Extending the kinetic solution of the classic Michaelis-Menten model of enzyme action

The principal aim of studies of enzyme-mediated reactions has been to provide comparative and quantitative information on enzyme-catalyzed reactions under distinct conditions. The classic Michaelis-Menten model (Biochem Zeit 49:333, 1913) for enzyme kinetic has been widely used to determine important parameters involved in enzyme catalysis, particularly the Michaelis-Menten constant (K (M) ) and the maximum velocity of reaction (V (max) ). Subsequently, a detailed treatment of the mechanisms of enzyme catalysis was undertaken by Briggs-Haldane (Biochem J 19:338, 1925). These authors proposed the steady-state treatment, since its applicability was constrained to this condition. The present work describes an extending solution of the Michaelis-Menten model without the need for such a steady-state restriction. We provide the first analysis of all of the individual reaction constants calculated analytically. Using this approach, it is possible to accurately predict the results under new experimental conditions and to characterize and optimize industrial processes in the fields of chemical and food engineering, pharmaceuticals and biotechnology.

Solution Polymerization of N-vinylcaprolactam in 1,4-dioxane. Kinetic Dependence on Temperature, Monomer, and Initiator Concentrations

The kinetics of the solution free radical polymerization of N-vinylcaprolactam, in 1,4-dioxane and under various polymerization conditions was studied. Azobisisobutyronitrile and 3-mercaptopropionic acid were used as initiator and as chain transfer agent (CTA), respectively. The influence of monomer and initiator concentrations and polymerization temperature on the rate of polymerizations (R(p)) was investigated. In general, high conversions were obtained. The order with respect to initiator was consistent with the classical kinetic rate equation, while the order with respect to the monomer was greater than unity. The overall activation energy of 53.6 kJ mol(-1) was obtained in the temperature range 60-80 degrees C. The decreasing of the absolute molecular weights when increasing the CIA concentration was confirmed by GPC/SEC/LALS analyses. It was confirmed by UV-visible analyses the effect of molecular weights on the lower critical solution temperature of the polymers. It was also verified that the addition of the CTA influenced the kinetic of the polymerizations. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 229-240, 2010

Adsorption of Cr(VI) from aqueous solution by hydrous zirconium oxide

A type of ZrO(2)center dot nH(2)O Was synthesized and its Cr(VI) removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The Cr(VI) adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model. The adsorption capacity increased from 61 to 66 mg g(-1) when the temperature was increased from 298 to 338 K. The positive values of both Delta H degrees and Delta S degrees suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. Delta G degrees values obtained were negative indicating a spontaneous adsorption process. The effective desorption of Cr(VI) on ZrO(2)center dot nH(2)O could be achieved using distilled water at pH 12. (C) 2009 Elsevier B.V. All rights reserved.

Corrosion behavior of Ti-xNb-13Zr alloys in Ringer`s solution

Ti-6Al-4V alloy has been widely used in restorative surgery due to its high corrosion resistance and biocompatibility. Nevertheless, some studies showed that V and Al release in the organism might induce cytotoxic effects and neurological disorders, which led to the development of V-free alloys and both V- and Al-free alloys containing Nb, Zr, Ta, or Mo. Among these alloys, Ti-13Nb-13Zr alloy is promising due to its better biomechanical compatibility than Ti-6Al-4V. In this work, the corrosion behavior of Ti, Ti-6Al-4V, and Ti-xNb-13Zr alloys (x=5, 13, and 20) was evaluated in Ringer`s solution (pH 7.5) at 37 degrees C through open-circuit potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Spontaneous passivity was observed for all materials in this medium. Low corrosion current densities (in the order of 10(-7) A/cm(2)) and high impedance values (in the order of 10(5) Omega cm(2) at low frequencies) indicated their high corrosion resistance. EIS results showed that the passivating films were constituted of an outer porous layer (very low resistance) and an inner compact layer (high resistance), the latter providing the corrosion resistance of the materials. There was evidence that the Ti-xNb-13Zr alloys were more corrosion resistant than both Ti and Ti-6Al-4V in Ringer`s solution.

Combined solution for fault location in three-terminal lines based on wavelet transforms

This work presents the study and development of a combined fault location scheme for three-terminal transmission lines using wavelet transforms (WTs). The methodology is based on the low- and high-frequency components of the transient signals originated from fault situations registered in the terminals of a system. By processing these signals and using the WT, it is possible to determine the time of travelling waves of voltages and/or currents from the fault point to the terminals, as well as estimate the fundamental frequency components. A new approach presents a reliable and accurate fault location scheme combining some different solutions. The main idea is to have a decision routine in order to select which method should be used in each situation presented to the algorithm. The combined algorithm was tested for different fault conditions by simulations using the ATP (Alternative Transients Program) software. The results obtained are promising and demonstrate a highly satisfactory degree of accuracy and reliability of the proposed method.

Chaos-Galerkin solution of stochastic Timoshenko bending problems

This paper presents an accurate and efficient solution for the random transverse and angular displacement fields of uncertain Timoshenko beams. Approximate, numerical solutions are obtained using the Galerkin method and chaos polynomials. The Chaos-Galerkin scheme is constructed by respecting the theoretical conditions for existence and uniqueness of the solution. Numerical results show fast convergence to the exact solution, at excellent accuracies. The developed Chaos-Galerkin scheme accurately approximates the complete cumulative distribution function of the displacement responses. The Chaos-Galerkin scheme developed herein is a theoretically sound and efficient method for the solution of stochastic problems in engineering. (C) 2011 Elsevier Ltd. All rights reserved.

Galerkin Solution of Stochastic Beam Bending on Winkler Foundations

In this paper, the Askey-Wiener scheme and the Galerkin method are used to obtain approximate solutions to stochastic beam bending on Winkler foundation. The study addresses Euler-Bernoulli beams with uncertainty in the bending stiffness modulus and in the stiffness of the foundation. Uncertainties are represented by parameterized stochastic processes. The random behavior of beam response is modeled using the Askey-Wiener scheme. One contribution of the paper is a sketch of proof of existence and uniqueness of the solution to problems involving fourth order operators applied to random fields. From the approximate Galerkin solution, expected value and variance of beam displacement responses are derived, and compared with corresponding estimates obtained via Monte Carlo simulation. Results show very fast convergence and excellent accuracies in comparison to Monte Carlo simulation. The Askey-Wiener Galerkin scheme presented herein is shown to be a theoretically solid and numerically efficient method for the solution of stochastic problems in engineering.

Solution of a heterogeneous modeling of a horizontal-flow anaerobic immobilized biomass (HAIB) reactor by the sequencing method

A modeling study was completed to develop a methodology that combines the sequencing and finite difference methods for the simulation of a heterogeneous model of a tubular reactor applied in the treatment of wastewater. The system included a liquid phase (convection diffusion transport) and a solid phase (diffusion reaction) that was obtained by completing a mass balance in the reactor and in the particle, respectively. The model was solved using a pilot-scale horizontal-flow anaerobic immobilized biomass (HAIB) reactor to treat domestic sewage, with the concentration results compared with the experimental data. A comparison of the behavior of the liquid phase concentration profile and the experimental results indicated that both the numerical methods offer a good description of the behavior of the concentration along the reactor. The advantage of the sequencing method over the finite difference method is that it is easier to apply and requires less computational time to model the dynamic simulation of outlet response of HAIB.

Influence of the Solvent Evaporation Rate on the Crystalline Phases of Solution-Cast Poly(Vinylidene Fluoride) Films

The influence of the solvent-evaporation rate on the formation of of. and P crystalline phases in solution-cast poly(vinylidene fluoride) (PVDF) films was systematically investigated. Films were crystallized from PVDF/N,N-dimethylformamide solutions with concentrations of 2.5, 5.0, 10, and 20 wt % at different temperatures. During crystallization, the solvent evaporation rate was monitored in situ by means of a semianalytic balance. With this system, it was possible to determine the evaporation rate for different concentrations and temperatures of the solution under specific ambient conditions (pressure, temperature, and humidity). Fourier-Transform InfraRed spectroscopy with Attenuated Total Reflectance revealed the P-phase content in the PVDF films and its dependence on previous evaporation rates. Based on the relation between the evaporation rate and the PVDF phase composition, a consistent explanation for the different amounts of P phase observed at the upper and lower sample surfaces is achieved. Furthermore, the role of the sample thickness has also been studied. The experimental results show that not only the temperature but also the evaporation rate have to be controlled to obtain the desired crystalline phases in solution-cast PVDF films. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 785-791, 2010

Buckling and post-buckling of extensible rods revisited: A multiple-scale solution

An exact non-linear formulation of the equilibrium of elastic prismatic rods subjected to compression and planar bending is presented, electing as primary displacement variable the cross-section rotations and taking into account the axis extensibility. Such a formulation proves to be sufficiently general to encompass any boundary condition. The evaluation of critical loads for the five classical Euler buckling cases is pursued, allowing for the assessment of the axis extensibility effect. From the quantitative viewpoint, it is seen that such an influence is negligible for very slender bars, but it dramatically increases as the slenderness ratio decreases. From the qualitative viewpoint, its effect is that there are not infinite critical loads, as foreseen by the classical inextensible theory. The method of multiple (spatial) scales is used to survey the post-buckling regime for the five classical Euler buckling cases, with remarkable success, since very small deviations were observed with respect to results obtained via numerical integration of the exact equation of equilibrium, even when loads much higher than the critical ones were considered. Although known beforehand that such classical Euler buckling cases are imperfection insensitive, the effect of load offsets were also looked at, thus showing that the formulation is sufficiently general to accommodate this sort of analysis. (c) 2008 Elsevier Ltd. All rights reserved.

Numerical solution of the two-phase expansion of a metastable flashing liquid jet using the dispersion-controlled dissipative scheme

This paper presents a study of the stationary phenomenon of superheated or metastable liquid jets, flashing into a two-dimensional axisymmetric domain, while in the two-phase region. In general, the phenomenon starts off when a high-pressure, high-temperature liquid jet emerges from a small nozzle or orifice expanding into a low-pressure chamber, below its saturation pressure taken at the injection temperature. As the process evolves, crossing the saturation curve, one observes that the fluid remains in the liquid phase reaching a superheated condition. Then, the liquid undergoes an abrupt phase change by means of an oblique evaporation wave. Across this phase change the superheated liquid becomes a two-phase high-speed mixture in various directions, expanding to supersonic velocities. In order to reach the downstream pressure, the supersonic fluid continues to expand, crossing a complex bow shock wave. The balance equations that govern the phenomenon are mass conservation, momentum conservation, and energy conservation, plus an equation-of-state for the substance. A false-transient model is implemented using the shock capturing scheme: dispersion-controlled dissipative (DCD), which was used to calculate the flow conditions as the steady-state condition is reached. Numerical results with computational code DCD-2D vI have been analyzed. Copyright (C) 2009 John Wiley & Sons, Ltd.

Surface tension of flotation solution and its influence on the selectivity of the separation between apatite and gangue minerals

This work presents and discusses the influence of the surface tension (gamma(LV)) of methanol/water mixtures on the flotation response of apatite versus gangue minerals conditioned with flotation reagents (75 g/t cornstarch and 100 g/t Berol 867) at pH 10.6. Berol 867 is a collector composed of sodium alkyl sarcosinate plus nonionic surfactant. The highest Schulz efficiency of separation (recovery of apatite minus recovery of gangue) was achieved at approximate to 51.0 mN/m. The critical surface tension of wettability (gamma(C)) of apatite was found to occur at 34.7 mN/m when determined by means of gamma flotation experiments, , and it was 33.9 mN/m when determined by Zisman`s approach.

A contribution to the exact modal solution of in-plane beam structures

The exact vibration modes and natural frequencies of planar structures and mechanisms, comprised Euler-Bernoulli beams, are obtained by solving a transcendental. nonlinear, eigenvalue problem stated by the dynamic stiffness matrix (DSM). To solve this kind of problem, the most employed technique is the Wittrick-Williams algorithm, developed in the early seventies. By formulating a new type of eigenvalue problem, which preserves the internal degrees-of-freedom for all members in the model, the present study offers an alternative to the use of this algorithm. The new proposed eigenvalue problem presents no poles, so the roots of the problem can be found by any suitable iterative numerical method. By avoiding a standard formulation for the DSM, the local mode shapes are directly calculated and any extension to the beam theory can be easily incorporated. It is shown that the method here adopted leads to exact solutions, as confirmed by various examples. Extensions of the formulation are also given, where rotary inertia, end release, skewed edges and rigid offsets are all included. (C) 2008 Elsevier Ltd. All rights reserved.

Evidences of the evolution from solid solution to surface segregation in Ni-doped SnO(2) nanoparticles using Raman spectroscopy

Ni-doped SnO(2) nanoparticles, promising for gas-sensing applications, have been synthesized by a polymer precursor method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile-type phase (tetragonal SnO(2)) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room-temperature Raman spectra of Ni-doped SnO(2) nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A(1g) mode with the Ni content, a solubility limit at similar to 2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above similar to 2 mol% Ni, the redshift of A(1g) mode suggests that the surface segregation of Ni ions takes place. Disorder-activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid-solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright (C) 2010 John Wiley & Sons, Ltd.

Selective corrosion of 550 degrees C aged Cu10Ni-3Al-1.3Fe alloy in NaCl aqueous solution

This work studied the electrochemical behavior of a solution treated or 550 degrees C aged Cu10Ni-3Al-1.3Fe alloy, in 0.01 M NaCl aqueous solution, through potentiodynamic polarization in both stagnant condition or under erosion process. Results showed the occurrence of a passivity break potential (E(pb)), related to the beginning of the denickelification process, which occurred as a localized attack under stagnant electrolyte. Under erosion conditions localized denickelification was not observed, despite of the presence of E(pb). This could indicate that selective corrosion of Ni, which caused the observed E(pb), occurred as a dissolution-redeposition process, with removal of the Cu deposits during erosion process. (C) 2011 Elsevier Ltd. All rights reserved.