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171.
Recently, we demonstrated via large-scale molecular dynamics simulations a "coexistence period" in polymer melt ordering before crystallization, where nucleation and growth mechanisms coexist with a phase-separation mechanism [Gee et al., Nat. Mater. 5, 39 (2006)]. Here, we present an extension of this work, where we analyze the directional displacements as a measure of the mobility of monomers as they order during crystallization over more than 100 ns of simulation time. It is found that the polymer melt, after quenching, rapidly separates into many ordered hexagonal domains separated by amorphous regions, where surprisingly, the magnitude of the monomer's displacement in the ordered state, parallel to the domain axial direction, is similar to its magnitude in the melt. The monomer displacements in the domain's lateral direction are found to decrease during the time of the simulation. The ordered hexagonal domains do not align into uniform lamellar structures during the timescales of our simulations. 相似文献
172.
Anne Landreau Samuel Bertrand Claudia Simoes-Pires Laurence Marcourt Dang Bach Taï Marc Litaudon 《Natural product research》2016,30(24):2754-2759
The study describes bioactive compounds as inhibitors of acetylcholinesterase (AChE), from the stem bark extract of Montrouziera cauliflora, selected among 19 dichloromethane extracts from Clusiaceae species. Our work focused on the development of an original normal phase HPLC microfractionation strategy to rapidly assess highly active zones from this crude active non-polar plant extract. Two different microfraction collection methods were evaluated for the assessment of the AChE inhibition. Two guttiferones and a tocotrienol were directly isolated among five compounds identified off-line by NMR after upscaling the fractionation and their AChE inhibition was evaluated. The strengths and weaknesses of the two microfractionation collection methods for HPLC-AChE activity-based profiling are discussed. 相似文献
173.
174.
Rich and complex Raman scattering and Raman optical activity (ROA) spectra have been measured monitoring the pH induced alpha-helix-to-disordered conformational transition in poly(L-glutamic acid). Two-dimensional (2D) correlation techniques have been applied to facilitate a comprehensive analysis of these two complementary spectral sets. Synchronous contour plots have identified band assignments of alpha-helical and disordered conformations, and have revealed bands characteristic of changes in the protonation state of the polypeptide. Asynchronous plots, on the other hand, have probed the relative sequential orders of intensity changes indicating a decrease in intensity of alpha-helical bands in the backbone skeletal stretch region, followed by a subsequent decrease in intensity in the extended amide III and amide I regions, underlying the appearance of disordered structure, including poly(L-proline) II (PPII) helix. The application of a 2D correlation 'moving' window has also disclosed two distinct phases during helix unfolding in the alpha-helix-to-disordered transition, occurring at approximately pH 4.9 and approximately pH 5.2, possibly a result of the difference in helical stability between the end and central regions of the alpha-helix. This paper demonstrates the potential value of combining 2D Raman, 2D ROA and moving window correlation techniques for the detailed investigation of complex and subtle changes of secondary structure during the unfolding mechanisms of polypeptides and proteins. 相似文献
175.
We present real-time observations by confocal microscopy of the dynamic behavior of multilamellar vesicles (MLVs), composed of charged synthetic lipids, when put in contact with oppositely charged polyelectrolyte (PE) molecules. We find that the MLVs exhibit astonishing morphological transitions, which result from the discrete and progressive binding of the charged bilayers induced by a high PE concentration gradient. Our physical picture is confirmed by quantitative measurements of the fluorescence intensity as the bilayers bind to each other. The shape transitions lead eventually to the spontaneous formation of hollow capsules, whose thick walls are composed of lipid multilayers condensed with PE molecules. This class of objects may have some (bio)technological applications. 相似文献
176.
Bouafsoun A Helali S Othmane A Kerkeni A Prigent AF Jaffrézic-Renault N Bessueille F Léonard D Ponsonnet L 《Macromolecular bioscience》2007,7(5):599-610
To study cell attachment to biomaterials, several proteins such as fibronectin, collagen IV, heparin, immunoglobulin G, and albumin have been deposited onto polystyrene adsorbed on a self-assembled monolayer (silane or thiol) on glass or gold, respectively. The different steps of this multilayer assembly have been characterized by electrochemical impedance spectroscopy (EIS). These data are compared to those of adhesion rate, viability percentage, and cytoskeleton labeling for a better understanding of the cell adhesion process to each protein. All the proteins are endothelial cell adhering biomolecules but not with the same features. A linear relationship has been established between adhesion rate and resistance of the endothelial cell/protein interface for all negatively charged proteins. 相似文献
177.
An asymptotic theory based on multipole expansions is presented for multiparticle interactions in unbounded, weakly viscoelastic, creeping flows. The theory accounts for non-Newtonian sphere–sphere interactions that are of order O(De(a/R)2), where De is the Deborah number, a the sphere radius and R is the sphere–sphere separation. Analytic expressions are derived for the non-Newtonian correction to the multisphere mobility matrix for non-neutrally buoyant sedimenting spheres, and for neutrally buoyant spheres suspended in a shear flow. It is shown that these expressions give rise to particle chaining in simulations of interacting spherical particles. 相似文献
178.
179.
Lignier P Morfin F Mangematin S Massin L Rousset JL Caps V 《Chemical communications (Cambridge, England)》2007,(2):186-188
The gold reference catalyst Au/TiO(2) exhibits high activity in the stereoselective epoxidation of trans-stilbene in methylcyclohexane in the presence of 5 mol% TBHP, by taking part in a chain reaction involving the activation of molecular oxygen by a radical produced from methylcyclohexane. 相似文献
180.
Complexes formed by a double-tail cationic surfactant, didodecyldimethyl ammonium bromide, and an anionic polyelectrolyte, an alternating copolymer of poly(styrene-alt-maleic acid) in its sodium salt form, were investigated with respect to variation in the charge ratio (x) between the polyelectrolyte negative charges and the surfactant positive charges. The morphology and microstructure of the complexes were studied by light microscopy and small-angle X-ray scattering for different preparation conditions. Independent of the sample preparation procedure and the charge ratio x, the X-ray results show that the microscopic structure of the complexes is a condensed lamellar phase. By contrast, the morphology of the complexes changes dramatically with the preparation procedure. The complexes formed by mixing a surfactant solution and a polyelectrolyte solution strongly depend on x and are always extremely heterogeneous in size and shape. Surprisingly, we show that, when the two solutions interdiffuse slowly, spherical complexes of micrometric and rather uniform size are systematically obtained, independently on the initial relative amount of surfactant and polyelectrolyte. The mechanism for the formation of these peculiar complexes is discussed. 相似文献