• Bulletin of the Korean Chemical Society
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• 제27권5호
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• pp.747-750
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• 2006

Research on tripodal complexes has grown in recent decades and has been subject of numerous reports.1-11 The reasons for this interest include their relevance to model functions of metalloenzymes1-3 and their potential applications in catalysis.13-17 The ligand system used most in this category has been tren, the tripodal tetraamine N(CH2CH2NH2)3, and its derivatives.4 The bz3tren is a versatile tetradentate ligand, known to form stable complexes not only with transition metals5-11 including Cu2+, Zn2+ and Co2+ but also anion species.12 However, only few results on the d10 metal complexes with bz3tren have been reported by us10 and others.6,7 As a part of on going efforts, we therefore focus our attention to extend other d10 system that includes heavy metal ions.

• 한국자기공명학회논문지
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• 제21권4호
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• pp.139-144
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• 2017

Ni(II) containing coenzyme F430 catalyzes the reduction of $CO_2$ in methanogen. Macrocyclic Ni(II) complexes with N,O shiff bases have been received a great attention since metal ions play an important role in the catalysis of reduction. The reducing power of metal complexes are supposed to be dependent on oxidoreduction state of metal ion and structural properties of macrocyclic ring moiety that can enhance electrochemical properties in catalytic process. Six different ${\alpha}$-oximinoketone compounds, precursor of macrocyclic ligands used in $CO_2$ reduction coenzyme F430 model complexes, were synthesized with yields over 90% and characterized by NMR. The molecular geometries of ${\alpha}$-oximinoketone analogues were fully optimized at Beck's-three-parameter hybrid (B3LYP) method in density functional theory (DFT) method with $6-31+G^*$ basis set using the ab initio program. In order to understand molecular planarity and substitutional effects that may enhance reducing power of metal ion are studied by computing the structure-dependent $^{13}C$-NMR chemical shift and comparing with experimental results.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.743-747
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• 2001

New azomethine metal complexes were synthesized systematically and characterized. Beryllium, magnesium, or zinc ions were used as a central metal cation and aromatic azomethines (L1-L4) were employed as a chelating anionic ligand. Emission peaks o f the complexes in both solution and solid states were observed mostly at the region of 400-500 nm in the luminescence spectra, where blue light was emitted. Three of them (BeL1 (Ⅰ), ZnL2 (Ⅱ), and ZnL3 (Ⅲ)) were sublimable and thus were applied to the organic light-emitting devices (OLED) as an emitting layer, respectively. The device including the emitting layer of Ⅰ exhibited white emission with the broad luminescence spectral range. The device with the emitting layer of Ⅱ showed blue luminescence with the maximum emission peak at 460 nm. Their ionization potentials, electron affinities, and electrochemical band gaps were investigated with cyclic voltammetry. The electrochemical gaps of 2.98 for I, 2.70 for Ⅱ, and 2.63 eV for Ⅲ were found to be consistent with their respective optical band gaps of 3.01, 2.95 and 2.61 eV within an experimental error. The structure of OLED manufactured in this study reveals that these complexes can work as electron transporting materials as well.

• Bulletin of the Korean Chemical Society
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• 제15권6호
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• pp.460-465
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• 1994

New silicon-monosubstituted (${\eta}^4$-2,3,4,5-tetraphenyl-l-silacyclopentadiene)transi tion metal complexes are described. (7-Alkyl-7-silanorbornadienyl)MLn(Alkyl=Methyl: MLn=CpRu$(CO)_2$: Alkyl=Methyl: MLn=CpNi(CO): Alkyl=Ethyl: MLn=CpNi(CO)) complexes were prepared from the corresponding silole-transition metal complexes with dimethylacetylenedicarboxylate. Cycloaddition products were obtained with 2,3-dimethyl-1,3-butadiene, 2,3-butanedione, and 1,4-benzoquinone through the ruthenium-substituted silylene. We have determined the crystal structure of (1-methyl-2,3,4,5-tetraphenyl-l-silacyclopentadien yl)cyclopentadienyldicarbonylruthenium by using graphite monochromated Mo-Ka radiation. The compound was crystallized in the monoclinic space group $P2_{1/c}$ with a = 9.838(l), b = 15.972(3), c = 18.327(3) ${\AA}$, and ${\beta}= 94.28(l)^{circ}$. The ruthenium moiety CpRu$(CO)_2$ on silicon is in an axial position.

• Bulletin of the Korean Chemical Society
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• 제19권10호
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• pp.1036-1042
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• 1998

The preconcentration and determination of trace elements in water samples were studied by a solvent sublation utilizing dithizonate complexation. After metal dithizonates were formed, trace amounts of cadmium, cobalt, copper and lead were floated and extracted into small volume of a water-immiscible organic solvent on the surface of sample solution and determined in the solvent directly by GF-AAS. Several experimental conditions as formation condition of metal-dithizonate complexes, pH of solution, amount of dithizone, stirring time, the type and amount of surfactants, N2 bubbling rate and so on were optimized for the complete formation and effective flotation of the complexes. And also four kinds of light solvents were compared each other to extract the floated complexes, effectively. After the pH was adjusted to 4.0 with 5 M HNO3, 8.0 mL of 0.05% acetone solution of dithizone was added to 1.00 L water sample. The dithizonate complexes were flotated and extracted into the upper methyl isobutylketone (MIBK) layer by the addition of 2.0 mL 0.2% ethanolic sodium lauryl sulfate solution and with the aid of small nitrogen gas bubbles. And this solvent sublation method was applied to the analysis of real water samples and good results of more than 85% recoveries were obtained in spiked samples.

• Bulletin of the Korean Chemical Society
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• 제25권7호
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• pp.1012-1019
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• 2004

The synthesis of novel group 9 metal complexes containing the S,S'-chelate ligands, $Li_2S_2C_2B_{10}H_{10}$ (2a) and $LiS(S=PMe_2)C_2B_{10}H_{10$} (2b), is described. Two new dinuclear complexes of the type $[{(cod)M}_2(S,S'-S_2C_2B_{10}H_{10})]$ (cod = 1,5-cyclooctadiene; M = Rh (3a), or Ir (3b)) were synthesized by the reaction of chloridebridged dimers $[M({\mu}-Cl)(cod)]_2$ with one molar equivalent of the corresponding dilithium dithiolato ligand $Li_2S_2C_2B_{10}H_{10}$ (2a). X-ray crystal structure analysis of 3a revealed a dinuclear structure in which each (cod)Rh unit is attached to a distinct sulfur atom of a 1,2-dithio-o-carboranyl ligand (2a). Additionally, the electrochemical properties of 3a and 3b were investigated by cyclic voltammetry. In an analogous manner, reaction of the lithium dithiolato ligand $LiS(S=PMe_2)C_2B_{10}H_{10}$ (2b) with $Cp^{\ast}CoI_2(CO)$ produced a mononuclear dithiolato complex, $[Cp^{\ast}CoI{(S,S'-S(S=PMe_2)C_2B_{10}H_{10})}]$ (4), which was characterized by single-crystal X-ray analysis.

• 한국정보통신학회:학술대회논문집
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• 한국정보통신학회 2021년도 추계학술대회
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• pp.646-648
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• 2021

The syntheses and properties of polynuclear metal complexes have been reported to develop the easy syntheses and noble photo-characteristics of those complexes for photodynamic diagnosis (PDD) or photodynamic therapy (PDT). We have been focused on the design and synthesis of polynuclear lanthanide dendritic molecule due to long life time of fluorescence. Therefore, we will be presented on the design of home (Eu or Gd) or hetero (Tb or Lu) polynuclear lanthanide dendritic molecule.

• Journal of Applied Biological Chemistry
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• 제64권2호
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• pp.159-164
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• 2021

토양 중 중금속은 자유이온, 유기산-중금속 복합체를 포함한 다양한 화학종으로 존재한다. 이 중 중금속 자유이온 비율은 식물체의 중금속 흡수와 밀접한 관련이 있는 것으로 알려져 있다. 본 연구는 중금속 자유이온과 유기산-중금속 복합체 존재 비율이 식물의 납, 카드뮴 흡수에 어떤 영향을 미치는지 알아보기 위하여 수행되었다. 이를 위해 순환식 양액재배 장치에서 28일간 키운 상추를 48시간 동안 납과 카드뮴 용액에 침지시키는 실험을 진행하였다. 침지 전 시트르산, 옥살산, 아세트산, 휴믹산을 이용해 납과 카드뮴 용액의 중금속 자유이온과 유기산-중금속 복합체의 비율이 100:0, 90:10, 70:30, 60:40이 되도록 조절하였다. 침지 후 상추 뿌리와 잎의 납, 카드뮴 농도를 분석한 결과, 용액 중 중금속 자유이온의 비율과 식물이 흡수한 납, 카드뮴 농도는 상관관계를 보이지 않았다. 반면에 처리한 유기산의 종류와 중금속 종류에 따른 차이가 더 큰 것으로 나타났다. 시트르산은 납 흡수는 증가시켰지만 카드뮴 흡수는 감소시켰다. 시트르산은 다른 유기산보다 상추의 납 흡수율을 높였는데 이는 시트르산이 분자량이 크기 때문에 중금속 이온과 복합체를 형성할 수 있는 용량이 더 크기 때문인 것으로 보인다. 그러므로 본 연구 결과는 식물에 의한 중금속 흡수가 단순히 자유이온의 양에 따라 달라지기 보다는 존재하는 유기산의 분자량에 의한 결합용량 차이가 중금속 종류에 따라 달리 작용하여 결정된다는 것을 보여준다.

• 대한화학회지
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• 제55권3호
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• pp.436-443
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• 2011

o-phenylenediamine, 3-acetyl-6-methyl-(2H)pyran,2,4(3H)-dione (dehydroacetic acid 또는 DHA) 및 2, 4-dihydroxy benzaldehyde에서 비롯된 4-hydroxy-3-(1-{2-(2,4-dihydroxy-benzylidene)-amino phenylimino}-ethyl)-6-methyl-pyran-2-one ($H_2$L)의 La(III), Ce(III), Pr(III), Nd(III), Sm(III) 및 Gd(III) 고체착물을 합성하여 원소분석, 전도도법, 자기수자율, UV-vis, FT-IR, 1H-NMR, X-선 회절, 열분석으로 특성을 규명하였으며, 항미생물 활성도를 조사하였다. FT-IR 스펙트럼 결과에 의하면 이 리간드는 중심금속에 대해 ONNO 주개원자를 통해 이염기성 사배위 리간드로 행동함을 알 수 있다. 원소분석 결과로부터 이들 착물의 화학량론비는 1:1 (금속: 리간드)임을 알 수 있다. 물리 및 화학적 실험결과로부터 La(III), Ce(III), Pr(III), Nd(III), Sm(III) 및 Gd(III) 착물은 일그러진 팔면체의 기하구조를 가짐을 알 수 있다. X-선 회절 데이터로부터 La(III) 및 Ce(III) 착물은 단사정계, 그리고 Pr(III) 및 Nd(III) 착물은 사방정계를 가짐을 알 수 있다. 이들 착물의 열적 행동(TG/DTA)을 연구하였으며, 속도론적 파라메타를 Horowitz-Metzger 및 Coats-Redfern 방법으로 결정하였다. 리간드와 그 착물의 항박테리아 활성도를 Staphylococcus aureus, Escherichia coli 및 Bacillus Sp.에 대해, 그리고 살균활성도를 Aspergillus Niger, Trichoderma 및 Fusarium oxysporum에 대해 각각 조사하였다.

• 대한화학회지
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• 제53권4호
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• pp.407-414
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• 2009

o-phenylenediamine, 3-acetyl-6-methyl-(2H) pyran, 2,4 (3H)-dione (dehydroacetic acid or DHA) 및 살리실 알데히드로부터 유도한 4-hydroxy-3-(1-{2-(2-hydroxy-benzylidene)-amino phenylimino}-ethyl)-6- methy-pyran-2-one (H2L) 의 Cu(II), Ni(II), Co(II), Mn(II) 및 Fe(III) 고체 착물을 합성한 후, 원소분석, 전도 도법, 수자율, 자외선-가시선, 적외선, $^1H$-NMR 스펙트라, X-선 회절, 열분석을 통해 특성을 규명하고 항균 활성을 조사하였다. IR 스펙트럼 데이터로부터 이 리간드가 중심 금속이온에 대해 ONNO 주개원자 배열을 갖는 이염기성 네자리 리간드로 행동함을 제안하였다. 원소분석 데이터로부터 이들 착물의 화학량론이 1:1 (금속:리간드)임을 알았다. 물리-화학적 데이타로부터 Cu(II) 및 Ni(II) 착물이 사각평면 기 하구조, 그리고 Co(II), Mn(II) 및 Fe(III) 착물이 팔면체 기하구조임을 제안하였다. X-선 회절 데이터로 부터 Cu(II) 착물이 사방정계(orthorhombic) 결정계, Ni(II), Co(II) 및 Fe(III) 착물이 단사계(monoclinic) 결정계 그리고 Mn(II) 착물이 정방정계(tetragonal) 결정계임을 제안하였다. 착물의 열적 행동(TG/DTA) 을 연구하였으며 Coats-Redfern 방법으로 반응속도 파라메터를 결정하였다. 리간드와 이들 금속 착물을 이용하여 Staphylococcus aureus 및 Escherichia coli에 대한 향균 활성과 Aspergillus Niger 및 Trichoderma 에 대한 살균 활성을 조사하였다.