• Bulletin of the Korean Chemical Society
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• v.17 no.11
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• pp.1031-1036
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• 1996

The synthesis and characterization of diastereomeric dodecanucleotides, d[GATCp(S)TCGAGATC], containing recognition sequence of the XhoI restriction endonuclease with a phosphorothioate internucleotidic linkage the cleavage site are described. Rp and Sp form of diastereomerically pure dinucleoside phosphorothioates d[Cp(S)T] were presynthesized and used for the addition to the growing oligonucleotide chain as a block. The stereochemistry of dinucleoside phosphorothioate was assigned by 31P NMR spectroscopy, enzyme digestion, and reverse-phase HPLC. XhoI restriction endonuclease cut only Rp diastereomer d[GATCp(S))TCGAGATC]. The rate of hydrolysis is slower than that of the unmodified dodecamer d[GATCTCGAGATC]. The phosphorothioate nucleotide is using for determination of the stereochemical course of the XhoI catalyzed reaction.

• Korean Journal of Environmental Agriculture
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• v.6 no.2
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• pp.1-11
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• 1987

The degradation of two chemicals seem to be clearly affected by soil microbial activity in submerged soil $conditions(30{\pm}1^{\circ}C)$. The Active ingredient of Diazinon disappeared about 5 times faster than that of Dursban. By Applying 300% higher concentrations of both chemicals. under the above soil conditions, however, degradation was retarded by about one day. Some of the metabolites of Diazinon were as follows: 0.0-diethyl phosphorothioate and sulfotep as hydrolytic products, and diazoxon, 0.0-diethyl-0-[2-(1-hydroxy-1, 1-dimethyl)-6-methyl]-pyrimidinyl phosphorothioate and 2-isopropyl-6-methyl-pyrimidine-4-one as degradation products of monooxygenase. But 0. 0-diethyl phosphorothioate was the only methabolite of Dursban.

• Journal of Radiation Protection and Research
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• v.8 no.2
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• pp.1-7
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• 1983

S-2-($\omega-aminoalkylamino) ethyl dihydrogen phosphorothioates and S-2-($\omega$-aminoalkylamino) ethyl isothiuronium bromides were prepared from easily available starting compounds via convenient synthetic processes. The isothiuronium derivatives showed extreme drug toxicities as compared to that of AET, which seemed to be due to an intramolecular rearrangement of these compounds. The propyl derivative of the phosphorothioate could show better radioprotective effect than those of AET and WR-638, whereas the ethyl derivative of the equivalent drug dose revealed far less protective effect. The correlation between radioprotective effects, drug toxicities, and chemical structures were discussed through infrared spectroscopy.

• Journal of Environmental Health Sciences
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• v.28 no.1
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• pp.67-77
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• 2002

This study was aimed to determine the urinary metabolite of IBP, one of the organophosphorus pesticides, as the biomarkers of exposure. Urine samples were collected for 24 hours in metabolic cages after oral administration and dermal application of IBP to rats. Identification of the derivatized urinary metabolite was determined by GC/MS and excretion time courses of the urinary metabolite was analyzed by GC/FPD. Urinary metabolite o IBP, diisopropyl phosphorothioate, was detected in rats urine both after oral administration and dermal application of IBP. Parent compound was not detected in the experiment. In GC/MS, the mass spectral confirmation for diisopropyl phosphorothioate ion was identified at m/z 254. Diisopropyl phosphorothioate was excreted within 48 hours and 72 hours after oral administration and dermal application of IBP, respectively. In this study, the same urinary metabolite of IBP was detected both in oral and dermal exposure. Generally, excretion of the urinary metabolite after oral administration was faster than after dermal application. It is suggested that urinary diisopropyl phosphorothioate could be used as the biomarkers of exposure to IBP.

• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.186-194
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• 1988

The electrochemical reduction of O,O-dimethyl-O-(3-methyl-4-nitrophenyl)-phosphorothioate (Fenitrothion) has been studied in acetonitrile solution containing surfactant micelle by direct current (DC)-differential pulse (DP) polarography, cyclic voltammetry (CV) and controlled potential coulometry (CPC). The partially reversible electron transfer-chemical reaction(EC, EC mechanism) of fenitrothion reduction proceeded by four electron transfer to form O,O-dimethyl-O-(3-methyl-4-hydroxyaminophenyl)-phosphorothioate which undergoes single bond of the phosphorus atom and phenoxy group cleaves to give p-amino-m-cresol and dimethyl thiophosphinic acid as major product by two electron transfer-protonation at higher negative potential. The polarograpic reduction waves shown to suppressed due to inhibitory effect of sodium lauryl sulfate micelle solution and split up on selectivity of anionic micelle effect in two step at the first reduction peak.

• YAKHAK HOEJI
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• v.16 no.1
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• pp.47-54
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• 1972

O,O-Dimethyl-S-(phthalimido)methylphosphorodithioate (PMP) is changed into phosphine, phosphate, and phosphorothioate, when it is treated with metallic zinc in acidic medium after alkaline hydrolysis. The amount of phosphine evolved is about five times as much in sulfuric acid medium as it is in hydrochloric acid. When one micro mole of hydrolyzed PMP is treated with 8 grams of metallic zinc and 30 ml of 10 N-sulfuric acid, it is changed into 0.42 micro moles of phosphine, 0.14 micro moles of phosphorothioate, and 0.44 micro moles of phosphate.

• The Korean Journal of Pesticide Science
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• v.6 no.3
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• pp.218-223
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• 2002

The rate of hydrolysis of insecticide, O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)phosphorothioate (Flupyrazofos) have been investigated in 25% (v/v) aqueous dioxane (${\mu}=0.1M$) at $45^{\circ}C$. The hydrolysis mechanism of flupyrazofos proceeds through the specific acid ($A_{AC}2$) catalysis below pH 4.0, specific base ($B_{AC}2$) catalysis above pH 11.0 and general acid & base ($B_{AC}2$) catalysis between pH 5.0 and pH 10.0 via trigonal-bipyramidal ($d^2sp^3$) intermediate as evidence by solvent effect ($|m|{\ll}|{\ell}|$), rate equation ($kt=ko+k_H+ [H_3O^+]+k_{OH}[OH^-]$) and product analysis. The half-life ($T\frac{1}{2}$) of hydrolytic degradation in neutral media at $45^{\circ}C$ was ca. 3 months.

• Journal of Radiation Protection and Research
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• v.7 no.1
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• pp.11-16
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• 1982

Cysteamine(Mercaptoethyiamine, MEA), S,2-Aminoethylisothiouronium Bromide. HBr (AET), and S-(2-Aminoethyl) Dihydrogen Phosphorothioate (WR-638) were prepared and radioprotective effects of these chemicals and their combinations against $^{60}Co$ ${\gamma}-ray$ radiation were studied ,in irradiated ICR mice. Intraperitonially administered chemicals or their combinations resulted drug deaths in cases of MEA, AET, and their combinations, whereas there were a slight or no drug death in cases of WR-638 and the combination of AET with WR-638. All tested chemicals and their combinations yielded radioprotective effects against $^{60}Co$ $\gamma-ray$ radiation. An additive radioprotection effect was observed in case of the combination of AET with WR-638.

• Korean Journal of Agricultural Science
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• v.11 no.2
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• pp.315-321
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• 1984

The electrochemical reduction of 0,0-dimethyl-0-(3-methyl-4 -nitrophenyl)-phosphorothioate ($Sumithion^{(R)}$) in acetonitrile solution has been studied by direct current (DC), differential pulse (DP) polarography and cyclic voltammetry methods. The irreversible electron-transfer chemical reaction (EC) mechanism of Sumithion proceeds by six electron-transfer to form radical and reduction of three-step which undergoes single bond of the phosphorus atom & phenoxy group by electron-transfer and protonation cleaved to give p-hydroxyamino-m-cresol and dimethylthiophosphonate as major product.

• Archives of Pharmacal Research
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• v.19 no.6
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• pp.435-440
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• 1996

The effect of benzalkonium chloride on skin permeability of partially modified antisense phosphorothioate oligonucleotides (PS-ODN), which are designed as scar formation inhibitor, was investigated using Franz Diffusion Cell. When the concentration ratio of PS-ODN-quarternary ammonium salt complex is more than 1:100, the apparent partition coefficient (APC) of each complex was increased in the following order; tetraphenyl phosphonium chloride (TPP) < cetyltrimethyl ammonium bromide(CTAB) < benzalkonium chloride (BZ). The permeability of PS-ODN through the rat skin increased in the presence of BZ. The fluxs of PS-ODN with BZ were increased by addition of Pluronic F 68 or Triton X-100 to phosphate buffered saline (PBS), respectively. When the mole ratio of PS-ODN to BZ is 1:10, the fluxs penetrated of PS-ODN with BZ was greatest. The increase of the permeability in the presence of BZ might be due to the formation of lipophilic ion-pair complex between PS-ODN and BZ. By regulation of mole ratio of PS-ODN to BZ, the development of topical dosage forms using PS-ODN as scar formation inhibitor will be possible with minimal systemic exposure.