Bending-driven patterning of solid inclusions in lipid membranes: Colloidal assembly and transitions in elastic 2D fluids.

Biological or biomimetic membranes are examples within the larger material class of flexible ultrathin lamellae and contoured fluid sheets that require work or energy to impose bending deformations. Bending elasticity also dictates the interactions and assembly of integrated phases or molecular clusters within fluid lamellae, for instance enabling critical cell functions in biomembranes. More broadly, lamella and other thin fluids that integrate dispersed objects, inclusions, and phases behave as contoured 2D colloidal suspensions governed by elastic interactions.

Thermal preconditioning of membrane stress to control the shapes of ultrathin crystals.

We employ the phospholipid bilayer membranes of giant unilamellar vesicles as a free-standing environment for the growth of membrane-integrated ultrathin phospholipid crystals possessing a variety of shapes with 6-fold symmetry. Crystal growth within vesicle membranes, where more elaborate shapes grow on larger vesicles is dominated by the bending energy of the membrane itself, creating a means to manipulate crystal morphology. Here we demonstrate how cooling rate preconditions the membrane tension before nucleation, in turn regulating nucleation and growth, and directing the morphology of crystals by the time they are large enough to be visualized.

Shape equilibria of vesicles with rigid planar inclusions.

Motivated by recent studies of two-phase lipid vesicles possessing 2D solid domains integrated within a fluid bilayer phase, we study the shape equilibria of closed vesicles possessing a single planar, circular inclusion. While 2D solid elasticity tends to expel Gaussian curvature, topology requires closed vesicles to maintain an average, non-zero Gaussian curvature leading to an elementary mechanism of shape frustration that increases with inclusion size. We study elastic ground states of the Helfrich model of the fluid-planar composite vesicles, analytically and computationally, as a function of planar fraction and reduced volume.

Flower-shaped 2D crystals grown in curved fluid vesicle membranes.

The morphologies of two-dimensional (2D) crystals, nucleated, grown, and integrated within 2D elastic fluids, for instance in giant vesicle membranes, are dictated by an interplay of mechanics, permeability, and thermal contraction. Mitigation of solid strain drives the formation of crystals with vanishing Gaussian curvature (i.e.

Contact Area and Deformation of Cells Adhered on a Cationic Surface.

When bacteria adhere to surfaces, the chemical and mechanical character of the cell-substrate interface guides cell function and the development of microcolonies and biofilms. Alternately on bactericidal surfaces, intimate contact is critical to biofilm prevention. The direct study of the buried cell-substrate interfaces at the heart of these behaviors is hindered by the small bacterial cell size and inaccessibility of the contact region.

Depletion attractions drive bacterial capture on both non-fouling and adhesive surfaces, enhancing cell orientation.

Depletion attractions, occurring between surfaces immersed in a polymer solution, drive bacteria adhesion to a variety of surfaces. The latter include the surfaces of non-fouling coatings such as hydrated polyethylene glycol (PEG) layers but also, as demonstrated in this work, surfaces that are bacteria-adhesive, such as that of glass. Employing a flagella free strain, we demonstrate that cell adhesion on glass is enhanced by dissolved polyethylene oxide (PEO), exhibiting a faster rate and greater numbers of captured cells compared with the slower capture of the same cells on glass from a buffer solution.

Motility Increases the Numbers and Durations of Cell-Surface Engagements for Flowing near Poly(ethylene glycol)-Functionalized Surfaces.

Bacteria are keenly sensitive to properties of the surfaces they contact, regulating their ability to form biofilms and initiate infections. This study examines how the presence of flagella, interactions between the cell body and the surface, or motility itself guides the dynamic contact between bacterial cells and a surface in flow, potentially enabling cells to sense physicochemical and mechanical properties of surfaces. This work focuses on a poly(ethylene glycol) biomaterial coating, which does not retain cells.

Interplay of physico-chemical and mechanical bacteria-surface interactions with transport processes controls early biofilm growth: A review.

Biofilms initiate when bacteria encounter and are retained on surfaces. The surface orchestrates biofilm growth through direct physico-chemical and mechanical interactions with different structures on bacterial cells and, in turn, through its influence on cell-cell interactions. Individual cells respond directly to a surface through mechanical or chemical means, initiating "surface sensing" pathways that regulate gene expression, for instance producing extra cellular matrix or altering phenotypes.

Depletion forces drive reversible capture of live bacteria on non-adhesive surfaces.

Because bacterial adhesion to surfaces is associated with infections and biofilm growth, it has been a longstanding goal to develop coatings that minimize biomolecular adsorption and eliminate bacteria adhesion. We demonstrate that, even on carefully-engineered non-bioadhesive coatings such as polyethylene glycol (PEG) layers that prevent biomolecule adsorption and cell adhesion, depletion interactions from non-adsorbing polymer in solution (such as 10 K PEG or 100 K PEO) can cause adhesion and retention of cells, defeating the antifouling functionality of the coating. The cells are immobilized and remain viable on the timescale of the study, at least up to 45 minutes.

Surface Chemistry Guides the Orientations of Adhering Cells Captured from Flow.

Motivated by observations of cell orientation at biofilm-substrate interfaces and reports that cell orientation and adhesion play important roles in biofilm evolution and function, we investigated the influence of surface chemistry on the orientation of cells captured from flow onto surfaces that were cationic, hydrophobic, or anionic. We characterized the initial orientations of nonmotile cells captured from gentle shear relative to the surface and flow directions. The broad distribution of captured cell orientations observed on cationic surfaces suggests that rapid electrostatic attractions of cells to oppositely charged surfaces preserve the instantaneous orientations of cells as they rotate in the near-surface shearing flow.

Swimming back Toward Stiffer Polyetheylene Glycol Coatings, Increasing Contact in Flow.

Bacterial swimming in flow near surfaces is critical to the spread of infection and device colonization. Understanding how material properties affect flagella- and motility-dependent bacteria-surface interactions is a first step in designing new medical devices that mitigate the risk of infection. We report that, on biomaterial coatings such as polyethylene glycol (PEG) hydrogels and end-tethered layers that prevent adhesive bacteria accumulation, the coating mechanics and hydration control the near-surface travel and dynamic surface contact of cells in gentle shear flow (order 10 s).

Switchable positioning of plate-like inclusions in lipid membranes: Elastically mediated interactions of planar colloids in 2D fluids.

We demonstrate how manipulating curvature in an elastic fluid lamella enables the reversible relative positioning of flat, rigid, plate-like micrometer-scale inclusions, with spacings from about a micrometer to tens of micrometers. In an experimental model comprising giant unilamellar vesicles containing solid domain pairs coexisting in a fluid membrane, we adjusted vesicle inflation to manipulate membrane curvature and mapped the interdomain separation. A two-dimensional model of the pair potential predicts the salient experimental observations and reveals both attractions and repulsions, producing a potential minimum entirely a result of the solid domain rigidity and bending energy in the fluid membrane.

Rapid Electrostatic Capture of Rod-Shaped Particles on Planar Surfaces: Standing up to Shear.

We compare the electrostatically driven capture of flowing rod-shaped and spherical silica particles from dilute solutions onto a flow chamber wall that carries the opposite electrostatic charge from the particles. Particle accumulation and orientation are measured in time at a fixed region on the wall of a shear flow chamber. Rod-shaped particle aspect ratios are 2.

Mechanical Properties and Concentrations of Poly(ethylene glycol) in Hydrogels and Brushes Direct the Surface Transport of Staphylococcus aureus.

Surface-associated transport of flowing bacteria, including cell rolling, is a mechanism for otherwise immobile bacteria to migrate on surfaces and could be associated with biofilm formation or the spread of infection. This work demonstrates how the moduli and/or local polymer concentration play critical roles in sustaining contact, dynamic adhesion, and transport of bacterial cells along a hydrogel or hydrated brush surface. In particular, stiffer more concentrated hydrogels and brushes maintained the greatest dynamic contact, still allowing cells to travel along the surface in flow.

Nanoscale Functionalized Particles with Rotation-Controlled Capture in Shear Flow.

Important processes in nature and technology involve the adhesive capture of flowing particles or cells on the walls of a conduit. This paper introduces engineered spherical microparticles whose capture rates are limited by their near surface motions in flow. Specifically, these microparticles are sparsely functionalized with nanoscopic regions ("patches") of adhesive functionality, without which they would be nonadhesive.

Tunable fluorescence quenching near the graphene-aqueous interface.

With increased interest in graphene-based sensors for biomolecules and other targets, we investigated the impact of ionic strength on the steady-state emissions from fluorescein labels on proteins adsorbing on pristine CVD (chemical vapor deposited)-graphene on a silica support. Using the model system of fluorescein-tagged fibrinogen we demonstrated that, for fluorescein tags on adsorbed fibrinogen, emission intensity was very sensitive to the salt concentration. This behavior was not seen for fluorescein-tagged fibrinogen in solution.

Evidence for negative charge near large area supported graphene in water: A study of silica microsphere interactions.

This study addresses the electrostatic and van der Waals interactions at the aqueous interface of large area CVD graphene, 1-3 layers thick on a silica support and assessed by Raman spectroscopy to have exclusive sp2 character. Ionic strength was found to substantially alter the interactions of silica microspheres with silica-supported graphene. Particles were nonadhesive at large Debye lengths but became irreversibly adherent at reduced Debye lengths about 2nm or less.

Surfaces for competitive selective bacterial capture from protein solutions.

Active surfaces that form the basis for bacterial sensors for threat detection, food safety, or certain diagnostic applications rely on bacterial adhesion. However, bacteria capture from complex fluids on the active surfaces can be reduced by the competing adsorption of proteins and other large molecules. Such adsorption can also interfere with device performance.

Statistically-based DLVO approach to the dynamic interaction of colloidal microparticles with topographically and chemically heterogeneous collectors.

Electrostatic surface heterogeneity on the order of a few nanometers is common in colloidal and bacterial systems, dominating adhesion and aggregation and inducing deviations from classical DLVO theory based on a uniform distribution of surface charge. Topographical heterogeneity and roughness also strongly influence adhesion. In this work, a model is introduced to quantify the spatial fluctuations in the interaction of microparticles in a flowing suspension with a wall aligned parallel to the flow.

Engineering nanoscale surface features to sustain microparticle rolling in flow.

Nanoscopic features of channel walls are often engineered to facilitate microfluidic transport, for instance when surface charge enables electro-osmosis or when grooves drive mixing. The dynamic or rolling adhesion of flowing microparticles on a channel wall holds potential to accomplish particle sorting or to selectively transfer reactive species or signals between the wall and flowing particles. Inspired by cell rolling under the direction of adhesion molecules called selectins, we present an engineered platform in which the rolling of flowing microparticles is sustained through the incorporation of entirely synthetic, discrete, nanoscale, attractive features into the nonadhesive (electrostatically repulsive) surface of a flow channel.

Hybrid copolymer-phospholipid vesicles: phase separation resembling mixed phospholipid lamellae, but with mechanical stability and control.

Vesicles whose bilayer membranes contain phospholipids mixed with co-polymers or surfactants comprise new hybrid materials having potential applications in drug delivery, sensors, and biomaterials. Here we describe a model polymer-phospholipid hybrid membrane system exhibiting strong similarities to binary phospholipid mixtures, but with more robust membrane mechanics. A lamella-forming graft copolymer, PDMS-co-PEO (polydimethylsiloxane-co-polyethylene oxide) was blended with a high melting temperature phospholipid, DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine), over a broad compositional range.

Antimicrobial surfaces containing cationic nanoparticles: how immobilized, clustered, and protruding cationic charge presentation affects killing activity and kinetics.

This work examines how the antimicrobial (killing) activity of net-negative surfaces depends on the presentation of antimicrobial cationic functionality: distributed versus clustered, and flat clusters versus raised clusters. Specifically, the ability to kill Staphylococcus aureus by sparsely distributed 10 nm cationic nanoparticles, immobilized on a negative surface and backfilled with a PEG (polyethylene glycol) brush, was compared with that for a dense layer of the same immobilized nanoparticles. Additionally, sparsely distributed 10 nm poly-L-lysine (PLL) coils, adsorbed to a surface to produce flat cationic "patches" and backfilled with a PEG brush were compared to a saturated adsorbed layer of PLL.

1,2-Dipalmitoyl-sn-glycero-3-phosphocholine (DPPC)-rich domain formation in binary phospholipid vesicle membranes: two-dimensional nucleation and growth.

Decades of study have probed phase transitions in model phospholipid bilayers and vesicles, especially in the context of the equilibrium phase diagram. Critical to the response of vesicles to environmental triggers, to the ultimate domain morphology, and to the approach to equilibrium (or not), we present here a study of domain formation in vesicles, focusing on a mechanism by which the cooling rate, tension, and composition affect the first appearance (nucleation) and subsequent growth of solid membrane domains. Employing a popular mixed membrane model based on DOPC and DPPC (1,2-dioleoyl-sn-glycero-3-phosphocholine and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, respectively), we examined phase separation in giant two-component vesicles that were cooled from the one-phase fluid (Lα) region of the phase diagram into a region of fluid (Lα)-solid coexistence.

Three dimensional (temperature-tension-composition) phase map of mixed DOPC-DPPC vesicles: Two solid phases and a fluid phase coexist on three intersecting planes.

Mapping the phase behavior of multicomponent phospholipid membranes has been an ongoing pursuit, motivated by interest in both fundamental physics and cell function. Prior investigations addressed temperature-composition space and the features of the associated domains. The current study additionally considers membrane tension, analogous to pressure in bulk materials.