Cation-induced morphological transitions and aggregation of thermoresponsive PNIPAM nanogels.

Poly(N-isopropylacrylamide) (PNIPAM) nanogels are promising responsive colloidal particles that can be used in pharmaceutical applications as drug carriers. This work investigates the temperature-dependent morphological changes and agglomeration of PNIPAM nanogels in the presence of mono- and multi-valent cationic electrolytes. We described the deswelling, flocculation, thermal reversibility behaviour and aggregated morphology of PNIPAM nanogels over a range of electrolyte concentrations and temperatures revealing the critical transition points from stable suspension to spontaneous agglomeration. We demonstrated that the flocculating ability and the rate of aggregate formation follow the order of deswelling behaviour. Transmission electron microscopy and atomic force microscopy analysis revealed the presence of a shell-like layer with varying density in the multivalent electrolyte solutions when compared to those in aqueous medium. We identified a concentration threshold of the thermally induced reversible aggregation/dispersion for the PNIPAM nanogels in the presence of Na+ and K+ ions at 10 mM, for Mg2+ and Ca2+ ions at 1 mM and for Al3+ ions at 0.1 mM concentrations. Such concentration thresholds indicated the effective destabilization of the electrolyte system with multivalency following the Schulze-Hardy rule. Our findings were supported by applying a Debye screening model that accounts for the shielding effect of multivalent cationic electrolytes on these nanogel systems. Our experiments and the models confirmed the compression of the electric double layer as the valency and ionic strength increased, except for Al3+ at higher concentrations which seemed to disrupt the electrical double layer and cause reversal of zeta potential. Our work highlights the significant impact the presence of multivalent cations can impose on the stability and morphology of nanogels, and this understanding will help in designing responsive nanogel systems based on PNIPAM nanogels.

Macromolecular crowding in chiral assembly of ellipsoidal nanoparticles.

Anisotropic colloidal particles have the ability to self-assemble into cholesteric structures. We used molecular dynamics to simulate the self-assembly of ellipsoidal particles with the objective to establish a general framework to reveal the primary factors driving chiral interactions. To characterize these interactions, we introduce a characteristic parameter following the crowding factor (CF) theory. Our simulations and statistical analysis showed good agreement with the CF theory; at the early stages of the assembly process, the ellipsoidal particles go through a critical aggregation point followed by further clustering toward nematic order. Furthermore, we demonstrate that under high CF conditions, small initial clusters may induce a chiral twist, which subsequently forms a cholesteric structure with no directional preference in higher organization states.

Encapsulation of Carbon Dots in a Core-Shell Mesh through Coaxial Direct Ink Writing for Improved Crop Growth.

Through coaxial direct ink writing, we fabricated a core-shell mesh system for the controlled release of carbon dots (C-dots). In the core ink, we developed an ink formulation with tuned viscosity using hydroxypropyl cellulose and polyethylene glycol to host C-dots. Polycaprolactone was employed as the main shell material, in combination with sodium alginate, to control the degradation rate of the shell. We investigated the degradation profile of the 3D-printed meshes and tracked the weekly release of C-dots in an aqueous medium by spectrofluorometry. We tested the efficacy of the C-dot release on plants by placing the meshes in transparent soil with Triticum aestivum L. seeds. We observed the in vivo translocation of the C-dots in the plant using confocal microscopy. We measured the root elongation and shoot length to assess the effect of C-dots on plant growth. Our study revealed that the plants exposed to C-dots grew 2.5-fold faster than the control group, indicating that C-dots are promising nanofertilizers for aggrotech and non-toxic fluorescent biolabels for in vivo applications.

Edible cellulose-based colorimetric timer.

A biocompatible and edible colorimetric timer is obtained by exploiting the dynamic colour changes of the cholesteric liquid crystalline mesophases of hydroxypropyl cellulose (HPC) in aqueous suspensions. The edible timer is encapsulated between semi permeable membranes made of shellac. The cholesteric organisation of the HPC provides vibrant colouration, while the shellac layers allow tuning of the evaporation rate of water from the mesophase, which results in a colour change. Due to the biocompatibility of the components and the direct read-out of the system, i.e. the colour change can be visually detected, and the developed timer can be implemented as a colorimetric sensor with potential to be used in food packaging, and as a smart labelling system.

Hierarchical Organization of Structurally Colored Cholesteric Phases of Cellulose via 3D Printing.

Structural color-a widespread phenomenon observed throughout nature is caused by light interference from ordered phases of matter. While state-of-the-art nanofabrication techniques can produce structural organization in small areas, cost-effective and scalable techniques are still lacking to generate tunable color at sub-micron length scales. In this work, structurally colored hydroxypropyl cellulose filaments are produced with a suppressed angular color response by 3D printing. The systematic study of the morphology of the filaments reveals the key stages in the induction of a two-degree hierarchical order through 3D printing. The first degree of order originated from the changing of the cholesteric pitch at a few hundred nm scale via chemical modification and tuning of the solid content of the lyotropic phase. Upon 3D printing, the secondary hierarchical order of periodic wrinkling is introduced through the Helfrich-Hurault deformation of the shear-aligned cholesteric phases. In single-layered filaments, four morphological zones with varying orders of wrinkles are identified. Detailed morphological characterization is carried out using SEM to shed light on the mechanism of the wrinkling behavior. Through this work, the possibility of modifying the wrinkling behavior is demonstrated and thus the angle dependence of the color response by changing the printing conditions.

Understanding the structural diversity of chitins as a versatile biomaterial.

Chitin is one of the most abundant biopolymers, and it has adopted many different structural conformations using a combination of different natural processes like biopolymerization, crystallization and non-equilibrium self-assembly. This leads to a number of striking physical effects like complex light scattering and polarization as well as unique mechanical properties. In doing so, chitin uses a fine balance between the highly ordered chain conformations in the nanofibrils and random disordered structures. In this opinion piece, we discuss the structural hierarchy of chitin, its crystalline states and the natural biosynthesis processes to create such specific structures and diversity. Among the examples we explored, the unified question arises from the generation of completely different bioarchitectures like the Christmas tree-like nanostructures, gyroids or helicoidal geometries using similar dynamic non-equilibrium growth processes. Understanding the in vivo development of such structures from gene expressions, enzymatic activities as well as the chemical matrix employed in different stages of the biosynthesis will allow us to shift the material design paradigms. Certainly, the complexity of the biology requires a collaborative and multi-disciplinary research effort. For the future's advanced technologies, using chitin will ultimately drive many innovations and alternatives using biomimicry in materials science. This article is part of the theme issue 'Bio-derived and bioinspired sustainable advanced materials for emerging technologies (part 1)'.

Nanocellulose and its Composites for Biomedical Applications.

Cellulose is a natural linear biopolymer, which is constituted of an assembly of cellulose nanofibrils in a hierarchical order. Nanocelluloses in particular show great promise as a cost-effective advanced material for biomedical applications because of their biocompatibility, biodegradability, and low cytotoxicity. Moreover, with their chemical functionality they can be easily modified to yield useful products. While nature uses the hierarchical nanostructure of cellulose as the load-bearing constituent in plants, a significant amount of research has been directed toward the fabrication of advanced cellulosic materials with various nanostructures and functional properties. Such nanocelluloses are widely applied in medical implants, tissue engineering, drug delivery, wound healing, diagnostics, and other medical applications with real examples in this field. There are also emerging fields being developed to use nanocelluloses and their composites in more novel ways in biomedical applications such as 3D printing and magnetically responsive materials. In this mini-review, recent advances in the design and fabrication of nanocellulose-based materials and composites are presented with a special emphasis on their suitability for material requirements for biomedical applications as well as the new directions and challenges that the materials might face in the future.

Shape Memory Cellulose-Based Photonic Reflectors.

Biopolymer-based composites enable to combine different functionalities using renewable materials and cost-effective routes. Here we fabricate novel thermoresponsive photonic films combining cellulose nanocrystals (CNCs) with a polydiolcitrate elastomer exhibiting shape memory properties, known as hydroxyl-dominant poly(dodecanediol-co-citrate) (PDDC-HD). Iridescent films of CNCs are first made by evaporation-induced self-assembly, then embedded in the PDDC-HD prepolymer, and finally cured to obtain a cross-linked composite with shape memory properties. The fabricated samples are characterized by polarized optical microscopy, scanning electron microscopy, and thermomechanical cycling. The obtained hybrid material combines both intense structural coloration and shape memory effect. The association of stiff cellulose nanocrystals and soft polydiolcitrate elastomer enhances the overall mechanical properties (increased modulus and reduced brittleness). This hybrid nanocomposite takes advantage of two promising materials and expands their possibilities to cover a wide range of potential applications as multiresponsive devices and sensors. As they perform from room to body temperatures, they could be also good candidates for biomedical applications.

Recent advances in the biomimicry of structural colours.

Nature has mastered the construction of nanostructures with well-defined macroscopic effects and purposes. Structural colouration is a visible consequence of the particular patterning of a reflecting surface with regular structures at submicron length scales. Structural colours usually appear bright, shiny, iridescent or with a metallic look, as a result of physical processes such as diffraction, interference, or scattering with a typically small dissipative loss. These features have recently attracted much research effort in materials science, chemistry, engineering and physics, in order to understand and produce structural colours. In these early stages of photonics, researchers facing an infinite array of possible colour-producing structures are heavily inspired by the elaborate architectures they find in nature. We review here the recent technological strategies employed to artificially mimic the structural colours found in nature, as well as some of their current and potential applications.

Digital color in cellulose nanocrystal films.

Cellulose nanocrystals (CNCs) form chiral nematic phases in aqueous suspensions that can be preserved upon evaporation of water. The resulting films show an intense directional coloration determined by their microstructure. Here, microreflection experiments correlated with analysis of the helicoidal nanostructure of the films reveal that the iridescent colors and the ordering of the individual nematic layers are strongly dependent on the polydispersity of the size distribution of the CNCs. We show how this affects the self-assembly process, and hence multidomain color formation in such bioinspired structural films.