Biosynthetic nerve grafts are desired as alternative to autologous nerve grafts in peripheral nerve reconstruction. Artificial nerve conduits still have their limitations and are not widely accepted in the clinical setting. Here we report an analysis of fine-tuned chitosan tubes used to reconstruct 10 mm nerve defects in the adult rat. The chitosan tubes displayed low, medium and high degrees of acetylation (DAI: ≈ 2%, DA: ≈ 5%, DAIII: ≈ 20%) and therefore different degradability and microenvironments for the regenerating nerve tissue. Short and long term investigations were performed demonstrating that the chitosan tubes allowed functional and morphological nerve regeneration similar to autologous nerve grafts. Irrespective of the DA growth factor regulation demonstrated to be the same as in controls. Analyses of stereological parameters as well as the immunological tissue response at the implantation site and in the regenerated nerves, revealed that DAI and DAIII chitosan tubes displayed some limitations in the support of axonal regeneration and a high speed of degradation accompanied with low mechanical stability, respectively. The chitosan tubes combine several pre-requisites for a clinical acceptance and DAII chitosan tubes have to be judged as the most supportive for peripheral nerve regeneration.

Polymer solutions are useful precursors to synthesize microparticles with microfluidic devices, but most polymer solutions are incompatible with microfluidic emulsification due to their non‐Newtonian flow characteristics. A technique is presented to form monodisperse particles from such solutions by surrounding them with a chaperoning Newtonian fluid and forcing both to pinch into preparticle drops.

Abstract:We describe a novel, low-cost and low-tech method for the fabrication of elastomeric Janus particles with diameters ranging from micrometers to millimeters. This consists of UV-irradiating soft urethane/urea elastomer spheres, which are then extracted in toluene and dried. The spheres are thus composed of a single material: no coating or film deposition steps are required. Furthermore, the whole procedure is carried out at ambient temperature and pressure. Long, labyrinthine corrugations ("wrinkles") appear on the irradiated portions of the particles' surfaces, the spatial periodicity of which can be controlled by varying the sizes of particles. The asymmetric morphology of the resulting Janus particles has been confirmed by scanning electron microscopy, atomic force microscopy, and optical microscopy. We have also established that the spheres behave elastically by performing bouncing tests with dried and swollen spheres. Results can be interpreted by assuming that each sphere consists of a thin, stiff surface layer ("skin") lying atop a thicker, softer substrate ("bulk"). The skin's higher stiffness is hypothesized to result from the more extensive cross-linking of the polymer chains located near the surface by the UV radiation. Textures then arise from competition between the effects of bending the skin and compressing the bulk, as the solvent evaporates and the sphere shrinks.

We present a proton NMR relaxometry study of the molecular dynamics in three liquid crystalline systems: 4'-n-pentyl-4-cyanobiphenyl (5CB), (S)-4'-(3-methylpentyl)-4-cyanobiphenyl (5CB*), and a 12% weight mixture of 5CB* in 5CB. The proton spin-lattice relaxation time (T1) was measured as a function of temperature and Larmor frequency in the isotropic, nematic, chiral nematic (N*), and smectic A phases of these liquid crystalline systems. A unified relaxation model was used to analyze the molecular dynamics, considering local molecular rotations/reorientations, translational self-diffusion, and collective motions as the relaxation mechanisms that contribute most effectively to the T1(-1) relaxation. Additionally, in the chiral nematic phase a fourth relaxation mechanism associated with the rotations induced by the translational diffusion along the helical axis (RMTD) was included in the model. All experimental results were consistently analyzed taking into account the physical parameters known for 5CB. The global analysis of the experimental results shows that the RMTDs are associated with the pitch value measured for the N* phases and that its contribution to the T1(-1) dispersion is observed at low frequencies. The T1(-1) dispersion in the smectic A phase of 5CB* is strongly dominated by the layer undulations relaxation mechanism over a broad frequency range from the low kilohertz regime to tens of megahertz. It was the first time such behavior was observed in a low molecular weight liquid crystalline system.

Chitin was extracted from Polybius henslowii, a swimming crab, captured in large quantities throughout the Portuguese coast by purse seine vessels as bycatch. After standard chitin extraction procedures, water-soluble chitosan products were obtained via two different methods: (1) N-acetylation with the addition of acetic anhydride and (2) a reaction with hydrogen peroxide. The chemical structure and molecular weight of chitosan derivatives, water-soluble chitosan (WSC) and chitooligosaccharides (COS), were confirmed by Fourier Transform Infrared Spectroscopy (FT-IR) and gel permeation chromatography (GPC). Antioxidant and metal chelation activities were evaluated, and the growth inhibition capacity was tested on four phytopatogens. The chitooligosaccharides from pereopods (pCOS) and shell body parts (sCOS) inhibited all fungal species tested, particularly Cryphonectria parasitica with 84.7% and 85.5%, respectively. Both radical scavenging and antifungal activities proved to be dose-dependent. Chitooligosaccharides with a low molecular weight (2.7, 7.4, and 10.4 Kg·mol−1) showed the highest activity among all properties tested. These results suggested that chitosan derivatives from P. henslowii raw material could potentially be used against phytopathogens or as ingredient in cosmetics and other products related to oxidative stress.

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We show that suspended nano and microfibres electrospun from liquid crystalline cellulosic solutions will curl into spirals if they are supported at just one end, or, if they are supported at both ends, will twist into a helix of one handedness over half of its length and of the opposite handedness over the other half, the two halves being connected by a short straight section. This latter phenomenon, known as perversion, is a consequence of the intrinsic curvature of the fibres and of a topological conservation law. Furthermore, agreement between theory and experiment can only be achieved if account is taken of the intrinsic torsion of the fibres. Precisely the same behaviour is known to be exhibited by the tendrils of climbing plants such as Passiflora edulis, albeit on a lengthscale of millimetres, i.e., three to four orders of magnitude larger than in our fibres. This suggests that the same basic, coarse-grained physical model is applicable across a range of lengthscales.

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