Topological Metadefects: Tangles of Dislocations.

The concept of topological defects is universal. In condensed matter, it applies to disclinations, dislocations, or vortices that are fingerprints of symmetry breaking during phase transitions. Using as a generic example the tangles of dislocations, we introduce the concept of topological metadefects, i.e., defects made of defects. We show that in cholesterics, dextrogyre and levogyre primary tangles are generated through the D_{2}→C_{2} symmetry breaking from the coplanar dislocation pair called Lehmann cluster submitted to a high enough tensile strain. The primary tangles can be wound up individually into double helices. They can also annihilate in pairs or associate into tangles of higher orders following simple algebraic rules.

Assessing the Genotoxicity of Cellulose Nanomaterials in a Co-Culture of Human Lung Epithelial Cells and Monocyte-Derived Macrophages.

Cellulose micro/nanomaterials (CMNMs) are innovative materials with a wide spectrum of industrial and biomedical applications. Although cellulose has been recognized as a safe material, the unique properties of its nanosized forms have raised concerns about their safety for human health. Genotoxicity is an endpoint that must be assessed to ensure that no carcinogenic risks are associated with exposure to nanomaterials. In this study, we evaluated the genotoxicity of two types of cellulose micro/nanofibrils (CMF and CNF) and one sample of cellulose nanocrystals (CNC), obtained from industrial bleached Eucalyptus globulus kraft pulp. For that, we exposed co-cultures of human alveolar epithelial A549 cells and THP-1 monocyte-derived macrophages to a concentration range of each CMNM and used the micronucleus (MN) and comet assays. Our results showed that only the lowest concentrations of the CMF sample were able to induce DNA strand breaks (FPG-comet assay). However, none of the three CMNMs produced significant chromosomal alterations (MN assay). These findings, together with results from previous in vitro studies using monocultures of A549 cells, indicate that the tested CNF and CNC are not genotoxic under the conditions tested, while the CMF display a low genotoxic potential.

Oil/Water Mixtures and Emulsions Separation Methods-An Overview.

Catastrophic oil spill accidents, oily industrial wastewater, and other types of uncontrolled release of oils into the environment are major global issues since they threaten marine ecosystems and lead to a big economic impact. It can also affect the public health of communities near the polluted area. This review addresses the different types of oil collecting methods. The focus of this work will be on the different approaches to materials and technologies for oil/water separation, with a special focus on water/oil emulsion separation. Emulsified oil/water mixtures are extremely stable dispersions being, therefore, more difficult to separate as the size of the droplets in the emulsion decreases. Oil-absorbent materials, such as sponges, foams, nanoparticles, and aerogels, can be adjusted to have both hydrophobic and oleophilic wettability while displaying a porous structure. This can be advantageous for targeting oil spills in large-scale environmental and catastrophic sets since these materials can easily absorb oil. Oil adsorbent materials, for example, meshes, textiles, membranes, and clays, involve the capture of the oily material to the surface of the adsorbent material, additionally attracting more attention than other technologies by being low-cost and easy to manufacture.

Genotoxicity of Three Micro/Nanocelluloses with Different Physicochemical Characteristics in MG-63 and V79 Cells.

(1) Background: Nanocellulose is an innovative engineered nanomaterial with an enormous potential for use in a wide array of industrial and biomedical applications and with fast growing economic value. The expanding production of nanocellulose is leading to an increased human exposure, raising concerns about their potential health effects. This study was aimed at assessing the potential toxic and genotoxic effects of different nanocelluloses in two mammalian cell lines; (2) Methods: Two micro/nanocelluloses, produced with a TEMPO oxidation pre-treatment (CNFs) and an enzymatic pre-treatment (CMFs), and cellulose nanocrystals (CNCs) were tested in osteoblastic-like human cells (MG-63) and Chinese hamster lung fibroblasts (V79) using the MTT and clonogenic assays to analyse cytotoxicity, and the micronucleus assay to test genotoxicity; (3) Results: cytotoxicity was observed by the clonogenic assay in V79 cells, particularly for CNCs, but not by the MTT assay; CNF induced micronuclei in both cell lines and nucleoplasmic bridges in MG-63 cells; CMF and CNC induced micronuclei and nucleoplasmic bridges in MG-63 cells, but not in V79 cells; (4) Conclusions: All nanocelluloses revealed cytotoxicity and genotoxicity, although at different concentrations, that may be related to their physicochemical differences and availability for cell uptake, and to differences in the DNA damage response of the cell model.

Cellulose Nanocrystal Aqueous Colloidal Suspensions: Evidence of Density Inversion at the Isotropic-Liquid Crystal Phase Transition.

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.

Analysis of the In Vitro Toxicity of Nanocelluloses in Human Lung Cells as Compared to Multi-Walled Carbon Nanotubes.

Cellulose micro/nanomaterials (CMNM), comprising cellulose microfibrils (CMF), nanofibrils (CNF), and nanocrystals (CNC), are being recognized as promising bio-nanomaterials due to their natural and renewable source, attractive properties, and potential for applications with industrial and economical value. Thus, it is crucial to investigate their potential toxicity before starting their production at a larger scale. The present study aimed at evaluating the cell internalization and in vitro cytotoxicity and genotoxicity of CMNM as compared to two multi-walled carbon nanotubes (MWCNT), NM-401 and NM-402, in A549 cells. The exposure to all studied NM, with the exception of CNC, resulted in evident cellular uptake, as analyzed by transmission electron microscopy. However, none of the CMNM induced cytotoxic effects, in contrast to the cytotoxicity observed for the MWCNT. Furthermore, no genotoxicity was observed for CNF, CNC, and NM-402 (cytokinesis-block micronucleus assay), while CMF and NM-401 were able to significantly raise micronucleus frequency. Only NM-402 was able to induce ROS formation, although it did not induce micronuclei. Thus, it is unlikely that the observed CMF and NM-401 genotoxicity is mediated by oxidative DNA damage. More studies targeting other genotoxicity endpoints and cellular and molecular events are underway to allow for a more comprehensive safety assessment of these nanocelluloses.

Tropisms of the Dowser Texture.

Due to its low symmetry C2v, the dowser texture is characterised by a 2D unitary vector field or alternatively by a unitary complex field. For the same symmetry reasons, the dowser texture is sensitive, in first order, to perturbations such as thickness gradients, electric fields or flows. We will focus on corresponding properties called respectively: cuneitropism, electrotropism and rheotropism. In particular we will show that topological defects, known as dowsons or monopoles, can be manipulated by means of these tropisms.

Playing the blues, the greens and the reds with cellulose-based structural colours.

Structural vivid colours can arise from the interference of light reflected from structures exhibiting periodicity on scales in the range of visible wavelengths. This effect is observed with light reflected from cell-walls of some plants and exoskeletons of certain insects. Sometimes the colour sequence observed for these structures consists of nearly circular concentric rings that vary in colour from Red, Orange, Yellow, Green, Cyan to Blue, from the periphery to the centre, similarly to the colour scheme sequence observed for the rainbow (ROYGB). The sequence of colours has been found for solid films obtained from droplets of aqueous cellulose nanocrystals (CNCs) suspensions and attributed to a "coffee ring" effect. In this work, coloured lyotropic solutions and solid films obtained from a cellulose derivative in the presence of trifluoroacetic acid (TFA), which acts as a "reactive solvent", are revisited. The systems were investigated with spectroscopy, using circularly and linearly polarised light, coupled with a polarised optical microscope (POM) and scanning electron microscopy (SEM). The lyotropic cholesteric liquid crystalline solutions were confined in capillaries to simplify 1D molecular diffusion along the capillary where an unexpected sequence of the structural colours was observed. The development and reappearance of the sequence of vivid colours seem consistent with the reaction-diffusion of the "reactive solvent" in the presence of the cellulosic chains. The strong TFA acts as an auto-catalyst for the chemical reaction between TFA and the hydroxyl groups, existing along the cellulosic chain, and diffuses to the top and bottom along the capillaries, carrying dissolved cellulosic chains. Uncovering the precise mechanism of colour sequence and evolution over time in cellulosic lyotropic solutions has important implications for future optical/sensors applications and for the understanding of the development of cellulose-based structures in nature.

Electro-osmosis and flexo-electricity in the dowser texture.

Due to its low symmetry, the long-lived pseudo-planar texture, dubbed "the dowser texture", has a flexo-electric spontaneous polarisation [Formula: see text]. Being degenerated, the dowser texture is easily aligned by the electric torque [Formula: see text] acting on [Formula: see text]. The dowser texture can also be aligned by Poiseuille flows driven by electro-osmosis. The hydrodynamic torques due to the electro-osmotic flows are linear in [Formula: see text] like the electrical one. It is shown that in 5CB the electro-osmotic flows can alter measurements of the flexo-electric polarisation.

Spotting plants' microfilament morphologies and nanostructures.

The tracheary system of plant leaves is composed of a cellulose skeleton with diverse hierarchical structures. It is built of polygonally bent helical microfilaments of cellulose-based nanostructures coated by different layers, which provide them high compression resistance, elasticity, and roughness. Their function includes the transport of water and nutrients from the roots to the leaves. Unveiling details about local interactions of tracheary elements with surrounding material, which varies between plants due to adaptation to different environments, is crucial for understanding ascending fluid transport and for tracheary mechanical strength relevant to potential applications. Here we show that plant tracheary microfilaments, collected from Agapanthus africanus and Ornithogalum thyrsoides leaves, have different surface morphologies, revealed by nematic liquid crystal droplets. This results in diverse interactions among microfilaments and with the environment; the differences translate to diverse mechanical properties of entangled microfilaments and their potential applications. The presented study also introduces routes for accurate characterization of plants' microfilaments.

Reversible water driven chirality inversion in cellulose-based helices isolated from Erodium awns.

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.

Flexo-electricity of the dowser texture.

The persistent quasi-planar nematic texture known also as the dowser texture is characterized by a 2D unitary vector field d. We show here that the dowser texture is sensitive, in first order, to electric fields. This property is due to the flexo-electric polarisation P collinear with d expected from R. B. Meyer's considerations on flexo-electricity in nematics. It is pointed out that due to the flexo-electric polarisation nematic monopoles can be manipulated by electric fields of appropriate geometry.

Rheotropism of the dowser texture.

In spite of its metastability, the pseudo-planar texture of a nematic layer confined between surfaces with homeotropic anchoring can be preserved indefinitely in certain conditions. The pseudo-planar texture, dubbed "the dowser texture", is degenerated and therefore sensitive to perturbations. It has been shown recently that the dowser texture is cuneitropic, that is to say, has a tendency to follow thickness gradients. Here, we point out that the dowser texture is also rheotropic or, in other words, has a weathercock behavior: it tends to follow the direction of Poiseuille flows. We observed this behavior in two experiments. In the first one it appears as a deformation of a wound up dowser texture submitted to a slowly alternating linear Poiseuille flow. In the second one we study rheotropic effects of elliptical flow patterns generated by modulation of the gap thickness in a system made of a rigid lens and a flexible glass slide. We show that such elliptical flows can wind the dowser texture and therefore can be used in studies of generation and annihilation of nematic monopoles.

Action of fields on captive disclination loops.

We report on two effects observed in experiments with captive disclination loops on polymeric fibers immersed in nematics and submitted to electric and/or magnetic fields. We show that the magnetic field oblique to a fiber with axial or helicoidal anchoring on its surface induces translation of disclination loops. Fields orthogonal to fibers with helicoidal anchoring make disclination loops rotate around the field direction. In the linear regime of this last chirogyral effect, the angle of rotation is proportional to the helix wave vector and its sense unveils the chirality of the helix. We propose a model explaining the origin and all features of these two effects.

Helical Microfilaments with Alternating Imprinted Intrinsic Curvatures.

There has been an intense research for developing techniques that can produce filaments with helical shapes, given the widespread of potential applications. In this work, how helices with different curvatures can be precisely imprinted in microfilaments is shown. It is also shown that using this technique, it is possible to produce, in a single fiber, helices with different curvatures. This striking and innovative behavior is observed when one side of the stretched filaments is irradiated with UV light, modifying the mechanical properties at surface. Upon release, the regions with higher curvature start to curl first, while regions with lower intrinsic curvature remain stretched until start to curl later. The results presented here can be important to understand why structures adopt a helical shape in general, which can be of interest in nanotechnology, biomolecular science, or even to understand why plant filaments curl.

Hedgehogs in the dowser state.

We show how to easily generate point defects called hedgehogs, in the so-called quasi-planar texture --the dowser state-- of a nematic layer confined between surfaces with homeotropic anchoring conditions. We point out that the dowser texture can be preserved infinitely in spite of its higher energy with respect to the homogeneous homeotropic texture. For topological reasons the dowser state in a squeezed droplet must contain at least one hedgehog. We submitted this hedgehog to a rotating magnetic field and controlled the continuous evolution, transitioning continuously between radial, hyperbolic and circular hedgehogs, which, just as in previous experiments by Lavrentovich et al., are topologically equivalent states. The dynamics of this transformation is shown to be directly sensitive to energy costs of different geometric configurations of the hedgehog defect and therefore can be used as a rough probe for elastic constants; knowing the principal elastic constants K1,2,3, one can retrieve information about the K24 constant. We propose also a method of generation of hedgehog pairs by application of a Poiseuille flow to a dowser state wound by a rotating magnetic field.

Persistent quasiplanar nematic texture: Its properties and topological defects.

In the so-called quasiplanar texture of a nematic layer confined between parallel plates with homeotropic anchoring conditions, the director field rotates by π between limit surfaces so that field lines have the shape of a dowsing Y-shaped wooden tool. The orientation of the director field at midheight of the layer is arbitrary for symmetry reasons and is thus very sensitive to perturbations. We point out that contrary to accepted ideas the quasiplanar texture can be preserved infinitely in spite of its metastability with respect to the homogeneous homeotropic texture. We propose to call such a long-lived version of the quasiplanar texture the dowser texture. We demonstrate both experimentally and theoretically that in samples of variable thickness, the director field is sensitive to the gradient of the sample thickness through a linear coupling term. As a result, it has a tendency to follow the direction of the thickness gradient. Because of its sensitivity to perturbations we propose to call the midplane director field the dowser field and its tendency to follow the thickness gradient cuneitropism. Under effect of the gradient field, the dowser field obeys the sine-Gordon equation and exhibits domain walls that correspond to the well-known solitonic solutions of the sine-Gordon model.

Perversions with a twist.

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.