quantifying-elastic-properties-environmental-biofilms-using-optical

Quantifying Elastic Properties of Environmental Biofilms using Optical Coherence Elastography

Biofilms are complex biomaterials comprising a well-organized network of microbial cells encased in self-produced extracellular polymeric substances ...

Northwestern University

DNA hybridization onto DNA-functionalized nanoparticle surfaces (e.g., in the form of a spherical nucleic acid (SNA)) is known to be enhanced relative to hybridization free in solution. Surprisingly, via isothermal titration calorimetry, we reveal that this enhancement is enthalpically, as opposed to entropically, dominated by ∼20 kcal/mol. Coarse-grained molecular dynamics simulations suggest that the observed enthalpic enhancement results from structurally confining the DNA on the nanoparticle surface and preventing it from adopting enthalpically unfavorable conformations like those observed in the solution case. The idea that structural confinement leads to the formation of energetically more stable duplexes is evaluated by decreasing the degree of confinement a duplex experiences on the nanoparticle surface. Both experiment and simulation confirm that when the surface-bound duplex is less confined, i.e., at lower DNA surface density or at greater distance from the nanoparticle surface, its enthalpy of formation approaches the less favorable enthalpy of duplex formation for the linear strand in solution. This work provides insight into one of the most important and enabling properties of SNAs and will inform the design of materials that rely on the thermodynamics of hybridization onto DNA-functionalized surfaces, including diagnostic probes and therapeutic agents.

The Role of Structural Enthalpy in Spherical Nucleic Acid Hybridization.

Modern particle-based simulations increasingly incorporate polarization charges arising from spatially nonuniform permittivity. For complex dielectric geometries, calculation of these induced many-body effects typically requires numerical solvers based upon boundary-element methods, which very significantly increase the required computational effort. For the special case of dielectric spheres, such as colloids or nanoparticles, we recently proposed a semianalytical spectrally accurate hybrid method that combines the method of moments, the image-charge method, and the fast multipole method. The hybrid method is efficient and accurate even when dielectric spheres are closely packed. Here, we extend the method to the evaluation of direct and induced electrostatic forces and demonstrate how this can be incorporated in molecular dynamics simulations. The choice of the relevant numerical parameters for molecular dynamics simulations is discussed in detail, as well as comparisons to the boundary-element method. As a concrete example, we examine the challenging case of binary crystal structures composed of close-packed dielectric colloidal spheres.

Efficient dynamic simulations of charged dielectric colloids through a novel hybrid method.

Spontaneous pattern formation plays an important role in a wide variety of natural phenomena and materials systems. A key ingredient for the occurrence of modulated phases is the presence of competing interactions, generally of different physical origins. We demonstrate that in dipolar films, a prototypical system for pattern formation, patterns can be induced by dielectric effects alone. A rich phase diagram arises, where striped and circular morphologies emerge with geometric properties that can be controlled through variation of particle shape and substrate permittivity or permeability. These effects are particularly enhanced by metamaterial substrates.

Dielectric Modulation of Two-Dimensional Dipolar Materials.

Nucleation and growth are universally important in systems from the atomic to the micrometre scale as they dictate structural and functional attributes of crystals. However, at the nanoscale, the pathways towards crystallization have been largely unexplored owing to the challenge of resolving the motion of individual building blocks in a liquid medium. Here we address this gap by directly imaging the full transition of dispersed gold nanoprisms to a superlattice at the single-particle level. We utilize liquid-phase transmission electron microscopy at low dose rates to control nanoparticle interactions without affecting their motions. Combining particle tracking with Monte Carlo simulations, we reveal that positional ordering of the superlattice emerges from orientational disorder. This method allows us to measure parameters such as line tension and phase coordinates, charting the nonclassical nucleation pathway involving a dense, amorphous intermediate. We demonstrate the versatility of our approach via crystallization of different nanoparticles, pointing the way to more general applications.

Kinetic pathways of crystallization at the nanoscale.

Granular biofilms are dense spherical complex biological systems composed mainly of multi-microbial cells, water, and extracellular polymeric substances (EPS). They facilitate efficient purification and settling of activated sludge in wastewater treatment processes. The viscoelastic properties of these complex biofilm systems are important characteristics that control their growth and dictate how they respond to hydrodynamic forces and chemical stimuli. However, the viscoelastic properties of granular biofilms are poorly understood. In this paper, we study granular biofilms' viscoelastic properties using optical coherence elastography (OCE), a nondestructive method that integrates optical coherence tomography (OCT) with elastic wave propagation. While quantitative viscoelastic characterization of granular biofilms is challenging due to their heterogeneous properties, we show that elastic waves are suitable for this purpose. First, we employ guided elastic waves in a thin section of a granular biofilm to reveal a two-layered profile for the viscoelastic properties. Next, we utilize circumferential elastic waves that propagate near the surface of a non-sectioned spherical biofilm to quantify the layered system's viscoelastic properties. To the best of our knowledge, this work is the first quantitative study that characterizes the layered viscoelastic properties of granular biofilms. The measurement approach may provide a platform to study the interplay between the viscoelastic properties and other characteristics of granular biofilms such as the complex microbial system, morphology, and oxygen distribution.

Layered viscoelastic properties of granular biofilms.

Organic crystals formed by small molecules can be highly functional but are often brittle or insoluble structures with limited possibilities for use or processing from a liquid phase. A possible solution is the nanoscale integration of polymers into organic crystals without sacrificing long-range order and therefore function. This enables the organic crystals to benefit from the advantageous mechanical and chemical properties of the polymeric component. We report here on a strategy in which small molecules cocrystallize with side chains of chemically disordered polymers to create hybrid nanostructures containing a highly ordered lattice. Synchrotron X-ray scattering, absorption spectroscopy, and coarse-grained molecular dynamics simulations reveal that the polymer backbones form an "exo-crystalline" layer of disordered chains that wrap around the nanostructures, becoming a handle for interesting properties. The morphology of this "hybrid bonding polymer" nanostructure is dictated by the competition between the polymers' entropy and the enthalpy of the lattice allowing for control over the aspect ratio of the nanocrystal by changing the degree of polymer integration. We observed that nanostructures with an exo-crystalline layer of polymer exhibit enhanced fracture strength, self-healing capacity, and dispersion in water, which benefits their use as light-harvesting assemblies in photocatalysis. Guided by computation, future work could further explore these hybrid nanostructures as components for functional materials.

Hybrid Nanocrystals of Small Molecules and Chemically Disordered Polymers.

Hydrogel-encapsulated catalysts are an attractive tool for low-cost intensification of (bio)-processes. Polyvinyl alcohol-sodium alginate hydrogels crosslinked with boric acid and post-cured with sulfate (PVA-SA-BS) have been applied in bioproduction and water treatment processes, but the low pH required for crosslinking may negatively affect biocatalyst functionality. Here, we investigate how crosslinking pH (3, 4, and 5) and time (1, 2, and 8 h) affect the physicochemical, elastic, and process properties of PVA-SA-BS beads. Overall, bead properties were most affected by crosslinking pH. Beads produced at pH 3 and 4 were smaller and contained larger internal cavities, while optical coherence tomography suggested polymer cross-linking density was higher. Optical coherence elastography revealed PVA-SA-BS beads produced at pH 3 and 4 were stiffer than pH 5 beads. Dextran Blue release showed that pH 3-produced beads enabled higher diffusion rates and were more porous. Last, over a 28-day incubation, pH 3 and 4 beads lost more microspheres (as cell proxies) than beads produced at pH 5, while the latter released more polymer material. Overall, this study provides a path forward to tailor PVA-SA-BS hydrogel bead properties towards a broad range of applications, such as chemical, enzymatic, and microbially catalyzed (bio)-processes.

Tailoring polyvinyl alcohol-sodium alginate (PVA-SA) hydrogel beads by controlling crosslinking pH and time.

Crystal growth from nanoscale constituents is a ubiquitous phenomenon in biology, geology and materials science. Numerous studies have focused on understanding the onset of nucleation and on producing high-quality crystals by empirically sampling constituents with different attributes and varying the growth conditions. However, the kinetics of post-nucleation growth processes, an important determinant of crystal morphology and properties, have remained underexplored due to experimental challenges associated with real-space imaging at the nanoscale. Here we report the imaging of the crystal growth of nanoparticles of different shapes using liquid-phase transmission electron microscopy, resolving both lateral and perpendicular growth of crystal layers by tracking individual nanoparticles. We observe that these nanoscale systems exhibit layer-by-layer growth, typical of atomic crystallization, as well as rough growth prevalent in colloidal systems. Surprisingly, the lateral and perpendicular growth modes can be independently controlled, resulting in two mixed crystallization modes that, until now, have received only scant attention. Combining analytical considerations with molecular dynamics and kinetic Monte Carlo simulations, we develop a comprehensive framework for our observations, which are fundamentally determined by the size and shape of the building blocks. These insights unify the understanding of crystal growth across four orders of magnitude in particle size and suggest novel pathways to crystal engineering.

Article	Year
The Role of Structural Enthalpy in Spherical Nucleic Acid Hybridization. Journal of the American Chemical Society\| PubMed ID: 29762017	2018
Efficient dynamic simulations of charged dielectric colloids through a novel hybrid method. The Journal of chemical physics\| PubMed ID: 31301698	2019
Dielectric Modulation of Two-Dimensional Dipolar Materials. Physical review letters\| PubMed ID: 31524462	2019
Kinetic pathways of crystallization at the nanoscale. Nature materials\| PubMed ID: 31659295	2020
Layered viscoelastic properties of granular biofilms. Water research\| PubMed ID: 34256191	2021
Hybrid Nanocrystals of Small Molecules and Chemically Disordered Polymers. ACS nano\| PubMed ID: 35588377	2022
Tailoring polyvinyl alcohol-sodium alginate (PVA-SA) hydrogel beads by controlling crosslinking pH and time. Scientific reports\| PubMed ID: 36460678	2022
Unravelling crystal growth of nanoparticles. Nature nanotechnology\| PubMed ID: 36997752	2023

Ziwei Wang

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