• Title/Summary/Keyword: intermediates

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Rice 7-Hydroxymethyl Chlorophyll a Reductase Is Involved in the Promotion of Chlorophyll Degradation and Modulates Cell Death Signaling

  • Piao, Weilan;Han, Su-Hyun;Sakuraba, Yasuhito;Paek, Nam-Chon
    • Molecules and Cells
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    • v.40 no.10
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    • pp.773-786
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    • 2017
  • The loss of green coloration via chlorophyll (Chl) degradation typically occurs during leaf senescence. To date, many Chl catabolic enzymes have been identified and shown to interact with light harvesting complex II to form a Chl degradation complex in senescing chloroplasts; this complex might metabolically channel phototoxic Chl catabolic intermediates to prevent oxidative damage to cells. The Chl catabolic enzyme 7-hydroxymethyl Chl a reductase (HCAR) converts 7-hydroxymethyl Chl a (7-HMC a) to Chl a. The rice (Oryza sativa) genome contains a single HCAR homolog (OsHCAR), but its exact role remains unknown. Here, we show that an oshcar knockout mutant exhibits persistent green leaves during both dark-induced and natural senescence, and accumulates 7-HMC a and pheophorbide a (Pheo a) in green leaf blades. Interestingly, both rice and Arabidopsis hcar mutants exhibit severe cell death at the vegetative stage; this cell death largely occurs in a light intensity-dependent manner. In addition, 7-HMC a treatment led to the generation of singlet oxygen ($^1O_2$) in Arabidopsis and rice protoplasts in the light. Under herbicide-induced oxidative stress conditions, leaf necrosis was more severe in hcar plants than in wild type, and HCAR-overexpressing plants were more tolerant to reactive oxygen species than wild type. Therefore, in addition to functioning in the conversion of 7-HMC a to Chl a in senescent leaves, HCAR may play a critical role in protecting plants from high light-induced damage by preventing the accumulation of 7-HMC a and Pheo a in developing and mature leaves at the vegetative stage.

Synthesis of Optically pure Epichlorohydrine using Dimeric Chiral Salen Catalyst Containing BF3 (BF3 함유 이분자형 키랄 살렌 촉매에 의한 고광학순도의 에피클로로히드린 합성)

  • Lee, Kwang-Yeon;Rahul, B. Kawthekar;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.18 no.4
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    • pp.330-336
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    • 2007
  • In this study, new dinuclear chiral Co (salen) complexes bearing $BF_3$ have been synthesized and their properties as the asymmetric catalyst have been examined. The NMR, UV and ESCA analyses were performed to determine the structure of synthesized catalysts. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of various terminal epoxides by hydrolytic kinetic resolution technology. The easily prepared dimeric complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ nucleophile, providing enantiomerically enriched terminal epoxides (> 99 %ee). The dimeric structured chiral salen showed remakablely enhanced reactivity and may be employed substantially lower loadings than its monomeric analogues, and in addition no racemization happened during the separation of product epoxides. The system described in this work is very efficient for the sinthesis of chiral epoxide and 1,2-diol intermediates.

Evaluation of the Antioxidant Potential and ldentification of Active Principles of Solanum nigrum L. on Antioxidant Defense Systems (까마중내 (Solanum nigrum L.) 항산화방어계의 항산화력 및 물질의 동정)

  • 임종국;정규영;정형진
    • Journal of Life Science
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    • v.11 no.6
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    • pp.509-516
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    • 2001
  • Enzymes and non-enzymatic antioxidants are involved in defense of oxgen free radical intermediates in all aerobic cells. The non -enzymatic antioxidants and antioxidant enzyme from the extracts of Solanum nigrum L. known to be anticancer medicinal plant were examined in other to utilize the discovery in natural products as cancer chem-opereventive agents. The DPPH(1,1-diphenyl-2-picryl-hydrazyl) free radical scavening activity on plant position of Solanum nigrum L. was the highest in root, with stem, whole plant, seed, leaf and flower, at higher activities respectively. In extraction methods, the DPPH free radical scavenging activity by circulating extraction with 80 % MeOH. The DPPH activity of L6 fraction by LH-20 column chromatography showed about 6.7 times higher than that of ethyl acetate-fraction. These were identified as phenolic compounds such as 2-6-methano-3-benzazocin-11-ol, 2[1H]-phyidinethione and 2-hydroxy -5-methyl-benzaldehyde. Peroxidase(POD) and superoxide dismutase(SOD) activities of stem and root were higher than that of other plant positions and those of plant positions according to growing stage were the highest in 60 days after seeding. The numbers of isozyme pattern of POD and SOD showed 10 hands and 5 bands, respectively, especially, 8 bands of POD and 3 bands of SOC showed a difference according to plant positions.

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An Electrochemical Reduction of TiO2 Pellet in Molten Calcium Chloride (CaCl2 용융염에서 TiO2 펠렛의 전기화학적 환원반응 특성)

  • Ji, Hyun-Sub;Ryu, Hyo-Yeol;Jeong, Ha-Myung;Jeong, Kwang-Ho;Jeong, Sang-Mun
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.10 no.2
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    • pp.97-104
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    • 2012
  • A porous $TiO_2$ pellet was electrochemically converted to the metallic titanium by using a $CaCl_2$ molten salt system at $850^{\circ}C$. Ni-$TiO_2$ and graphite electrodes were used as cathode and anode, respectively. The electrochemical behaviour of $TiO_2$ pellet was determined by a constant voltage control electrolysis. Various reaction intermediates such as $CaTiO_3$, $Ti_2O$ and $Ti_6O$ were observed by XRD analysis during electrolysis of the pellet. Once $TiO_2$ pellet was converted to a porous metallic structure, the porous structure disappeared by sintering and shrinking with increasing the reaction time at high temperature.

Photocatalytic activity of $TiO_2$ on nano-diamond powder prepared by Atomic Layer Deposition

  • Kim, Kwang-Dae;Dey, Nilay Kumar;Seo, Hyun-Ook;Kim, Dong-Wun;Nam, Jong-Won;Sim, Chae-Won;Jeong, Myung-Geun;Kim, Young-Dok
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.425-425
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    • 2011
  • The photocatalytic decomposition of toluene gas was investigated with $TiO_2$ on nano-diamond powder (NDP) under UV irradiation. Atomic layer deposition (ALD) was used for the growth of $TiO_2$ on the NDP. The structure and surface properties of catalysts were characterized by X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM). The photocatalytic activity for the toluene decomposition was evaluated by measuring the concentration change of toluene and $CO_2$ gas with gas chromatography (GC)-flame ionization detector (FID) system. The photocatalytic activities of $TiO_2$/NDP catalysts were compared with that of P-25. The rate of initial photocatalytic decomposition of toluene for the $TiO_2$/NDP catalysts was relatively lower when compared to P-25. The photocatalytic activity of P-25 was rapidly decreased with time, whereas, the deactivation of $TiO_2$/NDP catalysts was less pronounced. Therefore, as the reaction time increased, the photocatalytic activity of $TiO_2$/NDP catalysts became higher than that of P-25. The intermediates such as benzaldehyde or benzoic acid, etc were more easily adhered to the active site on the P-25 surface during reaction, resulting in easier deactivation of P-25. These results could be confirmed using FT-IR spectroscopy. We suggest that the NDP used as substrate can reduce the deactivation of $TiO_2$ on the surface.

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Development of the Efficient Synthetic Route for Itraconazole Antifungal Agent (이트라코나졸 항진균제의 효과적인 합성법 개발)

  • Baek, Du-Jong
    • Applied Chemistry for Engineering
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    • v.17 no.6
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    • pp.633-637
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    • 2006
  • In this study, the efficient large-scale synthetic route for itraconazole, triazole antifungal agent, was developed. The original synthetic route for medicinal chemistry reported by Janssen Pharmaceutica was linear (14 linear steps) starting from 2,4-dichloroacetophenone with the total yield of 1.4%, and potential hazardous materials such as methanesulfonyl chloride ($CH_{3}SO_{2}Cl$), hydrogen gas, and sodium hydride (NaH) were used. Furthermore, the expensive 1-acetyl-4-(4-hydroxyphenyl)piperazine and palladium were used in this medicinal chemistry route, thus the manufacturing cost would be practically high. In order to improve the commercial route, we developed the process of 12 step convergent synthesis combining two intermediates which are roughly halves of itraconazole with the total yield of 12.0%, and hazardous materials and expensive reagents were excluded in this process, thus the manufacturing cost could be cut down to a great extent.

Impurity profiling and chemometric analysis of methamphetamine seizures in Korea

  • Shin, Dong Won;Ko, Beom Jun;Cheong, Jae Chul;Lee, Wonho;Kim, Suhkmann;Kim, Jin Young
    • Analytical Science and Technology
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    • v.33 no.2
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    • pp.98-107
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    • 2020
  • Methamphetamine (MA) is currently the most abused illicit drug in Korea. MA is produced by chemical synthesis, and the final target drug that is produced contains small amounts of the precursor chemicals, intermediates, and by-products. To identify and quantify these trace compounds in MA seizures, a practical and feasible approach for conducting chromatographic fingerprinting with a suite of traditional chemometric methods and recently introduced machine learning approaches was examined. This was achieved using gas chromatography (GC) coupled with a flame ionization detector (FID) and mass spectrometry (MS). Following appropriate examination of all the peaks in 71 samples, 166 impurities were selected as the characteristic components. Unsupervised (principal component analysis (PCA), hierarchical cluster analysis (HCA), and K-means clustering) and supervised (partial least squares-discriminant analysis (PLS-DA), orthogonal partial least squares-discriminant analysis (OPLS-DA), support vector machines (SVM), and deep neural network (DNN) with Keras) chemometric techniques were employed for classifying the 71 MA seizures. The results of the PCA, HCA, K-means clustering, PLS-DA, OPLS-DA, SVM, and DNN methods for quality evaluation were in good agreement. However, the tested MA seizures possessed distinct features, such as chirality, cutting agents, and boiling points. The study indicated that the established qualitative and semi-quantitative methods will be practical and useful analytical tools for characterizing trace compounds in illicit MA seizures. Moreover, they will provide a statistical basis for identifying the synthesis route, sources of supply, trafficking routes, and connections between seizures, which will support drug law enforcement agencies in their effort to eliminate organized MA crime.

Nitration of Chlorobenzenes with NO2-O3 (이산화질소-오존을 이용한 클로로벤젠들의 니트로화 반응)

  • Lee, Bon-Su;Chung, Kyoo-Hyun;Lee, Won-Heui;Kim, Young-Su;Kim, Tae-Hyoung
    • Applied Chemistry for Engineering
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    • v.7 no.3
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    • pp.530-535
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    • 1996
  • Nitrochlorobenezenes are used as intermediates for dyes, pharmaceuticals and perfumes. By far the most common industrial nitration process employs a mixture of nitric acid and sulfuric acid. Due to water formed in the reaction, the mixed acid nitration requires subsequent separation of spent acid, mainly dilute sulfuric acid. In the stream of ozone, nitrogen dioxide can be used as a nitrating agent for the nitration of chlorobenzene. With 6eq of $NO_2$ and 1.0eq/hr of ozone flow, the mononitration of chlorobenzene ended within 3hr at $0^{\circ}C$ while the dinitration of chlorobenzene did in 12hr. This method can be employed for the nitration of some aromatic compounds to reduce pollutants from the present mixed-acid process.

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Techno-Economic Analysis of Methanol to Olefins Separation Processes (메탄올을 이용한 올레핀 생산 분리공정의 기술 및 경제성 분석)

  • Park, Jonghyun;Jeong, Youngmin;Han, Myungwan
    • Korean Chemical Engineering Research
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    • v.58 no.1
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    • pp.69-83
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    • 2020
  • Light olefins are important petrochemicals as well as primary building blocks for various chemical intermediates. As the number of ethane cracking center (ECC) process, in which ethylene accounts for most of the production, has increased in recent years, propylene supply is not catching up with steadily increasing propylene demand. This trend makes the conversion of methanol to olefins to get more industrial importance. The methanol to olefins (MTO) process produces methanol through syngas and obtain olefins such as propylene through methanol. Since the reaction from methanol to olefins provides different product compositions depending on the catalyst used for the reaction, it is important to choose an appropriate separation process for the reaction product with different composition. Four different separation processes are considered for four representative cases of product compositions. The separation processes for the reaction products are evaluated by techno-economic analysis based on the simulation results using Aspen plus. Guidelines are provided for selecting a suitable separation process for each of representative case of product compositions in the MTO process.

Thermal Development from Hybrid Gels of Compounds for Use in Fibre-Reinforced Oxide Ceramics

  • MacKenzie, Kenneth J.D.;Kemmitt, Tim;Meinhold, Richard H.;Schmucker, Martin;Mayer, Lutz
    • The Korean Journal of Ceramics
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    • v.4 no.4
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    • pp.323-330
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    • 1998
  • Mixed oxide compounds of potential usefulness for fibre coatings (hexagonal celsian, $BaAl_2Si_2O_8$ and lanthanum hexaluminate, $LaAl_{11}O_{18}$) or for matrix materials (yttrium aluminium garnet, $Y_3Al_5O_{12}$) were prepared by hybrid sol-gel synthesis and their thermal crystallisation was monitored by thermal analysis, X-ray diffraction and multinuclear solid state MAS NMR. All the gels convert to the crystalline phase below about $12200^{\circ}C$, via amorphous intermediates in which the Al shows and NMR resonance at 36-38 ppm sometimes ascribed to Al in 5-fold coordination. Additional information about the structural changes during thermal treatment was provided by $^{29}Si$, $^{137}Ba$ and $^{89}Y$ MAS NMR spectroscopy, showing that the feldspar framework of celsian begins to be established by about $500^{\circ}C$ but the Ba is still moving into its polyhedral lattice sites about $400^{\circ}C$ after the sluggish onset of crystallization. Lanthanum hexaluminate and YAG crystallise sharply at 1230 and $930^{\circ}C$ respectively, the former via $\gamma-Al_2O_3$, the latter via $YAlO_3$. Yttrium moves into the garnet lattice sites less than $100^{\circ}C$ after crystallisation.

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