96 resultados para dissociation constant
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Among various mutation detection methods, constant denaturant capillary electrophoresis (CDCE) is one of the most common techniques for rapid identification of known or unknown mutations. In this report, a CDCE analysis method with homemade linear polyacrylamide (LPA) kit was developed on ABI 310 genetic analyzer, the effect and relationship of various denaturing factors in CDCE analysis were investigated and K-ras gene mutations of 31 coloerctal cancer patients were detected. Results indicate that, with the increase of chemical danaturant concentration, the optimum temperature was lowered, and when the concentration of urea (formamide) was higher than 7 M (40%), the homoduplex and heteroduplex of mutant samples were separated with difficulty. Detection results of K-ras gene in colorectal samples indicated that mutations were present in eight (26%) of 31 patients; most mutations were localized in codon 12, which is thought to be a critical step and plays an important role in human colorectal carcinogenesisas. Copyright (C) 2004 John Wiley Sons, Ltd.
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Birefringent ring-banded spherulites with radial periodic variation of thicknesses were grown from poly(epsilon-caprolactone) (PCL) solutions under conditions for which the Solution concentration was held constant during the whole development of the morphology. The as-grown ring-banded spherulites were investigated by optical (OM) and atomic force (AFM) microscopies, by transmission electron microscopy (TEM) of samples sectioned parallel to the plane of film, and also by electron diffraction (ED) and grazing incidence X-ray diffraction (GIXD) techniques.
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BACKGROUND: Thermodynamics and kinetics data are both important to explain the extraction property. In order to develop a novel separation technology superior to current extraction systems, many promising extractants have been developed including calixarene carboxylic acids. The extraction thermodynamics behavior of calix[4]arene carboxylic acids has been reported extensively. In this study, the mass transfer kinetics of neodymium(III) and the interfacial behavior of calix[4]arene carboxylic acid were investigated.
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Extraction kinetics of thorium(IV) with primary amine N1923 in sulfate media has been investigated by a constant interfacial cell with laminar flow. Studies of interfacial tension and effects of the stirring rate, temperature, and specific interfacial area on mass transfer rate show that the most probable reaction zone takes place at the liquid-liquid interface. According to the experimental data correlated as a function of the concentration of the relevant species involved in the extraction reaction, the rate equation of extracting thorium has been obtained as follows: -d[Th(IV)]((o))/dt = 10(-3.10)center dot[Th(IV)](0.89)center dot[(RNH3)(2)SO4](0.74).
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The hybridization of immobilized oligonucleotides probe strands with solution phase targets is the underlying principle of microarraybased techniques for the analysis of DNA variation. To study the kinetics of DNA/DNA hybridization, target DNA is often prior labeled with markers. A label-free method of electrochemical impedance spectra (EIS) for study the hybridization in process was reported. The Langmuir model was used to determine the association rate constant (K-on), the dissociation rate constant (K-off) and the affinity rate constant (K-A), for perfect matched DNA hybridization. The results show that, EIS is a successful technique possessing high effectivity and sensitivity to study DNA/DNA hybridization kinetics. This work can provide another view on EIS for the studying of DNA/DNA hybridization.
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BACKGROUND: Thermodynamic studies on Ce(IV) extraction with primary amine N1923 demonstrate that primary amine N1923 is an excellent extractant for separation of Ce(IV) from Re(III). In order to clarify the mechanism of extraction and to optimize the parameters in practical extraction systems used in the rare earth industry, the extraction kinetics was investigated using a constant interfacial area cell with laminar flow in the present work.RESULTS: The data indicate that the rate constant (k(ao).) becomes constant when stirring speed exceeds 250 rpm. The apparent forward extraction rate is calculated to be 10(-1.70). The activation energy (E.) was calculated to be 20.5 kJ/mol from the slope of log kao against 1000/T. The minimum bulk concentration of the extractant necessary to saturate the interface (C-min) is lower than 10(-5) mol L-1.CONCLUSION: Studies of interfacial tension and the effects of stirring rate and specific interfacial area on the extraction rate show that the extraction rate is kinetically controlled, and a mass transfer model has been proposed. The rate equation has been obtained as: -d[Ce(IV)]/dt = 10(-1.70)[Ce(IV)] [(RNH3)(2)SO4](1.376). The rate-controlling step has been evaluated from analysis of the experimental results.
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In this work, a gradient polystyrene colloidal photonic crystal was fabricated by annealing in a graded temperature field. The lattice constant of the gradient crystal gradually varied along the temperature-gradient direction. The positional bandgap wavelength as well as the attenuation of the bandgap wavelength could be tuned dependent on the position of the gradient colloidal crystal along the gradient direction because of the lattice-constant variation.
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The extraction kinetics of Sc, Y, La and Gd(III) from the hydrochloric acid medium using Cyanex 302 (hereafter HL) in heptane solution have been measured by the constant interfacial cell with laminar flow. Reaction regions are explored at liquid-liquid interface. Extraction regimes are deduced to be diffusion-controlled for Sc(Ill) and mixed controlled for Y, La and Gd(Ill). Extraction mechanisms are discussed according to the dimeric model of Cyanex 302 in non-polar solution. From the temperature dependence of rate measurement, the values of E-a, Delta H-+/-, Delta S-+/- and Delta G(300)(+/-) are calculated and it is found that the absolute values of these parameters keep crescent trend for Sc, Y, La and Gd(III). At the same time, it is found that it can easily achieve the mutual separation among the Sc, Y and La(III) with kinetics extraction methods.
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Several methods have been used for the measurement of the electronic decay constant (beta) of organic molecules. However, each of them has some disadvantages. For the first time, electrochemical impedance spectroscopy (EIS) was used to obtain the 18 value by measuring the tunneling resistance through alkanedithiols. The tunneling resistance through alkanedithiols increases exponentially with the molecular length in terms of the mechanism of coherent nonresonant tunneling. beta was 0.51 +/- 0.01 per carbon.
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The transfer of sodium cation facilitated by (anthraquinone-1-yloxy) methane-15-crown-5(L) has been investigated at the water/1,2-dichloroethane microinterface supported at the tip of a micropipette. The diffusion coefficient of (anthraquinone-1-yloxy) methane-15-crown-5 obtained was (3.42 +/- 0.20) x 10(-6) cm(2) s(-1). The steady-state voltammograms were observed for forward and backward scans due to sodium ion transfer facilitated by L with 1:1 stoichiometry. The mechanism corresponded to an interfacial complexation (TIC) and interfacial dissociation (TID) process. The association constant was calculated to be log beta(o) = 11.08 +/- 0.03 in the DCE phase. The association constant of other alkali metals (Li+, K+, Rb+) were also obtained.
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The extraction and stripping kinetics of yttrium(III) with bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272, HA) dissolved in heptane as an acid extractant have been investigated by constant interfacial cell with laminar flow. The experimental hydrodynamic conditions have been chosen so that the contribution of diffusion to the measured rate of reaction is minimized. The plot of interfacial area on the rate has shown a linear relationship, which makes the interface the most probable local for the chemical reactions. At the same time, the extraction thermodynamic and kinetic methods are compared to determine the equilibrium extraction constant. A rate equation and the rate-determining step of the extraction and stripping of yttrium(III) have also been obtained, respectively.
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In the present work a nonmonotonic dependence of standard rate constant (k(0)) on reorganization energy (lambda) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k(0) on lambda is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of lambda, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the lambda dependence of k(0) for Process I is monotonic thoroughly, while for Process II on electrode surface the lambda dependence of k(0) could show a nonmonotonicity.
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Studies have been made on the kinetics of ytterbium(III) with bis-(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272, HA) in n-heptane using a constant interfacial cell with laminar flow. The stiochiometry and the equilibrium constant of the extracted complex formation reaction between Yb3+ and Cyanex 272 are determined. The extraction rate is dependent of the stirring rate. This fact together with the Ea value suggests that the mass transfer process is a mixed chemical reaction-diffusion controlled at lower temperature, whereas it is entirely diffusion controlled at higher temperature. The rate equations for the ytterbium extraction with Cyanex 272 have been obtained. The rate-determining step is also made by predictions derived from interfacial reaction models, and through the approximate solutions of the flux equation, diffusion parameters and thickness of the diffusion film have been calculated.
Resumo:
The yttrium(III) extraction kinetics and mechanism with bis-(2,4,4-trimethyl-pentyl) phosphinic acid (Cyanex 272, HA) dissolved in heptane have been investigated by constant interfacial cell with laminar flow. The data has been analyzed in terms of pseudo-first order constants. Studies on the effects of stirring rate, temperature, acidity in aqueous phase, and extractant concentration on the extraction rate show that the extraction regime is dependent on the extraction conditions. The plot of interfacial area on the rate has shown a linear relationship. This fact together with the strong surface activity of Cyanex 272 at heptane-water interfaces has made the interface the most probable location for the chemical reactions. The forward, reverse rate equations and extraction rate constant for the yttrium extraction with Cyanex 272 have been obtained under the experimental conditions. The rate-determining step has been also predicted from interfacial reaction models. The predictions have been found to be in good agreement with the rate equations obtained from experimental data, confirming the basic assumption that the chemical reaction is located at the liquid-liquid interface.