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Liquid mixtures composed of colloidal particles and much smaller non-adsorbing linear homopolymers can undergo a gelation transition due to polymer-mediated depletion forces. We now show that the addition of linear polymers to suspensions of soft colloids having the same hydrodynamic size yields a liquid-to-gel-to-re-entrant liquid transition. In particular, the dynamic state diagram of 1,4-polybutadiene star-linear polymer mixtures was determined with the help of linear viscoelastic and small angle X-ray scattering experiments. While keeping the star polymers below their nominal overlap concentration, a gel was formed upon increasing the linear polymer content. Further addition of linear chains yielded a re-entrant liquid. This unexpected behavior was rationalized by the interplay of three possible phenomena: (i) depletion interactions, driven by the size disparity between the stars and the polymer length scale which is the mesh size of this entanglement network; (ii) colloidal deswelling due to the increased osmotic pressure exerted onto the stars; and (iii) a concomitant progressive suppression of depletion efficiency on increasing polymer concentration due to reduced mesh size, hence a smaller range of attraction. Our results unveil an exciting new way to tailor the flow of soft colloids and highlight a largely unexplored path to engineer soft colloidal mixtures., Comment: 27 pages, 5 figures

We use molecular simulation to investigate the pH response of sequence-controlled polyampholyte brushes (PABs) with polymer chains consisting of alternating blocks of weakly acidic and basic monomers.

We examined the effects of alkyl carbon spacer length (CSL) and molecular weight on fouling resistance and release properties of zwitterionic poly(sulfobetaine methacrylate) brushes. Using surface-initiated atom transfer radical polymerization, we synthesized two series of brushes with CSL = 3 and 4 and molecular weight from 19 to 1500 kg ·mol

We report a colloid–polymer model system with tunable bridging interactions for microscopic studies of structure and dynamics using confocal imaging. The interactions between trifluoroethyl methacrylate-co- tert-butyl methacrylate copolymer particles and poly(acrylic acid) (PAA) polymers were controllable via polymer concentration and pH. The strength of adsorption of PAA on the particles, driven by pH-dependent interactions with polymer brush stabilizers on the particle surfaces, was tuned via solution pH. Particle–polymer suspensions formulated at low pH, where polymers strongly adsorbed to the particles, contained clusters or weak gels at particle volume fractions of ϕ = 0.15 and ϕ = 0.40. At high pH, where the PAA only weakly adsorbed to the particle surface, particles largely remained dispersed, and the suspensions behaved as a dense fluid. The ability to visualize the suspension structure is likely to provide insight into the role of polymer-driven bridging interactions in the behavior of colloidal suspensions.

We study the dynamics of nanoparticles in semidilute solutions of ring and linear polymers using hybrid molecular dynamics–multiparticle collision dynamics simulations. The dynamics of the monomers, the polymer centers-of-mass, and the nanoparticles coincide for these two architectures for solutions of the same monomer concentration. The long time diffusivities of the nanoparticles follow the predictions of a polymer coupling theory [Cai et al., Macromolecules 44, 7853–7863 (2011)], suggesting that nanoparticle dynamics are coupled to segmental relaxations for both polymer architectures examined here. At intermediate time scales, the nanoparticle dynamics are characterized by subdiffusive exponents, which markedly deviate from coupling theory and closely follow those of the polymers. Instead, the nanoparticle dynamics are strongly coupled to the polymer center-of-mass motions for both architectures, rather than to their segmental dynamics. The presence of ring concatenations does not affect the long-time diffusivity of the nanoparticles but leads to a slight decrease in the subdiffusive exponents of the nanoparticles and the polymer center-of-mass.

SummaryFascin1 expression in colorectal carcinomas (CRCs) is linked to a clinically aggressive disease with poor prognosis. Despite that fascin1’s role in the etiology of CRCs has not been directly investigated. We show fascin1 expression in one-third of all CRCs underscoring the critical need to identify fascin1’s function in colorectal carcinogenesis. Here, we identify for the first time, fascin1’s role as a mechanosensor that modulates CRC cell adherens junction (AJ) plasticity to induce tumor growth and metastasis. We show that fascin1 expression drives protein sorting to transform AJ mechanotransduction and we reveal how these force-sensitive pathways activate oncogenic signaling in CRC cells. We made the novel finding that AJ remodeling by fascin1 also controls “collective plasticity” and bidirectional cell migration. Few studies have examined AJ plasticity in cancer cells, which remains poorly understood and has not been therapeutically targeted. Our findings could have widespread implications for understanding and treating metastatic carcinomas.

We examine the coupling of the dynamics of flexible viral nanoparticles to the dynamics of comparably sized polymer chains. Using fluorescence microscopy, we quantify the dynamics of three filamentous viruses, potato virus M (PVM), M13, and pf1, that are suspended in semidilute solutions of partially hydrolyzed polyacrylamide. The dynamics of the viral nanoparticles are approximately diffusive on accessible time and length scales, but the distributions of displacements are non-Gaussian and exhibit increasingly extended tails as the aspect ratio of the viruses or the polymer concentration is increased. The long-time diffusion coefficients do not collapse onto a universal curve based on existing models for rodlike or spherical nanoparticles that are comparably sized to the polymer chains. Instead, the diffusivities appear to collapse as a function of the ratio of the polymer correlation length and a length scale intermediate between the virus radius and length, indicating that the hydrodynamic coupling to the polymer dynamics is affected by the virus anisotropy and flexibility.

The impact of brush molecular weight distribution on the conformation and response of weak polyacid brushes was investigated. We show that weight-average degree of polymerization (Nw) and dispersity (Đ) alter the pH-responsive conformation of poly(acrylic acid) (PAA) brushes grafted to silica nanoparticles. We quantified the average brush length (lb) at various pH using dynamic light scattering. The lb of low-Nw PAA brushes (Nw = 45) increased as Đ was increased from 1.09 to 1.69, but lb for the high-Nw PAA brushes (Nw ≈ 813) did not vary substantially when Đ was increased from 1.23 to 1.76. This result indicates that the presence of a small fraction of long chains in a broad dispersity brush has a greater impact on lb when Nw is low. Additionally, the extent of pH-response in lb/lb,max increased with Nw or Đ (when Nw is low), where the maximum brush length (lb,max) was lb measured at pH 10. The scaling of lb/lb,max with degree of dissociation (α), however, was influenced by Nw but not Đ, indicating the low- and high-Nw PAA brushes were in the quasi-neutral brush (q-NB) and salted brush (SB) regimes, respectively. Differing behaviors in the pH-response and α-response of lb at low Nw arose from subtle differences in dissociation behaviors among brushes of varying Đ. At low Đ, the low-Nw brush adopted a pH-independent extended conformation due to strong excluded volume interactions, whereas the conformation of the high-Nw brush varied from collapsed to stretched with increasing pH arising from electrostatic interactions. At high-Đ, we suggest the brush conformation also varied from collapsed to stretched with increasing pH regardless of Nw.

Molecular modifiers can display a wide range of interactions with crystal interfaces to impede their growth. In this work we evaluate the efficacy of a naturally derived phosphorous-containing molecule, phytate, as an inhibitor of barite crystallization compared to the performance of a commercial organophosphorus standard. We show that both compounds inhibit barite nucleation and growth, with phytate demonstrating enhanced potency over the benchmark compound. Our findings reveal that phytate operates by a distinct mode of action on multiple crystal facets, imparting exceptional efficacy, which combined with its biocompatibility and widespread availability make phytate a potentially viable environmentally-friendly alternative to current barite scale treatments.

Few (macro)molecular inhibitors of inorganic scale can suppress both nucleation and crystal growth. In this study, we examine a series of potential inhibitors of barium sulfate (barite), which is a common scale that poses systemic problems owing to its low solubility. We show that alginate (an acidic polysaccharide) is an anomaly among a diverse set of carboxylate-based modifiers of barite crystallization based on its ability to completely suppress both nucleation and crystal growth. Bulk crystallization assays reveal that alginate completely suppresses barite nucleation. Experiments to quantify barite crystal growth kinetics at the macroscopic level under different flow conditions revealed that alginate is also a potent inhibitor of crystal growth, with full suppression of crystallization occurring at a modifier concentration of 60 nM. Time-resolved microfluidics experiments revealed alginate's affinity to interact with all principal crystallographic faces of barite, which is uncommon among inhibitors of various inorganic crystals reported in literature. In situ atomic force microscopy experiments to probe the interactions between alginate and barite crystal surfaces revealed a transition from step bunching to step pinning modes of action at low and high alginate concentrations, respectively. The findings in this study highlight the dual roles and exceptional performance of alginate as a barite scale inhibitor. Owing to its natural abundance in brown algae, alginate is a promising and green alternative to current scale treatments.

A small fraction of infectious bacteria use persistence as a strategy to survive exposure to antibiotics. Periodic pulse dosing of antibiotics has long been considered a potentially effective strategy towards eradication of persisters. Recent studies have demonstrated throughin vitroexperiments that it is indeed feasible to achieve such effectiveness. However, systematic design of periodic pulse dosing regimens to treat persisters is currently lacking. Here we rigorously develop a methodology for the systematic design of optimal periodic pulse dosing strategies for rapid eradication of persisters. A key outcome of the theoretical analysis, on which the proposed methodology is based, is that bactericidal effectiveness of periodic pulse dosing depends mainly on the ratio of durations of the corresponding on and off parts of the pulse. Simple formulas for critical and optimal values of this ratio are derived. The proposed methodology is supported by computer simulations andin vitroexperiments.Author SummaryAdministering antibiotics in periodic pulses that alternate between high and low concentration has long been known as a possible dosing strategy to treat stubborn infections caused by bacteria known aspersisters. Such bacteria use clever mechanisms to survive otherwise lethal temporary exposure to antibiotics and to resume normal activity upon antibiotic removal. Persisters pose a serious health problem. Recent studies have elucidated mechanisms of persistence and have confirmed that pulse dosing, if designed appropriately, can indeed be effective. However, effective pulse dosing design has been mainly handled by trial and error, requiring relatively extensive experimentation. Here we develop a method for rapid systematic design of effective pulse dosing. The method relies on a simple mathematical model and a minimal amount of standard experimental data. We derive corresponding design formulas that explicitly characterize the shape of generally effective or optimal periodic pulses. We tested our method through computer simulations andin vitroexperiments, as well as on prior literature data. In all cases, the outcomes on persister bacteria eradication predicted by our method were confirmed. These results pave the way for ultimately developing effective pulse dosing regimens in realistic situationsin vivo.

The mobility of polystyrene nanoparticles ranging in diameter from 300 nm to 2 μm was measured in dilute and semidilute solutions of partially hydrolyzed polyacrylamide. In this model system, the ratio of particle to polymer size controls the long-time diffusivity of nanoparticles. The particle dynamics transition from subdiffusive on short time scales to Fickian on long time scales, qualitatively similar to predictions for polymer dynamics using a Rouse model. The diffusivities extracted from the long-time Fickian regime, however, are larger than those predicted by the Stokes-Einstein equation and the bulk zero-shear viscosity and moreover do not collapse according to hydrodynamic models. The size-dependent deviations of the long-time particle diffusivities derive instead from the coupling between the dynamics of the particle and the polymer over the length scale of the particle. Although the long-time diffusivities collapse according to predictions, deviations of the short-time scaling exponents and the crossover time between subdiffusive and Fickian dynamics indicate that the particles are only partially coupled to the relaxation modes of the polymer.

Motivated by the need for improved understanding of physical processes involved in bacterial biodegradation of catastrophic oil spills, we review biophysical methods to probe bacterial motility and adhesion at oil–water interfaces. This review summarizes methods that probe bulk, average behaviors as well as local, microscopic behaviors, and highlights opportunities for future work to bridge the gap between biodegradation and biophysics.

We investigate the mobility of polystyrene particles ranging from 100 to 790 nm in diameter in dilute and semidilute sodium polystyrene sulfonate (NaPSS) solutions using fluorescence microscopy. We tune the polymer conformations by varying the ionic strength of the solution. The nanoparticle mean-squared displacements evolve linearly with time at all time scales, indicating Fickian diffusive dynamics. In solutions of high ionic strength, chains adopt a random walk conformation and particle dynamics couple to the bulk zero-shear rate viscosity, according to the Stokes-Einstein picture. In solutions of low ionic strength, however, particle dynamics nonmonotonically deviate from bulk predictions as polymer concentration increases and are not accurately predicted by the available models. These nonmonotonic dynamics directly correlate with the non-Gaussianity in distributions of particle displacements, suggesting the emergence of a local confining length scale as polyelectrolyte concentration increases.

Adhesion of bacteria to liquid-liquid interfaces can play a role in the biodegradation of dispersed hydrocarbons and in biochemical and bioprocess engineering. Whereas thermodynamic factors underpinning adhesion are well studied, the role of bacterial activity on adhesion is less explored.Here, we show that bacterial motility enhances adhesion to surfactant-decorated oil droplets dispersed in artificial sea water. Motile Halomonas titanicae adhered to hexadecane droplets stabilized with dioctyl sodium sulfosuccinate (DOSS) more rapidly and at greater surface densities compared to nonmotile H. titanicae, whose flagellar motion was arrested through addition of a pro-ton uncoupler. Increasing the concentration of DOSS reduced the surface density of both motile and nonmotile bacteria as a result of the reduced interfacial tension.

The COVID-19 pandemic has highlighted the urgent need for sensitive, affordable, and widely-accessible testing at the point-of-care. Here we report the development of a sensitive chemiluminescence-based smartphone-readable lateral flow assay for the detection of SARS-CoV-2 nucleoprotein using M13 phage conjugated with antibodies and HRP enzymes as LFA reporter particles. We screened 84 anti-nucleoprotein monoclonal antibody pairs in phage LFA and identified an antibody pair that gave an LoD of 25 pg/mL nucleoprotein in nasal swab extract using a FluorChem gel documentation system and 100 pg/mL when the test was imaged and analyzed by an in-house-developed smartphone reader. The smartphone-read LFA signals for positive clinical samples tested (N = 15, with known Ct) were statistically different (p < 0.001) from negative clinical samples tested (N = 11). The translation-ready phage LFA technology combined with smartphone chemiluminescence imaging can enable the timely development of ultrasensitive, affordable point-of-care testing platforms for SARS-CoV-2 and beyond.

Control over dispersion of nanoparticles in polymer solutions through porous media is important for subsurface applications such as soil remediation and enhanced oil recovery. Dispersion is affected by the spatial heterogeneity of porous media, the non-Newtonian behavior of polymer solutions, and the Brownian motion of nanoparticles. Here, we use the Euler-Lagrangian method to simulate the flow of nanoparticles and inelastic non-Newtonian fluids (described by Meter model) in a range of porous media samples and injection rates. In one case, we use a fine mesh of more than 3 million mesh points to model nanoparticles transport in a sandstone sample. The results show that the velocity distribution of nanoparticles in the porous medium is non-Gaussian, which leads to the non-Fickian behavior of nanoparticles dispersion. Due to pore-space confinement, the long-time mean-square displacement of nanoparticles depends nonlinearly on time. Additionally, the gradient of shear stress in the pore space of the porous medium dictates the transport behavior of nanoparticles in the porous medium. Furthermore, the Brownian motion of nanoparticles increases the dispersion of nanoparticles along the longitudinal and transverse direction.

We investigate the effects of physicochemical attractions on the transport of finite-sized particles in three-dimensional ordered nanopost arrays using Stokesian dynamics simulations. We find that weak particle-nanopost attractions negligibly affect diffusion due to the dominance of Brownian fluctuations. Strong attractions, however, significantly hinder particle diffusion due to localization of particles around the nanoposts. Conversely, under flow, attractions significantly enhance longitudinal dispersion at low to moderate Péclet number (Pe). At high Pe, by contrast, advection becomes dominant and attractions weakly enhance dispersion. Moreover, attractions frustrate directional locking at moderate flow rates, and shift the onset of this behavior to higher Pe.

We identify factors leading to aggregation of bacteria in the presence of a surfactant using absorbance and microscopy. Two marine bacteria, Marinobacter hydrocarbonoclasticus SP17 and Halomonas titanicae Bead 10BA, formed aggregates of a broad size distribution in synthetic sea water in the presence of an anionic surfactant, dioctyl sodium sulfosuccinate (DOSS). Both DOSS at high concentrations and calcium ions were necessary for aggregate formation, but DOSS micelles were not required for aggregation. Addition of proteinase K but not DNase1 eliminated aggregate formation over two hours. Finally, swimming motility also enhanced aggregate formation.

We investigate the effects of array geometry and flow orientation on transport of finite-sized particles in ordered arrays using Stokesian dynamics simulations. We find that quiescent diffusion is independent of array geometry over the range of volume fraction of the nanoposts examined. Longitudinal dispersion under flow depends on the direction of incident flow relative to the array lattice vectors. Taylor-Aris behavior is recovered for flow along the lattice directions, whereas a nonmonotonic dependence of the dispersion coefficient on the P\'eclet number is obtained for flow orientations slightly perturbed from certain lattice vectors, owing to a competition between directional locking and spatial velocity variations.

Responsive or smart polymer brushes undergo pronounced changes in their surface properties and conformation in response to changes in their environment, including variation in temperature, solution pH or ionic strength, and presence of light. Because the brush stimulus response resembles the ability of natural systems to react to environmental changes, responsive polymer brushes have been incorporated into a number of soft biomimetic structures. Nonetheless, the ability to design soft matter systems that recreate the complexity of life remains limited. Here, we survey the use of responsive surface-grafted polymer brushes to mimic biological function. We summarize various ways in which surface-grafted brushes respond to stimuli. Next, we highlight examples of biomimetic engineering that mimic specific biological structures, including molecular motors, ion channels, leukocytes, and leaves. Finally, we discuss recent studies that design brushes to generate lifelike behavior and interrogate their response under the non-equilibrium, spatiotemporally heterogeneous conditions in living systems. Specifically, we focus on hysteresis in the brush response, as one example of nonlinear response; slow diffusion, used by biological systems to maintain chemical gradients; self-oscillation, as an example of auto-amplification of stimuli; and patterned responsiveness, as an example of compartmentalization. This focus emphasizes the emerging need to rationally design the response of brushes for use as soft components in dynamic, life-inspired systems.

We show that oil droplets suspended near a liquid-solid interface can be driven to rotate by motile bacteria adhered to the droplet surface. Droplets rotate clockwise when viewed from the liquid side, due to symmetry-breaking hydrodynamic interactions of bacteria with the interface. The angular speed of rotation for droplets decreases as their size is increased. Differences in the speed of rotation driven by Escherichia coli, Shewanella haliotis, and Halomonas titanicae bacteria reflects differences in the number of bacteria adhered at the droplet surface and their interfacial affinity. Adding surfactant reduces the number of adherent bacteria and hence lowers the speed of rotation. Together, these results demonstrate that bacterial activity can be used to manipulate suspended droplets.

The hierarchical structure and dynamics of polymer solutions control the transport of nanoparticles (NPs) through them. Here, we perform multi-particle collision dynamics simulations of solutions of semiflexible polymer chains with tunable persistence length lp to investigate the effect of chain stiffness on NP transport. The NPs exhibit two distinct dynamical regimes - subdiffusion on short time scales and diffusion on long time scales. The long-time NP diffusivities are compared with predictions from the Stokes-Einstein relation (SER), mode-coupling theory (MCT), and a recent polymer coupling theory (PCT). Increasing deviations from the SER as the polymer chains become more rigid (i.e. as lp increases) indicate that the NP motions become decoupled from the bulk viscosity of the polymer solution. Likewise, polymer stiffness leads to deviations from PCT, which was developed for fully flexible chains. Independent of lp, however, the long-time diffusion behavior is well-described by MCT, particularly at high polymer concentration. We also observed that the short-time subdiffusive dynamics are strongly dependent on polymer flexibility. As lp is increased, the NP dynamics become more subdiffusive and decouple from the dynamics of the polymer chain center-of-mass. We posit that these effects are due to differences in the segmental mobility of the semiflexible chains.

Summary About half of human cancers are associated with mutations of the tumor suppressor p53. Gained oncogenic functions of the mutants have been related to aggregation behaviors of wild-type and mutant p53. The thermodynamic and kinetic mechanisms of p53 aggregation are poorly understood. Here we find that wild-type p53 forms an anomalous liquid phase. The liquid condensates exhibit several behaviors beyond the scope of classical phase transition theories: their size, ca. 100 nm, is independent of the p53 concentration and decoupled from the protein mass held in the liquid phase. Furthermore, the liquid phase lacks constant solubility. The nucleation of p53 fibrils deviates from the accepted mechanism of sequential association of single solute molecules. We find that the liquid condensates serve as pre-assembled precursors of high p53 concentration that facilitate fibril assembly. Fibril nucleation hosted by precursors represents a novel biological pathway, which opens avenues to suppress protein fibrillation in aggregation diseases., Graphical Abstract, Highlights • Wild-type p53 forms anomalous liquid-phase condensates • The condensates are distinct from dense liquids seen with other proteins • The condensates serve as precursors for p53 fibril assembly • Fibril nucleation hosted by liquid precursors is an unexplored biological pathway, Chemistry; Biological Sciences; Biophysics

Crystallization of mineral scale components ubiquitously plagues industrial systems for water treatment, energy production, and manufacturing. Chemical scale inhibitors and/or dissolvers are often employed to control scale formation, but their efficacy in flow conditions remains incompletely understood. We present a microfluidic platform to elucidate the time-resolved processes controlling crystallization and dissolution of barite, a highly insoluble and chemically resistant component of inorganic scale, in the presence of flow. In a growth environment, increasing the flow rate leads to a crossover from a transport-limited to a reaction-limited kinetic regime. In situ optical microscopy reveals that addition of diethylenetriaminepentaacetic acid (DTPA), a common dissolution agent, alters the morphology of barite crystals grown under flow. In a dissolution environment (i.e. alkaline solutions without barium sulfate), increasing the flux of DTPA, whether by increasing the flow rate or DTPA concentration, enhances the rate of dissolution of barite. Trends in the rate of barite dissolution with DTPA concentration and flow rate indicate an optimal combination of these parameters. The combined use of microfluidics and optical microscopy provides a robust and broadly-useful platform for capturing crystallization kinetics and morphological transformation under dynamic flow conditions.

Bacterial biofilms are communities of bacteria that exist as aggregates that can adhere to surfaces or be free-standing. This complex, social mode of cellular organization is fundamental to the physiology of microbes and often exhibits surprising behavior. Bacterial biofilms are more than the sum of their parts: single-cell behavior has a complex relation to collective community behavior, in a manner perhaps cognate to the complex relation between atomic physics and condensed matter physics. Biofilm microbiology is a relatively young field by biology standards, but it has already attracted intense attention from physicists. Sometimes, this attention takes the form of seeing biofilms as inspiration for new physics. In this roadmap, we highlight the work of those who have taken the opposite strategy: we highlight the work of physicists and physical scientists who use physics to engage fundamental concepts in bacterial biofilm microbiology, including adhesion, sensing, motility, signaling, memory, energy flow, community formation and cooperativity. These contributions are juxtaposed with microbiologists who have made recent important discoveries on bacterial biofilms using state-of-the-art physical methods. The contributions to this roadmap exemplify how well physics and biology can be combined to achieve a new synthesis, rather than just a division of labor., Physical Biology, 18 (5), ISSN:1478-3975, ISSN:1478-3967

Barium sulfate (barite) scale poses significant challenges for processes ranging from water treatment to fossil fuel production. Here, we identify alginate (a polysaccharide derived from brown algae) as a potent, "green" alternative to commercial barite demineralizing agents. Unlike conventional treatments of inorganic scales that require caustic conditions, alginate polymers dissolve barite at near-neutral conditions. In this study, we benchmark the demineralizing efficacy of alginate against a commercial dissolver, diethylenetriaminepentaacetic acid (DTPA), using a combination of bulk dissolution assays, scanning probe microscopy, and molecular dynamics simulations. Time-resolved rates of dissolution measured in a microfluidic device show that demineralization is enhanced more than an order of magnitude under flow. In situ atomic force microscopy reveals that alginate and DTPA exhibit distinct mechanisms of surface dissolution; and surprisingly, their binary combination in alkaline media results in a synergistic cooperativity that enhances the overall rate of barite dissolution. These studies collectively demonstrate a unique approach to demineralization using an inexpensive and abundant biopolymer that enables environmentally friendly treatment of inorganic scales.

We have developed an immuno-PCR based diagnostic platform which couples detection antibodies to self-assembled, ultra-detectable DNA-avidin nanoparticles stabilized with poly(ethylene glycol) to link DNA amplification to target protein concentration. Electrostatic neutralization and cloaking of the PCR-amplifiable DNA labels by avidin and PEG coating reduces non-specific "stickiness" and enhances assay sensitivity. We further optimized the detectability of the nanoparticles by incorporating four repeats of a unique synthetic DNA PCR target into each nanoparticle. Using human chorionic gonadotropin hormone (hCG) as a model analyte, this platform was able to quantitate the target hCG protein in femtomolar concentrations using only standard laboratory equipment.

Dynamic coupling of small penetrants to slow, cooperative relaxations within crowded cells, supercooled liquids, and polymer matrices has broad consequences for applications ranging from drug delivery to nanocomposite processing. Interactions between the constituents of these and other disordered media alter the cooperative relaxations, but their effect on penetrant dynamics remains incompletely understood. We use molecular dynamics simulations to show that the motions of hard-sphere tracer particles probe differences in local structure and cooperative relaxation processes in attractive and repulsive glassy liquid matrices with equal bulk packing fractions and long-time diffusivities. Coupling of the tracer dynamics to collective relaxations in each matrix affects the shape of tracer trajectories, which are fractal within the repulsive matrix and more compact in the attractive. These results reveal that the structure of relaxations controls penetrant transport and dispersion in cooperatively relaxing systems and provide insight into dynamical heterogeneity within glassy liquids.

We investigate the dynamics of nanoparticles in semidilute polymer solutions when the nanoparticles are comparably sized to the polymer coils using explicit- and implicit-solvent simulation methods. The nanoparticle dynamics are subdiffusive on short time scales before transitioning to diffusive motion on long time scales. The long-time diffusivities scale according to theoretical predictions based on full dynamic coupling to the polymer segmental relaxations. In agreement with our recent experiments, however, we observe that the nanoparticle subdiffusive exponents are significantly larger than predicted by the coupling theory over a broad range of polymer concentrations. We attribute this discrepancy in the subdiffusive regime to the presence of an additional coupling mechanism between the nanoparticle dynamics and the polymer center-of-mass motion, which differs from the polymer relaxations that control the long-time diffusion. This coupling is retained even in the absence of many-body hydrodynamic interactions when the long-time dynamics of the colloids and polymers are matched.

We investigated the effect of two brush parameters, thickness and dispersity in the molecular weight distribution, on the adhesion of bacteria to pH-responsive poly(acrylic acid) (PAA) brushes synthesized using surface-initiated atom transfer radical polymerization. The attachment and detachment of Staphylococcus epidermidis to PAA brushes at pH 4 and pH 9, respectively, were examined with confocal microscopy. An optimal range of brush thickness, 13-18 nm, was identified for minimizing bacterial adhesion on PAA brushes at pH 4, and bacterial attachment did not depend on the brush dispersity. Increasing either the brush thickness or dispersity detached bacteria from the brushes when the pH was increased from 4 to 9. Bacterial detachment likely arose from an enhanced actuation effect in thick or high-dispersity brushes, as PAA brushes change conformation from collapsed to extended states when the pH is increased from 4 to 9. These results suggest that manipulating the molecular weight distribution provides a route to separately tune the attachment and detachment of bacteria.

Protein condensates play essential roles in physiological processes and pathological conditions. Recently discovered mesoscopic protein-rich clusters may act as crucial precursors for the nucleation of ordered protein solids, such as crystals, sickle hemoglobin polymers, and amyloid fibrils. These clusters challenge settled paradigms of protein condensation as the constituent protein molecules present features characteristic of both partially misfolded and native proteins. Here we employ the antimicrobial enzyme lysozyme and examine the similarities between mesoscopic clusters, amyloid structures, and disordered aggregates consisting of chemically modified protein. We show that the mesoscopic clusters are distinct from the other two classes of aggregates. Whereas cluster formation and amyloid oligomerization are both reversible, aggregation triggered by reduction of the intramolecular S-S bonds is permanent. In contrast to the amyloid structures, protein molecules in the clusters retain their enzymatic activity. Furthermore, an essential feature of the mesoscopic clusters is their constant radius of less than 50 nm. The amyloid and disordered aggregates are significantly larger and rapidly grow. These findings demonstrate that the clusters are a product of limited protein structural flexibility. In view of the role of the clusters in the nucleation of ordered protein solids, our results suggest that fine-tuning the degree of protein conformational stability is a powerful tool to control and direct the pathways of protein condensation.

We measure the dynamics of high molecular weight polystyrene grafted to silica nanoparticles dispersed in semidilute solutions of linear polymer. Structurally, the linear free chains do not penetrate the grafted corona but increase the osmotic pressure of the solution, collapsing the grafted polymer and leading to eventual aggregation of the grafted particles at high matrix concentrations. Dynamically, the relaxations of the grafted polymer are controlled by the solvent viscosity according to the Zimm model on short time scales. On longer time scales, the grafted chains are confined by neighboring grafted chains, preventing full relaxation over the experimental time scale. Adding free linear polymer to the solution does not affect the initial Zimm relaxations of the grafted polymer but does increase the confinement of the grafted chains. Our results elucidate the physics underlying the slow relaxations of grafted polymer.

Shear flow alters the rate at which crystals nucleate from solution, yet the underlying mechanisms remain poorly understood. To fill this knowledge gap, we explore the response to shear of dense liquid clusters, which may serve as crystal nucleation precursors. Solutions of the protein lysozyme were sheared in a Couette cell at rates from 0.3 to 200 s−1 for up to seven hours. The cluster size and total population volume were characterized by dynamic light scattering. We demonstrate that shear rates greater than 10 s−1 applied for longer than one hour reduce the volume of the cluster population. The likely mechanism of the observed response involves enhanced partial unfolding of the lysozyme molecules, which exposes hydrophobic surfaces between the constituent domains to the aqueous solution. We show that disruption of the intramolecular S-S bridges does not contribute to the mechanism of response to shear. The decrease of the cluster population volume with increasing shear rate or shear time implies that nucleation could be inhibited at moderate shear rates.

Increased shear thinning arising due to strong attractive interactions between colloidal particles is thought to obscure shear thickening. Here, we demonstrate how moderate attractions, induced by adding a nonadsorbing polymer, can instead enhance shear thickening. We measure the rheology of colloidal suspensions at a constant particle volume fraction of ϕ=0.40 with dilute to weakly semidilute concentrations of three polyacrylamide depletants of different molecular weights. Suspensions containing large polymer exhibit increased shear thickening and positive first normal stress differences at high shear stress, and increased heterogeneous fluctuations in the boundary stress. These results are consistent with a friction-based model for shear thickening, suggesting that the presence of large, extended polymers induces the formation of near-spanning networks of interparticle contacts.

We investigate the transport and localization of tracer probes in a glassy matrix as a function of relative size using dynamic X-ray scattering experiments and molecular dynamics simulations. The quiescent relaxations of tracer particles evolve with increasing waiting time, tw. The corresponding relaxation times increase exponentially at small tw and then transition to a power-law behavior at longer tw. As tracer size decreases, the aging behavior weakens and the particles become less localized within the matrix until they delocalize at a critical size ratio δ0 ≈ 0.38. Localization does not vary with sample age even as the relaxations slow by approximately an order of magnitude, suggesting that matrix structure controls tracer localization.

We examine the dynamics of silica particles grafted with high molecular weight polystyrene suspended in semidilute solutions of chemically similar linear polymer using X-ray photon correlation spectroscopy. The particle dynamics decouple from the bulk viscosity despite their large hydrodynamic size and instead experience an effective viscosity that depends on the molecular weight of the free polymer chains. Unlike for hard-sphere nanoparticles in semidilute polymer solutions, the diffusivities of the polymer-grafted nanoparticles do not collapse onto a master curve solely as a function of normalized length scales. Instead, the diffusivities can be collapsed across two orders of magnitude in free polymer molecular weight and concentration and one order of magnitude in grafted molecular weight by incorporating the ratio of free to grafted polymer molecular weights. These results suggest that the soft interaction potential between polymer-grafted nanoparticles and free polymer allows polymer-grafted nanoparticles to diffuse faster than predicted based on bulk rheology and modifies the coupling between grafted particle dynamics and the relaxations of the surrounding free polymer.

We investigate the structure and dynamics of silica nanoparticles and polymer chains in semidilute solutions of high molecular weight polystyrene in 2-butanone to determine the effect of long-range interparticle interactions on the coupling between particle and polymer dynamics. Particles at concentrations of 1–10 wt % are well dispersed in the semidilute polymer solutions and exhibit long-range electrostatic repulsions between particles. Because the particles are comparably sized to the radius of gyration of the polymer, the particle dynamics is predicted to couple to that of the polymer. We verify that the polymer structure and dynamics are not significantly affected by the particles, indicating that the particle–polymer coupling does not change with increasing particle loading. We find that the coupling between the dynamics of comparably sized particles and polymer results in subdiffusive particle dynamics, as expected. Over the interparticle distance, however, the particle dynamics is hindered and not...

We investigate the deposition and transient adhesion of Escherichia coli on alkyl and fluoroalkyl silanized glass surfaces of different carbon chain lengths. The rate at which bacteria deposit onto these surfaces decreases as the shear stress is increased from 3 to 67 mPa, but trends in the deposition rate across all surfaces cannot be predicted from extended DLVO calculations of the interaction potential. As the surface root-mean-square (rms) roughness increases, the deposition rate increases and the percentage of motile tethered cells decreases. Furthermore, on surfaces of root-mean-square roughness of less than 0.2 nm, bacteria exhibit mobile adhesion, for which surface-associated cells linearly translate distances greater than approximately 1.5 times their average body length along the flow direction. E. coli bacteria with and without flagella exhibit mobile adhesion, indicating that this behavior is not driven by these appendages. Cells that express fimbriae do not exhibit mobile adhesion. These results suggest that even subnanoscale roughness can influence the deposition and transient adhesion of bacteria and imply that strategies to reduce frictional interactions by making cells or surfaces smoother may help to control the initial fouling of surfaces by E. coli bacteria.