• 제목/요약/키워드: Reductive

검색결과 472건 처리시간 0.029초

Selective Deprotonation and Decarbonylation from Hydridocarbonyl-iridium(III) Compounds with Trimethylamine N-oxide

  • 천청식;오문현;원경식;조해연;신동찬
    • Bulletin of the Korean Chemical Society
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    • 제20권1호
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    • pp.85-88
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    • 1999
  • Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0.1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, C1O4-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (lb) to give IrCl(CO)(PPh3)2 (2b) is first order in both lb and Me3NO. The rate law d[2b]/dt=kobs[lb]=k2[lb][Me3NO] suggests the formation of (PPh3)2(CI)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis liaand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, C1O4-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-lr(H)(-CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

수축주의와 비환원주의 (Deflationism and Nonreductionism)

  • 이종왕
    • 철학연구
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    • 제105권
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    • pp.75-94
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    • 2008
  • 심리철학에서 수축주의(deflationism)와 비환원주의의 옹호자들은 모두 정신인과의 문제가 과장되어 있다고 주장하지만 그 정도와 이유에는 큰 차이가 있다. 수축주의자는 이 문제가 사이비 문제(a bogus problem)이기때문에 물리주의적 형이상학을 포기하고 인식론적 또는 과학적 설명에 집중해야한다고 주장한다. 이와는 대조적으로 비환원주의자들은 김재권이 제시하는 폐쇄의 원리(the principle of causal closure)와 배제의 원리(the principle of causal exclusion) 자체들을 받아들이기 때문에 - 비록 그들은 이 원리들이 수반과 함께 작용될 때 환원으로 가야하는 정당성을 제공하지는 않는다고 생각하지만 - 그것의 철학적 문제 성립에는 어느 정도 동의하지만 그 문제가 제기한 심각한 문제를 수축주의자들의 부분적 주장과 같이 수반개념으로 충분히 극복할 수 있다고 주장한다. 물론 수축주의자들은 형이상학적 주제인 수반을 물리주의자들이 인정하는 만큼 적절한 개념으로 간주하지는 않는다. 과연 수축주의자들은 무슨 근거로, 어떻게 배제논변에 의존한 정신인과의 문제를 사이비 문제라고 간주하는가? 이 논문에서 필자는 이런 다양한 의문들에 대한 비판적 검토를 하면서 현대판 심신문제인 정신인과의 문제에 대한 가장 적절한 대응이 무엇인지를 관련된 문제들의 명료화를 통해서 결정하려고 시도할 것이다.

Cr(VI)으로 오염된 부지의 안정화 기술에 의한 정화 타당성 연구 (Feasibility Study on Stabilization Technique of Cr(VI)-contaminated Site)

  • 윤근석;유종찬;고성환;심명호;조명현;백기태
    • 한국지하수토양환경학회지:지하수토양환경
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    • 제22권4호
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    • pp.27-32
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    • 2017
  • In this study, a remedial investigation using reductive stabilization was conducted to treat Cr(VI)-contaminated soil. The influences of various operational parameters, including reaction time and the mass of ferrous iron, were also evaluated. The study site was contaminated with a large amount of Cr(III) and Cr(VI), and the selected treatment method was to stabilize Cr(VI) with ferrous iron, which reduced Cr(VI) to Cr(III) and stabilized the chromium, although a greater mass of ferrous iron than the stoichiometric amount was required to stabilize the Cr(VI). However, some Cr(III) re-oxidized to Cr(VI) during the drying process, and addition of a strong reducing agent was required to maintain reducing conditions. With this reducing agent, the treated soil met the required regulatory standard, and the mass of Cr(III) re-oxidized to Cr(VI) was significantly reduced, compared to the use of only Fe(II) as a reducing agent.

Sodium Hydrogensulfite를 이용한 환원반응에서 2-Hydroxyphenyl Diazonium 유도체의 입체장애에 관한 연구 (Effects of Steric Hindrance of 2-Hydroxyphenyl Diazonium Derivatives in the Reductive Reaction by Using Sodium Hydrogensulfite)

  • 권오준;김지언;박세민;김근식;윤순도
    • 공업화학
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    • 제30권4호
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    • pp.509-511
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    • 2019
  • 정밀화학 및 의약품, 화장품에 사용되는 hydrazine 유도체는 diazonium salt로부터 환원반응을 통해 합성할 수 있다. $SnCl_2$를 이용한 환원방법은 반응 전환이 용이하나 반응 후 최종 제품에 중금속 잔류문제가 민감한 경우 사용에 제한을 받는다. 중금속이 없는 라말린(Ramalin)을 제조하기 위해 $NaHSO_3$를 이용한 환원방법을 개발하였으며, 이때 보호된 (2-hydoxyphenyl)diazonium 유도체의 diazonium 그룹을 hydrazine 그룹으로 전환하기 위한 환원반응에서, 하이드록시 그룹의 보호기 크기에 따른 입체장애 영향을 확인하였고, 보호기의 크기는 $C_1{\sim}C_5$ 직쇄형 보호기가 바람직하였다. 라말린 제조를 위한 경제성과 공업적 생산을 고려하여 다양한 보호기를 검토한 결과, 비교적 안정한 조건에서 탈보호할 수 있는 알릴 그룹을 사용할 경우 2-(allyloxy)aniline으로부터 (2-allyloxyphenyl)hydrazine를 수율 85%, 순도 99.7%로 가장 좋은 결과를 얻을 수 있었다.

팔라디움과 인디움을 담지한 Al 층간가교 몬모릴로나이트 촉매의 수중 질산성질소 환원 특성 (The Reduction Properties of Nitrate in Water with Palladium and Indium on Aluminum Pillared Montmorillonite Catalyst)

  • 정상조
    • 한국물환경학회지
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    • 제34권6호
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    • pp.621-631
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    • 2018
  • In this study, catalyst was made through incipient wetness method using palladium (Pd) as noble metal, indium (In) as secondary metal, and montmorillonite (MK10) and Al pillared montmorillonite (Al-MK10) as supporters. The nitrate reduction rate of the catalysts was measured by batch experiments where H2 gas was used as reducing agent and formic acid as pH controller. Transmission electron microscopy (TEM) equipped with energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were all used to determine the elemental distribution of Pd, In, Al, and Si on catalysts. It was observed that Al pillaring increased the Al/Si elemental composition ratio and point of zero charge of MK10, but decreased its BET specific surface area and pore volume. The nitrate reduction rate of Al-MK10 Pd/In was 2.0 ~ 2.5 times higher than that of MK10 Pd/In using artificial groundwater (GW) in ambient temperature and pressure. Nitrate reduction rates in GW were 1.2 ~ 1.7 times lower than those in distilled deionized water (DDW). Nitrate reduction rates in acidic conditions were higher than those in neutral condition in both GW and DDW. The amount of produced NH3-N over degraded NO3- at acid conditions was lower than that of neutral condition. Even though the leaching of Pd after reaction was measured in DDW it was not detected when both Al-MK10 Pd/In and MK10 Pd/In were used in GW. The modification of montmorillonite as a supporter significantly increased the reductive catalytic activities of nitrates. However, the ratio of producing ammonia by-products to degraded nitrates in ambient temperature and pressure was similar.

Biotransformation of Reactive Red 141 by Paenibacillus terrigena KKW2-005 and Examination of Product Toxicity

  • Sompark, Chalermwoot;Singkhonrat, Jirada;Sakkayawong, Niramol
    • Journal of Microbiology and Biotechnology
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    • 제31권7호
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    • pp.967-977
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    • 2021
  • A total of 37 bacterial isolates were obtained from dye-contaminated soil samples at a textile processing factory in Nakhon Ratchasima Province, Thailand, and the potential of the isolates to decolorize and biotransform azo dye Reactive Red 141 (RR141) was investigated. The most potent bacterium was identified as Paenibacillus terrigena KKW2-005, which showed the ability to decolorize 96.45% of RR141 (50 mg/l) within 20 h under static conditions at pH 8.0 and a broad temperature range of 30-40℃. The biotransformation products were analyzed by using UV-Vis spectrophotometry and Fourier-transform infrared spectroscopy. Gas chromatography-mass spectroscopy analysis revealed four metabolites generated from the reductive biodegradation, namely sodium 3-diazenylnaphthalene-1,5-disulfonate (I), sodium naphthalene-2-sufonate (II), 4-chloro-1,3,5-triazin-2-amine (III) and N1-(1,3,5-triazin-2-yl) benzene-1,4-diamine (IV). Decolorization intermediates reduced phytotoxicity as compared with the untreated dye. However, they had phytotoxicity when compared with control, probably due to naphthalene and triazine derivatives. Moreover, genotoxicity testing by high annealing temperature-random amplified polymorphic DNA technique exhibited different DNA polymorphism bands in seedlings exposed to the metabolites. They compared to the bands found in seedlings subjected to the untreated dye or distilled water. The data from this study provide evidence that the biodegradation of Reactive Red 141 by P. terrigena KKW2-005 was genotoxic to the DNA seedlings.

부지특성화을 위한 지하수의 수리화학 특성 연구: 주성분 분석을 중심으로 (Hydrochemical Investigation for Site Characterization: Focusing on the Application of Principal Component Analysis)

  • 유순영;김한석;전성천;이종화;윤성택;권만재;조호영
    • 한국지하수토양환경학회지:지하수토양환경
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    • 제27권spc호
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    • pp.34-50
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    • 2022
  • Principal component analysis (PCA) was conducted using hydrochemical data in four testbeds (A to D) built for the development of site characterization technologies to assess the hydrochemical processes controlling the hydrochemistry in each site. The PCA results indicated the nitrogen loading to deep bedrock aquifers through permeable fractures in Testbed A, the chemical weathering enhanced with the biodegradation of petroleum hydrocarbons in Testbed B, the reductive dechlorination in Testbed C, and the different hydrochemistry depending on the depth to bedrock in Testbed D, consistent with the characteristics of each site. In Testbeds B and D, outliers seemed to affect the PCA result probably due to the small number of samples, whereas the PCA result was still consistent with site characteristics. This study result indicates that the PCA is widely applicable to hydrochemical data for the assessment of major hydrochemical processes in contamination sites, which is useful for site characterization when combined with other site characterization technologies, e.g., geological survey, geophysical investigation, borehole logging. It is suggested that PCA is applied in contaminated sites to interpret hydrochemical data not only for the distribution of contamination levels but also for the assessment of major hydrochemical processes and contamination sources.

셀레늄으로 개질된 영가철을 이용한 과황산 활성화 속도 조절 및 활성종 전달율 향상에 관한 연구 (Control of Persulfate Activation Rate and Improvement of Active Species Transfer Rate Using Selenium-modified ZVI)

  • 권희원;박해성;황인성;김정진;김영훈
    • 한국환경과학회지
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    • 제32권1호
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    • pp.57-65
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    • 2023
  • The advanced oxidation treatment using persulfate and zero-valent iron (ZVI) has been evaluated as a very effective technology for remediation of soil and groundwater contamination. However, the high rate of the initial reaction of persulfate with ZVI causes over-consumption of an injected persulfate, and the excessively generated active species show a low transfer rate to the target pollutant. In this study, ZVI was modified using selenium with very low reactivity in the water environment with the aim of controlling the persulfate activation rate by controlling the reactivity of ZVI. Selenium-modified ZVI (Se/ZVI) was confirmed to have a selenium coating on the surface through SEM/EDS analysis, and low reductive reactivity to trichlroethylene (TCE) was observed. As a result of inducing the persulfate activation using the synthesized Se/ZVI, the persulfated consumption rate was greatly reduced, and the decomposition rate of the model contaminant, anisole, was also reduced in proportion. However, the final decomposition efficiency was rather increased, which seems to be the result of preventing persulfate over-consumption. This is because the transfer efficiency of the active species (SO4-∙) of persulfate to the target contaminant has been improved. Selenium on the surface of Se/ZVI was not significantly dissolved even under oxidation conditions by persulfate, and most of it was present in the form of Se/ZVI. It was confirmed that the persulfate activation rate could be controlled by controlling the reactivity of ZVI, which could greatly contribute to the improvement of the persulfate oxidation efficiency.

Estimating anaerobic reductive dechlorination of chlorinated compounds in groundwater by indigenous microorganisms

  • Park, Sunhwa;Kim, Deok Hyun;Yoon, JongHyun;Kwon, JongBeom;Choi, Hyojung;Kim, Ki-In;Han, Kyungjin;Kim, Moonsu;Shin, Sun-Kyoung;Kim, Hyun-Koo
    • Membrane and Water Treatment
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    • 제13권2호
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    • pp.85-95
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    • 2022
  • Tetrachloroethylene (PCE) and trichloroethylene (TCE), critical pollutants to human health and groundwater ecosystems, are managed by groundwater quality standards (GQS) in South Korea. However, there are no GQSs for their by-products, such as cis-dichloroethylene (DCE) and vinyl chloride (VC) produced through the dechlorination process of PCE and TCE. Therefore, in this study, we monitored PCE, TCE, cis-DCE, and VC in 111 national groundwater wells for three years (2016 to 2018) to evaluate their distributions, a biological dechlorination possibility, and human risk assessment. The detection frequency of them was 30.2% for PCE, 45.1% for TCE, 43.9% for cis-DCE and 13.4% for VC. The four chlorinated compounds were commonly detected in 21 out of 111 wells. In the results of statistical analysis with 21 wells data, DO and ORP also had a negative correlation with four organic chlorinated compounds, while EC and sulfate has a positive correlation with the compounds. This indicates that the 21 wells were relatively met with suitable environments for a biological dechlorination reaction compared to the other wells. Finally, cis-DCE had a non-carcinogenic risk of 10-1 and the carcinogenic risk of VC was 10-6 or higher. Through this study, the distribution status of the four chlorinated compounds in groundwater in South Korea and the necessity of preparing plans to manage cis-DCE and VC were confirmed.

보이차(Pu-erh tea)의 항산화 효과 (Antioxidant activities of Pu-erh tea)

  • 소은미;정은주;신장철;김성현;백순옥;김영만;김일광
    • 분석과학
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    • 제19권1호
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    • pp.39-44
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    • 2006
  • 보이차를 물로 추출하고, 항산화성 물질을 얻기위해 n-hexane, ethyl acetate(EA), butanol(BuOH)로 분획하였다. 분획은 자유라티칼 소거 활성과 환원력 측정의 두가지 방법으로 항산화활성 정도를 조사하였다. 이들 항산화활성을 butylated hydroxyanisole(BHA), butylated hydroxytoluene(BHT) 그리고 ${\alpha}$-tocopherol 같은 비교표준 항산화제와 비교하였다. 보이차의 EA분획은 BHA와 BHT 보다 더 높은 항산화활성을 보였다.