• Title/Summary/Keyword: ligand exchange reaction

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Preparation and Characterization of Cisplatin-Incorporated Chitosan Hydrogels, Microparticles, and Nanoparticles

  • Cha, Ju-Eun;Lee, Won-Bum;Park, Chong-Rae;Cho, Yong-Woo;Ahn, Cheol-Hee;Kwon, Ick-Chan
    • Macromolecular Research
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    • v.14 no.5
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    • pp.573-578
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    • 2006
  • Three different, polymer-platinum conjugates (hydrogels, microparticles, and nanoparticles) were synthesized by complexation of cis-dichlorodiammineplatinum(II) (cisplatin) with partially succinylated glycol chitbsan (PSGC). Succinic anhydride was used as a linker to introduce cisplatin to glycol chitosan (GC). Succinylation of GC was investigated systematically as a function of the molar ratio of succinic anhydride to glucosamine, the methanol content in the reaction media, and the reaction temperature. By controlling the reaction conditions, water-soluble, partially water-soluble, and hydrogel-forming PSGCs were synthesized, and then conjugated with cisplatin. The complexation of cisplatin with water-soluble PSGC via a ligand exchange reaction of platinum from chloride to the carboxylates induced the formation of nano-sized aggregates in aqueous media. The hydrodynamic diameters of PSGC/cisplatin complex nano-aggregates, as determined by light scattering, were 180-300 nm and the critical aggregation concentrations (CACs), as determined by a fluorescence technique using pyrene as a probe, were $20-30{\mu}g/mL$. The conjugation of cisplatin with partially water-soluble PSGC, i.e., borderline between water-soluble and water-insoluble PSGC, produced micro-sized particles $<500{\mu}m$. Cisplatin-complexed PSGC hydrogels were prepared from water-insoluble PSGCs. All of the cisplatin-incorporated, polymer matrices released platinum in a sustained manner without any significant initial burst, suggesting that they may all be useful as slow release systems for cisplatin. The release rate of platinum increased with the morphology changes from hydrogel through microparticle to nanoparticle systems.

A Study on the U(VI), Ca(II) and Lu(III) Metal Ions Utilizing Nitrogen-Donator Synthetic Resin (질소-주게 합성수지를 이용한 U(VI), Ca(II) 및 Lu(III) 금속 이온들에 관한 연구)

  • 정만태
    • Journal of environmental and Sanitary engineering
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    • v.15 no.1
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    • pp.25-33
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    • 2000
  • The new ion exchange resin was synthesized from chloromethylated styrene-1,4-divinylbenzene(DVB) with 1-aza-15-crown-5 macrocyclic ligand by substitution reaction. The effect of pH, time, dielectric constant of solvent and cross-linked of the matrix on the adsorption for $UO_2^{2+}$, $Ca^{2}$ and $Lu^{3+}$ was investigated. The metal ion was not adsorbed on the resins below pH 3 but above pH 4 fast adsorption behavior was showed. The optimum equilibrium time for adsorption of metallic ions was two hours. The adsorption selectivity determined in ethanol matrix was in increasing order $UO_2^{2+}>Ca^{2}>Lu^{3+}$. The adsorption power was in the order of 1%, 2%, 10% and 20% -crosslinked resin, but adsorption properties of resins decreased in proportion to the order of dielectric constant of solvents used. In addition, these metal ions could be separated in the column packed with 1% crosslinked resin by pH2.5 $HNO_3$ as an eluent.

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Molecular Strands and Related Properties of Silver(Ⅰ) Triflate with 3,3'-Oxybispyridine vs 3,3'-Thiobispyridine

  • Kim, Yu-Ju;Lee, Young-A;Park, Ki-Min;Chae, Hee K.;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.23 no.8
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    • pp.1106-1109
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    • 2002
  • Studies on subtle spacer ligand effects of AgCF3SO3 with 3,3'-Py2X (X = O vs S) have been carried out. The reaction of AgCF3SO3 with 3,3'-Py2O and 3,3'-Py2S produces [Ag(CF3SO3)(3,3'-Py2O)] and [Ag(3,3'-Py2S)] (CF3SO3), respectively. Crystallographic characterization of [Ag(CF3SO3)(3,3'-Py2O)] (monoclinic P1, a =8.405(2) $\AA$, b = 10.714(2) $\AA$, c = 18.031(2) $\AA$, $\alpha=$ 77.36(2), $\beta=107.83(2)^{\circ}$, $\gamma=$ 66.92(2), V = 1438.0(5) $\AA3$ , Z =2,R = 0.0486) reveals that the skeletal structure is an anion-bridged double-strand. The double-strands are packed like a plywood. The framework of [Ag(3,3'-Py2S)](CF3SO3) (orthorhombic Pcab, a = 17.330(2) $\AA$, b = 8.640(1) $\AA$, c = 19.933(6) $\AA$, V = 2985(1) $\AA3$ , Z =8, R = 0.0437) is a sinusoidal single-strand. The formation of each coordination polymer appears to be primarily associated with the donating ability and the confor ma-tional energy barrier of the spacer ligands. Thermal analyses indicate that [Ag(CF3SO3)(3,3'-Py2O)] and [Ag(3,3'-Py2S)](CF3SO3) are stable up to 250 $^{\circ}C$ and 210 $^{\circ}C$, respectively. For the anion exchangeability, the nature of the spacer ligand is more significant factor than the distance of silver(Ⅰ)···triflate.

Adsorption of Uranium (VI) Ion on the 1-Aza-12-Crown-4-Styrene-DVB Synthetic Resin Adsorbent (1-Aza-12-Crown-4-Styrene-DVB 합성수지 흡착제에 의한 우라늄(VI) 이온의 흡착)

  • Kim, Joon-Tae
    • Applied Chemistry for Engineering
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    • v.19 no.3
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    • pp.304-309
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    • 2008
  • Cryptand series ion exchange resins were synthesized with 1-aza-12-crown-4 macrocyclic ligand attached to styrene (4 series dangerous matter) divinylbenzene (DVB) copolymer with crosslink of 1%, 2%, 4% and 8% by a substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, electron micrograph, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of uranium (${UO_2}^{2+}$) ion were investigated. The uranium ion showed a fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium (${UO_2}^{2+}$) > nickel ($Ni^{2+}$) > gadolinium ($Gd^{3+}$) ion. The adsorption was in order of 1%, 2%, 4%, and 8% crosslinked resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.

Effects of Temperature on the Hydrophobic to Hydrophilic Ligand Ratio on the Surface of Amphiphilic Gold Nanoparticles (양친매성 금입자 표면의 소수성/친수성 비율에 대한 온도 영향)

  • Lee, Hwa-Jin;Kim, Hyun-Jin;Kim, Min-Guk;Chang, Ji Woong;Lee, Hee-Young
    • Applied Chemistry for Engineering
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    • v.30 no.3
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    • pp.308-312
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    • 2019
  • Amphiphilic gold nanoparticles were synthesized by the functionalization of gold nanoparticles with hydrophilic and hydrophobic ligands on their surfaces, which can be applied to many disciplines such as biology, photonics, electronics, and so on. The ratio of hydrophilic and hydrophobic ligands plays an important role in such applications since the ratio is closely related to physiochemical properties of the nanoparticles. In this paper, the effect of temperature during the ligand exchange reaction on the ratio of ligands on the gold nanoparticle surface was investigated. Hydrophilic ligands have higher affinity to the nanoparticle surface with an increase of the temperature. Furthermore, the amphiphilic nanoparticles at a higher temperature were more soluble in an aqueous solution even with a lower hydrophilicity of the nanoparticle surface.

Optical Resolution of DABS-Amino Acids with Mobile Chiral Chelate Addition (키랄킬레이트 이동상첨가법에 의한 답실아미노산의 광학이성질체 분리)

  • Lee, Seon Haeng;O, Dae Seop;Byeon, Seong Gu
    • Journal of the Korean Chemical Society
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    • v.34 no.4
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    • pp.345-351
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    • 1990
  • Optical isomers of DABS-amino acids have been separated in a reversed phae high performance liquid chromatography by adding Cu (Ⅱ)-L-Proline chelate to the mobile phase. The retention behaviors for the DABS-amino acids are discussed in terms of pH of the mobile phase and the concentrations of acetonitrile, Cu (Ⅱ) complex, and buffer. The selectivity of the optical isomers of DABS-amino acids increases with the pH of the mobile, and the concentration of the chelate, but decreases with concentration of the oganic modifier. The concentration of buffer does not affect the optical separation selectivity. A separation mechanism is illustrated by cis and trans formation based on the steric effect of the ligand exchange reaction between DABS-amino acids and the copper chelate.

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Condensable InP Quantum Dot Solids

  • Tung, Dao Duy;Dung, Mai Xuan;Jeong, Hyun-Dam
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.541-541
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    • 2012
  • InP quantum dots capped by myristic acid (InP-MA QDs) were synthesized by a typical hot injection method using MA as stablizing agent. The current density across the InP-MA QDs thin film which was fabricated by spin-coating method is about $10^{-4}A/cm^2$ at the electric field of 0.1 MV/cm from I-V measurement on a metal-insulator-metal (MIM) device. The low conductivity of the InP-MA QDs thin film is interpreted as due to the long interdistances among the dots governed by the MA molecules. Therefore, replacing the MA with thioacetic acid (TAA) by biphasic ligand exchange was conducted in order to obtain TAA capped InP QDs (InP-TAA). InP-TAA QDs were designed due to: 1) the TAA is very short molecule; 2) the thiolate groups on the surface of the InP-TAA QDs are expected to undergo condensation reaction upon thermal annealing which connects the QDs within the QD thin film through a very short linker -S-; and 3) TAA provides better passivation to the QDs both in the solution and thin film states which minimizing the effect of surface trapping states.

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Optical Resolution of Dansyl Amino acids by Xylenyl-L-proline Copper (Ⅱ) Complex (Xylenyl-L-proline 구리 (Ⅱ) 착물을 이용한 단실아미노산의 광학분리)

  • Lee, Seon Haeng;O, Dae Seop;Park, Bun Ja
    • Journal of the Korean Chemical Society
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    • v.34 no.1
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    • pp.76-84
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    • 1990
  • Optical isomers of dansyl amino acids were separated by a chiral mobile phase addition method. Two metha and para isomers of xylenyl-L-proline were prepared and used as the ligands of copper(Ⅱ) chelate to resolve the dansyl amino acids. Their elution behaviors were similar to those obtained from the addition of copper (Ⅱ) benzyl-L-proline chelate. The matrix effect of the mobile phase such as pH, concentration of buffer and compositions of organic solvent acetonitrile affected the optical resolution. The separation mechanism could be explained by a cis-trans effect of the ligand exchange reaction and hydrophobic interaction between the ternary complex and the stationary phase.

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Studies on the Biological Behaviors of Taxol Derivatives (Taxol 유도체들의 생물학적 거동에 관한 연구)

  • Awh, Ok-Doo;Yoo, Dae-Wung;Im, Sang-Moo
    • The Korean Journal of Nuclear Medicine
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    • v.31 no.4
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    • pp.440-451
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    • 1997
  • This study was designed to prospect the $^{111}In$-labelled paclitaxel as tumor imaging agent. In order to provide a taxol molecule with a functional group which is able to chelate In-111, taxol-DTPA conjugate and 2'-hemisuccinyltaxol were synthesized by esterification of taxol at C-2'on C-13 carbon with DTPA anhydride and succinic anhydride, respectively. Synthesis yield of the taxol derivatives was 34% for taxol-DTPA and 80% for 2'-hemisuccinyltaxol. Cytotoxicity of the taxol derivatives were measured by MTT method toward cell lines HT29, B16, P388, and CT26. The cytotoxic activities of the taxol derivatives were maintained, although less active than taxol. Radiolabelling of the taxol derivatives were proceeded directly with $^{111}InCl_3$ or indirectly with $^{111}In$-citrate(ligand-exchange method). The ligand-exchange method was not suitable because some precipitates appeared during the reaction. On the contrary, by direct radiolabelling method, we were able to obtain taxol-DTPA-$^{111}In$ in 100% radiochemical yield. However, 2'-hemisuccinyltaxol was not labelled by both methods. Yield and radiochemical purity of the radiolabelled com-pound were determined by HPLC, paper chromatography and instant thin layer chromatography. Taxol-DTPA-$^{111}In$ was characterized to be hydrophilic by lipophilicity test, and nearly non-adhesive to HT29, B16, P388, and CT26 by cell binding affinity test. Binding affinity of the taxol-DTPA-$^{111}In$ complex to serum proteins was also examined by protein precipitation with 30% trichloroacetic acid. The results showed that 30% of the taxol-DTPA-$^{111}In$ complex binds with serum proteins.

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Electrocatalytic Effect of Dioxygen Reduction at Glassy Carbon Electrode Modified with Schiff Base Co(II) Complexes (Schiff Base Co(II) 착물이 변성된 유리질 탄소전극에서 산소 환원의 전기촉매 효과)

  • Seong, Jeong-Sub;Chae, Hee-Nam;Choi, Yong-Kook
    • Analytical Science and Technology
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    • v.11 no.6
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    • pp.460-468
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    • 1998
  • Schiff base ligands such as $SOPDH_2$, $SNDH_2$, $EBNH_2$, and $PBNH_2$ and their Co(II) complexes such as [$Co(II)(SND)(H_2O)_2$], [$Co(II)(SOPD)(H_2O)_2$], [$Co(II)(EBN)(H_2O)$], and [$Co(II)(PBN)(H_2O)$] have been synthesized. The mole ratio of Shiff base ligand to cobalt(II) for the Co(II) complexes was found to be 1:1. Also these complexes have been configurated with hexa-coordination. Reduction of dioxygen was investigated by cyclic voltammetry at glassy carbon electrodes modified with Schiff base Co(II) complexes in 1 M KOH aqueous solution. At modified glassy carbon electrode with Schiff base Co(II) complexes, reduction peak current of oxygen was increased and peak potential was shifted to more positive direction compared to bare glassy carbon electrode. The electrokinetic parameters such as number of electron and exchange rate constant were calculated from the results of cyclic voltammogrms. The reduction of dioxygen at glassy carbon electrode has been $2e^-$ reaction pathway. Exchange rate constant at glassy carbon electrode modified with Co(II) complexes was increased 2~10 times compared to bare electrode.

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