Shear annealing of a self-interacting sheet.

2D materials such as graphene, graphene oxide, transition metal dichalcogenides, and 2D polymers have unique properties which allow them to be used in many applications from electronics to energy to biotechnology. Producing and applying these materials often involves solution processing. Previous computational studies have observed 2D sheets in shear and extensional flows, but have focused on steady flows, even though the dynamics of these materials might exhibit hysteresis.

Enumerating Stable Nanopores in Graphene and Their Geometrical Properties Using the Combinatorics of Hexagonal Lattices.

Nanopores in two-dimensional (2D) materials, including graphene, can be used for a variety of applications, such as gas separations, water desalination, and DNA sequencing. So far, however, all plausible isomeric shapes of graphene nanopores have not been enumerated. Instead, a probabilistic approach has been followed to predict nanopore shapes in 2D materials, due to the exponential increase in the number of nanopores as the size of the vacancy increases.

Discretized hexagonal boron nitride quantum emitters and their chemical interconversion.

Quantum emitters in two-dimensional hexagonal boron nitride (hBN) are of significant interest because of their unique photophysical properties, such as single-photon emission at room temperature, and promising applications in quantum computing and communications. The photoemission from hBN defects covers a wide range of emission energies but identifying and modulating the properties of specific emitters remain challenging due to uncontrolled formation of hBN defects. In this study, more than 2000 spectra are collected consisting of single, isolated zero-phonon lines (ZPLs) between 1.

A theory of mechanical stress-induced HO signaling waveforms in Planta.

Recent progress in nanotechnology-enabled sensors that can be placed inside of living plants has shown that it is possible to relay and record real-time chemical signaling stimulated by various abiotic and biotic stresses. The mathematical form of the resulting local reactive oxygen species (ROS) wave released upon mechanical perturbation of plant leaves appears to be conserved across a large number of species, and produces a distinct waveform from other stresses including light, heat and pathogen-associated molecular pattern (PAMP)-induced stresses. Herein, we develop a quantitative theory of the local ROS signaling waveform resulting from mechanical stress in planta.

Thermally fluctuating, semiflexible sheets in simple shear flow.

We perform Brownian dynamics simulations of semiflexible colloidal sheets with hydrodynamic interactions and thermal fluctuations in shear flow. As a function of the ratio of bending rigidity to shear energy (a dimensionless quantity we denote ) and the ratio of bending rigidity to thermal energy, we observe a dynamical transition from stochastic flipping to crumpling and continuous tumbling. This dynamical transition is broadened by thermal fluctuations, and the value of at which it occurs is consistent with the onset of chaotic dynamics found for athermal sheets.

Dynamics of a single polyampholyte chain.

Polymers that feature both positive and negative charges along chains, known as polyampholytes, represent a class of materials that hold promise for a new generation of energy storage devices, the design of which will require knowledge of the underlying structure and dynamics. Here, we develop a theory based on the Rouse model for the dynamic structure factor of a single polyampholyte chain in the weak coupling regime (negligible intramolecular electrostatics) or subjected to weak external electric fields (governed by linear response). Neglecting effects of small ions, we find deviations in scaling from the classic Rouse theory and make predictions for scattering experiments performed on polyampholytes.

Buckling, crumpling, and tumbling of semiflexible sheets in simple shear flow.

As 2D materials such as graphene, transition metal dichalcogenides, and 2D polymers become more prevalent, solution processing and colloidal-state properties are being exploited to create advanced and functional materials. However, our understanding of the fundamental behavior of 2D sheets and membranes in fluid flow is still lacking. In this work, we perform numerical simulations of athermal semiflexible sheets with hydrodynamic interactions in shear flow.

Collective mode Brownian dynamics: A method for fast relaxation of statistical ensembles.

Sampling equilibrium configurations of correlated systems of particles with long relaxation times (e.g., polymeric solutions) using conventional molecular dynamics and Monte Carlo methods can be challenging.

Implantable Nanosensors for Human Steroid Hormone Sensing In Vivo Using a Self-Templating Corona Phase Molecular Recognition.

Dynamic measurements of steroid hormones in vivo are critical, but steroid sensing is currently limited by the availability of specific molecular recognition elements due to the chemical similarity of these hormones. In this work, a new, self-templating synthetic approach is applied using corona phase molecular recognition (CoPhMoRe) targeting the steroid family of molecules to produce near infrared fluorescent, implantable sensors. A key limitation of CoPhMoRe has been its reliance on library generation for sensor screening.

Capacitance of thin films containing polymerized ionic liquids.

Electrode-polymer interfaces dictate many of the properties of thin films such as capacitance, the electric field experienced by polymers, and charge transport. However, structure and dynamics of charged polymers near electrodes remain poorly understood, especially in the high concentration limit representative of the melts. To develop an understanding of electric field-induced transformations of electrode-polymer interfaces, we have studied electrified interfaces of an imidazolium-based polymerized ionic liquid (PolyIL) using combinations of broadband dielectric spectroscopy, specular neutron reflectivity, and simulations based on the Rayleigh's dissipation function formalism.

Real-time detection of wound-induced HO signalling waves in plants with optical nanosensors.

Decoding wound signalling in plants is critical for understanding various aspects of plant sciences, from pest resistance to secondary metabolite and phytohormone biosynthesis. The plant defence responses are known to primarily involve NADPH-oxidase-mediated HO and Ca signalling pathways, which propagate across long distances through the plant vasculature and tissues. Using non-destructive optical nanosensors, we find that the HO concentration profile post-wounding follows a logistic waveform for six plant species: lettuce (Lactuca sativa), arugula (Eruca sativa), spinach (Spinacia oleracea), strawberry blite (Blitum capitatum), sorrel (Rumex acetosa) and Arabidopsis thaliana, ranked in order of wave speed from 0.

Short and Soft: Multidomain Organization, Tunable Dynamics, and Jamming in Suspensions of Grafted Colloidal Cylinders with a Small Aspect Ratio.

The yet virtually unexplored class of soft colloidal rods with a small aspect ratio is investigated and shown to exhibit a very rich phase and dynamic behavior, spanning from liquid to nearly melt state. Instead of the nematic order, these short and soft nanocylinders alter their organization with increasing concentration from isotropic liquid with random orientation to small domains with preferred local orientation and eventually a multidomain arrangement with a local orientational order. The latter gives rise to a kinetically suppressed state akin to structural glass with detectable terminal relaxation, which, on further increasing concentration, reveals features of hexagonally packed order as in ordered block copolymers.

Measuring the Accessible Surface Area within the Nanoparticle Corona Using Molecular Probe Adsorption.

The corona phase-the adsorbed layer of polymer, surfactant, or stabilizer molecules around a nanoparticle-is typically utilized to disperse nanoparticles into a solution or solid phase. However, this phase also controls molecular access to the nanoparticle surface, a property important for catalytic activity and sensor applications. Unfortunately, few methods can directly probe the structure of this corona phase, which is subcategorized as either a hard, immobile corona or a soft, transient corona in exchange with components in the bulk solution.

Single-Particle Tracking for Understanding Polydisperse Nanoparticle Dispersions.

Colloidal dispersions of nanomaterials are often polydisperse in size, significantly complicating their characterization. This is particularly true for materials early in their historical development due to synthetic control, dispersion efficiency, and instability during storage. Because a wide range of system properties and technological applications depend on particle dimensions, it remains an important problem in nanotechnology to identify a method for the routine characterization of polydispersity in nanoparticle samples, especially changes over time.

High-Resolution Nanoparticle Sizing with Maximum A Posteriori Nanoparticle Tracking Analysis.

The rapid and efficient characterization of polydisperse nanoparticle dispersions remains a challenge within nanotechnology and biopharmaceuticals. Current methods for particle sizing, such as dynamic light scattering, analytical ultracentrifugation, and field-flow fractionation, can suffer from a combination of statistical biases, difficult sample preparation, insufficient sampling, and ill-posed data analysis. As an alternative, we introduce a Bayesian method that we call maximum a posteriori nanoparticle tracking analysis (MApNTA) for estimating the size distributions of nanoparticle samples from high-throughput single-particle tracking experiments.

Addressing the isomer cataloguing problem for nanopores in two-dimensional materials.

The presence of extended defects or nanopores in two-dimensional (2D) materials can change the electronic, magnetic and barrier membrane properties of the materials. However, the large number of possible lattice isomers of nanopores makes their quantitative study a seemingly intractable problem, confounding the interpretation of experimental and simulated data. Here we formulate a solution to this isomer cataloguing problem (ICP), combining electronic-structure calculations, kinetic Monte Carlo simulations, and chemical graph theory, to generate a catalogue of unique, most-probable isomers of 2D lattice nanopores.

Tunable Pickering emulsions with polymer-grafted lignin nanoparticles (PGLNs).

Lignin is an abundant biopolymer that has native interfacial functions but aggregates strongly in aqueous media. Polyacrylamide was grafted onto kraft lignin nanoparticles using reversible addition-fragmentation chain transfer (RAFT) chemistry to form polymer-grafted lignin nanoparticles (PGLNs) that tune aggregation strength while retaining interfacial activities in forming Pickering emulsions. Polymer graft density on the particle surface, ionic strength, and initial water and cyclohexane volume fractions were varied and found to have profound effects on emulsion characteristics, including emulsion volume fraction, droplet size, and particle interfacial concentration that were attributed to changes in lignin aggregation and hydrophobic interactions.