• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1781-1786
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• 2007

Two copper(II) complexes, [CuL3](ClO4)2 bearing one N-CH2CH2CONH2 group as well as one N-CH2CH2CN group and [CuL4](ClO4)2 bearing two N-CH2CH2CONH2 groups, have been prepared by the selective hydrolysis of [CuL2](ClO4)2 (L2 = C-meso-1,8-bis(cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). The complex [CuL5](ClO4)2 bearing one N-CH2CH2C(=NH)OCH3 and one N-CH2CH2CN groups has been prepared as the major product from the reaction of [CuL2](ClO4)2 with methanol in the presence of triethylamine. In acidic aqueous solution, the N-CH2CH2C(=NH)OCH3 group of [CuL5](ClO4)2 undergoes hydrolysis to yield [CuL6](ClO4)2 bearing both N-CH2CH2COOCH3 and N-CH2CH2CN groups. The crystal structure of [CuL5](ClO4)2 shows that the complex has a slightly distorted square-pyramidal coordination polyhedron with an apical Cu-N (N-CH2CH2C(=NH)OCH3 group) bond. The apical Cu-N bond distance (2.269(3) A) is ca. 0.06 A longer than the apical Cu-O (N-CH2CH2CONH2 group) bond of [CuL4](ClO4)2. The pendant amide group of [CuL3](ClO4)2 is involved in coordination. The carboxylic ester group of [CuL6](ClO4)2 is also coordinated to the metal ion in various solvents but is removed from the coordination sphere in the solid state.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.707-710
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• 2012

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2565-2570
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• 2011

The reaction of bromoacetonitrile with 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{10}$) containing a N-$CH_2$-N linkage produces 17-cyanomethyl-3,14-dimethyl-2,6,13,17-tetraazatetracyclo-[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{11}$). The mono-N-functionalized macrocyclic complexes $[ML^2]^{2+}$ (M = Ni(II) or Cu(II); $L^2$ = 2-cyanomethyl-5,16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^{7.12}$]docosane) can be prepared by the reaction of $L^{11}$ with nickel(II) or copper(II) ion in acetonitrile. The N-$CH_2CN$ group attached to $[ML^2]^{2+}$ readily reacts with water or methanol to yield the corresponding complexes of $HL^3$ bearing one N-$CH_2CONH_2$ pendant arm or $L^4$ bearing one $N-CH_2C(=NH)OCH_3$ group. The $N-CH_2CONH_2$ or $N-CH_2C(=NH)OCH_3$ group of each complex is coordinated to the central metal ion. Both $[NiL^4(H_2O)]^{2+}$ and $[CuL^4]^{2+}$ are quite stable in acidic aqueous solutions, but undergo hydrolysis to yield $[Ni(HL^3)(H_2O)]^{2+}$ or $[Cu(HL^3)]^{2+}$ in basic aqueous solutions. In contrast to $[Cu(HL^3)]^{2+}$, $[Ni(HL^3) (H_2O)]^{2+}$ is readily deprotonated to form $[NiL^3 (H_2O)]^+$ ($L^3$ = a deprotonated form of $HL^3$) in basic aqueous solutions.

• Applied Chemistry for Engineering
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• v.22 no.4
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• pp.348-352
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• 2011

In this research, we have synthesized new pendant-type polyurethane polymers by introducing various chromophores with stilbene derivatives in the side-chain of the polymer backbone. The Stilbene monomers, N,N-bis(2-hydroxyethyl) amino-4'-cyanostilbene, N,N-bis(2-hydroxyethyl)amino-4'-methoxy stilbene, N,N-bis(2-hydroxyethyl)amino-4'-acetylstilbene, and N,N-bis(2-hydroxyethyl) amino stilbene, were synthesized by Wittig reaction. Another stilbene monomer, N,N-bis(2-hydroxyethyl)amino-4'-nitrostilbene, was synthesized by Knoevenagel condensation. By the measurement of UV-Vis absorption and Photoluminescence (PL) spectrum, we found that introduction of the electron-withdrawing group as a substituent shifts both UV-Vis and PL spectra to longer wavelength, and the introduction of the electron-donating group results in blue-shift of the spectrum. In case of polymer with $NO_2$ group as a substituent, PL is quenched.

• Journal of the Society of Cosmetic Scientists of Korea
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• v.46 no.1
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• pp.43-47
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• 2020

A novel series of adamantyl derivatives of N-aryl amides as androgen receptor antagonists were synthesized and their anti-androgenic activities were evaluated. The N-aryl amides containing adamantyl derivatives had more activity than those lacking adamantyl substitutions. The synergistic effect of bulkiness of the adamantyl group and modulation of electron density on the aromatic ring by pendant groups was crucial to the potent antagonism. Molecular modeling studies were performed to elucidate the interactions between ligands and receptors.

• Bulletin of the Korean Chemical Society
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• v.35 no.11
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• pp.3249-3253
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• 2014

A novel triazole-functionalized phenolic resin was developed, and its thermal and flame-retardant properties were investigated. The triazole group was incorporated as a pendant unit on the phenolic resin via copper-mediated click chemistry between propargylated phenolic resin and benzyl azide. The newly-developed triazole-functionalized phenolic resin showed higher thermal stability and char yield, together with a reduced total heat release (THR), than the non-functionalized bare phenolic resin, indicating enhanced flame retardancy for the triazole-functionalized phenolic resin.

• Proceedings of the Membrane Society of Korea Conference
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• 1992.10a
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• pp.47-48
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• 1992

Polymer containing monomers with pendant phospholipid polar group, 2-(metha-cryloyoxy) ethyl-2-(trimethylammonium) ethyl phosphate(MTP) were synthesized and blood compatibility of the copolymers was evaluated. Good permeability of biocomponents of molecular weight below 10$^4$ through cellulosic membrane coated with the copolymer of 2-(methacryloyoxy) ethyl-2-(tri-methylammonium)ethyl phosphate, butylmethacrylate(BMA), and glycidyl methacrylate(GMA) was observed, (Fig.1).

• Bulletin of the Korean Chemical Society
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• v.16 no.6
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• pp.518-523
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• 1995

New square planar nickel(Ⅱ) complexes with various 1-alkyl (4a-4c) and 1-hydroxyalkyl (4d-4f) derivatives of the 14-membered pentaaza macrocycle 8-ethyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane have been synthesized by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary amines. The nitro group and/or hydroxyl group of 4a-4f are not directly involved in the coordination. The nickel(Ⅱ) complexes exist in coordinating solvents such as MeCN, Me2SO, and H2O as equilibrium mixtures of the square planar [Ni(L)]2+(L=4a-4f) and octahedral species [Ni(L)S2]2+(S=solvent molecule). Although the ligand field strength and redox potentials of the complexes are not affected by the nature of the substituents, the formation of octahedral species for 4d-4f in MeCN is strongly restricted by the hydroxyl group. Synthesis, characterization, and solution behaviors of the nickel(Ⅱ) complexes are described.

• Bulletin of the Korean Chemical Society
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• v.29 no.10
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• pp.1905-1910
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• 2008

The reaction of 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.0$0^{1.18}.0^{7.12}$]docosane ($L^1$) with formaldehyde in warm methanol yielded 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.$1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^7$) containing one 1,3-diazacyclohexane subunit. In methanol, $L^7$ readily reacts with $Cu^{2+}$ ion to form [$CuL^7(H_2O)$]$^{2+}$ which is extremely inert against methanolysis. In the solution containing $Ni^{2+}$ ion, however, $L^7$ reacts with methanol to yield [$NiL^3$]$^{2+}$ ($L^3$ = 2-(methoxymethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.$0^{1.18}.0^{7.12}$]- docosane), in which one N-$CH_2OCH_3$ pendant arm is appended. The copper(II) complex [$CuL^7(H_2O)$]- $(ClO_4)_2{\cdot}3H_2O\;(I{\cdot}3H_2O)$ has a severely distorted trigonal bipyramidal coordination geometry with a 4-5- 6-5 chelate ring sequence. The crystal structure of [$NiL^3$]$(PF_6)_2{\cdot}2H_2O$ (IIb) shows that the N-$CH_2OCH_3$ pendant arm is not coordinated to the metal ion in the solid state. In various solvents (S), however, the nickel(II) complex exists as a mixture of [$NiL^3$(S)]$^{2+}$, in which the N-$CH_2OCH_3$ group as well as S is coordinated to the metal ion, and [$NiL^3$]^{2+}.

• Polymer(Korea)
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• v.32 no.3
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• pp.239-245
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• 2008

Block copolymers of the general formula $[(-CO-R'-CO-HN-Ar-NH-CO-R'-CO)_xNH(CH_2)_3-(Me_2SiO)_y(CH_2)_3NH_2]_n$, [n=18.00 to 1175.0] where $R'=CH_2CH(CH_2GeCl_3)$;$CH_2CHGeCl_3CH_2$; and $Ar=-C_6H_4$;$-(o.CH_3C_6H_4)_2$;$-o.CH_3OC_6H_4)_2$;$-(o.CH_3C_6H_4)$ were prepared by a polycondensation reaction of polyamide containing a pendant trichlorogermyl group and terminal acid chloride $Cl(-CO-R'-CO-NH-Ar-NH-CO-R'-CO-)_xCl$ with aminopropyl-terminated polydimethylsiloxane $H_2N(CH_2)_3(Me_2SiO)_y-(CH_2)_3NH_2]$, (PDMS). These polymers were characterized by elemental analysis, $T_g$, FT-IR, $^1H$-NMR, solid state $^{13}C$-NMR, and molecular weight determination. The thermal stability of these copolymers was examined using thermal analysis techniques, such as TGA and DSC. Their molecular weights as determined by laser light scattering technique ranged $5.13{\times}10^5$ to $331{\times}10^5\;g/mol$. These polymers display their $T_g$ in the range of 337 to $393^{\circ}C$ with an average decomposition temperature at $582^{\circ}C$.