• Bulletin of the Korean Chemical Society
• /
• v.18 no.11
• /
• pp.1158-1161
• /
• 1997

The potentiometric methods have been used to determined the protonation constants (logKiH) for the synthesized 1,7,13-trioxa-4,10,16-triazacyclooctadecane-N,N',N''-tri(methylacetic acid) [N3O3-tri(methylacetic acid)] and the stability constants (logKML) of the complexes of divalent and trivalent metal ions with the ligand N3O3-tri(methylacetic acid). The protonation constants of N3O3-tri(methylacetic acid) were 9.70 for logK1H, 9.18 for logK2H, 7.27 for logK3H, 3.38 for logK4H, and 2.94 for logK5H. The stability constants for the complexes of divalent metal ions with N3O3-tri(methylacetic acid) were 10.39 for Co2+, 10.68 for Ni2+, 13.45 for Cu2+, and 13.00 for Zn2+. The order of the stability constants for the complexes of the divalent metal ions with N3O3-tri(methylacetic acid) was Co2+ < Ni2+ < Zn2+ < Cu2+. The stability constants for the complexes of trivalent metal ions with N3O3-tri(methylacetic acid) were 16.20 for Ce3+, 16.40 for Eu3+, 16.27 for Gd3+, and 15.80 for Yb3+. The results obtained in this study were compared to those obtained for similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N"-tri(methylacetic acid) and 1,7,13-trioxa-4,10,16-triazacyclooctadecane-N,N',N"-triacetic acid, which have been previously reported.

• Bulletin of the Korean Chemical Society
• /
• v.16 no.7
• /
• pp.634-641
• /
• 1995

The metal-carbon σ-bond cluster complexes 1-Mn(CO)5-2-R-1,2-C2B10H10 (R=CH3 Ia, C6H5 Ib) have been prepared in good yields from readily available carboranyl lithium complexes, 1-Li+-2-R-1,2-C2B10H10- (R=CH3, C6H5), by direct reaction with (CO)5MnBr. These manganese metal complexes are rapidly converted to the corresponding manganese metal carbene complexes, 1-[(CO)4Mn=C(OCH3)(CH3)]-2-R-1,2-C2B10H10 (R=CH3 IIIa, C6H5 IIIb), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3. The crystal structure of IIIb was determined by X-ray diffraction. Thus, complex IIIb crystallizes in the orthorhombic space group P212121 with cell parameters a=15.5537(5), b=19.0697(5), c=7.4286(3) Å, V=2203.4(1) Å3, and Z=4. Of the reflections measured a total of 3805 unique reflections with F2>3σ(F2) was used during subsequent structure refinement. Refinement converged to R1=0.053 and R2=0.091. Structural studies showed that the manganese atom had a slightly distorted pseudo-octahedral configuration about the metal center with the carbene and ortho-carborane occupying the equatorial plane cis-orientation to each other.

• Bulletin of the Korean Chemical Society
• /
• v.12 no.2
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.18 no.10
• /
• pp.1061-1066
• /
• 1997

The complexes M(CO)4-1,2-(PPh2)2-1,2-C2B10H10 (M=Cr 2a, Mo 2b, W 2c) have been prepared in good yields from readily available bis-diphenylphosphino-o-carboranyl ligand, closo-1,2-(PPh2)2-1,2-C2B10H10 (1), by direct reaction with Group Ⅵ metal carbonyls. The infrared spectra of the complexes indicate that there is an octahedral disposition of chelate bis-diphenylphosphino-o-carboranyl ligand around the metal atom. The crystal structure of 2a was determined by X-ray diffraction. Complex 2a crystallizes in the monoclinic space group P21/n with cell parameters a = 12.2360(7), b = 17.156(1), c = 16.2040(6) Å, V = 3354.1(3) Å3, and Z =4. Of the reflections measured a total of 2514 unique reflections with F2 > 3σ(F2) was used during subsequent structure refinement. Refinement converged to R1 = 0.066 and R2 = 0.071. Structural studies showed that the chromium atom had a slightly distorted pseudo-octahedral configuration about the metal center with two phosphine groups of o-carborane occupying the equatorial plane cis-orientation to each other. These metal carbonyl complexes are rapidly converted to the corresponding metal carbene complexes, [(CO)3M=C(OCH3)(CH3)]-1,2-(PPh2)2-1,2-C2B10H10 (M= Cr 3a, Mo 3b, W 3c), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 1998.06a
• /
• pp.463-465
• /
• 1998

The peculiarities of the polyvinylpyrrolydone (PVP) interaction with transition metal ions of the first row in solution were studied. It was shown that PVP macromolecules due to their swelling conformation in organic solvents form the stable metal complexes. Metal ions were bond with oxygen and nitrogen atoms of PVP lactam rings. In water solution every metal ion interacts with one or two oxygen atoms out of 10-12 monomer units of the polymer. The additional contraction of PVP macromolecule coils in water have been found out by dissolving of the polymer metal complexes (PMC) synthesized in organic media. Toxicity, blood forming and immune stimulating activity and pharmaco-kinetic too of obtained polymers and their metal completes have been investigated. The factors and effects that responsible fur changing of PMC physical-chemical and biological properties have been estimated.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2013.02a
• /
• pp.85-85
• /
• 2013

Label-free, sensitive and selective detection methods with high spatial resolution are critically required for future applications in chemical sensor, biological sensor, and nanospectroscopic imaging. Here I describe the development of Plasmon Resonance Energy Transfer (PRET)-based molecular imaging in living cells as the first demonstration of intracellular imaging with PRET-based nanospectroscopy. In-vivo PRET imaging relied on the overlap between plasmon resonance frequency of gold nanoplasmonic probe (GNP) and absorption peak frequencies of conjugated molecules, which leads to create 'quantized quenching dips' in Rayleigh scattering spectrum of GNP. The position of these dips exactly matched with the absorption peaks of target molecules. As another innovative application of PRET, I present a highly selective and sensitive detection of metal ions by creating conjugated metal-ligand complexes on a single GNP. In addition to conferring high spatial resolution due to the small size of the metal ion probes (50 nm in diameter), this method is 100 to 1,000 folds more sensitive than organic reporter-based methods. Moreover, this technique achieves high selectivity due to the selective formation of Cu2+complexes and selective resonant quenching of GNP by the conjugated complexes. Since many metal ion ligand complexes generate new absorption peak due to the d-d transition in the metal ligand complex when a specific metal ion is inserted into the complex, we can match with the scattering frequency of nanoplasmonic metal ligand systems and the new absorption peak.

• Journal of the Korean Chemical Society
• /
• v.57 no.1
• /
• pp.52-62
• /
• 2013

The interaction of titanium (IV), yttrium (III), zirconium (IV), palladium (II) and cerium (IV) with deprotonated enrofloxacin leads to the formation of the neutral or cationic mononuclear complexes. The isolated solid complexes have been characterized with physicochemical and spectroscopic techniques and thermogravimeteric analyses. The spectroscopic data indicate that the enrofloxacin ligand is on the deprotonated mode acting as bidentate ligand coordinated to the metal ions through the ketone oxygen and a carboxylato oxygen and the metal ions completed the coordination number with water molecules. The thermal decomposition mechanisms proposed for enrofloxacin and their metal complexes were discussed. The activation energies, $E^*$, enthalpies, ${\Delta}H^*$, entropies, ${\Delta}S^*$ and Gibbs free energies, ${\Delta}G^*$, of the thermal decomposition reactions have been derived from thermogravimetric (TG) and differential thermogravimetric (DTG) curves, using Coats-Redfern (CR) and Horowitz-Metzeger (HM) methods. The antimicrobial activity has been evaluated against six different microorganisms.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.6
• /
• pp.515-521
• /
• 1989

The molecular interaction of $W_2(NH_2)_4Cl_4$ fragment with chlorine ligands has been studied by means of extended Huckel calculations. We have extended the Huckel calculation to unknown edge-sharing $W_2(NH_2)_4Cl_4({\eta}-X)_2$ complexes (X = CO, H) in order to compare the stability of the complexes. The calculations showed that the size and electronic property of bridged ligand are important in determining the stability. The stabilities of the related metal-metal bonded edge-sharing complexes are discussed.

• Archives of Pharmacal Research
• /
• v.16 no.1
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.12 no.2
• /
• pp.219-224
• /
• 1991

New binuclear Ni(Ⅱ) and Cu(Ⅱ) complexes with various alkyl derivatives of 1,2-bis(1,3,6,8,10,13-hexaaza-1-cyclotetradecyl) ethane, in which two fully saturated 14-membered hexaaza macrocyclic subunits are linked together by an ethylene chain, have been synthesized by the one step template condensations of formaldehyde with ethylenediamine and appropriate primary alkyl amines in the presence of the metal ions. Each macrocyclic subunit of the double-ring macrocyclic complexes contains one alkyl pendant arm and has a square planar geometry with a 5-6-5-6 chelate ring sequence. The visible spectra and oxidation properties indicate that the metal-metal interaction of the binuclear complexes are not significant. Synthesis, characterization, and the properties of the complexes are presented.