• 제목/요약/키워드: reaction pathway

검색결과 545건 처리시간 0.023초

Kinetic Study on SNAr Reaction of 1-Y-Substituted-phenoxy-2,4-dinitrobenzenes with Hydroxide Ion: Effect of Substituent Y on Reactivity and Reaction Mechanism

  • Kang, Tae-Ah;Cho, Hyo-Jin;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제35권7호
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    • pp.2135-2138
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    • 2014
  • A kinetic study is reported for the SNAr reaction of 1-Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1h) with OH- in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The second-order rate constant ($k_{OH^-}$) increases as the substituent Y in the leaving group changes from an electron-donating group (EDG) to an electronwithdrawing group (EWG). The Br${\o}$nsted-type plot for the reactions of 1a-1h is linear with ${\beta}_{lg}$ = -0.16, indicating that the reactivity of substrates 1a-1h is little affected by the leaving-group basicity. A linear Br${\o}$nsted-type plot with ${\beta}_{lg}=-0.3{\pm}0.1$ is typical for reactions reported previously to proceed through a stepwise mechanism in which formation of a Meisenheimer complex is the rate-determining step (RDS). The Hammett plot correlated with ${\sigma}_Y{^{\circ}}$ constants results in a much better correlation than that correlated with ${\sigma}_Y{^-}$constants, implyng that no negative charge is developing on the O atom of the leaving group (or expulsion of the leaving group is not advanced at all in the TS). This excludes a possibility that the $S_NAr$ reaction of 1a-1h with $OH^-$ proceeds through a concerted mechanism or via a stepwise pathway with expulsion of the leaving group being the RDS. Thus, the current reactions have been concluded to proceed through a stepwise mechanism in which expulsion of the leaving group occurs rapidly after the RDS.

항장요법(肛腸療法)에 의한 단삼추출액(丹蔘抽出液)의 알레르기반응 억제효과(抑制效果) (Inhibitory Effects of Allergic Reaction of Aqueous Extract of Salviae Radix Root by Anal Therapy)

  • 조정연;문석재;문구;원진희;김형민
    • 대한한의학회지
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    • 제20권1호
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    • pp.11-21
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    • 1999
  • Dansam, the root of Salvia miltiorrhiza BGE. (Labiatae), has a bitter and a slightly 'cold' property. and is nontoxic. It has been used for the treatment of diseases such as tumors, bruises, gynecologic diseases, menoxenia, anemia and so forth. As an oriental medicine pathway, anal therapy has many kinds of treatments, Retention enema is one the most useful, advantageous methods of anal therapy. This experiment was performed in order to study the effect of an aqueous extract of Salviae radix root(SRRAE) on Immediate type allergic reaction by Retention enema. The results were obtained as follows, 1. SRRAE inhibited compound 48/80-induced Immediate type allergic reaction 100% with the dose of 0.1g/kg by anal treatment. However, SRRAE showed no significant inhibitory effect on the same reaction by oral treatment. When mice were pretreated with SRRAE at a concentration ranging from 0.001 to 1.0g/kg, by intra-anal treatment, the serum histamine levels were reduced in a dose-dependent manner. 2. SRRAE also inhibited by 79.8% local cutaneous allergic reaction activated by anti-dinitrophenyl (DNP) IgE. 3. SRRAE close-dependently inhibited the histamine release from rat peritoneal mast cells(RPMC) by anti-DNP IgE., but SRRAE not inhibited compound 48/80-induced histamine release. 4. SRRAE dose-dependently inhibited tumor necrosis $factor-\;{\alpha}$ $(TNF-\;{\alpha}$) production from RPMC by anti-DNP IgE. Moreover, the level of cAMP in RPMC, when SRRAE was added, significantly increased compared with that of a normal control. According to the above results, anal therapy(Retention enema) of SRRAE may be beneficial in the treatment of systemic and local Immediate type allergic reactions.

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Panax ginseng-derived fraction BIOGF1K reduces atopic dermatitis responses via suppression of mitogen-activated protein kinase signaling pathway

  • Lorz, Laura Rojas;Kim, Donghyun;Kim, Mi-Yeon;Cho, Jae Youl
    • Journal of Ginseng Research
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    • 제44권3호
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    • pp.453-460
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    • 2020
  • Background: BIOGF1K, a fraction of Panax ginseng, has desirable antimelanogenic, anti-inflammatory, and antiphotoaging properties that could be useful for treating skin conditions. Because its potential positive effects on allergic reactions in skin have not yet been described in detail, this study's main objective was to determine its efficacy in the treatment of atopic dermatitis (AD). Methods: High-performance liquid chromatography was used to verify the compounds in BIOGF1K, and we used the (3-4-5-dimethylthiazol-2-yl)-2-5-diphenyltetrazolium bromide method to determine its cytotoxicity in RBL-2H3 and HMC-1 cell lines. RBL-2H3 cells were induced using both anti-DNP-IgE/DNP-BSA and calcium ionophore (A2187) treatments, whereas HMC-1 cells were induced using A2187 alone. To measure mast cell degranulation, we performed histamine (enzyme-linked immunosorbent assay) and β-hexosaminidase assays. To quantify interleukin (IL)-4, IL-5, and IL-13 levels in RBL-2H3 cells, we performed quantitative polymerase chain reaction (PCR); to quantify expression levels of IL-4 and IL-13 in HMC-1 cells, we used semiquantitative reverse transcription polymerase chain reaction (RT-PCR). Finally, we detected the total and phosphorylated forms of extracellular signal-regulated kinase, p-38, and c-Jun N-terminal kinase proteins by immunoblotting. Results: BIOGF1K decreased the AD response by reducing both histamine and β-hexosaminidase release as well as reducing the secretion levels of IL-4, IL-5, and IL-13 in RBL-2H3 cells and IL-4 and IL-13 in HMC-1 cells. In addition, BIOGF1K decreased MAPK pathway activation in RBL-2H3 and HMC-1 cells. Conclusions: BIOGF1K attenuated the AD response, hence supporting its use as a promising and natural approach for treating AD.

He와 Ar으로 희석된 합성가스 화염에서 루이스 수와 선호확산효과 (Effects of Lewis Number and Preferential Diffusion in Syngas Flame Diluted with He and Ar)

  • 김태형;박정;권오붕;박종호
    • 한국연소학회지
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    • 제19권4호
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    • pp.28-34
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    • 2014
  • Numerical study is conducted to grasp flame characteristics in $H_2/CO$ syngas counterflow diffusion flames diluted with He and Ar. An effective fuel Lewis number, applicable to premixed burning regime and even to moderately-stretched diffusion flames, is suggested through the comparison among fuel Lewis number, effective Lewis number, and effective fuel Lewis number. Flame characteristics with and without the suppression of the diffusivities of H, $H_2$, and He are compared in order to clarify the important role of preferential diffusion effects through them. It is found that the scarcity of H and He in reaction zone increases flame temperature whereas that of $H_2$ deteriorates flame temperature. Impact of preferential diffusion of H, $H_2$, and He in flame characteristics is also addressed to reaction pathways for the purpose of displaying chemical effects.

Degenerate Polymerase Chain Reaction을 통한 [NiFe]-Hydrogenase의 탐색 (Search for [NiFe]-Hydrogenase using Degenerate Polymerase Chain Reaction)

  • 정희정;김영환;차형준
    • 한국신재생에너지학회:학술대회논문집
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    • 한국신재생에너지학회 2005년도 제17회 워크샵 및 추계학술대회
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    • pp.631-633
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    • 2005
  • For biohydrogen production, hydrogenase is a key enzyme. In the present work we performed search of [NiFe]-hydrogenases from hydrogen producing microorganisms using degenerate polymerase chain reaction (PCR) strategy. Degenerate primers were designed from the conserved region of [NiFe]-hydrogenase group I especially on structural genes encoding for catalytic subunit of [NiFe]-hydrogenase from bacteria producing hydrogen. Most of [NiFe]-hydrogenase (group I) are expressed via complex mechanism with aid of auxiliary protein and localized through twin-arginine translocation pathway. [NiFe]-hydrogenase is composed of large and small subunits for catalytic activity. It is known that only small subunit has signal peptide for periplasmic localization and large & small subunitscome together before localization. During this process, large subunit is treated by endopeptidase for maturation. Based on these information we used signal peptide sequence and C-terminal of large subunit by recognized by endopeptidase as templates for degenerate primers. About 2,900 bp of PCR products were successfully amplified using the designed degenerate primers from genomic DNAs of several microorganisms. The amplified PCR products were inserted into T-vector and then sequenced to confirm.

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대향류 화염에서 $CO_2$ 재순환 산소부화연소의 NO 배출 특성 (NO Emission Characteristics of Oxygen-Enriched Combustion with $CO_2$ Recirculation in Counterflow Diffusion Flame)

  • 박준성;조한창;박정
    • 한국연소학회지
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    • 제12권1호
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    • pp.28-37
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    • 2007
  • Numerical study is conducted to grasp the flame structure and NO emissions for a wide range of oxy-fuel combustion (covering from air blown combustion to pure oxygen combustion) and for various mole fractions of recirculated $CO_2$ in $CH4-O_2/N_2/CO_2$ counterflow diffusion flames. Special concern is given to the difference of the flame structure and NO emissions between air blown combustion and oxy-fuel combustion w/o recirculated $CO_2$ and is also focused on chemical effects of recirculated $CO_2$. Air blown combustion and oxy-fuel combustion w/o recirculated $CO_2$ are shown to be considerably different in the flame structure and NO emissions. Modified fuel oxidation reaction pathways in oxygen-enriched combustion are provided in detail compared to those in air blown combustion w/o recirculated $CO_2$. The formation and destruction of NO through Fenimore and thermal mechanisms are also compared for air blown combustion and oxyegn-enriched combustion w/o recirculated $CO_2$, and the role of the recirculated $CO_2$ and its chemical effects are discussed. Importantly contributing reaction steps to the formation and destruction of NO are also estimated in oxygen-enriched combustion in comparison to air blown combustion.

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대기오염 물질 저감을 위한 저온 플라즈마 반응공정의 특성 (Characteristics of Non-Thermal Plasma Process for Air Pollution Control)

  • 송영훈;신동남;신완호;김관태;최연석;최영석;이원남;김석준
    • 한국대기환경학회지
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    • 제16권3호
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    • pp.247-256
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    • 2000
  • Basic characteristics of non-thermal plasma process to remove C2H4 and NO have been experimentally investigated with a packed-bed type reactor and an ac power supply. The performance of the non-thermal plasma generated by ac power supply was compared with that of a wire-plate type reactor equipped with a pulsed power supply. The result shows that the non-thermal plasma can be effectively generated with an AC power supply that can be easily fabricated with conventional techniques. In order to understand the basic reaction mechanisms of the non-thermal plasma process, parametric tests for different carrier gases(air and nitrogen) and for different reaction pathways have been performed. The test results show that O3 generated by non-thermal plasma plays an dominant role to oxidize C2H4 and NO over N and O radicals when these pollutant gases are carried by dry air under room temperature condition. Experimental observations, however, indicate that N and O radicals can significantly affect on the removal process of the pollutant gases under certain conditions.

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PET 말단에 대한 인계난연제의 라디칼계 부가반응 (1) - 비스페놀에이비스다이페닐포스페이트의 반응 - (Radical Addition Reaction of Phosphorous based Flame Retardant with End Groups of PET (1) - Reaction of Bisphenol A bis(diphenyl phosphate) -)

  • 김민관;김한도
    • 한국염색가공학회지
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    • 제24권1호
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    • pp.33-38
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    • 2012
  • In this study, to increase flame retardation of poly(ethylene terephthalate) (PET) in burning, bisphenol A bis(diphenyl phosphate) (BDP), a well known flame retardant containing phosphorous, was reacted on end groups of PET by radical pathway. End-capping mechanism of PET with BDP was suggested and confirmed by spectroscopic and thermal analysis. From 400 MHz $^{31}P$ solid state FT-NMR spectrum of end-capped PET (PET-BDP), phosphorus spectra peak in BDP was found at ca. -20 ppm. Furthermore, P-C bond stretching vibration peaks were found ca. $600cm^{-1}$ in FT-IR spectrums of PET-BDP. These results showed that BDP can be chemically added on end groups of PET by our method. Thermal characteristics of pure PET (pPET) and PET-BDP were measured and evaluated by TGA analysis. There was not significant changes in thermal characteristics of PET-BDP compared to that of pPET.

가동차 위치에 따른 인덕턴스 변화와 Push/Pull 효과를 고려한 가동코일형 LOA의 동특성 (Dynamic Characteristics of Moving Coil Linear Oscillatory Actuator Considering the Variable Inductance and Push/pull Effects)

  • 정상섭;장석명
    • 대한전기학회논문지:전기기기및에너지변환시스템부문B
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    • 제50권7호
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    • pp.307-314
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    • 2001
  • A moving coil linear oscillatory actuator is consisted of the NdFeB permanent magnets with high specific energy as the stator, a coil-wrapped nonmagnetic hollow rectangular structure and an iron core as a pathway for magnetic flux. The variation of mover position and the consequent changes of coil flux path affect the coil inductance, because coil flux leaks at the open region of LOA stator. The interaction between permanent magnet and armature field is to shift the airgap flux density variation due to the magnet alone by a certain amount. The unbalanced reciprocation force due to armature reaction field decreases the advantage of moving coil LOA, such as a high degree of linearity and controllability in the force ad motion control. This paper firstly describes the coil inductance, the deviation of flux density, and the unbalanced reciprocation force, which are derived form the permeance model of LOA. Secondly, the analytical method are verified using the 2D finite element method and tests. Finally, the dynamic simulation algorithm taking the armature reaction effect and variable inductance into account, is proposed and confirmed through the experiment.

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Synthesis of New 2-Thiouracil-5-Sulphonamide Derivatives with Antibacterial and Antifungal Activity

  • Fathalla O. A.;Awad S. M.;Mohamed M. S.
    • Archives of Pharmacal Research
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    • 제28권11호
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    • pp.1205-1212
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    • 2005
  • 2-Thiouracil-5-sulphonic acid N-(4-acetylphenyl) Amide (1) was reacted with a series of aromatic aldehydes giving chalcones 2 (Claisen-Schemidt reaction), some of these chalcones were reacted with urea and thiourea giving pyrimidine-2-one and pyrimidine-2 thione derivatives respectively of the type 3a,b and 4a,b. In addition many chalcones were reacted with hydroxylamine hydrochloride giving isoxazoline derivatives 5a,b. They could also reacted with phenylhydrazine to give pyrazoline derivatives 5a,b, chalcones also were reacted withethylcyano acetate and/or malononitryl in pyridine giving pyran derivatives 7a,c and 8a,c. In another pathway chalcones were epoxidised by $H_{2}O_{2}$ giving epoxides 9a,c which in turn were reacted with phenylhydrazine giving 4-hydroxypyrazoline derivatives 10a,c. In another reaction chalcones were reacted with ethylcyanoacetate in presence of amm.acetate giving pyridone derivatives 11a,d which could be prepared also in exellent yield from compound 1 by its reaction with certain aromatic aldehydes and ethylcyanoacetate in presence of ammonium acetate. Finally, compound 1 was reacted with semicarbazide giving semicarbazone intermediate 12 which in turn was reacted with thionyl chloride giving thiadiazole derivative 13. The biological effects of some of the new synthesized compounds were also investigated.