• Bulletin of the Korean Chemical Society
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• v.29 no.9
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• pp.1819-1822
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• 2008

• Journal of the Korean Chemical Society
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• v.48 no.4
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• pp.379-384
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• 2004

4-pyrimidylideneacetonitrile derivatives containing $BF_2$-chelate have been synthesized from H-chelates of 4-pyrimidylideneacetonitrile derivatives and boron trifluoride diethyl etherate. These H-chelates were prepared by the electrophilic substitution of 2-cyanomethylpyridine derivatives with electrophiles such as 4,6-dichloropyrimidine, 4,6-dichloro-2-methylpyrimidine, 4,6-dichloro-2-heptadecylpyrimidine, 4,6-dichloro-2-phenylpyrimidine, 4,6-dichloro-5-phenylpyrimidine and 4,6-dichloro-2,5-diphenylpyrimidine. Structures of the target molecules were identified by spectra methods.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.1990-1994
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• 2013

A novel multi-cationic borane, tri-N-methylpyridinium substituted triarylborane, $[BAr^N_3]I_3$ ($[2]I_3$) ($Ar^N=4-(4-C_5H_4N-Me)-2,6-Me_2-C_6H_2$) was prepared from the corresponding neutral tris-pyridyl borane, $BAr_3$ (2a) ($Ar=4-(4-C_5H_4N)-2,6-Me_2-C_6H_2$). The crystal structure of 2a determined by X-ray diffraction study reveals the presence of tri-coordinate boron center with peripheral pyridyl moieties. The fluoride ion affinity of the cationic borane, $[2]I_3$ was investigated by UV-vis absorption titrations and was compared with that of neutral 2a. While 2a binds fluoride with the binding constant of $1.9{\times}10^2\;M^{-1}$ in $THF/H_2O$ (9:1 v/v) mixture, $[2]I_3$ shows a very high binding constant ($K=1.0{\times}10^8\;M^{-1}$) that is greater by six orders of magnitude than that of 2a in the same medium. This result indicates that the fluorophilicity of triarylborane can be drastically enhanced by multiple pyridinium substitutions.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1859-1864
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• 2011

Two lanthanide complexes, $[Ln(NO_3)_2(H_2O)_3(L)_2](NO_3)(H_2O)$ {Ln = Eu (1), Tb (2); L = 2-(4-pyridylium)-ethanesulfonate, $(4-pyH)^+-CH_2CH_2-SO_3^-)$}, were prepared from lanthanide nitrate and 4-pyridineethanesulfonic acid in $H_2O$ under microwave-heating conditions. Complexes 1 and 2 are isostructural, and the lanthanide metal in both complexes is coordinated to nine oxygen atoms. The pyridyl nitrogen in the ligand is protonated to give a zwitter ion that possesses an $NH^+$ (pyridyl) positive end and an $SO_3^-$ negative end. All O-H and N-H hydrogen atoms participate in hydrogen bonds to generate a two-dimensional (complex 1) or a three-dimensional network (complex 2). Complex 1 exhibits an intense red emission, whereas complex 2 exhibits an intense green emission in the solid state at room temperature.

• 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.

• 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 $K_{ML}(Zn^{2+})=19.90$.

• Bulletin of the Korean Chemical Society
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• v.33 no.6
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• pp.2017-2022
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• 2012

Three isostructural lanthanide coordination polymers, $[Ln(L)_3(H_2O)_2](H_2O)_3$ {Ln = Eu (1), Tb (2), Gd (3); L = $trans$-3-(3-pyridyl)acrylate, (3-py)-CH=CH-COO}, were prepared from HL, lanthanide nitrate, and NaOH in $H_2O$ by microwave heating. In all coordination polymers, the metal is bonded to eight oxygen atoms, and all pyridyl nitrogen atoms do not coordinate to the metals. All polymers have a 1-D loop-connected chain structure. The hydrogen atoms in the aqua ligands and lattice water molecules all participate in the hydrogen bonds of the O-$H{\cdots}O$ or O-$H{\cdots}N$ type. The hydrogen bonds connect the 1-D chains to create a 2-D network. Polymer 1 exhibited red luminescence in the solid state at room temperature.

• Applied Biological Chemistry
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• v.48 no.2
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• pp.115-119
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• 2005

The catalytic hydrolysis reactivities of dinuclear nickel (II) complex, ${\mu}-aquapentaaqua[{\mu}-3,6-bis(6'-methyl-2'-pyridyl)pyridazine]chlorodinickel\;(II)$ trichloride trihydrate (APNT) for bis(p-nitrophenyl) phosphate (BNPP) as a DNA model compound were investigated. The dissociation constants of APNT were $pKa_1=7.9$ and $pKa_2=9.6$, respectively. The hydrolysis rate constant of BNPP compound by APNT was showed the rate enhancement of about 370,000 times in the case of none catalyst at pH 7.0 and $50^{\circ}C$. Based on the findings, we proposed the catalytic cycle for the hydrolysis of BNPP by APNT complex. The metal ions of dinuclear nickel (II) complex significantly enhance the transfer rate of phosphoryl group in the catalytic process and the water molecules as nucleophile and proton transfer agent act in different steps.

• 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.

• 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.