• Bulletin of the Korean Chemical Society
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• 제26권1호
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• pp.43-46
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• 2005

Reaction energies were determined for reductive ring-opening reactions of Li$^+$-coordinated ethylene carbonate (EC) and vinylene carbonate (VC) by a density functional method. We have also explored the ring-opening of Li$^+$-EC and Li$^+$-VC by reaction with a nucleophile (CH$_3$O$^-$.) thermodynamically. Our thermodynamic calculations led us to conclude that the possible reaction products are CH$_3$OCH$_2$CH$_2$OCO$_2$Li (O$_2$-C$_3$ cleavage) for Li$^+$-EC +CH$_3$O$^-$., and CH$_3$OCHCHOCO$_2$Li (O$_2$-C$_3$ cleavage) and CH$_3$OCO$_2$CHCHOLi (C$_1$-O$_2$ cleavage) for Li$^+$-VC +CH$_3$O$^-$.. The opening of VC would occur at the C$_1$-O$_2$ side by a kinetic reason, although the opening at the O$_2$-C$_3$ side is more favorable thermodynamically.

• Archives of Pharmacal Research
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• 제5권2호
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• pp.97-101
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• 1982

Depending upon the results obtained by the bromolactonization of olefinic acids (9-11) by means of N-bromosaccharin (4), the influence of the stabilities of the imidic anions resulted from heterolytic cleavage of N-haloimides, such as N-bromosuccinimide (1), N-bromophthalimde (2), and N-bromosaccharin (3) in dry N, N-dimethylformamide on the reactivity is elucidated.

• Bulletin of the Korean Chemical Society
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• 제25권11호
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• pp.1657-1660
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• 2004

Several critical geometries associated with the rearrangement of $CH_3SNO_2\;to\;CH_3SONO$ are calculated with the density functional theory (DFT) method and compared with those of the ab initio molecular orbital methods. There are two probable pathways for this rearrangement, one involving the transition state of an oxygen migration and the other through the homolytic decomposition to radicals. The reaction barrier via the transition state is about 60 kcal/mol and the decomposition energy into radicals about 35 kcal/mol, suggesting that the reaction pathway via the homolytic cleavage to radical species is energetically favorable. Since even the homolytic cleavage requires large energies, the rearrangement reaction is unlikely without the aid of catalysts.

• Bulletin of the Korean Chemical Society
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• 제29권2호
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• pp.301-302
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• 2008

• Bulletin of the Korean Chemical Society
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• 제33권9호
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• pp.3122-3124
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• 2012

• Bulletin of the Korean Chemical Society
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• 제29권10호
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• pp.1920-1926
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• 2008

We investigated the C-H bond activation mechanism of aldimine by the [RhCl$(PPH_3)_3$] model catalyst using DFT B3LYP//SBKJC/6-31G*/6-31G on GAMESS. Due to their potential utility in organic synthesis, C-H bond activation is one of the most active research fields in organic and organometallic chemistry. C-H bond activation by a transition metal catalyst can be classified into two types of mechanisms: direct C-H bond cleavage by the metal catalyst or a multi-step mechanism via a tetrahedral transition state. There are three structural isomers of [RhCl$(PH_3)_2$] coordinated aldimine that differ in the position of chloride with respect to the molecular plane. By comparing activation energies of the overall reaction pathways that the three isomeric structures follow in each mechanism, we found that the C-H bond activation of aldimine by the [RhCl$(PH_3)_3$] catalyst occurs through the tetrahedral intermediate.

• Archives of Pharmacal Research
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• 제20권2호
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• pp.184-190
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• 1997

A new method based on the chemical reaction has been devised for the sequential analysis of reducing oligosaccharides using 8-amino-2-naphthalenesulfonic acid (ANS), a fluorescent precolumn derivatization reagent for reducing saccharides. The procedure established includes 1) the derivatization of a reducing oligosaccharide to produce a Schiff base, 2) the reduction of the base with sodium cyanoborohydride $(NaBH_3/CN), 3)$ the methoxycarbonylation of the resultant secondary amino group, 4) the cleavage of the glycoside bond next to the reducing end, based on the intramolecular acid hydrolysis by the action of a sulfonic acid group of the ANS derivative, 5) the identification of the liberated reducing end by high-performance liquid chromatography (HPLC), and finally 6) the recovery of the resultant oligosaccharide fragment from the cleavage reaction mixture. The extensive examination of the conditions for the sequential analysis of reducing oligosaccharides resulted in the procedure of simplicity , high selectivity and high recovery. This procedure was found to be useful for the sequential analysis of di-, tri- and tetrasaccharides.

• Bulletin of the Korean Chemical Society
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• 제26권12호
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• pp.2033-2037
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• 2005

In vitro selection was used to isolate $Mg^{2+}$-dependent self-cleaving ribozymes with cis-cleavage activity from a pre-tRNA library having 40-mer random sequences attached to 5'-end of E. coli $tRNA^{Phe}$. After 8 rounds of SELEX (Systematic Evolution of Ligands by Exponential Enrichment), RNA molecules which can self-cleave at the high concentration of $Mg^{2+}$ were isolated. The selected ribozymes can carry out the self-cleavage reaction in the presence of 100 mM $Mg^{2+}$ but not in 10 mM $Mg^{2+}$. The cleavage sites of the ribozymes are located at +3 and +4 of $tRNA^{Phe}$, compared with +1 position of 5'-end cleavage site of pre-tRNA by RNase P. New RNA constructs deprived of its D stem-loop, anticodon stem-loop, variable loop and T stem-loop, respectively showed the cleavage specificity identical to a ribozyme having the intact tRNA structure. Also, the new ribozyme fused with both a ribozyme and $tRNA^{Leu}$ showed the cleavage activities at the various sites within its sequences, different from two sites of position +3 and +4 observed in the ribozyme with $tRNA^{Phe}$. Our results suggest that the selected ribozyme is not structural-specific for tRNA.

• Bulletin of the Korean Chemical Society
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• 제1권2호
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• pp.45-49
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• 1980

During the homolytic reactions of $CCl_4$ or $Cl_3CBr with ${\beta}-halo^1$-styrenes,$\beta$-haloradicals are key intermediates. They are to be stabilized via three pathways; $\beta$-cleavage, halogen transfer and telomerization. The three reaction paths are delicately controlled by the energetics of their formation and stabilization. When the formation of a $\beta$-haloradical is accompanied by considerable excess of energy from an exothermic reaction, $\beta$ -cleavage is often dominant over the halogen transfer. On the other hand, if the radical forms via a reversible reaction, two processes become competitive. $\beta$-Eliminated bromine atoms from ${\beta}$ -bromoradicals generate $Br_2$ via $Cl_3CBr + {\cdot}Br {\leftrightarrow} Br_2 + {CCl_3}{\cdot}{Br_2}$ may act as a better scavenger than Cl3CBr for the ${\beta}$-bromoradicals. Different reactivities of chlorine, bromine and trichloromethyl radicals towards olefinic pi-bond are clarified in terms of the beat content of the addition reactions.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2873-2876
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• 2010

Excess free iron generates oxidative stress that may contribute to the pathogenesis of various causes of neurodegenerative diseases. Previous studies have shown that one of the primary causes of increased brain iron may be the release of excess iron from intracellular iron storage molecules. In this study, we attempted to characterize the oxidative damage of DNA induced by the reaction of ferritin with $H_2O_2$. When DNA was incubated with ferritin and $H_2O_2$, DNA strand breakage increased in a time-dependent manner. Hydroxyl radical scavengers strongly inhibited the ferritin/$H_2O_2$ system-induced DNA cleavage. We investigated the generation of hydroxyl radical in the reaction of ferritin with $H_2O_2$ using a chromogen, 2,2'-azinobis-(2-ethylbenzthiazoline-6-sulfonate) (ABTS), which reacted with ${\cdot}OH$ to form $ABTS^{+\cdot}$. The initial rate of $ABTS^{+\cdot}$ formation increased as a function of incubation time. These results suggest that DNA strand breakage is mediated in the reaction of ferritin with $H_2O_2$ via the generation of hydroxyl radicals. The iron-specific chelator, deferoxamine, also inhibited DNA cleavage. Spectrophotometric study using a color reagent showed that the release of iron from $H_2O_2$-treated ferritin increased in a time-dependent manner. Ferritin enhanced mutation of the lacZ' gene in the presence of $H_2O_2$ when measured as a loss of $\alpha$-complementation. These results indicate that ferritin/$H_2O_2$ system-mediated DNA cleavage and mutation may be attributable to hydroxyl radical generation via a Fenton-like reaction of free iron ions released from oxidatively damaged ferritin.