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The present article entails the emergence of diverse crystal polymorphs following thermal quenching into various coexistence regions of binary azobenzene chromophore (ACh)/diacrylate (DA) solution and of azobenzene/nematic liquid crystal (E7) mixture. Development of various crystal topologies encompassing rhomboidal and hexagonal shapes can be witnessed in a manner dependent on thermal quenched depths into the crystal + liquid coexistence region of ACh/DA system. Upon spraying with compressed carbon dioxide (CO₂) fluid, the local temperature gradient is generated resulting in spherulitic morphology showing discrete lamellae undergoing twisting locally in some regions and branched dendrites or seaweeds in another. When ACh/E7 blend is sprayed using compressed CO₂fluid, hierarchical organization of various discrete faceted single crystals including needle, rectangular, rhombus, and truncated hexagonal crystals radiating from the spherulite core can be discerned in a brighter region (off cross‐polarization) polarized optical microscopy (POM) and nematic disclination in a darker cross‐polarized region. Of particular interest is that the observed faceted single‐crystal polymorphs in ACh/E7 may be contrasted to the lamellar twisting and branching observed in the ACh/DA system and plausible mechanisms of polymer spherulitic growth are discussed.

 

Each year, thousands of patients die from antimicrobial‐resistant bacterial infections that fail to respond to conventional antibiotic treatment. Antimicrobial polymers are a promising new method of combating antibiotic‐resistant bacterial infections. We have previously reported the synthesis of a series of narrow‐spectrum peptidomimetic antimicrobial polyurethanes that are effective against Gram‐negative bacteria, such asEscherichia coli; however, these polymers are not effective against Gram‐positive bacteria, such asStaphylococcus aureus. With the aim of understanding the correlation between chemical structure and antibacterial activity, we have subsequently developed three structural variants of these antimicrobial polyurethanes using post‐polymerization modification with decanoic acid and oleic acid. Our results show that such modifications converted the narrow‐spectrum antibacterial activity of these polymers into broad‐spectrum activity against Gram‐positive species such asS. aureus, however, also increasing their toxicity to mammalian cells. Mechanistic studies of bacterial membrane disruption illustrate the differences in antibacterial action between the various polymers. The results demonstrate the challenge of balancing antimicrobial activity and mammalian cell compatibility in the design of antimicrobial polymer compositions. © 2019 Society of Chemical Industry

 

Three-dimensional (3D) printing allows for creation of patient-specific implants. However, development of new synthetic materials for 3D printing has been relatively slow with only a few polymers available for tissue engineering applications. Most of these polymers require harsh processing conditions like high temperatures and pressures or are mixed with a combination of leachable additives like plasticizers, initiators, crosslinkers, and solvents to enable 3D printing. Therefore, to propel the development of new polymers for ambient temperature, additive-free 3D printing it is necessary to systematically understand the relationship between the structure of a polymer with its 3D printability. Herein, three homopolyesters were synthesized, each with a common backbone but differing in the length of their saturated, aliphatic pendant chains with 2, 6, or 15 carbons. The physical properties such as the glass transition temperature ( T g ) and the rheological properties like shear thinning, temperature response, and stress relaxation were correlated to the individual polymer's 3D printability. The 3D printability of the polymers was assessed based on four criteria: ability to be extruded as continuous filaments, shape fidelity, the retention of printed shape, and the ability to form free hanging filaments. We observed that the polymers with longer side chains can be extruded at low temperature and pressure because the long side chains act as internal diluents and increase the flowability of the polymer. However, their ability to retain the 3D printed shape is adversely affected by the increase in side chain length, unless the side chains form ordered structures leading to immediate recovery of viscosity. The insight derived from the systematic investigation of the effect of polymer structure on their rheology and 3D printability can be used to rationally design other polymers for extrusion-based direct-write 3D printing.