• Bulletin of the Korean Chemical Society
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• v.15 no.8
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• pp.644-649
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• 1994

The approximate rates and stoichiometry of reaction of excess dipyrrolinoaluminum hydride (DPAH) with selected organic compounds containing representative functional groups under standardized conditions (tetrahydrofuran, 0, reagent : compound=4 : 1) were examined in order to define the characteristics of the reagent for selective reductions. The reducing ability of DPAH was also compared with that of bis(diethylamino)aluminum hydride (BEAH). The reagent appears to be stronger than BEAH, but weaker than the parent reagent in reducing strength. DPAH shows a unique reducing characteristics. Thus, the reagent reduces aldehydes, ketones, esters, acid chlorides, epoxides, and nitriles readily. In addition to that, ${\alpha},\;{\beta}$-unsaturated aldehyde is reduced to the saturated alcohol. Quinone are reduced cleanly to the corresponding 1,4-reduction products. The examination for possibility of achieving a partial reduction to aldehydes was also performed. Both primary and tertiary aromatic carboxamides are converted to aldehydes with a limiting amount of DPAH. Finally, disulfides and sulfoxides are readily reduced to thiols and sulfides, respectively.

• YAKHAK HOEJI
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• v.50 no.6
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• pp.393-397
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• 2006

The synthesis of new 3-substituted 7-halocephalosporanates was described. 7-ACA was reacted with thiols at pH 6.5${\sim}$6.8 to afford the 3-substituted 7-ACA (1), which was treated with diphenyldiazomethane to give diphenylmethyl 7-aminocephalosporanate (2). The Halogenation of 7-aminocephalosporanate (2) with NaNO$_2$, KBr and H$_2$SO$_4$ gave 7-bro-mocephalosporanate (3) and with NaNO$_2$, HCI gave 7-chlorocephalosporanate (4). Diphenylmethyl cephalosporanate (2${\sim}$4) were deprotected by AIC1$_3$ in anisole and neutralized to give the sodium cephalosporanate (5${\sim}$7).

• Proceedings of the PSK Conference
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• 2003.10a
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• pp.74-74
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• 2003

Methylmercury (MeHg) is a ubiquitous environmental toxicant that can be exposed to humans by ingestion of contaminated food including fish and bread. MeHg has been suggested to exert its toxicity through its high reactivity to thiols, generation of arachidonic acid and reactive oxygen species (ROS), and elevation of intracellular $Ca^{2+}$ levels ([$Ca^{2+}$]i). However, the precise mechanism has not been fully defined. (omitted)

• Bulletin of the Korean Chemical Society
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• v.5 no.5
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• pp.187-190
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• 1984

Reaction of acid chlorides with primary alcohols, secondary alcohols, and aryl alcohols in the presence of a catalytic amount of zinc chloride gave the corresponding esters in high yields, whereas the reaction with tertiary alcohols failed to give the esters due to the fast solvolytic reactions of tertiary alcohols with hydrogen chloride generated from the reaction. The use of molecular sieves as a scavenger for hydrogen chloride was found to be moderately effective in the reaction of mesitoyl chloride with tertiary alcohols. Reaction of acid chlorides with thiols in the presence of zinc chloride in acetonitrile proceeded cleanly, yielding the corresponding thiol esters in high yields.

• Bulletin of the Korean Chemical Society
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• v.5 no.6
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• pp.215-218
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• 1984

A series of S-(2,2-diethoxycarbonyl-1-phenylethyl)-L-cysteine derivatives (10a-e) were synthesized from the reaction of $\beta$$\beta$-diethoxycarbonylstyrene with L-cysteine in 1:1 aqueous methanol. Thus, S-(2,2-diethoxycarbonyl-1-phenylethyl)-L-cysteine( 10a), S-[2,2-diethoxycarbonyl-1-(3',4'-methylendioxy)ph enylethyl]-L-cysteine (10b), S-[2,2-diethoxycarbonyl-1-(3',4',5'-trimethoxy)phe nylethyl]-L-cyseine (10c), S-[2,2-diethoxycarbonyl-1-(p-hydroxy)phenylethyl] -L-cysteine (10d), S-[2,2-diethoxycarbonyl-1-(p-methoxy)phenylethyl] -L-cysteine (10e) were obtained in moderate to excellent yields. The structure of the adducts was characterized by analytical and spectral data. The effects of pH upon the product yields were also briefly examined.

• Journal of the Korean Chemical Society
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• v.31 no.4
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• pp.364-368
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• 1987

The addition reactions of thioglycolic acid, benzenethiol and benzylmercaptan to ${\beta}-acetyl-{\beta}-benzoylstyrene$ were investigated. ${\beta}-Acetyl-{\beta}-benzoylstyrene$ derivatives easily underwent addition reactions with thioglycolic acid, benzenethiol, and benzylmercaptan to form five(2-acetyl-2-benzoyl-1-phenylethyl) thioglycolic acid derivatives (IIa-IIe), five (2-acetyl-2-benzoyl-1-phenylethyl)benzenethiol (IIIa-IIIe) derivatives and five (2-acetyl-2-benzoyl-1-phenylethyl)benzylmercaptan derivatives (IVa-IVe), respectively.

• Bulletin of the Korean Chemical Society
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• v.27 no.3
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• pp.403-406
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• 2006

The surface structure and electrochemical behavior of self-assembled monolayers (SAMs) formed by aromatic thiols on Au(111) were investigated by scanning tunneling microscopy (STM) and cyclic voltammetry. Benzenethiol (BT) forms disordered phases on Au(111) which are composed of many bright domains, while benzyl mercaptan (BM), with a methylene unit between the aromatic group and sulfur atom, forms twodimensional ordered SAMs on Au(111). In addition, two phase-separated domains consisting of disordered and ordered phases were observed in binary SAMs formed from a 1 : 1 mixed ethanol solution of BT and BM. From STM and CV measurements, we found that the blocking efficiency of aromatic thiol SAMs coated on an Au(111) electrode for an electron transfer reaction decreases as the structural order of the SAMs increases. Molecular-scale STM and CV results obtained here will be very useful in designing functional SAMs for further applications, such as the improvement of corrosion passivation of Au(111) on an aromatic thiolmodified Au(111) surface.

• Nutritional Sciences
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• v.6 no.1
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• pp.12-19
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• 2003

The measurement of the total antioxidant capacity (TAC) of human plasma has been widely applied in nutritional science, for example to evaluate the antioxidant contribution of dietary components and to study, although indirectly, the bioavailability of dietary antioxidants. Several methods have been proposed for the measurement of TAC, most of them based on the ability of plasma to withstand the oxidative damage induced by aqueous radicals. Although plasma contains both hydrophilic and lipophilic antioxidants that interact through extensive cross-talk in most of the methods employed for the TAC measurement, the hydrophilic antioxidants such as ascorbic acid, uric acid, and protein thiols mainly contribute to the total antioxidant plasma capacity (almost 70%) while lipophilic antioxidants embedded in the lipoproteins (carotenoids, a-tocopherol, ubiquino1-10) participate only in a negligible amount (less than 5%). The present paper reviews the analytical methods used to assess the TAC and in particular focuses on new approaches that are capable of distinguishing the antioxidant capacity of both the aqueous and lipid compartments of plasma. The general principle of the method as well as some in vitro and ex vivo applications will be discussed within the text.

• BMB Reports
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• v.35 no.1
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• pp.127-133
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• 2002

Nitrosative stress can prevent or induce apoptosis. It occurs via S-nitrosylation by the interaction of nitric oxide (NO) with the biological thiols of proteins. Cellular redox potential and non-heme iron content determine S-nitrosylation. Apoptotic cell death is inhibited by S-nitrosylation of the redox-sensitive thiol in the catalytic site of caspase family proteases, which play an essential role in the apoptotic signal cascade. Nitrosative stress can also promote apoptosis by the activation of mitochondrial apoptotic pathways, such as the release of cytochrome c, an apoptosis-inducing factor, and endonuclease G from mitochondria, as well as the suppression of NF-${\kappa}B$ activity. In this article we reviewed the mechanisms whereby S-nitrosylation and nitrosative stress regulate the apoptotic signal cascade.

• BMB Reports
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• v.43 no.6
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• pp.419-426
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• 2010

Aeromonas hydrophila is a bacterial pathogen that infects a large number of eukaryotes, including humans. The UDP-galactose 4'-epimerase (GalE) catalyzes interconversion of UDP-galactose to UDP-glucose and plays a key role in lipopolysaccharide biosynthesis. This makes it an important virulence determinant, and therefore a potential drug target. Our earlier studies revealed that unlike other GalEs, GalE of A. hydrophila exists as a monomer. This uniqueness necessitated elucidation of its structure and active site. Chemical modification of the 6xHis-rGalE demonstrated the role of histidine residue in catalysis and that it did not constitute the substrate binding pocket. Loss of the 6xHis-rGalE activity and coenzyme fluorescence with thiol modifying reagents established the role of two distinct vicinal thiols in catalysis. Chemical modification studies revealed arginine to be essential for catalysis. Site-directed mutagenesis indicated Tyr149 and Lys153 to be involved in catalysis. Use of glycerol as a cosolvent enhanced the GalE thermostability significantly.