• Bulletin of the Korean Chemical Society
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• v.27 no.2
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• pp.224-230
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• 2006

Escherichia coli transcription termination factor Rho catalyzes the unwinding of RNA/DNA duplex in reactions that are coupled to ATP binding and hydrolysis. We report here the kinetic mechanism of presteady state ATP binding and hydrolysis by the Rho-RNA complex. Presteady state chemical quenched-flow technique under multiple turnover condition was used to probe the kinetics of ATP binding and hydrolysis by the Rho-RNA complex. The quenched-flow presteady state kinetics of ATP hydrolysis studies show that three ATPs are bound to the Rho-RNA complex with a rate of $4.4\;{\times}\;10^5M^{-1}s^{-1}$, which are subsequently hydrolyzed at a rate of $88s^{-1}$ and released during the initiation process. Global fit of the presteady state ATP hydrolysis kinetic data suggests that a rapid-equilibrium binding of ATP to Rho-RNA complex occurs prior to the first turnover and the chemistry step is not reversible. The initial burst of three ATPs hydrolysis was proposed to be involved in the initialization step that accompanies proper complex formation of Rho-RNA. Based on these results a kinetic model for initiation process for Rho-RNA complex was proposed relating the mechanism of ATP binding and hydrolysis by Rho to the structural transitions of Rho-RNA complex to reach the steady state phase, which is implicated during translocation along the RNA.

• Environmental Engineering Research
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• v.18 no.4
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• pp.247-252
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• 2013

In this work, removal of phenol from aqueous solutions by activated red mud was investigated. Scanning electron microscopy and energy dispersive X-ray spectroscopy was used to observe the morphology and surface components of activated red mud, respectively. The effects of various parameters on the removal efficiency were studied, such as contact time, pH, initial phenol concentration, and adsorbent dosage. The removal percentage of phenol was initially increased, as the solution pH increased from 3 to 7, and then decreased above neutral pH. The removal percentage of phenol was decreased by increasing the initial phenol concentrations. Adsorption results show that equilibrium data follow the Freundlich isotherm, and kinetic data was well described by a pseudo-second-order kinetic model. Experimental results show that the activated red mud can be used to treat aqueous solutions containing phenol, as a low cost adsorbent with high efficiency.

• Bulletin of the Korean Chemical Society
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• v.23 no.10
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• pp.1459-1462
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• 2002

The kinetics of the addition of X-substituted benzylamines (BA) to Y-substituted Benzylideneacetylacetones (BAA) have been investigated in acetonitrile at $25.0^{\circ}C$. The reaction is studied under pseudo-first-order conditions by keeping a large excess of BA over BAA. The addition of BA to BAA occurs in a single step in which the addition of BA to $C_\alpha$ of BAA and proton transfer from BA to $C_\beta$ of BAA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($p_X$) and Bronsted ($\beta_x$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the cross-interaction constant, $p_{XY}$ (= -0.49), is comparatible to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($K_H/K_D$ > 1.0) and relatively low $\Delta$H^{${\neq}$}$ and large negative $\Delta$S^{${\neq}$}$ values are also consistent with the mechanism proposed.

• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.835-839
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• 2010

The rate constants of solvolyses of 2,2,2-trichloro-1,1-dimethylethyl chloroformate ($\underline{I}$) in 33 solvents can be well correlated using the extended Grunwald-Winstein equation, with incorporation of the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivities towards changes in the scale having values of $1.42\;{\pm}\;0.09$ for l and $0.39\;{\pm}\;0.05$ for m, respectively. The activation enthalpies are ${\Delta}H^{\neq}\;=\;12.3$ to $14.5\;kcal{\cdot}mol^{-1}$ and the activation entropies are -28.2 to $-35.5\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$, consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.14 in MeOH/MeOD is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.271-275
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• 2007

γ -Glutamyl transpeptidase (EC 2.3.2.2) plays a key role in glutathione metabolism by catalyzing the transfer of the γ -glutamyl residue and hydrolysis of glutathione. The functional residues at the active site of the rat kidney γ -glutamyl transpeptidase were investigated by kinetic studies at various pH, the treatment of diethylpyrocarbonate (DEPC), and photooxidation in presence of methylene blue. An ionizable group affecting the enzymatic activity with an apparent pKa value of 7.1, which is in the range of pKa values for a histidine residue in protein, was obtained by examining the pH-dependence of kinetic parameters. The pH effect on the photoinduced inactivation rate of the enzyme corresponds to that expected for the photooxidation of the free histidine. The involvement of a histidine in the catalytic site of the enzyme was further supported by DEPC modification accompanied by an increase in absorbance at 240 nm, indicating the formation of Ncarbethoxyhistidine. The histidine located at the position of 382 in the precursor of the enzyme is primarily suspected based on the amino acid sequence alignment of the transpeptidases from various organisms.

• Bulletin of the Korean Chemical Society
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• v.33 no.6
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• pp.1879-1884
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• 2012

The kinetic studies on the reactions of dipropyl chlorophosphate (3O) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.09-1.01) with the strongly basic anilines while secondary inverse ($k_H/k_D$ = 0.74-0.82) with the weakly basic anilines. The steric effects of the two ligands on the rates are extensively discussed for the anilinolyses of the ($R_1O$)($R_2O$)P(=O or S)Cl-type chlorophosphates and chlorothiophosphates. A concerted mechanism is proposed with a frontside nucleophilic attack involving a hydrogen-bonded four-center-type transition state for the strongly basic anilines and with a backside attack transition state for the weakly basic anilines on the basis of the DKIEs, primary normal and secondary inverse with the strongly and weakly basic anilines, respectively.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2003-2008
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Membrane and Water Treatment
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• v.9 no.2
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• pp.79-85
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• 2018

In this work, batch adsorption of anionic dye acid green-25 (AG-25) from aqueous solution has been carried out at room temperature using anion exchange membrane (DF-120B) as a noval adsorbent. The effect of various experimental parameters such as contact time, membrane dosage, ionic strength and temperature on the adsorption of dye were investigated. Kinetic models namely pseudo-first-order, pseudo-second-order, Elovich, liquid film diffusion, Bangham and modified freundlich models were employed to evaluate the experimental data. Parameters like adsorption capacities, rate constant and related correlation coefficients for every model are calculated and discussed. It showed that adsorption of AG-25 onto DF-120B followed pseudo-first-order rate expression. Thermodynamic study indicates that adsorption of AG-25 onto DF-120B is an exothermic and spontaneous process.

• Korean Journal of Environmental Biology
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• v.39 no.3
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• pp.298-310
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• 2021

Prediction of the behavior of heavy metals over time is important to evaluate the heavy metal toxicity in algae species. Various modeling studies have been well established, but there is a need for an improved model for predicting the chronic effects of metals on algae species to combine the metal kinetics and biological response of algal cells. In this study, a kinetic dynamics model was developed to predict the copper behavior(5 ㎍ L^-1, 10 ㎍ L^-1, and 15 ㎍ L^-1) for two freshwater algae (Pseudokirchneriella subcapitata and Chlorella vulgaris) in the chronic exposure experiments (8 d and 21 d). In the experimental observations, the rapid change in copper mass between the solutions, extracellular and intracellular sites occurred within initial exposure periods, and then it was slower although the algal density changed with time. Our model showed a good agreement with the measured copper mass in each part for all tested conditions with an elapsed time (R² for P. subcapitata: 0.928, R² for C. vulgaris: 0.943). This study provides a novel kinetic dynamics model that is compromised between practical simplicity and realistic complexity, and it can be used to investigate the chronic effects of heavy metals on the algal population.

• Bulletin of the Korean Chemical Society
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• v.25 no.3
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• pp.403-406
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• 2004