Fluorine-rich poly(arylene amine) membranes for the separation of liquid aliphatic compounds.

We explored the potential for membrane materials to reduce energy and carbon requirements for the separation of aliphatic hydrocarbon feedstocks and products. We developed a series of fluorine-rich poly(arylene amine) polymer membranes that feature rigid polymer backbones with segregated perfluoroalkyl side chains. This combination imbues the polymers with resistance to dilation induced by hydrocarbon immersion without the loss of solution-based membrane fabrication techniques.

Dynamics of Polymer Chains in Disperse Melts: Insights from Coarse-Grained Molecular Dynamics Simulations.

Synthetic polymers have a distribution of chain lengths which can be characterized by dispersity, . Their macroscopic properties are influenced by chain mobility in the melt, and controlling can significantly impact these properties. In this work, we present a detailed study of the static and dynamic behavior of fully flexible polymer chains that follow the Schulz-Zimm molecular weight distribution up to = 2.

Exploring the Thermostability of CRISPR-Cas12b using Molecular Dynamics Simulations.

CRISPR (clustered regularly interspaced short palindromic repeat)-based diagnostics are at the forefront of rapid detection platforms of infectious diseases. The integration of reverse transcription-loop-mediated isothermal amplification (RT-LAMP) with CRISPR-Cas protein systems has led to the creation of advanced one-pot assays. The sensitivity of these assays has been bolstered by the utilization of a thermophilic Cas12 protein, BrCas12b, and its engineered variant, which exhibits enhanced thermal stability and allows for broader operation temperatures of the assay.

Molecular Driving Forces in the Self-Association of Silaffin Peptide R5 from MD Simulations.

The 19-residue silaffin-R5 peptide has been widely studied for its ability to precipitate uniform SiO particles through mild temperature and pH pathways, in the absence of any organic solvents. There is consensus that post-translational modification (PTM) of side chains has a large impact on the biomineralization process. Thus, it is imperative to understand the precise mechanisms that dictate the formation of SiO from R5 peptide, including the effects of PTM on peptide aggregation and peptide-surface adsorption.

Impact of crystalline domains on long-term stability and mechanical performance of anisotropic silk fibroin sponges.

Sponge-like materials made from regenerated silk fibroin biopolymers are a tunable and advantageous platform for in vitro engineered tissue culture and in vivo tissue regeneration. Anisotropic, three-dimensional (3D) silk fibroin sponge-like scaffolds can mimic the architecture of contractile muscle. Herein, we use silk fibroin solution isolated from the cocoons of Bombyx mori silkworms to form aligned sponges via directional ice templating in a custom mold with a slurry of dry ice and ethanol.

PEGylation of Insulin and Lysozyme To Stabilize against Thermal Denaturation: A Molecular Dynamics Simulation Study.

Biologic drugs or "biologics" (proteins derived from living organisms) are one of the fastest-growing classes of FDA-approved therapeutics. These compounds are often fragile and require conjugation to polymers for stabilization, with many proteins too ephemeral for therapeutic use. During storage or administration, proteins tend to unravel and lose their secondary structure due to changes in solution temperature, pH, and other external stressors.

MARTINI-Compatible Coarse-Grained Model for the Mesoscale Simulation of Peptoids.

Peptoids (poly-N-substituted glycines) are a class of synthetic polymers that are regioisomers of peptides (poly-C-substituted glycines), in which the point of side-chain connectivity is shifted from the backbone C to the N atom. Peptoids have found diverse applications as peptidomimetic drugs, protein mimetic polymers, surfactants, and catalysts. Computational modeling is valuable in the understanding and design of peptoid-based nanomaterials.

Studies of Dynamic Binding of Amino Acids to TiO Nanoparticle Surfaces by Solution NMR and Molecular Dynamics Simulations.

Adsorption of biomolecules onto material surfaces involves a potentially complex mechanism where molecular species interact to varying degrees with a heterogeneous material surface. Surface adsorption studies by atomic force microscopy, sum frequency generation spectroscopy, and solid-state NMR detect the structures and interactions of biomolecular species that are bound to material surfaces, which, in the absence of a solid-liquid interface, do not exchange rapidly between surface-bound forms and free molecular species in bulk solution. Solution NMR has the potential to complement these techniques by detecting and studying transiently bound biomolecules at the liquid-solid interface.

Trimethylation of the R5 Silica-Precipitating Peptide Increases Silica Particle Size by Redirecting Orthosilicate Binding.

The unmodified R5 peptide from silaffin in the diatom Cylindrotheca fusiformis rapidly precipitates silica particles from neutral aqueous solutions of orthosilicic acid. A range of post-translational modifications found in R5 contribute toward tailoring silica morphologies in a species-specific manner. We investigated the specific effect of R5 lysine side-chain trimethylation, which adds permanent positive charges, on silica particle formation.

Molecular Driving Forces in Peptide Adsorption to Metal Oxide Surfaces.

Molecular recognition between peptides and metal oxide surfaces is a fundamental process in biomineralization, self-assembly, and biocompatibility. Yet, the underlying driving forces and dominant mechanisms remain unclear, bringing obstacles to understand and control this process. To elucidate the mechanism of peptide/surface recognition, specifically the role of serine phosphorylation, we employed molecular dynamics simulation and metadynamics-enhanced sampling to study five artificial peptides, DDD, DSS, DpSpS, DpSpSGKK, and DpSKGpSK, interacting with two surfaces: rutile TiO and quartz SiO.

Solid-State NMR and MD Study of the Structure of the Statherin Mutant SNa15 on Mineral Surfaces.

Elucidation of the structure and interactions of proteins at native mineral interfaces is key to understanding how biological systems regulate the formation of hard tissue structures. In addition, understanding how these same proteins interact with non-native mineral surfaces has important implications for the design of medical and dental implants, chromatographic supports, diagnostic tools, and a host of other applications. Here, we combine solid-state NMR spectroscopy, isotherm measurements, and molecular dynamics simulations to study how SNa15, a peptide derived from the hydroxyapatite (HAP) recognition domain of the biomineralization protein statherin, interacts with HAP, silica (SiO), and titania (TiO) mineral surfaces.

Impact of ion content and electric field on mechanical properties of coarse-grained ionomers.

Using a coarse-grained ionomer model for polyethylene-co-methacrylic acid that includes associating acid groups along with pendant anions and unbound counterions, we investigate how ionomer mechanical behavior depends on the acid and ion content. We find that the modulus and yield stress increase as the ion content increases, at all strain rates considered. This is in agreement with prior experimental results.

Influence of a nanoparticle on the structure and dynamics of model ionomer melts.

We simulate a single spherical nanoparticle (NP) surrounded by partially neutralized ionomers. The coarse-grained ionomers consist of a linear backbone of neutral monomer beads with charged pendant beads and counterions, along with pendant 'sticker' beads that represent unneutralized acid groups. Two different NP interactions are considered; one in which the NP interacts uniformly with all beads in the system (neutral NP) and another in which the NP has higher cohesive interactions with ions and stickers (sticky NP).

Impact of ionic aggregate structure on ionomer mechanical properties from coarse-grained molecular dynamics simulations.

Using coarse-grained molecular dynamics simulations, we study ionomers in equilibrium and under uniaxial tensile deformation. The spacing of ions along the chain is varied, allowing us to consider how different ionic aggregate morphologies, from percolated to discrete aggregates, impact the mechanical properties. From the equilibrium simulations, we calculate the stress-stress auto correlation function, showing a distinct deviation from the Rouse relaxation due to ionic associations that depends on ion content.