Observation of a Low-viscosity Interface Between Immiscible Polymer Layers

この論文は国立情報学研究所の電子図書館事業により電子化されました。研究会報告X-ray Photon Correlation Spectroscopy (XPCS) was employed in a surface standing wave geometry in order to resolve the thermally diffusive in-plane dynamics at both the surface/vacuum (top) and polymer/polymer (bottom) interfaces of a thin Polystyrene (PS) film on top of Poly (4-bromo styrene) (PBrS) and supported on a Si substrate. The top vacuum interface shows two relaxation modes: one fast and one slow, while the buried polymerpolymer interface shows a single slow mode. The slow mode of the top interface is similar in magnitude and wavevector dependence to the single mode of the buried interface. The dynamics are consistent with a low-viscosity mixed layer between the PS and PBrS and coupling of the capillary wave fluctuations between this layer and the PS

Cholesterol Partition and Condensing Effect in Phase-Separated Ternary Mixture Lipid Multilayers

The cholesterol partitioning and condensing effect in the liquid-ordered (Lo) and liquid-disordered (Ld) phases were systematically investigated for ternary mixture lipid multilayers consisting of 1:1 1,2-dipalmitoyl-sn-glycero-3-phosphocholine/1,2-dioleoyl-sn-glycero-3-phosphocholine with varying concentrations of cholesterol. X-ray lamellar diffraction was used to deduce the electron density profiles of each phase. The cholesterol concentration in each phase was quantified by fitting of the electron density profiles with a newly invented basic lipid profile scaling method that minimizes the number of fitting parameters. The obtained cholesterol concentration in each phase versus total cholesterol concentration in the sample increases linearly for both phases. The condensing effect of cholesterol in ternary lipid mixtures was evaluated in terms of phosphate-to-phosphate distances, which together with the estimated cholesterol concentration in each phase was converted into an average area per molecule. In addition, the cholesterol position was determined to a precision of (±0.7Å) and an increase of disorder in the lipid packing in the Lo phase was observed for total cholesterol concentration of 20∼30%

Accurate calibration and control of relative humidity close to 100% by X-raying a DOPC multilayer.

<p>In this study, we have designed a compact sample chamber that can achieve accurate and continuous control of the relative humidity (RH) in the vicinity of 100%. A 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) multilayer can be used as a humidity sensor by measuring its inter-layer repeat distance (d-spacing) via X-ray diffraction. We convert from DOPC d-spacing to RH according to a theory given in the literature and previously measured data of DOPC multilamellar vesicles in polyvinylpyrrolidone (PVP) solutions. This curve can be used for calibration of RH close to 100%, a regime where conventional sensors do not have sufficient accuracy. We demonstrate that this control method can provide RH accuracies of 0.1 to 0.01%, which is a factor of 10-100 improvement compared to existing methods of humidity control. Our method provides fine tuning capability of RH continuously for a single sample, whereas the PVP solution method requires new samples to be made for each PVP concentration. The use of this cell also potentially removes the need for an X-ray or neutron beam to pass through bulk water if one wishes to work close to biologically relevant conditions of nearly 100% RH.</p

Differential adsorption of a membrane skeletal protein, spectrin, in phospholipid membranes

The interaction of phospholipids with the peripheral membrane proteins like spectrin is important not only to understand the various physiological functions of cells, but also to gain insight into the mechanism involved in the self-assembly of polymer-like long chain molecules at the soft surfaces and interfaces. The lipid head-group specificity of adsorption of spectrin to supported phopsholipid bilayer model membranes has been investigated using the X-ray reflectivity (XRR) technique. Model lipid bilayers composed of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) head groups have been prepared on a soft polymer cushion and the XRR measurements have been carried out from the bilayers immersed in a water bath using high-energy synchrotron X-rays. Our results suggest that in PC-based membranes the spectrin chains form a uniform layer on top of the bilayer with their chains lying on the membrane surface, while in PE-based membranes with relatively smaller head groups, the spectrin chains are attached only through a few possible binding sites with the rest of the part projected out of the membrane surface. In addition, the reflectivity profiles reveal the penetration of spectrin polypeptide chains through the PE bilayer in its fluid phase. Pressure-area isotherm measurements on Langmuir monolayers also support similar observations on the adsorption of spectrin molecules to the membranes composed of PC and PE. The observed results were explained using a qualitative model based on the ion-mediated protein interaction in the PC-based membrane

Demonstration of feasibility of X-ray free electron laser studies of dynamics of nanoparticles in entangled polymer melts.

The recent advent of hard x-ray free electron lasers (XFELs) opens new areas of science due to their exceptional brightness, coherence, and time structure. In principle, such sources enable studies of dynamics of condensed matter systems over times ranging from femtoseconds to seconds. However, the studies of "slow" dynamics in polymeric materials still remain in question due to the characteristics of the XFEL beam and concerns about sample damage. Here we demonstrate the feasibility of measuring the relaxation dynamics of gold nanoparticles suspended in polymer melts using X-ray photon correlation spectroscopy (XPCS), while also monitoring eventual X-ray induced damage. In spite of inherently large pulse-to-pulse intensity and position variations of the XFEL beam, measurements can be realized at slow time scales. The X-ray induced damage and heating are less than initially expected for soft matter materials

Demonstration of Feasibility of X-Ray Free Electron Laser Studies of Dynamics of Nanoparticles in Entangled Polymer Melts

The recent advent of hard x-ray free electron lasers (XFELs) opens new areas of science due to theirexceptional brightness, coherence, and time structure. In principle, such sources enable studies of dynamicsof condensed matter systems over times ranging from femtoseconds to seconds. However, the studies of‘‘slow’’ dynamics in polymeric materials still remain in question due to the characteristics of the XFEL beamand concerns about sample damage. Here we demonstrate the feasibility of measuring the relaxationdynamics of gold nanoparticles suspended in polymer melts using X-ray photon correlation spectroscopy(XPCS), while also monitoring eventual X-ray induced damage. In spite of inherently large pulse-to-pulseintensity and position variations of the XFEL beam, measurements can be realized at slow time scales. TheX-ray induced damage and heating are less than initially expected for soft matter materials