• Title/Summary/Keyword: Kinetic Constant

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Adsorption of Arsenic on Goethite (침철석(goethite)과 비소의 흡착반응)

  • Kim, Soon-Oh;Lee, Woo-Chun;Jeong, Hyeon-Su;Cho, Hyen-Goo
    • Journal of the Mineralogical Society of Korea
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    • v.22 no.3
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    • pp.177-189
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    • 2009
  • Iron (oxyhydr)oxides commonly form as secondary minerals of high reactivity and large surface area resulting from alteration and weathering of primary minerals, and they are efficient sorbents for inorganic and organic contaminants. Accordingly, they have a great potential in industrial applications and are also of substantial interest in environmental sciences. Goethite (${\alpha}$-FeOOH) is one of the most ubiquitous and stable forms of iron (oxyhydr)oxides in terrestrial soils, sediments, and ore deposits, as well as a common weathering product in rocks of all types. This study focused on adsorption reaction as a main mechanism in scavenging arsenic using goethite. Goethite was synthesized in the laboratory to get high purity, and a variety of mineralogical and physicochemical features of goethite were measured and related to adsorption characteristics of arsenic. To compare differences in adsorption reactions between arsenic species, in addition, a variety of experiments to acquire adsorption isotherm, adsorption edges, and adsorption kinetics were accomplished. The point of zero charge (PZC) of the laboratory-synthesized goethite was measured to be 7.6, which value seems to be relatively higher, compared to those of other iron (oxyhydr)oxides. Its specific surface area appeared to be $29.2\;m^2/g$ and it is relatively smaller than those of other (oxyhydr)oxides. As a result, it was speculated that goethite shows a smaller adsorption capacity. It is likely that the affinity of goethite is much more larger for As(III) (arsenite) than for As(V) (arsenate), because As(III) was observed to be much more adsorbed on goethite than As(V) in equivalent pH conditions. When the adsorption of each arsenic species onto goethite was characterized in various of pH, the adsorption of As(III) was largest in neutral pH range (7.0~9.0) and decreased in both acidic and alkaline pH conditions. In the case of As(V), the adsorption appeared to be highest in the lowest pH condition, and then decreased with an increase of pH. This peculiarity of arsenic adsorption onto goethite might be caused by macroscopic electrostatic interactions due to variation in chemical speciation of arsenic and surface charge of goethite, and also it is significantly affected by change in pH. Parabolic diffusion model was adequate to effectively evaluate arsenic adsorption on goethite, and the regression results show that the kinetic constant of As(V) is larger than that of As(III).

Expression and Purification of the Phosphatase-like Domain of a Voltage-Sensing Phosphatase, Ci-VSP (막 전위 감지 탈인산화 효소, Ci-VSP의 유사 탈인산화 효소 도메인의 발현과 정제)

  • Kim, Sung-Jae;Kim, Hae-Min;Choi, Hoon;Kim, Young-Jun
    • Journal of Life Science
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    • v.21 no.7
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    • pp.1032-1038
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    • 2011
  • Recently identified Ciona intestinalis voltage sensor-containing phosphatase (Ci-VSP) consists of an ion channel-like transmembrane domain (VSD) and a phosphatase-like domain. Ci-VSP senses the change of membrane potential by its VSD and works as a phosphoinositide phosphatase by its phosphatase domain. In this study, we present the construction of His-tagged phosphatase-like domain of Ci-VSP, its recombinant expression and purification, and its enzymatic activity behavior in order to examine the biochemical behavior of phosphatase domain of Ci-VSP without interference. We found that Ci-VSP(248-576)-His can be eluted with an elution buffer containing 25 mM NaCl and 100 mM imidazole during His-tag purification. In addition, we found the proper measurement condition for kinetics study of Ci-VSP(248-576)-His against p-nitrophenyl phosphate (pNPP). We measured the kinetic constant of Ci-VSP(248-576)-His at $37^{\circ}C$, pH 5.0 or 5.5, under 30 min of reaction time, and less than $2.0\;{\mu}g$ of protein amount. With these conditions, we acquired that Ci-VSP(248-576)-His has $K_m$ of $354{\pm}0.143\;{\mu}M$, $V_{max}$ of $0.0607{\pm}0.0137\;{\mu}mol$/min/mg and $k_{cat}$ of $0.359{\pm}0.009751\;min^{-1}$ for pNPP dephosphorylation. Therefore, we produced a pure form of Ci-VSP(248-576)-His, and this showed a higher activity against pNPP. This purified protein will provide the road to a structural investigation on an interesting protein, Ci-VSP.

Effect of Phenolic Mediators and Humic Acid on the Removal of 1-Indanone Using Manganese Oxide (망간산화물(Birnessite)을 이용한 1- Indanone 제거 시 페놀계 반응매개체와 휴믹산(HA) 영향 평가)

  • Choi, Chan-Kyu;Eom, Won-Suk;Shin, Hyun-Sang
    • Journal of Korean Society of Environmental Engineers
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    • v.34 no.7
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    • pp.445-453
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    • 2012
  • An investigation for removal of 1-indanone (1-ID), which were commonly produced from the biological and/or chemical treatment and natural weathering of the PAHs-contaminated soils, via oxidative transformation mediated by birnessite in the presence of various phenolic mediators is described. This study also examines the potential effect of the natural occurring substance humic acid (HA) on the oxidative transformation. The experiment was carried out in aqueous phase as a batch test (10 mg/L 1-ID, 0.3 mM phenolic mediators, $1.0g/L\;{\delta}-MnO_2$, at pH 5). All of the 11 tested phenoilic mediators belong to the group of natural occurring phenols and are widely used as model constituents of humic substances. From the results of HPLC analysis, it is demonstrated that 1-ID was not reactive to birnessite itself, but it can be effectively removed in birnessite-mediated cross coupling reactions in the presence of the phenolic mediators. The percent removals of 1-ID after 2 day incubation were ranged from 9.2 to 71.2% depending on the phenolic mediators applied. The initial rate constant ($K_{int}$, $hr^{-1}$) values for the 1-ID removals obtained from the pseudo-first-order kinetic plots also widely ranged from 0.18 to 15.0. Results of the correlative analysis between the removal efficiencies and structural characteristics of phenolic mediators indicate that the transformation of the 1-ID was considerably enhanced by the addition of electron-donating substituents (e.g., -OH, $-OCH_3$) at the benzne ring, and much less enhanced by the addition of electron-withdrawing substituents (e.g., -COOH, -CHO). The presence of HA showed that removal efficiencies of 1-ID in the birnessite-phenolic mediator systems decreased with increasing HA concentrations. However at low concentration of HA (< 2 mg/L), it caused some enhancement in the removals of 1-ID as compared to the control.

Comparison of Kinetic Parameters, pH and Thermal Properties of Soluble and Immobilized Transglucosidase from Aspergillus niger (Aspergillus niger 유래의 Soluble과 고정화 Transglucosidase의 속도상수, pH 및 열 특성 비교)

  • Ahn, Jang-Woo;Park, Kwan-Hwa;Seo, Jin-Ho
    • Korean Journal of Food Science and Technology
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    • v.30 no.3
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    • pp.630-637
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    • 1998
  • Enzymatic properties of immobilized transglucosidase (TG) from Aspergillus niger was characterized and compared with soluble TG. Michaelis-Menten constant $(K_m)$ and maximum velocity $(V_{max})$ of immobilized TG were $122\;mM,\;3.9{\times}10^{-2}\;mM/min$ and in case of soluble TG, 21 mM, 0.4 mM/min. The optimum pH of immobilized TG was pH 5.0 like soluble TG but immobilized TG showed 16% and 45% higher activity than soluble TG at pH 5.0 and pH 6.0. Both of immobilized TG and soluble TG were stable from pH 2.0 to pH 9.0, and therefore their activities in these pH ranges were remained more than 90%. The temperature was optimal at $60{\sim}70^{\circ}C\;and\;70{\sim}80^{\circ}C$ for soluble TG and immobilized TG, respectively. The thermal stability of immobilized TG was significantly improved than that of soluble TG, and immobilized TG retained $32{\sim}40%$ higher activity than soluble TG. D-values from thermal inactivation of immobilized TG were 7690 sec at $65^{\circ}C$, 83 sec at $75^{\circ}C$, 7.2 sec at $80^{\circ}C$. Z-values of soluble and immobilized TG were $6.4^{\circ}C\;and\;5.3^{\circ}C$, respectively. The little difference of activation energies of soluble TG and immobilized TG supposed that there was little difference in mass transfer limitation during the reaction of soluble TG and immobilized TG.

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Chemical Reactions in Surfactant Solutions (II). Nucleophilic and Micellar Catalyses of Sodium 2-Alkylbenzimidazole-5-sulfonates on Hydrolyses of Carboxylic Esters in Aqueous and CTABr Solutions (계면활성제 용액속에서의 화학반응 (제 2 보). 카르복시산 에스테르의 가수 분해 반응에 미치는 2-알킬벤즈이미다졸-5-술포네이트의 친핵적 및 미셀효과)

  • Young Seuk Hong;Jeung Bae Kim;Hee Hyun Park;Dae Ryong Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.1
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    • pp.97-105
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    • 1989
  • This study deals with micellar effects on hydrolyses of p-nitrophenyl carboxylic esters(p-NPCE) mediated by 2-alkylbenzimidazole(R-BI) and sodium 2-alkylbenzimidazole-5-sulfonate(R-BISO$_3$Na) in aqueous and CTABr solutions. The reactions mediated by R-BI and R-BISO$_3$Na in micellar solutions are obviously slower than those by benzimidazole(BI) and sodium benzimidazole-5-sulfonate(BISO$_3$Na) respectively, and the reaction rates were decreased with increase of lengths of alkyl groups. This prestents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups for R-BI and R-BISO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(${\Delta}H^{\neq},\;{\Delta}G^{\neq}\;and\;{\Delta}S^{\neq}$) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole(BI) moiety of R-BISO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) which form a micelle of themselves increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr. We measured the isotope effects to elucidate the mechanism of hydrolyses of p-nitrophenyl carboxylic esters, and the relative first order rate constant($k'_{H_2O}/k'_{D_2O}$) are on range of 2.5∼3.2. This range is too high to conclude that the hydrolyses of p-NPA mediated by various R-BISO$_3$Na proceed by nucleophilic mechanism. In other words, the reactions are assumed to proceed in part by general basic one, as compared with the reaction catalyzed by imidazole(IM) in aqueous solution.

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