Interfacial Modulation of Ti3C2Tx MXene by Cellulose Nanofibrils to Construct Hybrid Fibers with High Volumetric Specific Capacitance.

The intrinsic poor rheological properties of MXene inks result in the MXene nanosheets in dried MXene microfibers prone to self-stacking, which is not conducive to ion transport and diffusion, thus affecting the electrochemical performance of fiber-based supercapacitors. Herein, robust cellulose nanofibrils (CNF)/MXene hybrid fibers with high electrical conductivity (916.0 S cm-1) and narrowly distributed mesopores are developed by wet spinning. The interfacial interaction between CNF and MXene can be enhanced by hydrogen bonding and electrostatic interaction due to their rich surface functional groups. The interfacial modulation of MXene by CNF can not only regulate the rheology of MXene spinning dispersion, but also enhance the mechanical strength. Furthermore, the interlayer distance and self-stacking effect of MXene nanosheets are also regulated. Thus, the ion transport path within the fiber material is optimized and ion transport is accelerated. In H2SO4 electrolyte, a volumetric specific capacitance of up to 1457.0 F cm-3 (1.5 A cm-3) and reversible charge/discharge stability are demonstrated. Intriguingly, the assembled supercapacitors exhibit a high-volume energy density of 30.1 mWh cm-3 at 40.0 mW cm-3. Moreover, the device shows excellent flexibility and cycling stability, maintaining 83% of its initial capacitance after 10 000 charge/discharge cycles. Practical energy supply applications (Power for LED and electronic watch) can be realized.

Tailoring the Heterogeneous Structure of Macro-Fibers Assembled by Bacterial Cellulose Nanofibrils for Tissue Engineering Scaffolds.

Bacterial cellulose/oxidized bacterial cellulose nanofibrils (BC/oxBCNFs) macro-fibers are developed as a novel scaffold for vascular tissue engineering. Utilizing a low-speed rotary coagulation spinning technique and precise solvent control, macro-fibers with a unique heterogeneous structure with dense surface and porous core are created. Enhanced by a polydopamine (PDA) coating, these macro-fibers offer robust mechanical integrity, high biocompatibility, and excellent cell adhesion. When cultured with endothelial cells (ECs) and smooth muscle cells (SMCs), the macro-fibers support healthy cell proliferation and exhibit a unique spiral SMC alignment, demonstrating their vascular suitability. This innovative strategy opens new avenues for advances in tissue engineering.

Amyloid Nanofibril-Assisted Spray Drying of Crumpled Supraparticles.

Nanofibrils are known to improve the cohesion of supraparticle (SP) assemblies. However, tailoring the morphology of SPs using nanofibrillar additives is not well developed. Herein, ß-lactoglobulin amyloid nanofibrils (ANFs) are investigated as means to impart morphological control over the assembly process of spray-dried SPs composed of 10-100 nm silica nanoparticles (SiNPs). Phytoglycogen (PG) and silver nanowires (AgNWs) are used to assess the influence of building block softness and aspect ratio, respectively. The results demonstrate that ANFs promote the onset of structural arrest during the particle consolidation enabling the preparation of corrugated SP morphologies. The critical ANF loading required to induce SP corrugation increases by roughly 1 vol% for every 10-nm increase in SiNP diameter, while the ensuing ANF network density decreases with SiNP volume fraction and increases with SiNP diameter. Results imply that ANF length starts to become influential when it approaches the SiNP diameter. ANFs display a reduced effectiveness in altering soft PG SP morphology compared with hard SiNPs of comparable size. In SiNP-AgNW SPs, ANFs induce a toroid-to-corrugated morphology transformation for sufficiently large SPs and small SiNPs. The results illustrate that ANFs are effective additives for the morphological engineering of spray-dried SPs important for numerous applications.

Equilibrium Moisture Mediated Esterification Reaction to Achieve Over 100% Lignocellulosic Nanofibrils Yield.

Lignocellulosic nanofibrils (LCNFs) isolation is recognized as an efficient strategy for maximizing biomass utilization. Nevertheless, achieving a 100% yield presents a formidable challenge. Here, an esterification strategy mediated by the equilibrium moisture in biomass is proposed for LCNFs preparation without the use of catalysts, resulting in a yield exceeding 100%. Different from anhydrous chemical thermomechanical pulp (CTMP0%), the presence of moisture (moisture content of 7 wt%, denoted as CTMP7%) introduces a notably distinct process for the pretreatment of CTMP, comprising the initial disintegration and the post-esterification steps. The maleic acid, generated through maleic anhydride (MA) hydrolysis, degrades the recalcitrant lignin-carbohydrate complex (LCC) structures, resulting in esterified CTMP7% (E-CTMP7%). The highly grafted esters compensate for the mass loss resulting from the partial removal of hydrolyzed lignin and hemicellulose, ensuring a high yield. Following microfluidization, favorable LCNF7% with a high yield (114.4 ± 3.0%) and a high charge content (1.74 ± 0.09 mmol g-1) can be easily produced, surpassing most previous records for LCNFs. Additionally, LCNF7% presented highly processability for filaments, films, and 3D honeycomb structures preparation. These findings provide valuable insights and guidance for achieving a high yield in the isolation of LCNFs from biomass through the mediation of equilibrium moisture.

Controlling 1D Nanostructures and Handedness by Polar Residue Chirality of Amphiphilic Peptides.

Peptide assemblies are promising nanomaterials, with their properties and technological applications being highly hinged on their supramolecular architectures. Here, how changing the chirality of the terminal charged residues of an amphiphilic hexapeptide sequence Ac-I4 K2 -NH2 gives rise to distinct nanostructures and supramolecular handedness is reported. Microscopic imaging and neutron scattering measurements show thin nanofibrils, thick nanofibrils, and wide nanotubes self-assembled from four stereoisomers. Spectroscopic and solid-state nuclear magnetic resonance (NMR) analyses reveal that these isomeric peptides adopt similar anti-parallel ß-sheet secondary structures. Further theoretical calculations demonstrate that the chiral alterations of the two C-terminal lysine residues cause the formation of diverse single ß-strand conformations, and the final self-assembled nanostructures and handedness are determined by the twisting direction and degree of single ß-strands. This work not only lays a useful foundation for the fabrication of diverse peptide nanostructures by manipulating the chirality of specific residues but also provides a framework for predicting the supramolecular structures and handedness of peptide assemblies from single molecule conformations.

Bioinspired H-Bonding Connected Gradient Nanostructure Actuators Based on Cellulose Nanofibrils and Graphene.

The construction of flexible actuators with ultra-fast actuation and robust mechanical properties is crucial for soft robotics and smart devices, but still remains a challenge. Inspired by the unique mechanism of pinecones dispersing seeds in nature, a hygroscopic actuator with interlayer network-bonding connected gradient structure is fabricated. Unlike most conventional bilayer actuator designs, the strategy leverages biobased polyphenols to construct strong interfacial H-bonding networks between 1D cellulose nanofibers and 2D graphene oxide, endowing the materials with high tensile strength (172 MPa) and excellent toughness (6.64 MJ m-3). Furthermore, the significant difference in hydrophilicity between GO and rGO, along with the dense interlayer H-bonding, enables ultra-fast water exchange during water absorption and desorption processes. The resulted actuator exhibits ultra-fast driving speed (154° s-1), excellent pressure-resistant and cyclic stability. Taking advantages of these benefits, the actuator can be fabricated into smart devices (such as smart grippers, humidity control switches) with significant potential for practical applications. The presented approach to constructing interlayer H-bonding in gradient structures is instructive for achieving high performance and functionalization of biomass nanomaterials and the complex of 1D/2D nanomaterials.

Large-Scale Engineerable Films Tailored with Cellulose Nanofibrils for Lighting Management and Thermal Insulation.

Fibrillated cellulose-based nanocomposites can improve energy efficiency of building envelopes, especially windows, but efficiently engineering them with a flexible ability of lighting and thermal management remains highly challenging. Herein, a scalable interfacial engineering strategy is developed to fabricate haze-tunable thermal barrier films tailored with phosphorylated cellulose nanofibrils (PCNFs). Clear films with an extremely low haze of 1.6% (glass-scale) are obtained by heat-assisted surface void packing without hydrophobization of nanocellulose. PCNF gel cakes serve here as templates for surface roughening, thereby resulting in a high haze (73.8%), and the roughened films can block heat transfer by increasing solar reflection in addition to a reduced thermal conduction. Additionally, obtained films can tune distribution of light from visible to near-infrared spectral range, enabling uniform colored lighting and inhibiting localized heating. Furthermore, an integrated simulation of lighting and cooling energy consumption in the case of office buildings shows that the film can reduce the total energy use by 19.2-38.1% under reduced lighting levels. Such a scalable and versatile engineering strategy provides an opportunity to endow nanocellulose-reinforced materials with tunable optical and thermal functionalities, moving their practical applications in green buildings forward.

Implantable Patch of Oxidized Nanofibrillated Cellulose and Lysozyme Amyloid Nanofibrils for the Regeneration of Infarcted Myocardium Tissue and Local Delivery of RNA-Loaded Nanoparticles.

Biopolymeric implantable patches are popular scaffolds for myocardial regeneration applications. Besides being biocompatible, they can be tailored to have required properties and functionalities for this application. Recently, fibrillar biobased nanostructures prove to be valuable in the development of functional biomaterials for tissue regeneration applications. Here, periodate-oxidized nanofibrillated cellulose (OxNFC) is blended with lysozyme amyloid nanofibrils (LNFs) to prepare a self-crosslinkable patch for myocardial implantation. The OxNFC:LNFs patch shows superior wet mechanical properties (60 MPa for Young's modulus and 1.5 MPa for tensile stress at tensile strength), antioxidant activity (70% scavenging activity under 24 h), and bioresorbability ratio (80% under 91 days), when compared to the patches composed solely of NFC or OxNFC. These improvements are achieved while preserving the morphology, required thermal stability for sterilization, and biocompatibility toward rat cardiomyoblast cells. Additionally, both OxNFC and OxNFC:LNFs patches reveal the ability to act as efficient vehicles to deliver spermine modified acetalated dextran nanoparticles, loaded with small interfering RNA, with 80% of delivery after 5 days. This study highlights the value of simply blending OxNFC and LNFs, synergistically combining their key properties and functionalities, resulting in a biopolymeric patch that comprises valuable characteristics for myocardial regeneration applications.

Reassembly of Peptide Nanofibrils on Live Cell Surfaces Promotes Cell-Cell Interactions.

Nature regulates cellular interactions through the cell-surface molecules and plasma membranes. Despite advances in cell-surface engineering with diverse ligands and reactive groups, modulating cell-cell interactions through scaffolds of the cell-binding cues remains a challenging endeavor. Here, we assembled peptide nanofibrils on live cell surfaces to present the ligands that bind to the target cells. Surprisingly, with the same ligands, reducing the thermal stability of the nanofibrils promoted cellular interactions. Characterizations of the system revealed a thermally induced fibril disassembly and reassembly pathway that facilitated the complexation of the fibrils with the cells. Using the nanofibrils of varied stabilities, the cell-cell interaction was promoted to different extents with free-to-bound cell conversion ratios achieved at low (31%), medium (54%), and high (93%) levels. This study expands the toolbox to generate desired cell behaviors for applications in many areas and highlights the merits of thermally less stable nanoassemblies in designing functional materials.

Improving therapeutic potential in breast cancer via histone deacetylase inhibitor loaded nanofibrils.

Epigenetic modifications play a significant role in cancer progression, making them potential targets for therapy. Histone deacetylase inhibitors have shown promise in inhibiting cancer cell growth, including in breast cancer (BC). In this research, we examined the potential of using suberoyl anilide hydroxamic acid (SAHA)-loaded ß-lg nanofibrils as a drug delivery system for triple-negative BC cell lines. We assessed their impact on cell cycle progression, apoptosis, levels of reactive oxygen species, and mitochondrial membrane potential in cancer cells. The combination of SAHA and ß-lg nanofibrils demonstrated enhanced efficacy in inhibiting cell growth, inducing cell cycle arrest, and promoting apoptosis (43.78%) compared to SAHA alone (40.09%). Moreover, it effectively targeted cancer cells without promoting drug resistance while using a low concentration of the nanofibrils. These findings underscore the promising potential of nanofibril-based drug delivery systems for BC treatment.

Mesoscale Confinement in Bagworm Silk: A Hidden Structural Organization.

While silk fibers produced by silkworms and spiders are frequently described as a network of amorphous protein chains reinforced by crystalline ß-sheet nanodomains, the importance of higher-order, self-assembled structures has been recognized for advanced modeling of mechanical properties. General acceptance of hierarchical structural models is, however, currently limited by lack of experimental results. Indeed, X-ray scattering studies of spider's dragline-type fibers have been particularly limited by low crystallinities. Here we are reporting on probing the local structure of exceptionally crystalline bagworm silk fibers by X-ray nanobeam scattering. Probing the comparable thickness of cross sections with an X-ray nanobeam allows removing the strong scattering background from the outer sericin layer and reveals a hidden structural organization due to a radial gradient in diameters of mesoscale nanofibrillar bundles in the fibroin phase. Our results provide direct support for lateral interactions between nanofibrils.

Characteristics of Dialdehyde Cellulose Nanofibrils Derived from Cotton Linter Fibers and Wood Fibers.

Two types of cellulose nanofibrils (CNFs) were isolated from cotton linter fibers and hardwood fibers through mechanical fibrillation methods. The dialdehyde cellulose nanofibrils (DACNFs) were prepared through the periodate oxidation method, and their morphological and structural properties were investigated. The characteristics of the DACNFs during the concentration process were also explored. The AFM analysis results showed that the mean diameters of wood fiber-based CNFs and cotton fiber-based CNFs were about 52.03 nm and 69.51 nm, respectively. However, the periodate oxidation treatment process obviously reduced the nanofibril size and destroyed the crystalline region of the nanofibrils. Due to the high crystallinity of cotton fibers, the cotton fiber-based DACNFs exhibited a lower aldehyde content and suspension stability compared to the wood fiber-based DACNFs. For the concentration process of the DACNF suspension, the bound water content of the concentrated cotton fiber-based DACNFs was lowered to 0.41 g/g, which indicated that the cotton fiber-based DACNFs could have good redispersibility. Both the wood fiber-based and cotton fiber-based DACNF films showed relatively good transmittance and mechanical strength. In addition, to the cotton fiber-based DACNF films had a very low swelling ratio, and the barrier water vapor and oxygen properties of the redispersed cotton fiber-based DACNF films decreased by very little. In sum, this study has demonstrated that cotton fibers could serve as an effective alternative to wood fibers for preparing CNFs, and that cotton fiber-based DACNFs have huge application prospects in the field of packaging film materials due to their stable properties during the concentration process.

Chitin Nanofibrils from Fungi for Hierarchical Gel Polymer Electrolytes for Transient Zinc-Ion Batteries with Stable Zn Electrodeposition.

Rechargeable batteries play an integral role toward carbon neutrality. Environmentally sustainable batteries should consider the trade-offs between material renewability, processability, thermo-mechanical and electrochemical performance, as well as transiency. To address this dilemma, we follow circular economy principles to fabricate fungal chitin nanofibril (ChNF) gel polymer electrolytes (GPEs) for zinc-ion batteries. These biocolloids are physically entangled into hierarchical hydrogels with specific surface areas of 49.5 m2 ·g-1 . Ionic conductivities of 54.1 mS·cm-1 and a Zn2+ transference number of 0.468 are reached, outperforming conventional non-renewable/non-biodegradable glass microfibre separator-liquid electrolyte pairs. Enabled by its mechanically elastic properties and large water uptake, a stable Zn electrodeposition in symmetric Zn|Zn configuration with a lifespan above 600 h at 9.5 mA·cm-2 is obtained. At 100 mA·g-1 , the discharge capacity of Zn/α-MnO2 full cells increases above 500 cycles when replacing glass microfiber separators with ChNF GPEs, while the rate performance remains comparable to glass microfiber separators. To make the battery completely transient, the metallic current collectors are replaced by biodegradable polyester/carbon black composites undergoing degradation in water at 70 °C. This work demonstrates the applicability of bio-based materials to fabricate green and electrochemically competitive batteries with potential applications in sustainable portable electronics, or biomedicine.

Core-Shell Filament with Excellent Wound Healing Property Made of Cellulose Nanofibrils and Guar Gum via Interfacial Polyelectrolyte Complexation Spinning.

Natural polymer-based sutures have attractive cytocompatibility and degradability in surgical operations. Herein, anionic cellulose nanofibrils (ACNF) and cationic guar gum (CGG) are employed to produce nontoxic CGG/ACNF composite filament with a unique core-shell structure via interfacial polyelectrolyte complexation (IPC) spinning. The comprehensive characterization and application performance of the resultant CGG/ACNF filament as a surgical suture are thoroughly investigated in comparison with silk and PGLA (90% glycolide and 10% l-lactide) sutures in vitro and in vivo, respectively. Results show that the CGG/ACNF filament with the typical core-shell structure and nervation pattern surface exhibits a high orientation index (0.74) and good mechanical properties. The tensile strength and knotting strength of CGG/ACNF suture prepared by twisting CGG/ACNF filaments increase by 69.5%, and CGG/ACNF suture has a similar friction coefficient to silk and PGLA sutures. Moreover, CGG/ACNF suture with antibiosis and cytocompatibility exhibits better growth promotion of cells than silk suture, similar to PGLA suture in vitro. In addition, the stitching experiment of mice with the CGG/ACNF suture further confirms better healing properties and less inflammation in vivo than silk and PGLA sutures do. Hence, the CGG/ACNF suture with a simple preparation method and excellent application properties is promising in surgical operations.

Nano techniques: an updated review focused on anthocyanin stability.

Anthocyanins (ACNs) are one of the subgroups of flavonoids and getting intensive attraction due to the nutritional values. However, their application of ACNs is limited due to their poor stability and bioavailability. Accordingly, nanoencapsulation has been developed to enhance its stability and bio-efficacy. This review focuses on the nano-technique applications of delivery systems that be used for ACNs stabilization, with an emphasis on physicochemical stability and health benefits. ACNs incorporated with delivery systems in forms of nano-particles and fibrils can achieve advanced functions, such as improved stability, enhanced bioavailability, and controlled release. Also, the toxicological evaluation of nano delivery systems is summarized. Additionally, this review summarizes the challenges and suggests the further perspectives for the further application of ACNs delivery systems in food and medical fields.

Utilizing protein nanofibrils as a scaffold for enhancing nutritional value in toned milk.

Toned milk is a lower-fat, healthier alternative to whole milk that still contains all essential nutrients. A number of methods have been developed to improve the functionality of toned milk and make it more appealing to the consumers. However, these methods often involve extensive processing techniques and can be expensive. Therefore, alternative methods are needed. Proteins are well known for their ability to form well-defined nanofibril materials that can be used as a scaffold for various applications. In this article, a straightforward self-assembly process was used to load inulin into protein nanofibrils, creating unique composite nanofibrils. Characterization using AFM and SEM revealed well-defined composite nanofibrils with an average diameter of 4-6 nm and lengths ranging from 0.25 µm up to 10 µm. FT-IR and in-vitro release assays show that inulin was successfully attached to prepared protein nanofibrils. The composite nanofibrils were tested on toned milk to enhance the physico/chemical properties and nutritional values. The findings can be applied to the food industry to create a number of novel functional food products cost-effectively.

Potential issues specific to cytotoxicity tests of cellulose nanofibrils.

Cellulose nanofibrils (also called cellulose nanofibers or nanofibrillated cellulose [CNFs]) are novel polymers derived from biomass with excellent physicochemical properties and various potential applications. However, the introduction of such new materials into the market requires thorough safety studies to be conducted. Recently, toxicity testing using cultured cells has attracted attention as a safety assessment that does not rely on experimental animals. This article reviews recent information regarding the cytotoxicity testing of CNFs and highlights the issues relevant to evaluating tests. In the literature, we found that a variety of cell lines and CNF exposure concentrations was evaluated. Furthermore, the results of cytotoxicity results tests differed and were not necessarily consistent. Numerous reports that we examined had not evaluated endotoxin/microbial contamination or the interaction of CNFs with the culture medium used in the tests. The following potential specific issues involved in CNF in vitro testing, were discussed: (1) endotoxin contamination, (2) microbial contamination, (3) adsorption of culture medium components to CNFs, and (4) changes in aggregation/agglomeration and dispersion states of CNFs resulting from culture medium components. In this review, the available measurement methods and solutions for these issues are also discussed. Addressing these points will lead to a better understanding of the cellular effects of CNFs and the development of safer CNFs.

Identifying Heterozipper ß-Sheet in Twisted Amyloid Aggregation.

Amyloid peptide (AP) self-assembly is a hierarchical process. However, the mechanistic rule of guiding peptides to organize well-ordered nanostructure in a clear and precise manner remains poorly understood. Herein we explored the molecular insight of AP motif aggregates underlying hierarchical process with helical fibrillar structure by atomic force microscope, cryo-electron microscopy (cryo-EM), and molecular dynamics simulation. AP assembly encompasses well-ordered twisted fibrils with uniform morphology, size, and periodicity. More importantly, a heterozipper ß-sheet was identified in a protofilament of AP assembly determined by cryo-EM with a high resolution of 3.5 Å. Each peptide heterozipper was further composed of two antiparallel ß strands and arranged by an alternative manner in a protofilament. The hydrophobic core and hydrophilic area in each zipper played the significant role for peptide assembling. This work proposed and verified the rule facilitating the basic building unit to form twisted fibrils and gave the explanation of peptide hierarchical assembling.

Multi-Point Nanoindentation Method to Determine Mechanical Anisotropy in Nanofibrillar Thin Films.

Biomaterials with outstanding mechanical properties, including spider silk, wood, and cartilage, often feature an oriented nanofibrillar structure. The orientation of nanofibrils gives rise to a significant mechanical anisotropy, which is extremely challenging to characterize, especially for microscopically small or inhomogeneous samples. Here, a technique utilizing atomic force microscope indentation at multiple points combined with finite element analysis to sample the mechanical anisotropy of a thin film in a microscopically small area is reported. The system studied here is the tape-like silk of the Chilean recluse spider, which entirely consists of strictly oriented nanofibrils giving rise to a large mechanical anisotropy. The most detailed directional nanoscale structure-property characterization of spider silk to date is presented, revealing the tensile and transverse elastic moduli as 9 and 1 GPa, respectively, and the binding strength between silk nanofibrils as 159 ± 13 MPa. Furthermore, based on this binding strength, the nanofibrils' surface energy is derived as 37 mJ m-2 , and concludes that van der Waals forces play a decisive role in interfibrillar binding. Due to its versatility, this technique has many potential applications, including early disease diagnostics, as underlying pathological conditions can alter the local mechanical properties of tissues.

Surface functionalization and size modulate the formation of reactive oxygen species and genotoxic effects of cellulose nanofibrils.

BACKGROUND: Cellulose nanofibrils (CNFs) have emerged as a sustainable and environmentally friendly option for a broad range of applications. The fibrous nature and high biopersistence of CNFs call for a thorough toxicity assessment, but it is presently unclear which physico-chemical properties could play a role in determining the potential toxic response to CNF. Here, we assessed whether surface composition and size could modulate the genotoxicity of CNFs in human bronchial epithelial BEAS-2B cells. We examined three size fractions (fine, medium and coarse) of four CNFs with different surface chemistry: unmodified (U-CNF) and functionalized with 2,2,6,6-tetramethyl-piperidin-1-oxyl (TEMPO) (T-CNF), carboxymethyl (C-CNF) and epoxypropyltrimethylammonium chloride (EPTMAC) (E-CNF). In addition, the source fibre was also evaluated as a non-nanosized material. RESULTS: The presence of the surface charged groups in the functionalized CNF samples resulted in higher amounts of individual nanofibrils and less aggregation compared with the U-CNF. T-CNF was the most homogenous, in agreement with its high surface group density. However, the colloidal stability of all the CNF samples dropped when dispersed in cell culture medium, especially in the case of T-CNF. CNF was internalized by a minority of BEAS-2B cells. No remarkable cytotoxic effects were induced by any of the cellulosic materials. All cellulosic materials, except the medium fraction of U-CNF, induced a dose-dependent intracellular formation of reactive oxygen species (ROS). The fine fraction of E-CNF, which induced DNA damage (measured by the comet assay) and chromosome damage (measured by the micronucleus assay), and the coarse fraction of C-CNF, which produced chromosome damage, also showed the most effective induction of ROS in their respective size fractions. CONCLUSIONS: Surface chemistry and size modulate the in vitro intracellular ROS formation and the induction of genotoxic effects by fibrillated celluloses. One cationic (fine E-CNF) and one anionic (coarse C-CNF) CNF showed primary genotoxic effects, possibly partly through ROS generation. However, the conclusions cannot be generalized to all types of CNFs, as the synthesis process and the dispersion method used for testing affect their physico-chemical properties and, hence, their toxic effects.