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Alice P Gast

Publications and source records attributed to Alice P Gast.

11 recordsLinked to original sources
PubMed2006

Starlike dendrimers in solutions: structural properties and internal dynamics.

We measured the shape and the internal dynamics of starlike dendrimers under good solvent conditions with small-angle neutron scattering and neutron spin-echo (NSE) spectroscopy, respectively. Architectural parameters such as the spacer length and generation were varied in a systematic manner. Structural changes occurring in the dendrimers as a function of these parameters are discussed, i.e., in terms of the fractal dimension and deviations of the radius of gyration from the Gaussian value. A first cumulant evaluation of the NSE spectra for each scattering vector q separately yields the length scale dependent relaxation rates. We observe a local minimum in the normalized relaxation rates Omega(q)q(3) on length scales corresponding to the overall dendrimer dimension. The dynamics is discussed within a Rouse-Zimm approach generalized to the case of starlike dendrimers of arbitrary geometry. The model allows an identification of the modes contributing to the relaxation of the dendrimer in the q and time range of the NSE experiment. The local minimum is due to collective breathing motions of (parts of) the dendrons relative to each other. Shape fluctuations are not observed.

Journal Article↗
PubMed2006

Phase behavior and the partitioning of caveolin-1 scaffolding domain peptides in model lipid bilayers.

The membrane binding and model lipid raft interaction of synthetic peptides derived from the caveolin scaffolding domain (CSD) of the protein caveolin-1 have been investigated. CSD peptides bind preferentially to liquid-disordered domains in model lipid bilayers composed of cholesterol and an equimolar ratio of dioleoylphosphatidylcholine (DOPC) and brain sphingomyelin. Three caveolin-1 peptides were studied: the scaffolding domain (residues 83-101), a water-insoluble construct containing residues 89-101, and a water-soluble construct containing residues 89-101. Confocal and fluorescence microscopy investigation shows that the caveolin-1 peptides bind to the more fluid cholesterol-poor phase. The binding of the water-soluble peptide to lipid bilayers was measured using fluorescence correlation spectroscopy (FCS). We measured molar partition coefficients of 10(4) M(-1) between the soluble peptide and phase-separated lipid bilayers and 10(3) M(-1) between the soluble peptide and bilayers with a single liquid phase. Partial phase diagrams for our phase-separating lipid mixture with added caveolin-1 peptides were measured using fluorescence microscopy. The water-soluble peptide did not change the phase morphology or the miscibility transition in giant unilamellar vesicles (GUVs); however, the water-insoluble and full-length CSD peptides lowered the liquid-liquid melting temperature.

Adsorption↗
PubMed2006

Reversible activation of diblock copolymer monolayers at the interface by pH modulation, 1: Lateral chain density and conformation.

This study focuses on the design of chemically regulated surfaces that allow for reversible control of the interactions between biological matter (cells and proteins) and planar substrates. As a tunable interlayer, we use a monolayer of a near-monodisperse poly[2-(dimethylamino)ethyl methacrylate-block-methyl methacrylate] (PDMAEMA-PMMA) diblock copolymer. Owing to the relatively large fraction (50%) of the hydrophobic PMMA block, this copolymer forms a stable Langmuir monolayer at the air/water interface. Both in situ and ex situ film balance experiments suggest that the hydrophilic PDMAEMA block adsorbs to the air/water interface in its uncharged state (pH 8.5), but stretches into the subphase in its charged state (pH 5.5). Optimization of the preparation protocols enables us to fabricate stable, homogeneous diblock copolymer films on hydrophobized substrates via Langmuir-Schaefer transfer at well-defined lateral chain densities. Ellipsometry and X-ray reflectivity studies of the transferred films confirm that the film thickness can be systematically regulated by the lateral chain densities. The transferred copolymer films remain stable in water for about a week, suggesting that they are promising materials for the creation of pH-controlled solid substrates for the support of biological matter such as proteins and cells.

Adsorption↗
PubMed2006

Reversible activation of diblock copolymer monolayers at the interface by pH modulation, 2: Membrane interactions at the solid/liquid interface.

A monolayer of the pH-responsive poly[2-(dimethylamino)ethyl methacrylate-block-methyl methacrylate] diblock copolymer [PDMAEMA-PMMA] was transferred from the air/water interface to a silicon substrate for evaluation as a tunable interlayer between biological material and solid substrates. Specular neutron reflectivity experiments revealed that the weak polyelectrolyte PDMAEMA chains at the solid/liquid interface can be reversibly activated by pH modulation. The thickness, scattering length density, and surface roughness of the polymer film can be systematically controlled by pH titration. As a simple model of plasma membranes, a lipid bilayer was deposited onto the polymer film. The membrane-substrate interaction was characterized by neutron reflectivity experiments, demonstrating that the membrane-substrate distance could be reversibly regulated by pH titration. These results confirm the potential of stimuli-responsive polymers for precise control of cell-surface interactions.

Biocompatible Materials↗
PubMed2005

Simultaneous observation of enzyme surface diffusion and surface reaction using microfluidic patterning of substrate surfaces.

We present a study of the simultaneous observation of protease reaction and surface diffusion as the enzyme interacts with a model substrate surface. We use micro-fluidic patterning to decorate a bovine serum albumin substrate surface with stripes of adsorbed enzyme in the absence of physical barriers. Spreading of the enzyme from the initial striped region indicates surface diffusion, while removal of the substrate provides a measure of reactivity. Microfluidic patterning provides a means to determine the relative importance of enzyme adsorption, surface diffusion, and reaction on the rate of substrate removal.

Animals↗
PubMed2004

Micromixing with linked chains of paramagnetic particles.

Paramagnetic colloidal particles aggregate into linear chains under an applied external magnetic field. These particles can be chemically linked to create chains that can be magnetically actuated to manipulate microscopic fluid flow. The flexibility of the chain can be adjusted by varying the length of the linker molecule. In this paper, we describe the use of a suspension of linked paramagnetic chains in a rotating magnetic field to perform microscale mixing. The effect of chain rotation and flexibility on the diffusion of molecules is studied by observing the mixing of an acid and base in a microchannel. We show that, as the chain rotation frequency increases, there is marked increase in the effective mixing between fluid streams; however, a maximum frequency exists and above this frequency the chains are no longer effective in mixing. More flexible chains are more effective at mixing over a larger range of frequencies.

Enzymes↗
PubMed2004

A neutron scattering study of the structure and water partitioning of selectively deuterated copolymer micelles.

We present a scattering study of a selectively deuterated micelle-forming diblock copolymer. The copolymer comprises a partially deuterated polystyrene (d,h-PS) block and an imidazolium-functionalized PS (IL) block. In toluene solutions, the copolymers assemble into elongated micelles where the IL block forms the micelle core. Through dynamic light scattering (DLS) measurements, we obtain the overall size of the micelles. In our small-angle neutron scattering (SANS) studies, we use contrast matching to characterize the IL core and the PS shell of the micelles independently. The PS block forming the micelle shell exhibits either a starlike or brushlike conformation depending upon the size of the core to which it is tethered. We find the IL block to be in an extended conformation, driving the formation of slightly elongated and relatively stiff micelle cores. The elongated micelle core cross-sectional radius and length depend linearly on the length of the IL block. We find that the micelles can sequester a few water molecules for each IL repeat unit; the addition of water slightly increases the cross section of the elongated micelles.

Deuterium↗
PubMed2004

Rotational dynamics of semiflexible paramagnetic particle chains.

Paramagnetic particles have the unique ability to reversibly form magnetic chains. We have taken advantage of this property by permanently linking the chains with three linking chemistries to create flexible chains whose behavior changes with the application of a magnetic field. We study the behavior of these chains in a rotating magnetic field and model them as elastic rods. Rigid chains rotate as a solid body while flexible chains deform under the influence of magnetic, viscous, and elastic stresses. We find that the shapes chains assume in rotating magnetic fields confirm the chain flexibility determined from previous micromechanics measurements.

Journal Article↗
PubMed2004

Micelles of imidazolium-functionalized polystyrene diblock copolymers investigated with neutron and light scattering.

We synthesize a series of block copolymers comprising a polystyrene (PS) block and an imidazolium-functionalized PS (IL) block and characterize their assembly properties. We use small-angle neutron scattering and dynamic light scattering to determine the micelle size and shape in dilute solutions and to assess the micelle interactions in concentrated solutions. By studying a series of copolymers with fixed PS block length, we find that the length of the IL block governs the micelle dimensions. Our data suggest that these copolymers form elongated micelle structures where the IL block is extended in the micelle core. We find that these micelles can sequester water and that interactions between the micelles lead to structure factor peaks at elevated concentrations.

Binding Sites↗
PubMed2003

Mechanics of semiflexible chains formed by poly(ethylene glycol)-linked paramagnetic particles.

Magnetorheological particles, permanently linked into chains, provide a magnetically actuated means to manipulate microscopic fluid flow. Paramagnetic colloidal particles form reversible chains by acquiring dipole moments in the presence of an external magnetic field. By chemically connecting paramagnetic colloidal particles, flexible magnetoresponsive chains can be created. We link the paramagnetic microspheres using streptavidin-biotin binding. Streptavidin coated microspheres are placed in a flow cell and a magnetic field is applied, causing the particles to form chains. Then a solution of polymeric linkers of bis-biotin-poly(ethylene glycol) molecules is added in the presence of the field. These linked chains remain responsive to a magnetic field; however, in the absence of an external magnetic field these chains bend and flex due to thermal motion. The chain flexibility is determined by the length of the spacer molecule between particles and is quantified by the flexural rigidity or bending stiffness. To understand the mechanical properties of the chains, we use a variety of optical trapping experiments to measure the flexural rigidity. Increasing the length of the poly(ethylene glycol) chain in the linker increases the flexibility of the chains.

Journal Article↗