• Title/Summary/Keyword: Metal cations

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Ionization and Divalent Cation Complexation of Quinolone Antibiotics in Aqueous Solution

  • Park, Hyeong Ryun;Jeong, Gwang Yeong;Lee, Hyeong Cheol;Lee, Jin Gi;Baek, Gi Min
    • Bulletin of the Korean Chemical Society
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    • v.21 no.9
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    • pp.849-854
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    • 2000
  • The protonation and divalent cation complexation equilibria of several quinolone antibiotics such as nalidixic acid (NAL),flumequine (FLU), oxolinic acid (OXO), ofloxacin (OFL), norfloxacin (NOR) and enoxacin (ENO) have been examined by potentiome tric titration and spectrophotometric method. The antibacterial activity of these drugs depends upon the pH and the concentration of metal cations such as Mg2+ , Ca2+ in solu-tion. The apparent ionization constants of NAL, FLU, OXO, OFL, NOR and ENO in aqueous solution were found to be 6.33, 6.51, 6.72, 7.18, 7.26, and 7.53, respectively. In aqueous solution, NAL, FLU and OXO were found to be present mainly as two chemical species : molecularand anionic; but OFL, NOR and ENO were present mainly as three chemical species : anionic, neutral zwitterionic and cationic form, in equilibrium. The pKa1 and pKa2are found to be 6.10 and 8.28 for OFL; 6.23 and 8.55 for NOR; 6.32 and8.62 for ENO, respec-tively. The complex formation constants between OFL, NOR or FLU and some divalent cations are measured at pH 7.5. The 1 : 1 complexes are formed mainly by ion-dipole interaction. FLU has somewhat larger Kf values than OFL and NOR because its molecular size is small and the FLU is present asanionic form at pH 7.5.

Isotachophoretically Assisted On-Line Complexation of Trace Metal Ions in a Highly Saline Matrix for Capillary Electrophoresis

  • Kim, Ji-Hye;Choi, Ki-Hwan;Cho, Sun-Young;Riaz, Asif;Chung, Doo-Soo
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.790-794
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    • 2012
  • Trace metal ions such as $Cd^{2+}$, $Ni^{2+}$, and $Zn^{2+}$ in a highly saline sample were subjected to on-line complexation with 4-(2-thiazolylazo) resorcinol (TAR) dissolved in a background electrolyte (BGE) under transient isotachophoresis (TITP) conditions. A long plug of the saline sample, containing the trace metal ions but devoid of TAR, was injected into a coated capillary filled with a BGE composed of 150 mM 2-(cyclohexylamino) ethanesulfonic acid (CHES) and 110 mM triethylamine (TEA) at pH 9.7. Since the electrophoretic mobility of TAR fell between the mobilities of the anionic leading electrolyte ($Cl^-$ in the sample) and the anionic terminating background electrolyte ($CHES^-$), a highly concentrated zone of TAR from the BGE was formed at the rear of the sample matrix and then the metal cations toward the cathode were swept by isotachophoretically assisted on-line complexation (IAOC) between the metal ions and the isotachophoretically stacked TAR. As a result, anionic metal-TAR complexes were formed efficiently, which satisfy the TITP conditions between $Cl^-$ and $CHES^-$. The enrichment factors of metal ions including $Cd^{2+}$ were up to 780-fold compared to a conventional CZE mode using absorbance detection. The detection limits were 17 nM, 15 nM, and 27 nM for $Ni^{2+}$, $Zn^{2+}$, and $Cd^{2+}$ in a 250 mM NaCl matrix, respectively. Our method was successfully applied to the analysis of urine samples without desalting.

Assessment of Risk Based Pollution Level of Pb and Cd in Metal Contaminated Soils Using Biotic Ligand Model (Biotic ligand model에 근거한 중금속 오염지역의 Pb 및 Cd 위해오염도 평가기법 개발)

  • An, Jin-Sung;Jeong, Seul-Ki;Moon, Hee-Sun;Nam, Kyoung-Phile
    • Journal of Soil and Groundwater Environment
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    • v.16 no.4
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    • pp.23-30
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    • 2011
  • Risk based pollution level of Pb and Cd in metal contaminated soils depending on physicochemical properties of soil in a target site was assessed using biotic ligand model. Heavy metal activity in soil solution defined as exposure activity (EA) was assumed to be toxic to Vibrio fischeri and soil organisms. Predicted effective activity (PEA) determined by biotic ligand model was compared to EA value to calculate risk quotient. Field contaminated soils (n = 10) were collected from a formes area and their risk based pollution levels were assessed in the present study using the calculated risk quotient. Concentrations of Pb determined by aqua regia were 295, 258, and 268 mg/kg in B, H and J points and concentrations of Cd were 4.73 and 6.36 mg/kg in G and I points, respectively. These points exceeded the current soil conservation standards. However, risk based pollution levels of the ten points were not able to be calculated because concentrations of Pb and Cd in soil solution were smaller than detection limits or one (i.e., non toxic). It was because heavy metal activity in soil solution was dominant toxicological form to organisms, not a total heavy metal concentration in soil. In addition, heavy metal toxicity was decreased by competition effect of major cations and formation of complex with dissolved organic carbon in soil solution. Therefore, it is essential to consider site-specific factors affecting bioavailability and toxicity for estimating reliable risk of Pb and Cd.

\Transport Phenomena of Alkali Metal Chlorides theough Poly(2-Hydroxyethyl Methacrylate) Hydrogel Membrane (Poly(2-Hydroxyethyl Methacrylate) 수화겔 막에 대한 알카리 금속 염화물의 수송현상)

  • Seong, Yong-Gil;Lee, Chun-Gi;Jeon, Mu-Sik
    • Journal of Biomedical Engineering Research
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    • v.8 no.2
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    • pp.123-134
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    • 1987
  • The transport phenomena of alkali metal chlorides through poly(2 hydroxyethyl methacrylate) hydrogel membrane have been studied using electrodialysis. The hydrogel membranes were prepared by the polymerization of 2-hydroxvethyl methacrylate in the presence of 45%(V/V) H2O and ethyleneglycodimethacrylate. The initiator used in the polymerization was azobismethylisobutyrate (AMIB) prepared from azobisiobtyronitrile (AIBN) using Mortimer method. The permeability of alkali metal chlorides such LiCl, NaCl and KCI at 50 voltage was obtained. The permeability of NaCl was also observed at 30, 40, 50, and 60 voltages respectively. The concentration of solutes permeated through the membrane was measurer by flame photometry. The experimental results have been discussed with the comparison of apparent solute molecular size, the self-diffusion coefficient of solutes, the transport number of cations in aqueous solution. These indic aloes that poly(2 hydroxyethyl methacrylate) hydrogel membrane shows a specific selectivity for sodium ion.

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APPLICATIONS OF SERICITE IN WASTEWATER TREATMENT : REMOVAL OF Cu(II) AND Pb(II) FROM AQUEOUS SOLUTIONS

  • Tiwari, Diwakar;Kim, Hyoung-Uk;Lee, Seung-Mok
    • Environmental Engineering Research
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    • v.11 no.6
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    • pp.303-310
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    • 2006
  • The aim of this study is to assess the applicability of sericite in wastewater treatment particularly the removal of two important heavy metal toxic ions viz., Cu(II) and Pb(II) from aqueous solutions. The batch type experiments showed that sericite is found to be one of useful natural sorbent for the removal of these two cations from aqueous solutions and it is also to be observed that with the increase in sorptive concentration amount of metal uptake increases and the concentration dependence data obtained are fitted well for the Langmuir adsorption isotherm rather than Freundlich adsorption model. Further, the Langmuir monolayer adsorption capacity is found to be $1.674\;mg\;g^{-1}$ for Cu(II) and $4.697\;mg\;g^{-1}$ for Pb(II). Kinetic studies enabled, an apparent equilibria can be achieved between soild/solution interface within ca 10 mins for Cu(II) and ca 90 mins for Pb(II). Moreover, the removal behavior of sericite for these two metal ions is greatly influenced by solution pH.

Synthesis and Exchange Properties of Sulfonated Poly(phenylene sulfide) with Alkali Metal Ions in Organic Solvents

  • Son, Won Geun;Kim, Sang Heon;Park, Su Gil
    • Bulletin of the Korean Chemical Society
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    • v.22 no.1
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    • pp.53-58
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    • 2001
  • Sulfonated poly(phenylene sulfide) (SPPS) polymers were prepared by sulfonation of poly[methyl[4-(phenylthio) phenyl]sulfonium trifluoromethanesulfonate] (PPST) with fumic sulfonic acid (10% $SO_3-H_2SO_4$) and demethylation with aqueous NaOH solution. The equilibrium constants of ion exchange reactions between alkali metal cations ($Li^+,\;Na^+,\;and\;K^+$) and SPPS ion exchanger in organic solvents such as tetrahydrofuran (THF) and dioxane were measured. The equilibrium constants of ion exchange reactions increased as the polarity of the solvent increased, and the reaction temperature decreased. The equilibrium constants of the ion exchange reaction ($K_{eq}$) also increased in the order of $Li^+,\;Na^+,\;and\;K^+$. To elucidate the spontaneity of the exchange reaction in organic solvents, the enthalpy, entropy, and Gibbs free energy were calculated. The enthalpy of reaction ranged from -0.88 to -1.33 kcal/mol, entropy ranged from 1.42 to 4.41 cal/Kmol, and Gibbs free energy ranged from -1.03 to -2.55 kcal/mol. Therefore, the exchange reactions were spontaneous because the Gibbs free energies were negative. The SPPS ion exchanger and alkali metal ion bounding each other produced good ion exchange capability in organic solvents.

Biochemical Characterization of Exoribonuclease Encoded by SARS Coronavirus

  • Chen, Ping;Jiang, Miao;Hu, Tao;Liu, Qingzhen;Chen, Xiaojiang S.;Guo, Deyin
    • BMB Reports
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    • v.40 no.5
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    • pp.649-655
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    • 2007
  • The nsp14 protein is an exoribonuclease that is encoded by severe acute respiratory syndrome coronavirus (SARS-CoV). We have cloned and expressed the nsp14 protein in Escherichia coli, and characterized the nature and the role(s) of the metal ions in the reaction chemistry. The purified recombinant nsp14 protein digested a 5'-labeled RNA molecule, but failed to digest the RNA substrate that is modified with fluorescein group at the 3'-hydroxyl group, suggesting a 3'-to-5' exoribonuclease activity. The exoribonuclease activity requires $Mg^{2+}$ as a cofactor. Isothermal titration calorimetry (ITC) analysis indicated a two-metal binding mode for divalent cations by nsp14. Endogenous tryptophan fluorescence and circular dichroism (CD) spectra measurements showed that there was a structural change of nsp14 when binding with metal ions. We propose that the conformational change induced by metal ions may be a prerequisite for catalytic activity by correctly positioning the side chains of the residues located in the active site of the enzyme.

Metal Biosorption by Surface-Layer Proteins from Bacillus Species

  • Allievi, Mariana Claudia;Florencia, Sabbione;Mariano, Prado-Acosta;Mercedes, Palomino Maria;Ruzal, Sandra M.;Carmen, Sanchez-Rivas
    • Journal of Microbiology and Biotechnology
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    • v.21 no.2
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    • pp.147-153
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    • 2011
  • Bacillus species have been involved in metal association as biosorbents, but there is not a clear understanding of this chelating property. In order to evaluate this metal chelating capacity, cultures and spores from Grampositive bacteria of species either able or unable to produce surface layer proteins (S-layers) were analyzed for their capacity of copper biosorption. Only those endowed of S-layers, like Bacillus sphaericus and B. thuringiensis, showed a significant biosorption capacity. This capacity (nearly 50%) was retained after heating of cultures, thus supporting that structural elements of the envelopes are responsible for such activity. Purified S-layers from two Bacillus sphaericus strains had the ability to biosorb copper. Copper biosorption parameters were determined for strain B. sphaericus 2362, and after analyses by means of the Langmuir model, the affinity and capacity were shown to be comparable to other bacterial biosorbents. A competitive effect of $Ca^{2+}$ and $Zn^{2+}$, but not of $Cd^{2+}$, was also observed, thus indicating that other cations may be biosorbed by this protein. Spores that have been shown to be proficient for copper biosorption were further analyzed for the presence of S-layer content. The retention of S-layers by these spores was clearly observed, and after extensive treatment to eliminate the S-layers, the biosorption capacity of these spores was significantly reduced. For the first time, a direct correlation between S-layer protein content and metal biosorption capacity is shown. This capacity is linked to the retention of S-layer proteins attached to Bacillus spores and cells.

Development and Application of Cation-exchange Membranes Including Chelating Resin for Efficient Heavy-metal Ion Removal (효율적인 중금속 이온 제거를 위한 킬레이팅 수지를 포함한 양이온 교환막의 개발 및 응용)

  • Kim, Do-Hyeong;Choi, Young-Eun;Park, Jin-Soo;Kang, Moon-Sung
    • Membrane Journal
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    • v.27 no.2
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    • pp.129-137
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    • 2017
  • In this study, we have developed cation-exchange membranes (CEMs) which can efficiently separate heavy-metal ions among the cations contained in a water system. Sulfonated polyetheretherketone (SPEEK) was used as a base polymer and a powdered chelating resin with strong binding ability to heavy-metal ions was added into it. In order to optimize the performance of the CEM, the content of chelating resin powder and the ion exchange capacity of SPEEK have been controlled. As a result, it was confirmed that the removal efficiency of heavy metal ion was improved by more than 20% by applying the CEM to membrane capacitive deionization (MCDI).

Adsorption Behaviors of Metal Elements onto Illite and Halloysite (일라이트, 할로이사이트에 대한 중금속 원소의 흡착특성)

  • 추창오;김수진;정찬호;김천수
    • Journal of the Mineralogical Society of Korea
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    • v.11 no.1
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    • pp.20-31
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    • 1998
  • Adsorption of metal elements onto illite and halloysite was investigated at $25^{\circ}C$ using pollutant water collected from the gold-bearing metal mine. Incipient solution of pH 3.19 was reacted with clay minerals as a function of time: 10 minute, 30 minute, 1 hour, 12 hour, 24 hour, 1 day, 2 day, 1 week, and 2 week. Twenty-seven cations and six anions from solutions were analyzed by AAs (atomic absorption spectrometer), ICP(induced-coupled plasma), and IC (ion chromatography). Speciation and saturation index of solutions were calculated by WATEQ4F and MINTEQA2 codes, indicating that most of metal ions exist as free ions and that there is little difference in chemical species and relative abundances between initial solution and reacted solutions. The adsorption results showed that the adsorption extent of elements varies depending on mineral types and reaction time. As for illite, adsorption after 1 hour-reaction occurs in the order of As>Pb>Ge>Li>Co, Pb, Cr, Ba>Cs for trace elements and Fe>K>Na>Mn>Al>Ca>Si for major elements, respectively. As for halloysite, adsorption after 1 hour-reaction occurs in the order of Cu>Pb>Li>Ge>Cr>Zn>As>Ba>Ti>Cd>Co for trace elements and Fe>K>Mn>Ca>Al>Na>Si for major elements, respectively. After 2 week-reaction, the adsorption occurs in the order of Cu>As>Zn>Li>Ge>Co>Ti>Ba>Ni>Pb>Cr>Cd>Se for trace elements and Fe>K>Mn>Al, Mg>Ca>Na, Si for major elements, respectively. No significant adsorption as well as selectivity was found for anions. Although halloysite has a 1:1 layer structure, its capacity of adsorption is greater than that of illite with 2:1 structure, probably due to its peculiar mineralogical characteristics. According to FTIR (Fourier transform infrared spectroscopy) results, there was no shift in the OH-stretching bond for illite, but the ν1 bond at 3695 cm-1 for halloysite was found to be stronger. In the viewpoint of adsorption, illite is characterized by an inner-sphere complex, whereas halloysite by an outer-sphere complex, respectively. Initial ion activity and dissociation constant of metal elements are regarded as the main factors that control the adsorption behaviors in a natural system containing multicomponents at the acidic condition.

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