Simple functionalization of cellulose beads with pre-propargylated chitosan for clickable scaffold substrates

Concerning the increased market for bio-based materials and environmentally safe practices, cellulose-based beads are one of the more attractive alternatives. Thus, this work focuses on the generation of functional cellulose-based beads with a relatively simple and direct method of blending a pre-modified chitosan bearing the targeted functional groups and cellulose, prior to the formation of the beads, as a mean to have functional groups in the formed structure. To this end, chitosan was chemically modified with propargyl bromide in homogenous reaction conditions and then combined with cellulose in sodium hydroxide/urea solution and coagulated in nitric acid to produce spherical shaped beads. The successful chemical modification of chitosan was assessed by elemental analysis, as well as by Fourier-transform infrared spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The alkynyl moieties from the chitosan derivative, served as reactive functional groups for click-chemistry as demonstrated by the tagging of the commercial fluorophore Azide-Fluor 488 via CuI-catalysed alkyne-azide cycloaddition reaction, in aqueous media. This work demonstrates the one-step processing of multiple polysaccharides for functional spherical beads as a template for bio-based scaffolds such as enzyme immobilization for stimuli-response applications and bioconjugations.

     

Molecular orientation of a commercial thermotropic liquid crystalline polymer in simple shear and complex flow

In-situ X-ray scattering methods have been used to measure the average degree of molecular orientation in the commercial thermotropic copolyesteramide, Vectra B. Experiments were conducted in both homogeneous shear flow and in extrusion-fed channel flows that provided mixed shear/extensional deformations. In the channel flows, extension has a dramatic effect on the average orientation state in the vicinity of stagnation points or expansions/contractions in cross-sectional area. Of particular note, a temporary increase and subsequent decay in orientation observed in a 4:1 slit-contraction flow provides additional indirect evidence supporting the hypothesis that Vectra B exhibits director tumbling. This is consistent with results from other fully aromatic copolyesters but contrasts with findings in model thermotropes incorporating flexible spacers. Thus, it seems that the stiffer backbone of commercial main chain LCPs is the main feature which, apparently, leads to tumbling. Measurements of average molecular orientation in transient shear flows show some connections with the corresponding mechanical response, but fail to show the distinctive characteristics that have previously been associated with either tumbling or aligning in LCPs using similar procedures. These experiments might be adversely affected by the comparatively slow rate of data acquisition, which leads to lengthy experiments in which the sample is more prone to degradation.     

Tensile,fracture and impact behavior of transparent Interpenetrating Polymer Networks with polyurethane-poly(methyl methacrylate)

Transparent Interpenetrating Polymer Networks (IPNs) with poly(methyl methacrylate) (PMMA) as the stiff phase and polyurethane (PU) as the ductile phase with varying PMMA:PU ratios in the range of 90:10 to 70:30 were formulated. Static tensile and fracture tests indicate significant failure strain and crack initiation toughness enhancements with a loss of stiffness relative to PMMA. Dynamic fracture tests were conducted using a long-bar impact loading apparatus in conjunction with an optical method and high-speed photography. Low-velocity impact tests were also performed using a drop-tower. Dynamic fracture and low-velocity impact responses show that an optimum range of PMMA:PU ratios in the IPNs can produce enhanced fracture toughness and impact energy absorption capability when compared to PMMA. Fractographic examination supports macro-measurements by showing a distinct change in surface morphology associated with improved macroscale fracture toughness.