• Title/Summary/Keyword: Rate-Determining

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The rate-determining step in the dark state recovery process in the photocycle of PYP

  • Sasaki, Jun;Kumauchi, Masato;Hamada, Norio;Tokunaga, Fumio
    • 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

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A new criterion for determining the sampling rate of digital controller (디지털제어기의 제어주기 결정방법에 관한 연구)

  • 이준화;문홍주;정병근
    • 제어로봇시스템학회:학술대회논문집
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    • 2000.10a
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    • pp.360-360
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    • 2000
  • In this paper, a new criterion f9r determining the sampling rate of digital conroller is proposed. This paper will introduce a method fur determining the appropriate sampling rate of digital controller which can be substituted with the given analog controller, using phase margin and gain cross over frequency, not rising time or bandwidth of the closed-loop system. This method also guarantees performance of the system. Without exact modeling functions of the plant, abstracting those functions, this paper can achieve stability and aimed performance of the system, and this paper proved it with proper modeling functions.

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Kinetic and Molecular Orbital Stuides on the Reaction of 5-nitrofurfural Hydrazone Formation

  • Lee, Kyung-Hee;Jee, Jong-Gi
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.280-284
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    • 1985
  • Kinetic measurements of the 5-nitrofurfural-hydrazine reaction in various pH ranges of aquous solution were carried out by ultraviolet spectrophotometry at $25^{\circ},\;35^{\circ}\;and\;45^{\circ}C$. The observed rate of the reaction varies with the change in pH, which gives characteristic "bell-type" rate acidity profile. The maximum rate is shown in the vicinity of pH 4. This reaction procceds with rate-determining attack of hydrazine on the 5-nitrofurfural at low pH and undergoes a change in rate-determining step to dehydration of the addition intermediate as pH increases. The reaction has a "reactant-like transition state" which precedes intermediate in low pH and "product-like transition state" which follows it in neutral pH. The geometry of 5-nitrofurfural-hydrazine intermediate was estimated with PCILO method associated with CNDO/2 scheme.

A Method for Determining Dead Times of a G.M. Defector as a Function of the Count Rate

  • Ro, Seung-Gy
    • Nuclear Engineering and Technology
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    • v.3 no.1
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    • pp.3-7
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    • 1971
  • A method for determining dead times of a G.M. detector as a function of the count rate has been investigated using the Mn$^{56}$ radioactive sample. The formula, (equation omitted), seems to be useful for determining a relation between the dead time and the count rate. Here (equation omitted)(N$_1$) is the dead time for the count rate N$_1$, N$_1$is the count rate at time zero, Nt is the count rate at time t, λ is the radioactive decay constant of the sample used, and t is the time between the first and second runs. When all the counting data were corrected for the dead times evaluated with this formula and then a variation of these corrected counting data with rime was observed, the results showed quite a good agreement with the published data for the radioactive decay of Mn$^{56}$ . Besides, it appears that the dead time decreases as the count rate increases in a dead time-to-count rate relation obtained by the same formula.

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A Method for Determining the k Most Vital Arcs in Maximum Flow Problem (최대유통문제에서 k-MVA를 결정하는 방법)

  • 정호연
    • Journal of the military operations research society of Korea
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    • v.25 no.2
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    • pp.106-116
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    • 1999
  • The purpose of this study is to present a method for determining the k most vital arcs in the maximum flow problem using genetic algorithms. Generally, the problem which determine the k most vital arcs in maximum flow problem has known as NP-hard. Therefore, in this study we propose a method for determining all the k most vital arcs in maximum flow problem using genetic algorithms. First, we propose a genetic algorithm to find the k most vital arcs removed at the same time and then present the expression and determination method of individuals compatible with the characteristics of the problem, and specify the genetic parameter values of constitution, population size, crossover rate, mutation rate and etc. of the initial population which makes detecting efficiency better. Finally, using the proposed algorithms, we analyzed the performance of searching optimal solution through computer experiment. The proposed algorithms found all alternatives within shorter time than other heuristic methods. The method presented in this study can determine all the alternatives when there exists other alternative solutions.

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A Study on the Electrochemical Kinetics of Electrowinning Process of Valuable Metals Recovered from Lithium-ion Batteries (폐리튬이온전지로부터 유가금속 회수를 위한 전해채취 공정 전기화학 반응속도론적 연구)

  • Park, Sung Cheol;Kim, Yong Hwan;Lee, Man Seung;Son, Seong Ho
    • 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.

Success Rate Analysis in GPS Attitude Determination Using a Unscented Kalman Filter (GPS반송파를 이용한 자세결정에서 UKF적용을 통한 성공률 변화 분석)

  • Kwon, Chul-Bum;Chun, Se-Bum;Lee, Eun-Sung;Kang, Tae-Sam;Jee, Gyu-In;Lee, Young-Jae
    • Journal of Institute of Control, Robotics and Systems
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    • v.11 no.3
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    • pp.222-227
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    • 2005
  • Resolving the integer ambiguity of GPS carrier phase measurements is the most important routine in precise positioning. In this paper, success rate is analyzed when using baseline information in the process of determining attitude. The result is verified through the simulation. Determining the initial position for the ambiguity resolution is estimated by using code measurement and baseline constraint. Success rate is estimated using covariance of the formed initial position. UKF has been used to overcome the nonlinear baseline condition during the process so that the higher success rate has been obtained compared with the general attitude determination.

Application of a geophysical well log technique for determining permeability in borehole

  • Kim Y.;Park J.
    • 한국지구물리탐사학회:학술대회논문집
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    • 2003.11a
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    • pp.432-436
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    • 2003
  • Geophysical well logging techniques which are useful for delineating permeability of geological formation have been reviewed. A new technique for obtaining permeability using conductivity log technique has been discussed. This conductivity logging technique has been tested by monitoring the conductivity change within the model hole using borehole environment water and incoming-outgoing water of different salinity with constant flow rate by maintaining balance between inflow and outflow. Conductivity variation features depended mainly on flow rate, density contrasts due to salinity and temperature contrasts between fluid within the hole and incoming-outgoing fluid. The results of the experiment show uniform change of fluid conductivity within bore hole with time, and a fairly good correlation between the flow rate and the conductivity change rate. This conductivity logging technique is expected to be an efficient tool for determining permeability.

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Effect of Amine Nature on Rates and Mechanism: Pyridinolyses of 4-Nitrophenyl Benzoate

  • Um, Ik-Hwan;Baek, Mi-Hwa;Han, Hyun-Joo
    • Bulletin of the Korean Chemical Society
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    • v.24 no.9
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    • pp.1245-1250
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    • 2003
  • Pseudo-first-order rate constants ($k_{obs}$) have been measured spectrophotometrically for the reactions of 4-nitrophenyl benzoate with a series of pyridines in $H_2O$ containing 20 mol % DMSO. The plots of kobs vs pyridine concentration are linear up to ca. 0.1 M pyridines, indicating that the effect of self-association of pyridines with their conjugate acids are insignificant in this concentration range. The Bronsted-type plot has been obtained to be linear with a ${\beta}_{nuc}$ value 1.11, suggesting that the pyridinolyses proceed through a rate-determining breakdown of the zwiterionic addition intermediate. The pyridines studied have shown higher reactivity than isobasic primary and secondary amines toward the substrate. 1-Benzoyl-4-dimethylaminopyridinium ion, a possible intermediate, has not been detected since the rate of its hydrolysis in the reaction condition is comparable with or even faster than its formation.

Dissolution Kinetics of Sphalerite in Aqueous Ferric Chloride Solution (염화제이철 수용액에서 섬아연광의 용해에 관한 속도론적 연구)

  • Yoo, Seung-Joon;Park, Hyung-Sang;Choi, Cheong-Song;So, Chil-Sup
    • 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.

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