyl benzoate (1), S-4-nitrophenyl thiobenzoate (2) and 4-nitrophenyl thionbenzoate (3) with alkoxides, aryloxides and thioaryloxides in absolute ethanol at 25.0 ${\pm}0.1$${\circ}C$. The substitution of O by polarizable S in the leaving group has little affected the reactivity of 2 toward the charge localized species (eg. $EtO^-$ and $CF_3CH_2O^-$), while the effect of the similar replacement in the carbonyl group has led to a decrease in reactivity by a factor of 10. However, the reactivity of these esters toward charge delocalized aryloxides has been found to be in the order $1<3{\le}2$. The effect of replaced sulfur atom on reactivity becomes more significant for the reaction with polarizable thioaryloxides, i.e. the reactivity increases in the order $1<2{\ll}3$. The difference in reactivity for the present system is attributed to a polarizability effect.

In the presence of stoichiometric (-)-${\alpha}$-isosparteine, 2-lithio-1,3-dithiane underwent enantioselective addition to aldehydes with moderate ee's (6-70%).

We have re-examined the linear solvation energy relationships in reversed phase liquid chromatography by considering various solutes including quite a number of compounds of strong hydrogen bond capability. We observed that solutes of strong hydrogen bond ability should be excluded in order to obtain resonable correlations between In k' and solute polarity parameters and that inclusion of one or two such solutes causes severe distortions of correlation results. This anomaly may be due to existence of residual silanol groups in the stationary phase, that is, their specific interactions with solutes.

The approximate rate and stoichiometry of the reaction of excess diisobutylaluminum hydride-dimethyl sulfide complex($DIBAH-SMe_2$) with organic compounds containing representative functional group under standardized conditions (toluene, $0{\circ}C$) were examined in order to define the reducing characterstics of the reagent and to compare the reducing power with DIBAH itself. In general, the reducing action of the complex is similar to that of DIBAH. However, the reducing power of the complex is weaker than that of DIBAH. All of the active hydrogen compounds including alcohols, amines, and thiols evolve hydrogen slowly. Aldehydes and ketones are reduced readily and quantitatively to give the corresponding alcohols. However, $DIBAH-SMe_2$ reduces carboxylic acids at a faster rate than DIBAH alone to the corresponding alcohols with a partial evolution of hydrogen. Similarly, acid chlorides, esters, and epoxides are readily reduced to the corresponding alcohols, but the reduction rate is much slower than that of DIBAH alone. Both primary aliphatic and aromatic amides examined evolve 1 equiv of hydrogen rapidly and are reduced slowly to the amines. Tertiary amides readily utilize 2 equiv of hydride for reduction. Nitriles consume 1 equiv of hydride rapidly but further hydride uptake is quite slow. Nitro compounds, azobenzene, and azoxybenzene are reduced moderately. Cyclohexanone oxime liberates ca. 0.8 equiv of hydrogen rapidly and is reduced to the N-hydroxylamine stage. Phenyl isocyanate is rapidly reduced to the imine stage, but further hydride uptake is quite sluggish. Pyridine reacts at a moderate rate with an uptake of one hydride in 48 h, while pyridine N-oxide reacts rapidly with consumption of 2 equiv of hydride for reduction in 6h. Similarly, disulfides and sulfoxide are readily reduced, whereas sulfide, sulfone, and sulfonic acid are inert to this reagent under these reaction conditions.

The approximate rates and stoichiometry of the reaction of excess sodium tris(diethylamino)aluminum hydride (ST-DEA) with selected organic compounds containing representative functional groups under standardized conditions(tetrahydrofuran, $0{\circ}$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of STDEA was also compared with those of the parent sodium aluminum hydride (SAH) and lithium tris(diethylamino)aluminum hydride (LTDEA). The reagent appears to be milder than LTDEA. Nevertheless, the reducing action of STDEA is very similar to that observed previously for LTDEA, as is the case of the corresponding parent sodium and lithium aluminum hydrides. STDEA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and 1-hexanol evolved hydrogen slowly, whereas 3-hexanol and 3-ethyl-3-pentanol, secondary and tertiary alcohols, were essentially inert to STDEA. Primary amine, such as n-hexylamine, evolved only 1 equivalent of hydrogen slowly. On the other hand, thiols examined were absolutely stable. STDEA reduced aidehydes and ketones rapidly to the corresponding alcohols. The stereoselectivity in the reduction of cyclic ketones by STDEA was similar to that by LTDEA. Quinones, such as p-benzoquinone and anthraquinone, were reduced to the corresponding 1,4-dihydroxycyclohexadienes without evolution of hydrogen. Carboxylic acids and anhydrides were reduced very slowly, whereas acid chlorides were reduced to the corresponding alcohols readily. Esters and epoxides were also reduced readily. Primary carboxamides consumed hydrides for reduction slowly with concurrent hydrogen evolution, but tertiary amides were readily reduced to the corresponding tertiary amines. The rate of reduction of aromatic nitriles was much faster than that of aliphatic nitriles. Nitrogen compounds examined were also reduced slowly. Finally, disulfide, sulfoxide, sulfone, and cyclohexyl tosylate were readily reduced without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent: like LTDEA, STDEA converted ester and primary carboxamides to the corresponding aldehydes in good yields. Furthermore, the reagent reduced aromatic nitriles to the corresponding aldehydes chemoselectively in the presence of aliphatic nitriles. Consequently, STDEA can replace LTDEA effectively, with a higher selectivity, in most organic reductions.

A comparative molecular field analysis (CoMFA) on the substituent effect of the palladium(Ⅱ) catalyzed [3,3]-sigmatropic rearrangement of allylic esters was studied to show a good correlation between the electrostatic property of substituents and the reaction rate. The CoMFA result suggests that the reaction rate will increase as the electron-donating ability of substituents increases.

Reactions of mer, trans-$Re({\equiv}NC_6H_5)(PPh_3)_2Cl_3$, I, with $PMe_3$ and $P(OMe)_34 at room temperature, led to mer, trans-$Re({\equiv}NC_6H_5)(PPh_3)(PMe_3)Cl_3$, II, and fac-$Re({\equiv}NC_6H_5)(PPh_3)(P(OMe)_3)Cl_34, III, respectively. The crystal structures of II and III were determined through X-ray diffraction. Ⅱ crystallizes in the orthorhombic system, space group $Pna2_1$ with cell parameters a=19.379(4) ${\AA}$, b=11.867(2) ${\AA}$, c = 12.676(3) ${\AA}$, and Z = 4. Least-squares refinement of the structure led to a $R(wR_2)$ factor of 0.0251 (0.0621) for 2203 unique reflections of $I>2{\sigma}(I)$ and for 306 variables. III crystallizes in the monoclinic system, space group $P2_1/n$ with cell parameters a=11.399(3) ${\AA}$, b=14.718(4) ${\AA}$, c=17.558(5) ${\AA}$, ${\beta}=97.79(2){\circ}$, and Z=4. Least-squares refinement of the structure led to a $R(wR_2)$ factor of 0.0571 (0.1384) for 3739 unique reflections of $I>2{\sigma}(I)$ and for 344 variables. Structural studies showed that the relative orientations of the two phosphines in both complexes are different, probably due to the differences in the coordinating abilities between $PMe_3$ and $P(OMe)_3$ to the 5-coordinate fluxional intermediate.

The pH-dependent reduction behavior of N-monosubstituted-4,4'-bipyridinium ions ($RBPY^+: R=methyl(C_1)$; benzyl; n-octyl; n-dodecyl) has been investigated by electrochemical and spectroelectrochemical techniques. At acidic condition, $RBPY^+$ is protonated and the protonated species are reduced by two consecutive one-electron processes. The $2e^-$ reduced species undergoes a chemical reaction with $H^+$. The second-order rate constant $(k_H)$ of the homogeneous chemical process is $(3.7{\pm}0.3){\times}10^3M^{-1}s^{-1}$ for the two electron reduction product of $C_1BPY^+$. At high pH, the electrode reduction of $RBPY^+$ is one-step $2e^-$ transfer process with concomitant addition of $H^+$, which is confirmed by cyclic voltammetric study using a microdisk electrode.