(Non)Parallel Evolution

Parallel evolution across replicate populations has provided evolutionary biologists with iconic examples of adaptation. When multiple populations colonize seemingly similar habitats, they may evolve similar genes, traits, or functions. Yet, replicated evolution in nature or in the laboratory often yields inconsistent outcomes: Some replicate populations evolve along highly similar trajectories, whereas other replicate populations evolve to different extents or in distinct directions. To understand these heterogeneous outcomes, biologists are increasingly treating parallel evolution not as a binary phenomenon but rather as a quantitative continuum ranging from parallel to nonparallel. By measuring replicate populations’ positions along this (non)parallel continuum, we can test hypotheses about evolutionary and ecological factors that influence the extent of repeatable evolution. We review evidence regarding the manifestation of (non)parallel evolution in the laboratory, in natural populations, and in applied contexts such as cancer. We enumerate the many genetic, ecological, and evolutionary processes that contribute to variation in the extent of parallel evolution

Mechanically adaptive nanocomposites for neural interfacing

The recording of neural signals with microelectrodes that are implanted into the cortex of the brain is potentially useful for a range of clinical applications. However, the widespread use of such neural interfaces has so far been stifled because existing intracortical electrode systems rarely allow for consistent long-term recording of neural activity. This limitation is usually attributed to scar formation and neuron death near the surface of the implanted electrode. It has been proposed that the mechanical property mismatch between existing electrode materials and the brain tissue is a significant contributor to these events. To alleviate this problem, we utilized the architecture of the sea cucumber dermis as a blueprint to engineer a new class of mechanically adaptive materials as substrates for "smart” intracortical electrodes. We demonstrated that these originally rigid polymer nanocomposites soften considerably upon exposure to emulated physiological and in vivo conditions. The adaptive nature of these bioinspired materials makes them useful as a basis for electrodes that are sufficiently stiff to be easily implanted and subsequently soften to better match the stiffness of the brain. Initial histological evaluations suggest that mechanically adaptive neural prosthetics can more rapidly stabilize neural cell populations at the device interface than rigid systems, which bodes well for improving the functionality of intracortical device

LCPOM: Precise Reconstruction of Polarized Optical Microscopy Images of Liquid Crystals

When viewed with a cross-polarized optical microscope (POM), liquid crystals display interference colors and complex patterns that depend on the material's microscopic orientation. That orientation can be manipulated by application of external fields, which provides the basis for applications in optical display and sensing technologies. The color patterns themselves have a high information content. Traditionally, however, calculations of the optical appearance of liquid crystals have been performed by assuming that a single-wavelength light source is employed, and reported in a monochromatic scale. In this work, the original Jones matrix method is extended to calculate the colored images that arise when a liquid crystal is exposed to a multi-wavelength source. By accounting for the material properties, the visible light spectrum and the CIE color matching functions, we demonstrate that the proposed approach produces colored POM images that are in quantitative agreement with experimental data. Results are presented for a variety of systems, including radial, bipolar, and cholesteric droplets, where results of simulations are compared to experimental microscopy images. The effects of droplet size, topological defect structure, and droplet orientation are examined systematically. The technique introduced here generates images that can be directly compared to experiments, thereby facilitating machine learning efforts aimed at interpreting LC microscopy images, and paving the way for the inverse design of materials capable of producing specific internal microstructures in response to external stimuli.Comment: 12 pages, 5 figures (main text). 6 pages, 6 figures (appendices

Stress-transfer in anisotropic and environmentally adaptive cellulose whisker nanocomposites

Quantitative insights into the stress-transfer mechanisms that determine the mechanical properties of tunicate cellulose whisker/poly(vinyl acetate) nanocomposites were gained by Raman spectroscopy. The extent of stress-transfer is influenced by local orientation (or anisotropy) of the whiskers, which in turn is governed by the processing conditions used to fabricate the nanocomposites. Solution-cast materials display no microscopic anisotropy, while samples that were cast and subsequently compression molded contain both isotropic regions as well as domains of locally oriented whiskers. Polarized optical microscopy showed these regions to have dimensions in the hundreds of μm. Polarized Raman spectroscopy of the 1095 cm⁻¹ Raman band, associated with C−O ring stretching of the cellulose backbone, was used to quantify the local orientation of the cellulose whiskers. Clear and discernible shifts of this Raman band upon uniaxial deformation of nanocomposite films were further used to determine the level of stress experienced by the cellulose whiskers, ultimately reflecting the levels of stress-transfer predominantly between the poly(vinyl acetate) matrix and the tunicate whiskers, but also between the whiskers within the network. In the isotropic regions, where whiskers form a percolating network, the observed Raman shift rate with respect to strain is smaller than in the regions where the whiskers are uniaxially orientated. The Raman shift is strongly affected by the presence of water, leading to a lack of stress-transfer when the samples are fully hydrated, which is clearly detected by the Raman technique. Heating of the nanocomposites above the glass transition temperature of the poly(vinyl acetate) matrix also reduces the stress experienced by the individual whiskers

Experimental results for nulling the effective thermal expansion coefficient of fused silica fibres under a static stress

We have experimentally demonstrated that the effective thermal expansion coefficient of a fused silica fibre can be nulled by placing the fibre under a particular level of stress. Our technique involves heating the fibre and measuring how the fibre length changes with temperature as the stress on the fibre was systematically varied. This nulling of the effective thermal expansion coefficient should allow for the complete elimination of thermoelastic noise and is essential for allowing second generation gravitational wave detectors to reach their target sensitivity. To our knowledge this is the first time that the cancelation of the thermal expansion coefficient with stress has been experimentally observed

Structural, Ionic, and Electronic Properties of Solid-State Phthalimide-Containing Polymers for All-Organic Batteries

Redox-active polymers serving as the active materials in solid-state electrodes offer a promising path toward realizing all-organic batteries. While both cathodic and anodic redox-active polymers are needed, the diversity of the available anodic materials is limited. Here, we predict solid-state structural, ionic, and electronic properties of anodic, phthalimide-containing polymers using a multiscale approach that combines atomistic molecular dynamics, electronic structure calculations, and machine learning surrogate models. Importantly, by combining information from each of these scales, we are able to bridge the gap between bottom-up molecular characteristics and macroscopic properties such as apparent diffusion coefficients of electron transport (Dapp). We investigate the impact of different polymer backbones and of two critical factors during battery operation: state of charge and polymer swelling. Our findings reveal that the state of charge significantly influences solid-state packing and the thermophysical properties of the polymers, which, in turn, affect ionic and electronic transport. A combination of molecular-level properties (such as the reorganization energy) and condensed-phase properties (such as effective electron hopping distances) determine the predicted ranking of electron transport capabilities of the polymers. We predict Dapp for the phthalimide-based polymers and for a reference nitroxide radical-based polymer, finding a 3 orders of magnitude increase in Dapp (≈10{–6} cm2 s{–1}) with respect to the reference. This study underscores the promise of phthalimide-containing polymers as highly capable redox-active polymers for anodic materials in all-organic batteries, due to their exceptional predicted electron transport capabilities

Organo-disulfide-based particles enable controlled stimulus-triggered cleaning of electrode surfaces

Electrode fouling resulting in reduced performance is an ongoing challenge in electrochemical flow cells based on redox active polymers (RAPs). An avenue that holds substantial promise yet remains relatively unexplored involves the strategic design of RAPs capable of undergoing electrochemical stimulation to facilitate in situ electrode cleaning within a flow cell. Herein, a new electrode cleaning strategy is demonstrated through the application of redox-active poly(glycidyl methacrylate) particles crosslinked with 2-amino-1,3,4-thiadiazole disulfide (PGMA–ATDDS). The resulting particles can de-crosslink through cleavage of the disulfide bond using stimuli, such as electrochemical reduction or UV photoexcitation. Using a custom flow cell, applying such a stimulus to an ITO electrode artificially fouled with PGMA–ATDDS in the presence of a fluid flow leads to a significant particle removal (80%) that is over six times more efficient relative to the case when no stimulus is applied. Confocal fluorescence imaging of the electrochemically stimulated electrode highlighted localized disulfide reduction of particles near the electrode surface. It is posited that this selective de-crosslinking and concomitant electrolyte swelling at the particle/electrode interface facilitate particle removal in the presence of a fluid flow. In addition, the regeneration of electrode performance upon cleaning was demonstrated through charging of a redox-active particle suspension of poly(vinylbenzyl chloride) functionalized with dimethylaminoferrocene (PVBC–Fc). Upon electrochemical cleaning of the fouled ITO electrode, the accessible charge of PVBC–Fc was statistically equivalent to the accessible charge measured using a pristine ITO electrode. Overall, this study introduces a new approach for leveraging stimulus-responsive chemistries for RAPs to impart inherent functionality to facilitate in-line electrode cleaning in electrochemical flow cells

Melt-functionalization of cellulose nanocrystals using dynamic hindered ureas

Cellulose nanocrystal (CNC)-reinforced composites are gaining commercial attention on account of their high strength and sustainable sourcing. Grafting polymers to the CNCs in these composites has the potential to improve their properties, but current solution-based synthesis methods limit their production at scale. Utilizing dynamic hindered urea chemistry, a new method for the melt-functionalization of cellulose nanocrystals has been developed. This method does not require toxic solvents during the grafting step and can achieve grafting densities competitive with state-of-the-art solution-based grafting methods. Using cotton-sourced, TEMPO-oxidized CNCs, multiple molecular weights of poly(ethylene glycol) (PEG) as well as dodecane, polycaprolactone, and poly(butyl acrylate) were grafted to the CNC surface. With PEG-grafted nanoparticles, grafting densities of 0.47 chains nm−2 and 0.10 chains nm−2 were achieved with 2000 and 10,000 g mol−1 polymer chains respectively, both of which represent significant improvements over previous reports for solution-based PEG grafting onto CNCs