• 제목/요약/키워드: EnCo

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산 촉매하에서 cis-$[Co(en)_2(N_3)_2]^+$ 와 Fe(II) 와의 산화-환원반응에 대한 반응속도와 메카니즘 (Kinetics and Mechanism for Redox Reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in Acidic Solution)

  • 박병각;김광진;임주상
    • 대한화학회지
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    • 제33권3호
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    • pp.309-314
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    • 1989
  • 산 용액내에서 cis-$[Co(en)_2(N_3)_2]^+$와 Fe(II)간의 산화-환원 반응속도를 UV/vis-분광광도계로 측정하였다. 여기서 촉매 $H^+$가 관여한 반응속도상수와 각 반응물의 반응차수 그리고 활성화파라메타를 구하여 이들 자료를 바탕으로 타당한 반응메카니즘을 제안하였다. 본 연구의 실험결과를 보면, Co(III)와 Fe(II) 그리고 $H^+$에 대해서 각각 1차로 총괄반응이 3차 반응이다. 이때 반응속도상수 $K_H^+$$3.27{\times}10^{-2}l^2{\cdot}mol^{-2}{\cdot}sec^{-1}$이였다. 그리고 활성화에너지 $E_a$는 14.8Kcal/mol, 활성화엔탈피 ${\Delta}H^{\neq}$는 14.2Kcal/mol, 활성화엔트로피 ${\Delta}S^{\neq}$는 -16.7e.u.였다. 이러한 실험적 사실을 바탕으로, 본 반응계에서 $H^+$가 촉매로 작용하여 내부권(inner-sphere) 메카니즘으로 산화-환원반응이 진행되는 타당한 반응메카니즘을 제안하였다.

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$Hg^{2+}$수용액에서 $cis-[Co(en)_2(NH_3)Cl]^{2+}$의 아쿠아반응에 대한 속도론적 연구 (Kinetic Study for Aquation of $cis-[Co(en)_2(NH_3)Cl]^{2+}$ in $Hg^{2+}$ Aqueous Solution)

  • 박병각;이길준;이재원;임주상
    • 대한화학회지
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    • 제32권3호
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    • pp.227-232
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    • 1988
  • $Hg^{2+}$촉매 존재하에서 cis-amminechlorobis(ethylenediamine)cobalt(III)의 Cl이 $H_2O$로 치환되는 반응을 전자흡수 스펙트라로 속도론적 연구를 하였다. 그 결과 $cis-[Co(en)_2(NH_3)Cl]^{2+}$에 대해서 각각 1차인 총괄반응이 2차반응이다. 활성화 파라메타인 ${\Delta}H^{\neq}$${\Delta}S^{\neq}$는 각각 12.9 kcal/mol, -19.3 e.u 이고 $Hg^{2+}$에 의한 반응속도상수는 $1.65{\times}10^{-2}l/mol.sec$가 됨을 알았다. 이러한 속도 자료로부터 본 반응계의 Cl이 $H_2O$로 치환되는 반응은 촉매인 $Hg^{2+}$가 관여하는 Id 메카니즘을 제안하였다.

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아세톤-물 혼합용매에서 trans-$[Co(en)_2Cl-2]^+$, trans-$[Co(N-eten)_2Cl-2]^+$, trans-$[Co(N-meen)_2Cl_2]^+$, trans-$[Co(tn)_2Cl_2]^+$ 착이온의 가용매 분해반응에 대한 압력과 용매조성의 영향. 반응메카니즘과 자유에너지 변화사이클 및 Excess 자유에너지 (The Effects of Solvent Composition and Pressure on the Rate of Solvolysis of trans-$[Co(en)_2Cl_2]^+$, trans-$[Co(N-eten)_2Cl-2]^+$, trans-$[Co(N-meen)_2Cl-2]^+$ and trans-$[Co(tn)_2Cl-2]^+$ in Aceton-Water Mixture. Excess Free Energy & Free Energy Cycle and Reaction Mechanism)

  • 박유철;조영제
    • 대한화학회지
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    • 제29권6호
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    • pp.629-636
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    • 1985
  • 아세톤-물 혼합용매에서 trans-$[Co(AA)_2Cl_2]^+$ 착이온의 가용매분해반응속도를 전도도법과 분광광도법을 사용하여 1~2000bar의 압력범위ㅣ에서 측정하였다. 여기서 AA는 에틸렌디아민(en), N-에틸에틸렌디아민(N-eten), N-메틸에틸렌디아민(N-meen)과 트리메틸렌디아민(tn)을 각각 의미한다. 속도상수에 대한 압력의 영향으로부터 구한 활성화 체적은 AA가 en, N-eten, N-meen 및 tn 일때 각각 -0.2∼0.9 $cm^3mole^{-1}$, -0.2∼0.6 $cm^3mole^{-1}$, -0.8∼6.0 $cm^3mole^{-1}$, 0.7∼7.0$cm^3mole^{-1}$이었다. 이들 착이온의 가용매분해반응성은 excess 자유에너지와 자유에너지 사이클로부터 얻을 결과를 비교하여 검토하였다. 가용매분해반응성은 압력이 감소할수록, 그리고 아세톤의 함량이 증가할수록 $S_N1$ 경향성이 증가하였다. 또한 가용매 분해반응의 메카니즘에 미치는 하전분리 효과도 고찰하였다.

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지중해담치, Mytilus galloprovincialis의 배 발생에 미치는 다환방향족탄화수소류 (2-methylnaphthalene, fluorene, dibenzothiophene, phenanthrene, pyrene) 의 영향 (Effect of five PAHs (2-methylnaphthalene, fluorene, dibenzothiophene, phenanthrene, and pyrene) on the embryonic development in the mussel, Mytilus galloprovincialis)

  • 성찬경;박판수;이종현;이창훈
    • 한국패류학회지
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    • 제30권3호
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    • pp.177-187
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    • 2014
  • Mussels have been commonly used in bioassay for quality assessments of environment. Moreover, several standard protocols for the developmental bioassay of bivalves have been proposed. In this study, the EC50 of polycyclic aromatic hydrocarbons (PAHs) was determined using mussel, Mytilus galloprovincialis embryonic developmental bioassay. To determine the sensitivity of M. galloprovincialis, their fertilized eggs were exposed to five PAHs (2-metylnaphthalene, fluorene, dibenzothiophene, phenanthrene, pyrene). The EC50 of 2-metylnaphthalene, fluorene, dibenzothiophene, phenanthrene, and pyrene were 232, 273, 67.9, 43.2, and $33.1{\mu}g/L$, respectively. The overall sensitivity of M. galloprovincialis in the present developmental bioassay was similar to or more sensitive than that of other marine organisms commonly used in aquatic bioassays. The results of this study could be provide with fundamental data of setting standard for protection of marine life and or can use prediction the aquatic toxicity of PAHs.

Triterpenoids from the Flower of Campsis grandiflora K. Schum. As Human Acyl-CoA: Cholesterol Acyltransferase Inhibitors

  • Kim, Dong-Hyun;Han, Kyung-Min;Chung, In-Sik;Kim, Dae-Keun;Kim, Sung-Hoon;Kwon, Byoung-Mog;Jeong, Tae-Sook;Park, Mi-Hyun;Ahn, Eun-Mi;Baek, Nam-In
    • Archives of Pharmacal Research
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    • 제28권5호
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    • pp.550-556
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    • 2005
  • The flower of Campsis grandiflora K. Schum. Was extracted with 80% aqueous MeOH, and the concentrated extract was partitioned with EtOAc, n-BuOH and H$_2$O. From the EtO Ac fraction, seven triterpenoids were isolated through the repeated silica gel, ODS column chromatographies and preparative HPLC. From the result of physico- chemical data including NMR, MS and IR, the chemical structures of the compounds were determined as 3${\beta}$-hydroxyolean-12-en-28-oic acid (oleanolic acid, 1), 3${\beta}$-hydroxyurs-12-en-28-oic acid (ursolic acid, 2), 3${\beta}$-hydroxyurs-12-en-28-al (ursolic aldehyde, 3), 2${\alpha}$,3${\beta}$-dihydroxyolean-12-en-28-oic acid (maslinic acid, 4), 2${\alpha}$,3${\beta}$-dihydroxyurs-12-en-28-oic acid (corosolic acid, 5), 3${\beta}$,23-dihydroxyurs-12- en-28-oic acid (23-hydroxyursolic acid ,6) and 2${\alpha}$,3${\beta}$,23-trihydroxyolean-12-en-28- oic acid (arjunolic acid, 7). These teriterpenoids were isolated for the first time from this plant. Also, compounds 4, 5, 6, and 7 revealed relatively high hACAT-1 inhibitory activity with the value of 46.2${\pm}$1.1, 46.7${\pm}$0.9, 41.5${\pm}$1.3 and 60.8${\pm}$1.1% at the concentration of 100${\mu}$g/mL, respectively.

Application of Indigenous Benthic Amphipods as Sediment Toxicity Testing Organisms

  • Lee, Jung-Suk;Lee, Kyu-Tae;Kim, Dong-Hoon;Kim, Chao-Kook;Lee, Jong-Hyeon;Park, Kun-Ho
    • Ocean Science Journal
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    • 제40권1호
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    • pp.17-24
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    • 2005
  • A series of experiments were conducted to develop standard test organisms and test protocols for measuring sediment toxicity using candidate amphipods such as Mandibulophoxus mai, Monocorophium acherusicum, Haustorioides indivisus, and Haustorioides koreanus, which are indigenous to Korea. The relevant association of test species with sediment substrates was one of the important factors in sediment bioassay. The indigenous amphipods M mai and M. acherusicum were well associated with test sediments when they were exposed to various sediment substrates from sand to mud. The tolerant limits to various physico-chemical factors affecting bioassay results such as temperature, salinity and ammonia, as well as sensitivities to reference toxicant and contaminated sediments, were investigated using M. mai and M. acherusicum in the present study. These amphipods were tolerant to relatively wide ranges of salinity $(10{\sim}30\;psu)$ and ammonia (<50 ppm), and displayed relevant sensitivity to temperature as well. They are more sensitive to Cd, the reference toxicant, when compared to the standard test species used in other countries. Field-sediment toxicity tests revealed that M. mai would be more sensitive to sediment-associated pollutants than M. acherusicum, while the sensitivity of M. acherusicum was comparable to that of Leptocheirus plumulosus, which has been used as a standard test species in the United States of America. Overall results of this first attempt to develop an amphipod sediment toxicity test protocol in Korea indicated that M. mai and M. acherusicum would be applicable in the toxicity assessment of contaminated sediments, following the further evaluation encompassing various ecological and toxicological studies in addition to test method standardization.

cis-[Co(en)2NH3Cl]2+ 이온의 수화반응과 염기성 가수분해반응에 미치는 미셀의 효과 (Micellar Effect of the Aquation and the Base Hydrolysis of cis-[Co(en)2NH3Cl]2+ Ion)

  • 정종재;백성오;이정아
    • 대한화학회지
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    • 제38권4호
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    • pp.265-270
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    • 1994
  • 여러 가지 농도의 SDS용액에서 [Co(en)$_2$NH$_3$Cl]$^{2+}$의 수화반응과 염기성 가수분해반응의 속도상수를 UV분광법으로 구하였다. 그리고 염기성 가수분해 반응에서는 염화나트륨의 농도를 0, 0.05, 0.1 mol dm$^{-3}$로 변화시키면서 반응속도에 미치는 염의 영향을 조사하였다. 수화반응은 SDS의 농도가 CMC보다 진한 미셀상태에서의 속도(kH$^M$)가 CMC보다 아주 묽은 수용액 상태에서의 속도(kH$^W$)보다 약간 빠른 경향을 보였다. 염기성 가수분해반응에서 속도상수(kOH)는 CMC보다 낮은 온도에서는 SDS농도가 증가하여도 일정한 값을 가지나, CMC부근에서는 급격히 감소하였다. CMC보다 진한 농도에서는 CMC이전과 마찬가지로 SDS의 농도가 증가하여도 속도상수의 변화가 거의 없었다. 염기성 가수분해반응에서 첨가한 염화나트륨의 효과는 이온교환모델로 설명할 수 있었다.

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이산화탄소로 산성화된 해수에 노출된 돌돔(Oplegnathus fasciatus) 혈구세포에 대한 유전독성(DNA 손상) (Genotoxicity (DNA damage) on Blood Cells of Parrot Fish (Oplegnathus fasciatus) Exposed to Acidified Seawater Making of CO2)

  • 최태섭;이지혜;성찬경;이정석;박영규;강성길
    • 한국환경과학회지
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    • 제23권3호
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    • pp.483-492
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    • 2014
  • DNA damage such as genotoxicity was identified with comet assay, which blood cell of a marine parrot fish (Oplegnathus fasciatus) was exposed to an acidified seawater, lowered pH gradient making of $CO_2$ gas. The gradient of pH were 8.22, 8.03, 7.81, 7.55 with control as HBSS solution with pH 7.4. DNA tail moment of fish blood cell was $0.548{\pm}0.071$ exposed seawater of pH 8.22 condition, on the other hand, DNA tail moment $1.601{\pm}0.197$ exposed acidified seawater of pH 7.55 lowest condition. The approximate difference with level of DNA damage was 2.9 times between highest and lowest of pH. DNA damage with decreasing pH was significantly increased with DNA tail moment on blood cell of marine fish (ANOVA, p < 0.001). Ocean acidification, especially inducing the leakage of sequestered $CO_2$ in geological structure is a consequence from the burning of fossil fuels, and long term effects on marine habitats and organisms are not fully investigated. The physiological effects on adult fish species are even less known. This result shown that the potential of dissolved $CO_2$ in seawater was revealed to induce the toxic effect on genotoxicity such as DNA breakage.

산 수용액내에서 [Co(en)2(CO3)]+의 아쿠아 반응속도와 반응메커니즘 (Kinetics and Mechanism for aquation of [Co(en)2(CO3)]+ in [H+] aqueous solution)

  • 이철재;김동엽
    • 한국산업융합학회 논문집
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    • 제8권3호
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    • pp.155-160
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    • 2005
  • Kinetic studies were carried out for aquation of carbonatobis(ethylenediamine)cobalt(III) complexes in [H+] aqueous solution by UV/VIS-spectrophotometry. The rate law that in deduced from rate data is $rate=k_H{^+}[H^+]^{1.4}$ {$[Co(en)_2(CO_3)]^+$}1.0 where $k_H{^+}$ is the rate constant considering acidic catalyst, $H^+$ ion whose value is $0.241l{\cdot}mol^{-1}{\cdot}sec^{-1}$. The values of activation parameters Ea, ${\Delta}H^{\ast}$ and ${\Delta}S^{\ast}$ were $15.33Kcal{\cdot}mol^{-1}$, $14.52Kcal{\cdot}mol^{-1}$ and -57.49 e.u. respectively. On the basis of kinetic data and the observed activation parameters, we have proposed the mechanism that proceeds with two step protonations. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation. It has been seen that our modified mechanism for Harris's proton freequilibrium one prefer to the his concerted mechanism, and more the last product substitute $H_2O$ for $OH^-$ the Harris's mechanism in the acidity range 2 < pH < 5.

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