• Title/Summary/Keyword: Pyridyl-N

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A Novel Linking Schiff-Base Type Ligand (L: py-CH=N-C6H4-N=CH-py) and Its Zinc Coordination Polymers:Preparation of L, 2-Pyridin-3-yl-1H-benzoimidazol, trans-[Zn(H2O)4L2].(NO3)2.(MeOH)2[Zn(NO3)(H2O)2(L)].(NO3).(H2O)2 and [Zn(L)(OBC)(H2O)] (OBC = 4,4'-Oxybis(benzoate))

  • Kim, Han-Na;Lee, Hee-K.;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • v.26 no.6
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    • pp.892-898
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    • 2005
  • A long, bis(monodentate), linking Schiff-base ligand L (py-CH=N-$C_6H_4$-N=CH-py) was prepared from 1,4-phenylenediamine and 3-pyridinecarboxaldehyde by the Schiff-base condensation. Ligand L has two terminal pyridyl groups capable of coordinating to metals through their nitrogen atoms. In contrast, the same reaction between 1,2-phenylenediamine and 3-pyridinecarboxaldehyde produced a mixture of imidazol isomers (2-pyridin-3-yl-1H-benzoimidazole), which are connected to one another by the N-H…N hydrogen bonding to form a tetramer. From Zn($NO_3)_2{\cdot}6H_2O$ and ligand L under various conditions, one discrete molecule, trans- [Zn($H_2O)_4L_2]{\cdot}(NO_3)_2{\cdot}(MeOH)_2$, and two 1-D zinc polymers, [Zn$(NO_3)(H_2O)_2(L)]{\cdot}(NO_3){\cdot}(H_2O)_2$ and [Zn(L) (OBC)($H_2O$)], were prepared. In ligand L, the N$\ldots$N separation between the terminal pyridyl groups is 13.994 $\AA$, with their nitrogen atoms at the meta positions (3,3’) in a trans manner. The corresponding N$\ldots$N separations in its compounds range from 13.853 to 14.754 $\AA$.

Structure of [$CoL_2(MeOH)(NO_3)_2$] [L = N1-(1-(pyridin-4-yl)ethylidene)naphthalene-1,5-diamine)] ($CoL_2(MeOH)(NO_3)_2$의 구조 [L=N1-(1-(pyridin-4-yl)ethylidene)naphthalene-1,5-diamine)])

  • Kim, Sung-Hoon;Huh, Hyun-Sue;Lee, Soon-W.
    • Korean Journal of Crystallography
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    • v.18 no.1_2
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    • pp.21-25
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    • 2007
  • When a $CH_2Cl_2$ solution of the dipyridyl species L' (N,N'-bis-(1-pyridin-4-yl-ethylidene)-naphthalene-1,5-diamine) was layered onto the top of a MeOH solution of $Co(NO_3)_2{\cdot}6H_2O$, a molecular cobalt compound [$CoL_2(MeOH)(NO_3)_2$] (1), not a coordination polymer, was formed. X-ray structural analysis of compound 1 revealed that it contains the pyridyl-amine ligand L (N1-(4-imino-1-methyl-but-2-enylidene)-naphthalene-1,5-diamine), instead of L'. Structure of compound 1 strongly suggests that the original ligand L' has been hydrolyzed to ligand L during the reaction.

Synthesis of New pyridyl Squarine Dyes and Application to Poly(vinyl cinnamoyl actate)(III) (신규 pyridyl Squarine Dyes의 합성 및 Poly(vinyl cinnamoyl actate)의 고감도화(III))

  • 손세모
    • Journal of the Korean Graphic Arts Communication Society
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    • v.18 no.2
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    • pp.143-151
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    • 2000
  • A previous paper was reported in being sensetized photopolymer, poly(vinyl cinnamoyl acetate)(PVCiA)$^{1.2)}$ with some squarylium dyes such as 1,3-bis(4 or 6-trifluoromethyl-1,3,3-trimethylindo)squarylium dyes(TFSQ) and 1,3-bis(4 or 6-nitro-1,3,3-trimethylindo)(NISQ). Here, we synthesized new 1,3-bis(1,3,3-trimethylpyridylindo)squarylium dyes(PSQD) to sensetize photopolymer, such as poly(vinyl cinnamoyl acetate). Absorption's coefficient of (PSQDI) was 9.78$\times$10$^{5}$ , highest absorption's coefficient among them synthesized by author, and the sensitivity of PVCiA added with PSQD1 (3%) was highly sensitized about 16 times than not added, and higher than NISQ(3%). PSQD1 with substituted 4 and 7 positions by nitrogen is rich in n-$\pi$* transition, resulted in high absorption's coefficient, red shift for another squarylium dyes, and afforded to the highest sensitivity of PVCiA.

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First Example of Monometallic Palladium(II) Compound with Trans-Chelating Tridentate Ligand: Synthesis, Crystal Structure, and Characterizations

  • Tae Hwan Noh
    • Mass Spectrometry Letters
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    • v.14 no.3
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    • pp.110-115
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    • 2023
  • The reaction of (COD)PdCl2 with new C3-symmetric tridentate L (COD = 1,5-cyclooctadien; L = 1,3,5-tris(picolinoyloxyethyl)cyanurate) in a mixture of acetone and dichloromethane produces single crystals consisting of unprecedented monometallacyclic [PdCl2(L)]. This cyclic compound arises from trans-chelation of two of three donating pyridyl groups of L, while the third pyridyl group remains uncoordinated. Electrospray ionization mass spectrometry (ESI-MS) data on L exhibited the major peak corresponding to [C27H24N6O9 + H+]+. Fast atom bombardment mass spectrometry (FABMS) data on [PdCl2(L)], however, showed the mass peak corresponding to the L instead of the present palladium(II) compound species, due to the insolubility and dissociation in solution. The physicochemical properties of the present palladium(II) compound were fully characterized by means of infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy, thermal analysis, single-crystal X-ray diffraction (SC-XRD) measurement.

Ozone Inhalation with 4-(N-methyl-N-nitrosamino)-1-(3-pyridyl)- 1-butanone and/or Dibutyl Phthalate Induced Cell Cycle Alterations via Wild-type p53 Instability in B6C3F1 Mice

  • Kim, Min-Young;Song, Kyung-Suk;Park, Gun-Ho;Kim, Hyun-Woo;Park, Jin-Hong;Kim, Jun-Sung;Jin, Hwa;Kook-Jong, Eu;Cho, Hyun-Sun
    • Toxicological Research
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    • v.20 no.1
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    • pp.71-82
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    • 2004
  • Changes in cell cycle control in the lungs and liver of the B6C3F1 mice (20 males per each group) exposed to ozone (0.5 ppm), 4-(N-methyl-N-nitrosamino)-1-(3-pyridyl)-1-butanone (NNK, 1.0 mg/kg), and dibutyl phthalate (DBP, 5,000 ppm) after 52 weeks were examined through Western, Northern blot, and immunohistochemistry based on alterations in protein expression levels of G1/S checkpoints (cyclin D1, cyclin E, and PCNA), G2/M checkpoints (cyclin B1, cyclin G, and cyclin A), negative regulators (p53, p21, GADD45, and p27), and positive regulator (mdm2). Expression levels of cyclins D1, E, G, PCNA, mutant p53, and mdm2 proteins were higher in the lungs and livers treated with combination of toxicants than in those treated with ozone only. Expression levels of the wild-type and mutant p53, p21, GADD45, p27, and mdm2 proteins and mRNAs were higher in toxicant-treated groups than those of the control. Immunohistochemical analysis revealed staining intensities of the PCNA, cyclin D1, c-myc and mdm2 protein- treated lungs and livers were stronger than those of the control group. Our results showed that combined treatment of ozone with NNK/DBP altered the cell cycle control through instability of the wild-type p53 gene. Such pivotal p53-mediated cell cycle alterations may be responsible for the toxicity observed under our experimental condition. These results may be applied to risk assessment of mixture-induced toxicity.

Synthesis and Crystal Structure of Cyclodimetric Ag(I) Complex with 2,3-Bis(2-pyridyl)pyrazine (고리 이합체 2,3-비스(2-피리딜)피라진(트라이플루오르아세테이토)은(I) 착물의 합성 및 결정 구조)

  • Kim, Yun-Ju;Lee, Young-A;Lee, Uk;Jung, Ok-Sang
    • Korean Journal of Crystallography
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    • v.11 no.1
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    • pp.28-33
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    • 2000
  • The slow of 2,3-bis(2-pyridyl)pyarzine(bpp) with Ag(CF₃CO₂) produces crystalline product suitable for X-ray crystallography. Crystallographic characterization of the crystal (C/sub 32/H/sub 20/-F/sub 6/N/sub 8/O₄Ag₂: triclinic P1, a=8.518(5)Å, b=9.546(2)Å, c=10.632(1)Å, α=81.11(1)°, β=87.61(3)°, γ=75.66(3)°, V=827.5(5)ų, Z=1, R=0.0431) has provided that the complex is a cyclic dimer [Ag(bpp)(CF₃CO₂)]₂. Each bpp ligand connects two tetrahedral silver(I) ions in a tridentate mode (Ag-N, 2.26()-2.43(2)Å), and the trifluoroacetato anion is bonded to each silver(I) atom in a monodentate fashion (Ag-O, 2.38(1); 2.39(2) Å). The skeletal cyclic dimer is stable up to 212℃, and drastically decomposes around this temperature.

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Synthesis, Protonation Constants and Stability Constants for $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$, and $Zn^{2+}$ Ions of 1,15-bis(2-pyridyl)-2,5,8,11,14-pentaazapentadecane

  • Kim, Sun-Deuk;Kim, Jun-Kwang;Jung, Woo-Sik;Chung, Koo-Chun
    • Analytical Science and Technology
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    • v.9 no.4
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    • pp.411-415
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    • 1996
  • The new potentially heptadentate $N_7$ ligand 1, 15-bis(2-pyridyl)-2, 5, 8, 11, 14-pentaazapentadecane(pytetren) has been synthesized and characterized by EA, IR, NMR, and mass spectrometry. Its proton association constants (log $K{_H}^n$) and stability constants(log $K_{ML}$) for $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$, and $Zn^{2+}$ ions were determined at 298.1K and ionic strength=0.100M($KNO_3$) by potentiometry: log $K{_H}^1=9.36$, log $K{_H}^2=9.12$, log $K{_H}^3=8.09$, log $K{_H}^4=6.62$, log $K{_H}^5=4.02$, log $K{_H}^6=2.54$: log $K_{ML}(CO^{2+})=22.67$, log $K_{ML}(Ni^{2+})=26.25$. log $K_{ML}(Cu^{2+})=28.46$, log $K_{ML}(Zn^{2+})=19.90$.

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A Kinetic Study on Aminolysis of 2-Pyridyl X-Substituted Benzoates: Effect of Changing Leaving Group from 4-Nitrophenolate to 2-Pyridinolate on Reactivity and Mechanism

  • Lee, Jong-Pal;Bae, Ae-Ri;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.3588-3592
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    • 2010
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2-pyridyl X-substituted benzoates 8a-e with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 8a-e are slightly smaller than the corresponding reactions of 4-nitrophenyl X-substituted benzoates 1a-e (e.g., $kN^{1a-e}/k_N^{8a-e}$ = 1.1 ~ 3.1), although 2-pyridinolate in 8a-e is ca. 4.5 $pK_a$ units more basic than 4-nitrophenolate in 1a-e. The Br$\o$nsted-type plot for the aminolysis of 8c (X = H) is linear with $\beta_{nuc}$ = 0.77 and $R^2$ = 0.991 (Figure 1), which is typical for reactions reported previously to proceed through a stepwise mechanism with breakdown of a zwitterionic tetrahedral intermediate $T^{\pm}$ being the rate-determining step (RDS), e.g., aminolysis of 4-nitrophenyl benzoate 1c. The Hammett plot for the reactions of 8a-e with piperidine consists of two intersecting straight lines (Figure 2), i.e., $\rho$ = 1.71 for substrates possessing an electron-donating group (EDG) while $\rho$ = 0.86 for those bearing an electron-withdrawing group (EWG). Traditionally, such a nonlinear Hammett plot has been interpreted as a change in RDS upon changing substituent X in the benzoyl moiety. However, it has been proposed that the nonlinear Hammett is not due to a change in RDS since the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with $\rho$ = 0.85 and r = 0.62 ($R^2$ = 0.995, Figure 3). Stabilization of substrates 8a-e in the ground state has been concluded to be responsible for the nonlinear Hammett plot.

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.

Cd(II) and Zn(II) Complexes Containing N,N'-Bidentate N-(Pyridin-2-ylmethylene)cyclopentanamine: Synthesis, Characterisation and Methyl Methacrylate Polymerisation

  • Song, Yujin;Kim, Dongil;Lee, Ha-Jin;Lee, Hyosun
    • Bulletin of the Korean Chemical Society
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    • v.35 no.10
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    • pp.2929-2934
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    • 2014
  • The reaction between $[CdBr_2{\cdot}4H_2O]$ and anhydrous $[ZnCl_2]$ with N,N'-bidentate N-(pyridin-2-ylmethylene)-cyclopentanamine (impy) in ethanol yields dimeric $[(impy)Cd({\mu}-Br)Br]_2$ and monomeric $[(impy)ZnCl_2]$ complexes, respectively. The X-ray crystal structure of Cd(II) and Zn(II) complexes revealed that the cadmium atom in $[(impy)Cd({\mu}-Br)Br]_2$ and zinc in $[(impy)ZnCl_2]$ formed a distorted trigonal-bipyramidal and tetrahedral geometry, respectively. Both complexes showed moderate catalytic activity for the polymerisation of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO), with polymethylmethacrylate (PMMA) syndiotacticity of about 0.70.