• Title/Summary/Keyword: 배위

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Synthesis of pt(II) Complexes Containing Diphosphines and Evaluation of Antitumor Activity (디포스핀류 배위자를 함유한 백금(II) 착체의 합성과 항암효과)

  • Noh, Young-Soo;Masahide, Noji
    • Journal of Pharmaceutical Investigation
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    • v.20 no.4
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    • pp.217-222
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    • 1990
  • New antitumor-active pt(II) complexes of trans-l-diamine cyclohexane containing diphosphines as a leaving group were synthesized. The structures of the pt(II) complexes were determined by analyzing the infrared and $^{31}P-nuclear$ magnetic resonance spectra. Antitumor activities of the pt(II) complexes were tested against murine leukemia $L_{l210}$ according to the protocol of the National Cancer Institute. All the pt(II) complexes Synthesized were antitumor-active. In particular, water-soluble $[pt(trans-l-dach) (DPPP)](NO_3)_2$ exhibited excellent antitumor activity, giving T/C % values of 341 and 356 respectively, each with four cured mice out of six at a dose of 25 mg/kg. These pt(II) complexes are considered to be worthy of further development.

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Study on Technical Alternatives of Electricity Supply to Remote Islands and Inland (도서벽지 신재생 전력공급 기술적 대안분석)

  • Bae, Wi-Sup;Chung, Tae-Moon;Choi, Sung-Ho;Heo, Eun-Yeong;Cho, Dong-Ho
    • 한국신재생에너지학회:학술대회논문집
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    • 2006.06a
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    • pp.329-332
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    • 2006
  • 현행 농어촌전화촉진법에 의한 10호이상 도서전화사업이 2006년 말까지 완료될 예정임에 따라 전국적으로 43개에 달하는 10호미만 미전화유인도서 및 벽지지역에 대한 전화사업의 필요성이 제기되었다. 10호미만 도서지역의 전화사업을 위하여 도서전화사업의 기본취지인 전력정책의 보편공급목표를 달성하면서 사회적 경제적비용을 최소화할 수 있는 방법의 채택이 요구되었다 본 연구에서는 대부분의 도서지역이 채택하고 있는 기존의 디젤방식과 최근 활발한 보급이 이루어지고 있는 태양광 풍력 등 신재생에너지에 의한 발전방식의 기술적 옵션에 대한 타당성 분석을 실시하였다. 10호미만 도서지역과 5호미만 벽지지역에 디젤엔진과 태양광 등 신재생에너지를 보급할 경우 발생될 기술적, 경제적 비용의 분석을 실시하였으며 연구 결과 소규모 도서지역과 벽지에서는 태양광이 디젤엔진보다 경제적인 대안으로 판명되었다.

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Macrocyclic Complexes of Actinide and Lanthanide Metals (Ⅰ). Formation and Properties of Cation Complexes with Macrocyclic Ligands (악틴 및 란탄족금속의 거대고리 착물 (제 1 보). 거대고리 리간드의 금속착물의 형성과 성질)

  • Jeong, O Jin;Choe, Chil Nam;Yun, Seok Jin;Son, Yeon Su
    • Journal of the Korean Chemical Society
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    • v.34 no.2
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    • pp.143-158
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    • 1990
  • Metal complexes were prepared by reacting uranium (Ⅵ), thorium (Ⅳ) and rare earth metal (Ⅲ) ions including Nd (Ⅲ), Sm (Ⅲ) and Ho (Ⅲ) with macrocyclic ligands including five crown ethers, nine crownands and one cryptand ligands, and subjected to NMR studies in order to examine coordination sites of the ligands and compositions of the complexes formed. Among the marcocyclic ligands, crown ethers and crownand ligands have shown down-field shifts of the methylene protons of the lcigands by forming stable complexes with all the metal ions and the differences of chemical shifts were decreased as increasing of the cavity-size of crown ethers for the same metal ions and decreasing of the atomic number of the rare earth metals for the same ligands. It has been found that crownand 22 gave a stable complex with uranium(Ⅵ) ion by the coordination through both oxygen and nitrogen atoms of the ligand whereas no complex was formed with the rare earth metal(Ⅲ) ions, which on the other hand were found to form stable complexes with cryptand 221. The rest of the crowand ligands have also been found to form stable complexes with uranium(Ⅵ) ion by coordinating through all the oxygen and nitrogen atoms of the ligands whereas no complexes were formed with the rare earth metal(Ⅲ) ions. It has also been shown by 1H-NMR study that uranium(Ⅵ), thorium(Ⅳ) and rare earth metal(Ⅲ) ions formed 1:1 complexes with the macrocyclic ligands except for thorium(Ⅳ) complex of 12C4 in which the mole ratio of metal to ligand is 1:2. More stable metal complexes show larger changes in chemical shifts of the coordinated ligand protons. Finally, the rare earth metal(Ⅲ) complexes of 18C6 have shown ligand exchange reaction with the solvent molecules in acetylacetone solution, which was not observed for the uranium (Ⅵ) complexes.

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Determination of Electron Spin Relaxation Time of the Gadolinium-Chealted MRI Contrast Agents by Using an X-band EPR Technique (EPR을 통한 상자성 자기공명 조영제의 전자스핀 이완시간의 결정)

  • Sung-wook Hong;Yongmin Chang;Moon-jung Hwang;Il-su Rhee;Duk-Sik Kang
    • Investigative Magnetic Resonance Imaging
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    • v.4 no.1
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    • pp.27-33
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    • 2000
  • Purpose: To determine the electronic spin relaxation times, $T_{le}$, of three commercially available Gd-chelated MR contrast agents, Gd-DTPA, Gd-DTPA-BMA and Gd-DOTA, using Electron Paramagnetic Resonance(EPR) technique. Material and Methods: The paramagnetic MR contrast agents, Gd-DTFA(Magnevist) , Gd-DTFA-BMA(OMNISCAN) and Gd-DOTA(Dotarem), were used for this study, The EPR spectra of these contrast agents, which were prepared 2:1 methanol/water solution, were obtained at low temperatures, from $-160^{\circ}C~20^{\circ}C$. The glassy-state EPR spectra for these contrast agents were then fitted by the simulation spectra generated with different zero-field splitting (ZFS) parameters by a computer simulation program 'GEN', which generates the EPR powder spectrum using a given ZFS in $3{\times}3$ tensor. Finally, the spin relaxation times of the contrast agents were then determined from the $T_{2e}$, D, and E values of the best simulation spectra using the McLachlan's theory of average relaxation rate. Results: The electronic transverse spin relaxation times, $T_{2e}'s$, of Gd-DTPA, Gd-DTPA-BMA and Gd-DOTA were 0.113ns, 0.147ns and 1.81ns respectively. The g-values were 1.9737, 1.9735 and 1.9830 and the electronic spin relaxation times, $T_{1e}'s$, were 18.70ns, 33.40ns and $1.66{\mu}s$, respectively. Conclusion: The results of these studies reconfirm that the paramagnetic MR contrast agents with larger ZFS parameters should have shorter $T_{1e}'s$. Among three contrast agents used for this study, Gd-DOTA chelated with cyclic ligand structure shows better electronic property then the others with linear structure. Thus, it is concluded that the exact determination of ZFS parameters is the important factor in evaluating relaxation enhancement effect of the agents and in developing new contrast agents.

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Effect of Boron Content on Atomic Structure of Boron-bearing Multicomponent Oxide Glasses: A View from Solid-state NMR (비정질 소듐 보레이트와 붕소를 함유한 다성분계 규산염 용융체의 붕소의 함량에 따른 원자 구조에 대한 고상 핵자기 공명 분광분석 연구)

  • Lee, A Chim;Lee, Sung Keun
    • Journal of the Mineralogical Society of Korea
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    • v.29 no.3
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    • pp.155-165
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    • 2016
  • Understanding the effect of boron content on atomic structures of boron-bearing multicomponent silicate melts is essential to reveal the atomistic origins of diverse geochemical processes involving silica-rich magmas, such as explosive volcanic eruption. The detailed atomic environments around B and Al in boron-bearing complex aluminosilicate glasses yield atomistic insights into reactivity of nuclear waste glasses in contact with aqueous solutions. We report experimental results on the effect of boron content on the atomic structures of sodium borate glasses and boron-bearing multicomponent silicate melts [malinkoite ($NaBSiO_4$)-nepheline ($NaAlSiO_4$) pseudo-binary glasses] using the high-resolution solid-state NMR ($^{11}B$ and $^{27}Al$). The $^{11}B$ MAS NMR spectra of sodium borate glasses show that three-coodrinated boron ($^{[3]}B$) increases with increasing $B_2O_3$ content. While the spectra imply that the fraction of non-ring species decreases with decreasing boron content, peak position of the species is expected to vary with Na content. Therefore, the quantitative estimation of the fractions of the ring/non-ring species remains to be explored. The $^{11}B$ MAS NMR spectra of the glasses in the malinkoite-nepheline join show that four-coordinated boron ($^{[4]}B$) increases as $X_{Ma}$ [$=NaBSiO_4/(NaBSiO_4+NaAlSiO_4)$] increases while $^{[3]}B$ decreases. $^{27}Al$ MAS NMR spectra of the multicomponent glasses confirm that four-coordinated aluminum ($^{[4]}Al$) is dominant. It is also observed that a drastic decrease in the peak widths (full-width at half-maximum, FWHM) of $^{[4]}Al$ with an addition of boron ($X_{Ma}=0.25$) in nepheline glasses. This indicates a decrease in structural and topological disorder around $^{[4]}Al$ in the glasses with increasing boron content. The quantitative atomic environments around boron of both binary and multicomponent glasses were estimated from the simulation results of $^{11}B$ MAS NMR spectra, revealing complex-nonlinear variation of boron topology with varying composition. The current results can be potentially used to account for the structural origins of the change in macroscopic properties of boron-bearing oxide melts with varying boron content.

Synthesis of Fe­Garnet for tile Immobilization of High Level Radioactive Waste (고준위 방사성폐기물의 고정화를 위한 Fe­석류석 합성 연구)

  • ;;;Yudintsev, S. V.
    • Journal of the Mineralogical Society of Korea
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    • v.16 no.4
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    • pp.307-320
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    • 2003
  • Garnet has been considered as a possible matrix for the immobilization of radioactive actinides. It is expected that Fe­based garnet be able to have the high substitution ability of actinide elements because ionic radius of Fe in tetrahedral site is larger than that of Si of Si­based garnet. Accordingly, we synthesized Fe­garnet with the batch composition of $Ca_{2,5}$C $e_{0.5}$Z $r_2$F $e_3$ $O_{12}$ and $Ca_2$CeZrFeF $e_3$ $O_{12}$ and studied their phase relations and properties. Mixed samples were fabricated in pellet forms under the pressure of 400 kg/$\textrm{cm}^2$ and were sintered in the temperature range of 1100∼140$0^{\circ}C$ in atmospheric conditions. Phase identification and chemical composition of synthesized samples were analyzed by XRD and SEM/EDS. In results, where the compounds were sintered at 130$0^{\circ}C$, we optimally obtained Fe­garnets as the main phase, even though some minor phases like perovskite were included. The compositions of Fe­garnets synthesized from the batch compositions of $Ca_{2,5}$C $e_{0.5}$Z $r_2$F $e_3$ $O_{12}$ and $Ca_2$CeZrFeF $e_3$ $O_{12}$, are $Ca_{2.5­3.2}$C $e_{0.3­0.7}$Z $r_{1.8­2.8}$F $e_{1.9­3.2}$ $O_{12}$ and $Ca_{2.2­2.5}$C $e_{0.8­1.0}$Z $r_{1.3­1.6}$ F $e_{0.4­.07}$ F $e_{3­3.2}$ $O_{12}$, respectively. Ca contents were exceeded and Ce contents were exceeded or depleted in 8­coodinated site, comparing to the initial batch composition. These results were caused by the compensation of the difference of ionic radius between Ca and Ce.

The rite of worshiping heaven's ritual analysis from end of Koryo to beginning of Choson period (려말선초(麗末鮮初) 제천례(祭天禮)의 의례적 분석 - 명대와의 비교를 중심으로 -)

  • Kim, Sang-tae
    • Journal of Korean Historical Folklife
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    • no.45
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    • pp.291-325
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    • 2014
  • This study is about examining the changing process of worshiping heaven in the end of the Koryo dynasty and early Chosun dynasty. For this, it was compared with book of national rites. This paper will outline the differences of commemorative rites of worshiping heaven between Korea and China and its reason for changing process. Also, it shows the understanding of the historic characteristics of commemorative rites of worshiping heaven in the end of the Koryo dynasty and early Chosun dynasty through analyzing conducted religious service. Following methodological approach was used to achieve the aim of the study. The study includes historical changing process and basic ritual of commemorative rites of worshiping heaven from Koryo dynasaty to King Sejo period through various chronicles and books of rites. Understanding the trend transition of operating commemorative rites of worshiping heaven is expressed differently based on the situation in those days even though it is the same operation of commemorative rites of worshiping heaven. The existing study only primarily considered the rites of worshiping heaven in the end of the Koryo dynasty and early Chosun dynasty through the resources within the country. However, the process of settlement of commemorative rites of worshiping heaven is closely related to settlement of Confucian formality. As the problems cannot be solved if institutional changes are researched only though the resources within the nation, this following study also considered the transition of commemorative rites of worshiping heaven in China for sure. Through this approach, the study understood how China's rites of worshiping heaven settled down and formed in Korea and found differences of the rites of worshiping heaven between the two nations by comparing China's book with ornamental "seal" characters throughout many generations. Furthermore, it also illustrated historical characteristics of rites of worshiping heaven in the end of the Koryo dynasty and early Chosun dynasty by analyzing carried out religious service. Although it seems like there are many similarities of Chinese ritual procedure between Koryo dynasty and Chosun dynasty, there are existing significant differences in the context. Moreover, it is clear that there are differences of ritual between Tang, Song, Ming dynasty. These differences are directly connected to Korea and also with transition of king's power. Generally, Tang and Song dynasty show similar trend whilst Ming clarifies the differences between the two. For instance, there are differences between deep bow and superintendent of cho-hun, a-hun, and jong-hun. Transition of configuration is also one of the major differences. Changing of configuration has considerably important meaning refer to status of king's power. Analyzing specific features, such as size of altar, ancestral tablet, people who participate in sacrifices, okpye, configuration, and etc., made possible to consider the actual differences, not just examining different features of vaguely. Based on this foundation, the study closely examined the differences among the periods between the nations and gave the significance of the differences.

Pressure-load Calibration of Multi-anvil Press at Ambient Temperature through Structural Change in Cold Compressed Amorphous Pyrope (비정질 파이로프의 저온 압축에 따른 구조 변화를 이용한 멀티 앤빌 프레스의 상온 압력-부하 보정)

  • Lhee, Juho;Kim, Yong-Hyun;Lee, A Chim;Kim, Eun Jeong;Lee, Seoyoung;Lee, Sung Keun
    • Korean Journal of Mineralogy and Petrology
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    • v.35 no.1
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    • pp.65-73
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    • 2022
  • The proper estimation of physical and chemical properties of Earth materials and their structures at high pressure and high temperature conditions is key to the full understanding of diverse geological processes in Earth and planetary interiors. Multi-anvil press - high-pressure generating device - provides unique information of Earth materials under compression, mainly relevant to Earth's upper mantle. The quantitative estimation of the relationship between the oil load within press and the actual pressure conditions within the sample needs to be established to infer the planetary processes. Such pressure-load calibration has often been based on the phase transitions of crystalline earth materials with known pressure conditions; however, unlike at high temperature conditions, phase transitions at low (or room) temperatures can be sluggish, making the calibration at such conditions challenging. In this study, we explored the changes in Al coordination environments of permanently densified pyrope glasses upon the cold compression using the high-resolution 27Al MAS and 3QMAS NMR. The fractions of highly coordinated Al in the cold compressed pyrope glasses increase with increasing oil load and thus, the peak pressure condition. Based on known relationship between the peak pressure and the Al coordination environment in the compressed pyrope glasses at room temperature, we established a room temperature pressure-load calibration of the 14/8 HT assembly in 1,100-ton multi-anvil press. The current results highlight the first pressure-load calibration of any high pressure device using high-resolution NMR. Irreversible structural densification upon cold compression observed for the pyrope glasses provides insights into the deformation and densification mechanisms of amorphous earth materials at low temperature and high pressure conditions within the subducting slabs.

Electrochemical Reduction for trans-Complexes of Cobalt (III) with Bis(ethylenediamine) and Monodendate Ligands (한자리 리간드를 포함하는 트란스비스 (에틸렌디아민) 코발트 (III) 이온의 전극 환원반응)

  • Jung-Ui Hwang;Jong-Jae Chung;Jae-Duck Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.215-224
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    • 1989
  • Electrochemical reductions of $trans-[Co(en)_2X_2](ClO_4)_n$ (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. $trans-[Co(en)_2(CN)_2]ClO_4$ was reduced to Co(II) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(II) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except $trans-[Co(en)_2(CN)_2]ClO_4$ were reduced to cobalt(II) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. $trans-[Co(en)_2(NO_2)_2]ClO_4$ was reduced to cobalt(Ⅱ) complex, and $NO_2^-$ ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(III) were reduced to Co(II) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.

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Cobalt(II) Complex of 1,2-Bis(2,2'-bipyridyl-6-yl)ethane. Crystallization Process and Structural Analysis of Two Shapes of Crystals (1,2-비스(2,2'-디피리딜-6일)에탄의 코발트 착물. 두 가지 형태의 결정화 과정 및 구조 분석적 접근)

  • Park, Sung-Ho;Yoo, Kyung-Ho;Jung, Ok-Sang
    • Analytical Science and Technology
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    • v.12 no.5
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    • pp.421-427
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    • 1999
  • Two shapes of crystals have been isolated by the interdiffusion of $Co(NCS)_2$ dissolved in methanol with 1,2-bis(2,2'-bipyridyl-6-yl)ethane (bbpe) dissolved in chloroform. The two crystals have been elucidated as $trans-Co^{II}(NCS)_2(bbpe)$ and $trans-Co^{II}(NCS)_2(bbpe){\cdot}2CHCl_3$, by X-ray crystallography, elemental analysis, IR, and thermal analysis. The two molecular structures are very similar except for the absence or presence of chloroform solvate molecules. The bbpe ligand coordinates to the cobalt(II) ion in an open-ended tetradentate mode, resulting in discrete mononuclear cobalt(II) complex. The cobalt atom adopts a typical octahedral arrangement with six nitrogen donating atoms with two NCS groups in trans positions. A significant solid-to-solid phase transition occurs presumably due to the change of conformationally flexible bbpe ligand. The formation of both crystals oeeurs in a successive two-step process, the formation of $trans-Co^{II}(NCS)_2(bbpe)$ and its transformation into $trans-Co^{II}(NCS)_2(bbpe){\cdot}2CHCl_3$. The thermal stability and favorable formation of the solvate crystals may be ascribed to the interaction between S atom of NCS group and Cl of chloroform.

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