• 대한화학회지
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• 제35권5호
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• pp.512-519
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• 1991

유기용매$(CH_2Cl_2,\;C_6H_6,\;CH_3NO_2,\;(CH_3)_2CO,\;CHCl_3,\;DMF,\;DMSO)$에서 Zn(II)-, Cu(II)- 및 Ni(II)-tetrakis(o-chlorophenyl)porphyrin(o-ClTPP)과 Zn(II)-, Cu(II)- 및 Ni(II)-tetraphenylporphyrin(TPP) 착물과 질소원자를 포함한 염기성 리간드(pyridine, imidazole, 1-methylimidazole 및 2,6-lutidine)간의 결합 반응성을 이온강도 0.01M에서 연구하였다. metalloporphyrin과 염기성 리간드간의 평형상수는 온도범위 15 ~ 35${\circ}C$에서 분광광도법을 이용하여 결정하였으며, 이 때 M(II)-TPP에서 관찰된 평형상수는 입체적 장애가 더 큰 M(II)-(o-Cl)TPP에서 보다 큰 값을 나타내었다. M(II)-TPP에서 logK값은 염기성 리간드의 pKa값이 커질수록 증가하였지만 입체적장애를 받는 M(II)-(o-Cl)TPP에서 logK는 리간드의 $pK_a$값에 비례하지 않았다. 열역학적 파라미터 분석결과 M(o-Cl)TPP의 안정도는 거의 반응엔트로피에 의존하였으나, M(II)-TPPL의 안정도는 반응엔탈피와 반응엔트로피에 거의 비슷한 영향을 나타내었다. metalloporphyrin에 대한 용매의 배위능을 DMF, DMSO, $CHCl_3,\;(CH_3)_2CO$에서 측정하였고, 이들 결과로부터 평형상수에 대한 용매효과를 논의하였다.

• Fisheries and Aquatic Sciences
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• 제14권1호
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• pp.43-54
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• 2011

Gene structure of copper/zinc-superoxide dismutase (Cu/Zn-SOD; sod1) was characterized in Hemibarbus mylodon (Teleostei; Cypriniformes), an endangered freshwater fish species in Korean peninsula. Full-length cDNA of H. mylodon SOD1 consisted of a 796-bp open reading frame sequence encoding 154 amino acids, and the deduced polypeptide sequence shared high sequence homology with other orthologs, particularly with regard to metal-coordinating ligands. Genomic structure of the H. mylodon sod1 gene (hmsod1; 1,911 bp from the ATG start codon to the stop codon) was typical quinquepartite (i.e., five exons interrupted by four introns); the lengths of the exons were similar among species belonging to various taxonomic positions. The molecular phylogeny inferred from sod1 genes in the teleost lineage was in accordance with the conventional taxonomic assumptions. 5'-flanking upstream region of hmsod1, obtained using the genome walking method, contained typical TATA and CAAT boxes. It also showed various transcription factor binding motifs that may be potentially involved in stress/immune response (e.g., sites for activating proteins or nuclear factor kappa B) or metabolism of xenobiotic compounds (e.g., xenobiotic response element; XRE). The hmsod1 transcripts were ubiquitously detected among tissues, with the liver and spleen showing the highest and lowest expression, respectively. An experimental challenge with Edwardsiella tarda revealed significant upregulation of the hmsod1 in kidney (4.3-fold) and spleen (3.1-fold), based on a real-time RT-PCR assay. Information on the molecular characteristics of this key antioxidant enzyme gene could be a useful basis for a biomarker-based assay to understand cellular stresses in this endangered fish species.

• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.269-273
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• 2003

The synthesis and properties of 2,13-bis(3'-pyridylmethyl) $(L^3)$, 2,13-bis(4'-pyridylmethyl) $(L^4)$, and 2,13-bis(phenylmethyl) $(L^5)$ derivatives of 5,16-dimethyl-2,6,13,17-tetraazatrcyclo$[16.4.0.^{1.18}0^{7.12}]$docosane are reported. The 3- or 4-pyridylmethyl groups of $[ML^3](ClO_4)_2\;or\;[ML^4](ClO_4)_2$ (M = Ni(Ⅱ) or Cu(Ⅱ)) are not involved in coordination, and the coordination geometry (square-planar) and ligand field strength of the complexes are quite similar to those of $[ML^5](ClO_4)_2$, bearing two phenylmethyl pendant arms. However, the complex formation reactions of $L^3\;and\;L^4$ are strongly influenced by the pyridyl groups, which can interact with a proton or metal ion outside the macrocyclic ring. The macrocycle $L^5$ exhibits a high copper(Ⅱ) ion selectivity against nickel(Ⅱ) ion; the ligand readily reacts with copper(Ⅱ) ion to form $[CuL^5]^{2+}$ but does not react with hydrated nickel(Ⅱ) ion in methanol solutions. On the other hand, $L^3\;and\;L^4$ form their copper(Ⅱ) and nickel(Ⅱ) complexes under a similar condition, without showing any considerable metal ion selectivity. The ligands $L^3\;and\;L^4$ react with copper(Ⅱ) ion more rapidly than does $L^5$ at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3- or 4-pyridylmethyl pendant arms on the complex formation reaction of $L^3\;and\;L^4$ are discussed.

• Bulletin of the Korean Chemical Society
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• 제19권6호
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• pp.671-676
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• 1998

The formation and dissociation rates of $Ce^{3+}$ Complexes of the 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-NN', N",N"'-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetrapropionic acid (3) have been measured by the use of stopped-flow spectrophotometry. Observations were made at 25.0±0.1 ℃ and at an ionic strength of 0.10 M $NaClO_4$. The complexation of $Ce^{3+}$ ion with 1 and 2 proceeds through the formation of an intermediate complex $(CeH_3L^{2+})^*$ in which the $Ce^{3+}$ ion is incompletely coordinated. This may then lead to be a final product in the rate-determining step. Between pH 4.76 and 5.76, the diprotonated $(H_2L^{2-})$ from is revealed to be a kinetically active species despite of its low concentration. The stability constants $(logK(CeH_3L^{2+}))$ and specific water-assisted rate constants $(k_{OH})$ of intermediate complexes have been determined from the kinetic data. The dissociation reactions of $Ce^{3+}$ complexes of 1, 2, and 3 were investigated with $Cu^{2+}$, ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed contributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on the dissociation rate of $Ce^{3+}$ complexes is discussed in terms of the side-pendant arms and the chelate ring sizes of the ligands.

• 유기물자원화
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• 제7권2호
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• pp.25-34
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• 1999

프로피온산의 혐기성 분해시 구리의 잠재적인 저해효과를 평가하기 위하여 회분식 실험을 수행하였다 프로피온산의 혐기성 분해시 구리의 저해효과는 중간 생성물, 최종 메탄 수율 및 비메탄 활성도를 이용하여 평가하였다. 구리의 농도 $2.5mg\;Cu^{2+}/1$에서는 저해 현상이 거의 발생하지 않았으나. 농도 증가에 따라 저해효과가 점차 증가하는 경향을 보였다. 최종 메탄 발생량 및 비메탄 활성도를 이용하여 산정한 50% 저해농도는 각각 33.8 및 $24.1mg\;Cu^{2+}/gVSS$로 나타났다. 최종 메탄 수율을 이용하여 산정한 저해효과는 운전기간이 지속됨에 따라 미생물 적응 및 첨가한 구리의 용존성 리간드와 체외효소와 결합으로 인하여 점차 저감되는 현상이 나타났다. 초기 메탄 발생속도를 근거로 산정한 비메탄 활성도는 이와 같은 영향을 상대적으로 제외할 수 있으므로 중금속에 의한 저해효과를 보다 정확하게 산정할 수 있을 것으로 판단된다. 황산염을 첨가한 경우 황산염 환원 미생물의 길항작용으로 인하여 첨가한 구리가 환원된 황화물과 결합하여 구리에 의한 저해효과는 거의 없는 것으로 나타났다. 구리를 첨가한 경우 초기 프로피온산의 분해가 지연되었으나, 점차 분해되는 경향을 보였으며. 프로피온산의 초산으로의 전환을 고려서 프로피온산의 분해가 초산의 분해 보다 구리의 영향을 많이 받는 것으로 나타났다. 이와 같은 결과를 고려시 구리에 의한 저해효과는 수소이용 메탄균이 초산 이용 메탄균에 비해 보다 민감한 것으로 판단된다.

• Nuclear Medicine and Molecular Imaging
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• 제41권4호
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• pp.326-334
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• 2007

에스트로젠 수용체 양성 유방암에서 과발현되는 에스트로젠 수용체는 $[^{18}F]FES$와 같은 $^{18}F$이 표지된 스테로이드계 에스트로젠 수용체 리간드를 사용하여 양전자방출단층촬영기로 영상을 얻을 수 있다. 반감기가 12.7시간인 $^{64}Cu$에 비해 1.8시간인 $^{18}F$은 반감기가 짧고, $^{64}Cu$로 표지 하는 경우보다 수율이 낮은 단점이 있다. 사이클렌은 구리, 인듐, 갈륨, 가돌리륨 등과 같은 금속과 안정한 착물을 형성한다. 이를 근거로 2개의 페놀 하이드록시 그룹을 가지고 있는 사이클렌을 기본구조로 한 구리 착물을 합성하였다. 재료 및 방법 : 1,7 위치에 보호기를 가지고 있는 1,7-bis(benzyloxy-carbonyl)-cyclen은 기존에 알려진 방법에 따라 합성 되어졌다. 여기에 4,10 위치에 2개의 4-benzyloxybenzyl groups을 도입한 후, Pd/C상에서의 수소화 반응으로 benzyloxycarbonyl과 benzyl groups이 모두 제거됨으로써 1,7-bis(4-hydroxybenzyl)-cyclen (1)을 성공적으로 합성할 수 있었다. 결과: 우리가 합성한 물질 1은 $^1H,\;^{13}C-NMR$ 그리고 질량분석기로 만들어졌는지 여부를 확인하였다. 이 물질들은 구리 이온과 반응하여 $[Cu(1)]^{2+}2(ClO_4)^-$와 $[Cu(1)Cl]^+Cl^-$를 형성하였고, 고분해능 FAB 질량분석기로 확인하였다. 결론: 우리는 질소원자에 trans 방향으로 2개의 페놀 그룹을 가지고 있는 cyclen 유도체를 합성하는데 성공하였고, 구리이온과 반응하여 각각 전체 전하가 +2그리고 +1인 구리 착물을 합성하였으며, 이들은 에스트로젠 수용체의 영상화를 위한 PET 추적자로 쓰일 수 있는 가능성이 있다.

• Bulletin of the Korean Chemical Society
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• 제27권10호
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• pp.1648-1650
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• 2006

The synthesis of a new C,N-bipyrazolic ligand with a functionalized donor-group is reported. The binding properties of the ligand and two other ligand of similar structures towards heavy metal ions ($Hg^{2+}$, $Cd^{2+}$, $Pb^{2+}$, $Zn^{2+}$, $Cu^{2+}$) and alkaline metal ions ($K^+$, $Na^{+}$, $Li^+$) were studied by a liquid-liquid extraction process and the extracted cation percentage was determined by atomic absorption measurements. The selectivity of the ligand to Hg(II) has been mentioned in the abstract.

• 대한핵의학회지
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• 제39권4호
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• pp.215-223
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• 2005

Current interest in the regioselective N-functionalization of tetraazacycloalkanes (cyclen and cyclam) stems mainly from their complexes with radioactive metals for applications in diagnostic ($^{64}Cu,\;^{111}In,\;^{67}Ga$) and therapeutic ($^{90}Y$) medicine, and with paramagnetic ions for magnetic resonance imaging ($Gd^{+3}$). Selective methods for the N-substitution of cyclen and cyclam is a crucial step in most syntheses of cyclen and cyclam-based radiometal complexes and bifunctional chelating agents. In addition, mixing different pendent groups to give hetero-substituted cyclen derivatives would be advantageous in many applications for fine-tuning the compound's physical properties. So far, numerous approaches for the regioselective N-substitution of tetraazacycloalkanes and more specifically cyclen and cyclam are reported. Unfortunately, none of them are general and every strategy has its own strong points and drawbacks. Herein, we categorize numerous regioselective N-alkylation methods into three strategies, such as 1) direct substitution of the macrocycle, 2) introductiou of the functional groups prior to cyclization, and 3) protection/iunclionallrationideproteclion. Our discussion is also split into the methods of mono- and tri-functionalization and di-functionalizataion based on number of substituents. At the end, we describe new trials for the new macrocycles which iorm more stable metal complexes with various radiometals, and briefly mention the commercially available tetraazacycloalkanes which are used for the biconjugation of biomolecules.

• 환경영향평가
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• 제9권1호
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• pp.1-11
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• 2000

An environmental geochemical survey of heavy metal distribution in marine surface sediments around the ocean of Samcheonpo coal-fired power plant was conducted to investigate the possibility of coal-ash leakage from ash pond and the associated heavy metal pollution in sedimental deposits due to the operation of the coal-fired power plant. The X-Ray Diffractometry (XRD) analysis showed that the main leakage point of coal-ash was limited to a single site of the first ash pond. It also appeared that the amounts of organic carbon and metal elements were positively correlated to the grain size distribution, and that Co, Cr, Cu, Fe, Ni, and Zn were bounded to organic ligands. However, the distributions of Cd, Hg, and Mn did not have any significant correlation with the sediment grain size and organic matters. In particular, the distribution of Cd appeared to be affected by the concentration of the carbonate materials in the study area.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.65-65
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• 2012

Copper zinc tin sulfide ($Cu_2ZnSnS_4$, CZTS) is a very promising material as a low cost absorber alternative to other chalcopyrite-type semiconductors based on Ga or In because of the abundant and economical elements. In addition, CZTS has a band-gap energy of 1.4~1.5eV and large absorption coefficient over ${\sim}10^4cm^{-1}$, which is similar to those of $Cu(In,Ga)Se_2$(CIGS) regarded as one of the most successful absorber materials for high efficient solar cell. Most previous works on the fabrication of CZTS thin films were based on the vacuum deposition such as thermal evaporation and RF magnetron sputtering. Although the vacuum deposition has been widely adopted, it is quite expensive and complicated. In this regard, the solution processes such as sol-gel method, nanocrystal dispersion and hybrid slurry method have been developed for easy and cost-effective fabrication of CZTS film. Among these methods, the hybrid slurry method is favorable to make high crystalline and dense absorber layer. However, this method has the demerit using the toxic and explosive hydrazine solvent, which has severe limitation for common use. With these considerations, it is highly desirable to develop a robust, easily scalable and relatively safe solution-based process for the fabrication of a high quality CZTS absorber layer. Here, we demonstrate the fabrication of a high quality CZTS absorber layer with a thickness of 1.5~2.0 ${\mu}m$ and micrometer-scaled grains using two different non-vacuum approaches. The first solution-processing approach includes air-stable non-toxic solvent-based inks in which the commercially available precursor nanoparticles are dispersed in ethanol. Our readily achievable air-stable precursor ink, without the involvement of complex particle synthesis, high toxic solvents, or organic additives, facilitates a convenient method to fabricate a high quality CZTS absorber layer with uniform surface composition and across the film depth when annealed at $530^{\circ}C$. The conversion efficiency and fill factor for the non-toxic ink based solar cells are 5.14% and 52.8%, respectively. The other method is based on the nanocrystal dispersions that are a key ingredient in the deposition of thermally annealed absorber layers. We report a facile synthetic method to produce phase-pure CZTS nanocrystals capped with less toxic and more easily removable ligands. The resulting CZTS nanoparticle dispersion enables us to fabricate uniform, crack-free absorber layer onto Mo-coated soda-lime glass at $500^{\circ}C$, which exhibits a robust and reproducible photovoltaic response. Our simple and less-toxic approach for the fabrication of CZTS layer, reported here, will be the first step in realizing the low-cost solution-processed CZTS solar cell with high efficiency.