• Title/Summary/Keyword: ion complex

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Metal Ion Catalysis in Nucleophilic Displacement Reactions of 2-Pyridyl X-Substituted Benzoates with Potassium Ethoxide in Anhydrous Ethanol

  • Lee, Jae-In;Kang, Ji-Sun;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.3543-3548
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    • 2010
  • A kinetic study on nucleophilic displacement reactions of 2-pyridyl X-substituted benzoates 1a-e with potassium ethoxide (EtOK) in anhydrous ethanol is reported. Plots of pseudo-first-order rate constants ($k_{obsd}$) vs. $[EtOK]_o$ exhibit upward curvature. The $k_{obsd}$ value at a fixed $[EtOK]_o$ decreases steeply upon addition of 18-crown-6-ether (18C6) to the reaction mixture up to [18C6]/$[EtOK]_o$ = 1 and then remains nearly constant thereafter. In contrast, $k_{obsd}$ increases sharply upon addition of LiSCN or KSCN. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ has revealed that ion-paired EtOK is more reactive than dissociated $EtO^-$, indicating that $K^+$ ion acts as a Lewis acid catalyst. Hammett plots for the reactions of 1a-e with dissociated $EtO^-$ and ion-paired EtOK result in excellent linear correlation with $\rho$ values of 3.01 and 2.67, respectively. The $k_{EtOK}/k_{EtO^-}$ ratio increases as the substituent X in the benzoyl moiety becomes a stronger electron-donating group. $K^+$ ion has been concluded to catalyze the current reaction by stabilizing the transition state through formation of a 6-membered cyclic complex.

Fluorescence Anisotropy Study on the Effect of Phellodendri Cortex's Berberine on Regulation of the Function of DNA (황백(黃柏)의 berberine이 DNA의 기능조절에 미치는 영향에 관한 형광이방성 연구)

  • Lee, Seong Kyung;Han, Hyo Sang;Huh, Sung Ho
    • The Korea Journal of Herbology
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    • v.33 no.5
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    • pp.105-110
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    • 2018
  • Objectives : We tried to observe the fluorescence anisotropy and intensity of ethidium ion in the intercalating binding interaction between DNA and ethidium ions in the presence of berberine, and then tried to explain the effect of berberine on the intercalating interaction of ethidium ion with DNA. Methods : DNA(calf thymus DNA), berberine and ethidium bromide(EtBr) were purchased from Sigma-Aldrich Co. Proper amount of each compound was dissolved in 20 mM sodium phosphate buffer(pH 7.0) containing 100 mM of NaCl to prepare stock solutions. Collections of the fluorescence anisotropy and intensity data were performed on JASCO FP-8300 spectrofluorometer equipped with a polarizer and a Peltier temperature controller. The excitation of ethidium ion was done at 550 nm and the emission data were collected at 600 nm. For Stern-Volmer plot, the fluorescence data were collected at $18^{\circ}C$ and $30^{\circ}C$. Results : According to the results of this research, the weak competitive binding pattern between ethidium ion and berberine appeared in binding with DNA at low ratio of DNA to ethidium ion. But at high ratio of DNA to ethidium ion, this weak competition disappeared. Instead, berberine might bind to DNA by intercalating way. In other words, berberine could de-intercalate ethidium ion from DNA at low concentration of DNA relative to ethidium ion, but could not at high concentration of DNA relative to ethidium ion. In addition, the mechanism of fluorescence quenching of ethidium ion could also proceed differently, depending on the ratio of the amount of DNA to that of ethidium ion. Conclusions : The effect of berberine on the DNA-ethidium ion intercalating interaction could work differently, depending on the relative ratio of the amount of DNA to that of ethidium ion. This study also showed that fluorescence anisotropy analysis is very useful method to obtain detailed information for investigation of the complex binding interactions. In order to fully understand the mechanism of action of the pharmacological effect by berberine, studies on the effect of berberine on the action of proteins such as various enzymes closely related to berberine-induced medicinal effects should be continued.

The Phosphorus Removal from Water by Zirconium Mesoporous Structure (지르코늄 메조기공 구조체를 이용한 수중의 인 제거)

  • Lee, Byoung-cheun;Lee, Kwan-yong;Lee, Sang-hyup;Choi, Yong-su;Park, Ki-young
    • Journal of Korean Society of Water and Wastewater
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    • v.19 no.4
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    • pp.455-461
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    • 2005
  • This study was designed to investigate the fundamental aspects of a possible recovery of phosphorus strategy from wastewater by using the zirconium mesoporous structured materials as a new type of ion exchangers. Zirconium mesoporous structure material was synthesized by hydro-thermal synthesis. The synthesized zirconium mesoporous structure was examined by X-ray diffraction (XRD) and Transmission electron micrograph (TEM). From the results of XRD and TEM, it was found out that hexagonal mesoporous structure, pore size was about $47{\AA}$, was synthesized. Experimental results showed that the complex of zirconium sulfate tetrahydrate and surfactant micelles had very high ability for capture of phosphorus. The amount of phosphate ions exchanged into the solid was as great as 3.4mmol/g-ZS. And the ion exchange reaction was occurred between $PO_4{^{3-}}$ and $SO_4{^{2-}}$ and also between $PO_4{^{3-}}$ and $OH^-$. Therefore, it is possible to get the higher removal efficiency than other ion exchange media and adsorbent.

mPW1PW91 Calculated Structures and IR Spectra of Thiacalix[4]biscrown-5 Complexed with Alkali Metal Ions

  • Choe, Jong-In
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1685-1691
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    • 2011
  • The molecular structures of thiacalix[4]biscrown-5 (1) and p-tert-butylthiacalix[4]biscrown-5 (2) and their alkali-metal-ion complexes were optimized using the DFT BLYP/6-31G(d) and mPW1PW91/6-31G(d,p) (hybrid HF-DF) calculations. The total electronic energies, the normal vibrational modes, and the Gibbs free energies of the mono- and di-topic complexes of each host with the sodium and potassium ions were analyzed. The $K^+$-complexes exhibited relatively stronger binding efficiencies than $Na^+$-complexes for both the monoand di-topic complexes of 1 and 2 comparing the efficiencies of the sodium and potassium complexes with an anisole and phenol. The mPW1PW91/6-31G(d,p) calculated distances between the oxygen atoms and the alkali metal ions were reported in the alkali-metal-ion complexes ($1{\cdot}Na^+$, $1{\cdot}2Na^+$, $1{\cdot}K^+$, $1{\cdot}2K^+$, $2{\cdot}Na^+$, $2{\cdot}Na^+$, $2{\cdot}K^+$, $2{\cdot}2K^+$). The BLYP/6-31G(d) calculated IR spectra of the host 1 and its mono-topic alkali-metal-ion complexes are compared.

Copper(II) Selective PVC Membrane Electrodes Based on Schiff base 1,2-Bis (E-2-hydroxy benzylidene amino)anthracene-9,10-dione Complex as an Ionophore

  • Jeong, Eun-Seon;Lee, Hyo-Kyoung;Ahmed, Mohammad Shamsuddin;Seo, Hyung-Ran;Jeon, Seung-Won
    • Bulletin of the Korean Chemical Society
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    • v.31 no.2
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    • pp.401-405
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    • 2010
  • The Schiff base 1,2-bis(E-2-hydroxy benzylidene amino)anthracene-9,10-dione has been synthesized and explored as ionophore for preparing PVC-based membrane sensors selective to the copper ($Cu^{2+}$) ion. Potentiometric investigations indicate high affinity of these receptors for copper ion. The best performance was shown by the membrane of composition (w/w) of ionophore: 1 mg, PVC: 33 mg, DOP: 66 mg and KTpClPB as additive were added 50 mol % relative to the ionophore in 1 ml THF. The proposed sensor's detection limit is $2.8{\times}10^{-7}$ M over pH 5 at room temperature (Nernstian slope 31.76 mV/dec.) with a response time of 15 seconds and showed good selectivity to copper ion over a number of interfering cations.

Effect of Pine Needle Extract on Fe ion and Active Oxygen Related Lipid Oxidation in Oil Emulsion (Fe ion과 활성산소 관련 지방산화반응에 미치는 솔잎 추출물의 영향)

  • 김수민;조영석
    • Food Science and Preservation
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    • v.6 no.1
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    • pp.115-120
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    • 1999
  • This study was carried out to investigate the effect of Pine needle extract on lipid oxidation and free radical reaction in iron sources reacted with active oxygen species. The results were summarized as follow; The pine needle extracts didn`t show a distinct effect on reduction of lipid oxidation if the iron ion didn`t exist in oil emulsion. The pine needle extracts played role as a strong chelating agents to bind iron ion if Ferrous iron(Fe\ulcorner) exist in oil emulsion. Ferric iron(Fe) was lower effect than Ferrous iron(Fe) on free radical reaction in oil emulsion. And also, the Fe\ulcorner reacted with pine needle extract did not show distinct effect on free radical reaction, compared to Fe\ulcorner reacted with pine needle extract. And also, Pine needle extracts reacted with H\ulcornerO\ulcorner were tended to show a low oxygen scavenging ability in case of H\ulcornerO\ulcorner only was existed, compared to those of H\ulcornerO\ulcorner + Fe\ulcorner complex. Pine needle extracts were the most powerful Fe\ulcorner binding agents, compared to other strong synthetic antioxidants such as EDTA and DTPA.

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Luminescence Intensity Change Using N-Carbamoylglycine, N-Salicylideneaniline and Metal ions (N-Carbamoylglycine 및 N-Salicylideneaniline과 Metal ions들에 의한 발광 세기의 변화)

  • Kim, Ji Ung;Kim, Yeong Hae
    • Journal of the Korean Chemical Society
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    • v.46 no.6
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    • pp.502-508
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    • 2002
  • We have used PET chemosensors in the determination of N-carbamoylglycine. When N-carbam-oylglycine reacts with complex already made by the fluorophore and metal ion, the luminescence intensity can be changed and this phenomenon can be utilized in quantification. We used three metal ions, $Zn^{2+}$, $Ni^{2+}$, $Cu^{2+}$ and in order to investigate selectivity an acetic acid was used. $Ni^{2+}$ ion showed change in the eT mechanism by the anions. $Cu^{2+}$ ion showed the ability to distinguish N-carbamoylglycine from an acetic acid and it is noteworthy that $Zn^{2+}$ ion can change luminescence sensitively according to concentration.

Gas Permeability of Polymeric LB Films Containing Imidazole-Metal Ion Complexes (이미다졸-금속 이온 착체를 포함하는 고분자 LB막의 기체 투과성)

  • 김병주;이범종
    • Polymer(Korea)
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    • v.24 no.4
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    • pp.453-458
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    • 2000
  • The permeability of oxygen and nitrogen was investigated from the polymeric LB films containing imidazole-metal ion complexes and compared with its corresponding cast films on porous membrane filters. The amphiphilic polymer, poly(N- (2-(4-imidazolyl)ethyl)-maleimide-alt-1-octadecene) (IM-O), was synthesized by reaction of poly(maleic anhydride-alt-1-octadecene) with histamine. The IM-O nonolayer showed high stability on Fe (III) ion-containing subphase. The molecular structure in the LB films was investigated by means of FT-IR spectroscopy. The metal ion concentration incorporated into the LB films was determined by means of XPS measurements. The mechanical stability and uniformity of the LB films on porous substrates were indirectly evidenced by SEM observation. The LB and cast films showed more or less higher selectivity toward nitrogen, and high permeability was found to both the oxygen and nitrogen.

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Lead(II)-selective Polymeric Electrode Using a Schiff Base Complex of N,N'-Bis-thiophene-2-ylmethylene-ethane-1,2-diamine as an Ion Carrier

  • Jeong, Tae-Jun;Jeong, Dae-Cheol;Lee, Hyo-Kyoung;Jeon, Seung-Won
    • Bulletin of the Korean Chemical Society
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    • v.26 no.8
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    • pp.1219-1224
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    • 2005
  • We prepared lead ion-selective PVC membranes that were based on N,N'-bis-thiophene-2-ylmethylene-ethane-1,2-diamine as a membrane carrier. The membrane electrode has a linear dynamic range between 1.0 ${\times}$ $10^{-5}$ and 1.0 ${\times}$ $10^{-1}$ M with a Nernstian slope of 29.79 mV per decade, and its detection limit was 2.04 ${\times}$ $10^{-6}$ M at room temperature. The potentiometric response is independent of the pH of the solution in the pH range of 5-7. The proposed electrode revealed good selectivity and response for $Pb^{2+}$ over a wide variety of other metal ions in pH 5.0 buffer solutions, and there was good reproducibility of the base line on the subsequent measurements. The membrane electrode has a relatively fast response time, satisfactory reproducibility and a relatively long life time.

Ionic Equilibria and Ion Exchange of Molybdenum(VI) from Strong Acid Solution

  • Lee, Man-Seung;Sohn, Seong-Ho;Lee, Myung-Ho
    • Bulletin of the Korean Chemical Society
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    • v.32 no.10
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    • pp.3687-3691
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    • 2011
  • Ion exchange experiments of molybdenum(VI) from strong HCl and $H_2SO_4$ solution have been done to investigate the existence of anionic complexes. The concentration of HCl and $H_2SO_4$was changed from 1 to 9 M. From the data on the complex formation of molybdenum in aqueous solution, a new distribution diagram of Mo(VI) was constructed in the pH range from zero to 10. AG 1 X-8, an anion exchange resin, and Diphonix, a cation exchange resin were used in the loading experiments. Ion exchange results indicate that anionic complexes of Mo(VI) begins to form from 3 M HCl and 1 M $H_2SO_4$ solution and the tendency to form anionic complexes is stronger in HCl than in $H_2SO_4$ solution. Our results can be utilized in the analysis of Mo(VI) in strong acid solution and in the design of a process to separate Mo(VI).