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Unusual Fluorescence Spectroscopic Properties of 9-Anthrylethylene Derivatives : Photoisomerization

  • 최정권;Mahipal A. Reddy;윤민중
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.973-980
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    • 1998
  • The fluorescence spectroscopic properties of both trans and cis forms of 9-anthryiethylene derivatives such as 9-AnthCH=$CHCO_2CH_3$ [Ⅰ] and 9-AnthCH=CHCN [Ⅱ] as well as 9-AnthCH=>TEX>$CHCH_2O_2CCH_3$ [Ⅲ] and 9-AnthCH=$CHCH_2OH$ [Ⅳ] have been measured in various solvents. In nonpolar solvent, the trans-I and trans-Ⅱ show dual emission spectral bands at 340 nm and 460 nm when exciting with 270 nm while the other trans derivatives show single emission band at 430 or 460 nm. The dual emissions exhibit different excitation spectra, indicating that two emissive states are different from each other. It is interesting to note that the 340 nm emission of both trans-Ⅰ and trans-Ⅱ is enhanced at the expense of the drastic quenching of the 460 nm emission as the solvent polarity increases. The dual emissions are also observed for both cis-Ⅰ and cis-Ⅱ. The solvent dependence of the fluorescence decay times and quantum yields can be correlated with the solvent and excitation wavelength dependences of the trans→cis photoisomerization quantum yields. These results indicate that the 340 nm emission is originated from the $S_2$ state of the cis-form, and the $S_1$ state is the only singlet excited state presenting a large CT (charge transfer) character to facilitate the photoisomerization.

Theoretical Studies on the Hydrogen Atom Transfer Reaction (Ⅱ)$^*$

  • Lee, Ik-Choon;Song, Chang-Hyun;Lee, Byung-Choon
    • Bulletin of the Korean Chemical Society
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    • v.6 no.6
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    • pp.362-366
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    • 1985
  • The hydrogen atom transfer reaction between substituted methane, $CH_3X,$ and its radical, $CH_2X(X=H,F,CH_3,CN,OH\;and\;NH_2$ was studied by MINDO/3 method. The transition state(TS) structure and energy barriers were determined and variation of the transition state and of the reactivity due to the change of X were analyzed based on the potential energy surface characteristics. It was found that the greater the radical stabilization energy. the looser the TS becomes; the TS occurs at about 15% stretch of the C-H bond, which becomes longer as the radical stabilization energy of $CH_2X$ increasers. The intrinsic barrier, ${\Delta}E*_{x.x},$ of the reaction with X was found to increase in the order $H The degree of bond stretch of the C-H bond stretch of the C-H bond at the TS also had the same order indicating that the homolytic bond cleavage of the C-H bond is rate-determining. Orbital interactions at the TS between LUMO of the fragment $C{\ldots}H{\ldots}C$ and the symmetry adapted pair of nonbonding, $n{\pm}(=n_1{\pm}n_2),$ or pi orbitals of the two X atoms were shown to be the dominant contribution in determining tightness or looseness of the TS. The Marcus equation was shown to apply to the MINDO/3 barriers and energy changes of the reaction.

Phase Equilibria and $^{13}C$ NMR Analysis of the Double Semi-Clathrates Containing TBAB (TBAB를 포함하는 혼합 하이드레이트의 상평형 및 $^{13}C$ NMR 분석)

  • Lee, Seung-Min;Park, Sung-Min;Lee, Young-Jun;Lee, Sung-Won;Seo, Yong-Won
    • Korean Chemical Engineering Research
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    • v.49 no.3
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    • pp.367-371
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    • 2011
  • TBAB (tetra-n-butyl ammonium bromide) forms a semi-clathrate with water under atmospheric pressure conditions and recently has attracted great attention due to its usage as a thermodynamic promoter in gas storage and separation process using gas hydrate formation. In this study, we measured the three-phase (hydrate (H) - liquid water ($L_{w}$)-vapor (V)) equilibria of the ternary $CH_{4}$+TBAB+water and $CO_{2}$+TBAB+water mixtures at the TBAB concentrations of 5 and 32 wt% to investigate promoting characteristics of TBAB. The greater promotion effect of TBAB was observed at 32 wt% than at 5 wt%. This result was in good agreement with that from pure TBAB semi-clathrate phase diagram under atmospheric pressure conditions. Through $^{13}C$ NMR analysis of the $CH_{4}$+TBAB semi-clathrate, it was found that $CH_{4}$ molecules are enclathrated in the cages of the double semi-clathrate and the position of resonance peak from encaged $CH_{4}$ molocules in the double semi-clathrate is the same as that from encaged $CH_{4}$ molocules in the pure $CH_{4}$ hydrate of structure I.

Effect of Herbal-acupuncture with Chaenomelis Fructus Solution at the Joksamni($ST_{36}$) of Mice with Collagen-induced Aarthritis (목과(木瓜) 약침(藥鍼)이 Collagen-induced Arthritis 억제 및 면역조절에 미치는 영향)

  • Shin, Dong-Soo;Kim, Young-Il;Lee, Hyun
    • Journal of Acupuncture Research
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    • v.24 no.3
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    • pp.127-143
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    • 2007
  • Objectives : The purpose of this study was to observe the effects of Chaenomelis Fructus herbal-acupuncture solution (ChF-HAS) at the Joksamni ($ST_{36}$) on arthritis induced by Collagen II in mice. Methods : The author performed several experimental items. The severity of arthritis, changes of mouse weight, size of the spleen and the degree of stenosis, changes of cytokine level, IgG, IgM and anti-collagen II, changes of immunocyte count, histological changes of the CIA mouse joint were analyzed and the conclusions are as follows. Results: 1. In the ChF-HA, the arthritis index, the incidence of arthritis, the degree of joint edema was significantly decreased. 2. In the ChF-HA, weight, spleen size and stenosis rate was low and maintained as the normal group was. 3. In the ChF-HA, cytokine level, IgG, IgM and anti-collagen II were significantly decreased. 4. In the ChF-HA, on changes of immunocyte count were maintained to the levels of normal group. 5. In histological changes of the CIA mouse joint, the cartilage destruction and synovial cell proliferation were decreased. Conclusions: These results suggest that ChF-HA at the $ST_{36}$ has an important role to control the immune reactions and suppress inflammatory response on the collagen induced rheumatoid arthritis. This study can be a significant supporting evidence that ChF-HA is chosen to be the principal therapy for clinical practice of the rheumatoid arthritis in the future.

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Conjugation of Cyclohexane Metabolite in Liver Damaged Rats

  • Joh, Hyun-Sung;Yoon, Chong-Guk
    • Biomedical Science Letters
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    • v.12 no.4
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    • pp.361-370
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    • 2006
  • To evaluate an effect of pathological liver damage on the conjugation of cyclohexane metabolites, rats were pretreated with 50% $CCl_4$ dissolved in olive oil (0.1 ml/100 g body weight) 10 or 17 times intraperitoneally at intervals of every other day. On the basis of liver function, the animals pretreated with $CCl_4$ 10 times were identified as acutely liver damaged ones and the animals pretreated with $CCl_4$ 17 times were identified as severly liver damaged ones. To these liver damaged animals, cyclohexane (a single dose of 1.56 g/kg body weight, i.p.) was administered at 48 hr after the last injection of $CCl_4$. The rats were sacrificed at 4 or 8 hr after injection of cyclohexane. The cyclohexane metabolites, cyclohexanol (CH-ol), cyclohexane-1,2-diol (CH-1,2-diol), cyclohexane-1,4-diol (CH-1,4-diol), and their glucuronyl conjugates and cyclohexanone were detected in the urine of cyclohexane treated rats. The urinary concentration of cyclohexane metabolites was generally more increased in liver damaged animals than normal ones, and the increasing rate was higher in $CCl_4$ 17 times injected rats than 10 times injected ones. And liver damaged.ats, especially $CCl_4$ 17 times treated ones, had an enhanced ability of glucuronyl conjugation to CH-ol analogues compared with normal group. Futhermore, CH-1,2 and 1,4-diol were all conjugated with glucuronic acid in $CCl_4$ 17 times injected animals. On the other hand, the increasing rate of activities of hepatic cytochrome P450 dependent aniline hydroxylase, alcohol dehydrogenase and urine diphosphate glucuronyl transferase was higher in 17 times $CCl_4$-treated rats compared with normal and $CCl_4$ 10 times injected animals. Taken all together, it is assumed that an increased urinary excretion amount of cyclohexane metabolites in liver damaged rats might be caused by an increase in the activities of cyclohexane metabolizing enzymes. And enhanced conjugating ability of CH-ol in liver damaged animals and novel finding of conjugating form of CH-1,2 and 1,4-diol might be caused by increase in the activity of hepatic diphosphouridine glucuronyltransferase.

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A study for behavior analysis of rockfish (Sebastes inermis) corresponding to the LED light by image analysis (영상분석을 통한 LED 광원에 대한 볼락 (Sebastes inermis)의 행동 연구)

  • HEO, Gyeom;KIM, Min-Son;SHIN, Hyeon-Ok
    • Journal of the Korean Society of Fisheries and Ocean Technology
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    • v.52 no.2
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    • pp.96-102
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    • 2016
  • In order to establish the basic data for the active use of the LED light source in the aquaculture industry, the experiment about the behavior of rockfish (Sebastes inermis) corresponding to the LED light was conducted by image analysis. LED lights for the experiment were one red light (wave length: 622 nm; light power: 811 mW) and two green lights (wave length: 518 nm; light power: 648 mW, wave length: 518 nm; light power: 810 mW). Behavior of the rockfish was analyzed using a moving distance (MD5) for 5 minutes where MD5s during the period of feeding were 20.0 m, 19.6 m, 16.3 m and 20.5 m in the ch1, ch2, ch3 and ch4. At the sunrise, mean MD5 of the entire channel about right before and right after were 6.3 m and 8.2 m. At the sunrise, mean MD5s of the entire channel about right before and right after were 13.6 m and 12.0 m. In the ch1, ch2 and ch3, mean MD5s during the period of 24 hours were 13.2 m, 9.6 m and 6.8 m at experiment 1and 5.2 m, 3.8 m and 2.9 m in the experiment 2.

The Effect of the Oxygen-Enrichment on the PAH Production in Fuel-Rich $CH_4/CH_3Cl$ Premixed Flames (과농조건인 $CH_4/CH_3Cl$ 예혼합화염에서 산소부화가 PAH 생성에 미치는 효과)

  • Lee, Ki-Yong
    • Journal of the Korean Society of Combustion
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    • v.15 no.4
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    • pp.9-14
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    • 2010
  • Numerical simulations of freely propagating fuel-rich $CH_4/CH_3Cl$ premixed flames were performed at atmospheric pressure in order to understand the effect of the oxygen enrichment on the production of PAH. A chemical kinetic mechanism was used, which involved 157 gas-phase species and 1693 forward reactions. The calculated flame speeds were compared with the experiments for the flames established on the equivalence ratios of 1~1.6, the results of which were in good agreement. As the level of oxygen enrichment was increased, the concentrations of one or four ring aromatic hydrocarbons were decreased. This might cause the fact that the contribution of PAH species to soot was weakened.

Effects of Acrylonitrile and Acrylamide on Nitrile Hydratase Action of Brevibacterium sp. CH1 and CH2

  • Lee, Cheo-Young;Hwang, Jun-Sik;Chang, Ho-Nam
    • Journal of Microbiology and Biotechnology
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    • v.1 no.3
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    • pp.182-187
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    • 1991
  • The effects of acrylonitrile and acrylamide on the enzyme action of nitrile hydratase of Brevibacterium sp. CH1 and CH2 strains used for the biotransformations of nitriles were studied. The excessive substrate (acrylonitrile) and product (acrylamide) inhibited the enzyme activity competitively. In comparison with 0.2 mol/l of CH1 strain, the substrate inhibition of CH2 strain began to appear only at a high acrylonitrile concentration of 0.91 mol/l. In a packed bed reactor, dispersed plug flow model was proposed and this model was proved to be valid by the experiment. Also acrylamide productivity decreased sharply when acrylamide concentration in the substrate solution exceeded 20% (wt/v).

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Synthesis of Cubic Cu2O from Organic-Inorganic Hybrid (유기-무기 혼성화합물로 부터 정육면체 Cu2O 합성)

  • Heo, Yeong-Deok;Song, Ha-Cheol;Guk, Won-Geun
    • Journal of the Korean Chemical Society
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    • v.50 no.1
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    • pp.60-64
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    • 2006
  • has been synthesized using the layered organic-inorganic hybrids, Cu2(OH)3(CH3COO)·H2O as a precursor. Cubic Cu2O is synthesized by reducing Cu2(OH)3(CH3COO)·H2O with glucose in water at 75oC. The effects of precursor and glucose are investigated. The structure of Cu2(OH)3(CH3COO)·H2O plays an important role in preparing the uniform size of Cu2O.

Nucleophilic Substitutions at a Carbonyl Carbon Atom (ⅩⅡ). Solvolysis of Methylchloroformate and Its Thioanalogues in $CH_3CN-H_2O$ and $CH_3COCH_3-H_2$ Mixtures (카르보닐탄소원자의 친핵성 치환반응 (제 12 보).아세토니트릴-물 및 아세톤-물 혼합용 매속에서 메틸클로로훠메이트와 그 티오유도체들의 가용매분해반응에 관한 연구)

  • Sangmoo La;Kyeong Shin Koh;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.8-14
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    • 1980
  • Solvolysis rate constants for methylchloroformate, $CH_3O$(CO)Cl, methylthiono-chloroformate, $CH_3O$(CS)Cl, and methylthiolchloroformate, $CH_3S$(CO)Cl, have been determined conductometrically in acetone-water and acetonitrile-water mixtures, and activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, have been derived. Results show that in water-rich regions the order of rate increases as $$CH_3O(CO)Cl while in dipolar aprotic solvent-rich region this order reverses. The plots of log k vs. solvent parameters, Y, $\frac{D-1}{2D+1}$ and log($H_2$) show that the order of rate increase in water-rich region is the results of increase in $S_N1$ character. It is concluded that $CH_3S$(CO)Cl solvolyzes via $S_N1$ mechanism whereas $CH_3O$(CO)Cl reacts via $S_N2$ and $CH_3O$(CS)Cl via intermediate mechanism in water-rich region.

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