Giraudeau P.,Universite Ibn Tofail
Magnetic Resonance in Chemistry | Year: 2014
Two-dimensional (2D) liquid-state NMR has a very high potential to simultaneously determine the absolute concentration of small molecules in complex mixtures, thanks to its capacity to separate overlapping resonances. However, it suffers from two main drawbacks that probably explain its relatively late development. First, the 2D NMR signal is strongly molecule-dependent and site-dependent; second, the long duration of 2D NMR experiments prevents its general use for high-throughput quantitative applications and affects its quantitative performance. Fortunately, the last 10 years has witnessed an increasing number of contributions where quantitative approaches based on 2D NMR were developed and applied to solve real analytical issues. This review aims at presenting these recent efforts to reach a high trueness and precision in quantitative measurements by 2D NMR. After highlighting the interest of 2D NMR for quantitative analysis, the different strategies to determine the absolute concentrations from 2D NMR spectra are described and illustrated by recent applications. The last part of the manuscript concerns the recent development of fast quantitative 2D NMR approaches, aiming at reducing the experiment duration while preserving - or even increasing - the analytical performance. We hope that this comprehensive review will help readers to apprehend the current landscape of quantitative 2D NMR, as well as the perspectives that may arise from it. Copyright © 2014 John Wiley & Sons, Ltd.
Goldbeter A.,Universite Ibn Tofail
FEBS Letters | Year: 2013
Oscillations occur in a number of enzymatic systems as a result of feedback regulation. How Michaelis-Menten kinetics influences oscillatory behavior in enzyme systems is investigated in models for oscillations in the activity of phosphofructokinase (PFK) in glycolysis and of cyclin-dependent kinases in the cell cycle. The model for the PFK reaction is based on a product-activated allosteric enzyme reaction coupled to enzymatic degradation of the reaction product. The Michaelian nature of the product decay term markedly influences the period, amplitude and waveform of the oscillations. Likewise, a model for oscillations of Cdc2 kinase in embryonic cell cycles based on Michaelis-Menten phosphorylation-dephosphorylation kinetics shows that the occurrence and amplitude of the oscillations strongly depend on the ultrasensitivity of the enzymatic cascade that controls the activity of the cyclin-dependent kinase. © 2013 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.
Amstutz S.,Universite Ibn Tofail |
Novotny A.A.,Laboratorio Nacional Of Computacao Cientifica Lncc Mct
Structural and Multidisciplinary Optimization | Year: 2010
The topological asymptotic analysis provides the sensitivity of a given shape functional with respect to an infinitesimal domain perturbation. Therefore, this sensitivity can be naturally used as a descent direction in a structural topology design problem. However, according to the literature concerning the topological derivative, only the classical approach based on flexibility minimization for a given amount of material, without control on the stress level supported by the structural device, has been considered. In this paper, therefore, we introduce a class of penalty functionals that mimic a pointwise constraint on the Von Mises stress field. The associated topological derivative is obtained for plane stress linear elasticity. Only the formal asymptotic expansion procedure is presented, but full justifications can be deduced from existing works. Then, a topology optimization algorithm based on these concepts is proposed, that allows for treating local stress criteria. Finally, this feature is shown through some numerical examples. © Springer-Verlag 2009.
Polettini M.,Universite Ibn Tofail
Journal of Physics A: Mathematical and Theoretical | Year: 2015
We provide an exact expression for the statistics of the fluxes of Markov jump processes at all times, improving on asymptotic results from large deviation theory. The main ingredient is a generalization of the BEST theorem in enumeratoric graph theory to Eulerian tours with open ends. In the long-time limit we reobtain Sanov's theorem for Markov processes, which expresses the exponential suppression of fluctuations in terms of relative entropy. The finite-time power-law term, increasingly important with the system size, is a spanning-tree determinant that, by introducing Grassmann variables, can be absorbed into the effective Lagrangian of a Fermionic ghost field on a metric space, coupled to a gauge potential. With reference to concepts in nonequilibrium stochastic thermodynamics, the metric is related to the dynamical activity that measures net communication between states, and the connection is made to a previous gauge theory for diffusion processes. © 2015 IOP Publishing Ltd.
Delay E.,Universite Ibn Tofail
Differential Geometry and its Application | Year: 2011
We show that two smooth nearby Riemannian metrics can be glued interpolating their scalar curvature. The resulting smooth metric is the same as the starting ones outside the gluing region and has scalar curvature interpolating between the original ones. One can then glue metrics while maintaining inequalities satisfied by the scalar curvature. We also glue asymptotically Euclidean metrics to Schwarzschild ones and the same for asymptotically Delaunay metrics, keeping bounds on the scalar curvature, if any. This extends the Corvino gluing near infinity to non-constant scalar curvature metrics. © 2011 Elsevier B.V.