MXene-Vitrimer Nanocomposites: Photo-Thermal Repair, Reinforcement, and Conductivity at Low Volume Fractions Through a Percolative Voronoi-Inspired Microstructure.

An innovative process to multifunctional vitrimer nanocomposites with a percolative MXene minor phase is reported, marking a significant advancement in creating stimuli-repairable, reinforced, sustainable, and conductive nanocomposites at diminished loadings. This achievement arises from a Voronoi-inspired biphasic morphological design via a straight-forward three-step process involving ambient-condition precipitation polymerization of micron-sized prepolymer powders, aqueous powder-coating with 2D MXene (TiCT), and melt-pressing of MXene-coated powders into crosslinked films. Due to the formation of MXene-rich boundaries between thiourethane vitrimer domains in a pervasive low-volume fraction conductive network, a low percolation threshold (≈0.

Defluorination of Organofluorine Compounds Using Dehalogenase Enzymes from (D4B).

Organofluorine compounds have been widely used as pharmaceuticals, agricultural pesticides, and water-resistant coatings for decades; however, these compounds are recognized as environmental pollutants. The capability of microorganisms and enzymes to defluorinate organofluorine compounds is both rare and highly desirable to facilitate environmental remediation efforts. Recently, a strain of (D4B) was identified with potential biodegradation activity toward perfluoroalkyl substances (PFAS) and other organofluorine compounds.

Rational Approach to Optimizing Conformation-Switching Aptamers for Biosensing Applications.

The utilization of structure-switching aptamers (SSAs) has enabled the development of novel sensing platforms for the sensitive and continuous detection of molecules. development of SSAs, however, is complex and laborious. Here we describe a rational approach to SSA optimization that simultaneously improves aptamer binding affinity and introduces target-dependent conformation-switching for compatibility with real-world biosensor applications.

Continuous flow synthesis of pyridinium salts accelerated by multi-objective Bayesian optimization with active learning.

We report a human-in-the-loop implementation of the multi-objective experimental design a Bayesian optimization platform (EDBO+) towards the optimization of butylpyridinium bromide synthesis under continuous flow conditions. The algorithm simultaneously optimized reaction yield and production rate (or space-time yield) and generated a well defined Pareto front. The versatility of EDBO+ was demonstrated by expanding the reaction space mid-campaign by increasing the upper temperature limit.

Programming Fluorogenic DNA Probes for Rapid Detection of Steroids.

The ability of aptamers to recognize a variety of different molecules has fueled their emergence as recognition agents to probe complex media and cells. Many detection strategies require aptamer binding to its target to result in a dramatic change in structure, typically from an unfolded to a folded state. Here, we report a strategy based on forced intercalation (FIT) that increases the scope of aptamer recognition by transducing subtle changes in aptamer structures into fluorescent readouts.

3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure.

Liquid crystalline hydrogels are an attractive class of soft materials to direct charge transport, mechanical actuation, and cell migration. When such systems contain supramolecular polymers, it is possible in principle to easily shear align nanoscale structures and create bulk anisotropic properties. However, reproducibly fabricating and patterning aligned supramolecular domains in 3D hydrogels remains a challenge using conventional fabrication techniques.

In Silico Discovery and Validation of Neuropeptide-Y-Binding Peptides for Sensors.

Wearable sensors for human health, performance, and state monitoring, which have a linear response to the binding of biomarkers found in sweat, saliva, or urine, are of current interest for many applications. A critical part of any device is a biological recognition element (BRE) that is able to bind a biomarker at the surface of a sensor with a high affinity and selectivity to produce a measurable signal response. In this study, we discover and compare 12-mer peptides that bind to neuropeptide Y (NPY), a stress and human health biomarker, using independent and complimentary experimental and computational approaches.

Anion-Mediated Effects on the Size and Mechanical Properties of Enzymatically Crosslinked Suckerin Hydrogels.

The suckerin family of proteins, identified from the squid sucker ring teeth assembly, offers unique mechanical properties and potential advantages over other natural biomaterials. In this study, a small suckerin isoform, suckerin-12, is used to create enzymatically crosslinked, macro-scale hydrogels. Upon exposure to specific salt conditions, suckerin-12 hydrogels contracted into a condensed state where mechanical properties are found to be modulated by the salt anion present.

Advancing Peptide-Based Biorecognition Elements for Biosensors Using in-Silico Evolution.

Sensors for human health and performance monitoring require biological recognition elements (BREs) at device interfaces for the detection of key molecular biomarkers that are measurable biological state indicators. BREs, including peptides, antibodies, and nucleic acids, bind to biomarkers in the vicinity of the sensor surface to create a signal proportional to the biomarker concentration. The discovery of BREs with the required sensitivity and selectivity to bind biomarkers at low concentrations remains a fundamental challenge.

Structured DNA Aptamer Interactions with Gold Nanoparticles.

DNA aptamers that bind biomolecular targets are of interest as the recognition element in colorimetric sensors based on gold nanoparticles (AuNP), where sensor functionality is related to changes in AuNP colloidal stability upon target binding. In order to understand the role of target binding on DNA-AuNP colloidal stability, we have used high-resolution NMR to characterize the interactions of the 36 nucleotide cocaine-binding aptamer (MN4) and related aptamers with AuNPs, cocaine, and cocaine metabolites. Changes in the aptamer imino proton NMR spectra with low (20 nM) concentrations of AuNP show that the aptamers undergo fast-exchange adsorption on the nanoparticle surface.

Tuning Hydrophobicity in Abiotic Affinity Reagents: Polymer Hydrogel Affinity Reagents for Molecules with Lipid-like Domains.

Hydrophobic interactions often dominate the associative forces between biomacromolecules. A synthetic affinity reagent must be able to exploit and optimize these interactions. We describe synthesis of abiotic affinity reagents that sequester biomacromolecules with lipid-like domains.

Single-Round Patterned DNA Library Microarray Aptamer Lead Identification.

A method for identifying an aptamer in a single round was developed using custom DNA microarrays containing computationally derived patterned libraries incorporating no information on the sequences of previously reported thrombin binding aptamers. The DNA library was specifically designed to increase the probability of binding by enhancing structural complexity in a sequence-space confined environment, much like generating lead compounds in a combinatorial drug screening library. The sequence demonstrating the highest fluorescence intensity upon target addition was confirmed to bind the target molecule thrombin with specificity by surface plasmon resonance, and a novel imino proton NMR/2D NOESY combination was used to screen the structure for G-quartet formation.

Keratin-based antimicrobial textiles, films, and nanofibers.

The combination of appealing structural properties, biocompatibility, and the availability of renewable and inexpensive raw materials, make keratin-based materials attractive for a variety of applications. In this paper, we report on the antimicrobial functionalization of keratin-based materials, including wool cloth and regenerated cellulose/keratin composite films and nanofibers. The functionalization of these materials was accomplished utilizing a facile chlorination reaction that converts the nitrogen-bearing moieties of keratin into halamine compounds.

The impact of culture medium on the development and physiology of biofilms of Pseudomonas fluorescens formed on polyurethane paint.

Microbial biofilms cause the deterioration of polymeric coatings such as polyurethanes (PUs). In many cases, microbes have been shown to use the PU as a nutrient source. The interaction between biofilms and nutritive substrata is complex, since both the medium and the substratum can provide nutrients that affect biofilm formation and biodeterioration.

Stability, surface features, and atom leaching of palladium nanoparticles: toward prediction of catalytic functionality.

Surfactant-stabilized metal nanoparticles have shown promise as catalysts although specific surface features and their influence on catalytic performance have not been well understood. We quantify the thermodynamic stability, the facet composition of the surface, and distinct atom types that affect rates of atom leaching for a series of twenty near-spherical Pd nanoparticles of 1.8 to 3.

Sporicidal/bactericidal textiles via the chlorination of silk.

Bacterial spores, such as those of the Bacillus genus, are extremely resilient, being able to germinate into metabolically active cells after withstanding harsh environmental conditions or aggressive chemical treatments. The toughness of the bacterial spore in combination with the use of spores, such as those of Bacillus anthracis, as a biological warfare agent necessitates the development of new antimicrobial textiles. In this work, a route to the production of fabrics that kill bacterial spores and cells within minutes of exposure is described.

Structure of peptides on metal oxide surfaces probed by NMR.

Peptides that bind inorganic surfaces and template the formation of nanometer-sized inorganic particles are of great interest for the self- or directed assembly of nanomaterials for sensors and diagnostic applications. These surface-recognizing peptides can be identified from combinatorial phage-display peptide libraries, but little experimental information is available for understanding the relationship between the peptide sequence, structure at the nanoparticle surface, and function. We have developed NMR methods to determine the structures of peptides bound to inorganic nanoparticles and report on the structure of three peptides bound to silica and titania surfaces.

Canopy dynamics in nanoscale ionic materials.

Nanoscale ionic materials (NIMS) are organic-inorganic hybrids in which a core nanostructure is functionalized with a covalently attached corona and an ionically tethered organic canopy. NIMS are engineered to be liquids under ambient conditions in the absence of solvent and are of interest for a variety of applications. We have used nuclear magnetic resonance (NMR) relaxation and pulse-field gradient (PFG) diffusion experiments to measure the canopy dynamics of NIMS prepared from 18-nm silica cores modified by an alkylsilane monolayer possessing terminal sulfonic acid functionality, paired with an amine-terminated ethylene oxide/propylene oxide block copolymer canopy.

Structure and dynamics of surfactant interfaces in organically modified clays.

Organic modification of clays with surfactants is required for the preparation of polymer-clay nanocomposites for a variety of applications. We have studied the structure and dynamics of interfaces in synthetic clays modified with phosphonium surfactants. The chemical shifts, line widths, and relaxation times measured by 31P, 13C, and 1H NMR and the relaxation times measured by impedance spectroscopy allow us to monitor the dynamics over a wide range of time scales.

Dynamics of alkyl ammonium intercalants within organically modified montmorillonite: Dielectric relaxation and ionic conductivity.

The low-frequency (0.01 Hz-10 MHz) dynamic characteristics of alkyl quaternary ammonium exchanged montmorillonite (SC20A) were investigated to determine the correlation between temperature-dependent changes in the interlayer structure and collective mobility of the surfactant. From 25 to 165 degrees C, SC20A exhibits two interlayer transitions, one ascribed to the melting of the intercalated alkyl chains of the surfactant (20-40 degrees C) and another associated with an abrupt decrease in the interlayer's coefficient of thermal expansion (100 degrees C).

Inorganic oxide core, polymer shell nanocomposite as a high K gate dielectric for flexible electronics applications.

Organic/inorganic core shell nanoparticles have been synthesized using high K TiO(2) as the core nanoparticle, and polystyrene as the shell. This material is easy to process and forms transparent continuous thin films, which exhibit a dielectric constant enhancement of over 3 times that of bulk polystyrene. This new dielectric material has been incorporated into capacitors and thin film transistors (TFTs).

Fast magic-angle spinning proton NMR studies of polymers at surfaces and interfaces.

Solid-state proton NMR with fast magic-angle sample spinning has been used to study the structure and dynamics of polymers and the water interface in porous glass composites. The composites were prepared by photopolymerization of poly(ethyl acrylate) and other acrylate formulations in a high surface-area rigid glass matrix with 40-A interconnected pores. High resolution solid-state proton spectra were obtained for polymer films and composites with 15 kHz magic-angle sample spinning at temperatures above the polymer glass transition temperature.

WIM/WISE NMR studies of chain dynamics in solid polymers and blends.

Wideline separation (WISE) NMR with window-less isotropic mixing (WIM) is developed as a method to study the dynamics of polymers and blends. This experiment is designed to measure the dynamics of polymers through the proton lineshapes that are correlated with the carbon chemical shifts in two-dimensional NMR experiments. If the atoms experience large amplitude fluctuations that are fast compared to the dipolar broadening, then the proton lines will be narrowed relative to rigid solids.

Solid-state multipulse proton Nuclear Magnetic Resonance (NMR) characterization of self-assembling polymer films.

Multipulse solid-state proton Nuclear Magnetic Resonance (NMR) has been used to study the domain structure in poly(styrene-b-isoprene-b-styrene) triblock copolymers in clear and self-assembled polymer films. Films containing ordered arrays of microcavities (3-5 microm) were obtained by casting the polymer from carbon disulfide solution in a moist environment, while clear films were obtained by solvent evaporation under nitrogen. The domain sizes for the polystyrene and polyisoprene blocks were measured by proton spin diffusion using the dipolar filter pulse sequence.