• Title/Summary/Keyword: Radical reaction position

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Syntheses and Iron(II) Induced Reactions of Phenyl-Substituted 1,2,4-Trioxanes

  • 오창호;Gary H. Posner
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.644-648
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    • 1997
  • Introduction of an alkyl substituent at the $C_{4\beta}$ position of antimalarial trioxanes has caused them to become more active in their antimalarial activity. We have designed a structurally simple 4β-phenyl substituted trioxane (3) as an active antimalarial since it can form a more stable carbon radical when reacting with ferrous bromide. The trioxane 3 has been prepared along with the corresponding isomer 4 according to the previously reported procedure. The synthesized trioxanes 3 and 4 were finally separated by using HPLC and assigned their stereochemistry by spectroscopy and X-ray crystallography. Their antimalarial activities were surprisingly low. The low activity was then rationalized based on the product distribution of the ferrous ion induced reaction of these trioxanes. These trioxanes with ferrous bromide did not produce any detectable amount of the corresponding $C_4$-hydroxylated product, consistent with the fact that neither $C_{4\beta}$-phenyl substituted nor $C_{4\alpha}$-phenyl substituted trioxane has any antimalarial activity. It implies that a $C_4$ substituent of antimalarial trioxanes has to stabilize an adjacent carbon-centered radical in a specific stability range in order to show a good antimalarial activity. This study, combined with related studies, could help develop more potent antimalarial trioxanes.

Mechanistic Studies on the Reaction of Thioxanthylium Ion with Dimedone (티오크잔틸이움 이온과 디메돈의 반응메카니즘에 관한 연구)

  • Kwang Hyun Ahn;Kyongtae Kim
    • Journal of the Korean Chemical Society
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    • v.26 no.2
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    • pp.107-113
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    • 1982
  • Addition of dimedone to thioxanthylium ion generated from the oxidation of thioxanthene by thianthrene cation radical perchlorate in acetonitrile gave 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthylium perchlorate (2), whereas from the reverse addition between two reactants was obtained initially 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthene (1), which then underwent further reaction to give 2. The compound 2 was readily deprotonated in aq acetone to give 9-(4,4-dimethylcyclohexane-2,6-dionylidene)thioxanthene (3). However, 3 turned out to be in equilibrium with 2 in which three isosbestic points at 219, 289, and 348 nm were recorded in aq acetonitrile. The intensity and the position of the maximum absorption of 3 near 380 nm vary depending on the solvents which has been explained in terms of the solvent-solute interactions.

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Enhancement of OH Radical Generation of Dielectric Barrier Discharge Plasma Gas Using Air-automizing Nozzle (이류체 노즐을 이용한 유전체장벽방전 플라즈마 가스의 OH 라디칼 생성 향상)

  • Park, Young-Seek
    • Journal of Environmental Science International
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    • v.27 no.8
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    • pp.621-629
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    • 2018
  • Many chemically active species such as ${\cdot}H$, ${\cdot}OH$, $O_3$, $H_2O_2$, hydrated $e^-$, as well as ultraviolet rays, are produced by Dielectric Barrier Discharge (DBD) plasma in water and are widely use to remove non-biodegradable materials and deactivate microorganisms. As the plasma gas containing chemically active species that is generated from the plasma reaction has a short lifetime and low solubility in water, increasing the dissolution rate of this gas is an important challenge. To this end, the plasma gas and water within reactor were mixed using the air-automizing nozzle, and then, water-gas mixture was injected into water. The dissolving effect of plasma gas was indirectly confirmed by measuring the RNO (N-Dimethyl-4-nitrosoaniline, indicator of the formation of OH radical) solution. The plasma system consisted of an oxygen generator, a high-voltage power supply, a plasma generator and a liquid-gas mixing reactor. Experiments were conducted to examine the effects of location of air-automizing nozzle, flow rate of plasma gas, water circulation rate, and high-voltage on RNO degradation. The experimental results showed that the RNO removal efficiency of the air-automizing nozzle is 29.8% higher than the conventional diffuser. The nozzle position from water surface was not considered to be a major factor in the design and operation of the plasma reactor. The plasma gas flow rate and water circulation rate with the highest RNO removal rate were 3.5 L/min and 1.5 L/min, respectively. The ratio of the plasma gas flow rate to the water circulation rate for obtaining an RNO removal rate of over 95% was 1.67 ~ 4.00.

Isolation of a Natural Antioxidant, Dehydrozingerone from Zingiber officinale and Synthesis of lts Analogues for Recognition of Effective Antioxidant and Antityrosinase Agents

  • Kuo, Ping-Chung;Damu, Amooru G.;Cherng, Ching-Yuh;Jeng, Jye-Fu;Teng, Che-Ming;Lee, E-Jian;Wu, Tian-Shung
    • Archives of Pharmacal Research
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    • v.28 no.5
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    • pp.518-528
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    • 2005
  • In the present study, the antioxidative and inhibitory activity of Zingiber officinale Rosc. Rhizomes-derived materials (on mushroom tyrosinase) were evaluated. The bioactive co mponents of Z. officinale rhizomes were characterized by spectroscopic analysis as zingerone and dehydrozingerone, which exhibited potent antioxidant and tyrosinase inhibition activities. A series of substituted dehydrozingerones [(E)-4-phenyl-3-buten-2-ones] were prepared in admirable yields by the reaction of appropriate benzaldehydes with acetone and the products were evaluated in terms of variation in the dehydrozingerone structure. The synthetic analogues were examined for their antioxidant and antityrosinase activities to probe the most potent analogue. Compound 26 inhibited Fe$^{2+}$-induced lipid peroxidation in rat brain homogenate with an IC$_{50}$ = 6.3${\pm}$0.4 ${\mu}$M. In the 1,1-diphenyl- 2-picrylhydrazyl (DPPH) radical quencher assay, compounds 2, 7, 17, 26, 28, and 29 showed radical scavenging activity equal to or higher than those of the standard antioxidants, like ${\alpha}$-tocopherol and ascorbic acid. Compound 27 displayed superior inhibition of tyrosinase activity relative to other examined analogues. Compounds 2, 17, and 26 exhibited non-competitive inhibition against oxidation of 3,4- dihydroxyphenylalanine (L-DOPA). From the present study, it was observed that both number and position of hydroxyl groups on aromatic ring and a double bond between C-3 and C-4 played a critical role in exerting the antioxidant and antityrosinase activity.

Formation and Inhibition of Cholesterol Oxidation Products (COPs) in Foods; An Overview (식품 내 콜레스테롤 산화 생성물(COPs)의 생성 및 억제; 개요)

  • Joo-Shin Kim
    • Journal of the Korean Applied Science and Technology
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    • v.40 no.5
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    • pp.1163-1175
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    • 2023
  • Cholesterol is prone to oxidation, which results in the formation of cholesterol oxidation products (COPs). This occurs because it is a monounsaturated lipid with a double bond on C-5 position. Cholesterol in foods is mostly non-enzymatically oxidized by reactive oxygen species (ROS)-mediated auto-oxidative reaction. The COPs are found in many common foods of animal-origin and are formed during their manufacture process. The formation of COPs is mainly related to the temperature and the heating time the food is processed, storage condition, light exposure and level of activator present such as free radical. The level of COPs in processed foods could reach up to 1-10 % of the total cholesterol depending on the foods. The most predominant COPs in foods including meat, eggs, dairy products as well as other foods of animal origin were 7-ketocholesterol, 7 α-hydroxycholesterol (7α-OH), 7β-hydroxycholesterol (7β-OH), 5,6α-epoxycholesterol (5,6α-EP), 5,6β-epoxycholesterol (5,6β-EP), 25-hydoxycholesterol (25-OH), 20-hydroxycholesterol (20-OH) and cholestanetriol (triol). They are mainly formed non-enzymatically by cholesterol autoxidation. The COPs are known to be potentially more hazardous to human health than pure cholesterol. The procedure to block cholesterol oxidation in foods should be similar to that of lipid oxidation inhibition since both cholesterol and lipid oxidation go through the same free radical mechanism. The formation of COPs in foods can be stopped by decreasing heating time and temperature, controlling storage condition as well as adding antioxidants into food products. This review aims to present, discuss and respond to articles and studies published on the topics of the formation and inhibition of COPs in foods and key factors that might affect cholesterol oxidation. This review may be used as a basic guide to control the formation of COPs in the food industry.

A Study on Blend Effect of Fuel in Flame Spread Along An One-Dimensional Droplet Array (일차원 액적 배열의 화염 퍼짐에 있어서 연료의 혼합 효과에 관한 연구)

  • Park, Jeong;Kobayashi, Hideaki;Niioka, Takashi
    • Journal of the Korean Society of Combustion
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    • v.3 no.2
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    • pp.1-11
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    • 1998
  • Experimental investigation on flame spread of blended fuel droplet arrays has been conducted for droplet diameters of 1.0mm and 0.75mm using high-speed chemiluminescence images of OH radical. The flame spread rate is measured with blended fuel composition, droplet diameter, and droplet spacing. Flame spread is categorized into two: a continuous mode and an intermittent one. There exist a limit droplet spacing, above which flame does not spread, and a droplet spacing of maximum flame spread, which is closely related to flame diameter. It is seen that flame spread rate is mainly dependent upon the relative position of flame zone within a droplet spacing. In case of large droplet, the increase of % volume of Heptane induces the shift of limit droplet spacing to a larger spacing since volatile Heptane plays a role of an enhancer of flame spread rate. In case of small droplet, the increase of % volume of Heptane leads to the shift of limit droplet spacing to a smaller droplet spacing. This is so because of the delayed chemical reaction time by the rapid increase of mass flux of fuel vapor for small droplet.

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The Graft Polymerization of Acrylic Acid in Vapour Phase onto Poly(ethylene terephthalate) by Cold Plasma Part (I) (저온 Plasma를 이용한 Poly(ethylene terephthalate)에의 Acrylic Acid의 기상 Graft 공중합 반응(I))

  • 천태일;최석철;모상영
    • Textile Coloration and Finishing
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    • v.1 no.1
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    • pp.7-18
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    • 1989
  • The distinguishing characteristic of the glow discharge is that chemical reaction induced by partially ionized gases are limited only to the substrate surface. Most studies have been done on the plasma etching and polymerization. The graft polymerization in vapour phase by cold plasma has been rarely investigated. In this study the system of tub3ar reaction chamber with capacitively coupled electrode of alternative current of 60 Hz was employed for the graft polymerization. The graft polymerization of Acylic Acid(AA) onto the poly (ethylene terephthalate) (PET) was carried out by treatment of PET film and fabric by cold plasma (glow discharge of argon gas), followed by the supply of AA vapour. The graft yield was about 1 wt%. The surface property was determined by contact angle, the surface tension was evaluated by zisman’s plot and equation of surface tension mesurement. The results were as follows: 1. In order to obtain lower contact angle, it was effective to avoid the vicinity of electrodes for a setting position of substrate. 2. Contact angle affected on the monomer pressure and its duration of exposure to the acid vapour. 3. Polymer radical formation was influenced by the changes of the value of current density and plasma treatment time. 4. Total surface tension of plasma grafted PET film increased. With an increase in the carboxylic acid content, the dispersion force decreased, while, the polar force and hydrogen bonding force increased. 5. The contact angle decreased from $75^\circ$ to around $30^\circ$ by plasma grafting. There was no ageing effect on the contact angle after 4 months.

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A Study on the Ozone Consumption Rate for Drinking Water Treatment Process with Ozone Application (오존의 정수처리 적용을 위한 오존소비인자에 관한 연구)

  • Kang, Tae-Hee;Oh, Byung-Soo;Kwon, Soon-Buhm;Sohn, Byeong-Yong;Kang, Joon-Wun
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.6
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    • pp.663-669
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    • 2005
  • The aim of this study was to investigate the ozone decay pattern for the effective application of ozone in drinking water treatment. In order to measure the ozone decomposition in water, ozone measuring instrument was developed with flow injection analysis (FIA) method. From the result of continuous residual ozone concentration in water, it was confirmed that the ozone decay pattern was divided with instantaneous ozone demand(I.D) and pseudo first-order rate($k_c$) phases, which were influenced by the variation of ozone dose. The empirical model obtained from I.D and $k_c$ values enabled us to predict the residual ozone concentration according to the reaction time, showing the high correlation between model and experimental values. The concentration of OH radical and $R__{ct}$ could be indirectly measured by OH radical probe compound. In both I.D and $k_c$ phases, the production pattern of OH radical could be observed, which was also affected by the variation of ozone dose. Finally, it was confirmed that the ozone consumption rate was varied according to the each drinking water treatment process and seasoning. Therefore, the optimum position and dosage of ozone have to be selected by considering various factors.

Effects of Oxygen Enrichment on the Structure of Premixed Methane/Fluorinated Compound Flames (메탄-불소계 화합물의 예혼합화염 구조에서 산소 부화의 효과)

  • Lee, Ki-Yong
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.35 no.8
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    • pp.839-845
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    • 2011
  • We performed numerical simulations of freely propagating premixed flames at atmospheric pressure to investigate the influence of trifluoromethane on $CH_4/O_2/N_2$ flames under oxygen enrichment. Trifluoromethane significantly contributed toward a reduction in flame speed, the magnitude of which was larger in terms of the physical effect than the chemical effect. More trifluoromethane could be added and consumed on oxygen-enriched $CH_4/O_2/N_2$ flames. $CHF_3$ was decomposed primarily via $CF_3{\rightarrow}CF_2{\rightarrow}CF{\rightarrow}CF:O{\rightarrow}CO$ and $CHF_3+M{\rightarrow}CF_2+HF+M$ played an important role in oxygen-enhanced flames. When an inhibitor was added to oxygen-enriched flames, the position of the maximum concentration of active radicals was shifted to a relatively low temperature range, and the net rate of OH became higher than that of H.

Synthesis and pesticidal activity of ricinine derivatives (Ricinine 유도체(誘導體)의 합성(合成) 및 농약활성(農藥活性))

  • Kwon, Oh-Kyung;Lim, Soo-Kil;Hong, Su-Myeong;Lee, Sung-Eun;Kyung, Suk-Hun
    • The Korean Journal of Pesticide Science
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    • v.2 no.1
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    • pp.24-31
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    • 1998
  • Chemical derivative synthesis of ricinine, an active compound of Ricinus communis which showed high mortality against brown planthopper (Nilaparvata lugens), was performed to improve its pesticidal activity and the toxicity of 12 synthetic derivatives against major insect pests and phytopathogenic fungi were examined. Carbamate derivatives of ricinine could be synthesized from the precursor of ricinine, chloronorricinine and norricinine, whereas the derivatives were not synthesized from chlororicinic acid and ricinic acid having ketone group of pyridine ring. In organophosphates, reaction with oxon type of phosphate gave better yield than thiono type. Among the organophosphate derivatives of ricinine, thiono type of derivative structure gave $96.3%{\sim}100%$ mortality of the brown planthopper and the two-spotted spider mite (Tetranychus urticae) at 500 ${\mu}g/ml$ level. On the other hand, carbamate derivatives did not show insecticidal activity. In the fungicidal activity of ricinine derivatives, the derivative having amino radical at the 2 position of ricinine gave 85 to 100% of mycelium growth inhibition effect against ten major plant pathogens at the 200 ${\mu}g/ml$ level. In particular, the control value of the derivative on the rice blast (Pyricularia grisea) and barley powdery mildew (Erysiphe graminis) at the 250 ${\mu}g/ml$ level in vivo under greenhouse conditions was 92% and 96%, respectively.

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