282 resultados para redox-active disulfide


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Fluorescence quenching of biologically active carboxamide namely (E)-2-(4-chlorobenzylideneamino)-N-(2-chlorophenyl)-4,5,6,7-tetrahydrobe nzo[b]thiophene-3-carboxamide [ECNCTTC] by aniline and carbon tetrachloride (CCl(4)) quenchers in different solvents using steady state method and time resolved method using only one solvent has been carried out at room temperature to understand the role of quenching mechanisms. The Stern-Volmer plot has been found to be linear for all the solvents studied. The probability of quenching per encounter p (p') was determined in all the solvents and was found to be less than unity. Further, from the studies of rate parameters and life time measurements in n-heptane and cyclohexane with aniline and carbon tetrachloride as quenchers have been shown that, the phenomenon of quenching is generally governed by the well-known Stern-Volmer (S-V) plot. The activation energy E(a) (or E(a)') of quenching was determined using the literature values of activation energy of diffusion E(d) and the experimentally determined values of p (or p'). It has been found that, the activation energy E(a) (E(a)') is greater than the activation energy for diffusion E(d) in all solvents. Hence, from the magnitudes of E(a) (or E(a)') as well as p (or p') infer that, the quenching mechanism is not solely due to the material diffusion, but there is also contribution from the activation energy. (C) 2011 Elsevier B.V. All rights reserved.

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A majority of enzymes show a high degree of specificity toward a particular metal ion in their catalytic reaction. However, Type II restriction endonuclease (REase) R.KpnI, which is the first member of the HNH superfamily of REases, exhibits extraordinary diversity in metal ion dependent DNA cleavage. Several alkaline earth and transition group metal ions induce high fidelity and promiscuous cleavage or inhibition depending upon their concentration. The metal ions having different ionic radii and co-ordination geometries readily replace each other from the enzyme's active site, revealing its plasticity. Ability of R KpnI to cleave DNA with both alkaline earth and transition group metal ions having varied ionic radii could imply utilization of different catalytic site(s). However, mutation of the invariant His residue of the HNH motif caused abolition of the enzyme activity with all of the cofactors, indicating that the enzyme follows a single metal ion catalytic mechanism for DNA cleavage. Indispensability of His in nucleophile activation together with broad cofactor tolerance of the enzyme indicates electrostatic stabilization function of metal ions during catalysis. Nevertheless, a second metal ion is recruited at higher concentrations to either induce promiscuity or inhibit the DNA cleavage. Regulation of the endonuclease activity and fidelity by a second metal ion binding is a unique feature of R.KpnI among REases and HNH nucleases. The active site plasticity of R.KpnI opens up avenues for redesigning cofactor specificities and generation of mutants specific to a particular metal ion.

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Active-clamp dc-dc converters are pulsewidth-modulated converters having two switches featuring zero-voltage switching at frequencies beyond 100 kHz. Generalized equivalent circuits valid for steady-state and dynamic performance have been proposed for the family of active-clamp converters. The active-clamp converter is analyzed for its dynamic behavior under current control in this paper. The steady-state stability analysis is presented. On account of the lossless damping inherent in the active-clamp converters, it appears that the stability region in the current-controlled active-clamp converters get extended for duty ratios, a little greater than 0.5 unlike in conventional hard-switched converters. The conventional graphical approach fails to assess the stability of current-controlled active-clamp converters, due to the coupling between the filter inductor current and resonant inductor current. An analysis that takes into account the presence of the resonant elements is presented to establish the condition for stability. This method correctly predicts the stability of the current-controlled active-clamp converters. A simple expression for the maximum duty cycle for subharmonic-free operation is obtained. The results are verified experimentally.

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A flexible robot arm can be modeled as an Euler-Bernoulli beam which are infinite degrees of freedom (DOF) system. Proper control is needed to track the desired motion of a robotic arm. The infinite number of DOF of beams are reduced to finite number for controller implementation, which brings in error (due to their distributed nature). Therefore, to represent reality better distributed parameter systems (DPS) should be controlled using the systems partial differential equation (PDE) directly. In this paper, we propose to use a recently developed optimal dynamic inversion technique to design a controller to suppress nonlinear vibration of a beam. The method used in this paper determines control forces directly from the PDE model of the system. The formulation has better practical significance, because it leads to a closed form solution of the controller (hence avoids computational issues).

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In order to demonstrate the feasibility of Active Fiber Composites (AFC) as sensors for detecting damage, a pretwisted strip made of AFC with symmetric free-edge delamination is considered in this paper. The strain developed on the top/bottom of the strip is measured to detect and assess delamination. Variational Asymptotic Method (VAM) is used in the development of a non-classical non-linear cross sectional model of the strip. The original three dimensional (3D) problem is simplified by the decomposition into two simpler problems: a two-dimensional (2D) problem, which provides in a compact form the cross-sectional properties using VAM, and a non-linear one-dimensional (1D) problem along the length of the beam. This procedure gives the non-linear stiffnesses, which are very sensitive to damage, at any given cross-section of the strip. The developed model is used to study a special case of cantilevered laminated strip with antisymmetric layup, loaded only by an axial force at the tip. The charge generated in the AFC lamina is derived in closed form in terms of the 1D strain measures. It is observed that delamination length and location have a definite influence on the charge developed in the AFC lamina. Also, sensor voltage output distribution along the length of the beam is obtained using evenly distributed electrode strip. These data could in turn be used to detect the presence of damage.

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A combined electrochemical method and X-ray photo electron spectroscopy (XPS) has been utilized to understand the Pd(2+)/CeO(2) interaction in Ce(1-x)Pd(x)O(2-delta) (x = 0.02). A constant positive potential (chronoamperometry) is applied to Ce(0.98)Pd(0.02)O(2-delta) working electrode which causes Ce(4+) to reduce to Ce(3+) to the extent of similar to 35%, while Pd remains in the +2 oxidation state. Electrochemically cycling this electrode between 0.0-1.2 V reverts back to the original state of the catalyst. This reversibility is attributed to the reversible reduction of Ce(4+) to Ce(3+) state. CeO(2) electrode with no metal component reduces to CeO(2-y) (y similar to 0.4) after applying 1.2 V which is not reversible and the original composition of CeO(2) cannot be brought back in any electrochemical condition. During the electro-catalytic oxygen evolution reaction at a constant 1.2 V for 1000 s, Ce(0.98)Pd(0.02)O(2-delta) reaches a steady state composition with Pd in the +2 states and Ce(4+) : Ce(3+) in the ratio of 0.65 : 0.35. This composition can be denoted as Ce(0.63)(4+)Ce(0.35)(4+)Pd(0.02)O(2-delta-y) (y similar to 0.17). When pure CeO(2) is put under similar electrochemical condition, it never reaches the steady state composition and reduces almost to 85%. Thus, Ce(0.98)Pd(0.02)O(2-delta) forms a stable electrode for the electro-oxidation of H(2)O to O(2) unlike CeO(2) due to the metal support interaction.

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In arriving at the ideal filter transfer function for an active noise control system in a duct, the effect of the auxiliary sources (generally loudspeakers) on the waves generated by the primary source has invariably been neglected in the existing literature, implying a rigid wall or infinite impedance. The present paper presents a fairly general analysis of a linear one-dimensional noise control system by means of block diagrams and transfer functions. It takes into account the passive as well as active role of a terminal primary source, wall-mounted auxiliary source, open duct radiation impedance, and the effects of mean flow and damping. It is proved that the pressure generated by a source against a load impedance can be looked upon as a sum of two pressure waves, one generated by the source against an anechoic termination and the other by reflecting the rearward wave (incident on the source) off the passive source impedance. Application of this concept is illustrated for both the types of sources. A concise closed-form expression for the ideal filter transfer function is thus derived and discussed. Finally, the dynamics of an adaptive noise control system is discussed briefly, relating its standing-wave variables and transfer functions with those of the progressive-wave model presented here.

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Till date load-commutated inverter (LCI)-fed synchronous motor drive configuration is popular in high power applications (>10 MW). The leading power factor operation of synchronous motor by excitation control offers this simple and rugged drive structure. On the contrary, LCI-fed induction motor drive is absent as it always draws lagging power factor current. Therefore, complicated commutation circuit is required to switch off thyristors for a current source inverter (CSI)-driven induction motor. It poses the major hindrance to scale up the power rating of CSI-fed induction motor drive. Anew power topology for LCI-fed induction motor drive for medium-voltage drive application is proposed. A new induction machine (active-reactive induction machine) with two sets of three-phase winding is introduced as a drive motor. The proposed power configuration ensures sinusoidal voltage and current at the motor terminals. The total drive power is shared among a thyristor-based LCI, an insulated gate bipolar transistor (IGBT)-based two-level voltage source inverter (VSI), and a three-level VSI. The benefits of SCRs and IGBTs are explored in the proposed drive. Experimental results from a prototype drive verify the basic concepts of the drive.