Orientation and morphology control in acid-catalyzed covalent organic framework thin films.

As thin films of semiconducting covalent organic frameworks (COFs) are demonstrating utility for ambipolar electronics, channel materials in organic electrochemical transistors (OECTs), and broadband photodetectors, control and modulation of their thin film properties is paramount. In this work, an interfacial growth technique is utilized to synthesize imine TAPB-PDA COF films at both the liquid-liquid interface as well as at the liquid-solid interface on a Si/SiO substrate. The concentration of acetic acid catalyst in the aqueous phase is shown to significantly influence the thin film morphology of the liquid-solid growth, with concentrations below 1 M resulting in no film nucleation, concentrations of 1-4 M enabling smooth film formation, and concentrations greater than 4 M resulting in films with a higher density of particulates on the surface.

Self-Assembly of Uniaxial Fullerene Supramolecules Aligned within Carbon Nanotube Fibers.

The conductivity and strength of carbon nanotube (CNT) wires currently rival those of existing engineering materials; fullerene-based materials have not progressed similarly, despite their exciting transport properties such as superconductivity. This communication reveals a new mechanically robust wire of mutually aligned fullerene supramolecules self-assembled between CNT bundles, where the fullerene supramolecular internal crystal structure and outer surface are aligned and dispersed with the CNT bundles. The crystallinity, crystal dimensions, and other structural features of the fullerene supramolecular network are impacted by a number of important production processes such as fullerene concentration and postprocess annealing.

Modifying Poly(caprolactone) Degradation through C-H Functionalization.

There is a growing need for degradable polymers for applications in sustainable plastics and medical implants. To enhance the utility of degradable polymers, both better understanding of the factors that influence their degradation and new tools to modulate degradation are needed. We report the C-H xanthylation of poly(caprolactone), a biodegradable polyester, which results in changes in materials properties even at small incorporations.

Fundamentals of Crystalline Evolution and Properties of Carbon Nanotube-Reinforced Polyether Ether Ketone Nanocomposites in Fused Filament Fabrication.

As fused filament fabrication (FFF) continues to gain popularity, many studies are turning to nanomaterials or optimization of printing parameters to improve the materials' properties; however, many overlook how materials formulation and additive manufacturing (AM) processes cooperatively engineer the evolution of properties across length scales. Evaluating the in-process evolution of the nanocomposite using AM will provide a fundamental understanding of the material's microstructure, which can be tailored to create unique characteristics in functionality and performance. In this study, the crystallinity behavior of polyetheretherketone (PEEK) was studied in the presence of carbon nanotubes (CNTs) as a nucleation aid for improved crystallization during FFF processing.

Hybrid Metal-Organic Frameworks/Carbon Fibers Reinforcements for Additively Manufactured Composites.

Additively manufactured (AM) composites based on short carbon fibers possess strength and stiffness far less than their continuous fiber counterparts due to the fiber's small aspect ratio and inadequate interfaces with the epoxy matrix. This investigation presents a route for preparing hybrid reinforcements for AM that comprise short carbon fibers and nickel-based metal-organic frameworks (Ni-MOFs). The porous MOFs furnish the fibers with tremendous surface area.

Structural insights into self-assembly of a slow-evolving and mechanically robust supramolecular gel time-resolved small-angle neutron scattering.

The supramolecular assembly process is a widespread phenomenon found in both synthetically engineered and naturally occurring systems, such as colloids, liquid crystals and micelles. However, a basic understanding of the evolution of self-assembly processes over time remains elusive, primarily owing to the fast kinetics involved in these processes and the complex nature of the various non-covalent interactions operating simultaneously. With the help of a slow-evolving supramolecular gel derived from a urea-based gelator, we aim to capture the different stages of the self-assembly process commencing from nucleation.

Polyimide Hybrid Nanocomposites with Controlled Polymer Filling and Polymer-Matrix Interaction.

Polyimide hybrid nanocomposites with the polyimide confined at molecular length scales exhibit enhanced fracture resistance with excellent thermal-oxidative stability at low density. Previously, polyimide nanocomposites were fabricated by infiltration of a polyimide precursor into a nanoporous matrix followed by sequential thermally induced imidization and cross-linking of the polyimide under nanometer-scale confinement. However, byproducts formed during imidization became volatile at the cross-linking temperature, limiting the polymer fill level and degrading the nanocomposite fracture resistance.

In Operando Monitoring of Dynamic Recovery in 3D-Printed Thermoset Nanocomposites by XPCS.

Extrusion-based additive manufacturing methods, such as direct-write of carbon fiber-reinforced epoxy inks, have become an attractive route toward development of structural composites in recent years, because of emerging techniques such as big area additive manufacturing. The development of improved materials for these methods has been a major focus area; however, an understanding of the effects of the printing process on the structural and dynamic recovery in printed materials remains largely unexplored. The goal of this work is to capture multiscale and temporal morphology and dynamics within thermosetting composite inks to determine the parameters during the printing process that influence the recovery of the printed material.

Synthesis of Elastomeric Liquid Crystalline Polymer Networks via Chain Transfer.

Materials capable of complex shape changes have broad reaching applications spanning biomimetic devices, componentless actuators, artificial muscles, and haptic displays. Liquid crystal elastomers (LCE) are a class of shape programmable materials which display anisotropic mechanical deformations in response external stimuli. This work details a synthetic strategy to quickly and efficiently prepare LCEs through the usage of chain transfer agents (CTA).

Photonic Sorting of Aligned, Crystalline Carbon Nanotube Textiles.

Floating catalyst chemical vapor deposition uniquely generates aligned carbon nanotube (CNT) textiles with individual CNT lengths magnitudes longer than competing processes, though hindered by impurities and intrinsic/extrinsic defects. We present a photonic-based post-process, particularly suited for these textiles, that selectively removes defective CNTs and other carbons not forming a threshold thermal pathway. In this method, a large diameter laser beam rasters across the surface of a partly aligned CNT textile in air, suspended from its ends.

Synthesis of Polyimides in Molecular-Scale Confinement for Low-Density Hybrid Nanocomposites.

In this work, we exploit a confinement-induced molecular synthesis and a resulting bridging mechanism to create confined polyimide thermoset nanocomposites that couple molecular confinement-enhanced toughening with an unprecedented combination of high-temperature properties at low density. We describe a synthesis strategy that involves the infiltration of individual polymer chains through a nanoscale porous network while simultaneous imidization reactions increase the molecular backbone stiffness. In the extreme limit where the confinement length scale is much smaller than the polymer's molecular size, confinement-induced molecular mechanisms give rise to exceptional mechanical properties.

Highly Concentrated Seed-Mediated Synthesis of Monodispersed Gold Nanorods.

The extremely large optical extinction coefficient of gold nanorods (Au-NRs) enables their use in a diverse array of technologies, rnging from plasmonic imaging, therapeutics and sensors, to large area coatings, filters, and optical attenuators. Development of the latter technologies has been hindered by the lack of cost-effective, large volume production. This is due in part to the low reactant concentration required for symmetry breaking in conventional seed-mediated synthesis.

High-Resolution Mapping of Thermal History in Polymer Nanocomposites: Gold Nanorods as Microscale Temperature Sensors.

A technique is reported for measuring and mapping the maximum internal temperature of a structural epoxy resin with high spatial resolution via the optically detected shape transformation of embedded gold nanorods (AuNRs). Spatially resolved absorption spectra of the nanocomposites are used to determine the frequencies of surface plasmon resonances. From these frequencies the AuNR aspect ratio is calculated using a new analytical approximation for the Mie-Gans scattering theory, which takes into account coincident changes in the local dielectric.

Atomic-scale identification of Pd leaching in nanoparticle catalyzed C-C coupling: effects of particle surface disorder.

C-C coupling reactions are of great importance in the synthesis of numerous organic compounds, where Pd nanoparticle catalyzed systems represent new materials to efficiently drive these reactions. Despite their pervasive utility, the catalytic mechanism of these particle-based reactions remains highly contested. Herein we present evidence of an atom leaching mechanism for Stille coupling under aqueous conditions using peptide-capped Pd nanoparticles.

Morphology dependent field emission of acid-spun carbon nanotube fibers.

Acid spun carbon nanotube (CNT) fibers were investigated for their field emission properties and performance was determined to be dependent on fiber morphology. The fibers were fabricated by wet-spinning of pre-made CNTs. Fiber morphology was controlled by a fabrication method and processing conditions, as well as purity, size, and type of the CNT starting material.

Population structure of a microparasite infecting Daphnia: spatio-temporal dynamics.

Background: Detailed knowledge of spatial and temporal variation in the genetic population structure of hosts and parasites is required for understanding of host - parasite coevolution. As hot-spots of contemporary coevolution in natural systems are difficult to detect and long-term studies are restricted to few systems, additional population genetic data from various host - parasite systems may provide important insights into the topic. This is particularly true for parasites, as these players have been under-investigated so far due to the lower availability of suitable molecular markers.

Performance of dielectric nanocomposites: matrix-free, hairy nanoparticle assemblies and amorphous polymer-nanoparticle blends.

Demands to increase the stored energy density of electrostatic capacitors have spurred the development of materials with enhanced dielectric breakdown, improved permittivity, and reduced dielectric loss. Polymer nanocomposites (PNCs), consisting of a blend of amorphous polymer and dielectric nanofillers, have been studied intensely to satisfy these goals; however, nanoparticle aggregates, field localization due to dielectric mismatch between particle and matrix, and the poorly understood role of interface compatibilization have challenged progress. To expand the understanding of the inter-relation between these factors and, thus, enable rational optimization of low and high contrast PNC dielectrics, we compare the dielectric performance of matrix-free hairy nanoparticle assemblies (aHNPs) to blended PNCs in the regime of low dielectric contrast to establish how morphology and interface impact energy storage and breakdown across different polymer matrices (polystyrene, PS, and poly(methyl methacrylate), PMMA) and nanoparticle loadings (0-50% (v/v) silica).

Vertically aligned peptide nanostructures using plasma-enhanced chemical vapor deposition.

In this study, we utilize plasma-enhanced chemical vapor deposition (PECVD) for the deposition of nanostructures composed of diphenylalanine. PECVD is a solvent-free approach and allows sublimation of the peptide to form dense, uniform arrays of peptide nanostructures on a variety of substrates. The PECVD deposited d-diphenylalanine nanostructures have a range of chemical and physical properties depending on the specific discharge parameters used during the deposition process.

TNF-α and its receptors modulate complex behaviours and neurotrophins in transgenic mice.

Unlabelled: Tumour necrosis factor-α (TNF-α) plays an important role not only in immunity but also in the normal functioning of the central nervous system (CNS). At physiological levels, studies have shown TNF-α is essential to maintain synaptic scaling and thus influence learning and memory formation while also playing a role in modulating pathological states of anxiety and depression. TNF-α signals mainly through its two receptors, TNF-R1 and TNF-R2, however the exact role that these receptors play in TNF-α mediated behavioural phenotypes is yet to be determined.

Dynamics of amphiphilic surfactants confined in montmorillonite slits with different cation exchange capacities.

Alkylammonium surfactants were nanoscopically confined between montmorillonite layers of varied negative surface charge, i.e., of varied cation exchange capacities.

Dielectric breakdown strength of regenerated silk fibroin films as a function of protein conformation.

Derived from Bombyx mori cocoons, regenerated silk fibroin (RSF) exhibits excellent biocompatibility, high toughness, and tailorable biodegradability. Additionally, RSF materials are flexible, optically clear, easily patterned with nanoscale features, and may be doped with a variety bioactive species. This unique combination of properties has led to increased interest in the use of RSF in sustainable and biocompatible electronic devices.

Nonisotropic Self-Organization of Single-Component Hairy Nanoparticle Assemblies.

Solvent-free assemblies of hairy nanoparticles (HNPs) are providing avenues to avoid issues of mixing, agglomeration, and limited inorganic content that plague nanocompositses based on polymer-nanoparticle blending. Here we demonstrate that the order within, and the elongational characteristics of, the neat HNP assembly (aHNP) evolve as the architecture of the polymeric corona in solution transitions from the concentrated (CPB) to semidilute (SDPB) polymer brush regimes (silica nanoparticle: radius = 8 nm with 120 kDa polystyrene grafts at σ = 0.01-0.

Do Clopidogrel Nonresponders Have an Increased Risk of Adverse Events during Supra-Aortal Angioplasty and Stenting?

Objective. The aim of the present study was to correlate new periprocedural diffusion-weighted imaging (DWI) lesions during stenting of supra-aortal arteries with the level of platelet inhibition using point-of-care analysis. Background.

Nanolaminates: increasing dielectric breakdown strength of composites.

Processable, low-cost, high-performance hybrid dielectrics are enablers for a vast array of green technologies, including high-temperature electrical insulation and pulsed power capacitors for all-electric transportation vehicles. Maximizing the dielectric breakdown field (E(BD)), in conjunction with minimization of leakage current, directly impacts system performance because of the field's quadratic relationship with electrostatic energy storage density. On the basis of the extreme internal interfacial area and ultrafine morphology, polymer-inorganic nanocomposites (PNCs) have demonstrated modest increases in E(BD) at very low inorganic loadings, but because of insufficient control of the hierarchal morphology of the blend, have yielded a precipitous decline in E(BD) at intermediate and high inorganic volume fractions.