• Title/Summary/Keyword: Reductive

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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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    • v.20 no.1
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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.

Deflationism and Nonreductionism (수축주의와 비환원주의)

  • Lee, Jong-Wang
    • Journal of Korean Philosophical Society
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    • v.105
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    • pp.75-94
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    • 2008
  • In philosophy of mind, both reductionism and deflationism claim that the problem of mental causation is overstated, but the reason why they claim that way is quite different. On the one hand, for deflationism, since the problem of mental causation is bogus problem we need to focus on epistemology or scientific explanation rather than metaphysics. On the other hand, although the proponents of nonreductionism seem to think of the principles of causal closure of the physical and causal exclusion proposed by Jaegwon Kim as tenable, they do not go with the reductive approach to the problem of mental causation. Instead they stay with the concept of supervenience to overcome mental causation problem that, reductionists think, leads us to the dilemma situation. Of course, deflationists do not think that supervenience is plausible not as much as supervenience physicalists think that it is. If so, in what way and how do deflationists regard the problem of mental causation as a bogus problem? In this paper, I shall examine the most plausible response to mental causation problem, the contemporary version of mind-body problem by critically discussing and clarifying matters concerning the problem.

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

  • Yoon, Geun Seok;Yoo, Jong Chan;Ko, Sung-Hwan;Shim, Myung-Ho;Cho, Myung-Hyun;Baek, Kitae
    • Journal of Soil and Groundwater Environment
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    • v.22 no.4
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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.

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

  • Kwon, O-Zoon;Kim, Jieun;Park, Se-Min;Kim, Keun-Sik;Yoon, Soon-Do
    • Applied Chemistry for Engineering
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    • v.30 no.4
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    • pp.509-511
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    • 2019
  • Hydrazine derivatives used in fine chemicals, pharmaceuticals and cosmetics can be synthesized by reduction reaction from diazonium derivatives. The reduction method using $SnCl_2$ facilitates the reaction conversion, but the use of $SnCl_2$ is limited when residual heavy metals are issued in the final product. For the conversion of protected (2-hydroxyphenyl)diazonium derivatives into its hydrazine derivatives in Ramalin preparation process, the reduction method was developed by using $NaHSO_3$. In this study, the effect of steric hindrance according to the protected 2-hydroxygroupinphenyldiazonium derivatives was found, and linear C1~C5 alkyl groups for the hydroxy protection were preferable during the diazonium reduction reaction. Considering the economical efficiency and industrial production for the preparation of Ramalin, a variety of protecting groups were investigated. As a result, 2-(allyloxyphenyl)hydrazine was obtained with 85% yield and 99.7% purity when the hydroxy protecting group was used as an allyl group that could be easily deprotected.

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

  • Jeong, Sangjo
    • Journal of Korean Society on Water Environment
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    • v.34 no.6
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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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    • v.31 no.7
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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.

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

  • Yu, Soonyoung;Kim, Han-Suk;Jun, Seong-Chun;Yi, Jong Hwa;Yun, Seong-Taek;Kwon, Man Jae;Jo, Ho Young
    • Journal of Soil and Groundwater Environment
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    • v.27 no.spc
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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.

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

  • Hee-won Kwon;Hae-Seong Park;In-seong Hwang;Jeong-Jin Kim;Young-Hun Kim
    • Journal of Environmental Science International
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    • v.32 no.1
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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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    • v.13 no.2
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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.

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

  • So, Eun Mee;Jung, Eun Joo;Shin, Chang Chul;Kim, Sung Hyun;Baek, Soon Ok;Kim, Young Man;Kim, Il Kwang
    • Analytical Science and Technology
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    • v.19 no.1
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    • pp.39-44
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    • 2006
  • Puh-erh tea was extracted with water and then fractionated sequentially with n-hexane, ethyl acetate, n-butanol to find antioxidative compounds. The fractions were examined on the antioxidant activity using two different methods, free radical scavenging activity measurement and reductive potential. Those antioxidant activities were compared to standard antioxidants such as butylated hydroxyanisole(BHA), butylated hydroxytoluene (BHT), and ${\alpha}$-tocopherol. EA fraction of Pu-erh tea was showed excellent antioxidative activities over BHA and BHT.