• Title/Summary/Keyword: Deprotonation

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Mechanism on the Formation of Bis-9,9'-thioxanthenylmethane from the Reaction of Thioxanthylium Ion With Dimethylmercury(I)

  • Kim, Sung-Hoon;Kim, Kyong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.3 no.4
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    • pp.157-162
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    • 1982
  • 9-Methylenethioxanthene(6) was synthesized and for the first time good mp and spectral data were taken. Reaction of (6) with thioxanthylium ion (1) in acetonitrile led to a carbenium addition adduct (8) which then was either attacked by a variety of nucleophiles subsequently added or underwent deprotonation reaction to give an olefin (13). From these reactions, was obtained bis-9,9'-thioxanthenylmethane (2). These results indicate clearly that (2) can be formed via (8) by accepting hydride. Isolation of (2) and (6) from the reaction of (1) with 9-methylthioxanthylium ion (18) also supports the involvement of (8) in the reaction of (1) with dimethylmercury. However, addition of thioxanthene radical (4) to (6) has not been ruled out.

Formation of Zn(II) Complexes of Physiological Buffer Amino alcohols in Aqueous Solution (수용액 중에서 생리학적 완충제 아미노 알코올과 Zn(II) 이온과의 착물 형성)

  • Hong, Kyung-Hee;Chun, Yong-Jin
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.16 no.11
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    • pp.7555-7563
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    • 2015
  • The complex formation from Zn(II) ion and 2-(2-hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol (Monotris), Bis(2-hydroxyethyl)imino-tris(hydroxymethyl)methane(Bistris) in aqueous solution at $25^{\circ}C$ and at an ionic strength of 0.10 M have been studied potentiometrically. For the Zn(II)-Monotris system, in the Monotris (L) complex $ZnL^{2+}$, one of the hydroxyl oxygen atoms as well as the amine nitrogen of the ligand are coordinated. In basic media, the coordinated hydroxyl group is deprotonated. For the Zn(II)-Bistris system, in the Bistris(L) complex $ZnL^{2+}$, two of the hydroxyl oxygen atoms as well as the amine nitrogen of the ligand are coordinated. In basic media, one of the coordinated hydroxyl groups is deprotonated. In very high basic media, an additional hydroxyl group undergoes deprotonation. The equilibrium constants for the formation of $ZnL^{2+}$, $ZnLH_{-1}{^+}$, $ZnLH_{-2}$, $Zn_2L_2H_{-2}{^{2+}}$ and $Zn_2L_2H_{-3}{^+}$ have been determined.

Adsorption Characteristics of Cd(II) and Cu(II) by Zeolites Synthesized from Hwangto (황토로부터 합성한 제올라이트에 의한 Cd(II) 및 Cu(II) 흡착특성)

  • 감상규;홍정연;허철구;이민규
    • Journal of Environmental Science International
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    • v.12 no.7
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    • pp.817-824
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    • 2003
  • Various kinds of zeolites, such as analcime (ANA), cancrinite (CAN), Na-Pl and sodalite octahydrate (SOD) could be synthesized from Hwangto by hydrothermal reaction in a high-pressure vessel. The adsorption characteristics of Cu(II) and Cd(II) by Hwangto and its synthetic zeolites were investigated using the chemical and electrochemical surface parameters of these adsorbents. The heavy metal adsorptivity among the adsorbents decreased in the following sequences: Na-Pl > SOD > ANA > CAN > Hwangto. This sequence was the same with the values of surface site density (Ns) of these adsorbents and was correlated inversely with the values of pHpzc (pH of the point of zero charge) and the va]ues of K$\_$a2/(int) (intrinsic surface deprotonation constant) of the adsorbents for synthetic zeolites, i.e., the adsorbents with higher values of Ns and with lower values of pHpzc and K$\_$a2/(int) for synthetic zeolites showed higher heavy metal adsorptivity. With increasing pH, the heavy metal adsorptivity increased greatly between pHpzc and pH 6 or 7 because of the steep increase of negatively charged sites for synthetic zeolites, but for Hwangto, it increased broadly because of slow increase of negatively charged sites based on its lower surface sites.

Hydrolytic Behavior of Vinylsulfonyl Reactive Dyes - Easiness of Dimerization -

  • Kim, In Hoi
    • Textile Coloration and Finishing
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    • v.27 no.1
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    • pp.1-10
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    • 2015
  • The aim of the current study is to identify the dimerization and decomposition kinetics of the F-$D_M$ type. The regeneration of F-VS from $F_iF_j-D_M$ or the reversibility of the dimerizations were investigated. The order of real rate constants of the dimerization('$K_D{^{ij}}$) would seem to be similar to that of rate constants of a dimerization($K_D{^{ij}}$) for VS dyes at a given pH because of the constancy of the equilibrium constants($K_a{^j}$-value). The reverse reactions of the $D_M$ types are appeared to occur in two steps, the deprotonation of ${\alpha}$-carbon of the $D_M$ types and disproportionation. The ratio of the decomposition of the $D_M$ type to F-Hy and F-VS appears to be related with the ratio of $K_i/K_j$. Similarities were also found among various other reactions, including homo- and mixed dimerization. VS dyes undergoing fast hydrolysis have difficulty in forming a dimer. The higher the reactivity with cellulose or hydroxide ion, the smaller the dimerization. The easiness of the dimerization was thus found to be inversely proportional to the rate of hydrolysis.

Dyeing Properties of Nylon Fabric with Reactive Dyes Having Different Reactive Group

  • Lee, Byung-Sun;Lee, Jin-Ah;Lee, Kwon-Sun;Park, Jong-Ho;Kim, Sung-Dong
    • Textile Coloration and Finishing
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    • v.18 no.5 s.90
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    • pp.1-7
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    • 2006
  • The dyeing properties of the several reactive dyes possessing different types of the reactive group on nylon 6 fabric have been investigated. Dyeing of nylon fiber with commercial reactive dyes was dependent on the dye bath pH. As pH increased, the extent of exhaustion decreased due to the deprotonation of the amino end group. But, the extent of fixation increased because of the enhanced reactivity with nylon fiber. It was found that all reactive dyes could be applied to nylon 6 reasonably at pH 5-6. But, the conflicting requirements of dye exhaustion and covalent bond formation limited the extent of fixation efficiency. The best method to improve the extent of the fixation efficiency of the reactive dyes was the conversion of sulphatoethylsulphone group to vinylsulphone group before dyeing with trisodium phosphate. The converted Supra type reactive dye gave the highest extent of fixation efficiency, which was about 90%.

Effect of Humidity on Polymorphic Transformation of Hydrous Aluminum Oxide (알루미나수화물(水和物)의 결정전이(結晶轉移)에 미치는 습도(濕度)의 영향(影響))

  • Rhee, Gye-Ju;Yoo, Byeong-Tae
    • Journal of Pharmaceutical Investigation
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    • v.13 no.1
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    • pp.1-9
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    • 1983
  • The effect of humidity on crystallization and polymorphic transformation of hydrous aluminum oxide under various humidity at $37^{\circ}$ was examined by means of X-ray diffraction, scanning electron micrograph, IR spectra and DTA. The humidity was an important factor influencing crystallization of hydrous aluminum oxide. The growth or crystal was strongly accelerated by humidity. The aging process is assumed that it is composed of two seperate steps, an increase of the diffraction around $36{\sim}42^{\circ}$, and an appearance and its development of the peak at $18{\sim}20^{\circ}$ of $2{\theta}$ value. The former is considered to be nucleation and the latter correspond to the growth period on crystallization. The crystalline form of aging products was various depending on the degree of humidity, directly it leads to the eventual formation of bayerite in more than 72%, $b{\"{o}}hmite$ in 50% and resembled to Nordstandite in 0% relative humidity, respectively but once formed, it was mostly stable in each surroundings and does not transform to the other more stable form in solid state even after aging for five years. The mechanism responsible for aging is further polymerization process of six-membered rings by deprotonation-dehydration reaction in which positively charged polynuclear hydroxy aluminum complexes formed in the presence of moisture are joined at their edges by double hydroxide bridges.

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Electrochemical Characteristics of Ruthenium Oxide Electrode-Organic Electrolyte System (유기전해액에서 루테늄산화물 전극의 전기화학적 특성)

  • Doh, Chil-Hoon;Choi, Sang-Jin;Moon, Seong-In;Yun, Mun-Soo;Yug, Gyeong-Chang;Kim, Sang-Gil
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2002.07b
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    • pp.1125-1128
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    • 2002
  • Electrochemical capacitor made with metal oxide electrode uses rapid and reversible protonation/deprotonation of metal oxide material under the aqueous acidic solution, generally. Electrochemical stability window of aqueous electrolyte-type capacitor is narrow compared to that of organic electrolyte-type capacitor. Electrochemical characteristics of electrochemical capacitor made with metal oxide electrode and lithium cation based organic electrolyte were evaluated. Electrochemical capacitor based on $RuO_2$ electrode material and 1M $LiPF_6$ in mixed solvents of EC, DEC, and EMC has anodic and cathodic specific capacitance of 145 and 142 F/g-$RuO_2{\cdot}nH_2O$, respectively, by using cyclic voltammetry with scan rate of 2 mV/sec g-$RuO_2$ in potential range of 2.0~4.2V(Li|$Li^+$).

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Kinetic Study on Aminolysis of 4-Nitrophenyl Isonicotinate in Acetonitrile: Effect of Amine Basicity on Reactivity and Reaction Mechanism

  • Shin, Minah;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.7
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    • pp.2130-2134
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    • 2014
  • A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl isonicotinate (7) with a series of cyclic secondary amines in MeCN. The plots of $k_{obsd}$ vs. [amine] curve upward for the reactions with weakly basic amines (e.g., morpholine, 1-(2-hydroxyethyl)piperazine, and piperazine) but are linear for those with strongly basic amines (e.g., piperidine and 3-methylpiperidine). The curved plots for the reactions with the weakly basic amines are typical for reactions reported previously to proceed through uncatalyzed and catalyzed routes with two intermediates (e.g., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). In contrast, the linear plots for the reactions with the strongly basic amines indicate that the catalytic route (i.e., the deprotonation process to yield $T^-$ from $T^{\pm}$ by a second amine molecule) is absent. The Br${\o}$nsted-type plots for $Kk_2$ and $Kk_3$ (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) exhibit excellent linear correlations with ${\beta}_{nuc}$ = 0.99 and 0.69, respectively. The effect of amine basicity on the reaction mechanism is discussed in detail.

Effects of Salts on the Conformation and Catalytic Properties of D-Amino Acid Aminotransferase

  • Ro, Hyeon-Su
    • BMB Reports
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    • v.35 no.3
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    • pp.306-312
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    • 2002
  • The effects of salts on the biochemical properties of D-amino acid aminotransferase from Bacillus sp. YM-1 have been studied to elucidate both the inhibitory effects of salts on the activity and the protective effects of salts on the substrate-induced inactivation. The results from UV-visible spectroscopy studies on the reaction of the enzyme with D-serine revealed that salt significantly reduced the rate of the formation of the quinonoid intermediate and its accumulation. The kinetic and spectroscopy studies of the reaction with $\alpha$-[$^2H$]-DL-serine in different concentrations of NaCl provided evidence that the rate-limiting step was changed from the deprotonation of the external aldimine to another step(s), presumably to the hydrolysis of the ketimine. Gel filtration chromatography data in the presence of NaCl showed that the enzyme volume was reduced sharply with the increasing NaCl concentration, up to 100 mM. An additional increase of the NaCl concentration did not affect the elution volume, which suggests that the enzyme has a limited number of salt-binding groups. These results provide detailed mechanistic evidence for the way salts inhibit the catalytic activity of D-amino acid aminotransferase.

Thermo- and Acid/base-induced Spectral Switching of a Poly(N-isopropylacrylamide) Copolymer Containing Benzopyran-based D-π-A type Dye Units

  • Lee, Eun-Mi;Gwon, Seon-Yeong;Ji, Byung-Chul;Kim, Sung-Hoon
    • Textile Coloration and Finishing
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    • v.22 no.3
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    • pp.181-186
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    • 2010
  • A thermoresponsive poly(NIPAM-co-dye) labeled with benzopyran-based D-$\pi$-A type dye was prepared by typical radical copolymerization. It can be also constructed a acid/base-induced molecular switch by modulation of intramolecular charge transfer with protonation/deprotonation. The lower critical solution temperature behavior was investigated by means of UV-vis spectroscopy which allows the measurement of the phase transition from $25^{\circ}C$ to $45^{\circ}C$ in aqueous DMSO solution. The morphology of the internal microstructure of the poly(NIPAM-co-dye) hydrogel was observed by scanning electron microscopy. The reversible switch could be obtained by thermal and acid/base stimuli.