(3R,4R)-4-Acetoxy-3-[(1'R-tert-butyldimethylsilyloxy)ethyl]-2-azetidinone, one of the best synthons for carbapenems and penems was efficiently synthesized from readily available L-threonine via double azetidinone ring formation.

In a recent paper[Bull. Kor. Chem. Soc. 17, 735 (1996)] we reported results of molecular dynamic (MD) simulations for the thermodynamic and structural properties of liquid n-alkanes, from n-butane to n-heptadecane, using three different models. Two of the three classes of models are collapsed atomic models while the third class is an atomistically detailed model. In the present paper we present results of MD simulations for the dynamic properties of liquid n-alkanes using the same models. The agreement of two self-diffusion coefficients of liquid n-alkanes calculated from the mean square displacements (MSD) via the Einstein equation and the velocity auto-correlation (VAC) functions via the Green-Kubo relation is excellent. The viscosities of n-butane to n-nonane calculated from the stress auto-correlation (SAC) functions and the thermal conductivities of n-pentane to n-decane calculated from the heat-flux auto-correlation (HFAC) functions via the Green-Kubo relations are smaller than the experimental values by approximately a factor of 2 and 4, respectively.

The angular and planar heterocyclic compounds containing nitrogen, sulfur and oxygen were synthesized by reaction of 6,7-dichloro-5,8-quinoxalinedione with aromatic and aliphatic dinucleophiles. Nucleophilic reactivity was somewhat different between 2,3-dichloro-1,4-naphthoquinone and 6,7-dichloro-5,8-quinolinedione with dinucleophiles. The distribution of electron in heterocycle appeared to contribute to this difference. The intercalation comple of planar heterocyclic compound between GC/GC base pairs showed the optimum intercalation but the intercalation of angular heterocyclic compound was not good. Thus, the planar compound was expected to have antitumor activity.

The stability of bridgehead olefins containing 8 and 10 membered rings has been investigated by the MMX molecular mechanics calculation together with the GMMX conformational searching program. A number of 'hyperstable' bridgehead olefins, which have negative olefin strain values, have been found from the calculated values of strain energy and olefin strain for the series of in- and out-bicyclo[n.3.3]alk-1-ene and in- and out-bicyclo[n.4.4]alk-1-ene (n=1 to 8). For the bridgehead olefins with 'out' topology, hyperstable olefins were found in the systems having cyclononene or larger rings. For the bridgehead olefins with 'in' topology, hyperstable olefins were found in the systems having cyclodecene or larger rings.

Electrochemical behavior of mer-tris(2-pyridinethiolato)cobalt(Ⅲ) in dimethylformamide was studied on a platinum electrode by means of cyclic voltammetry, chronoamperometry, and chronocoulometry. It was found that the neutral complex molecule was electroactive between the potential region of 1.0 and - 1.2 V vs. a nonaqueous Ag/Ag+ electrode. The Co(Ⅲ) complex was reversibly reduced to Co(Ⅱ) species by one-electron transfer at about - 1.1 V, followed by an irreversible dissociation reaction. However, the oxidation process at around 0.8 V, was responsible for an irreversible two-electron transfer that occurred at a ligand site.

In recent papers[Bull. Kor. Chem. Soc. 1996, 17, 735; ibid 1997, 18, 478] we reported results of molecular dynamics (MD) simulations for the thermodynamic, structural, and dynamic properties of liquid normal alkanes, from n-butane to n-heptadecane, using three different models. Two of the three classes of models are collapsed atomic models while the third class is an atomistically detailed model. In the present paper we present results of MD simulations for the corresponding properties of liquid branched-chain alkanes using the same models. The thermodynamic property reflects that the intermolecular interactions become weaker as the shape of the molecule tends to approach that of a sphere and the surface area decreases with branching. Not like observed in the straight-chain alkanes, the structural properties of model Ⅲ from the site-site radial distribution function, the distribution functions of the average end-to-end distance and the root-mean-squared radii of gyration are not much different from those of models Ⅰ and Ⅱ. The branching effect on the self diffusion of liquid alkanes is well predicted from our MD simulation results but not on the viscosity and thermal conductivity.

We studied the interaction of 4',6-diamidino-2-phenylindole (DAPI) with single stranded poly(dA) using optical spectroscopic methods, including absorption, circular dichroism (CD), and fluorescence spectroscopy. The temperature-dependent conformation of poly(dA) was also investigated. The conformation of poly(dA) varied with temperature, which is explained by the stacking-destacking process of the adenine bases, resulting from the sugar conformation. The hypochromicity and red-shift in the absorption spectroscopy, the lack of CD change in the drag absorption region, and the fluorescence behavior, especially a great accessibility of the I2 quencher to the poly(dA)-bound DAPI, suggest that DAPI binds to the outside of poly(dA). The Job plot for the DAPI-poly(dA) mixture demonstrated that a stoichiometry of one DAPI molecule binds to the one phosphate of poly(dA).

In a competitive enzyme immunoassay, the performance was tested with different analyte-enzyme conjugates (signal generators) in their binding constants to antibody. Analyte (progesterone)-enzyme (glucose oxidase; GO) conjugates were chemically synthesized and purified by using a gel column with an immobilized antibody to progesterone. In an elution range from the column, four peaks were detected by measuring total enzyme activities. Results from further analysis indicated that the first peak contained mainly unreacted GO while the next three peaks conjugated GO with progesterone. These three conjugate preparations were compared in dose-response curves along with the unpurified mixture. The purified conjugates showed higher detection capabilities than did the mixture. Especially, the preparation in the second peak next to the free GO peak improved the detection limit five times. This performance was comparable to that of a progesterone-horseradish peroxidase conjugate that has been identified to have one progesterone ligand.

A series of new ligands having convergent dicarboxylic acid functions, based-upon Rebek's cleft-type ionophore, have been prepared and their ion binding properties were investigated by the competitive extraction and transport experiments. The main purpose of the modification was to increase the lipophilicity of the Rebek's ionophore, which was attempted by utilizing propyl analog of Kemp's triacid or by changing the bridging unit. Ionophores 5 and 6 were found to have a pronounced ion-binding property toward Ca2+ ion. The selectivity in competitive extraction of ionophore 5 at pH 9 for Ca2+ over Mg2+ and Sr2+ is 2.0 and 59.3, respectively. The selectivity in competitive transport of ionophore 5 for Ca2+ over Mg2+ and Sr2+ is 29.8 and 99.3, and that of ionophore 6 is 10.0 and 23.2, respectively.

Apparent second-order rate constants (kapp) have been measured spectrophotometrically for the reaction of 2,4-dinitrophenyl benzoate (DNPB) with 6 secondary cyclic amines in H2O containing 20 mole% DMSO at 25.0±0.1 ℃. The Bronsted-type plot (log kapp vs. pKa) shows a break at pKa near 9.1, e.g. two straight lines with βapp values of 0.67 and 0.44 for the low basic (pKa < 9.1) and the highly basic (pKa > 9.1) amines, respectively. Using an estimated k2 value of 3×109 sec-1, all the other microconstants (k1, k-1 and K) involved in the present aminolysis have been calculated. The k value decreases with increasing the basicity of amines while k1 and K values increase with increasing the amine basicity, as expected. Good linear Bronsted-type plots have been obtained for these microconstants of the present aminolysis of DNPB. The magnitudes of the slope of the Bronsted-type plots, k1 and k-1 have been calculated to be 0.43 and - 0.24, respectively, indicating the k-1 step is about two folds less sensitive than the k1 step to the amine basicity. The K value has been calculated to be 0.66, which appears to be much smaller than the one for other aminolyses showing general base catalysis. The small K value has been attributed to the absence of general base catalysis in the present aminolysis of DNPB.

The conformation and stabilization effects of acridine derivatives 9-aminoacridine, an acridine with an aminoalkyl side chain, bis acridine (two acridines linked by an aminoalkyl side chain), and proflavin in the triplex helical poly(dA)·[poly(dT)]2 were investigated by optical spectroscopies. Based on the negative LD and weak positive CD in the acridine absorption wavelength region, we concluded that the acridine moiety of all derivatives are intercalated. We also examined the melting temperatures. Of all the compounds examined, the acridine with an amino alkyl side chain had the strongest effect on the stabilization of the third strand of a poly (dA)·[poly(dT)]2 triplex. The role of the side chain, based on this observation, is discussed.

4H,6H-Furo[3,4-c]isoxazoles (Ⅰ-Ⅳ), potential fungicides, have been designed and synthesized via intramolecular [2+3] cycloaddition of nitroalkyne 3 as a key step. The broad spectrum of fungicidal activities of furoisoxazoles (Ⅰ-Ⅳ) were observed on plant pathogens at 250 ppm. Furoisoxazoles Ⅱ, Ⅲ with chlorophenyl at 6-position and methyl or alkylated oxime group at 3-position gave effective control of plant diseases. The furoisoxazole Ⅳ with a chlorophenyl group at 4-position also resulted in high fungicidal activities.