386 research outputs found
Combining Diffusion NMR and Small-Angle Neutron Scattering Enables Precise Measurements of Polymer Chain Compression in a Crowded Environment
The effect of particles on the behavior of polymers in solution is important in a number of important phenomena such as the effect of “crowding” proteins in cells, colloid-polymer mixtures, and nanoparticle “fillers” in polymer solutions and melts. In this Letter, we study the effect of spherical inert nanoparticles (which we refer to as “crowders”) on the diffusion coefficient and radius of gyration of polymers in solution using pulsed-field-gradient NMR and small-angle neutron scattering (SANS), respectively. The diffusion coefficients exhibit a plateau below a characteristic polymer concentration, which we identify as the overlap threshold concentration
c⋆. Above c⋆, in a crossover region between the dilute and semidilute regimes, the (long-time) self-diffusion coefficients are found, universally, to decrease exponentially with polymer concentration at all crowder packing fractions, consistent with a structural basis for the long-time dynamics. The radius of gyration obtained from SANS in the crossover regime changes linearly with an increase in polymer concentration, and must be extrapolated to c⋆ in order to obtain the radius of gyration of an individual polymer chain. When the polymer radius of gyration and crowder size are comparable, the polymer size is very weakly affected by the presence of crowders, consistent with recent computer simulations. There is significant chain compression, however, when the crowder size is much smaller than the polymer radius gyration
Two Experimental Tests of the Halperin-Lubensky-Ma Effect at the Nematic-Smectic-A Phase Transition
We have conducted two quantitative tests of predictions based on the
Halperin-Lubensky-Ma (HLM) theory of fluctuation-induced first-order phase
transitions. First, we explore the effect of an external magnetic field on the
nematic-smectic-A (NA) transition in a liquid crystal. Second, we examine the
dependence of the first-order discontinuity as a function of mixture
concentration in pure 8CB and three 8CB-10CB mixtures. We find the first
quantitative evidence for deviations from the HLM theory.Comment: 4 pages, 2 figure
Deuterium NMR and rheology of microgel colloids at ambient and high pressure
Microgel colloids exhibit a polymer collapse transition resulting in a large reduction in colloid size at high temperatures or pressures. Our goal is to obtain a microscopic understanding of the internal structure and microscopic dynamics of microgels by examining the temperature and pressure dependence of the collapse transition. We have conducted a systematic study of how the nature of this collapse transition is affected by crosslink density (Cd). We used deuterium NMR (2H-NMR) to probe the microscopic dynamics of cross-linked poly-N-isopropylacrylamide (p-nipam) chains, in microgel colloids, as a function of temperature and pressure. Four differently crosslinked microgels colloids were synthesized with deuteron labels on the nipam backbone (d3- nipam). Corresponding macroscopic properties of unlabeled colloids having the same crosslink densities were characterized by dynamic light scattering (DLS) and rheology. Rheological characterization as a function of temperature (T) and particle concentration (c), and for 4 crosslink densities, showed that the microgel viscosity decreases as temperature is increased, and that in the high T/low c regime, there is a collapse of the viscosity as a function of T and c when plotted against volume fraction: this yields a measure of the water content in the particles as function of T. 2H-NMR spectra of the d3-nipam suspensions for all Cd indicated freely moving chains at low temperature and a nearly immobilized fraction above 35°C. This is consistent with DLS observations of a transition from swollen to collapsed colloids. 2H-NMR spectra for the dry powder indicated totally immobilized segments in the particle. Nipam segments in the collapse phase of the d3-nipam suspension were more mobile than those in the dry powder. This suggests significant amounts of water in the collapsed phase, a finding consistent with the rheology observations. For the highest two values of Cd, microgel spectra showed the presence of an immobilized fraction of segments even in the swollen phase. Variable pressure NMR (up to 90 MPa) showed a slight increase in transition temperature with pressure for all Cd values studied
Field induced magnetic order in the frustrated magnet Gadolinium Gallium Garnet
Gd3Ga5O12, (GGG), has an extraordinary magnetic phase diagram, where no long
range order is found down to 25 mK despite \Theta_CW \approx 2 K. However, long
range order is induced by an applied field of around 1 T. Motivated by recent
theoretical developments and the experimental results for a closely related
hyperkagome system, we have performed neutron diffraction measurements on a
single crystal sample of GGG in an applied magnetic field. The measurements
reveal that the H-T phase diagram of GGG is much more complicated than
previously assumed. The application of an external field at low T results in an
intensity change for most of the magnetic peaks which can be divided into three
distinct sets: ferromagnetic, commensurate antiferromagnetic, and
incommensurate antiferromagnetic. The ferromagnetic peaks (e.g. (112), (440)
and (220)) have intensities that increase with the field and saturate at high
field. The antiferromagnetic reflections have intensities that grow in low
fields, reach a maximum at an intermediate field (apart from the (002) peak
which shows two local maxima) and then decrease and disappear above 2 T. These
AFM peaks appear, disappear and reach maxima in different fields. We conclude
that the competition between magnetic interactions and alternative ground
states prevents GGG from ordering in zero field. It is, however, on the verge
of ordering and an applied magnetic field can be used to crystallise ordered
components. The range of ferromagnetic and antiferromagnetic propagation
vectors found reflects the complex frustration in GGG.Comment: 6 pages, 7 figures, HFM 2008 conference pape
External-field-induced tricritical point in a fluctuation-driven nematic-smectic-A transition
We study theoretically the effect of an external field on the
nematic-smectic-A (NA) transition close to the tricritical point, where
fluctuation effects govern the qualitative behavior of the transition. An
external field suppresses nematic director fluctuations, by making them
massive. For a fluctuation-driven first-order transition, we show that an
external field can drive the transition second-order. In an appropriate liquid
crystal system, we predict the required magnetic field to be of order 10 T. The
equivalent electric field is of order .Comment: revtex, 4 pages, 1 figure; revised version, some equations have been
modifie
Influence of nonlocal electrodynamics on the anisotropic vortex pinning in
We have studied the pinning force density Fp of YNi_2B_2C superconductors for
various field orientations. We observe anisotropies both between the c-axis and
the basal plane and within the plane, that cannot be explained by usual mass
anisotropy. For magnetic field , the reorientation structural
transition in the vortex lattice due to nonlocality, which occurs at a field
, manifests itself as a kink in Fp(H). When , Fp is
much larger and has a quite different H dependence, indicating that other
pinning mechanisms are present. In this case the signature of nonlocal effects
is the presence of a fourfold periodicity of Fp within the basal plane.Comment: 4 pages, 3 figure
Magnetic Dynamics in Underdoped YBa₂Cu₃O₇₋ₓ: Direct Observation of a Superconducting Gap
Polarized and unpolarized triple-axis neutron measurements were performed on an underdoped crystal of YBa2Cu3O7-x (x = 0.4 ± 0.02, Tc = 62.7 K). Our results indicate, contrary to earlier evidence, that the spin excitations in the superconducting state are essentially the same as those in the fully doped material except that the unusual 41 meV resonance is observed at 34.8 meV. The normal state spin excitations are characterized by a weakly energy-dependent continuum whose temperature dependence shows the clear signature of a superconducting gap at Tc. The enhancement at the resonance is accompanied by a suppression of magnetic fluctuations at both higher and lower energies
- …