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R. Martínez-Hincapié P. Sebastián-Pascual V. Climent J. M. Feliu 《Russian Journal of Electrochemistry》2017,53(3):227-236
The concepts of total and free charge of platinum single crystal electrodes are revised in this paper, together with the associated concepts of potential of zero total and free charge. Total charges can be measured from CO displacement method. Results on solution of different pH are described. A novel buffer composition is used to attain pH values close to neutrality while avoiding interferences from anion adsorption processes. Stress is made on the fact that free charges are not accessible through electrochemical measurement for systems at equilibrium since adsorption processes (hydrogen and hydroxyl) interfere with free charge determination. Still, a model is described that allows, under some assumptions, extract free charge values and the corresponding potential of zero free charge for Pt(111) electrodes. On the other hand, fast measurement outside equilibrium can separate free charges from adsorption processes based on their different time constant. In this way, the laser induced temperature jump experiment allows determination of the potential of maximum entropy, a magnitude that is intimately related with the potential of zero free charge. Values of the potential of maximum entropy as a function of pH are given for the different basal planes of platinum. 相似文献
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C. Martín Saravia Sebastián P. Machado Víctor H. Cortínez 《European Journal of Mechanics - A/Solids》2011,30(3):432-441
The dynamic stability behavior of thin-walled rotating composite beams is studied by means of the finite element method. The analysis is based on Bolotin’s work on parametric instability for an axial periodic load. The influence of fiber orientation and rotating speeds on the natural frequencies and the unstable regions is studied for symmetrically balanced laminates. The regions of instability are obtained and expressed in non-dimensional terms. The “modal interchange” phenomenon arising in rotating beams is described. The dynamic stability problem is formulated by means of linearizing a geometrically nonlinear total Lagrangian finite element with seven degrees of freedom per node. This finite element formulation is based on a thin-walled beam theory that takes into account several non-classical effects such as anisotropy, shear flexibility and warping inhibition. 相似文献
295.
Esteban Bertsch Sebastián Suñer Dr. Silvana Pinheiro Prof. Dr. William J. Zamora 《Chemphyschem》2023,24(24):e202300548
Lipophilicity is a physicochemical property with wide relevance in drug design, computational biology, food, environmental and medicinal chemistry. Lipophilicity is commonly expressed as the partition coefficient for neutral molecules, whereas for molecules with ionizable groups, the distribution coefficient (D) at a given pH is used. The logDpH is usually predicted using a pH correction over the logPN using the pKa of ionizable molecules, while often ignoring the apparent ion pair partitioning . In this work, we studied the impact of on the prediction of both the experimental lipophilicity of small molecules and experimental lipophilicity-based applications and metrics such as lipophilic efficiency (LipE), distribution of spiked drugs in milk products, and pH-dependent partition of water contaminants in synthetic passive samples such as silicones. Our findings show that better predictions are obtained by considering the apparent ion pair partitioning. In this context, we developed machine learning algorithms to determine the cases that should be considered. The results indicate that small, rigid, and unsaturated molecules with logPN close to zero, which present a significant proportion of ionic species in the aqueous phase, were better modeled using the apparent ion pair partitioning . Finally, our findings can serve as guidance to the scientific community working in early-stage drug design, food, and environmental chemistry. 相似文献
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