How melatonin interacts with lipid bilayers: a study by fluorescence and ESR spectroscopies

AbstractESR spectra of spin labels placed at the membrane surface and at different depths of the bilayer core, and melatonin fluorescence in the presence of lipid vesicles, suggest an average shallow position for the hormone in the membrane. However, according to the melatonin ability to cross lipid bilayers, nitroxides placed deep in the bilayer were able to quench the melatonin fluorescence. Melatonin membrane partition coefficients were calculated for bilayers in different packing states, and similar and rather high values were found. The data presented here may be quite important to the understanding of melatonin physiological actions at the membrane level

Comparative EPR and fluorescence conformational studies of fully active spin-labeled melanotropic peptides

Similar to melanocyte stimulating hormone (alpha -MSH), its potent and long-acting analogue, [Nle(4), D-Phe(7)]alpha -MSH, when labeled with the paramagnetic amino acid probe 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (Toac), maintains its full biological potency, thus validating any comparative structural investigations between the two labeled peptides, Correlation times, calculated from tire electron paramagnetic resonance signal of Toac bound to the peptides, and Toac-Trp distances, estimated from the Toac fluorescence quenching of the Trp residue present in the peptides, indicate a more rigid and folded structure for the potent analogue as compared to the hormone, in aqueous medium. (C) 2001 Published by Elsevier Science B.V. on behalf of the Federation of European Biochemical Societies.Universidade Federal de São Paulo, Dept Biofis, BR-04044020 São Paulo, BrazilUniv São Paulo, Inst Fis, BR-66318 São Paulo, BrazilUniv São Paulo, Inst Biociencias, Dept Fisiol, BR-11176 São Paulo, BrazilUniversidade Federal de São Paulo, Dept Biofis, BR-04044020 São Paulo, BrazilWeb of Scienc

First synthesis of a fully active spin-labeled peptide hormone

For the first time in the electron spin resonance (ESR) and peptide synthesis fields, a fully active spin-labeled peptide hormone was reported. the ESR spectra of this alpha-melanocyte stimulating hormone (alpha-MSH) analogue (acetyl-Toac(0)-alpha-MSH) where Toac is the paramagnetic amino acid probe 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid, suggested a pH-independent conformation and a more restricted movement comparatively to the free Toac, Owing to its equivalent biological potency in a skin pigmentation assay as compared to the native alpha-MSH and its unique characteristic (paramagnetic, naturally fluorescent and fully active), this analogue is of great potential for investigation of relevant physiological roles reported for a-MSH, (C) 1999 Federation of European Biochemical Societies.Universidade Federal de São Paulo, Dept Biofis, BR-04044020 São Paulo, BrazilUniv São Paulo, Inst Fis, BR-01498 São Paulo, BrazilUniv São Paulo, Inst Biociencias, Dept Fisiol, BR-01498 São Paulo, BrazilUniversidade Federal de São Paulo, Dept Biofis, BR-04044020 São Paulo, BrazilWeb of Scienc

Systèmes tolérants aux défauts (analyse et synthèse stochastique)

Dans cette thèse, nous nous sommes intéressés aux contraintes résultants de l'intégration d'un module de diagnostic de pannes et d'un module de reconfiguration de lois de commandes. Contraintes pouvant conduire à une perte de performances, voir une instabilité, du système. La formalisation mathématique de cette problématique nous a amené à nous intéresser à une classe de systèmes hybrides stochastiques à sauts markoviens. La première partie du travail de thèse a été consacrée à la synthèse de lois de commande, par retour de sortie, stabilisant stochastiquement cette classe de systèmes à des bruits multiplicatifs. Les approches développées sont basées sur la théorie de Lyapunov et de Supermartingale. Les différentes conditions de synthèse sont données en termes d inégalités matricielles non linéaires. Des algorithmes d'optimisation non convexe nt alors été proposés pour la résolution de ces différentes conditions. En deuxième partie de thèse, nous nous sommes intéressés au problème de commande multi-performances de cette classe de systèmes. Plus particulièrement, nous avons considéré des critères H et des critères H2. Là aussi, et nous avons proposé des conditions sous forme LMI, BMI et NLMI pour la résolution de ce problème. En dernière partie de thèse, nous nous sommes intéressés au cas des systèmes à temps discret. Nous avons là aussi considéré des problèmes de stabilisation stochastique et de commande multi-objectifs, pour lesquels des conditions sous forme LMI et NLMI ont été établies. Nous avons ensuite appliqué ces résultats à la problématique de commande de systèmes en réseaux sujets à des retards, des pertes de paquets et d'éventuels pannes.Despite the evident interaction between FDI and reconfiguration algorithms, it is true that the research on FDI and reconfiguration methods has often evolved separately, certainly because of the difficulty of each of these problems. The main contribution of this work is to use a mathematical model that includes in the same analysis framework the FDI and reconfiguration algorithms. Such a model belongs to the class of Markovian jump linear systems. In this class of systems, two random processes are defined: the first represents system components failures and the second represents the FDI process. The first problematic considered in this thesis is related to the synthesis of output feedback controllers that stochastically stabilize this class of systems subject to Brownian motion. The developed results are based essentially on Lyapunov theory and Supermartingale notion. The different synthesis conditions are formulated as nonlinear matrix inequalities problematic. Noncovex optimization algorithms were then proposed to solve these conditions. The second problematic addressed in this work concerns the multi-objective control of this class of Markovian jump systems. The specifications and objectives under consideration include stochastic stability, H2 and H performances. Output feedback controllers synthesis conditions were also proposed in term of LMI, BMI and NLMI. Finally, we have addressed the discrete-time counterpart and proposed H2/H synthesis conditions. The developed results were applied to the problematic of control of networked systems subject to delays, packet loss and failures.NANCY1-SCD Sciences & Techniques (545782101) / SudocSudocFranceF

The peculiar thermo-structural behavior 93790 (2008) 930e938of the anionic lipid DMPG, Chem. Phys. Lipids 122

Abstract Aqueous dispersions of the anionic phospholipid dimyristoyl phosphatidylglycerol (DMPG), around 100 mM ionic strength, are known to exhibit a thermal behavior similar to that of the largely studied lipid dimyristoyl phosphatidylcholine (DMPC), which undergoes a gel to liquid crystalline phase transition at 23 8C, well characterized by differential scanning calorimetry (DSC), and other methods. However, at low ionic strength, DMPG has been shown to present a large gel Á/fluid transition region, ranging from 18 to 35 8C. This intermediate phase is optically transparent and characterized by a continuous change in membrane packing. Structural properties of the DMPG gel Á/ fluid transition region will be discussed, based on results obtained by several techniques: electron spin resonance (ESR) of spin labels at the membrane surface and intercalated at different depths in the bilayer; light scattering; DSC; small angle X-ray scattering (SAXS); and fluorescence spectroscopy of probes in the bilayer.