Effect of Molecular Weight of Methylphenylsiloxy-Containing Vinyl-Functionalized Terpolysiloxanes on Their UV-Activated Crosslinking by Hydrosilylation and Mechanical Properties of Crosslinked Elastomers.

Effects of molecular weight of methylphenyl-containing vinylsiloxy-functionalized terpolysiloxanes on their UV-activated crosslinking by hydrosilylation at room temperature in air, shelf life stability of "all-in-one" pastes prepared from them for additive manufacturing, and mechanical properties of the resulting crosslinked elastomers, are investigated. It is found that while rheology of pastes containing base polymers, trimethylsilylated silica fillers, and thixotropic additives is not significantly affected by the base polymer molecular weight but is dominated by the filler concentration, the pastes based on higher molecular weight polymers exhibit faster crosslinking (corresponding to higher catalyst turnover numbers) and their crosslinked elastomers show transient strain-induced crystallization. The latter appears in networks from terpolymers with degrees of polymerization (DP) of 240 and above (corresponding to about one half of the critical polydimethylsiloxane chain length for entanglement formation of DP = 460), within the temperature range of -80 to -30 °C, characteristic for polydimethylsiloxane melting transition. It is believed that this is the first time an observation of this chain length effect is reported for polysiloxane elastomers and that the properties reported herein can be expected to have major implications on the application potential of these polymers in both additive manufacturing and performance of their elastomers at sub-ambient temperatures.

Resolving transitions in the mesoscale domain configuration in VO2 using laser speckle pattern analysis.

The configuration and evolution of coexisting mesoscopic domains with contrasting material properties are critical in creating novel functionality through emergent physical properties. However, current approaches that map the domain structure involve either spatially resolved but protracted scanning probe experiments without real time information on the domain evolution, or time resolved spectroscopic experiments lacking domain-scale spatial resolution. We demonstrate an elegant experimental technique that bridges these local and global methods, giving access to mesoscale information on domain formation and evolution at time scales orders of magnitude faster than current spatially resolved approaches. Our straightforward analysis of laser speckle patterns across the first order phase transition of VO2 can be generalized to other systems with large scale phase separation and has potential as a powerful method with both spatial and temporal resolution to study phase separation in complex materials.

Methanol fractionation of softwood Kraft lignin: impact on the lignin properties.

The development of technologies to tune lignin properties for high-performance lignin-based materials is crucial for the utilization of lignin in various applications. Here, the effect of methanol (MeOH) fractionation on the molecular weight, molecular weight distribution, glass transition temperature (Tg ), thermal decomposition, and chemical structure of lignin were investigated. Repeated MeOH fractionation of softwood Kraft lignin successfully removed the low-molecular-weight fraction. The separated high-molecular-weight lignin showed a Tg of 211 °C and a char yield of 47 %, much higher than those of as-received lignin (Tg 153 °C, char yield 41 %). The MeOH-soluble fraction of lignin showed an increased low-molecular-weight fraction and a lower Tg (117 °C) and char yield (32%). The amount of low-molecular-weight fraction showed a quantitative correlation with both 1/Tg and char yield in a linear regression. This study demonstrated the efficient purification or fractionation technology for lignin; it also established a theoretical and empirical correlation between the physical characteristics of fractionated lignins.

Lectin-functionalized poly(glycidyl methacrylate)-block-poly(vinyldimethyl azlactone) surface scaffolds for high avidity microbial capture.

Microbial exopolysaccharides (EPS) play a critical and dynamic role in shaping the interactions between microbial community members and their local environment. The capture of targeted microbes using surface immobilized lectins that recognize specific extracellular oligosaccharide moieties offers a nondestructive method for functional characterization of EPS content. In this report, we evaluate the use of the block copolymer, poly(glycidyl methacrylate)-block-4,4-dimethyl-2-vinylazlactone (PGMA-b-PVDMA), as a surface scaffold for lectin-specific microbial capture. Three-dimensional polymer films were patterned on silicon substrates to provide discrete, covalent coupling sites for Triticum vulgare and Lens culinaris lectins. This material increased the number of Pseudomonas fluorescens microbes captured by up to 43% compared to control scaffolds that did not contain the copolymer. These results demonstrate that PGMA-b-PVDMA scaffolds provide a platform for improved microbe capture and screening of EPS content by combining high avidity lectin surfaces with three-dimensional surface topography.

Layer-by-layer templated assembly of silica at the nanoscale.

Bioinspired bottom-up assembly and layer-by-layer (LbL) construction of inorganic materials from lithographically defined organic templates enables the fabrication of nanostructured systems under mild temperature and pH conditions. Such processes open the door to low-impact manufacturing and facile recycling of hybrid materials for energy, biology, and information technologies. Here, templated LbL assembly of silica was achieved using a combination of electron beam lithography, chemical lift-off, and aqueous solution chemistry. Nanopatterns of lines, honeycomb-lattices, and dot arrays were defined in polymer resist using electron beam lithography. Following development, exposed areas of silicon were functionalized with a vapor deposited amine-silane monolayer. Silicic acid solutions of varying pH and salt content were reacted with the patterned organic amine-functional templates. Vapor treatment and solution reaction could be repeated, allowing LbL deposition. Conditions for the silicic acid deposition had a strong effect on thickness of each layer, and the morphology of the amorphous silica formed. "Defects" in the arrays of silica nanostructures were minor and do not affect the overall organization of the layers. The bioinspired method described here facilitates the bottom-up assembly of inorganic nanostructures defined in three dimensions and provides a path, via LbL processing, for the construction of layered hybrid materials under mild conditions.

Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation.

We report a facile synthetic strategy based on a grafting through approach to prepare well-defined molecular bottlebrushes composed of regioregular poly(3-hexylthiophene) (rr-P3HT) as the conjugated polymeric side chain. To this end, the exo-norbornenyl-functionalized P3HT macromonomer was synthesized by Kumada catalyst transfer polycondensation (KCTP) followed by postpolymerization modifications, and the resulting conjugated macromonomer was successfully polymerized by ring-opening metathesis polymerization (ROMP) in a controlled manner. The P3HT molecular bottlebrushes display an unprecedented strong physical aggregation upon drying during recovery, as verified by several analyses of the solution and solid states. This remarkably strong aggregation behavior is attributed to a significant enhancement in the number of π-π interactions between grafted P3HT side chains, brought about due to the bottlebrush architecture. This behavior is qualitatively supported by coarse-grained molecular dynamics simulations.

Versatility of alkyne-modified poly(glycidyl methacrylate) layers for click reactions.

Functional soft interfaces are of interest for a variety of technologies. We describe three methods for preparing substrates with alkyne groups, which show versatility for "click" chemistry reactions. Two of the methods have the same root: formation of thin, covalently attached, reactive interfacial layers of poly(glycidyl methacrylate) (PGMA) via spin coating onto silicon wafers followed by reactive modification with either propargylamine or 5-hexynoic acid. The amine or the carboxylic acid moieties react with the epoxy groups of PGMA, creating interfacial polymer layers decorated with alkyne groups. The third method consists of using copolymers comprising glycidyl methacrylate and propargyl methacrylate (pGP). The pGP copolymers are spin coated and covalently attached on silicon wafers. For each method, we investigate the factors that control film thickness and content of alkyne groups using ellipsometry, and study the nanophase structure of the films using neutron reflectometry. Azide-terminated polymers of methacrylic acid and 2-vinyl-4,4-dimethylazlactone synthesized via reversible addition-fragmentation chain transfer polymerization were attached to the alkyne-modified substrates using "click" chemistry, and grafting densities in the range of 0.007-0.95 chains nm(-2) were attained. The maximum density of alkyne groups attained by functionalization of PGMA with propargylamine or 5-hexynoic acid was approximately 2 alkynes nm(-3). The alkyne content obtained by the three decorating approaches was sufficiently high that it was not the limiting factor for the click reaction of azide-capped polymers.

Nonfunctionalized polydimethyl siloxane superhydrophobic surfaces based on hydrophobic-hydrophilic interactions.

Superhydrophobic surfaces based on polydimethyl siloxane (PDMS) were fabricated using a 50:50 PDMS-poly(ethylene glycol) (PEG) blend. PDMS was mixed with PEG, and incomplete phase separation yielded a hierarchic structure. The phase-separated mixture was annealed at a temperature close to the crystallization temperature of the PEG. The PEG crystals were formed isothermally at the PDMS/PEG interface, leading to an engineered surface with PDMS spherulites. The resulting roughness of the surface was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The PDMS spherulites, a few micrometers in diameter observed from SEM images, were found to have an undulated (rippled) surface with nanometer-sized features. The combination of micrometer- and nanometer-sized surface features created a fractal surface and increased the water contact angle (WCA) of PDMS more than 60°, resulting in a superhydrophobic PDMS surface with WCA of >160°. The active surface layer for the superhydrophobicity was approximately 100 µm thick, illustrating that the material had bulk superhydrophobicity compared to conventional fluorocarbon or fluorinated coated rough surfaces. Theoretical analysis of the fractal surface indicates that the constructed surface has a fractal dimension of 2.5, which corresponds to the Apollonian sphere packing.

Immobilization of biomolecules on poly(vinyldimethylazlactone)-containing surface scaffolds.

We describe the successful development of a procedure for the step-by-step formation of a reactive, multilayer polymer scaffold incorporating polymers based on 2-vinyl-4,4-dimethylazlactone (VDMA) on a silicon wafer and the characterization of these materials. Also discussed is the development of a procedure for the nonsite specific attachment of a biomolecule to a modified silicon wafer, including scaffolds modified via drop-on-demand (DOD) inkjet printing. VDMA-based polymers were used because of their hydrolytic stability and ability of the pendant azlactone rings to form stable covalent bonds with primary amines without byproducts via nucleophilic addition. This reaction proceeds without a catalyst and at room temperature, yielding a stable amide linkage, which adds to the ease of construction expected when using VDMA-based polymers. DOD inkjet printing was explored as an interesting method for creating surfaces with one or more patterns of biomolecules because of the flexibility and ease of pattern design.