• Title/Summary/Keyword: Kinetic studies

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Kinetic Investigation of Olefin Oxidation by Al(III)-Porphyrin Complexes (Al(lll)-Porphyrin착물에 의한 올레핀 산화반응 메카니즘 연구)

  • Na, Hun-Gil;Han, Man-So
    • Journal of the Korean Chemical Society
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    • v.50 no.1
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    • pp.46-52
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    • 2006
  • studies of olefin oxidation using Al(III)-porphyrin complexes as catalyst are investigated in CH2Cl2, in which NaClO is used as terminal oxidant. Porphyrins are TPP(5,10,15,20-Tetraphenylporphyrin) and (p-X)TPP(X=CH3O, CH3, F, Cl). Olefins are styrene and (p-X)styrene (X=CH3O, CH3, Cl, Br). The values of Km and Vmax are calculated from the Michaelis-Menten equation. According to the substituents of substrate and catalyst, kinetic parameters will be measured. Investigating the correlation between the Michaelis-Menten rate parameters and the substituent constants, we were able to analyze the influence on the changes of catalytic activity or the rate determining step during the process of the formation and the dissociation of the M-oxo-olefin.

A Substrate Serves as a Hydrogen Atom Donor in the Enzyme-Initiated Catalytic Mechanism of Dual Positional Specific Maize Lipoxygenase-1

  • Huon, Thavrak;Jang, Sung-Kuk;Cho, Kyoung-Won;Rakwal, Randeep;Woo, Je-Chang;Kim, Il-Chul;Chi, Seung-Wook;Han, Ok-Soo
    • Bulletin of the Korean Chemical Society
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    • v.30 no.4
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    • pp.917-923
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    • 2009
  • The maize lipoxgyenase-1 is a non-traditional dual positional specific enzyme and the reaction proceeds via enzyme-initiated catalysis. Bioinformatic analysis indicated that the maize lipoxygenase-1 is structurally more similar to soybean LOX1 than pea LOXN2 in that it has an additional external loop (residues 318-351) in the carboxy-terminal catalytic domain. We analyzed the dependence of product distribution on concentration of linoleic acid and monitored the formation of hydroperoxyoctadecadienoic acid as a function of enzyme concentration. Product distribution was strongly influenced by substrate concentration, such that kinetically-controlled regioisomers were enriched and thermodynamically-controlled regioisomers were depleted at high substrate concentration. Kinetic studies indicated that the formation of hydroperoxyoctadecadienoic acid saturated rapidly in an enzyme concentration-dependent manner, which implied that reactivation by reoxidation of inactive Fe(II) failed to occur. Our results support the previously proposed enzyme-initiated catalytic mechanism of the maize lipoxgyenase-1 and reveals that a substrate molecule serves as a hydrogen atom donor in its enzyme-initiated catalysis.

Molecular Docking and Kinetic Studies of the A226N Mutant of Deinococcus geothermalis Amylosucrase with Enhanced Transglucosylation Activity

  • Hong, Seungpyo;Siziya, Inonge Noni;Seo, Myung-Ji;Park, Cheon-Seok;Seo, Dong-Ho
    • Journal of Microbiology and Biotechnology
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    • v.30 no.9
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    • pp.1436-1442
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    • 2020
  • Amylosucrase (ASase, E.C. 2.4.1.4) is capable of efficient glucose transfer from sucrose, acting as the sole donor molecule, to various functional acceptor compounds, such as polyphenols and flavonoids. An ASase variant from Deinococcus geothermalis, in which the 226th alanine is replaced with asparagine (DgAS-A226N), shows increased polymerization activity due to changes in the flexibility of the loop near the active site. In this study, we further investigated how the mutation modulates the enzymatic activity of DgAS using molecular dynamics and docking simulations to evaluate interactions between the enzyme and phenolic compounds. The computational analysis revealed that the A226N mutation could induce and stabilize structural changes near the substrate-binding site to increase glucose transfer efficiency to phenolic compounds. Kinetic parameters of DgAS-A226N and WT DgAS were determined with sucrose and 4-methylumbelliferone (MU) as donor and acceptor molecules, respectively. The kcat/Km value of DgAS-A226N with MU (6.352 mM-1min-1) was significantly higher than that of DgAS (5.296 mM-1min-1). The enzymatic activity was tested with a small phenolic compound, hydroquinone, and there was a 1.4-fold increase in α-arbutin production. From the results of the study, it was concluded that DgAS-A226N has improved acceptor specificity toward small phenolic compounds by way of stabilizing the active conformation of these compounds.

Batch and Flow-Through Column Studies for Cr(VI) Sorption to Activated Carbon Fiber

  • Lee, In;Park, Jeong-Ann;Kang, Jin-Kyu;Kim, Jae-Hyun;Son, Jeong-Woo;Yi, In-Geol;Kim, Song-Bae
    • Environmental Engineering Research
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    • v.19 no.2
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    • pp.157-163
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    • 2014
  • The adsorption of Cr(VI) from aqueous solutions to activated carbon fiber (ACF) was investigated using both batch and flow-through column experiments. The batch experiments (adsorbent dose, 10 g/L; initial Cr(VI) concentration, 5-500 mg/L) showed that the maximum adsorption capacity of Cr(VI) to ACF was determined to 20.54 mg/g. The adsorption of Cr(VI) to ACF was sensitive to solution pH, decreasing from 9.09 to 0.66 mg/g with increasing pH from 2.6 to 9.9; the adsorption capacity was the highest at the highly acidic solution pHs. Kinetic model analysis showed that the Elovich model was the most suitable for describing the kinetic data among three (pseudo-first-order, pseudo-second-order, and Elovich) models. From the nonlinear regression analysis, the Elovich model parameter values were determined to be ${\alpha}$ = 162.65 mg/g/h and ${\beta}$ = 2.10 g/mg. Equilibrium isotherm model analysis demonstrated that among three (Langmuir, Freundlich, Redlich-Peterson) models, both Freundlich and Redlich-Peterson models were suitable for describing the equilibrium data. In the model analysis, the Redlich-Peterson model fit was superimposed on the Freundlich fit. The Freundlich model parameter values were determined to be $K_F$ = 0.52 L/g and 1/n = 0.56. The flow-through column experiments showed that the adsorption capacities of ACF in the given experimental conditions (column length, 10 cm; inner diameter, 1.5 cm; flow rate, 0.5 and 1.0 mL/min; influent Cr(VI) concentration, 10 mg/L) were in the range of 2.35-4.20 mg/g. This study demonstrated that activated carbon fiber was effective for the removal of Cr(VI) from aqueous solutions.

Redeveloping Turbelent Boundary Layer after Separation-Reattachment(II) -A Consideration on Turbulence Models- (박리-재부착 이후의 재발달 난류경계층 II -난류 모델들에 관한 고찰-)

  • 백세진;유정열
    • Transactions of the Korean Society of Mechanical Engineers
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    • v.13 no.5
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    • pp.999-1011
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    • 1989
  • A consideration on the trubulence models for describing the redeveloping turbulent boundary layer beyond separation-reattachment in the flow over a backward-facing step is given through experimental and numerical studies. By considering the blance among the measured values of respective terms in the transport equations for the turbulent kinetic energy and the turbulent shear stress, the recovering process of the redeveloping boundary layer from non-equilibrium to equilibrium has been investigated, which takes place slowly over a substantial distance in the downstream direction. In the numerical study, the standard K-.epsilon. model and the Reynolds stress model have been applied to two kinds of flow regions, one for the entire downstream region after the backward-facing step and another for the downstream region after reattachment. Then the results are compared to a meaningful extent, with the experimental values of the turbulent kinetic energy k, the turbulent energy production term P, the dissipation term K-.epsilon. model, a necessity for a new modelling has been brought forward, which can be also applied to the case of the nonequlibrium turbulent flow.

Evaluation of Adsorption Characteristics of 2-Picoline onto Sylopute (실로퓨트에 대한 2-피콜린의 흡착 특성 평가)

  • Yang, Ji-Won;Kim, Jin-Hyun
    • Korean Chemical Engineering Research
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    • v.57 no.2
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    • pp.210-218
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    • 2019
  • Batch experiment studies were carried out on the adsorption of the major tar compound, 2-picoline, derived from the plant cell cultures of Taxus chinensis, using Sylopute while varying parameters such as initial 2-picoline concentration, contact time and adsorption temperature. The experimental data were fitted to the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models. Comparison of results revealed that the Langmuir isotherm model could account for the adsorption isotherm data with the highest accuracy among the four isotherm models considered. From the analysis of adsorption isotherms, it was found that adsorption capacity decreased with increasing temperature and the adsorption of 2-picoline onto Sylopute was favorable. The kinetic data were well described by the pseudo-second-order kinetic model, while intraparticle diffusion and boundary layer diffusion did not play a dominated role in 2-picoline adsorption according to the intraparticle diffusion model. Thermodynamic parameters revealed the exothermic, irreversible and non-spontaneous nature of adsorption. The isosteric heat of adsorption decreased as surface loading ($q_e$) increased, indicating a heterogeneous surface.

Photocatalysis and Adsorption of Reactive Black 5(RB5) by HAP/TiO2 Media (HAP/TiO2 여재를 이용한 Reactive Black 5(RB5)의 광촉매 반응과 흡착)

  • Chun, Sukyoung;Chang, Soonwoong
    • Journal of the Korean GEO-environmental Society
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    • v.12 no.11
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    • pp.31-37
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    • 2011
  • This study investigated on the adsorption and photocatalysis of Reactive Black 5(RB5) by the hydroxyapatite(HAP)/Titanium dioxide($TiO_{2}$) media. The adsorption of RB5 on $TiO_{2}$, HAP and $TiO_{2}$/HAP was investigated during a series of batch adsorption experiments. The amounts adsorbed at equilibrium were measured. Langmuir and Freundlich isotherm models were tested for their applicability. The result of equilibrium studies of $TiO_{2}$, HAP and $TiO_{2}$/HAP adsorbent were found to follow Langmuir isotherm model. The adsorbed amounts(Qmax) were found to be 5.28mg/g on single $TiO_{2}$, 12.45mg/g on single HAP and 9.03mg/g on $TiO_{2}$/HAP, respectively. The experimental data were analysed using the pseudo-first-order adsorption and photocatalysis kinetic models. According to these models, RB5 degradation by $TiO_{2}$/HAP was affected by interaction effect of photocatalysis and adsorption.

Separation of cadmium and chromium heavy metals from industrial wastewater by using Ni-Zn nanoferrites

  • Thakur, Atul;Punia, Pinki;Dhar, Rakesh;Aggarwal, R.K.;Thakur, Preeti
    • Advances in nano research
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    • v.12 no.5
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    • pp.457-465
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    • 2022
  • The potentials of NixZn1-xFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) nanoadsorbents were investigated for removal of Cd and Cr from contaminated water from an electroplating industry in Himachal Pradesh, India. Optimal values were recorded under batch adsorption experiments performed to remove dissolved heavy metal ions from industrial wastewater. The specific surface area (SSA) of nanoadsorbents perceived to vary in a range 35.75-45.29 cm2/g and was calculated from the XRD data. The influence of two operating parameters, contact time and dopant (Ni) concentration was also investigated at pH ~7 with optimum dosage. Kinetic studies were conducted within a time range of 2-10 min with rapid adsorption of cadmium and chromium ions onto Ni0.2Zn0.8Fe2O4 nanoadsorbents. Pseudo-second-order kinetic model was observed to be well fitted with the adsorption data that confirmed the only existence of chemisorption throughout the adsorption process. The maximum adsorption efficiency values observed for Cd and Cr were 51.4 mg/g and 40.12 mg/g, respectively for different compositions of prepared series of nanoadsorbents. The removal percentage of Cd and Cr was found to vary in a range of 47.7%-95.25% and 21%-50% respectively. The prepared series of nanoferrite found to be suitable enough for adsorption of both heavy metal ions.

Arsenic Contamination of Groundwater a Grave Concern: Novel Clay-based Materials for Decontamination of Arsenic (V)

  • Amrita Dwivedi;Diwakar Tiwari;Seung Mok Lee
    • Applied Chemistry for Engineering
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    • v.34 no.2
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    • pp.199-205
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    • 2023
  • Arsenic is a highly toxic element, and its contamination is widespread around the world. The natural materials with high selectivity and efficiency toward pollutants are important in wastewater treatment technology. In this study, the mesoporous synthetic hectorite was synthesized by facile hydrothermal crystallization of gels comprising silica, magnesium hydroxide, and lithium fluoride. Additionally, the naturally available clay was modified using zirconium at room temperature. Both synthetic and modified natural clays were employed in the removal of arsenate from aquatic environments. The materials were fully characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and Fourier transform-infrared (FT-IR) analyses. The synthesized materials were used to remove arsenic (V) under varied physicochemical conditions. Both materials, i.e., Zr-bentonite and Zr-hectorite, showed high percentage removal of arsenic (V) at lower pH, and the efficiency decreased in an alkaline medium. The equilibrium-state sorption data agrees well with the Langmuir and Freundlich adsorption isotherms, and the maximum sorption capacity is found to be 4.608 and 2.207 mg/g for Zr-bentonite and Zr-hectorite, respectively. The kinetic data fits well with the pseudo-second order kinetic model. Furthermore, the effect of the background electrolytes study indicated that arsenic (V) is specifically sorbed at the surface of these two nanocomposites. This study demonstrated that zirconium intercalated synthetic hectorite as well as zirconium modified natural clays are effective and efficient materials for the selective removal of arsenic (V) from aqueous medium.

Effects of the Patellar Tendon Strap on Kinematics, Kinetic Data and Muscle Activity During Gait in Patients With Chronic Knee Osteoarthritis

  • Eun-Ji Lee;Ki-Song Kim;Young-In Hwang
    • Physical Therapy Korea
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    • v.30 no.2
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    • pp.110-119
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    • 2023
  • Background: Osteoarthritis is a common condition with an increasing prevalence and is a common cause of disability. Osteoarthritic pain decreases the quality of life, and simple gait training is used to alleviate it. Knee osteoarthritis limits joint motion in the sagittal and lateral directions. Although many recent studies have activated orthotic research to increase knee joint stabilization, no study has used patellar tendon straps to treat knee osteoarthritis. Objects: This study aimed to determine the effects of patellar tendon straps on kinematic, mechanical, and electromyographic activation in patients with knee osteoarthritis. Methods: Patients with knee osteoarthritis were selected. After creating the Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC), leg length difference, Q-angle, and thumb side flexion angle of the foot were measured. Kinematic, kinetic, and muscle activation data during walking before and after wearing the orthosis were viewed. Results: After wearing the patellar tendon straps, hip adduction from the terminal stance phase, knee flexion from the terminal swing phase, and ankle plantar flexion angle increased during the pre-swing and initial swing phases. The cadence of spatiotemporal parameters and velocity increased, and step time, stride time, and foot force duration decreased. Conclusion: Based on the results of this study, the increase in plantar flexion after strap wearing is inferred by an increase due to neurological mechanisms, and adduction at the hip joint is inferred by an increase in adduction due to increased velocity. The increase in cadence and velocity and the decrease in gait speed and foot pressure duration may be due to joint stabilization. It can be inferred that joint stabilization is increased by wearing knee straps. Thus, wearing a patellar tendon strap during gait in patients with knee osteoarthritis influences kinematic changes in the sagittal plane of the joint.