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Smile Rearrangement of Herbicidal Flazasulfuron (제초성 Flazasulfuron의 Smile 자리옮김 반응)

  • Lee, Gwnag-Jae;Kim, Yong-Jip;Kim, Dae-Whang;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.39 no.1
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    • pp.70-76
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    • 1996
  • A series of the herbicidal pyridylsulfonyl areas, none substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(2-pyridylsulfonyl) urea, 3 and 3-trifluoromethyl substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(3-trifluoromethyl-2-pyridylsulfonyl) urea, 5(Flazasulfuron) were synthesizied and the rate of hydrolysis of their has been studied in 25%(v/v) aqueous dioxane at $45^{\circ}C$. From the results of solvent effect($m{\ll}1,\;n{\ll}3\;&\;{\mid}m{\mid}{\ll}{\mid}{\ell}{\mid}$), thermodynamic parameter (${\Delta}S^{\neq}=0.54{\sim}\;-2.19\;e.u.\;&\;{\Delta}H^{\neq}=0.025\;Kcal.mol.^{-1}$), hydrolysis product analysis, $pK_a$ constant(3: 4.9 & 5: lit.4.6) and the rate equation, a marked difference in the kinetics of the reaction of 3 and 5(Flazasulfuron) was observed. It may be concluded that the hydrolysis of 5 proceeds through the $A-S_N2Ar$ reaction via conjugate acid$(5H^+)$ below pH 7.0, whereas, above pH 9.0, the hydrolysis proceeds through irreversibly $(E_1)_{anion}$ and reversibly $(E_1CB)_R$ mechanism via conjugate base(CB), respectively. But in case of 5, $A-S_N2Ar,\;(E_1)anion\;and\;(E_1CB)_R$ mechanism involved Smile rearrangement. The mate of rearrangement of 5 to a 3-trifluoromethyl-2-pyridylpyrimidinyl urea(PPU) in acid and 3-trifluoromethyl-2-pyridyl-4.6-dimethoxypyridinyl amine (PPA) in base was increased about 3.5 times by the introduction of trifluoromethyl group in the 3-position on the 2-pyridyl ring. From the basis of these findings, a possible mechanism for the hydrolysis of 5 was proposed and discussed.

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Synthesis and Luminescent Characteristics of Anthracene Fluoroionophores (안트라센 형광 단위를 가지는 Fluoroionophore의 합성 및 발광특성)

  • Jeon Young-Min;Kim Jong-Gyu;Jang Ji-Geun;Chang Ho-Jung;Kim Yung-Sup;Gong Myoung-Seon
    • Polymer(Korea)
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    • v.30 no.5
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    • pp.426-431
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    • 2006
  • Novel azacrown ether containing blue -light emitting anthracene fluorophore, 9,10-bis [p-(1-aza-18-crown-6)methylphenyl] anthracene (3) and N,N-bis [9-(p-methylphenyl) anthracenyl-methyl] -1,6-diaza-18-crown-6 (4) were prepared by reacting anthracene derivatives 1 and 2 with mono- and diaza-18-crown-6, respectively Also, crown ether containing fluorophore copolymer (5) were prepared by reacting 1,6-diaza-18-crown-6 with 1. Their fluorescence emission spectral studies were investigated by binding group I, group II and various metal cations. The fluorophores showed an absorption at ${\lambda}_{max}$= 372 nm and an emission at ${\lambda}_{max}$= 430 nm. pH Dependency of fluorescence emission intensity were examined to determine the optimum pH for the fluorophores.

Gas Sensing Characteristics and Preparation of SnO2 Nano Powders (SnO2 나노 분말의 합성 및 가스 감응 특성)

  • Lee, Ji-Young;Yu, Yoon-Sic;Yu, Il
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.24 no.7
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    • pp.589-593
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    • 2011
  • [ $SnO_2$ ]nano powders were prepared by solution reduction method using tin chloride($SnCl_2{\cdot}2H_2O$), hydrazine($N_2H_4$) and NaOH. The $SnO_2$ thick films for gas sensors were fabricated by screen printing method on alumina substrates and annealed at $300^{\circ}C$ in air, respectively. XRD patterns of the $SnO_2$ nano powders showed the tetragonal structure with (110) dominant orientation. The particle size of $SnO_2$ nano powders at the ratio of $SnCl_2:N_2H_4$+NaOH= 1:6 was about 60 nm. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a test box. Sensitivity of $SnO_2$ gas sensor to 5 ppm $CH_4$gas and 5 ppm $CH_3CH_2CH_3$ gas was investigated for various $SnCl_2:N_2H_4$+NaOH proportion. The highest sensitivity to $CH_4$ gas and $CH_3CH_2CH_3$ gas of $SnO_2$ sensors was observed at the $SnCl_2:N_2H_4$+NaOH= 1:8 and $SnCl_2:N_2H_4$+NaOH= 1:6, respectively. Response and recovery times of $SnO_2$ gas sensors prepared by $SnCl_2:N_2H_4$+NaOH= 1:6 was about 40 s and 30 s, respectively.

Synthesis and Aminolysis of N,N-Diethyl Carbamic Ester of HOBt Derivatives

  • Khattab, Sherine Nabil;Hassan, Seham Yassin;Hamed, Ezzat Awad;Albericio, Fernando;El-Faham, Ayman
    • Bulletin of the Korean Chemical Society
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    • v.31 no.1
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    • pp.75-81
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    • 2010
  • The reaction of N,N-diethyl carbamates of 1H-[1,2,3]triazolo[4,5-b]pyridin-1-ol (4-HOAt) 7, 3H-[1,2,3]triazolo[4,5-b]pyridin-3-ol (7-HOAt) 8, 1H-benzo[d][1,2,3]triazol-1-ol (HOBt) 9, 6-chloro-1H-benzo[d][1,2,3]triazol-1-ol (Cl-HOBt) 10, 6-(trifluoromethyl)-1H-benzo[d][1,2,3]triazol-1-ol ($CF_3$-HOBt) 11, and 6-nitro-1H-benzo[d][1,2,3]triazol-1-ol ($NO_2$-HOBt) 12 with morpholine and piperidine in $CH_3CN$ underwent acyl nucleophilic substitution to give the corresponding carboxamide derivatives. The reactants and products were identified by elemental analysis, IR and NMR. We measured the kinetics of these reactions spectrophotometrically in $CH_3CN$ at a range of temperatures. The rates of morpholinolysis and piperidinolysis were found to fit the Hammett equation and correlated with $\sigma$-Hammett values. The values were 1.44 - 1.21 for morpholinolysis and 1.95 - 1.72 for piperidinolysis depending on the temperature. The $Br{\phi}$nsted-type plot was linear with a $\beta_lg = -0.49 \pm 0.02$ and $-0.67 \pm 0.03$. The kinetic data and structure-reactivity relationships indicate that the reaction of 9-12 with amines proceeds by a concerted mechanism. The deviation from linearity of the correlation ${\Delta}H^#$ vs. ${\Delta}S^#$ and plot of $logk_{pip}$ vs. $logk_{morph}$ and $Br{\phi}$nsted-type correlation indicate that the reactions of amines with carbamates 7 and 8 is attributed to the electronic nature of their leaving groups.

Effect of Timed Artificial Insemination Protocols on the Pregnancy Rate Per Insemination and Pregnancy Loss in Dairy Cows and Korean Native Cattle under Heat Stress

  • Uhm, Hyun-Boem;Jeong, Jae-Kwan;Kang, Hyun-Gu;Kim, Ill-Hwa
    • Journal of Veterinary Clinics
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    • v.37 no.5
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    • pp.235-241
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    • 2020
  • We aimed to determine the effect of timed artificial insemination (TAI) protocols on the pregnancy rate per insemination and pregnancy loss compared with AI performed at detected estrus in dairy cows and Korean Hanwoo cattle under heat stress. In dairy cattle, 1,250 sets of data that underwent AI during heat stress (temperature-humidity index ≥ 72) were categorized according to their TAI protocols or as controls: 1) PGF-36 h-estradiol benzoate (EB)-36 h-TAI (PG-EB group, n = 113); 2) GnRH-7 days-PGF-56 h-GnRH-16 h-TAI (Ovsynch group, n = 455); or 3) GnRH-6 days-Ovsynch (G6G group, n = 136). The remaining cows underwent AI at detected estrus (AIDE group, n = 546). The probability of pregnancy per AI 45 days after AI was higher (P < 0.01) in the PG-EB (odds ratio [OR]: 1.68), Ovsynch (OR: 1.48), and G6G (OR: 1.79) groups than in the AIDE group. However, the prevalence of pregnancy loss between 30 and 45 days after AI did not differ among the groups. In Hanwoo cattle, 617 sets of data inseminated artificially under heat stress were categorized into AIDE (n = 281), PG-EB (n = 194), and combined Ovsynch or G6G (n = 142) groups. The probability of pregnancy per AI 45 days after AI and the prevalence of pregnancy loss between 30 and 45 days after AI did not differ among the groups. Thus, implementation of a TAI protocol (PG-EB, Ovsynch, or G6G) in dairy cows under heat stress improves the pregnancy rate per AI versus AIDE, whereas there is no beneficial effect of TAI on the pregnancy rate of Hanwoo cattle under heat stress.

Synthesis of Histamine $H_2$-receptor antagonists - Synthesis of 5,6-dihydro[2,1-b]thiazole derivatives - (Histamine $H_2$-수용체길항제의 합성 - 5,6-Dihydroimidazo[2,1-b]thiazole 유도체의 합성 -)

  • 박상우;이강노
    • YAKHAK HOEJI
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    • v.35 no.5
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    • pp.368-371
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    • 1991
  • For the development of new antiulcer agents 5, 6-dihydroimidazo[2, 1-b]- thiazoles substituted at the 3-position are sythesized. Thus, the reaction of 3-chloromethyl-5, 6-dihydroimidazo[2, 1-b]thiazole(2) with thiourea and subsequently with 3-chloro-propionitrile gives 3-[3-[5, 6-dihydroimidazo[2, 1-b]thiazolyl]methylthio]propionitrile(4), which by partial alcoholysis with methanol is converted into methyl-3-[3-[5, 6-dihydro-imidazo[2, 1-b]thiazoyl]methylthio]propionimidate(5) . This compound(5) is treated finally with sulfamide or sulfonamides. 3-[3-[5, 6-dihydroimidazo[2, 1-b]thiazoyl]methylthiol-N$^{2}$-sulfamoyl-propionamidine(6) inhibited gastric acid secretion (45%) when administered intraduodenally (100 mg/kg) to pylorus-ligated rats.

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N,N'-Dimethylethylenediamine-N,N'-di-α-butyric Acid Cobalt(III) Complexes Utilizing Oxidation of Sulfur of S-Methyl-L-cysteine

  • Kim, Hyun-Jin;Youm, Kyoung-Tae;Yang, Jung-Sung;Jun, Moo-Jin
    • Bulletin of the Korean Chemical Society
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    • v.23 no.6
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    • pp.851-856
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    • 2002
  • The Reaction of S-methyl-S-cysteine(L-Smc) with racemic $s-cis-[Co(demba)Cl_2]-1$ (Hydmedba = $NN'-dimethylethylenediamine-NN'-di-\alpha-butyric$, acid) yields ${\Delta}$-s-cis-[Co(dmedba)(L-Smc)] 2 with N, O-chelation. Oxidation of sulfur of 2 with $H_2O_2$ in a 1 : 1 mole ratio gives ${\Delta}$-s-cis[Co(dmedba)(L-S(O)mc)] 3 having an uncoordinated sulfenate group. Oxidation of sulfur of L-Sm with $H_2O_2in$ a 1: 1 mole ratio produces S-methyl-L-cysteinesulfenate (L-S(O)me) 5. Direct reaction of 1 with 5 in basic medium gives an N.O-chelated ${\Delta}$s-cis[Co(dmedba)(L-S(O)mc)-N.O], which turmed out be same as obtained by oxidation of 2, while an N, S-chelated ${\Delta}$-s-cis-[Co(dmedba)(S-S(O)mc)-N,O] complex 4 is obtained in acidic medium from the reaction of 1 with 5. This is one of the rare $[$Co^{III}$(N_2O_2-type$ ligand)(amino acid)] type complex preparations, where the reaction conditions determine which mode of N, O and N, S caelation modes is favored.

Biodegradation test of the alternatives of perfluorooctanesulfonate (PFOS) and PFOS salts (PFOS salts 및 PFOS 대체물질에 대한 미생물분해시험)

  • Choi, Bong-In;Na, Suk-Hyun;Son, Jun-hyo;Shin, Dong-Soo;Ryu, Byung-taek;Chung, Seon-yong
    • Journal of Environmental Health Sciences
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    • v.42 no.2
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    • pp.112-117
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    • 2016
  • Objectives: In this study, we investigated the biodegradation rates of 8 perfluorooctanesulfonate (PFOS) alternatives synthesized at the at Changwon National University in comparison to those of PFOS potassium salt and PFOS sodium salt. Methods: A biodegradability test was performed for 28 days with microorganisms cultured in the good laboratory practice laboratory at the Korea Environment Corporation following the OECD Guidelines for the testing of chemicals, Test No. 301 C Results: While $C_5H_8F_3SO_3K$, $C_8F_{17}SO_3K$ and $C_8F_{17}SO_3Na$ were not degraded after 28 days, the 3 alternatives were biodegraded at the rates of 31.4% for $C_8H_8F_9SO_3K$, 25.6% for $C_{10}H_8F_{13}SO_3K$, 23.6% for $C_{25}F_{17}H_{32}S_3O_{13}Na_3$, 20.9% for $C_{15}F_9H_{21}S_2O_8Na_2$, 15.5% for $C_{23}F_{18}H_{28}S_2O_8Na_2$, 8.5% for $C_{17}F_9H_{25}S_2O_8Na_2$ and 4.8% for $C_6H_8F_5SO_3K$. When the concentration was the same(500 mg/L), $C_{23}F_{18}H_{28}S_2O_8Na_2$ had the lowest tension with 20.94 mN/m, which was followed by $C_{15}F_9H_{21}S_2O_8Na_2$ (23.36 mN/m), $C_{17}F_9H_{25}S_2O_8Na_2$ (27.31 mN/m), $C_{25}F_{17}H_{32}S_3O_{13}Na_3$ (28.17 mN/m), $C_{10}H_8F_{13}SO_3K$ (29.77 mN/m) and $C_8H_8F_9SO_3K$ (33.89 mN/m). Having higher surface tension of 57.64 mN/m and 67.57 mN/m, respectively, than those of the two types of PFOS salts, $C_6H_8F_5SO_3K$ and $C_5H_8F_3SO_3K$ were found valueless as substitute for PFOS. Conclusion: The biodegradation test suggest that 6 compounds could be used as substitutes for PFOS. $C_{23}F_{18}H_{28}S_2O_8Na_2$ and $C_{15}F_9H_{21}S_2O_8Na_2$ were found to be the best substitutes based on biodegradation rate and surface tension, followed by $C_{25}F_{17}H_{32}S_3O_{13}Na_3$, $C_8H_8F_9SO_3K$ and $C_{10}H_8F_{13}SO_3K$. $C_{17}F_9H_{25}S_2O_8Na_2$ was found to have relatively low value as an alternative but it still had a potential to substitute the conventional PFOS.

Effects of Melatonin on Gene Expression of IVM/IVF Porcine Embryos

  • Jang, H.Y.;Kong, H.S.;Choi, K.D.;Jeon, G.J.;Yang, B.K.;Lee, C.K.;Lee, H.K.
    • Asian-Australasian Journal of Animal Sciences
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    • v.18 no.1
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    • pp.17-21
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    • 2005
  • The effect of melatonin on in vitro embryo development and the expression of antioxidant enzyme gene in preimplantation porcine embryos was determined by modified semi-quantitative single cell RT-PCR. Porcine embryos derived from in vitro maturation /in vitro fertilization were cultured in 5% $CO_2$ and 20% $O_2$ at $37^{\circ}C$ in NCSU23 medium. Melatonin was added to medium at concentration of 1nM, 5 nM, and 10 nM. When treated with 1nM (39.0%) of melatonin, the developmental rate of embryos beyond the morula stage were higher than that of control group (31.0%) (p<0.05). Number of inner cell mass and tropectoderm cell in control (23.0${\pm}$0.5 and 17.3${\pm}$0.8), 1 nM (23.6${\pm}$0.6 and 19.0${\pm}$0.5), and 5 nM (23.3${\pm}$1.1 and 16.3${\pm}$0.8) treated with melatonin were higher than in 10 nM (20.0${\pm}$0.5 and 13.3${\pm}$0.8) treated with melatonin (p<0.05). To develop an mRNA phenotypic map for the expression of catalase, bax and caspase-3, single cell RT-PCR analysis were carried out in porcine IVM/IVF embryo. Catalase was detected in 0, 1 and 5 nM supplemented with melatonin, but bax and caspase-3 were detected in 10 nM treated with melatonin.

Study on 4,4-pentamethylene-1,3-oxazolidine-5-one-2-thione (4,4-pentamethylene-1,3-oxazolidine-5-one-2-thione에 관한 연구)

  • 국채호;조윤상;주상섭
    • YAKHAK HOEJI
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    • v.16 no.2
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    • pp.85-89
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    • 1972
  • 4,4-Pentamethylene-1,3-oxazolidine-5-one-2-thione is to be obtained from 1-amino cyclohexane carboxylic acid and thiophosgene, however, it was not isolated because of its unstability. When it was treated with $C_{6}H_{5}NH_{2},$ N-phenyl-(1-aminocyclohexane) carboxylic acid and N-(1-carboxycyclohexyl), N-phenyl thiourea were obtained. When refluxed in $H_{2}O$ at pH 2, pH 12 and neutral condition, the resulting carboxylic compound, being anticipated by us, was 1-aminocyclohexane carboxylic acid. From the above results, we have got the suggestion f the chemical behavior of 4,4-pentamethylene-1,3-oxazolidine-5-one-2-thione and also some informations of the reaction mechanism between 1-aminocyclohexane carboxylic acid and thiophosgene.

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