23 research outputs found

    Stages of the bilayer-micelle transition in the system phosphatidylcholine-C12E8 as studied by deuterium- and phosphorous-NMR, light scattering, and calorimetry.

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    The perturbation of phospholipid bilayer membranes by a nonionic detergent, octaethyleneglycol mono-n-dodecylether (C12E8), was investigated by 2H- and 31P-NMR, static and dynamic light scattering, and differential scanning calorimetry. Preequilibrated mixtures of the saturated phospholipids 1,2-dipalmitoyl-sn-glycero-3-phosphorylcholine (DPPC), 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC), and 1,2-dilauroyl-sn-glycero-3-phosphorylcholine (DLPC) with the detergent were studied over a broad temperature range including the temperature of the main thermotropic phase transition of the pure phospholipids. Above this temperature, at a phospholipid/detergent molar ratio 2:1, the membranes were oriented in the magnetic field. Cooling of the mixtures below the thermotropic phase transition temperatures of the pure phospholipids led to micelle formation. In mixtures of DPPC and DMPC with C12E8, a narrow calorimetric signal at the onset temperature of the solubilization suggested that micelle formation was related to the disorder-order transition in the phospholipid acyl chains. The particle size changed from 150 nm to approximately 7 nm over the temperature range of the bilayer-micelle transition. The spontaneous orientation of the membranes at high temperatures enabled the direct determination of segmental order parameters from the deuterium spectra. The order parameter profiles of the phospholipid acyl chains could be attributed to slow fluctuations of the whole membrane and to detergent-induced local perturbations of the bilayer order. The packing constraints in the mixed bilayers that eventually lead to bilayer solubilization were reflected by the order parameters of the interfacial phospholipid acyl chain segments and of the phospholipid headgroup. These results are interpreted in terms of the changing average shape of the component molecules. Considering the decreasing cross sectional areas in the acyl chain region and the increasing hydration of the detergent headgroups, the bilayer-micelle transition is the result of an imbalance in the chain and headgroup repulsion. A neutral or pivotal plane can be defined on the basis of the temperature dependence of the interfacial quadrupolar splittings

    Solute effects on the colloidal and phase behavior of lipid bilayer membranes: ethanol-dipalmitoylphosphatidylcholine mixtures.

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    By means of the scanning differential calorimetry, x-ray diffractometry, and the dynamic light scattering, we have systematically studied the phase and packing properties of dipalmitoylphosphatidylcholine vesicles or multibilayers in the presence of ethanol. We have also determined the partial ternary phase diagram of such dipalmitoylphosphatidylcholine/water/ethanol mixtures. The directly measured variability of the structural bilayer parameters implies that ethanol binding to the phospholipid bilayers increases the lateral as well as the transverse repulsion between the lipid molecules. This enlarges the hydrocarbon tilt (by up to 23 degrees) and molecular area (by < or = 40%). Ethanol-phospholid association also broadens the interface and, thus, promotes lipid headgroup solvation. This results in excessive swelling (by 130%) of the phosphatidylcholine bilayers in aqueous ethanol solutions. Lateral bilayer expansion, moreover, provokes a successive interdigitation of the hydrocarbon chains in the systems with bulk ethanol concentrations of 0.4-1.2 M. The hydrocarbon packing density as well as the propensity for the formation of lamellar gel phases simultaneously increase. The pretransition temperature of phosphatidylcholine bilayers is more sensitive to the addition of alcohol (initial shift: delta Tp = 22 degrees C/mol) than the subtransition temperature (delta Ts reversible 5 degrees C/mol), whereas the chain-melting phase transition temperature is even less affected (delta Tm = 1.8 degrees C/mol). After an initial decrease of 3 degrees for the bulk ethanol concentrations below 1.2 M, the Tm value increases by 2.5 degrees above this limiting concentration. The gel-phase phosphatidylcholine membranes below Tm are fully interdigitated above this limiting concentration. The chain tilt on the fringe of full chain interdigitation is zero and increases with higher ethanol concentrations. Above Tm, some of the lipid molecules are solubilized by the bound ethanol molecules. More highly concentrated ethanol solutions (> 7 M) solubilize the phosphatidylcholine bilayers with fluid chains fully and result in the formation of mixed lipid-alcohol micelles

    Catalogue Des Collections De Monsieur Arthur Löbbecke À Brunswick, De Feu Monsieur L. M. Beels Van Heemstede, À Heemstede, E. A. (1929, 17 Juin)

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    CATALOGUE DES COLLECTIONS DE MONSIEUR ARTHUR LÖBBECKE À BRUNSWICK, DE FEU MONSIEUR L. M. BEELS VAN HEEMSTEDE, À HEEMSTEDE, E. A. Catalogue / J. Schulman (-) Catalogue Des Collections De Monsieur Arthur Löbbecke À Brunswick, De Feu Monsieur L. M. Beels Van Heemstede, À Heemstede, E. A. (1929, 17 Juin) ( - ) Cover ( - ) Titelseite ( - ) Conditions de la Vente. / Abréviations principales. ( - ) Médailles Artistiques (1) Italie (1) France (12) Pays-Bas. (17) Angleterre (21) Espagne (21) Allemagne (22) Autriche (29) Plaquettes (35) Italie (35) Allemagne (43) Pays-Bas (45) France (46) Varia. (46) Index Alphabétique (47) Noms Des Artistes. (47) Noms Des Personnages, Pays, Villes Et Sujets Divers. (48) Pl. XXVII ( -

    Continuous Flow Desulfurization of a Model Fuel Catalysed by Titanium Functionalized UiO‐66

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    The porous material UiO‐66 is one of the most stable MOFs, retaining its properties under a relatively wide range of chemical and physical conditions, making it attractive for post‐synthetic modifications and catalytic applications. A Titanium functionalization of UiO‐66 has been carried out and the synthesized material has been efficiently used as catalyst in the continuous oxidative desulfurization of a model fuel with aqueous H2O2. Using dibenzothiophene as sulfur source, only a partial desulfurization has been achieved, nevertheless the functionalized MOF showed better performances compared to the standard UiO‐66. The titanium containing MOF allowed to completely removing thioanisole from the oil phase within only eight minutes. The pore sizes of UiO‐66 are playing an important role in allowing a fast oxidation of the thioanisole compared to dibenzothiophene
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