Viscoelastic Phase Patterning in Artificial Protein Hydrogels

Viscoelastic forces can affect the dynamics of pattern formation during phase separation in polymeric materials. We programmed an artificial protein hydrogel to undergo viscoelastic phase separation above a critical temperature. Highly dynamic phase patterns that coarsened under the influence of viscoelastic stresses spontaneously emerged in these gels. Local oxidative crosslinking promoted by mild photobleaching could be used to initiate phase separation locally, enabling the creation of non-equilibrium patterns that evolved under the influence of surface tension and viscoelastic stresses to yield dynamic structures of controlled size and shape

Mechanisms of diffusion in associative polymer networks: evidence for chain hopping

Networks assembled by reversible association of telechelic polymers constitute a common class of soft materials. Various mechanisms of chain migration in associative networks have been proposed; yet there remains little quantitative experimental data to discriminate among them. Proposed mechanisms for chain migration include multichain aggregate diffusion as well as single-chain mechanisms such as “walking” and “hopping”, wherein diffusion is achieved by either partial (“walking”) or complete (“hopping”) disengagement of the associated chain segments. Here, we provide evidence that hopping can dominate the effective diffusion of chains in associative networks due to a strong entropic penalty for bridge formation imposed by local network structure; chains become conformationally restricted upon association with two or more spatially separated binding sites. This restriction decreases the effective binding strength of chains with multiple associative domains, thereby increasing the probability that a chain will hop. For telechelic chains this manifests as binding asymmetry, wherein the first association is effectively stronger than the second. We derive a simple thermodynamic model that predicts the fraction of chains that are free to hop as a function of tunable molecular and network properties. A large set of self-diffusivity measurements on a series of model associative polymers finds good agreement with this model

Mechanisms of diffusion in associative polymer networks: evidence for chain hopping

Networks assembled by reversible association of telechelic polymers constitute a common class of soft materials. Various mechanisms of chain migration in associative networks have been proposed; yet there remains little quantitative experimental data to discriminate among them. Proposed mechanisms for chain migration include multichain aggregate diffusion as well as single-chain mechanisms such as “walking” and “hopping”, wherein diffusion is achieved by either partial (“walking”) or complete (“hopping”) disengagement of the associated chain segments. Here, we provide evidence that hopping can dominate the effective diffusion of chains in associative networks due to a strong entropic penalty for bridge formation imposed by local network structure; chains become conformationally restricted upon association with two or more spatially separated binding sites. This restriction decreases the effective binding strength of chains with multiple associative domains, thereby increasing the probability that a chain will hop. For telechelic chains this manifests as binding asymmetry, wherein the first association is effectively stronger than the second. We derive a simple thermodynamic model that predicts the fraction of chains that are free to hop as a function of tunable molecular and network properties. A large set of self-diffusivity measurements on a series of model associative polymers finds good agreement with this model

Analysis and Control of Chain Mobility in Protein Hydrogels

Coiled-coil domains can direct the assembly of protein block copolymers into physically cross-linked, viscoelastic hydrogels. Here, we describe the use of fluorescence recovery after photobleaching (FRAP) to probe chain mobility in reversible hydrogels assembled from engineered proteins bearing terminal coiled-coil domains. We show that chain mobility can be related to the underlying dynamics of the coiled-coil domains by application of a three-state “hopping” model of chain migration. We further show that genetic programming allows the effective mobility of network chains to be varied 500-fold through modest changes in protein sequence. Destabilization of the coiled-coil domains by site-directed mutagenesis increases the effective diffusivity of probe chains. Conversely, probe mobility is reduced by expanding the hydrophobic surface area of the coiled-coil domains through introduction of the bulky leucine surrogate homoisoleucine. Predictions from the three-state model imply asymmetric sequential binding of the terminal domains. Brownian Dynamics simulations suggest that binding asymmetry is a general feature of reversible gels, arising from a loss in entropy as chains transition to a conformationally restricted bridged state

v4: A small, but sensitive observable for heavy ion collisions

Higher order Fourier coefficients of the azimuthally dependent single particle spectra resulting from noncentral heavy ion collisions are investigated. For intermediate to large transverse momenta, these anisotropies are expected to become as large as 5 %, and should be clearly measurable. The physics content of these observables is discussed from two different extreme but complementary viewpoints, hydrodynamics and the geometric limit with extreme energy loss.Comment: as published: typos corrected, Fig. 3 slightly improved in numerics and presentatio

Connected Green function approach to ground state symmetry breaking in Φ1+14\Phi^4_{1+1}-theory

Using the cluster expansions for n-point Green functions we derive a closed set of dynamical equations of motion for connected equal-time Green functions by neglecting all connected functions higher than $4^{th}$ order for the $\lambda \Phi^4$-theory in $1+1$ dimensions. We apply the equations to the investigation of spontaneous ground state symmetry breaking, i.e. to the evaluation of the effective potential at temperature $T=0$. Within our momentum space discretization we obtain a second order phase transition (in agreement with the Simon-Griffith theorem) and a critical coupling of $\lambda_{crit}/4m^2=2.446$ as compared to a first order phase transition and $\lambda_{crit}/4m^2=2.568$ from the Gaussian effective potential approach.Comment: 25 Revtex pages, 5 figures available via fpt from the directory ugi-94-11 of [email protected] as one postscript file (there was a bug in our calculations, all numerical results and figures have changed significantly), ugi-94-1

What Have We Learned from RHIC?

In this talk, I present what I believe we have learned from the recent RHIC heavy ion experiments. The goal of these experiments is to make and study matter at very high energy densities, greater than an order of magnitude larger than that of nuclear matter. Have we made such matter? What have we learned about the properties of this matter? What do we hope and expect to learn in the future?Comment: 34 figure

Results from the NASA Capability Roadmap Team for In-Situ Resource Utilization (ISRU)

On January 14, 2004, the President of the United States unveiled a new vision for robotic and human exploration of space entitled, "A Renewed Spirit of Discovery". As stated by the President in the Vision for Space Exploration (VSE), NASA must "... implement a sustained and affordable human and robotic program to explore the solar system and beyond " and ".. .develop new technologies and harness the moon's abundant resources to allow manned exploration of more challenging environments." A key to fulfilling the goal of sustained and affordable human and robotic exploration will be the ability to use resources that are available at the site of exploration to "live off the land" instead of bringing everything from Earth, known as In-Situ Resource Utilization (ISRU). ISRU can significantly reduce the mass, cost, and risk of exploration through capabilities such as: mission consumable production (propellants, fuel cell reagents, life support consumables, and feedstock for manufacturing & construction); surface construction (radiation shields, landing pads, walls, habitats, etc.); manufacturing and repair with in-situ resources (spare parts, wires, trusses, integrated systems etc.); and space utilities and power from space resources. On January 27th, 2004 the President's Commission on Implementation of U.S. Space Exploration Policy (Aldridge Committee) was created and its final report was released in June 2004. One of the report's recommendations was to establish special project teams to evaluate enabling technologies, of which "Planetary in situ resource utilization" was one of them. Based on the VSE and the commission's final report, NASA established fifteen Capability Roadmap teams, of which ISRU was one of the teams established. From Oct. 2004 to May 2005 the ISRU Capability Roadmap team examined the capabilities, benefits, architecture and mission implementation strategy, critical decisions, current state-of-the-art (SOA), challenges, technology gaps, and risks of ISRU for future human Moon and Mars exploration. This presentation will provide an overview of the ISRU capability, architecture, and implementation strategy examined by the ISRU Capability Roadmap team, along with a top-level review of ISRU benefits, resources and products of interest, and the current SOA in ISRU processes and systems. The presentation will also highlight the challenges of incorporating ISRU into future missions and the gaps in technologies and capabilities that need to be filled to enable ISRU