Chitosan-Based Biomaterials: Insights into Chemistry, Properties, Devices, and Their Biomedical Applications.

Chitosan is a marine-origin polysaccharide obtained from the deacetylation of chitin, the main component of crustaceans' exoskeleton, and the second most abundant in nature. Although this biopolymer has received limited attention for several decades right after its discovery, since the new millennium chitosan has emerged owing to its physicochemical, structural and biological properties, multifunctionalities and applications in several sectors. This review aims at providing an overview of chitosan properties, chemical functionalization, and the innovative biomaterials obtained thereof. Firstly, the chemical functionalization of chitosan backbone in the amino and hydroxyl groups will be addressed. Then, the review will focus on the bottom-up strategies to process a wide array of chitosan-based biomaterials. In particular, the preparation of chitosan-based hydrogels, organic-inorganic hybrids, layer-by-layer assemblies, (bio)inks and their use in the biomedical field will be covered aiming to elucidate and inspire the community to keep on exploring the unique features and properties imparted by chitosan to develop advanced biomedical devices. Given the wide body of literature that has appeared in past years, this review is far from being exhaustive. Selected works in the last 10 years will be considered.

PFAS-free superhydrophobic chitosan coating for fabrics.

In view of health and environmental concerns, together with the upcoming restrictive regulations on per- and polyfluoroalkyl substances (PFAS), less impactful materials must be explored for the hydrophobization of surfaces. Polysaccharides, and especially chitosan, are being explored for their desirable properties of film formation and ease of modification. We present a PFAS-free chitosan superhydrophobic coating for textiles deposited through a solvent-free method. By contact angle analysis and drop impact, we observe that the coating imparts hydrophobicity to the fabrics, reaching superhydrophobicty (θA = 151°, θR = 136°) with increased amount of coating (from 1.6 g/cm2). This effect is obtained by the combination of chemical water repellency of the modified chitosan and the nano- and micro-roughness, assessed by SEM analysis. We perform a comprehensive study on the durability of the coatings, showing good results especially for acidic soaking where the hydrophobicity is maintained until the 8th cycle of washing. We assess the degradation of the coating by a TGA-IR investigation to define the compounds released with thermal degradation, and we confirm the coating's biodegradability by biochemical oxygen consumption. Finally, we demonstrate its biocompatibility on keratinocytes (HaCaT cell line) and fibroblasts (HFF-1 cell line), confirming that the coating is safe for human skin cells.

Withdrawn: Low ice adhesion on soft surfaces: Elasticity or lubrication effects?

This article has been withdrawn at the request of the author(s) and/or editor. The Publisher apologizes for any inconvenience this may cause. The full Elsevier Policy on Article Withdrawal can be found at https://www.elsevier.com/about/policies/article-withdrawal.

Discontinuity-enhanced icephobic surfaces for low ice adhesion.

HYPOTHESIS: Passive low ice-adhesion surfaces are frequently composed of soft materials; however, soft materials potentially present durability issues, which could be overcome by fabricating composite surfaces with patterned rigid and soft areas. Here we propose the innovative concept of discontinuity-enhanced icephobic surfaces, where the stress concentration at the edge between rigid and soft areas, i.e. where discontinuities in elasticity are located, facilitates ice detachment. EXPERIMENTS: Composite model surfaces were fabricated with controlled rigid-soft ratios and discontinuity line lengths. The ice adhesion values were measured while recording the ice/substrate interface, to unravel the underpinning ice detachment mechanism. The experiments were complemented by numerical simulations that provided a better understanding of the ice detachment mechanism. FINDINGS: It was found that when a surface contains rigid and soft areas, stress is concentrated at the edge between soft and hard areas, i.e. at the discontinuity line, rather than all over the soft or rigid areas. An unexpected non-unidirectional crack propagation was observed for the first time and elucidated. When rigid and deformable materials are present, the crack occurs on the discontinuity line and propagates first on rigid and then on soft areas. Moreover, it was demonstrated that an increase in discontinuities promotes crack initiation and leads to a reduction of ice adhesion.

Low ice adhesion on soft surfaces: Elasticity or lubrication effects?

HYPOTHESIS: Soft materials are promising candidates for designing passive de-icing systems. It is unclear whether low adhesion on soft surfaces is due to elasticity or lubrication, and how these properties affect the ice detachment mechanism. This study presents a systematic analysis of ice adhesion on soft materials with different lubricant content to better understand the underpinning interaction. EXPERIMENTS: The wetting and mechanical properties of soft polydimethylsiloxane with different lubricant content were thoroughly characterized by contact angle, AFM indentation, and rheology measurements. The collected information was used to understand the relationship with the ice adhesion results, obtained by using different ice block sizes. FINDINGS: Three different de-icing mechanisms were identified: (i) single detachment occurs when small ice blocks are considered, and the ice completely detaches in a single event. In the case of larger ice blocks, the reattachment of the ice block is promoted by either: (ii) stick-slip or, (iii) interfacial slippage, depending on the lubricant content. It was confirmed that the ice adhesion strength not only depends on material properties but also on experimental conditions, such as the ice dimensions. Moreover, differently than on hard surfaces, where wetting primarily determines the icephobic performance, also elasticity and lubrication should be considered on soft surfaces.

Chitosan derivatives as dynamic coatings for transferrin glycoform separation in capillary electrophoresis.

Chitosan and its derivatives are interesting biopolymers for different field of analytical chemistry, especially in separation techniques. The present study was aimed at testing chitosan water soluble derivatives as dynamic coating agents for application to capillary electrophoresis. In particular, chitosan was modified following three different chemical reactions (nucleophilic substitution, reductive amination, and condensation) to introduce differences in charge and steric hindrance, and to assess the effect of these physico-chemical properties in capillary electrophoresis. The effects were tested on the capillary electrophoretic separation of the glycoforms of human transferrin, an important iron-transporting serum protein, one of which, namely disialo-transferrin (CDT), is a biomarker of alcohol abuse. Chitosan derivatives were characterized by using NMR and 1H NMR, HP-SEC-TDA, DLS, and rheology. The use of these compounds as dynamic coatings in the electrolyte running buffer in capillary electrophoresis was tested assessing the peak resolution of the main glycoforms of human transferrin and particularly of disialo-transferrin. The results showed distinct changes of the peak resolution produced by the different derivatives. The best results in terms of peak resolution were achieved using polyethylene glycol (PEG)-modified chitosan, which, in comparison to a reference analytical approach, provided an almost baseline resolution of disialo-transferrin from the adjacent peaks.

Keratinous and corneous-based products towards circular bioeconomy: A research review.

Keratins and corneous proteins are key components of biomaterials used in a wide range of applications and are potential substitutes for petrochemical-based products. Horns, hooves, feathers, claws, and similar animal tissues are abundant sources of α-keratin and corneous ß-proteins, which are by-products of the food industry. Their close association with the meat industry raises environmental and ethical concerns regarding their disposal. To promote an eco-friendly and circular use of these materials in novel applications, efforts have focused on recovering these residues to develop sustainable, non-animal-related, affordable, and scalable procedures. Here, we review and examine biotechnological methods for extracting and expressing α-keratins and corneous ß-proteins in microorganisms. This review highlights consolidated research trends in biomaterials, medical devices, food supplements, and packaging, demonstrating the keratin industry's potential to create innovative value-added products. Additionally, it analyzes the state of the art of related intellectual property and market size to underscore the potential within a circular bioeconomic model.

Chitosan-based coatings with tunable transparency and superhydrophobicity: A solvent-free and fluorine-free approach by stearoyl derivatization.

One of the current greatest challenges in materials science and technology is the development of safe- and sustainable-by-design coatings with enhanced functionalities, e.g. to substitute fluorinated substances raising concerns for their potential hazard on human health. Bio-based polymeric coatings represent a promising route with a high potential. In this study, we propose an innovative sustainable method for fabricating coatings based on chitosan with modified functionality, with a fine-tuning of coating properties, namely transparency and superhydrophobicity. The process consists in two main steps: i) fluorine-free modification of chitosan functional groups with stearoyl chloride and freeze-drying to obtain a superhydrophobic powder, ii) coating deposition using a novel solvent-free approach through a thermal treatment. The modified chitosan is characterized to assess its chemico-physical properties and confirm the functionality modification with fatty acid tails. The deposition method enables tuning the coating properties of transparency and superhydrophobicity, maintaining good durability.

Chitosan Film Sensor for Ammonia Detection in Microdiffusion Analytical Devices.

Chitosan films have attracted increased attention in the field of sensors because of chitosan's unique chemico-physical properties, including high adsorption capacity, filmability and transparency. A chitosan film sensor was developed through the dispersion of an ammonia specific reagent (Nessler's reagent) into a chitosan film matrix. The chitosan film sensor was characterized to assess the film's properties by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). A gas diffusion device was prepared with the chitosan film sensor, enabling the collection and detection of ammonia vapor from biological samples. The chitosan film sensor color change was correlated with the ammonia concentration in samples of human serum and artificial urine. This method enabled facile ammonia detection and concentration measurement, making the sensor useful not only in clinical laboratories, but also for point-of-care devices and wherever there is limited access to modern laboratory facilities.

Capillary-Driven Water Transport by Contrast Wettability-Based Durable Surfaces.

Controlling water transport and management is crucial for continuous and reliable system operation in harsh weather conditions. Passive strategies based on nonwetting surfaces are desirable, but so far, the implementation of superhydrophobic coatings into real-world applications has been limited by durability issues and, in some cases, lack of compliance with environmental regulations. Inspired by surface patterning observed on living organisms, in this study we have developed durable surfaces based on contrast wettability for capillary-driven water transport and management. The surface fabrication process combines a hydrophobic coating with hard-anodized aluminum patterning, using a scalable femtosecond laser microtexturing technique. The concept targets heavy-duty engineering applications; particularly in aggressive weather conditions where corrosion is prevalent and typically the anodic aluminum oxide-based coating is used to protect the surface from corrosion, the concept has been validated on anodic aluminum oxide coated aluminum alloy substrates. Such substrates with contrast wettable characteristics show long-term durability in both natural and lab-based artificial UV and corrosion tests where superhydrophobic coatings tend to degrade.

Supramolecular Structuring of Hyaluronan-Lactose-Modified Chitosan Matrix: Towards High-Performance Biopolymers with Excellent Biodegradation.

Non-covalent interactions in supramolecular chemistry provide useful systems to understand biological processes, and self-assembly systems are suitable assets to build-up innovative products for biomedical applications. In this field, polyelectrolyte complexes are interesting, especially when polysaccharides are involved, due to their non-toxicity and bio-absorbability. In this work, we investigated a polyelectrolyte formed by hyaluronic acid (HA), a negatively charged linear polysaccharide, with Chitlac (Ch), a positively charged lactose-modified chitosan. The aim of the study was the investigation of a novel Ch-HA polyelectrolyte complex, to understand the interaction between the two polysaccharides and the stability towards enzymatic activity. By means of gel permeation chromatography-triple detector array (GPC-TDA), nuclear magnetic resonance (NMR), dynamic viscosity, Zeta Potential and scanning electron microscopy (SEM), the polyelectrolyte complex properties were identified and compared to individual polysaccharides. The complex showed monodisperse molecular weight distribution, high viscosity, negative charge, and could be degraded by specific enzymes, such as hyaluronidase and lysozyme. The results suggest a close interaction between the two polysaccharides in the complex, which could be considered a self-assembly system.

Hybrid Interface in Sepiolite Rubber Nanocomposites: Role of Self-Assembled Nanostructure in Controlling Dissipative Phenomena.

Sepiolite (Sep)⁻styrene butadiene rubber (SBR) nanocomposites were prepared by using nano-sized sepiolite (NS-SepS9) fibers, obtained by applying a controlled surface acid treatment, also in the presence of a silane coupling agent (NS-SilSepS9). Sep/SBR nanocomposites were used as a model to study the influence of the modified sepiolite filler on the formation of immobilized rubber at the clay-rubber interface and the role of a self-assembled nanostructure in tuning the mechanical properties. A detailed investigation at the macro and nanoscale of such self-assembled structures was performed in terms of the organization and networking of Sep fibers in the rubber matrix, the nature of both the filler⁻filler and filler⁻rubber interactions, and the impact of these features on the reduced dissipative phenomena. An integrated multi-technique approach, based on dynamic measurements, nuclear magnetic resonance analysis, and morphological investigation, assessed that the macroscopic mechanical properties of clay nanocomposites can be remarkably enhanced by self-assembled filler structures, whose formation can be favored by manipulating the chemistry at the hybrid interfaces between the clay particles and the polymers.

A Green Approach for Preparing High-Loaded Sepiolite/Polymer Biocomposites.

Global industry is showing a great interest in the field of sustainability owing to the increased attention for ecological safety and utilization of renewable materials. For the scientific community, the challenge lies in the identification of greener synthetic approaches for reducing the environmental impact. In this context, we propose the preparation of novel biocomposites consisting of natural rubber latex (NRL) and sepiolite (Sep) fibers through the latex compounding technique (LCT), an ecofriendly approach where the filler is directly mixed with a stable elastomer colloid. This strategy favors a homogeneous dispersion of hydrophilic Sep fibers in the rubber matrix, allowing the production of high-loaded sepiolite/natural rubber (Sep/NR) without the use of surfactants. The main physicochemical parameters which control Sep aggregation processes in the aqueous medium were comprehensively investigated and a flocculation mechanism was proposed. The uniform Sep distribution in the rubber matrix, characteristic of the proposed LCT, and the percolative filler network improved the mechanical performances of Sep/NR biocomposites in comparison to those of analogous materials prepared by conventional melt-mixing. These outcomes indicate the suitability of the adopted sustainable procedure for the production of high-loaded clay⁻rubber nanocomposites with remarkable mechanical features.