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P E Schoen

Publications and source records attributed to P E Schoen.

7 recordsLinked to original sources

A temperature study of diacetylenic phosphatidylcholine vesicles.

Dispersions of the diacetylenic phosphatidylcholine, 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine, DC8,9PC, undergo a change from vesicles to hollow tubes on cooling. We report here a light scattering and multinuclear NMR study of the lipid vesicles over the temperature range 0-50 degrees C. The 'splitting' of the N+(CH3)3 resonance increases with decreasing temperature, consistent with the light scattering measurements which show a decrease in vesicle size with decreasing temperature. The NMR spectrum remains well-resolved over this temperature range, even at temperatures as low as 3 degrees C. Phosphorus NMR also indicates that the 'bilayer structure' is maintained over this temperature range. The various proton resonances and the phosphorous signal from the lipid vesicles broaden as the temperature is lowered. These results will be helpful in developing a model for the tubule-forming ability of DC8,9PC.

Alkynes↗

Fabrication of surfaces resistant to protein adsorption and application to two-dimensional protein patterning.

Proteins were attached in defined geometric patterns on a surface. A prerequisite to making a pattern of proteins is generation of surfaces resistant to nonspecific protein adsorption. This was accomplished via oxidation of the thiol terminus of an organosilane self-assembled monolayer film by deep ultraviolet (DUV) irradiation. The resultant surface exhibited marked resistance to protein adsorption. Using a mask to protect regions of the silanized surface from irradiation, proteins were selectively adsorbed or attached via covalent linkage at locations protected from the DUV light. Antibodies immobilized in patterns using this procedure retained their antigen-binding capability. Thus chemistry and DUV lithography were combined to create patterns of active biomolecules which could be used in the microfabrication of electronic devices and biosensors.

Adsorption↗

Structure of polymerizable lipid bilayers. I--1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine, a tubule-forming phosphatidylcholine.

This report presents the first X-ray diffraction data on diacetylenic phospholipids. The tubule-forming polymerizable lipid, 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine (DC8,9PC), was studied by low angle X-ray diffraction from partially dehydrated oriented multibilayers in both polymerized and unpolymerized form. Bilayers of this material were found to be highly ordered, yielding as many as 16 orders of lamellar diffraction, in both the polymerized and unpolymerized states. The unit cell dimension was very small for a lipid of this size. In addition to the features usually observed in the electron density profile structure of phospholipid bilayers, the electron-dense diacetylenic portions of the fatty acyl chain produced electron density maxima at two well-defined levels on each side of the bilayer approximately 15 A and 9 A from the bilayer midplane. A model molecular conformation deduced from the one-dimensional electron density map features all-trans acyl chains tilted at approximately 28 degrees from the bilayer normal that are interdigitated with chains of the opposing monolayer by approximately two carbons at the bilayer center. The linear diacetylene moieties on beta- and gamma-chains appear at different positions along the bilayer normal axis and are roughly parallel to the bilayer surface. This model is discussed in terms of a polymerization mechanism.

Diynes↗

Differential scanning calorimetric study of the thermotropic phase behavior of a polymerizable, tubule-forming lipid.

A comparative study of the polymorphism exhibited by the polymerizable, tubule-forming phospholipid 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3- phosphocholine (DC23PC) and its saturated analog 1,2-ditricosanoyl-sn-glycero-3-phosphocholine (DTPC) in aqueous suspension is reported. Differential scanning calorimetry (DSC), as well as freeze-fracture electron microscopy and Raman spectroscopy, have been used to study the influence on phase behavior of rigid diacetylene groups in the fatty acyl chains of a phosphatidylcholine. DTPC large multilamellar vesicle (MLV) and small unilamellar vesicle (SUV) suspensions were found to retain liposome morphology after chain crystallization had occurred. In marked contrast, diacetylenic DC23PC suspensions do not maintain liposomal morphology in converting to the low temperature phase. Large MLVs of DC23PC with outer diameters in excess of 1 micron convert to a gel phase with cylindrical or tubular morphology at 38 degrees C, just a few degrees below the lipid's chain melting temperature (TM(H), i.e. temperature of an endothermic event observed during a heating scan) of 43.1 degrees C. Unlike the large MLVs, small MLVs or SUVs of DC23PC, with diameters of 0.4 +/- 0.3 micron and 0.04 +/- 0.02 micron, respectively, exhibit metastability in the liquid-crystalline state for several tens of degrees below the chain melting temperature prior to converting to a gel phase which, by electron microscopy, manifests itself as extended multilamellar sheets. Raman data collected at TM(H) -40 degrees C demonstrate that the gel state formed by DC23PC is very highly ordered relative to that of DTPC, suggesting that special chain packing requirements are responsible for the novel phase behavior of DC23PC.

Calorimetry, Differential Scanning↗

Orientation of lipid tubules by a magnetic field.

Lipid tubules, which are straight hollow cylinders consisting of lipid bilayers, are shown to orient in strong magnetic fields. Birefringence measurements were made of dilute samples of tubules of 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine (DC23PC) in magnetic fields of up to 4 T. The tubules were found to orient with their long axes parallel to the field direction, with saturated orientation [P2 (cos theta] approximately greater than 0.95) found at approximately 2 T. From known distributions of lengths and the number of bilayers in the walls, a value delta chi = (-7 +/- 1) X 10(-9) erg cm-3 G-2 was calculated for the tubules, which compares well with some previously reported values for phosphatidylcholines. Magnetic alignment will permit more sophisticated structural studies of monomeric and polymeric tubules, and provide a method of orienting macromolecules in the tubule walls or interior.

Birefringence↗