Nature abounds with helical filaments designed for specific tasks. For instance, some plants use tendrils to coil and attach to the surroundings, while Spiroplasma, a helical bacterium, moves by inverting the helical handedness along the filament axis. Therefore, developing methods to shape filaments on demand to exhibit a diversity of physical properties and shapes could be of interest to many fields, such as the textile industry, biomedicine or nanotechnology. Electrospinning is a simple and versatile technique that allows the production of micro and nanofibres with many different helical shapes. In this work, we review the different electrospinning procedures that can be used to obtain helical shapes similar to those found in natural materials. These techniques also demonstrate that the creation of helical shapes at the micro/nanoscale is not limited by the chirality of the building blocks at the molecular level, a finding which opens new horizons on filament shaping.
Lyotropic colloidal aqueous suspensions of cellulose nanocrystals (CNCs) can, after solvent evaporation, retain their chiral nematic arrangement. As water is removed the pitch value of the suspension decreases and structural colour-generating films, which are mechanically brittle in nature, can be obtained. Increasing their flexibility while keeping the chiral nematic structure and biocompatible nature is a challenging task. However, if achievable, this will promote their use in new and interesting applications. In this study, we report on the addition of different amounts of hydroxypropyl cellulose (HPC) to CNCs suspension within the coexistence of the isotropic-anisotropic phases and infer the influence of this cellulosic derivative on the properties of the obtained solid films. It was possible to add 50 wt.% of HPC to a CNCs aqueous suspension (to obtain a 50/50 solids ratio) without disrupting the LC phase of CNCs and maintaining a left-handed helical structure in the obtained films. When 30 wt.% of HPC was added to the suspension of CNCs, a strong colouration in the film was still observed. This colour shifts to the near-infrared region as the HPC content in the colloidal suspension increases to 40 wt.% or 50 wt.% The all-cellulosic composite films present an increase in the maximum strain as the concentration of HPC increases, as shown by the bending experiments and an improvement in their thermal properties.
Perversions connecting two helices with symmetric handedness are a common occurrence in nature, for example in tendrils. These defects can be found in our day life decorating ribbon gifts or when plants use tendrils to attach to a support. Perversions arise when clamped elastic filaments coil into a helical shape but have to conserve zero overall twist. We investigate whether other types of perversions exist and if they display different properties. Here we show mathematically and experimentally that a continuous range of different perversions can exist and present different geometries. Experimentally, different perversions were generated using micro electrospun fibres. Our experimental results also confirm that these perversions behave differently upon release and adopt different final configurations. These results also demonstrate that it is possible to control on demand the formation and shape of microfilaments, in particular, of electrospun fibres by using ultraviolet light.
Among the movements observed in some cellulosic structures produced by plants are those that involve the dispersion and burial of seeds, as for example in Erodium from the Geraniaceae plant family. Here we report on a simple and efficient strategy to isolate and tune cellulose-based hygroscopic responsive materials from Erodium awns’ dead tissues. The stimuli-responsive material isolated forms left-handed (L) or right-handed (R) helical birefringent transparent ribbons in the wet state that reversibly change to R helices when the material dries. The humidity-driven motion of dead tissues is most likely due to a composite material made of cellulose networks of fibrils imprinted by the plant at the nanoscale, which reinforces a soft wall polysaccharide matrix. The inversion of the handedness is explained using computational simulations considering filaments that contract and expand asymmetrically. The awns of Erodium are known to present hygroscopic movements, forming R helices in the dry state, but the possibility of actuating chirality via humidity suggests that these cellulose-based skeletons, which do not require complicated lithography and intricate deposition techniques, provide a diverse range of applications from intelligent textiles to micro-machines.
The colloidal suspensions of aqueous cellulose nanocrystals (CNCs) are known to form liquid crystalline (LC) systems above certain critical concentrations. From an isotropic phase, tactoid formation, growth, and sedimentation have been determined as the genesis of a high‐density cholesteric phase, which, after drying, originates solid iridescent films. Herein, the coexistence of a liquid crystal upper phase and an isotropic bottom phase in CNC aqueous suspensions at the isotropic–nematic phase separation is reported. Furthermore, isotropic spindle‐like domains are observed in the low‐density LC phase and high‐density LC phases are also prepared. The CNCs isolated from the low‐ and high‐density LC phases are found to have similar average lengths, diameters, and surface charges. The existence of an LC low‐density phase is explained by the presence of air dissolved in the water present within the CNCs. The air dissolves out when the water solidifies into ice and remains within the CNCs. The self‐adjustment of the cellulose chain conformation enables the entrapment of air within the CNCs and CNC buoyancy in aqueous suspensions.
24 January 2017 in Macromolecular Rapid Communications