• 제목/요약/키워드: Complex metal-ion

검색결과 239건 처리시간 0.024초

New Cryptand Complexes of Lanthanides(Ⅲ) and Dioxouranium(Ⅵ) Nitrates

  • Oh-Jin Jung;Chil-Nam Choi;Hak-Jin Jung
    • Bulletin of the Korean Chemical Society
    • /
    • 제12권2호
    • /
    • pp.130-137
    • /
    • 1991
  • The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.

이온교환체로서 금속-디-2-피리딜케톤옥심-산성의약품 3원 착물을 이용한 산성의약품의 정량 (Determination of Acidic Drug with ISEs Using Ternary Complex of Metal-di-2-pyridyl Ketone Oxime-acidic Drug as Ion-Exchanger)

  • 안문규;오원정;이언경;이순영;이재윤;정문모;허문회
    • 약학회지
    • /
    • 제46권5호
    • /
    • pp.320-323
    • /
    • 2002
  • A method for the determination of acidic drug, mefenamic acid and ibuprofen with ion-selective electrode(ISE) using Fe(II)-di-2-pyridyl ketone oxime complex as a counter ion were developed. Benzyl-2-nitrophenyl ether(BNPE) plasticized membrane was more selective and sensitive than the other tested membranes. The acidic drug selective electrode exhibits a linear response for 10$^{-2}$ M 510$^{-5}$ M of acidic drugs, mefenamic acid and ibuprofen with a slope of -55.9 and -56.3 mV/dec. in borate buffer solution (pH 8.9). Potentiometric selectivity measurements revealed negligible interferences from aromatic and aliphatic carboxylic acid salts. The electrodes were found to be useful for the direct determination of mefenamic acid and ibuprofen in pharmaceutical preparations.

Characterization of Functional Groups of Protonated Sargassum polycystum Biomass Capable of Binding Protons and Metal Ions

  • Yun, Yeoung-Sang
    • Journal of Microbiology and Biotechnology
    • /
    • 제14권1호
    • /
    • pp.29-34
    • /
    • 2004
  • Biosorption technology is recognized as an economically feasible alternative for the removal and/or recovery of metal ions from industrial wastewater sources. However, the structure of biosorbents is quite complex when compared with synthetic ion-exchange resins, which makes it difficult to quantify the ion-binding sites. Accordingly, this report describes a well-defined method to characterize the pK values and numbers of biomass functional groups from potentiometric titration data. When the proposed method was applied to Sargassum polycystum biomass as a model biosorbent, it was found that the biomass contained three types of functional groups. In addition, the carboxyl group (pK=$3.7{\pm}0.09$) was found to be the major binding sites ($2.57{\pm}0.06 mmol/g$) for positively-charged heavy-metal ions.

금속이온 착체방법에 의한 G4-48PyP 덴드리머의 전기적 특성 (Electrical Properties by different method of metal complex of G4-48PyP Dendrimer)

  • 김성언;정상범;김정균;박재철;장정수;권영수
    • 대한전기학회:학술대회논문집
    • /
    • 대한전기학회 2003년도 하계학술대회 논문집 C
    • /
    • pp.1532-1534
    • /
    • 2003
  • We attempted to fabricate a dendrimer Langmuir-Blodgett(LB) films containing 48 pyridinepropanol functional end group. As the pyridinepropanol functional group could form a complex structure with metal ions. In this study the samples for electrical measurement were fabricated to two types metal complexes with $Pt^{4+}$ ions by LB method. And we have investigated the surface activity at the air-water interface as well as the electrical properties for the monolayers of G4-48PyP dendrimer complex with metal ions($Pt^{4+}$ ions) by different method. In the surface pressure-area(${\pi}$-A) isotherms of the dendrimers, the stable condensed films formed at the air-water interface and the different method of metal complex showed the difference on molecular behavior. We have studied the electrical properties of the ultra thin dendrimer LB films investigated by the current-voltage (I-V) characteristics of metal/dendrimer LB films/metal(MIM) structure. In conclusion, it is demonstrated that the metal ion around G4-48PyP dendrimer can contribute to make formation of network structure among dendrimers and it result from the change of electrical properties.

  • PDF

Molecular Dynamics Simulation and Density Functional Theory Investigation for Thiacalix[4]biscrown and its Complexes with Alkali-Metal Cations

  • Hong, Joo-Yeon;Lee, Che-Wook;Ham, Si-Hyun
    • Bulletin of the Korean Chemical Society
    • /
    • 제31권2호
    • /
    • pp.453-456
    • /
    • 2010
  • The structural and energetic preferences of thiacalix[4]biscrown-5 with and without alkali metal ions ($Na^+$, $K^+$, $Rb^+$, and $Cs^+$) have been theoretically investigated for the first time using molecular dynamic (MD) simulations and density functional theory (MPWB1K/6-31G(d)//B3LYP/6-31G(d)) methods. The formation of the metal ion complex by the host is mainly driven by the electrostatic attraction between crown-5 oxygens and a cation together with the minor contribution of the cation-$\pi$ interaction between two facing phenyl rings around the cation. The computed binding energies and the atomic charge distribution analysis for the metal binding complexes indicate the selectivity toward a potassium ion. The theoretical results herein explain the experimentally observed extractability order by this host towards various alkali metal ions. The physical nature and the driving forces for cation recognition by this host are discussed in detail.

Metal-Ion Interactions with Sugars. The Crystal Structure of CaCl2-Fructose Complex

  • Guo, Jianyu;Lu, Yan;Whiting, Roger
    • Bulletin of the Korean Chemical Society
    • /
    • 제33권6호
    • /
    • pp.2028-2030
    • /
    • 2012
  • The single-crystal structure of $CaCl_2{\cdot}2C_6H_{12}O_6{\cdot}3H_2O$ was determined with Mr=525.34, a=16.054(7) ${\AA}$, b=7.864(4) ${\AA}$, c=10.909(5) ${\AA}$, ${\beta}=127.894(8)^{\circ}$, V=1086.9(9) ${\AA}^3$, C2, Z=2 and $R$=0.0227 for 1727 observed reflections. The fructose moiety of the complex exists as a ${\beta}$-D-pyranose. The calcium ion is surrounded by eight oxygen atoms, These are arranged in symmetry-related pairs derived from four sugar and two water molecules. Three nonvicinal hydroxyl groups of fructose are involved in calcium binding. All the hydroxyl groups and water molecules are involved in forming an extensive hydrogen-bond network.

Potentiometric studies on Ternary Complexes of Some Heavy Metal lons Containing N-(2-Acetamido)-iminodiacetic and Amino Acids

  • Mahmoud, Mohamed Rafat;Maher Mohamed Ahmed -Hamed;Ahmed, Iman Tawfik
    • Archives of Pharmacal Research
    • /
    • 제16권1호
    • /
    • pp.78-81
    • /
    • 1993
  • Solution equilibria of the thmary systems $UO_2(II)$, La(III), Ce(III)-N-(2-acetamido)-iminodiacetic acid and dicarboxylic amino acids are studied potentiometrically. The formation of 1:1:1 mixed ligand complexes are inferred from the potentiometric titration curves. The formation constants of the different binary and thmary complexes in such system are evaluated at t=$24\pm{0.1}^\circ{C}\;and\;\mu=0.1\;mol\;dm^{-3}(kNO_3)$. It is deduced that the temary complex is more stable than the corresponding binary amino acid anion complex. Moreover, the order og stability of the binary or temary complexes in terms of nature of amino acid and metal ion is investigated and discussed.

  • PDF

mPW1PW91 Study of Complexation of Alkali Metal Ions with Mixed [2 + 2'] Calix[4]aryl Derivatives

  • Choe, Jong-In
    • Bulletin of the Korean Chemical Society
    • /
    • 제33권10호
    • /
    • pp.3321-3330
    • /
    • 2012
  • The complexation characteristics of mixed [2 + 2'] calix[4]aryl derivatives (3 and 4) with alkali metal cations were investigated by the mPW1PW91 (hybrid HF-DF) calculation method. The total electronic and Gibbs free energies of the various complexes (cone, partial-cone, 1,2-alternate, and 1,3-alternate) of sodium and potassium cations with 3 and 4 were analyzed and compared. The structures of the endo- or exo-complexes of the alkali metal cation with the host 3 were optimized using the mPW1PW91/6-31G(d) method, followed by mPW1PW91/6-311+G(d) calculations. The structures of the endo- or exo-complexes of the alkali metal cation with the host 4 were optimized using the mPW1PW91/6-31G(d,p) method. The mPW1PW91 calculated relative energies of the various conformations of the free hosts (3 and 4) suggest that the cone conformers of 3 and 4 are the most stable. The mPW1PW91calculations also suggest that the complexation efficiencies of the sodium ion with hosts 3 and 4 are about 24 and 27 kcal/mol better than those of the potassium ion, respectively. These trends are in good agreement with the experimental results. The exo-complexation efficiencies of the sodium ion toward the conformers of hosts 3 and 4 are roughly 14 and 17 kcal/mol better than those for the endo-$Na^+$-complexes of 3 and 4, respectively. The exo-complexation of the cone isomer of 3 with cation could be confirmed by the differences of the diagnostic C=O bands in the free host and its complex's IR spectra.

Quercetin과 (+)-Catechin의 카드뮴(II)에 대한 착물반응 (Complexation Studies for Cadmium (II) with Quercetin and (+)-Catechin)

  • 이정호;신선우;백승화
    • 약학회지
    • /
    • 제53권6호
    • /
    • pp.342-350
    • /
    • 2009
  • The interaction of cadmium (II) ion with quercetin and (+)-catechin was investigated in aqueous solution at various pH. The flavonoid/cadmium stochiometries for cadmium (II) binding to quercetin and (+)-catechin have been determined by UV-vis spectroscopy. 1 : 1 Cd (II)-Flavonoid complex had a maximum absorbance and showed the bathochromic shift of the long-wavelength band of the UV-vis spectra in the alkaline pH, that occurs upon complexation, due to a ligandto-metal charge transfer. These results suggest that Cd (II)-flavonoid complex has the optimal condition of chelation in 0.2 M $NH_3$ - 0.2 M $NH_4Cl$ (pH 8.0) solution.

Copper(II), Nickel(II) and Palladium(II) Complexes of 2-Oximino-3-thiosemicarbazone-2,3-butanedione

  • Al-Kubaisi, Abdulla H.
    • Bulletin of the Korean Chemical Society
    • /
    • 제25권1호
    • /
    • pp.37-41
    • /
    • 2004
  • A new tridentate ligand incorporating a monoxime and thiosemi-carbozone moieties has been synthesized. Its copper(II), nickel(II) and palladium(II) complexes have been prepared and characteirzed by physical and spectral methods. Elemental analyses and spectroscopic data of the metal complexes are consistent with the formation of a mononuclear copper(II) complex and binuclear complex with both nickel(II) and palladium(II). In the copper(II) complex the fourth coordination site is occupied by nitrate ion. In the binculear complexes the fourth coordination site is occupied by the deprotonated oxime oxygen of the ligand coordinated to the other metal.