• EDISON SW 활용 경진대회 논문집
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• 제3회(2014년)
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• pp.197-209
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• 2014

환경 오염에 대한 우려의 목소리가 높아지면서 Green chemistry 분야가 각광을 받고 있다. 이 분야에서는 환경에 영향을 적게 미치기 위한 방법의 일환으로 촉매를 연구하며, 그 촉매는 착화합물인 경우가 많다. 그러나 착화합물 내에서 리간드와 금속 이온간의 결합은 예측하기 어렵다. 이는 전형금속보다는 전이금속에서 더욱 심하며, 그 중 한 예로 전이금속에서는 여러 개의 금속 이온이 서로 직접적으로 결합한 채 리간드와 결합하는 착화합물이 발견되기도 한다. 다중 금속 착화합물(Multimetal Complex)로 부르는 이러한 구조는 특유의 복잡함 때문에 잘 알려져 있지 않음에도 불구하고 착화합물의 물리적, 화학적 성질에 직접적으로 영향을 주기에 촉매나 센서, 특히 이를 이용하여 구조체를 만드는 MOF(Metal-Organic Framework) 분야에서는 꼭 알고 있어야 하는 사항이다. 이 연구에서는 GAMESS로 density functional theory (B3LYP functional)를 이용한 양자계산을 수행하여 그 중 가장 간단한 구조인 Dimetal Complex, 그 중에서도 MOF 내에서 많이 발견되는 수차 형태(Paddle wheel) 착화합물에 대해서 다루었다. Cu를 기준으로 그와 비슷한 주기나 족에 있는 Ru, Ag, Zn 등의 금속으로 만든 Paddle wheel 구조의 에너지를 비교하여 Cu가 다른 금속에 비해 이 구조를 안정하게 형성할 수 있는 이유를 알아보았다. 더 나아가 이 구조가 MOF의 형성과 성질에 어떠한 연관성이 있는지 분석함으로써 어떠한 조건이 MOF의 성질을 극대화시킬 수 있는지도 알아보았다.

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3385-3390
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• 2010

$Li^+$ ion complex of azacrown ether with restricted motion of freedom and pseudo-bilateral symmetry was studied by infrared spectroscopy, which has shown simplified and broadened vibrational features. The C=O and N-H stretching bands, in particular, shows anomalous broadening nearly ${\sim}50\;cm^{-1}$. The density functional calculation at the level of BP86/6-31+$G^{**}$ shows that $Li^+$ ion is trapped and rather free to move around inside the cavity, as much as about $0.70\;{\AA}$. Through the relocation of $Li^+$ ion inside the cavity, the conformational changes would occur rapidly in its symmetry $C_1\;{\rightleftarrows}\;C_2\;{\rightleftarrows}\;C_1$$. The potential barrier was obtained to be merely ~2.2 kJ/mol for $C_1\;{\rightarrow}\;C_2$. During this conformational alteration, the amide backbone twists concurrently its dihedral angle side to side about up to ${\pm}3$ degree. Selected vibrational modes were interpreted in terms of the force constant variations of local symmetry coordinates between conformations in the framework of $C_1\;{\rightleftarrows}\;C_2\;{\rightleftarrows}\;C_1$.

• 약학회지
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• 제18권2호
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• pp.133-144
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• 1974

The metal indicator, acidic azo dyes NN, EBT and Calcon are utilized to analyse quantitatively chlorpheniramine, tripelenamine and diphenhydramine forming insoluble ion pair in aqueous solution at proper pH values between the acidic azo dyes and the sample molecules, these compexes are extracted by organic polar solvents, and organic layer is determined spectrophotometrically. Generally, the absorption maxima of the complexes are shifted to longer wavelengths compare to the absorption maxima of the dyes themselves. The binding ratio of the ion pair forming complex molecules in chloroform soln, are as follows ; NN-antihistamines (chlorpheniramine, tripelennamine, diphenhydramine) are NN-1 to antihisamine-1, EBT-antihistamines are EBT-2 to antithistamines a and Calcon-antihistamines are Calcon-3 to antithistamines-1. These coomplexes in chloroform soln. are very stable, and show higher absorbance than the other organic polar solvents. The binding state of complexes were presumed intermolecular hydrogen bond by their infrared spectra. In the mixture solution of three samples, the aqueous phase is buffered at pH 1.0, and benzene is used to extract ion pair of diphenhydramine EBT complex selectively. At pH 1.0 of aqueous layer, Calon-diphenhydramine complex is also extracted selectively by benzene. However, in this case very small amount of chlorpheniramine-calcon calcon simultaneously. The binding state of diphenhydramine-EBT and diphenhydramine-calcon in benzene are smae as the complexes in chloroform. But the absorption maxima of the complexes in benzene are shifted to shorter wavelenlgths than the complexes in chloroform.

• 대한화학회지
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• 제55권4호
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• pp.666-672
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• 2011

Vanadium 치환체인 polyoxometalate 1, [Cu(2,2'-bipy)]$[Cu(2,2'-bipy)_2]_2[PMo_8V_6O_{42}]{\cdot}1.5H_2O$을 가지고 있는 inorganicorganic complex의 촉매 활성도를 Biginelli 반응에 적용하여 연구하였다. Dihydropyrimidinones를 one-pot 합성하는 반응에서, $H_3PMo_{12}O_{40}$ 촉매 보다[Cu(2,2'-bipy)]$[Cu(2,2'-bipy)_2]_2[PMo_8V_6O_{42}]{\cdot}1.5H_2O$ 촉매가 더 좋은 결과를 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제9권5호
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• pp.292-295
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• 1988

Macrocyclic ligands have been studies as cation carriers in a bulk liquid membrane system. $Cu^{2+}$ has been transported using nitrogen substituted macrocycles as carriers and several transition metal ions($M^{n+}\;=\;Mn^{2+},\;Co^{2+},\;Ni^{2+},\;Cd^{2+},\;Pb^{2+}\;and\;Ag^{+}$) have been transported using $DBN_3O_2,\;DBN_2O_2,\;Me_6N_414C4$ and DA18C6 as carriers in a bulk liquid membrane system. Competitive $Cu^{2+}-M2^+$ transport studies have also been carried out for the same system. In single cation transport experiments, the best macrocyclic ligand for transport is a ligand that gives a moderately stable rather than very stable complex in the extraction. However, when both cations are present in the source phase, the cation which forms the most stable complex with carrier is favored in transport over other cations. Generally, the nitrogen substiituted macrocycles transport $Cu^{2+}$ selectively over $Mn^+$. Ligand structure, equilibrium constant (or stability constant) for complex formation, source phase pH and carrier concentration are also important parameters in transport experiments.

• Bulletin of the Korean Chemical Society
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• 제17권4호
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• pp.331-334
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• 1996

New copper(Ⅱ) complex of the pentaaza non-macrocyclic ligand 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl)-1,3-diazacyclohexane (2) and a dinuclear copper(Ⅱ) compex of the bis(macrocyclic) ligand 3, in which two 1,5,8,10,12,15-hexaazabicyclo[11.3.11.5]heptadecane subunits are linked together by an ethylene chain through the uncoordinated nitrogen (N10) atoms, have been prepared selectively by the reaction of the metal ion, 1,4,8-triazaoctane, ethylenediamine, and formaldehyde. The dinuclear complex [Cu2(3)]4+ has been also prepared by the reaction of [Cu(2)]2+ with ethylenediamine and formaldehyde. The reaction products largely depend on the molar ratio of the reactants employed. The mononuclear complex or each macrocyclic subunit of the dinuclear complex contains one 1,3-diazacyclohexane ring and has a square-planar geometry with a 5-6-5 or 5-6-5-6 chelate ring sequence. In acidic solution, the copper(Ⅱ) complex of 2 dissociates more slowly than those of other related non-cyclic polyamines.

• Bulletin of the Korean Chemical Society
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• 제14권6호
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• pp.687-691
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• 1993

Complexation of $Cd^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions with four cryptands were studied by potentiometry and solution calorimetry in various weight percent methanol-aqueous solvent at 25${\circ}$C under $CO_2$free nitrogen atmosphere. The stabilities of the complexes were dependent on the cavity size of macrocycles. The $Hg^{2+}$ ion stability constants are higher than those of $Cd^{2+}\;and\;Pb^{2+}$ ion. All the cryptands formed complexes having 1 : 1 (metal to ligand) mole-ratio except for $Hg^{2+}-L_1$ (cryptand 1,2b: 3,5-benzo-9,14,17-trioxa-1,7-diazabicyclo-(8,5,5) heptadecane) and $Cd^{2+}-L_2$ (cryptand 2,2b: 3,5-benzo-10,13,18,21-tetraoxa-1,7-diazabicyclo (8,5,5) eicosane) complexes. $Hg^{2+}-L_1$ complex was a sandwitch type, and the $Cd^{2+}-L_2$ complex showed two stepwise reactions. Thermodynamic parameters of the $Cd^{2+}-L_2$ complex were $6.08(log\;K_1)$, -7.28 Kcal/mol $({\Delta}H_1)$, and $4.78\;(log\;K_2)$, -4.62 Kcal/mol $({\Delta}H_2)$, respectively, for 1 : 1 and 2: 1 mole-ratio. The sequences of the selectivity were increased in the order of $Hg^{2+}\;>Pb^{2+}\;>Cd^{2+}$ ion for $L_3\;and\;L_4$ macrocycles, and the $L_2$-macrocycle has a selectivity for $Cd^{2+}$ ion relative to $Zn^{2+},\;Ni^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions. Thus, it is expected that the $L_2$ can be used as carrier for seperation of the post transition metals by macrocycles-mediated liquid membrane because $L_2$ is not soluble in water, and the difference of stability constants of the metal complexes with $L_2$ are large as compared with the other transition metal complexes. The $^1H\;and\;^{13}C-NMR studies indicated that the nitrogen atoms of cryptands have greater affinity to the post transition metal ions than the oxygen atoms, and that the planarities of the macrocycles were lost by complexation with the metal ions because of the perturbation of ring current of benzene molecule attached to macrocycles and counter-anions.

• 한국산업보건학회지
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• 제34권3호
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• pp.193-201
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• 2024

Objectives: Paints contain various types of metal substances. However, our review of MSDS (Material Safety Data Sheets) for paints found that their components were often kept secret or exact content information was otherwise not provided. We analyzed the metal elements in various inorganic pigment-based paints available in South Korea in this study and checked whether they contain hazardous metal substances as defined by the Occupational Safety and Health Acts. We investigated issues of health hazard classification related to the metal elements. The study is intended to contribute to strengthening the management of hazardous substances by suggesting improvements to MSDS. Methods: We randomly selected 19 samples that were predicted to contain hazardous inorganic pigments after reviewing MSDS among paints currently in use. The samples were analyzed using XRF (X-ray Fluorescence spectrometry), ICP_OES (Inductively Coupled Plasma-Optical Emission Spectroscopy) and SP-ICP-MS (Single Particle-ICP-Mass Spectroscopy). Results: The most common elements in the samples were Al (aluminum), Fe (iron), Ti (titanium), Ca (calcium), and Si (silica). One sample contained more lead than allowed by the limits. There were ten samples that could potentially contain nanoforms, seven samples that contained titanium dioxide, and six samples that contained complex inorganic color pigments (CICPs). Conclusions: Inorganic pigments in paints should be evaluated for hazards separately from other metallic compounds and reflected in the MSDS because they have different characteristics than other metallic compounds. These include particle size, crystal structure, and complex substances. The results of this study can be helpful for determining whether a paint contains sufficient hazardous metal compounds to affect its classification, and it can be a guideline for improving MSDS through comparative review and rationalization with the manufacturer's MSDS. This would make it possible to contribute to the management of chemical substances in the workplace through the proper MSDS disclosure of paints.

• 한국염색가공학회:학술대회논문집
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• 한국염색가공학회 2008년도 제38차 학술발표대회
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• pp.159-161
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• 2008

• 한국대기환경학회:학술대회논문집
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• 한국대기환경학회 2008년도 추계학술대회 논문집
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• pp.237-238
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• 2008