• Title/Summary/Keyword: Chelate formation

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A Chromo- and Fluoroionophoric Thiaoxaaza-Macrocycle Functionalized with Nitrobenzofurazan Exhibiting Mercury(II) Selectivity

  • Lee, Ji-Eun;Lee, Shim-Sung;Choi, Kyu-Seong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3707-3710
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    • 2010
  • A chromo/fluorogenic $NO_2S_2$-macrocycle L functionalized with nitrobenzofurazan unit as a dual-signaling probe was synthesized and structurally characterized by single crystal X-ray analysis. In a cation-induced color change experiment, L exhibited excellent $Hg^{2+}$ ion selectivity by showing the color change from orange-red to yellow. However, this hypochromic shift by $Hg^{2+}$ was observed for the weaker coordinating anion system such as ${NO_3}^-$ and ${ClO_4}^-$ ions. The observed anion effect is due to the strong coordination of anions inhibits the bond formation between $Hg^{2+}$ and the macrocyclic tert-N atom, which is sensitive to induce the color change. In the fluorometric experiment, L showed chelate-enhanced fluorescence change effect only with $Hg^{2+}$ ion, together with a change from yellow to green emission. The sensing ability for $Hg^{2+}$ with the proposed chemosensor L is due to the stable complexation with 1:1 stoichiometry (metal-to-ligand).

Synthesis, Characterization, DFT Modeling and Antimicrobial Studies on the Ti(IV), Y(III) and Ce(IV) Ofloxacin Solid Complexes

  • Sadeek, Sadeek A.;Zordok, Wael A.;El-Shwiniy, Walaa H.
    • Journal of the Korean Chemical Society
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    • v.57 no.5
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    • pp.574-590
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    • 2013
  • A new solid complexes of Ti(IV), Y(III) and Ce(IV) have been synthesized with ofloxacin. The formulae and structure of the complexes have been proposed in the light of analytical, spectral ($^1H$ NMR, IR and UV-Visible), magnetic, molar conductivities and thermal studies. The complexes are soluble in DMSO-$d_6$ and DMF. The measured molar conductance values indicate that, the three complexes are electrolyte in nature. The results support the formation of the complexes and indicated that ofloxacin reacts as a bidentate ligand chelate to the metal ion through the pyridone oxygen and one carboxylato oxygen. The kinetic parameters of thermogravimetric and its differential have been evaluated by using Coats Redfern (CR) and Horowitz-Metzeger (HM) methods. The thermodynamic data reflect the thermal stability for all complexes. The metal- ligand binding of the Ti(IV), Y(III) and Ce(IV) complexes is predicted using density funcational theory at the B3LYP-CEP-31G level of theory and total energy, dipole moment estimation of different Ti(IV), Y(III) and Ce(IV) ofloxacin structures. The biological activities of the ofloxacin, inorganic salts and their metal complexes were assayed against different bacterial species.

Synthesis and Analytical Application of Chelating Resins Containing Polyamines (폴리아민류를 작용기로 하는 킬레이트수지의 합성 및 분석적 응용)

  • Kim Sun Deuk;Park Jung Eun;Park Myon Yong
    • Journal of the Korean Chemical Society
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    • v.36 no.5
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    • pp.652-660
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    • 1992
  • The polyamine resins were synthesized by reacting amines such as diethylenetriamine(dien), triethylenetetramine(trien), tetraethylenepentamine(tetren), and pentaethylenehexamine(penten). Stepwise dissociation constants of amines, enthalpy and free energy of metal chelate were determined. Formation constants $(log k_1) of metal chelates were in order of Cu(Ⅱ) > Ni(Ⅱ) > Cd(Ⅱ) > Zn(Ⅱ) > Co(Ⅱ) and tendency of stabilities were proportional to nitrogen numbers of ligand such as dien < trien < tetren > penten. Elutional selectivites of metal ions on resin were agreed to formation constants of metal chelates. {\Delta}H and {\Delta}G were calculated by Van't Hoff equation. Stability constants (log k1) of metalic complexes were in order Cu(Ⅱ) > Ni(Ⅱ) > Cd(Ⅱ) > Zn(Ⅱ) > Co(Ⅱ), and tendency of stabilities were {\circledP}_L-Dien < {\circledP}_L-Trien < {\circledP}_L-Tetren < {\circledP}_L-Penten. The elutional selectivities of metal ions were agreed to stability constants of metal chelates.

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A Study on Rust Cleaning of Various Industrial Equipment Using Cosmetic and Food Materials (화장품과 식품 재료를 이용한 각종 산업장비 녹(rust) 세정에 관한 연구)

  • Yeom, Seok-Jae;Jung, Sundo;Oh, Eunha
    • Journal of the Korean Applied Science and Technology
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    • v.38 no.1
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    • pp.19-28
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    • 2021
  • Corrosion is the degradation of metals by reaction with the environment. It is difficult to completely remove. Corrosion proceeds rapidly after the protective barrier is destroyed, and several reactions occur that alter the composition and properties of the metal surface and local environments, such as diffusion of metal cations into the matrix, the formation of oxides, and local pH changes. The study of corrosion of steel and iron is of theoretical and practical interest and is receiving considerable attention. Acid solutions, which are widely used in industrial pickling, acid descaling, cleaning and acidification of oil wells, require the use of corrosion inhibitors to suppress corrosion attacks on metallic materials. Physical removal of rust requires expensive special equipment, and chemical removal of it can cause corrosion or shorten the life of the metal. In this study, an eco-friendly rust cleaner was developed using cosmetics and food materials by applying the concept of perm reducing agent and chelate, and applied to remove rust from industrial and hot water pipes and various industrial devices. As a result, it was found that rust cleaners remove rust more effectively and safely compared to conventional treatment methods. At the same time, the rust removal efficiency was 1.75 to 2.5 times better for industrial piping and 1.56 to 2.2 times better for boiler hot water than conventional methods.

One-Pot Reaction Involving Two Different Amines and Formaldehyde Leading to the Formation of Poly(Macrocyclic) Cu(II) Complexes

  • Lee, Yun-Taek;Kang, Shin-Geol
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2517-2522
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    • 2012
  • New polynuclear poly(hexaaza macrocyclic) copper(II) complexes $[1](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, $[2](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, and $[3](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$ have been prepared by the one-pot reaction of formaldehyde with ethylenediamine and 1,2-bis(2-aminoethoxy)ethane, 1,3-diaminopropane, or 1,6-diaminohexane in the presence of the metal ion. The polymer complexes contain fully saturated 14-membered hexaaza macrocyclic units (1,3,6,8,10,13-hexaazacyclotetradecane) that are linked by $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-N$, $N-(CH_2)_3-N$, or $N-(CH_2)_6-N$ chains. The mononuclear complex $[Cu(H_2L^5)](ClO_4)_4$ ($H_2L^5$ = a protonated form of $L^5$) bearing two $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-NH_2$ pendant arms has also been prepared by the metal-directed reaction of ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, and formaldehyde. The polymer complexes were characterized employing elemental analyses, FT-IR and electronic absorption spectra, molar conductance, X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron micrograph (SEM). Electronic absorption spectra of the complexes show that each macrocyclic unit of them has square-planar coordination geometry with a 5-6-5-6 chelate ring sequence. The polymer complexes as well as $[Cu(H_2L^5)]^{4+}$ are quite stable even in concentrated $HClO_4$ solutions. Synthesis and characterization of the polynuclear and mononuclear copper(II) complexes are reported.

Preparation and Luminescence Properties of $Y_{2-x}Gd_xO_3:Eu$ Phosphors by Pechini Method (페치니법에 의한 $Y_{2-x}Gd_xO_3:Eu$ 형광체의 제조와 발광 특성)

  • Lee, Dong-Kyu;Lee, Jin-Hwa;Ahn, Byung-Chul;Jun, Sang-Bae
    • Journal of the Korean Applied Science and Technology
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    • v.23 no.3
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    • pp.207-214
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    • 2006
  • $Y_{2-x}Gd_xO_3:Eu$, phosphors for plasma display panel(PDP), were prepared by Pechini method which use yttriun chloride, gadolinium chloride, and europium oxide as starting materials. This method is a different way to the synthesis of europium(Eu)-doped phosphors, and it consists of the formation of a polymeric resin obtained by polyesterification between metal chelate compounds and a polyfunctional alcohol. This needs lower temperature than solid-state synthetic method. The prepared $Y_{2-x}Gd_xO_3:Eu$ phosphor particles had spherical shape and coherence. The luminescence intensity of $Y_{2-x}Gd_xO_3:Eu$ phosphor particles increased according to the increase of gadolinium(Gd) content(to 0.8mol%), and $Y_{1.2}Gd_{0.8}O_3:Eu$ phosphors had the highest luminescence intensity under vacuum ultra violet(VUV) excitation. The optimum concentration of Eu in the phosphor and optimum calcination temperature was 3wt% and $1100^{\circ}C$. The prepared phosphors were consist of particle, and its size was between 100nm and 150nm. Among the different polyfunctional alcohols, diethylene glycol(DEG) improved the luminescence intensities of phosphors more than other additives. The Pechini method proved that it is demonstrated to be suitable for the synthesis of phosphors used in PDP.

Effect of Low Molecular Weight Silk Fibroin on the Inhibition of Tyrosinase Activity

  • Kang, Gyung Don;Lee, Ki Hoon;Shin, Bong Seob;Nahm, Joong Hee;Park, Young Hwan
    • International Journal of Industrial Entomology and Biomaterials
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    • v.9 no.1
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    • pp.29-33
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    • 2004
  • Low molecular weight silk fibroin (LMSF), which was prepared by hydrolysis of silk fibroin using high-temperature and high-pressure method, was found to inhibit the oxidation of L-3,4,-dihydroxyphenylalanine (L-DOPA) catalyzed by mushroom tyrosinase (EC 1.14.18.1). LMSF contained mostly free amino acids such as L-glycine, L-alanine, and L-serine and oligopeptides, mainly glycine-alanine dimer. As a result of analyzing the inhibition kinetics from Lineweaver-Burk plots, L-glycine and glycine-alanine dimer showed noncompetitive behavior while uncompetitive behavior was observed in L-alanine, and L-serine. When weight percent concentration of ${ID_50}$ was compared, L-glycine was most effective on the inhibition and LMSF was also good enough for the inhibition effect of tyrosinase activity. LMSF showed a mixed-type inhibition and the inhibitory mechanism of LMSF might be caused by free amino acids and oligopeptides. As a result of spectroscopic observation with time, initial rate of increase of DOPAchrome decreased remarkably and the time to reach maximum absorbance increased as an increase of the concentration of L-glycine, meaning that L-glycine made itself mainly responsible for the formation of chelate with ${Cu^2+}$ in tyrosinase. However, in case of L-alanine, L-serine, and especially glycine-alanine dimmer, the production of DOPAchrome after an arrival at maximum absorbance decreased, indicating the production of adducts through the reaction with DOPAquinone.

Separation of Optical Isomers of DNS-Amino Acids in High-Performance Liquid Chromatography (고성능 액체크로마토 그래피에 의한 Dansyl-아미노산 광학이성질체의 분리)

  • Sun Haing Lee;Tae Sub O;Kyung Sug Park
    • Journal of the Korean Chemical Society
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    • v.30 no.2
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    • pp.216-223
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    • 1986
  • Separation of optical isomers of DNS derivatized amino acids by a reversed-phase high-performance liquid chromatography has been studied by adding a complex of an optically active amino acid (L-arginine) with the metal ion (Cu(II), Zn(II), Cd(II), Ni(II)) to the mobile phase. The separations are affected by the concentrations of acetonitrile, chelate and buffer. They are also affected by the pH and the kinds of metal and buffer. A separation mechanism, which is based on steric effect of the ligand exchange reaction for the formation of ternary complexes by the D,L-DNS-amino acids and the chiral additive associated with the stationary phase, is proposed to interpret the elution behaviors of D, L-dansyl-amino acids.

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Standard Transfer Free Energy of Sodium and Cupric Ions in Water-Acetylacetone Solvent System (물-아세틸아세톤 용매계에서 나트륨이온과 구리이온의 표준이동 자유에너지)

  • Lee Heung Lark;Park Jong-Taek
    • Journal of the Korean Chemical Society
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    • v.36 no.5
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    • pp.632-637
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    • 1992
  • Standard transfer free energies of sodium and cupric perchlorates in water-acetylacetone solvent system have been determined by electromotive force measurements of galvanic cell and these energies of sodium and cupric ions in this solvent system have been evaluated by the tetrabutylammonium tetraphenylborate assumption as the extrathermodynamic procedure. Standard transfer free energy values of sodium and cupric ions from water to acetylacetone solvent were 5.09 and 4.16 kcal/mol at 25${\circ}C$, respectively. These values mean that acetylacetone is much weaker donor solvent to sodium and cupric ions than water. The standard transfer free energy value of cupric ion from water to mixture solvents which contain small amount of acetylacetone is changed by an unusual form. This is because of the chelate formation effect of acetylacetone to cupric ion.

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Effect of Interaction between Protocatechualdehyde Produced from Streptomyces lincolnensis M-20 and Copper Ions on Antioxidant and Pro-oxidant Activities (Streptomyces lincolnensis M-20 균주에서 생산된 Protocatechualdehyde와 구리 이온의 상호 작용이 항 산화 및 산화 촉진 활성에 미치는 영향)

  • Kim, Kyoung-Ja;Lee, Jae-Hun;Yang, Yong-Joon
    • Korean Journal of Microbiology
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    • v.50 no.1
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    • pp.22-26
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    • 2014
  • Protocatechualdehyde (PA) is phenolic compound having antioxidative and antitumor activities. PA was purified from supernatant of Streptomyces lincolnensis M-20. In the presence of copper ion, PA acted as pro-oxidant. The antioxidant activity was assessed with the 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay, and the pro-oxidant effect of PA on DNA damage as pBR322 plasmid DNA-cleaving agents in the presence of Cu(II) ions was investigated. The involvement of reactive oxygen species (ROS) in the DNA damage was confirmed by the inhibition of the DNA breakage by using glutathione (GSH), specific scavenger of ROS. When the increase in ROS reaches a certain level (the toxic threshold), it may trigger cell death. The formation of the PA/Cu(II) chelate complex was confirmed by reaction with ethylenediamine-tetraacetic acid (EDTA), a well-known chelating agent for metal ions, by using UV/Vis spectroscopic analysis.