No abstract

Three silicon and nitrogen-centered cyanate monomers tetrakis(4-cyanatophenyl)silane, tetrakis(4-cyanatobiphenyl)silane, and tris(4-cyanatobiphenyl)amine were designed and synthesized, which were then polymerized via thermal cyclotrimerization reaction to create highly porous cyanate resin networks with systematically varied nodes and linking struts. The chemical structures of monomers and polymers were confirmed by 1 H NMR, FTIR, solid-state 13 C CP/MAS NMR spectra, and elemental analysis. The products are amorphous with 5% weight-loss temperatures over 428 °C. The results based on N 2 and CO 2 adsorption isotherms show that the pores in these polymers mainly locate in the microporous region, and the BET surface areas are up to 960 m 2 g −1 , which is the highest value for the porous cyanate resin reported to date. The nitrogen-and oxygen-rich characteristics of cyanate resins lead to the networks strong affinity for CO 2 and thereby high CO 2 adsorption capacity of 11.1 wt % at 273 K and 1.0 bar. The adsorption behaviors of H 2 , CO 2 , benzene, n-hexane, and water vapors were investigated by correlating with the chemical composition and porosity parameters of the networks as well as the physicochemical nature of adsorbates.

PEDOT-co-EPh copolymers with systematic variations in composition were prepared by electrochemical polymerization from mixed monomer solutions in acetonitrile. The EPh monomer is a trifunctional crosslinking agent with three EDOTs around a central benzene ring. With increasing EPh content, the color of the copolymers changed from blue to yellow to red due to decreased absorption in the near infrared (IR) spectrum and increased absorption in the visible spectrum. The surface morphology changed from rough and nanofibrillar to more smooth with rounded bumps. The electrical transport properties dramatically decreased with increasing EPh content, resulting in coatings that either substantially lowered the impedance of the electrode (at the lowest EPh content), leave the impedance nearly unchanged (near 1% EPh), or significantly increase the impedance (at 1% and above). The mechanical properties of the films were substantially improved with EPh content, with the 0.5% EPh films showing an estimated 5x improvement in modulus measured by AFM nanoindentation. The PEDOT-co-EPh copolymer films were all shown to be non-cytotoxic toward and promote the neurite outgrowth of PC12 cells. Given these results, we expect that the films of most interest for neural interface applications will be those with improved mechanical properties that maintain the improved charge transport performance (with 1% EPh and below).

Conjugated polymers such as poly(3,4-ethylenedioxythiphene) (PEDOT) are of interest for a variety of applications including interfaces between electronic biomedical devices and living tissue. The mechanical properties, strength, and adhesion of these materials to solid substrates are all vital for long-term applications. We have been developing methods to quantify the mechanical properties of conjugated polymer thin films. In this study the stiffness, strength and the interfacial shear strength (adhesion) of electrochemically deposited PEDOT and PEDOT-co-1,3,5-tri[2-(3,4-ethylene dioxythienyl)]-benzene (EPh) were studied. The estimated Young’s modulus of the PEDOT films was 2.6 ± 1.4 GPa, and the strain to failure was around 2%. The tensile strength was measured to be 56 ± 27 MPa. The effective interfacial shear strength was estimated with a shear-lag model by measuring the crack spacing as a function of film thickness. For PEDOT on gold/palladium-coated hydrocarbon film substrates an interfacial shear strength of 0.7 ± 0.3 MPa was determined. The addition of 5 mole% of a tri-functional EDOT crosslinker (EPh) increased the tensile strength of the films to 283 ± 67 MPa, while the strain to failure remained about the same (2%). The effective interfacial shear strength was increased to 2.4 ± 0.6 MPa.

This composite 3D-printing technology is based on a capillary effect through thermal gradient applied onto carbon fibers to allow deposited liquid polymers to simultaneously flow and become solid so as to form 3D structures. We also developed a robotic system consisting of a uniquely designed printing head and an automated robot arm, yielding a 3D printer that enables us to print a thermosetting composite with arbitrary shape and complex geometry on 2D and 3D substrates or in free space without supporting structures.

Alginate is a negative ionic polysaccharide that is found abundantly in nature. Calcium is usually used as a cross-linker for alginate. However, calcium cross-linked alginate is used only forin vitroculture. In the present work, alginate was modified with glycidyl methacrylate (GMA) to produce a thermal polymerizable alginate-GMA (AA-GMA) macromonomer. The molecular structure and methacrylation (%DM) of the macromonomer were determined by1H NMR. After mixing with the correct amount of initiator, the AA-GMA aqueous solution can be polymerized at physiological temperature. The AA-GMA hydrogels exhibited a three-dimensional porous structure with an average pore size ranging from 50 to 200 μm, directly depending on the macromonomer concentration. Biocompatibility of the AA-GMA hydrogel was determined byin vivomuscle injection and cell encapsulation. Muscle injectionin vivoshowed that the AA-GMA solution mixed with initiator could form a hydrogelin situand had a mild inflammatory effect. Human umbilical vein endothelial cells (HUVECs) were encapsulated in the AA-GMA hydrogelsin situat 37°C. Cell viability and proliferation were unaffected by macromonomer concentrations, which suggests that AA-GMA has a potential application in the field of tissue engineering, especially for myocardial repair.

No abstract

Fractionation of petroleum during migration through sedimentary rock matrices has been observed across lengths of meters to kilometers. Selective adsorption of specific chemical moieties at mineral surfaces and/or the phase behavior of petroleum during pressure changes typically are invoked to explain this behavior. Such phenomena are of interest as they impact both the quality and recoverability of petroleum resources. Given the current emphasis on unconventional (continuous) resources, there is a need to understand petroleum fractionation occurring during expulsion and migration at the nanometer to micrometer scale, due to the fine-grained nature of petroliferous mudrocks. Here, we explore organic matter compositional differences observed within kukersites (petroleum source beds containing acritarch Gloeocapsomorpha prisca) and the overlying carbonate reservoir layer from the Ordovician Stonewall Formation using a suite of spectroscopic methods, primarily through atomic force microscopy-based infrared spectroscopy (AFM-IR). AFM-IR is capable of providing spatial resolution approaching 50 nm and allows for assessment of the molecular fingerprint of kukersite organic matter across transition zones from organic-rich “source” layers into neighboring carbonate “reservoir” layers ∼150 μm away. Results indicate that organic matter composition begins to vary immediately following expulsion from source layers, with loss of carbonyl groups and a concomitant decrease in alkyl chain-length, as migration distance increases. These chemical transitions correlate with a decrease in fluorescence intensity, increase in solid bitumen reflectance, and increase in Raman aromaticity proxies (D-G band separation) in the organic matter. Our findings are consistent with the retention of polar compounds onto mineral grains during expulsion and migration, following primary cracking and bituminization of the Gloeocapsomorpha prisca kerogen.