• Title/Summary/Keyword: Carboxylate Ion

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Synthesis of the Water Dispersible L-Valine Capped ZnS:Mn Nanocrystal and the Crystal Structure of the Precursor Complex: [Zn(Val)2(H2O)]

  • Hwang, Cheong-Soo;Lee, Na-Rae;Kim, Young-Ah;Park, Youn-Bong
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1809-1814
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    • 2006
  • The L-Valinate anion coordinating zinc complex, [$Zn(val)_2(H-2O)$], was isolated and structurally characterized by single crystal X-ray crystallography. The crystal possess orthorhombic symmetry with a space group $P2_12_12_1$, Z = 4, and a = 7.4279(2)$\AA$, b = 9.4342(2)$\AA$, c =20.5862(7)$\AA$ respectively. The compound features a penta-coordinate zinc ion in which the two valine anion molecules are directly coordinating the central zinc metal ion via their N (amine) and O (carboxylate) atoms, and an additional coordination to zinc is made by water molecule (solvent) to form a distorted square pyramidal structure. In addition, further synthesis of the valine capped ZnS:Mn nanocrystal from the reaction of [$Zn(val)_2(H-2O)$] precursor with $Na_2S$ and 1.95 weight % of $Mn^{2+}$ dopant is described. Obtained valine capped nanocrystal was water dispersible and was optically characterized by UV-vis and solution PL spectroscopy. The solution PL spectrum for the valine capped ZnS:Mn nanocrystal showed an excitation peak at 280 nm and a very narrow emission peak at 558 nm respectively. The measured and calculated PL efficiency of the nanocrystal in water was 15.8%. The obtained powders were characterized by XRD, HR-TEM, and EDXS analyses. The particle size of the nanocrystal was also measured via a TEM image. The measured average particle size was 3.3 nm.

Stability Constants of First-row Transition Metal and Trivalent Lanthanide Metal Ion Complexes with Macrocyclic Tetraazatetraacetic and Tetraazatetramethylacetic Acids

  • 홍춘표;김동원;최기영;김창태;최용규
    • Bulletin of the Korean Chemical Society
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    • v.20 no.3
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    • pp.297-300
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    • 1999
  • The protonation constants of the macrocyclic ligands, 1,4-dioxa-7,10,13,16-tetraaza-cyclooctadecane-N,N',N",N"'-tetra(acetic acid) [N-ac4[18]aneN402] and 1,4-dioxa-7,10,13,16-tetraazacyclooctadecane-1,4-dioxa-7,10,13,16-N,N',N",N"'-tetra(methylacetic acid) [N-meac4[18]aneN4O2] have been determined by using potentiometric method. The protonation constants of the N-ac4[18]aneN4O2 were 9.31 for logK1H, 8.94 for logK2H, 7.82 for logK3H, 4.48 for logK4H and 2.94 for logK5H. And the protonation constants of the N-meac4[18]aneN4O2 were 9.34 for logK1H, 9.13 for logK2H, 8.05 for logK3H, 5.86 for logK4H, and 3.55 for logK5H. The stability constants of complexes on the divalent transition ions (Co2+, Ni2+, Cu2+, and Zn2+) and tiivalent metal ions (Ce3+, Eu3+, Gd3+, and Yb3+) with ligands N-ac4[18]-aneN4O2 and N-meac4[18]aneN4O2 have been obtained from the potentiometric data with the aid of the BEST program. The three higher values of the protonation constants for synthesized macrocyclic ligands correspond to the protonation of nitrogen atoms, and the fourth and fifth values correspond to the protonation of the carboxylate groups for the N-ac4[18]aneN4O2 and N-meac4[18]aneN4O2. The meatal ion affinities of the two tetra-azamacrocyclic ligands with four pendant acetate donor groups or methylacetate donor groups are compared. The effects of the metal ions on the stabilities are discussed, and the trends in stability constants resulting from changing the macrocyclic ring with pendant donor groups and acidity of the metal ions.

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part I); Synthesis and Characterization of Cr(III)-Benzoato and Chlorobenzoato Macrocyclic Complexes

  • Byun, Jong-Chul;Kim, Goo-Cheul;Han, Chung-Hun
    • Bulletin of the Korean Chemical Society
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    • v.25 no.7
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    • pp.977-982
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    • 2004
  • The reaction of $cis-[Cr([14]-decane)(OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = benzoate(bz) or chlorobenzoate(cbz)} leads to a new compound $[Cr([14]-decane)(bz)_2]ClO_4$ or $[Cr([14]-decane)(cbz)_2]ClO_4$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. The crystal structure of $[Cr([14]-decane)(cbz)_2]^+$ was determined. The complex shows a distorted octahedral coordination environment with the macrocycle adopting a folded cis-V conformation. The angle $N_{axial}-Cr-N_{axial}$ deviates by $14.5^{\circ}$ from the ideal value of $180^{\circ}$for a perfect octahedron. The bond angle cis-O-Cr-O between the Cr(III) ion and the two carboxylate oxygen atoms of the monodentate p-chlorobenzoate ligands is close to 90$^{\circ}$. The FAB mass spectra of the $cis-[Cr([14]-decane)(La)_2]ClO_4$ display peaks due to the molecular ions $[Cr([14]-decane)(bz)_2-H]^\;,\;[Cr([14]-decane)(cbz)_2-2H]^$ at m/z 578, 646, respectively.

Effect of Two-step Surface Modification of Activated Carbon on the Adsorption Characteristics of Metal Ions in Wastewater I. Equilibrium and Batch Adsorptions

  • Park, Geun-Il;Lee, Jae-Kwang;Ryu, Seung-Kon;Kim, Joon-Hyung
    • Carbon letters
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    • v.3 no.4
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    • pp.219-225
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    • 2002
  • The two-step surface modifications of activated carbon was carried out to improve the adsorption capacity of toxic heavy metal ions in liquid phase. Physical and chemical properties of the as-received activated carbon (AC) and two kinds of surface-modified activated carbons ($1^{st}AC$ and $2^{nd}AC$) were evaluated through the BET analysis, surface acidity, and oxides measurements. Specific surface area and pore volume did not significantly change, but surface oxide-group remarkably increased by the surface modification. Equilibrium and batch adsorptions of the various metals, such as Pb, Cd, and Cr, using AC, $1^{st}AC$, and $2^{nd}AC$ were performed at initial pH 5. The adsorption capacity and rate of $2^{nd}AC$ were higher than those of AC and $1^{st}AC$. The carboxylic/sodium carboxylate complex groups were developed from the two-step surface modification of activated carbon, which strongly affected the adsorption of metal ions.

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Quantitative Analysis of SO2 and NO2 Adsorption and Desorption on Quartz Crystal Microbalance Coated with Cobalt Gallate Metal-Organic Framework

  • Junhyuck Ahn;Taewook Kim;Sunghwan Park;Young-Sei Lee;Changyong Yim
    • Journal of Sensor Science and Technology
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    • v.32 no.3
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    • pp.147-153
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    • 2023
  • Metal-organic frameworks (MOFs) of cobalt gallate were synthesized and deposited on gold electrodes using self-assembly monolayers (SAMs) and hydrothermal processing. These MOF films exhibit strong adsorption capabilities for gaseous particulates, and the use of SAMs allows the synthesis and deposition processes to be completed in a single step. When cobalt gallate is mixed with SAMs, a coordination bond is formed between the cobalt ion and the carboxylate or hydroxyl groups of the SAMs, particularly under hydrothermal conditions. Additionally, the quartz crystal microbalance (QCM) gas sensor accurately measures the number of particulates adsorbed on the MOF films in real-time. Thus, the QCM gas sensor is a valuable tool for quantitatively measuring gases, such as SO2, NO2, and CO2. Furthermore, the QCM MOF film gas sensor was more effective for gas adsorption than the MOF particles alone and allowed the accurate modeling of gas adsorption. Moreover, the QCM MOF films accurately detect the adsorption-desorption mechanisms of SO2 and NO2, which exist as gaseous particulate matter, at specific gas concentrations.

Structural characterization of ladder-type cadmium(II) citrate complex, (C3H12N2)[{Cd(H2O)(C6H5O7)}2]·6H2O

  • Kim, Chong-Hyeak;Lee, Sueg-Geun
    • Analytical Science and Technology
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    • v.20 no.4
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    • pp.355-360
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    • 2007
  • The title complex, $(C_3H_{12}N_2)[\{Cd(H_2O)(C_6H_5O_7)\}_2]{\cdot}6H_2O$, I, has been prepared and its structure characterized by FT-IR, EDS, elemental analysis, ICP-AES, and X-ray single crystallography. It is triclinic system, $P{\bar{1}}$ space group with a = 10.236(2), b = 11.318(2), c = $13.198(2){\AA}$, ${\alpha}=77.95(1)^{\circ}$, ${\beta}=68.10(1)^{\circ}$, ${\gamma}=78.12(1)^{\circ}$, V = $1373.5(3){\AA}^3$, Z = 2. Complex I has constituted by protonated 1,3-diaminopropane cations, citrate coordinated cadmium(II) anions, and free water molecules. The central cadmium atoms have a capped trigonal prism geometry by seven coordination with six oxygen atoms of three different citrate ligands and one water molecule. Citrate ligands are bridged to three different cadmium atoms. Each cadmium atom is linked by carboxylate and hydroxyl groups of citrate ligand to construct an one-dimensional ladder-type assembly structure. The polymeric crystal structure is stabilized by three-dimensional networks of the intermolecular O-H${\cdots}$O and N-H${\cdots}$O hydrogen-bonding interaction.

pH, Alkaline Earth Metal Ion Effects and Miscibility with Hexadecanol on the Monolayer of Palmitic Acid at the Air-Water Interface (기-액 계면에서 Palmitic Acid 단분자막에 대한 pH, 알칼리토금속 이온의 영향 및 Hexadecanol 분자와의 섞임성)

  • Jong-Jae Chung;Byung-Il Seo;Hai-Won Lee;Min-Young Ju
    • Journal of the Korean Chemical Society
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    • v.37 no.3
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    • pp.294-301
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    • 1993
  • ${\pi}$-A isotherms of the Palmitic acid(PA) with increasing pH shifted to the low area/molecule due to the dissociation of PA at the air-water interface. More condensation of PA monolayers occurred by the addition of Mg$^{2+}$, Ca$^{2+}$ and Ba$^{2+}$ ion in subphase. This condensing effect was increased with increasing the concentration of these ions. Due to the interaction with each ion, PA were formed Mg, Ca, Ba-Palmitate complex. The binding structure between alkaline earth ion and carboxylate ligand in PA has been identified by IR spectrometry. The order of condensing effect of alkaline earth ions at pH 8 was Ca$^{2+}$ > Ba$^{2+}$+ > Mg$^{2+}$. The condensing effect except for Mg$^{2+}$ decreased with increasing atomic number. Whereas, the condensing effect in pure water system decreased with decreasing atomic number in the sequence: Ba$^{2+}$ > Ca$^{2+}$ > Mg$^{2+}$. The miscibility of binary system of PA and hexadecanol in monolayer showed that the miscibility was good for the pure water system. But, in the buffered pH 8 system, bad miscibility was found.

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Characterization of the Nature of Cd(II) Ion Binding Sites on Poly(acrylic acid) Using$^{113}Cd$NMR (카드뮴-113 NMR을 이용한 폴리아크릴산의 카드뮴(Ⅱ) 이온에 대한 결합자리의 특성연구)

  • Chung, Kun Ho;Koo, Ja-Eung;Shin, Hyun Sang;Moon, Hichung
    • Journal of the Korean Chemical Society
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    • v.40 no.1
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    • pp.44-49
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    • 1996
  • The cadmium(Ⅱ)-carboxylate complexes of monocarboxylates and poly(acrylic acid) (PAA) in an aqueous solution were investigated using 113Cd NMR spectroscopy. From these spectral data the chemical shifts of the monocarboxylate (e.g. acetate, benzoate and propanoate) complexes of Cd(Ⅱ) were evaluated (CdL+: -22 to -24 ppm range; CdL2: -39 to -40 ppm range; L: carboxylate). The chemical shift of cadmium(Ⅱ) bound on PAA changed in value from -36.6 to -38.2 ppm when the [PAA]/[Cd] ratios were varied from 12 to 118 eq/mol at a constant pH of 6. The 113Cd chemical shift was sensitive to the change in solution pH: the chemical shift changed from 1.6 to -37.6 ppm when the pH was rasied from 1 to 6 at a constant [PAA]/[Cd] ratio of 39 eq/mol. These results show that under these conditions, the dominant species formed in solution is 1 : 2 complex (CdL2), and 1 : 1 complex (CdL+) is only formed at low pH, when polyanion concentration is low.

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Purification and Characterization of 5,10-Methenyltetrahydrofolate Synthetase from Chicken Liver (닭의 간 유래의 5,10-Methenyltetrahydrofolate Synthetase의 정제 및 특성)

  • Cho, Yong-Kweon
    • Journal of the Korean Chemical Society
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    • v.54 no.5
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    • pp.567-572
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    • 2010
  • 5,10-Methenyltetrahydrofolate synthetase from chicken liver was purified through 30-70% ammonium sulfate fractionation, Q Sepharose Fast Flow anion exchange and Source 15Phe hydrophobic interaction chromatography. Specific activities of cell extract, ammonium sulfate, Q Sepharose Fast Flow and Source 15Phe were 0.0085, 0.031, 0.80 and 1.27 U/mg, respectively. Purification fold activities of cell extract, ammonium sulfate, Q Sepharose Fast Flow and Source 15Phe were 1, 3.7, 94.1 and 149.4, respectively. HPLC gel permeation chromatography and SDS-polyacrylamide electrophoresis experiments indicated that the enzyme is a monomeric protein with a molecular weight of 22.8 kDa. Km for 5-methyl THF and Mg-ATP were $7.1\;{\mu}M$ and $63\;{\mu}M$, respectively. Optimum temperature and pH were $30^{\circ}C$ and 6.0, respectively. The data for metal ion specificity and stoichiometry showed that the maximum activity was obtained with a 1:l. ratio of $Mg^{2+}$. The ATP and Km values increased in the order of MgATP, MgCTP, MgUTP and MgGTP, and the maximum activities also decreased in the same order, indicating MgATP as the most efficient substrate. The enzyme was chemically modified only by tetranitrometane and 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimide, indicating that tyrosine and carboxylate are present in the active site.

Surface Chemical Aspects of Coagulation, Deposition, and Filtration Processes: Variation of Electrokinetic Potential at Metal Oxide-Water and Organic-Water Interfaces in the $Na^+$ and $Ca^{2+}$ Ion Solutions

  • Kim, Sung-Jae
    • Environmental Sciences Bulletin of The Korean Environmental Sciences Society
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    • v.4 no.3
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    • pp.173-183
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    • 2000
  • This study measured the zeta potential of both latex colloidal particles with carboxylate surface groups and glass beads (collectors) with silanol surface group employing various solution with different chemical characteristics. The results have been compared with the surface chemistry theory. The zeta potential of the particle and collector increased with increasing pH up to 5.0 regardless of the solution chemistry. For a monovalent electrolyte solution(sodium chloride solution) the zeta potential steadily increased until the pH reached 9.5. In contrast, little change in zeta potential was made between 5.0 and 9.5 for a divalent electrolyte solution (sodium chloride solution) the zeta potential steadily increased until the pH reached 9.5. In contrast, little change in zeta potential was made between 5.0 and 9.5 for a divalent electrolyte solution (calcium chloride solution). In other words, the more the pH decreases, the larger the effect of neutral salts, such as NaCl and CaCl$_2$, have on the ζ-potential values. In this study, the PZPC(point of zero proton condition) of the particle and collector occurred below a pH of 3.1, H(sup)+ and OH(sup)- acted as a PDI (potential determining ion), and Na(sup)+ acted as an IDI(indifferent ion). The magnitude of the negative ζ-potential values of the particle and collector monotonically increased as the concentrations of Na(sup)+ or Ca(sup)2+([Na(sup)+] or [Ca(sup)2+]) decreased (the values of pNa or pCa increased). In the case of latex particles, the ζ-potential should aproach zero (isoelectric point; IEP) asymptotically as the pNa approaches zero, while in the case of calcium chloride electrolyte, ζ-potential reversal may be expected to occur around 3.16$\times$10(sup)-2MCaCl$_2$(pCa=1.5). pH, valance and ionic strength can be used in various ways to improve the water treatment efficiency by modifying the charge characteristics of the particle and collector. Predictive capability is far less certain when EDL(electrical double layer) repulsive forces exist between the particle and collector.

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