Shear stress dependence of force networks in 3D dense suspensions.

The geometric organization and force networks of 3D dense suspensions that exhibit both shear thinning and thickening have been examined as a function of varying strength of interparticle attractive interactions using lubrication flow discrete element simulations. Significant rearrangement of the geometric topology does not occur at either the local or global scale as these systems transition across the shear thinning and shear thickening regimes. In contrast, massive rearrangements in the balance of attractive, lubrication, and contact forces are observed with interesting behavior of network growth and competition. In agreement with prior work, in shear thinning regions the attractive force is dominant, however as the shear thickening region is approached there is growth of lubrication forces. Lubrication forces oppose the attraction forces, but as viscosity continues to increase under increasing shear stress, the lubrication forces are dominated by contact forces that also resist attraction. Contact forces are the dominant interactions during shear thickening and are an order of magnitude higher than their values in the shear-thinning regime. At high attractive interaction strength, contact networks can form even under shear thinning conditions, however high shear stress is still required before contact networks become the driving mechanism of shear thickening. Analysis of the contact force network during shear thickening generally indicates a uniformly spreading network that rapidly forms across empty domains; however the growth patterns exhibit structure that is significantly dependent upon the strength of interparticle interactions, indicating subtle variations in the mechanism of shear thickening.

Global topology of contact force networks: Insight into shear thickening suspensions.

Highly concentrated particle suspensions (also called slurries) can undergo a sharp increase in viscosity, or shear thickening, under applied stress. Understanding the fundamental features leading to such rheological change is crucial to optimize flow conditions or to design flow modifiers for slurry processing. While local changes to the particle environment under applied shear can be related to changes in viscosity, there is a broader need to connect the shear thickening transition to the fundamental organization of particle-interaction forces which lead to long-range organization. In particular, at a high volume fraction of particles, recent evidence indicates frictional forces between contacting particles is of importance. Herein, the network of frictional contact forces is analyzed within simulated two-dimensional shear thickening suspensions. Two topological metrics are studied to characterize the response of the contact force network (CFN) under varying applied shear stress. The metrics, geodesic index and the void parameter, reflect complementary aspects of the CFN: One is the connectedness of the contact network and the second is the distribution of spatial areas devoid of particle-particle contacts. Considered in relation to the variation of the viscosity, the topological metrics show that the network grows homogeneously at large scales but with many local regions devoid of contacts, indicating clearly the role of CFN growth in causing the large change in the rheological response at the shear thickening transition.

Self-Sterilizing, Self-Cleaning Mixed Polymeric Multifunctional Antimicrobial Surfaces.

Mitigation of bacterial adhesion and subsequent biofilm formation is quickly becoming a strategy for the prevention of hospital-acquired infections. We demonstrate a basic strategy for surface modification that combines the ability to control attachment by microbes with the ability to inactivate microbes. The surface consists of two active materials: poly(p-phenylene ethynylene)-based polymers, which can inactivate a wide range of microbes and pathogens, and poly(N-isopropylacrylamide)-based polymers, which can switch between an hydrophobic "capture" state and a hydrophilic "release" state. The combination of these materials creates a surface that can both bind microbes in a switchable way and kill surface-bound microbes efficiently. Considerable earlier work with cationic poly(p-phenylene ethynylene) polyelectrolytes has demonstrated and characterized their antimicrobial properties, including the ability to efficiently destroy or deactivate Gram-negative and Gram-positive bacteria, fungi, and viruses. Similarly, much work has shown (1) that surface-polymerized films of poly(N-isopropylacrylamide) are able to switch their surface thermodynamic properties from a swollen, relatively hydrophilic state at low temperature to a condensed, relatively hydrophobic state at higher temperature, and (2) that this switch can control the binding and/or release of microbes to poly(N-isopropylacrylamide) surfaces. The active surfaces described herein were fabricated by first creating a film of biocidal poly(p-phenylene ethynylene) using layer-by-layer methods, and then conferring switchable adhesion by growing poly(N-isopropylacrylamide) through the poly(p-phenylene ethynylene) layer, using surface-attached polymerization initiators. The resulting multifunctional, complex films were then characterized both physically and functionally. We demonstrate that such films kill and subsequently induce widespread release of Gram-negative and Gram-positive bacteria.

AFM images of the dark biocidal action of cationic conjugated polyelectrolytes and oligomers on Escherichia coli.

Polymers and oligomers with conjugated phenylene ethynylene or thiophene ethynylene backbones have been shown to be potent antimicrobials. The mechanisms by which they act have been unclear, though AFM imaging of Escherichia coli cells before and after exposure to two such biocides, PPE-Th polymer and EO-OPE-1(C3), shows their effects on cell surface structure. Dried, unexposed E. coli cells could be imaged at resolution high enough to discern the physical structure of the cell surfaces, including individual porin proteins and their distribution on the cell. Exposure to 30 µg/mL PPE-Th polymer caused major cell surface disruption due to either emulsification of the outer membrane or the formation of polymer aggregates or both. In contrast, exposure to 30 µg/mL EO-OPE-1(C3) oligomer did not cause large-scale membrane disruption but did cause apparent reorganization of the surface proteins into linear arrays or protein-lipid-OPE complexes that dominate on a small scale. E. coli cells were also successfully imaged underwater, allowing a real-time AFM image series as cells were exposed to 30 µg/mL EO-OPE-1(C3). Solution exposure caused the cell surfaces to noticeably increase their roughness over time. These results agree with proposed mechanisms for cell killing by PPE-Th and EO-OPE-1(C3) put forth by Wang et al.1 in which PPE-Th kills by large-scale disruption of the outer membrane and EO-OPE-1(C3) kills by membrane reorganization with possible pore formation.

Conditions for liposome adsorption and bilayer formation on BSA passivated solid supports.

Planar solid supported lipid membranes that include an intervening bovine serum albumen (BSA) cushion can greatly reduce undesirable interactions between reconstituted membrane proteins and the underlying substrate. These hetero-self-assemblies reduce frictional coupling by shielding reconstituted membrane proteins from the strong surface charge of the underlying substrate, thereby preventing them from strongly sticking to the substrate themselves. The motivation for this work is to describe the conditions necessary for liposome adsorption and bilayer formation on these hetero-self-assemblies. Described here are experiments that show that the state of BSA is critically important to whether a lipid bilayer is formed or intact liposomes are adsorbed to the BSA passivated surface. It is shown that a smooth layer of native BSA will readily promote lipid bilayer formation while BSA that has been denatured either chemically or by heat will not. Atomic force microscopy (AFM) and fluorescence microscopy was used to characterize the surfaces of native, heat denatured, and chemically reduced BSA. The mobility of several zwitterionic and negatively charged lipid combinations has been measured using fluorescence recovery after photobleaching (FRAP). From these measurements diffusion constants and percent recoveries have been determined and tabulated. The effect of high concentrations of beta-mercaptoethanol (ß-ME) on liposome formation as well as bilayer formation was also explored.

Coarse-grained model DNA: structure, sequences, stems, circles, hairpins.

A coarse-grained model for DNA that is intended to function realistically at the level of individual bases is reported. The model is composed of residues with up to eight coarse-grained beads each, which is sufficient for DNA-like base stacking and base-base recognition by hydrogen bonding. The beads interact by means of short-ranged pair potentials and a simple implicit solvent model. Movement is simulated by Brownian dynamics without hydrodynamic coupling. The main stabilizing forces are base stacking and hydrogen bonding, as modified by the effects of solvation. Complementary double-stranded chains of such residues form stable double helices over long runs (~10 µs) at or near room temperature, with structural parameters close to those of B-form DNA. Most mismatched chains or mismatched regions within a complementary molecule melt and become disordered. Long-range fluctuations and elastic properties, as measured by bending and twisting persistence lengths, are close to experimental values. Single-stranded chains are flexible, with transient stretches of free bases in equilibrium with globules stabilized by intrastrand stacking and hydrogen bonding. Model DNAs in covalently closed loops form right- or left-handed supercoils, depending on the sign of overtwist or undertwist. Short stem-loop structures melt at elevated temperatures and reanneal when the temperature is carefully lowered. Overall, most qualitative properties of real DNA arise naturally in the model from local interactions at the base-pair level.