• Journal of Photoscience
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• v.9 no.2
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• pp.130-133
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• 2002

The last step in the photocycle of photoactive yellow protein (PYP) is a spontaneous recovery of the dark state from the active state in which the p-coumaric acid chromophore is thermally isomerized, concomitantly with the deprotona- tion of the chtomophore and the refolding of the protein moicty. For the purpose of understanding the mechanism of the thermal back-isomerization, we have investigated the rate-determining step by analyzing mutant PYPs of Met100, which was previously shown to play a major role in facilitating the reaction (1). The mutation to Lys, Leu, Ala, or Glu decelerated the dark state recovery by 1 to 3 three orders of magnitude. By evaluating temperature-dependence and pH-dependence of the kinetics of the dark state recovery, it was found that the retardation by mutations resulted from elevation of the activation enthalpy ( H$\^$┿/) and that the pKa of the chromophore, which was affected by the mutation, is in a linier correlation with the amplitude of the rate constants. It was, therefore, deduced from the correlation that the free energy for crossing the activated state in the dark recovery process is proportional to the free energy for the deprotonation of the chromophore, identifying the rate-determining step as the deprotonation of the chromophore. (1) Devanathan, S. Genick, U. K. Canestrelli, I. L. Meyer, T. E. Cusanovich, M. A. Getzoff, E. D. Tollin, G., Biochemistry 1998, 37, 11563 - 11568

• Resources Recycling
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• v.31 no.5
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• pp.59-66
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• 2022

To investigate the rate-determining step of nickel, cobalt and copper electrowinning, experiments were conducted by varying the electrolyte temperature and agitation speed using a rotating disc electrode. Analyzing the rate-determining step by calculating the activation energy in the electrowinning process, it was found that nickel electrowinning is controlled by a mixed mechanism (partly by chemical reaction and partly by mass transport), cobalt is controlled by chemical reaction, and copper is controlled by mass transfer. Electrowinning of nickel, cobalt and copper was performed by varying the electrolyte temperature and agitation speed, and the comparison of the current efficiencies was used the determine the rate-determining step.

• Economic and Environmental Geology
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• v.26 no.3
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• pp.421-429
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• 1993

Dissolution reactions of chemical grade zinc sulfide and natural sphalerite were studied in ferric chloride solution as an oxidant. To enhance the leaching reaction, ultrasonic technique was employed in this investigation. For the reaction with pure zinc sulfide, chemical reaction was the rate limiting step in the range of low conversion irrespective of applying ultrasonic wave. And the diffusion through liquid film instead of diffusion through product layer of free sulfur was the rate determining step because ultrasonic vibration removes the product from reaction zone. In the case of sphalerite with the ultrasonic vibrator, it was found that inert mineral layer diffusion was the rate determining step, in which the elemental sulfurs formed were removed by the ultrasonic action. Experimental results showed that the ultrasonic technique proved to be the methods which can significants improve the leaching performance.

• Bulletin of the Korean Chemical Society
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• v.19 no.12
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• pp.1298-1299
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• 1998

• Journal of Ocean Engineering and Technology
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• v.11 no.4
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• pp.213-220
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• 1997

In this study, a design for a shape of centrifugal pump impeller has been performed using a p.c. under a Windows environment. Interaction between a user and a computer has been easily established using the Visual Basic. In determining an outer diameter of an impeller, steps are divided into two, a basic computational step and a refinment step. In this way user can enter his/her experience at the refinment step and hence can expect to lessen the nonlinear nature inherent to the design. In determining a shape of a side view of an impeller, the Bezier cubic curve has been used, and it can be seen that the Bezier cubic curves are well suited in the shape design under a Windows environment. By simply manipulating the four control points, one can generate various cubic curves among which one is selected. Also, a simple method, which can determine the curved position of an impeller vane, has been developed. These data can be used for final CAD drawings.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.580-584
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• 2008

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of Y-substituted phenyl benzoates (1a-h) with azide ion (N3) in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the azidolysis exhibits a downward curvature, i.e., the slope (b lg) changes from 0.97 to 0.20 as the basicity of the leaving group decreases. The pKao (defined as the pKa at the center of the Brnsted curvature) is 4.8, which is practically identical to the pKa of the conjugate acid of N3 ion (4.73). Hammett plots correlated with s o and s constants exhibit highly scattered points for the azidolysis. On the contrary, the corresponding Yukawa-Tsuno plot results in an excellent linear correlation with r = 2.45 and r = 0.40, indicating that the leaving group departs in the rate-determining step. The curved Brnsted-type plot has been interpreted as a change in the rate-determining step in a stepwise mechanism. The microscopic rate constants (k1 and k2/k1 ratio) have been calculated for the azidolysis and found to be consistent with the proposed mechanism.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.585-589
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• 2008

Second-order rate constants (kN) have been measured for reactions of Y-substituted phenyl 2-thiophenecarboxylates (6a-h) with morpholine and piperidine in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the reactions of 6a-h with morpholine is linear with b lg = 1.29, indicating that the reactions proceed through a tetrahedral zwitterionic intermediate (T?). On the other hand, the Brnsted-type plot for the reactions of 6a-h with piperidine exhibits a downward curvature, implying that a change in the rate-determining step occurs on changing the substituent Y in the leaving group. Dissection of kN into microscopic rate constants (i.e., k1 and k2/k1 ratio) has revealed that k1 is smaller for the reactions of 6a-h than for those of Y-substituted phenyl 2-furoates (5a-h), while the k2/k1 ratio is almost the same for the reactions of 5a-h and 6a-h. It is also reported that modification of the nonleaving group from the furoyl (5a-h) to the thiophenecarbonyl (6a-h) does not influence pKao (defined as the pKa at the center of the Brnsted curvature) as well as the k2/k1 ratio.

• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.220-224
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• 2007

Second-order rate constants (kN) have been determined spectrophotometrically for reactions of 2,4-dintrophenyl 2-furoate (2) with a series of alicyclic secondary amines in 80 mol % H2O/20 mol % dimethyl sulfoxide (DMSO) at 25.0 oC. The furoate 2 is more reactive than 2,4-dintrophenyl benzoate (1) toward all the amines studied. The higher acidity of 2-furoic acid (pKa = 3.16) compared with benzoic acid (pKa = 4.20) has been suggested to be responsible for the reactivity order, at least in part. The Brønsted-type plots for the reactions of 1 and 2 are curved downwardly, indicating that the aminolyses of both 1 and 2 proceed through a zwitterionic tetrahedral intermediate (T±) with a change in the rate-determining step on changing the amine basicity. Dissection of the kN values into their microscopic rate constants has revealed that the pKao and k2/k-1 ratios for the reactions of 1 and 2 are identical, indicating that the nature of the nonleaving group (i.e., benzoyl and 2-furoyl) does not affect the reaction mechanism. The k1 values have been found to be larger for the reactions of 2 than for those of 1, which is fully responsible for the fact that the former is more reactive than the latter.

• Bulletin of the Korean Chemical Society
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• v.26 no.12
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• pp.1981-1985
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• 2005

Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $\rho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $\rho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${\Delta}S^\neq$ value determined in the present system is consistent with the proposed mechanism.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.659-662
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• 1992

The pressure-jump relaxation method has been used to determine the rate constants for the formation and dissociation of maganese(Ⅱ), cobalt(Ⅱ), and nickel(Ⅱ) with some dicarboxylates in aqueous solution at zero ionic strength. The carboxylate ligands used are 3-nitrophthalate, 4-nitrophthalate, and phenylmalonate. The activation parameters have alse been obtained from the temperature dependence of the rate constants. A dissociative interchange mechanism with a chelate ring closure step as rate determining is employed to interpret the kinetic data of manganese(Ⅱ) and cobalt(Ⅱ) complexes. The rates of formation of nickel(Ⅱ) complexes are controlled by both the solvent exchange step and the chelate ring closure step.