Single-Step Control of Liquid-Liquid Crystalline Phase Separation by Depletion Gradients.

Fine-tuning nucleation and growth of colloidal liquid crystalline (LC) droplets, also known as tactoids, is highly desirable in both fundamental science and technological applications. However, the tactoid structure results from the trade-off between thermodynamics and nonequilibrium kinetics effects, and controlling liquid-liquid crystalline phase separation (LLCPS) in these systems is still a work in progress. Here, a single-step strategy is introduced to obtain a rich palette of morphologies for tactoids formed via nucleation and growth within an initially isotropic phase exposed to a gradient of depletants.

Hybrid Amyloid-Chitin Nanofibrils for Magnetic and Catalytic Aerogels.

In the quest for a sustainable and circular economy, it is essential to explore environmentally friendly alternatives to traditional petroleum-based materials. A promising pathway toward this goal lies in the leveraging of biopolymers derived from food waste, such as proteins and polysaccharides, to develop advanced sustainable materials. Here, we design versatile hybrid materials by hybridizing amyloid nanofibrils derived by self-assembly of whey, a dairy byproduct, with chitin nanofibrils exfoliated from the two distinct allomorphs of α-chitin and β-chitin, extracted from seafood waste.

From Soy Waste to Bioplastics: Industrial Proof of Concept.

The global plastic waste problem is pushing for the development of sustainable alternatives, encouraged by stringent regulations combined with increased environmental consciousness. In response, this study presents an industrial-scale proof of concept to produce self-standing, transparent, and flexible bioplastic films, offering a possible solution to plastic pollution and resource valorization. We achieve this by combining amyloid fibrils self-assembled from food waste with methylcellulose and glycerol.

Cholesteric Tactoids with Tunable Helical Pitch Assembled by Lysozyme Amyloid Fibrils.

Amyloid fibrils are biological rod-like particles showing liquid-liquid crystalline phase separation into cholesteric phases through a complex behavior of nucleation, growth, and order-order transitions. Yet, controlling the self-assembly of amyloids into liquid crystals, and particularly the resulting helical periodicity, remains challenging. Here, a novel cholesteric system is introduced and characterized based on hen egg white lysozyme (HEWL) amyloid fibrils and the results rationalized via a combination of experiments and theoretical scaling arguments.

Structural Colors from Amyloid-Based Liquid Crystals.

The helical periodicity and layered structure in cholesteric liquid crystals (CLCs) may be tuned to generate structural color according to the Bragg's law of diffraction. A wide range of natural-based materials such as condensed DNA, collagen, chitin, cellulose, and chiral biopolymers exhibit cholesteric phases with left-handed helixes and ensued structural colors. Here, the possibility of using amyloid CLCs is reported to prepare films with iridescent color reflection and opposite handedness.

Probing the Protein Folding Energy Landscape: Dissociation of Amyloid-β Fibrils by Laser-Induced Plasmonic Heating.

Insoluble amyloid fibrils made from proteins and peptides are difficult to be degraded in both living and artificial systems. The importance of studying their physical stability lies primarily with their association with human neurodegenerative diseases, but also owing to their potential role in multiple bio-nanomaterial applications. Here, gold nanorods (AuNRs) were utilized to investigate the plasmonic heating properties and dissociation of amyloid-β fibrils formed by different peptide fragments (Aβ/Aβ/Aβ) related to the Alzheimer's disease.

Turning Food Protein Waste into Sustainable Technologies.

For each kilogram of food protein wasted, between 15 and 750 kg of CO end up in the atmosphere. With this alarming carbon footprint, food protein waste not only contributes to climate change but also significantly impacts other environmental boundaries, such as nitrogen and phosphorus cycles, global freshwater use, change in land composition, chemical pollution, and biodiversity loss. This contrasts sharply with both the high nutritional value of proteins, as well as their unique chemical and physical versatility, which enable their use in new materials and innovative technologies.

Shape and structural relaxation of colloidal tactoids.

Facile geometric-structural response of liquid crystalline colloids to external fields enables many technological advances. However, the relaxation mechanisms for liquid crystalline colloids under mobile boundaries remain still unexplored. Here, by combining experiments, numerical simulations and theory, we describe the shape and structural relaxation of colloidal liquid crystalline micro-droplets, called tactoids, where amyloid fibrils and cellulose nanocrystals are used as model systems.

Hierarchically Fabricated Amyloid Fibers Evaporation-Induced Self-Assembly.

Multiscale hierarchical nano- and microstructures of amyloid fibrils are fabricated by evaporation-induced self-assembly combined with topographic surface patterning techniques. The continuous stick-and-slip motion induces uniaxial alignment of amyloid fibrils characterized by high orientational order during the drying process. The optical textures of the resultant amyloid aggregates are directly observed by polarized optical microscopy (POM) and atomic force microscopy (AFM).

Polysaccharide-reinforced amyloid fibril hydrogels and aerogels.

β-Lactoglobulin amyloid fibrils are bio-colloids of high interest in many fields (e.g. water purification, cell growth, drug delivery and sensing).

Sustainable Removal of Microplastics and Natural Organic Matter from Water by Coagulation-Flocculation with Protein Amyloid Fibrils.

Water contamination is a global threat due to its damaging effects on the environment and human health. Water pollution by microplastics (MPs), dissolved natural organic matter (NOM), and other turbid particles is ubiquitous in water treatment. Here, we introduce lysozyme amyloid fibrils as a novel natural bio-flocculant and explore their ability to flocculate and precipitate the abovementioned undesired colloidal objects.

Liquid-liquid crystalline phase separation in biological filamentous colloids: nucleation, growth and order-order transitions of cholesteric tactoids.

The process of liquid-liquid crystalline phase separation (LLCPS) in filamentous colloids is at the very core of multiple biological, physical and technological processes of broad significance. However, the complete theoretical understanding of the process is still missing. LLCPS involves the nucleation, growth and up-concentration of anisotropic droplets from a continuous isotropic phase, until a state of equilibrium is reached.

Elastic constants of biological filamentous colloids: estimation and implications on nematic and cholesteric tactoid morphologies.

Biological liquid crystals, originating from the self-assembly of biological filamentous colloids, such as cellulose and amyloid fibrils, show a complex lyotropic behaviour that is extremely difficult to predict and characterize. Here we analyse the liquid crystalline phases of amyloid fibrils, and sulfated and carboxylated cellulose nanocrystals and measure their Frank-Oseen elastic constants K1, K2 and K3 by four different approaches. The first two approaches are based on the benchmark of the predictions of: (i) a scaling form and (ii) a variational form of the Frank-Oseen energy functional with the experimental critical volumes at order-order liquid crystalline transitions of the tactoids.

Flow-induced order-order transitions in amyloid fibril liquid crystalline tactoids.

Liquid crystalline droplets, also known as tactoids, forming by nucleation and growth within the phase diagram region where isotropic and nematic phases coexist, challenge our understanding of liquid crystals under confinement due to anisotropic surface boundaries at vanishingly small interfacial tension, resulting in complex, non-spherical shapes. Little is known about their dynamical properties, since they are mostly studied under quiescent, quasi-equilibrium conditions. Here we show that different classes of amyloid based nematic and cholesteric tactoids undergo order-order transitions by flow-induced deformations of their shape.

Relaxation dynamics in bio-colloidal cholesteric liquid crystals confined to cylindrical geometry.

Para-nematic phases, induced by unwinding chiral helices, spontaneously relax to a chiral ground state through phase ordering dynamics that are of great interest and crucial for applications such as stimuli-responsive and biomimetic engineering. In this work, we characterize the cholesteric phase relaxation behaviors of β-lactoglobulin amyloid fibrils and cellulose nanocrystals confined into cylindrical capillaries, uncovering two different equilibration pathways. The integration of experimental measurements and theoretical predictions reveals the starkly distinct underlying mechanism behind the relaxation dynamics of β-lactoglobulin amyloid fibrils, characterized by slow equilibration achieved through consecutive sigmoidal-like steps, and of cellulose nanocrystals, characterized by fast equilibration obtained through smooth relaxation dynamics.

Six-fold director field configuration in amyloid nematic and cholesteric phases.

Chiral liquid crystals, or cholesteric phases, have been widely studied in the last decades, leading to fundamental advances and a multitude of applications and technologies. In general, the rich phenomenology of these systems depends directly on the molecular traits and conditions of the system, imposing precise symmetry to the resulting nematic field. By selecting amyloid fibrils as model filamentous chiral colloids, we report an unprecedented breadth of liquid crystalline morphologies, where up to six distinct configurations of the nematic field are observed under identical conditions.

Ion-Induced Formation of Nanocrystalline Cellulose Colloidal Glasses Containing Nematic Domains.

Controlling the assembly of colloids in dispersion is a fundamental approach toward the production of functional materials. Nanocrystalline cellulose (NCC) is a charged nanoparticle whose colloidal interactions can be modulated from repulsive to attractive by increasing ionic strength. Here, we combine polarized optical microscopy, rheology, and small-angle scattering techniques to investigate (i) the concentration-driven transition from isotropic dispersion to cholesteric liquid crystals and (ii) salt-induced NCC phase transitions.

Amyloid Fibrils Length Controls Shape and Structure of Nematic and Cholesteric Tactoids.

Amyloid fibrils offer the possibility of controlling their contour length, aspect ratio, and length distribution, without affecting other structural parameters. Here we show that a fine control in the contour length distribution of β-lactoglobulin amyloid fibrils, achieved by mechanical shear stresses of different levels, translates into the organization of tactoids of different shapes and morphologies. While longer fibrils lead to highly elongated nematic tactoids in an isotropic continuous matrix, only sufficiently shortened amyloid fibrils lead to cholesteric droplets.