Critical fluctuations and random-anisotropy glass transition in nematic elastomers

We carry out a detailed deuterium NMR study of local nematic ordering in polydomain nematic elastomers. This system has a close analogy to the random-anisotropy spin glass. We find that, in spite of the quadrupolar nematic symmetry in 3-dimensions requiring a first-order transition, the order parameter in the quenched ``nematic glass'' emerges via a continuous phase transition. In addition, by a careful analysis of the NMR line shape, we deduce that the local director fluctuations grow in a critical manner around the transition point. This could be the experimental evidence for the Aizenman-Wehr theorem about the quenched impurities changing the order of discontinuous transition

A model for the generic alpha relaxation of viscous liquids

Dielectric measurements on molecular liquids just above the glass transition indicate that alpha relaxation is characterized by a generic high-frequency loss varying as $\omega^{-1/2}$, whereas deviations from this come from one or more low-lying beta processes [Olsen et al, Phys. Rev. Lett. {\bf 86} (2001) 1271]. Assuming that long-wavelength fluctuations dominate the dynamics, a model for the dielectric alpha relaxation based on the simplest coupling between the density and dipole density fields is proposed here. The model, which is solved in second order perturbation theory in the Gaussian approximation, reproduces the generic features of alpha relaxation

Participatory modeling updates expectations for individuals and groups, catalyzing behavior change and collective action in water-energy-food nexus governance

Participatory modeling is a potentially high-impact approach for catalyzing fundamental sustainability transformations. We test if participation in a group system dynamics modeling exercise increases participants' agency through a novel method to evaluate potential behavioral change using expectations measures. A water-energy-food nexus a functionally interdependent but under-conceptualised system with low consensus and high scientific uncertainty -- was mapped and its evolution simulated by 46 participants in three interventions in a region undergoing hydropower infrastructure development in North-eastern Cambodia. Participants' system-related expectations were measured before and after the interventions. Our results suggest that participants became significantly more optimistic about their individual agency to increase agricultural and fishing income, and interestingly, less likely to participate in local government development planning procedures. Findings also reveal how some uncertainties for multiple variables were reduced within and across the groups. Such converging expectations suggest that participatory modelling could contribute to making collective solutions and institutionalised agreements more likely. This research contributes to innovation in sustainability because it unpacks some underlying mechanics of how participatory processes can lead to new adaptive capacities, shared perspectives and collective actions

Diffusion on random site percolation clusters. Theory and NMR microscopy experiments with model objects

Quasi two-dimensional random site percolation model objects were fabricate based on computer generated templates. Samples consisting of two compartments, a reservoir of H$_2$O gel attached to a percolation model object which was initially filled with D$_2$O, were examined with NMR (nuclear magnetic resonance) microscopy for rendering proton spin density maps. The propagating proton/deuteron inter-diffusion profiles were recorded and evaluated with respect to anomalous diffusion parameters. The deviation of the concentration profiles from those expected for unobstructed diffusion directly reflects the anomaly of the propagator for diffusion on a percolation cluster. The fractal dimension of the random walk, $d_w$, evaluated from the diffusion measurements on the one hand and the fractal dimension, $d_f$, deduced from the spin density map of the percolation object on the other permits one to experimentally compare dynamical and static exponents. Approximate calculations of the propagator are given on the basis of the fractional diffusion equation. Furthermore, the ordinary diffusion equation was solved numerically for the corresponding initial and boundary conditions for comparison. The anomalous diffusion constant was evaluated and is compared to the Brownian case. Some ad hoc correction of the propagator is shown to pay tribute to the finiteness of the system. In this way, anomalous solutions of the fractional diffusion equation could experimentally be verified for the first time.Comment: REVTeX, 12 figures in GIF forma

Aggregation of full length immunoglobulin light chains from AL amyloidosis patients is remodeled by epigallocatechin-3-gallate

Intervention into amyloid deposition with anti-amyloid agents like the polyphenol Epigallocatechin-3-gallate (EGCG) is emerging as an experimental secondary treatment strategy in systemic light chain amyloidosis (AL). In both AL and Multiple Myeloma (MM), soluble immunoglobulin light chains (LC) are produced by clonal plasma cells, but only in AL they form amyloid deposits in vivo. We investigated the amyloid formation of patient-derived LC and their susceptibility to EGCG in vitro to probe commonalities and systematic differences in their assembly mechanisms. We isolated nine LC from urine of AL and MM patients. We quantified their thermodynamic stabilities, and monitored their aggregation under physiological conditions by ThT fluorescence, light scattering, SDS-stability and atomic force microscopy. LC from all patients formed amyloid-like aggregates, albeit with individually different kinetics. LC existed as dimers, ~50% of which were linked by disulfide bridges. Our results suggest that cleavage into LC monomers is required for efficient amyloid formation. The kinetics of AL LC displayed a transition point in concentration dependence, which MM LC lacked. The lack of concentration dependence of MM LC aggregation kinetics suggests that conformational change of the light chain is rate-limiting for these proteins. Aggregation kinetics displayed two distinct phases, which corresponded to the formation of oligomers and amyloid fibrils, respectively. EGCG specifically inhibited the second aggregation phase and induced the formation of SDS-stable, non-amyloid LC aggregates. Our data suggest that EGCG intervention does not depend on the individual LC sequence and is similar to the mechanism observed for amyloid-{beta} and {alpha}-synuclein

Polymer chain dynamics under nanoscopic confinements

It is shown that the confinement of polymer melts in nanopores leads to chain dynamics dramatically different from bulk behavior. This so-called corset effect occurs both above and below the critical molecular mass and induces the dynamic features predicted for reptation. A spinodal demixing technique was employed for the preparation of linear poly(ethylene oxide) (PEO) confined to nanoscopic strands that are in turn embedded in a quasi-solid and impenetrable methacrylate matrix. Both the molecular weight of the PEO and the mean diameter of the strands were varied to a certain degree. The chain dynamics of the PEO in the molten state was examined with the aid of field-gradient NMR diffusometry (time scale, 10-2-100 s) and field-cycling NMR relaxometry (time scale, 10-9-10-4 s). The dominating mechanism for translational displacements probed in the nanoscopic strands by either technique is shown to be reptation. On the time scale of spin-lattice relaxation time measurements, the frequency dependence signature of reptation (i.e., T 1∼ν3/4) showed up in all samples. A "tube" diameter of only 0.6 nm was concluded to be effective on this time scale even when the strand diameter was larger than the radius of gyration of the PEO random coils. This corset effect is traced back to the lack of the local fluctuation capacity of the free volume in nanoscopic confinements. The confinement dimension is estimated at which the crossover from confined to bulk chain dynamics is expected. © 2005 Elsevier Inc. All rights reserved

Chain dynamics in mesoscopically confined polymer melts. A field-cycling NMR relaxometry study

Polymer chain dynamics were studied with the aid offield-cycling NMR relaxometry (time scale: 10-9s⋯10-4s) supplemented by field gradient NMR diffusometry( time scale: 10-4s⋯100s). Three sorts of samples of mesoscopically confined polymer melts were examined. In the first sample series, linear poly(ethylene oxide) was incorporated in strands embedded in a quasi-solid and impenetrable methacrylate matrix. The strand diameters ranged from 10 to 60 nm. It was shown that chain dynamics becomes dramatically different from bulk behavior. This so-called "corset effect" occurs both above and below the critical molecular mass and reveals dynamic feature spredicted for reptation. On the time scale of spin-lattice relaxation, the frequency and molecular weight, signature of reptation, T1 ∼ M0v3/4, that is limit II ofthe Doi/Edwards formalism corresponding to the mean squared segment displacement law (r2) ∼ M0 t1/4, showed up. A "tube" diameter of only 0.6 nm was concluded to be effective on this time scale even when the strand diameter was larger than the radius of gyration of the PEO random coils. The corset effect is traced back to the lack of the local fluctuation capacity of the free volume under nanoscopic confinements. The confinement dimension at which the cross-over from confined to bulk chain dynamics is expected was estimated to be micrometers. Using the so-called roll-coating technique, micrometer thick polymer melt layers between Kapton foils were prepared. Perceptible differences from the bulk materials were found. The polymer species studied in this case was perfluoropolyether with Flory radii in the order of 7 nm. Remarkably, the confinement effect was shown to reach polymer-wall distances of the order 100 Flory radii. As a third confinement system, melts of perfluoropolyether were filled into a porous silica glass (Vycor; 4 nm nominal pore size). In this case, a crossover from Rouse dynamics in the bulk to reptation in the Doi/Edwards limit III (T1 ∼ M-1/2v1/2 corresponding to (r2) ∼ M-1/2t1/2) was observed. © EDP Sciences/Societé Italiana di Fisica/Springer-Verlag 2007

Confinement effect of chain dynamics in micrometer thick layers of a polymer melt below the critical molecular weight

Polymer melts confined in micrometer thick layers were examined with the aid of field-cycling NMR relaxometry. It is shown that chain dynamics under such moderate confinement conditions are perceptibly different from those observed in the bulk material. This is considered to be a consequence of the corset effect, which predicts a crossover between Rouse and reptationlike dynamics for molecular weights below the critical value at confinement length scales much larger than 10RF, where RF is the Flory radius of the bulk polymer coil [Fatkullin et al., New J. Phys. 6, 46 (2004)]. For the polymer species studied, a perfluoropolyether with a molecular weight of 11 000, the Flory radius is of the order 10 nm, so that the experiment refers to the far end of the predicted crossover region from confined to bulk chain dynamics. Remarkably the confinement effect is shown to reach polymer-wall distances of the order 100 Flory radii. © 2005 American Institute of Physics

Reptation in artificial tubes and the corset effect of confined polymer dynamics

A spinodal demixing technique was employed for the preparation of linear poly(ethylene oxide) (PEO) confined to nanoscopic strands which in turn are embedded in a quasi-solid and impenetrable methacrylate matrix. Both the molecular weight of the PEO and the mean diameter of the strands are variable to a certain degree. Chain dynamics of the PEO in the molten state was examined with the aid of field-gradient NMR diffusometry (time scale: 10-2 s... 100 s) and field-cycling NMR relaxometry (time scale: 10 -9 s... 10-4 s). The dominating mechanism for translational displacements probed in the nanoscopic strands by either technique is shown to be reptation. A corresponding evaluation formalism for NMR difrusometry is presented. It permits the estimation of the mean PEO strand diameter. Depending on the chemical composition of the matrix, the diameters range from 9 to 58 nm. The strands were visualized by electron microscopy. On the time scale of spin-lattice relaxation time measurements, the frequency dependence signature of reptation, that is T1 ∝ νV 3/4, showed up in all samples. A "tube" diameter of only 0.6 nm was concluded to be effective on this time scale even when the strand diameter was larger than the radius of gyration of the PEO random coils. This "corset effect" is traced back to the lack of the local fluctuation capacity of the free volume in nanoscopic confinements. The confinement dimension is estimated at which the cross-over from "confined" to "bulk" chain dynamics is expected

Reptation in artificial tubes and the corset effect of confined polymer dynamics

A spinodal demixing technique was employed for the preparation of linear poly(ethylene oxide) (PEO) confined to nanoscopic strands which in turn are embedded in a quasi-solid and impenetrable methacrylate matrix. Both the molecular weight of the PEO and the mean diameter of the strands are variable to a certain degree. Chain dynamics of the PEO in the molten state was examined with the aid of field-gradient NMR diffusometry (time scale: 10-2 s... 100 s) and field-cycling NMR relaxometry (time scale: 10 -9 s... 10-4 s). The dominating mechanism for translational displacements probed in the nanoscopic strands by either technique is shown to be reptation. A corresponding evaluation formalism for NMR difrusometry is presented. It permits the estimation of the mean PEO strand diameter. Depending on the chemical composition of the matrix, the diameters range from 9 to 58 nm. The strands were visualized by electron microscopy. On the time scale of spin-lattice relaxation time measurements, the frequency dependence signature of reptation, that is T1 ∝ νV 3/4, showed up in all samples. A "tube" diameter of only 0.6 nm was concluded to be effective on this time scale even when the strand diameter was larger than the radius of gyration of the PEO random coils. This "corset effect" is traced back to the lack of the local fluctuation capacity of the free volume in nanoscopic confinements. The confinement dimension is estimated at which the cross-over from "confined" to "bulk" chain dynamics is expected