Water Dynamics in Composite Aqueous Suspensions of Cellulose Nanocrystals and a Clay Mineral Studied through Magnetic Resonance Relaxometry.

1H spin-lattice relaxation time (T1) measurements were performed to probe the dynamic behavior of water in aqueous suspensions of cellulose nanocrystals (CNCs) and a layered smectite clay mineral with different degrees of concentration. 1H-T1 experiments were carried out over a wide frequency domain, ranging from a few kilohertz to 500 MHz, with the aid of conventional and fast field cycling nuclear magnetic resonance (NMR) techniques. The experimental relaxometry data illustrate differences between the dynamic behavior of bulk water and that confined in the vicinity of CNC-clay surfaces. Clay alone in moderate concentration was found to enforce almost no effect on the water dynamics, whereas introducing CNCs to the system presented a significantly enhanced relaxivity. The modeling of the relaxation dispersions allowed the determination of dynamical processes and variables explaining the dynamic behavior of water in CNC-clay suspensions. It turned out that reorientations mediated by translational displacements are a leading NMR relaxation mechanism for water interacting with the surfaces of CNC-clay particles in the low-frequency domain. In the high-frequency regime, however, the inner-sphere paramagnetic relaxation mechanism dominates, which is caused by the interaction of water protons with dissolved Fe ions.

Cellulose-Based Biomimetics and Their Applications.

Nature has been producing cellulose since long before man walked the surface of the earth. Millions of years of natural design and testing have resulted in cellulose-based structures that are an inspiration for the production of synthetic materials based on cellulose with properties that can mimic natural designs, functions, and properties. Here, five sections describe cellulose-based materials with characteristics that are inspired by gratings that exist on the petals of the plants, structurally colored materials, helical filaments produced by plants, water-responsive materials in plants, and environmental stimuli-responsive tissues found in insects and plants. The synthetic cellulose-based materials described herein are in the form of fibers and films. Fascinating multifunctional materials are prepared from cellulose-based liquid crystals and from composite cellulosic materials that combine functionality with structural performance. Future and recent applications are outlined.

Functional Stimuli-Responsive Gels: Hydrogels and Microgels.

One strategy that has gained much attention in the last decades is the understanding and further mimicking of structures and behaviours found in nature, as inspiration to develop materials with additional functionalities. This review presents recent advances in stimuli-responsive gels with emphasis on functional hydrogels and microgels. The first part of the review highlights the high impact of stimuli-responsive hydrogels in materials science. From macro to micro scale, the review also collects the most recent studies on the preparation of hybrid polymeric microgels composed of a nanoparticle (able to respond to external stimuli), encapsulated or grown into a stimuli-responsive matrix (microgel). This combination gave rise to interesting multi-responsive functional microgels and paved a new path for the preparation of multi-stimuli "smart" systems. Finally, special attention is focused on a new generation of functional stimuli-responsive polymer hydrogels able to self-shape (shape-memory) and/or self-repair. This last functionality could be considered as the closing loop for smart polymeric gels.

Bio-inspired production of chitosan/chitin films from liquid crystalline suspensions.

Inspired by chitin based hierarchical structures observed in arthropods exoskeleton, this work reports the capturing of chitin nanowhiskers' chiral nematic order into a chitosan matrix. For this purpose, highly crystalline chitin nanowhiskers (CTNW) with spindle-like morphology and average aspect ratio of 24.9 were produced by acid hydrolysis of chitin. CTNW were uniformly dispersed at different concentrations in aqueous suspensions. The suspensions liquid crystalline phase domain was determined by rheological measurements and polarized optical microscopy (POM). Chitosan (CS) was added to the CTNW isotropic, biphasic and anisotropic suspensions and the solvent was evaporated to allow films formation. The Films' morphologies as well as the mechanical properties were explored. A correlation between experimental results and a theoretical model, for layered matrix' structures with fibers acting as a reinforcement agent, was established. The results evidence the existence of two different layered structures, one formed by chitosan layers induced by the presence of chitin and another formed by chitin nanowhiskers layers. By playing on the ratio chitin/chitosan one layered structure or the other can be obtained allowing the tunning of materials' mechanical properties.

Mind the Microgap in Iridescent Cellulose Nanocrystal Films.

A new photonic structure is produced from cellulose nanocrystal iridescent films reflecting both right and left circularly polarized light. Micrometer-scale planar gaps perpendicular to the films' cross-section between two different left-handed films' cholesteric domains are impregnated with a nematic liquid crystal. This photonic feature is reversibly tuned by the application of an electric field or a temperature variation.

Sensing and tuning microfiber chirality with nematic chirogyral effect.

Microfibers with their elongated shape and translation symmetry can act as important components in various soft materials, notably for their mechanics on the microscopic level. Here we demonstrate the mechanical response of a micro-object to imposed chirality, in this case, the tilt of disclination rings in an achiral nematic medium caused by the chiral surface anchoring on an immersed microfiber. This coupling between chirality and mechanical response, used to demonstrate sensing of chirality of electrospun cellulose microfibers, is revealed in the optical micrographs due to anisotropy in the elastic response of the host medium. We provide an analytical explanation of the chirogyral effect supported with numerical simulations and perform an experiment to test the effect of the cell confinement and fiber size. We controllably twist the microfibers and demonstrate the response of the nematic medium. More generally the demonstrated study provides means for experimental discrimination of surface properties and allows mechanical control over the shape of disclination rings.

Carbon Nanotubes as Reinforcement of Cellulose Liquid Crystalline Responsive Networks.

The incorporation of small amount of highly anisotropic nanoparticles into liquid crystalline hydroxypropylcellulose (LC-HPC) matrix improves its response when is exposed to humidity gradients due to an anisotropic increment of order in the structure. Dispersed nanoparticles give rise to faster order/disorder transitions when exposed to moisture as it is qualitatively observed and quantified by stress-time measurements. The presence of carbon nanotubes derives in a improvement of the mechanical properties of LC-HPC thin films.

Revealing the Hierarchical Mechanical Strength of Single Cellulose Acetate Electrospun Filaments through Ultrasonic Breakage.

The tensile strength of single cellulose acetate electrospun fibers is determined through sonication-induced fragmentation in water using a model previously developed by Terentjev and co-workers. The fragmentation of the electrospun fibers results in a gradual shortening of their length until a constant modal length is achieved. A single electrospun CA fiber tensile strength of ≈ 150 MPa (55-280 MPa) is determined based on fracture statistics. It is also observed that the fragmented fibers show bunches of nanofilaments at their ends with similar diameters to those of round structures observed in the cross-section of the initial electrospun fibers (≈ 38 nm). The sonication of these nanofilaments gives rise to spherical particles with similar diameter dimensions, which allows the estimation of a value of the tensile strength of the order of 2 MPa for these nanostructures. The aggregation and the alignment of the nano filaments inside the electrospun fiber should be the source of its higher strength value.

First curl, then wrinkle.

The excellent properties of elastomers are exploited to trigger wrinkling instabilities in curved shells. Micro- and nano-fibres are produced by electrospinning and UV irradiated: each fibre consists of a soft core and a stiff outer half-shell. Upon solvent de-swelling, the fibres curl because the shell and the core have different natural lengths. Wrinkling only starts after the fibre has attained a well-defined helical shape. A simple analytical model is proposed to find the curling curvature and wrinkle wavelength, as well as the transition between the "curling" and "wrinkling" regimes. This new instability resembles that found in the tendrils of climbing plants as they dry and lignify.

Cellulose Perversions.

Cellulose micro/nano-fibers can be produced by electrospinning from liquid crystalline solutions. Scanning electron microscopy (SEM), as well as atomic force microscopy (AFM) and polarizing optical microscopy (POM) measurements showed that cellulose-based electrospun fibers can curl and twist, due to the presence of an off-core line defect disclination, which was present when the fibers were prepared. This permits the mimicking of the shapes found in many systems in the living world, e.g., the tendrils of climbing plants, three to four orders of magnitude larger. In this work, we address the mechanism that is behind the spirals' and helices' appearance by recording the trajectories of the fibers toward diverse electrospinning targets. The intrinsic curvature of the system occurs via asymmetric contraction of an internal disclination line, which generates different shrinkages of the material along the fiber. The completely different instabilities observed for isotropic and anisotropic electrospun solutions at the exit of the needle seem to corroborate the hypothesis that the intrinsic curvature of the material is acquired during liquid crystalline sample processing inside the needle. The existence of perversions, which joins left and right helices, is also investigated by using suspended, as well as flat, targets. Possible routes of application inspired from the living world are addressed.