• Bulletin of the Korean Chemical Society
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• v.8 no.6
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• pp.471-475
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• 1987

Benzotriazol-1-yl Diethyl phosphate and benzotriazol-1-yl diphenyl phosphate were conveniently prepared in essentially quantitative yields by the reaction of diethyl chlorophosphate and diphenyl chlorophosphate with equal amounts of 1-hydroxybenzotriazole and triethylamine in tetrahydrofuran at room temperature, respectively. Benzotriazol-1-yl diethylphosphate was effective for the preparation of amides from carboxylic acids amines. Young test and Anderson test for racemization studies using benzotriazol-1-yl diethyl phosphate were investigated and practically no racemization occurred. However, racemization occurred to some extent during coupling of Z-Phe-Val-OH with Pro-OBu. Several dipeptides and tripeptides were prepared without little racemization using benzotriazol-1-yl diethyl phosphate. Benzotriazol-1-yl diphenyl phosphate was less effective than benzotriazol-1-yl diethyl phosphate in terms of the degree of racemization.

• Applied Biological Chemistry
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• v.37 no.3
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• pp.210-215
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• 1994

${\underline{O}},{\underline{O}}-Diethyl-{\underline{S}}-phenyl\;phosphorothiolate-^{18}O$ and other related compounds were prepared and oxidized with m-chloroperbenzoic acid (MCPBA). Each reaction was followed by $^{31}P$ NMR and the products were analyzed by GC-MS. ${\underline{O}},{\underline{O}}-Diethyl-{\underline{S}}-phenyl\;phosphorothiolate-^{18}O$ was converted to diethyl methyl phosphate in methanol by MCPBA and it was confirmed to contain $^{18}O$, which proved that the originally proposed mechanism of Segall and Casida operates in the oxidative reaction.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.489-492
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• 2009

• Bulletin of the Korean Chemical Society
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• v.12 no.3
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• pp.286-289
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• 1991

The changed isotropic absolute Raman intensities of the phosphate residue in the complexes of positive charge oligopeptides, lys-lys, arg-arg, lys-aromat-lys, negative charge diethyl phosphoric acid (DEP) and polyriboadenylic acid{poly(rA)} were reported and discussed. Our measurements showed that the absolute intensities of phosphate stretch vibration in complexes were different according to the reaction partners. Due to the partial electrical charge and molecular structure of oligopeptides for the complex formation lysine can interact more strongly than arginine when the reaction partners have short chain and no steric hindrance. Owing to these reasons the intensity of phosphate stretching vibration is very sensitive according to the circumstance of reaction. From our results we could suggest that we can discriminate any one of the the lysine and arginine in the complicated biological molecule during interaction between nucleotides and proteins. The activity of reaction of two basical oligopeptides is not quite similar for complex formation in aqueous solution. The activity of dipeptides depends upon the structure of molecule and environment for complex formation. Aromatic ring contributes to electrostatic interaction in complexes. The amount of the absolute intensity for pure stacking interaction is smaller than electrostatic interaction in macromolecular complexes.

• Journal of the Korean Chemical Society
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• v.26 no.6
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• pp.421-426
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• 1982

Free radical-initiated copolymerization of diethyl isopropenyl phosphate (DEIPA) with vinyl acetate (VAc) and acrylonitrile (AN) was studied. The monomer reactivity ratios for the monomer pairs, determined at $60^{\cric}C$ using benzoyl peroxide as an initiator, are: ${\gamma}_1$(VAc) = 1.56, ${\gamma}_2$(DEIPA) = 0.44: ${\gamma}_1$(AN) = 15.2, ${\gamma}_2$(DEIPA) = 0.031. The values of the Alfrey-Price constants, Q and e, for DEIPA were calculated to be 0.015 and 0.39, respectively, from the VAc system, and 0.014 and 0.34, respectively, from AN/DEIPA pair. These results indicate that ${\alpha}$-methyl substituent of vinyl phosphate monomer decreases the general reactivity in free radical copolymerization. The intrinsic viscosity and number-average molecular weight of copolymers decreased as their content of DEIPA units increased, indicating a high degree of chain transfer caused by DEIPA, as previously learned in DEVPA system.

• Journal of Environmental Health Sciences
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• v.45 no.6
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• pp.583-593
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• 2019

Objectives: The purpose of this study was to evaluate the relationship between the frequency score of wearing personal protective equipment (PPE) and concentration of urinary organophosphorus pesticide metabolites in farmers. Methods: The study was conducted in Chungcheongnam-do Province of South Korea. We collected urine samples from 308 farmers from September to December 2017 and May to July 2018. Among them, 17 farmers with urinary creatinine levels outside the normal range were excluded. Information on the frequency of wearing PPE was obtained from the farmers through face-to-face survey. Each frequency of wearing for seven types of PPE was converted into a score and expressed as a total score, which was divided into quartiles. Four types of urinary organophosphorus pesticide metabolites were analyzed using a gas chromatography mass selective detector. Multiple linear regression analysis was used to identify concentrations of urinary organophosphorus pesticide metabolites affected by the frequency of wearing PPE. Results: The average frequency score of wearing PPE was 8.0. The quartiles of frequency score of wearing PPE were divided as follows: 1st quartile (≤1), 2nd quartile (1-6), 3rd quartile (6-12), and 4th quartile (>12). Compared with subjects with a low frequency score of wearing PPE (reference), subjects with a high frequency score of wearing PPE (4th quartile) had lower concentrations of urinary diethyl phosphate (DEP) (p<0.01) and dialkyl phosphate (ΣDAP) (p<0.05), which is the sum of dimethyl phosphate (DMP), DEP, dimethyl thiophosphate (DMTP), and diethyl thiophosphate (DETP). Conclusion: Concentrations of urinary organophosphorus pesticide metabolites were associated with frequency score of wearing PPE. Particularly as the frequency score of wearing PPE increased, concentrations of urinary DMP, DEP, DETP, and ΣDAP significantly decreased. The findings of this study can contribute to the management of health effects among farmers working with pesticides.

• Bulletin of the Korean Chemical Society
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• v.21 no.8
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• pp.785-792
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• 2000

Mass spectral fragmentations of six chlorinated organophosphorus pesticides were investigated using electron impact mass spectrometry. Understanding the fragmentation pathways, based on the fragment ions of mass spectra, should be useful in the structural elucidation and chemical identification of these compounds. The pro-posed fragmentation pathways were verified by collision-induced dissociation B/E-linked scan spectra. ln most cases,the structures of characteristic fragment ions could be expected by the observation of the peak clusters due to 35Cl and 37Cl isotopes. According to substituted groups on phosphorus atom, phosphate and phospho-rothioate exhibited significantIy differentfragmentation patterns. Especially, phosphate and phosphorothioate with diethyl ester produced more diverse fragment ions than that with dimethyl ester.

• Applied Biological Chemistry
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• v.36 no.6
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• pp.469-475
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• 1993

In order to elucidate the metabolism of the systemic insecticide, phosphamidon(2-chloro-2-diethylcarbamoyl-1-methylvinyl dimethyl phosphate), treated to pine trees against pine leaf gall midges (Thecodiplosis japonensis Uchida et Inouye), $[vinyl,\;carbonyl-^{14}C]$phosphamidon was implanted into the trunks of 10-year-old Korean red pine (Pinus densiflora Sieb. et Zucc.) and Japanese black pine (Pinus thunbergii Parl.), respectively. This chemical was degraded very quickly in pine trees after implanting, as confirmed by TLC/autoradiography of the extracts of pine needles. Phosphamidon metabolites in phosphate buffer extracts of pine needles include the major metabolite, ${\alpha}-chloroacetoacetic$ acid diethyl-amide, ${\alpha}-chloroacetoacetic$ acid ethylamide, 3-hydroxy-N,N-d iethylbutanamide, acetoacetamide, and trimethyl phosphate. The metabolism within pine trees is expected to be similar to this. Based on these findings, it is believed that the major pathway leading to the metabolites would be related to the P-O-vinyl hydrolysis of the chemical structure.

• Ocean and Polar Research
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• v.32 no.3
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• pp.203-212
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• 2010

Distribution of organophosphorous pesticides (OPs) was studied from February to September 2008 in the seawater of Asan Bay, Korea. Among the 29 types of OPs detected during the study period, IBP(S-benzyl O,O-diisopropyl phosphorothioate), ranging from <1 ng/l to 377 ng/l, was the most abundant. Other commonly observed OPs concentrations in the study area included diazinon (Diethyl 2-isopropyl-4-methyl-6-pyrimidinyl phosphorothionate; <1~307 ng/l), azinphos ethyl (3,4-Dihydro-4-oxo-3-benzotriazinylmethyl O,O-diethyl phosphorodithioate; <1~1997 ng/l), malathion (1,2-Di(ethoxycarbonyl)ethyl O,Odimethyl phosphordithioates; <1~3013 ng/l), demeton-O (Diethyl 2-(ethylthio)ethyl phosphorothionate; <1~2403 ng/l), and DDVP (2,2-dichlorovinyl dimethyl phosphate; <1~283 ng/l). Seasonal distribution of OPs in seawater is dependent on the OP application period. In August, OPs concentrations were generally decreased with the increased salinity of seawater, implying progressive dilution of pesticides in the estuarine system. OPs were deposited into Asan Bay from Asan and Sabkyo Lakes as well as surrounding tributaries. Ten OPs, including diazinon, were detected in the suspended particles of Asan Bay.

• Korean Journal of Veterinary Research
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• v.35 no.4
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• pp.793-807
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• 1995

This study was carried out to investigate the effects of diethyl maleate(DEM) on the carcinogenesis of forestomach and pyloric glandular stomach in rats caused by N-methyl-N'-nitro-N-nitrosoguanidine(MNNG). A total of 60 male 6-week-old Wistar rats were given twice intragastric injection of MMNG(200mg/kg BW), then were given diets containing 5% NaCl for 3 weeks until 4th week of the experiment. And then the animals of groups of 1 and 2 were placed on diets containing 0.2% DEM for 16 weeks until the end of 20 weeks of the experiment. On the other hand, the animals of groups of 3 and 4 were placed on basal diets for the same periods. The tissues of forestomach and liver of each group were frozen in liquid nitrogen and the activities of quinone reductase(QR) were determined by measurement of the dicoumarol-sensitive reduction of dichloro-indophenol by NADPH at 600nm. All rats were sacrificed at the end of 20 weeks of the experiment. Every animal was fasted for 24 hrs prior to sacrifice. The forestomach was fixed in 10% neutral phosphate buffered formalin for histology and the pyloric gland was fixed in sublimated formalin for immunohistochemistry of pepsinogen 1 altered pyloric gland(PAPG). The final body weight of the group given MNNG and treated with 5% NaCI and DEM was significantly decreased compared with that of the group 4(p<0.05). Food and water consumption rates were not significantly changed. The preneoplastic and neoplastic lesions of the forestomach given MNNG and treated with 5% NaCI and DEM were significantly increased compared to those of the group 4(p<0.0l). The incidence of PAPG in the groups treated with 0.2% DEM was significantly increased compared with that of the group 4(group 1:p<0.01, group 2:p<0.05). The activities of QR of forestomach in the groups treated with 0.2% DEM were significanitly increased compared with those of the group 4(p<0.001), but those of liver were not significant. These results indicate that DEM exert the enhancing effect of forestomach and glandular stomach carcinogenesis in rats pretreated with MNNG and NaCl.