• Journal of the Korean Chemical Society
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• v.40 no.1
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• pp.11-19
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• 1996

The cationic polymerization of energetic substituted oxetanes which have pendant energetic group such as azido and nitrato are investigated theoretically, using semiempirical HF/3-21G, MINDO/3, MNDO and AM1 method. The stereo- and electronic structure of binary molecular complex composed of energetic substituted oxetane and boron trifluoride can be explain by molecular orbital theory. The reactivity of propagation in the copolymerization of oxetanes can be presented by the positive charge on carbon(C2) atom of oxetane and energy level of the lowest unoccupied molecular orbital(LUMO) of propagating species of oxetanes. The reactivity ratios for copolymerization of oxetanes are a random copolymer-zation which is agree with MO calculated and experimental results. The relative equlibrium concentration of cyclic oxonium and open carbenium ions is found to be a major determinant of mechanism, owing to the rapid equilibrium of these cation forms and the expectation based on calculation that in the prepolymer propagation step, SN1 mechanism will be at least as fast as that for SN2 mechanism.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.8-15
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• 1965

Justifications for the use of ${\sigma}$ and Y as independent potential energy variables in the general equation have been reviewed and some mechanistic significances of the relationship discussed. Analysis of the activation parameters for the solvolysis of benzyl chlorides in ethanol-water mixture showed that there are two distinct series of substrate constants ${\alpha}'$, which can be correlated linearly within a series with the substituent constants ${\sigma}$ conforming to the generally accepted concept of change in mechanism from $S_N1$ to $S_N2$.

• Proceedings of the KOSOMBE Conference
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• v.1997 no.05
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• pp.457-460
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• 1997

The photoconductive gain mechanism in various types of hydrogenated amorphous silicon devices, such as p-i-n, n-i-n and n-i-p-i-n structures was investigated in connection with applications to radiation detection. We measured the photoconductive gain in two time scales: one for short pulses of visible light $(<1{\mu}sec)$ which simulate the transit of energetic charged particles, and the other for rather long pulses of light $(\sim1msec)$ which simulate x-ray exposure in medical imaging. We used two definitions of photoconductive gain: current gain and charge gain which is an integration of the current gain. We found typical charge gains of $3\sim9$ for short pulses and a few hundred for long pulses at a dark current density level of $10mA/cm^2$.

• Journal of the Korean Chemical Society
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• v.62 no.4
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• pp.265-268
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• 2018

The solvolyses of anthraquinone-2-carbonyl chloride (1) were studied kinetically in 27 pure and various mixed solvents. The analysis using the extended Grunwald-Winstein equation in the solvolyses of anthraquinone-2-carbonyl chloride (1) obtained the l value of $2.11{\pm}0.11$, the m value of $0.54{\pm}0.06$, and the correlation coefficient of 0.955. The solvolysis reaction of 1 might proceed via an associative $S_N2$ mechanism enhancing bond making than bond breaking in the transition state (TS). This interpretation is further supported by a relatively large solvent kinetic isotope effect (SKIE, 2.27).

• Proceedings of the PSK Conference
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• 2003.10b
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• pp.183.1-183.1
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• 2003

The synthesis of various cyclic carbamate compounds and amino alcohols has attracted attention in the past because of their potential as antibiotics, antitumor, analgenics, anticonvulsants. Several methods for the preparation of cyclic carbamate compounds have previously been reported including the use of heterocumulenes. We have recently described the novel synthetic method for N-protected amines from various ethers using Chlorosulfonyl isocyanate(CSI) and found that the mechanism of our CSI reaction is a competitive reaction of $S_N1$ and $S_ Ni$ mechanisms according to the stability of carbocation intermediates. (omitted)

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1105-1109
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• 1998

A chiral stationary phase derived from (S)-N-(3,5-dinitrobenzoyl)leucine N-phenyl N-alkyl amide (CSP 2) was applied in separating the two enantiomers of various π-basic aromatic derivatives of leucine N-propyl amide in order to evaluate π-basic aromatic groups as an effective derivatizing group for the resolution of a-amino acids. Subsequently N-(3,5-dimethoxybenzoyl) group was found to be very effective as a π-basic aromatic derivatizing group. Based on these results, N-(3,5-dimethoxybenzoyl) derivatives of various a-amino N-propyl amides, N,N-diethyl amides and esters were resolved on the CSP derived from (S)-N-(3,5-dinitrobenzoyl) leucine N-phenyl N-alkyl amide (CSP 2) and the resolution results were compared with those on the CSP derived from (S)-N-(3,5-dinitrobenzoyl)leucine N-alkyl amide (CSP 1). The enantioselectivities exerted by CSP 2 were much greater than those exerted by CSP 1. In addition, racemic N-(3,5-dimethoxybenzoyl)-a-mino N,Ndiethyl amides were resolved much better than the corresponding N-(3,5-dimethoxybenzoyl)-a-mino N-propyl amides and esters on both CSPs. Based on these results, a chiral recognition mechanism utilizing the π-π donor-acceptor interaction and the two hydrogen bondings between the CSP and the analyte was proposed.

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.282-288
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• 1986

Kinetic studies were carried out for the substitution of $H-2$O for $Cl^-$ ligand of chloropentaamminecobalt(III) in the presence of $Hg^{2+}$ catalyst by UV spectrophotometer. It has been found that $Hg^{2+}$ ion appears first order dependence and the overall reaction is second order. The reaction system can be believed to occur via $S_N2$ reaction, because the calculated rate equation for our presumed $S_N2$ mechanism is in agreement with the observed one.

• Journal of environmental and Sanitary engineering
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• v.21 no.1 s.59
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• pp.21-34
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• 2006

To investigate anti-HIV-1 activity of water soluble chitosans, sulfated chitosan derivatives were prepared in mild condition. Various sulfated chitosan derivatives (N-3,6-O-S-chitosan, N-desulfated 3,6-O-S-chitosan, 3,6-O-S-chitin, and 3,6-O-sulfated-N-(o-carboxybenzoyl) chitosan) were synthesized with sulfurtrioxidepyridene complex in pyridine solvent. Characterization of the sulfated chitosan derivatives was carried out by $^{13}C$ NMR and IR spectroscopies. To observe ionic reaction properties, pKas of the sulfated chitosan derivatives and chitosan of low molecular weight were estimated by potentiometric titration. The sulfated chitosan derivatives had high water solubility, pKas (pKa : 7.7) of N-3,6-O-S-chitosan and N-desulfated 3,6-O-S-chitosan were increased than pKa of water insoluble chitosan (pKa : 6.2), These results suggest the participation of electrostatic interaction of amino and sulfate groups on the sulfated chitosans. Anti-HIV-1 drugs, such as AZT, ddC, and ddI for anti-HIV activity had higher selective index compared with SCB-chitosan but N-3,6-O-S-chitosan has shown higher selective index compared with ddC and ddI as HIV drugs.. These results suggest that sulfated chitosan derivatives were expected as an anti-HIV drug with differential driving force mechanism against some nucleoside analogs drug in the future.

• Bulletin of the Korean Chemical Society
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• v.32 no.5
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• pp.1539-1542
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• 2011

The aminolysis of O-methyl S-aryl thiocarbonates with benzylamines are studied in acetonitrile at -45.0$^{\circ}C$. The ${\beta}_X$(${\beta}_{nuc}$) values are in the range 0.62-0.80 with a negative cross-interaction constant, ${\rho}_{XZ}$ = -0.42, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles ($XC_6H_4CH_2ND_2$) are large, $k_H/k_D$ = 1.29-1.75, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the MeO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.

• Journal of Microbiology and Biotechnology
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• v.18 no.3
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• pp.397-403
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• 2008

Nikkomycins are a group of peptidyl nucleoside antibiotics with potent fungicidal, insecticidal, and acaricidal activities. sanN was cloned from the partial genomic library of Streptomyces ansochromogenes 7100. Gene disruption and complementation analysis demonstrated that sanN is essential for nikkomycin biosynthesis in S. ansochromogenes. Primer extension assay indicated that sanN is transcribed from two promoters (sanN-P1 and sanN-P2), and sanN-P2 plays a more important role in nikkomycin biosynthesis. Purified recombinant SanN acts as a dehydrogenase to convert benzoate-CoA to benzaldehyde in a random-order mechanism in vitro, with respective $K_{cat}/K_m$$ values of $3.8mM^{-1}s^{-1}\;and\;12.0mM^{-1}s^{-1}$ toward benzoate-CoA and NADH, suggesting that SanN catalyzes the formation of picolinaldehyde during biosynthesis of nikkomycin X and Z components in the wild-type stain. These data would facilitate us to understand the biosynthetic pathway of nikkomycins and to consider the combinatorial synthesis of novel antibiotic derivatives.