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. Specifically, the transition behaviors are elucidated from homogenous nematic, bipolar nematic to cholesteric tactoids following the classic Onsager model and the free energy functional model from Frank-Oseen elasticity theory. Additionally, the critical effects of pH and ionic strength on these order-order-transitions, as well as on the shape and helical pitch of the cholesteric tactoids are demonstrated. It is found that a small increase in pH from 2.0 to 2.8 results in a 34% decrease in pitch, while, on the contrary, increasing ionic strength from 0 to 10 mm leads to a 39% increase in pitch. The present study provides an approach to obtain controllable chiral nematic structures from HEWL amyloid fibrils, and may contribute further to the application of protein-based liquid crystals in pitch-sensitive biosensors or biomimetic architectures.

Fast Probing Amyloid Polymorphism via Nanopore Translocation.

Neurodegenerative diseases are characterized by the presence of cross-ß-sheet amyloid fibrils and a rich mesoscopic polymorphism, requiring noninvasive detection with high fidelity. Here, we introduce a methodology that can probe via a sensitive synthetic nanopore the complex polymorphism of amyloid fibrils by an automated and fast screening protocol. Statistically analyzing the translocation events on two model amyloid systems derived from ß-lactoglobulin and lysozyme allows extracting the cross-sectional configuration of hydrated amyloid fibrils from current block amplitude and correlating dwell time with fibril length. These findings are consistent with the amyloid polymorphs observed in solution by atomic force microscopy. Furthermore, the ionic current signal of a single translocation event can reveal abnormally aggregated conformations of amyloid fibrils without potential artifacts associated with microscopy methods. This study introduces an effective approach to physically discriminating and separating amyloid and may serve in the rapid diagnosis of early aggregating pathological amyloidosis.

Highly Adhesive Amyloid-Polyphenol Hydrogels for Cell Scaffolding.

Rationally designing microstructures of soft hydrogels for specific biological functionalization is a challenge in tissue engineering applications. A novel and affordable soft hydrogel scaffold is constructed here by incorporating polyphenol modules with lysozyme amyloid fibrils (Lys AFs) via non-covalent self-assembly. Embedded polyphenols not only trigger hydrogel formation but also determine gel behavior by regulating the polyphenol gallol density and complex ratio. The feasibility of using a polyphenol-Lys AF hydrogel as a biocompatible cell scaffold, which is conducive to cell proliferation and spreading, is also shown. Notably, introducing polyphenols imparts the corresponding hydrogels a superior cell bioadhesive efficiency without further biofunctional decoration and thus may be successfully employed in both healthy and cancer cell lines. Confocal laser scanning microscopy also reveals that the highly expressed integrin-mediated focal adhesions form due to stimulation of the polyphenol-AF composite hydrogel, direct cell adhesion, proliferation, and spreading. Overall, this work constitutes a significant step forward in creating highly adhesive tissue culture platforms for in vitro culture of different cell types and may greatly expand prospects for future biomaterial design and development.

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. Right-handed CLCs assembled by left-handed amyloid fibrils are dried into layered structures with variable pitch controlled by the addition of glucose. Circularly polarized light with the same handedness of amyloid CLCs helix is reflected in the Bragg regime. Varying the drying speed leads to the switching between films with a rainbow-like color gradient and large area uniform color. It is confirmed that the origin of the colors derives from the layered structures of the amyloid CLCs, given the negligeable birefringence of the films, calculated from optical rotatory dispersion. These findings provide a facile approach to constructing biosourced cholesteric materials and introduce an original class of proteinaceous materials for the generation of structural colors from right-handed circularly polarized light.

Single-site iron-anchored amyloid hydrogels as catalytic platforms for alcohol detoxification.

Constructing effective antidotes to reduce global health impacts induced by alcohol prevalence is a challenging topic. Despite the positive effects observed with intravenous applications of natural enzyme complexes, their insufficient activities and complicated usage often result in the accumulation of toxic acetaldehyde, which raises important clinical concerns, highlighting the pressing need for stable oral strategies. Here we present an effective solution for alcohol detoxification by employing a biomimetic-nanozyme amyloid hydrogel as an orally administered catalytic platform. We exploit amyloid fibrils derived from ß-lactoglobulin, a readily accessible milk protein that is rich in coordinable nitrogen atoms, as a nanocarrier to stabilize atomically dispersed iron (ferrous-dominated). By emulating the coordination structure of the horseradish peroxidase enzyme, the single-site iron nanozyme demonstrates the capability to selectively catalyse alcohol oxidation into acetic acid, as opposed to the more toxic acetaldehyde. Administering the gelatinous nanozyme to mice suffering from alcohol intoxication significantly reduced their blood-alcohol levels (decreased by 55.8% 300 min post-alcohol intake) without causing additional acetaldehyde build-up. Our hydrogel further demonstrates a protective effect on the liver, while simultaneously mitigating intestinal damage and dysbiosis associated with chronic alcohol consumption, introducing a promising strategy in effective alcohol detoxification.

Amine-Functionalized Amyloid Aerogels for CO2 Capture.

Climate change caused by excessive CO2 emissions constitutes an increasingly dire threat to human life. Reducing CO2 emissions alone may not be sufficient to address this issue, so that the development of emerging adsorbents for the direct capture of CO2 from the air becomes essential. Here, we apply amyloid fibrils derived from different food proteins as the solid adsorbent support and develop aminosilane-modified amyloid fibril-templated aerogels for CO2 capture applications. The results indicate that the CO2 sorption properties of the aerogels depend on the mixing ratio of aminosilane featuring different amine groups and the type of amyloid fibril used. Notably, amine-functionalized ß-lactoglobulin (BLG) fibril-templated aerogels show the highest CO2 adsorption capacity of 51.52 mg (1.17 mmol) CO2 /g at 1 bar CO2 and 25.5 mg (0.58 mmol) CO2 /g at 400 ppm; similarly, the CO2 adsorption capacity of chitosan-BLG fibril hybrid aerogels is superior to that of pure chitosan. This study provides a proof-of-concept design for an amyloid fibril-templated hybrid material facilitating applications of protein-based adsorbents for CO2 capture, including direct air capture.

Functional Coating from Amyloid Superwetting Films.

Tailoring the hydrophilicity of solid surfaces with a strong affinity to water has been extensively explored in the last 20 years, but studies have been limited to the single function of wettability. Here, the multifunctional properties of tailored surface films are extended from exhibiting superwettability to facilitating biological activities. It is shown that amyloid fibrils can be universally coated onto various substrates, such as fabrics (non-woven organic masks), metal meshes, polyethersulfone (PES), glass, and more, endowing the resulting surfaces with excellent performance in oil/water mixture and emulsion separation, antifouling, and antifogging. Moreover, the biocompatible crosslinked amyloid fibril coatings can serve as a platform for biocatalytic activities by immobilizing enzymes, as shown in the 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) diammonium salt (ABTS) oxidation and Reactive Black 5 (RB5) degradation by laccase from Trametes versicolor. The study provides a universal approach to modifying surface morphology and chemical properties via fibrous protein templates, opening the way to unexplored bio-based applications and functionalities.

Membrane-based technologies for per- and poly-fluoroalkyl substances (PFASs) removal from water: Removal mechanisms, applications, challenges and perspectives.

Water purification from per- and poly-fluoroalkyl substances (PFASs), as a group of persistent and mobile fluoro-organic contaminants, is receiving increasing attention worldwide due to the ubiquitous presence of these highly toxic compounds. To reduce the risk of exposure of human life to PFASs and their dispersion in the environment, various techniques, primarily based on membrane technologies, have been rapidly developed. Here we critically review and analyze the current state-of-the-art of membrane-based techniques for PFASs removal, including direct membrane filtrations, adsorption-based membranes, and hybrid membrane processes. Membranes performance, treatment efficiencies, characteristic parameters and mechanisms for PFASs removal are discussed in detail. We highlight and discuss advantages and limitations, as well as challenges and prospects of individual membrane-based PFASs treatments, pointing towards the practical and sustainable application of these technologies.