Beads on a string: structure of bound aggregates of globular particles and long polymer chains.

Macroscopic properties of suspensions, such as those composed of globular particles (e.g., colloidal or macromolecular), can be tuned by controlling the equilibrium aggregation of the particles. We examine how aggregation - and, hence, macroscopic properties - can be controlled in a system composed of both globular particles and long, flexible polymer chains that reversibly bind to one another. We base this on a minimal statistical mechanical model of a single aggregate in which the polymer chain is treated either as ideal or self-avoiding, and, in addition, the globular particles are taken to interact with one another via excluded volume repulsion. Furthermore, each of the globular particles is taken to have one single site to which at most one polymer segment may bind. Within the context of this model, we examine the statistics of the equilibrium size of an aggregate and, thence, the structure of dilute and semidilute suspensions of these aggregates. We apply the model to biologically relevant aggregates, specifically those composed of macromolecular proteoglycan globules and long hyaluronan polymer chains. These aggregates are especially relevant to the materials properties of cartilage and the structure-function properties of perineuronal nets in brain tissue, as well as the pericellular coats of mammalian cells.

Speed dependence of thermochemical nanolithography for gray-scale patterning.

Thermochemical nanolithography (TCNL) is a high-resolution lithographic technique and, owing to its fast speed, versatility, and unique ability to fabricate arbitrary, gray-scale nanopatterns, this scanning probe technique is relevant both for fundamental scientific research as well as for nanomanufacturing applications. In this work, we study the dependence of the TCNL driven chemical reactions on the translation speed of the thermal cantilever. The experimental data compares well with a model of the chemical kinetics for a first-order reaction. The impact of higher order reactions on the optimization of TCNL is addressed. The reported quantitative description of the speed dependence of TCNL is exploited and illustrated by fabricating controlled gradients of chemical concentration.

Fabricating nanoscale chemical gradients with ThermoChemical NanoLithography.

Production of chemical concentration gradients on the submicrometer scale remains a formidable challenge, despite the broad range of potential applications and their ubiquity throughout nature. We present a strategy to quantitatively prescribe spatial variations in functional group concentration using ThermoChemical NanoLithography (TCNL). The approach uses a heated cantilever to drive a localized nanoscale chemical reaction at an interface, where a reactant is transformed into a product. We show using friction force microscopy that localized gradients in the product concentration have a spatial resolution of ~20 nm where the entire concentration profile is confined to sub-180 nm. To gain quantitative control over the concentration, we introduce a chemical kinetics model of the thermally driven nanoreaction that shows excellent agreement with experiments. The comparison provides a calibration of the nonlinear dependence of product concentration versus temperature, which we use to design two-dimensional temperature maps encoding the prescription for linear and nonlinear gradients. The resultant chemical nanopatterns show high fidelity to the user-defined patterns, including the ability to realize complex chemical patterns with arbitrary variations in peak concentration with a spatial resolution of 180 nm or better. While this work focuses on producing chemical gradients of amine groups, other functionalities are a straightforward modification. We envision that using the basic scheme introduced here, quantitative TCNL will be capable of patterning gradients of other exploitable physical or chemical properties such as fluorescence in conjugated polymers and conductivity in graphene. The access to submicrometer chemical concentration and gradient patterning provides a new dimension of control for nanolithography.

Sculpting Enzyme-Generated Giant Polymer Brushes.

We present a simple yet versatile method for sculpting ultra-thick, enzyme-generated hyaluronan polymer brushes with light. The patterning mechanism is indirect, driven by reactive oxygen species created by photochemical interactions with the underlying substrate. The reactive oxygen species disrupt the enzyme hyaluronan synthase, which acts as the growth engine and anchor of the end-grafted polymers. Spatial control over the grafting density is achieved through inactivation of the enzyme in an energy density dose-dependent manner, before or after polymerization of the brush. Quantitative variation of the brush height is possible using visible wavelengths and illustrated by the creation of a brush gradient ranging from 0 to 6 µm in height over a length of 56 µm (approximately a 90 nm height increase per micron). Building upon the fundamental insights presented in this study, this work lays the foundation for the flexible and quantitative sculpting of complex three-dimensional landscapes in enzyme-generated hyaluronan brushes.

O-Specific Antigen-Dependent Surface Hydrophobicity Mediates Aggregate Assembly Type in Pseudomonas aeruginosa.

Bacteria live in spatially organized aggregates during chronic infections, where they adapt to the host environment, evade immune responses, and resist therapeutic interventions. Although it is known that environmental factors such as polymers influence bacterial aggregation, it is not clear how bacterial adaptation during chronic infection impacts the formation and spatial organization of aggregates in the presence of polymers. Here, we show that in an in vitro model of cystic fibrosis (CF) containing the polymers extracellular DNA (eDNA) and mucin, O-specific antigen is a major factor determining the formation of two distinct aggregate assembly types of Pseudomonas aeruginosa due to alterations in cell surface hydrophobicity. Our findings suggest that during chronic infection, the interplay between cell surface properties and polymers in the environment may influence the formation and structure of bacterial aggregates, which would shed new light on the fitness costs and benefits of O-antigen production in environments such as CF lungs. IMPORTANCE During chronic infection, several factors contribute to the biogeography of microbial communities. Heterogeneous populations of Pseudomonas aeruginosa form aggregates in cystic fibrosis airways; however, the impact of this population heterogeneity on spatial organization and aggregate assembly is not well understood. In this study, we found that changes in O-specific antigen determine the spatial organization of P. aeruginosa cells by altering the relative cell surface hydrophobicity. This finding suggests a role for O-antigen in regulating P. aeruginosa aggregate size and shape in cystic fibrosis airways.