Electrostatic Dissipation in 3D-Printable Silicone.

In this report, we describe the incorporation of single-walled carbon nanotubes (CNTs) into 3D printable siloxane elastomers for electrostatic dissipation. The composite was characterized, focusing on how rheological and mechanical properties of the siloxane are affected at various CNT loading levels. Electrical properties were also characterized to develop materials with effective electrostatic dissipation.

A simple, highly efficient route to electroless gold plating on complex 3D printed polyacrylate plastics.

Compared to tedious, multi-step treatments for electroless gold plating of traditional thermoplastics, this communication describes a simpler three-step procedure for 3D printed crosslinked polyacrylate substrates. This allows for the synthesis of ultralight gold foam microlattice materials with great potential for architecture-sensitive applications in future energy, catalysis, and sensing.

Custom 3D Printable Silicones with Tunable Stiffness.

Silicone elastomers have broad versatility within a variety of potential advanced materials applications, such as soft robotics, biomedical devices, and metamaterials. A series of custom 3D printable silicone inks with tunable stiffness is developed, formulated, and characterized. The silicone inks exhibit excellent rheological behavior for 3D printing, as observed from the printing of porous structures with controlled architectures.

Printable enzyme-embedded materials for methane to methanol conversion.

An industrial process for the selective activation of methane under mild conditions would be highly valuable for controlling emissions to the environment and for utilizing vast new sources of natural gas. The only selective catalysts for methane activation and conversion to methanol under mild conditions are methane monooxygenases (MMOs) found in methanotrophic bacteria; however, these enzymes are not amenable to standard enzyme immobilization approaches. Using particulate methane monooxygenase (pMMO), we create a biocatalytic polymer material that converts methane to methanol.

Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed "Tension Trapped Transition State".

The dynamics of reactions at or in the immediate vicinity of transition states are critical to reaction rates and product distributions, but direct experimental probes of those dynamics are rare. Here, s-trans, s-trans 1,3-diradicaloid transition states are trapped by tension along the backbone of purely cis-substituted gem-difluorocyclopropanated polybutadiene using the extensional forces generated by pulsed sonication of dilute polymer solutions. Once released, the branching ratio between symmetry-allowed disrotatory ring closing (of which the trapped diradicaloid structure is the transition state) and symmetry-forbidden conrotatory ring closing (whose transition state is nearby) can be inferred.

Ultralow Density, Monolithic WS2, MoS2, and MoS2/Graphene Aerogels.

We describe the synthesis and characterization of monolithic, ultralow density WS2 and MoS2 aerogels, as well as a high surface area MoS2/graphene hybrid aerogel. The monolithic WS2 and MoS2 aerogels are prepared via thermal decomposition of freeze-dried ammonium thio-molybdate (ATM) and ammonium thio-tungstate (ATT) solutions, respectively. The densities of the pure dichalcogenide aerogels represent 0.

Deterministic control over high-Z doping of polydicyclopentadiene-based aerogel coatings.

We report on simple and efficient routes to dope polydicyclopentadiene (PDCPD)-based aerogels and their coatings with high-Z tracer elements. Initially, direct halogenation of PDCPD wet gels and aerogels with elemental iodine or bromine was studied. Although several pathways were identified that allowed doping of PDCPD aerogels by direct addition of bromine or iodine to the unsaturated polymer backbone, they all provided limited control over the amount and uniformity of doping, especially at very low dopant concentrations.

A backbone lever-arm effect enhances polymer mechanochemistry.

Mechanical forces along a polymer backbone can be used to bring about remarkable reactivity in embedded mechanically active functional groups, but little attention has been paid to how a given polymer backbone delivers that force to the reactant. Here, single-molecule force spectroscopy was used to directly quantify and compare the forces associated with the ring opening of gem-dibromo and gem-dichlorocyclopropanes affixed along the backbone of cis-polynorbornene and cis-polybutadiene. The critical force for isomerization drops by about one-third in the polynorbornene scaffold relative to polybutadiene.

Tension trapping of carbonyl ylides facilitated by a change in polymer backbone.

Epoxidized polybutadiene and epoxidized polynorbornene were subjected to pulsed ultrasound in the presence of small molecules capable of being trapped by carbonyl ylides. When epoxidized polybutadiene was sonicated, there was no observable small molecule addition to the polymer. Concurrently, no appreciable isomerization (cis to trans epoxide) was observed, indicating that the epoxide rings along the backbone are not mechanically active under the experimental conditions employed.

Microstructure of Copolymers Formed by the Reagentless, Mechanochemical Remodeling of Homopolymers via Pulsed Ultrasound.

The high shear forces generated during the pulsed ultrasound of dilute polymer solutions lead to large tensile forces that are focused near the center of the polymer chain, but quantitative experimental evidence regarding the force distribution is rare. Here, pulsed ultrasound of quantitatively -dihalocyclopropanated (DHC) polybutadiene provides insights into the distribution. Pulsed ultrasound leads to the mechanochemical ring-opening of the DHC mechanophore to a 2,3-dihaloalkene.

Molecular stress relief through a force-induced irreversible extension in polymer contour length.

Single-molecule force spectroscopy is used to observe the irreversible extension of a gem-dibromocyclopropane (gDBC)-functionalized polybutadiene under tension, a process akin to polymer necking at a single-molecule level. The extension of close to 28% in the contour length of the polymer backbone occurs at roughly 1.2 nN (tip velocity of 3 μm/s) and is attributed to the force-induced isomerization of the gDBCs into 2,3-dibromoalkenes.

Trapping a diradical transition state by mechanochemical polymer extension.

Transition state structures are central to the rates and outcomes of chemical reactions, but their fleeting existence often leaves their properties to be inferred rather than observed. By treating polybutadiene with a difluorocarbene source, we embedded gem-difluorocyclopropanes (gDFCs) along the polymer backbone. We report that mechanochemical activation of the polymer under tension opens the gDFCs and traps a 1,3-diradical that is formally a transition state in their stress-free electrocyclic isomerization.

Anion binding of short, flexible aryl triazole oligomers.

The flexible, electropositive cavity of linear 1,4-diaryl-1,2,3-triazole oligomers provides a suitable host for complexation of various anions. The binding affinities for various combinations of oligomer and anion were determined by (1)H NMR titrations. Effective ionic radius is found to be a primary determinant of the relative binding interactions of various guests, with small but measurable deviations in the case of nonspherical anions.

gem-Dichlorocyclopropanes as abundant and efficient mechanophores in polybutadiene copolymers under mechanical stress.

When gem-dichlorocyclopropane (gDCC) copolymers derived from polybutadiene are subjected to ultrasonication, the gDCCs undergo ring opening to form 2,3-dichloroalkenes. The reactivity is not observed in low-molecular-weight (6.5 kDa) copolymers or side-chain gDCCs, consistent with mechanically induced reactivity due to the elongational strain of the polymers in the sonication flow fields.

Self-exchange electron transfer in high oxidation state non-oxo metal complexes: amavadin.

The electron transfer self-exchange rate constant between the oxidized and reduced forms of amavadin equals approximately 1 x 10(5) dm3 mol(-1) s(-1) at 25 degrees C and represents the first unambiguous example for a vanadium(IV/V) couple.