Water Droplet Equilibration on Silicone Elastomer Substrates Containing Mobile Silicones.

Understanding interfacial behavior at the water/silicone elastomer interface is vital in many applications, including microfluidics, antibiofouling, and self-cleaning surfaces. Silicone elastomers are not always static systems, however. Unreacted silicone molecules within a substrate may change the water-wetting behavior compared to fully reacted substrates.

Enhanced Triboelectric Charge Stability by Air-Stable Radicals.

This paper demonstrates that air-stable radicals enhance the stability of triboelectric charge on surfaces. While charge on surfaces is often undesirable (e.g.

Continuous Ligand-Free Catalysis Using a Hybrid Polymer Network Support.

Although the pharmaceutical and fine chemical industries primarily utilize batch homogeneous reactions to carry out chemical transformations, emerging platforms seek to improve existing shortcomings by designing effective heterogeneous catalysis systems in continuous flow reactors. In this work, we present a versatile network-supported palladium (Pd) catalyst using a hybrid polymer of poly(methylvinylether--maleic anhydride) and branched polyethyleneimine for intensified continuous flow synthesis of complex organic compounds via heterogeneous Suzuki-Miyaura cross-coupling and nitroarene hydrogenation reactions. The hydrophilicity of the hybrid polymer network facilitates the reagent mass transfer throughout the bulk of the catalyst particles.

UV- and thermally-active small bi-functional gelator for creating gradient polymer network coatings.

We present a versatile one-pot synthesis method for creating surface-anchored orthogonal gradient networks using a small bi-functional gelator, 4-azidosulfonylphenethyltrimethoxysilane (4-ASPTMS). The sulfonyl azide (SAz) group of 4-ASPTMS is UV (≤254 nm) and thermally active (≥100 °C) and, thus, enables us to vary the cross-link density in orthogonal directions by controlling the activation of SAz groups via UV and temperature means. We deposit a thin layer (∼200 nm) of a mixture comprising ∼90% precursor polymer and ∼10% 4-ASPTMS in a silicon wafer.

PDMS networks meet barnacles: a complex and often toxic relationship.

The biological impact of chemical formulations used in various coating applications is essential in guiding the development of new materials that directly contact living organisms. To illustrate this point, an investigation addressing the impact of chemical compositions of polydimethylsiloxane networks on a common platform for foul-release biofouling management coatings was conducted. The acute toxicity of network components to barnacle larvae, the impacts of aqueous extracts of crosslinker, silicones and organometallic catalyst on trypsin enzymatic activity, and the impact of assembled networks on barnacle adhesion was evaluated.

Nonwoven Membranes with Infrared Light-Controlled Permeability.

This study presents the development of the first composite nonwoven fiber mats (NWFs) with infrared light-controlled permeability. The membranes were prepared by coating polypropylene NWFs with a photothermal layer of poly(-isopropylacrylamide) (PNIPAm)-based microgels impregnated with graphene oxide nanoparticles (GONPs). This design enables "photothermal smart-gating" using light dosage as remote control of the membrane's permeability to electrolytes.

Degradable Anti-Biofouling Polyester Coatings with Controllable Lifetimes.

To achieve degradable, anti-biofouling coatings with longer lifetimes and better mechanical properties, we synthesized a series of degradable co-polyesters composed of cyclic ketene acetals, di-(ethylene glycol) methyl ether methacrylate, and a photoactive curing agent, 4-benzoylphenyl methacrylate, using a radical ring-opening polymerization. The precursor co-polyesters were spin-coated on a benzophenone-functionalized silicon wafer to form ca. 60 nm films and drop-casted on glass to form ∼32 μm films.

Counterpropagating Gradients of Antibacterial and Antifouling Polymer Brushes.

We report on the formation of counterpropagating density gradients in poly([2-dimethylaminoethyl] methacrylate) (PDMAEMA) brushes featuring spatially varying quaternized and betainized units. Starting with PDMAEMA brushes with constant grafting density and degree of polymerization, we first generate a density gradient of quaternized units by directional vapor reaction involving methyl iodide. The unreacted DMAEMA units are then betainized through gaseous-phase betainization with 1,3-propanesultone.

Dynamic Surfaces-Degradable Polyester Networks that Resist Protein Adsorption.

We synthesized a series of novel degradable alternating copolyesters composed of diglycolic anhydride (DGA) and two epoxides, epoxymethoxytriethylene glycol (ETEG) and a photoactive crosslinking agent epoxy benzophenone (EBP). After UV crosslinking, soaking the films in a good solvent (tetrahydrofuran) removed uncrosslinked material, and the resulting film gel fractions were calculated. These network films were then degraded in buffer solutions of varying pH values.

UV- and Thermally-Active Bifunctional Gelators Create Surface-Anchored Polymer Networks.

A versatile one-step synthesis of surface-attached polymer networks using small bifunctional gelators (SBG), namely 4-azidosulfonylphenethyltrimethoxysilane (4-ASPTMS) and 6-azidosulfonylhexyltriethoxysilane (6-ASHTES) is reported. A thin layer (≈200 nm) of a mixture comprising ≈90% precursor polymer and 10% of 4-ASPTMS or 10% 6-ASHTES on a silicon wafer is deposited. Upon UV irradiation (≈l-254 nm) or annealing (>100 °C) layers, sulfonyl azides (SAz) release nitrogen by forming singlet and triplet nitrenes that concurrently react with any C─H bond in the vicinity resulting in sulfonamide crosslinks.

Antipathogenic properties and applications of low-dimensional materials.

A major health concern of the 21 century is the rise of multi-drug resistant pathogenic microbial species. Recent technological advancements have led to considerable opportunities for low-dimensional materials (LDMs) as potential next-generation antimicrobials. LDMs have demonstrated antimicrobial behaviour towards a variety of pathogenic bacterial and fungal cells, due to their unique physicochemical properties.

DFT Analysis of Organotin Catalytic Mechanisms in Dehydration Esterification Reactions for Terephthalic Acid and 2,2,4,4-Tetramethyl-1,3-cyclobutanediol.

Polyesters synthesized from 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and terephthalic acid (TPA) are improved alternatives to toxic polycarbonates based on bisphenol A. In this work, we use ωB97X-D/LANL2DZdp calculations, in the presence of a benzaldehyde polarizable continuum model solvent, to show that esterification of TMCD and TPA will reduce and subsequently dehydrate a dimethyl tin oxide catalyst, becoming ligands on the now four-coordinate complex. This reaction then proceeds most plausibly by an intramolecular acyl-transfer mechanism from the tin complex, aided by a coordinated proton donor such as hydronium.

Effect of Poly(vinyl butyral) Comonomer Sequence on Adhesion to Amorphous Silica: A Coarse-Grained Molecular Dynamics Study.

Modulating a comonomer sequence, in addition to the overall chemical composition, is the key to unlocking the true potential of many existing commercial copolymers. We employ coarse-grained molecular dynamics (MD) simulations to study the behavior of random-blocky poly(vinyl butyral--vinyl alcohol) (PVB) melts in contact with an amorphous silica surface, representing the interface found in laminated safety glass. Our two-pronged coarse-graining approach utilizes both macroscopic thermophysical data and all-atom MD simulation data.

Attributes, Fabrication, and Applications of Gallium-Based Liquid Metal Particles.

This work discusses the attributes, fabrication methods, and applications of gallium-based liquid metal particles. Gallium-based liquid metals combine metallic and fluidic properties at room temperature. Unlike mercury, which is toxic and has a finite vapor pressure, gallium possesses low toxicity and effectively zero vapor pressure at room temperature, which makes it amenable to many applications.

Effect of surface interactions on the settlement of particles on a sinusoidally corrugated substrate.

Naturally-occurring surface topographies abound in nature and endow diverse properties, , superhydrophobicity, adhesion, anti-fouling, self-cleaning, anti-glare, anti-bacterial, and many others. Researchers have attempted to replicate such topographies to create human-made surfaces with desired functionalities. For example, combining the surface topography with judicial chemical composition could provide an effective, non-toxic solution to combat non-specific biofouling.

Charge Density Gradients of Polymer Thin Film by Gaseous Phase Quaternization.

We report on the rapid formation of charge density gradients in polymer films by exposing poly([2-dimethylaminoethyl] methacrylate) (PDMAEMA) films resting on flat silica substrates to methyl iodide (i.e., MI, also known as iodomethane) vapors.

Controlled heating and alignment platform enhances versatility in colloidal probe fabrication.

A colloidal probe, comprising a colloidal particle attached to an atomic force microscope cantilever, is employed to measure interaction forces between the particle and a surface. It is possible to change or even destroy a particle while attaching it to a cantilever, thus limiting the types of systems to which the colloidal probe technique may be applied. Here, we present the Controlled Heating and Alignment Platform (CHAP) for fabricating colloidal probes without altering the original characteristics of the attached particle.

Extending the fused-sphere SAFT-γ Mie force field parameterization approach to poly(vinyl butyral) copolymers.

SAFT-γ Mie, a molecular group-contribution equation of state with foundations in the statistical associating fluid theory framework, is a promising means for developing accurate and transferable coarse-grained force fields for complex polymer systems. We recently presented a new approach for incorporating bonded potentials derived from all-atom molecular dynamics simulations into fused-sphere SAFT-γ Mie homopolymer chains by means of a shape factor parameter, which allows for bond distances less than the tangent-sphere value required in conventional SAFT-γ Mie force fields. In this study, we explore the application of the fused-sphere SAFT-γ Mie approach to copolymers.

Dependence of deposition method on the molecular structure and stability of organosilanes revealed from degrafting by tetrabutylammonium fluoride.

We probe the structure of self-assembled monolayers (SAMs) comprising organosilanes deposited on flat silica-based surfaces prepared by liquid and vapor deposition by removing the organosilane molecules gradually from the underlying substrate via tetrabutylammonium fluoride (TBAF). Removal of organosilanes from the surface involves the cleavage of all pertinent Si-O bonds that anchor the organosilane molecules to the SAM, i.e.

Liquid Metal Nanoparticles as Initiators for Radical Polymerization of Vinyl Monomers.

Sonication of gallium or gallium-based liquid metals in an aqueous solution of vinyl monomers leads to rapid free radical polymerization (FRP), without the need for conventional molecular initiators. Under ambient conditions, a passivating native oxide separates these metals from solution and renders the metal effectively inert. However, sonication generates liquid metal nanoparticles (LMNPs) of ∼100 nm diameter and thereby increases the surface area of the metal.

Mechanochemical Degrafting of a Surface-Tethered Poly(acrylic acid) Brush Promoted Etching of Its Underlying Silicon Substrate.

The stability of surface-tethered polyelectrolyte brushes has been investigated during the past few years. We have previously reported on the degrafting of poly(acrylic acid) (PAA) polymer brushes from flat silicon substrates. Here, we present a detailed study on the effects of NaCl concentration and the grafting density and molecular weight on the stability of PAA brushes during incubation in 0.

Growth dynamics and domoic acid production of Pseudo-nitzschia sp. in response to oil and dispersant exposure.

The diatom genus Pseudo-nitzschia is a common component of phytoplankton communities in the Gulf of Mexico and is potentially toxic as some species produce the potent neurotoxin domoic acid. The impact of oil and chemical dispersants on Pseudo-nitzschia spp. and domoic acid production have not yet been studied; preliminary findings from a mesocosm experiment suggest this genus may be particularly resilient.

Influence of surface topography attributes on settlement and adhesion of natural and synthetic species.

Surface topographies of various sizes, shapes, and spatial organization abound in nature. They endow properties such as super-hydrophobicity, reversible adhesion, anti-fouling, self-cleaning, anti-glare, and anti-bacterial, just to mention a few. Researchers have long attempted to replicate these structures to create artificial surfaces with the functionalities found in nature.