• Title/Summary/Keyword: Pyridyl

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Anionic Synthesis of Dipyridine Chain End-Functionalized Polystyrene and Polybutadiene (리빙 음이온 중합에 의한 Dipyridine 말단 관능화 폴리스티렌 및 폴리부타디엔의 합성)

  • Ji, Sang-Chul;Lee, Jong-Seop;Kim, Doo-Hwan;Kang, Cheol-Han;Park, Jong-Hyuk;Lee, Bum-Jae
    • Polymer(Korea)
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    • v.34 no.2
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    • pp.159-165
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    • 2010
  • Dipyridine-terminated polystyrenes and polybutadienes were synthesized by the chain endfunctionalization reaction of polystyryllithium (PSLi) and polybutadienyllithium (PBDLi) with di(2-pyridyl) ketone(DPK) using a living anionic polymerization method in the Ar-glove box. Living polymeric lithiums with low molecular weights (Mw=1000~2000 g/mol) were used to investigate the chain end-functionalization yield with DPK and the degree of coupling reaction by the attack of organolithium to the pyridine ring in the presence of TMEDA using GPC, $^1H$-NMR, $^{13}C$ analysis. DPK-terminated PBD exhibited much higher functionalization yield and less amount of coupling reaction compared with DPK-terminated PS. 86% functionalization yield with 9% degree of coupling was obtained when the PBDLi was added dropwise to DPK solution at room temperature. The functionalization yield was increased as the reaction temperature decreased, however, no LiCl effect was observed in this chain end-functionalization reaction with DPK.

A high-effective method to separate nicotine from the tobacco-specific carcinogen 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) mixtures using electrodialysis

  • Ge, Shaolin;Li, Wei;Zhang, Zhao;Li, Chuanrun;Wang, Yaoming
    • Membrane and Water Treatment
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    • v.8 no.3
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    • pp.245-257
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    • 2017
  • The separation of nicotine and tobacco-specific N-nitrosamines is a tough problem in tobacco industry. In this study, separation of nicotine from 4-(methylnitrosamino) -1-(3-pyridyl)-1-butanone (NNK) mixtures was investigated using electrodialysis by taking the principle of the protonation status difference between these two components. The results indicated that the solution pH has a dominant impact on the separation process. In a pH range of 5-7, nicotine molecules are existed as mono- and di-protonated ions and can be separated from the uncharged NNK molecules. The acidic electrolyte is conducive to the separation process from the point of flux and energy consumption; while the alkaline electrolyte has negative impact on the separation process. A current density of $10mA/cm^2$ is an appropriate value for the separation process. The lowest energy consumption of the separation process is 0.58 kWh/kg nicotine with the process cost to be estimated at only $0.208 /kg nicotine. Naturally, electrodialysis is a high-efficiency, cost-effective, and environmentally friendly process to separate and purify nicotine from tobacco juice.

Studies of Pharmacological Activity on New Oral Cephalosporins (새로운 경구용 세팔로스포린의 약효평가)

  • La, Sung-Bum;Kim, Wan-Joo;Jee, Ung-Kil
    • YAKHAK HOEJI
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    • v.38 no.2
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    • pp.140-148
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    • 1994
  • ${\beta}-Lactamase$ stability, chemotherapeutic activity, and pharmacokinetics of 7-[(Z)-2-(2-aminothiazole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyridyl)piperazinyl]thiocarbonylthiomethyl-3-cephem-4-carboxylic acid(CEN1), 7-[(Z)-2-(2-aminothiazole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyrimidyl)piperazinyl]thiocarbonylthiomethyl-3-cephem-4-carboxylic acid(CEN2), pivaloyloxymethyl-7-[(Z)-2-(2-aminothizaole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyridyl)piperazinyl]thiocarbonyl-thiomethyl-3-cephem-4-carboxylate(CEN1P), and pivaloyloxymethyl-7-{(Z)--2-(2-aminothizaole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyridyl)piperazinyl]thiocarbonyl-thiomethyl-3-cephem-4-carboxylate(CEN2P) were examined. CEN1, CEN2, CEN1P, and CEN2P were very stable to the ${\beta}-lactamase$ obtained from three strains(Enterobacter cloacae P99, Escherichia coli TEM, and Citrobacter freundii). Chemotherapeutic activities$(ED_{50})$ of CEN2 and CEN2P against experimental systemic infections due to Streptococcus pyogenes 77A and Escherichia coli 078 were superior to those of CEN1 and CEN1P, respectively. The $ED_{50}$ values of CEN1, CEN2 were 5.82 mg/kg, 0.89 mg/kg(s.c., S. pyogenes 77A) while those of CEN1P, CEN2P were 14.56mg/kg, 6.40mg/kg(p.o., S. pyogenes 77A), respectively. The pharmacokinetics of CEN1, CEN2, CEN1P, and CEN2P were investigated in mice and rats. In mice, peak blood levels of $1.25\;{\mu}g/ml$ were recorded within 20 min after oral administration of a single dose equivalent to 40 mg/kg CEN1P. Cmax of CEN1P was much higher than that of CEN1 in mice and rats. Oral absorption of CEN2P was much higher than that of CEN2.

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A Novel Al-Bridged Trinuclear Iron(II) Bis(imino)pyridyl Complex with Catalytic Ethylene Polymerization Behavior

  • Long, Zerong;Li, Zhongquan;Ma, Ning;Wu, Biao
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2537-2543
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    • 2011
  • A self-assembled Al-bridged diiminopyridine-based ligand (3) was synthesized and characterized by FT-IR, ESI-MS and NMR spectroscopy. Electron spectral titrations were performed to confirm the formation of a novel trinuclear bis(imino)pyridyl iron(II) complex (4) upon addition of $FeCl_2$ into Al-bridged ligand 3 in methanol solution. Simultaneously, a typical bis(imino)pyridine-iron(II) complex (2) was synthesized and fully characterized. The X-ray crystal study of the iron(II) complex 2 disclosed a five-coordinate, distorted square-pyramidal structure with the tridentate N^N^N ligand and chlorides. The optimal molecular structure of 4 was obtained by means of molecular mechanics, which showed that each iron atom in the complex 4 is surrounded by two chlorides, a tridentate N^N^N ligand and one oxygen atom, supporting considerations about the possibility of six-coordinate geometry from MMAO or the ethylene access. A comparison of 4 with the reference 2 revealed a remarkable decrease of the catalytic activity and MMAO consumption (activity up to $0.41{\times}10^3\;kg\;{mol_{Fe}}^{-1}h^{-1}bar^{-1}$, Al/Fe = 650 for 4 and $7.02{\times}10^3\;kg\;{mol_{Fe}}^{-1}h^{-1}bar^{-1}$, Al/Fe = 1600 for 2).

The Co-luminescence Groups of Sm-La-pyridyl Carboxylic Acids and the Binding Characteristics between the Selected Doped Complex and Bovine Serum Albumin

  • Yang, Zhengfa;Tang, Ruiren;Tang, Chunhua
    • Bulletin of the Korean Chemical Society
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    • v.33 no.4
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    • pp.1303-1309
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    • 2012
  • A novel ligand N,N'-(2,6-pyridinedicarbonyl)bis[N-(carboxymethyl)] (L1) was designed and synthesized. Four co-luminescence groups of Sm-La-pyridyl carboxylic acids systems were researched, which are $K_4Sm_{(1-x)}-La_x(L_1)Cl_3{\cdot}y_1H_2O$, $K_4Sm_{(1-x)}La_x(L_2)Cl_3{\cdot}y_2H_2O$, $K_6Sm_{2(1-x)}La_{2x}(L_3)Cl_6{\cdot}y_3H_2O$, $K_4Sm_{(1-x)}La_x(L_4)Cl_3{\cdot}y_4H_2O$. The results indicated the addition of La(III) could sensitize the luminescence of Sm(III) obviously in a certain range, enhancing emission intensity of Sm-pyridyl carboxylic acids relative to the undoped ones. The optimal mole percentages of La(III) in the mixed ions for $L_1$, $L_2$, $L_3$, $L_4$ were confirmed to be 0.6, 0.5, 0.3, 0.6, respectively. The mechanism of the fluorescence enhancement effect was discussed in detail. Furthermore, the binding interaction of $K_4Sm_{0.4}La_{0.6}(L_4)Cl_3{\cdot}5H_2O$ with bovine serum albumin (BSA) have been investigated due to its potential biological activity. The binding site number n was equal to 1.0 and binding constant $K_a$ was about $2.5{\times}10^5\;L{\cdot}mol^{-1}$.

Metal Ion Catalysis in Nucleophilic Displacement Reactions of 2-Pyridyl X-Substituted Benzoates with Potassium Ethoxide in Anhydrous Ethanol

  • Lee, Jae-In;Kang, Ji-Sun;Im, Li-Ra;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3543-3548
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    • 2010
  • A kinetic study on nucleophilic displacement reactions of 2-pyridyl X-substituted benzoates 1a-e with potassium ethoxide (EtOK) in anhydrous ethanol is reported. Plots of pseudo-first-order rate constants ($k_{obsd}$) vs. $[EtOK]_o$ exhibit upward curvature. The $k_{obsd}$ value at a fixed $[EtOK]_o$ decreases steeply upon addition of 18-crown-6-ether (18C6) to the reaction mixture up to [18C6]/$[EtOK]_o$ = 1 and then remains nearly constant thereafter. In contrast, $k_{obsd}$ increases sharply upon addition of LiSCN or KSCN. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ has revealed that ion-paired EtOK is more reactive than dissociated $EtO^-$, indicating that $K^+$ ion acts as a Lewis acid catalyst. Hammett plots for the reactions of 1a-e with dissociated $EtO^-$ and ion-paired EtOK result in excellent linear correlation with $\rho$ values of 3.01 and 2.67, respectively. The $k_{EtOK}/k_{EtO^-}$ ratio increases as the substituent X in the benzoyl moiety becomes a stronger electron-donating group. $K^+$ ion has been concluded to catalyze the current reaction by stabilizing the transition state through formation of a 6-membered cyclic complex.

Synthesis and Characterization of Homobinuclear Complexes of UO2(VI), ZrO(IV) and Th(IV) ions with 3-Benzylidine/Furfurylidine/(Pyridyl/Thienyl-2'-methylene) imino-5-p-sulphonamido phenyl azo-2-thiohydantoins (3-Benzylidine/Furfurylidine/(Pyridyl/Thienyl-2'-methylene) imino-5-p-sulphonamido phenyl azo-2-thiohydantoins와 UO2(VI), ZrO(IV) 및 Th(IV) 이온의 동종이핵 착물에 대한 합성 및 특성)

  • Dash, D.C.;Mahapatra, A.;Naik, P.;Mohapatra, R.K.;Naik, S.K.
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.412-417
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    • 2011
  • A series of homobinuclear complexes of the type [$M_2L(NO_3)_n(H_2O)_m$] where M=$UO_2$(VI), ZrO(IV), Th(IV); L=3-benzylidine-imino-5-p-sulphonamido phenyl azo-2-thiohyatoin(bispt), 3-furfurylidine-imino-5-p-sulphonamido phenyl azo-2-thiohydantoin(fispt),3-pyridyl-2'-methylene-imino-5-p-sulphonamido phenyl azo-2-thiohydantoin(pmispt) and 3-thienyl-2'-methylene-imino-5-p-sulphoanamido phenyl azo-2-thiohydantoin(tmispt); n=8 for Th(IV) and 4 for others, m=4 for bispt and 3 for others have been synthesized and characterized on the basis of elemental analysis, thermal analysis, molar conductance, magnetic moment and spectroscopic data (IR, electronic and $^1H$-NMR). In the light of this information, the ligands can be visualized as tetradentate co-ordinating through azomethine nitrogen, carbonyl oxygen to one metal centre where as azo nitrogen and thioimido nitrogen to the other metal centre yielding homo binuclear complexes of the above composition. The fungi toxicity of the ligands & their zirconyl complexes against some fungal pathogen has been studied.