Microstructure and elasticity of dilute gels of colloidal discoids.

The linear elasticity of dilute colloidal gels formed from discoidal latex particles is quantified as a function of aspect ratio and modeled by confocal microscopy characterization of their fractal cluster microstructure. Colloidal gels are of fundamental interest because of their widespread use to stabilize complex fluids in industry. Technological interest in producing gels of desired moduli using the least number of particles drives formulators to produce gels at dilute concentrations. However, dilute gels self-assembled from isotropic spheres offer limited scope for rheological tunability due to the universal characteristics of their fractal microstructure. Our results show that changing the building block shape from sphere to discoid yields very large shifts in gel elasticity relative to the universal behavior reported for spheres. This shift - tunable through aspect ratio - yields up to a 100-fold increase in elastic modulus at a fixed volume fraction. From modeling the results using the theory for fractal cluster gel rheology, which is applicable at the dilute conditions of this study, we reveal that the efficient generation of elasticity by the colloidal discoids is the consequence of the combined effects of shape anisotropy on the fractal microstructure of the gel network, the anisotropy of the attractive interparticle pair potentials, and the volumetric compactness of the fractal cluster. These results extend prior characterizations of the rheology of non-spherical particulate gels by providing quantitative estimates of how the specific mechanisms of fractality, pair potential, and clustering mediate the profound effects of particle shape anisotropy on the elastic rheology of colloidal gels.

High-density equilibrium phases of colloidal ellipsoids by application of optically enhanced, direct current electric fields.

We use direct current (DC) electric fields in conjunction with ultraviolet light to self-assemble highly dense structures of colloidal ellipsoids with three-dimensional order and volume fraction as large as 67%. Ellipsoidal phases of colloids are of fundamental interest because novel packing structures are predicted to occur at high volume fractions; the symmetries of these crystal unit cells can also contribute to a variety of applications, including structural color materials. Previously, the very high volume fraction range of ellipsoidal phases has been inaccessible because of limitations such as vitrification and kinetic trapping. Here we report that the coupling of light to DC electric fields causes electrophoretic deposition that yields ellipsoid phases that are significantly denser than previous reports. The applied voltage across the capacitor-like device used for self-assembly was varied from 1.75-2.3 V and the power density of incident UV light was varied between 75-400 W m-2. As the coupled field strengths were increased, the assembled colloids underwent a phase transition from an isotropic fluid to a nematic liquid crystal phase consistent with previous reports. When the voltage and light intensity were between 1.9-2.1 V and 100-200 W m-2 respectively, the assembly had a high degree of orientational ordering and a degree of positional order along axes both parallel and perpendicular to the plane of the electrode surface. For the densest assembly achieved, the interlaying spacing is 0.9D, where D is the ellipsoid minor axis.

Extracellular DNA facilitates the formation of functional amyloids in Staphylococcus aureus biofilms.

Persistent staphylococcal infections often involve surface-associated communities called biofilms. Staphylococcus aureus biofilm development is mediated by the co-ordinated production of the biofilm matrix, which can be composed of polysaccharides, extracellular DNA (eDNA) and proteins including amyloid fibers. The nature of the interactions between matrix components, and how these interactions contribute to the formation of matrix, remain unclear. Here we show that the presence of eDNA in S. aureus biofilms promotes the formation of amyloid fibers. Conditions or mutants that do not generate eDNA result in lack of amyloids during biofilm growth despite the amyloidogeneic subunits, phenol soluble modulin peptides, being produced. In vitro studies revealed that the presence of DNA promotes amyloid formation by PSM peptides. Thus, this work exposes a previously unacknowledged interaction between biofilm matrix components that furthers our understanding of functional amyloid formation and S. aureus biofilm biology.

Artificial biofilms establish the role of matrix interactions in staphylococcal biofilm assembly and disassembly.

We demonstrate that the microstructural and mechanical properties of bacterial biofilms can be created through colloidal self-assembly of cells and polymers, and thereby link the complex material properties of biofilms to well understood colloidal and polymeric behaviors. This finding is applied to soften and disassemble staphylococcal biofilms through pH changes. Bacterial biofilms are viscoelastic, structured communities of cells encapsulated in an extracellular polymeric substance (EPS) comprised of polysaccharides, proteins, and DNA. Although the identity and abundance of EPS macromolecules are known, how these matrix materials interact with themselves and bacterial cells to generate biofilm morphology and mechanics is not understood. Here, we find that the colloidal self-assembly of Staphylococcus epidermidis RP62A cells and polysaccharides into viscoelastic biofilms is driven by thermodynamic phase instability of EPS. pH conditions that induce phase instability of chitosan produce artificial S. epidermidis biofilms whose mechanics match natural S. epidermidis biofilms. Furthermore, pH-induced solubilization of the matrix triggers disassembly in both artificial and natural S. epidermidis biofilms. This pH-induced disassembly occurs in biofilms formed by five additional staphylococcal strains, including three clinical isolates. Our findings suggest that colloidal self-assembly of cells and matrix polymers produces biofilm viscoelasticity and that biofilm control strategies can exploit this mechanism.

Elasticity of microscale volumes of viscoelastic soft matter by cavitation rheometry.

Measurement of the elastic modulus of soft, viscoelastic liquids with cavitation rheometry is demonstrated for specimens as small as 1 µl by application of elasticity theory and experiments on semi-dilute polymer solutions. Cavitation rheometry is the extraction of the elastic modulus of a material, E, by measuring the pressure necessary to create a cavity within it [J. A. Zimberlin, N. Sanabria-DeLong, G. N. Tew, and A. J. Crosby, Soft Matter 3, 763-767 (2007)]. This paper extends cavitation rheometry in three ways. First, we show that viscoelastic samples can be approximated with the neo-Hookean model provided that the time scale of the cavity formation is measured. Second, we extend the cavitation rheometry method to accommodate cases in which the sample size is no longer large relative to the cavity dimension. Finally, we implement cavitation rheometry to show that the theory accurately measures the elastic modulus of viscoelastic samples with volumes ranging from 4 ml to as low as 1 µl.

Direct current electric field assembly of colloidal crystals displaying reversible structural color.

We report the application of low-voltage direct current (dc) electric fields to self-assemble close-packed colloidal crystals in nonaqueous solvents from colloidal spheres that vary in size from as large as 1.2 µm to as small as 0.1 µm. The assemblies are created rapidly (∼2 min) from an initially low volume fraction colloidal particle suspension using a simple capacitor-like electric field device that applies a steady dc electric voltage. Confocal microscopy is used to observe the ordering that is produced by the assembly method. This spatial evidence for ordering is consistent with the 6-fold diffraction patterns identified by light scattering. Red, green, and blue structural color is observed for the ordered assemblies of colloids with diameters of 0.50, 0.40, and 0.29 µm, respectively, consistent with spectroscopic measurements of reflectance. The diffraction and spectrophotometry results were found to be consistent with the theoretical Bragg's scattering expected for closed-packed crystals. By switching the dc electric field from on to off, we demonstrate reversibility of the structural color response on times scales ∼60 s. The dc electric field assembly method therefore represents a simple method to produce reversible structural color in colloidal soft matter.

Molar mass, entanglement, and associations of the biofilm polysaccharide of Staphylococcus epidermidis.

Biofilms are microbial communities that are characterized by the presence of a viscoelastic extracellular polymeric substance (EPS). Studies have shown that polysaccharides, along with proteins and DNA, are a major constituent of the EPS and play a dominant role in mediating its microstructure and rheological properties. Here, we investigate the possibility of entanglements and associative complexes in solutions of extracellular polysaccharide intercellular adhesin (PIA) extracted from Staphylococcus epidermidis biofilms. We report that the weight average molar mass and radius of gyration of PIA isolates are 2.01×10(5)±1200 g/mol and 29.2±1.2 nm, respectively. The coil overlap concentration, c*, was thus determined to be (32±4)×10(-4) g/mL. Measurements of the in situ concentration of PIA (cPIA,biofilm) was found to be (10±2)×10(-4) g/mL.Thus, cPIA,biofilm

Complement c5a generation by staphylococcal biofilms.

Biofilms production is a central feature of nosocomial infection of catheters and other medical devices used in resuscitation and critical care. However, the very effective biofilm forming pathogen Staphylococcus epidermidis often produces a modest host inflammatory response and few of the signs and symptoms associated with more virulent pathogens. To examine the impact of bacterial biofilm formation on provocation of an innate immune response, we studied the elaboration of the major complement anaphylatoxin C5a by human serum upon contact with S. epidermidis biofilms. Wild-type S. epidermidis and mutants of sarA (a regulatory protein that promotes synthesis of the biofilm-forming polysaccharide intercellular adhesin [PIA]) and icaB (responsible for postexport processing of PIA) were studied. C5a release, as a function of exposed biofilm surface area, was on the order of 1 fmol · cm · s and was dependent on the presence of PIA. Experimental results were used to inform a physiologically based pharmacokinetic model of C5a release by an infected central venous catheter, one of S. epidermidis' primary means of causing human disease. These simulations revealed that the magnitude of C5a release on a superior vena cava catheter completely covered with S. epidermidis would be lower than necessary to alert circulating leukocytes. Combined, the experimental and computational results are highly consistent with clinical observations in which the clinical signs of central line-associated bloodstream infection are often muted in association with this important pathogen.

Use of adsorption using granular activated carbon (GAC) for the enhancement of removal of chromium from synthetic wastewater by electrocoagulation.

The present work deals with removal of hexavalent chromium from synthetic effluents in a batch stirred electrocoagulation cell with iron-aluminium electrode pair coupled with adsorption using granular activated carbon (GAC). Several working parameters such as pH, current density, adsorbent concentration and operating time were studied in an attempt to achieve higher removal capacity. Results obtained with synthetic wastewater revealed that most effective removal capacities of chromium (VI) could be achieved when the initial pH was near 8. The removal of chromium (VI) during electrocoagulation, is due to the combined effect of chemical precipitation, coprecipitation, sweep coagulation and adsorption. In addition, increasing current density in a range of 6.7-26.7mA/cm2 and operating time from 20 to 100min enhanced the treatment rate to reduce metal ion concentration below admissible legal levels. The addition of GAC as adsorbent resulted in remarkable increase in the removal rate of chromium at lower current densities and operating time, than the conventional electrocoagulation process. The method was found to be highly efficient and relatively fast compared to existing conventional techniques.