RESUMEN
As a versatile nanomaterial derived from renewable sources, nanocellulose has attracted considerable attention for its potential applications in various sectors, especially those focused on water treatment and remediation. Here, we have combined atomic force microscopy (AFM) and reactive molecular dynamics (RMD) simulations to characterize the interactions between cellulose nanofibers modified with carboxylate or phosphate groups and the protein foulant model bovine serum albumin (BSA) at pH 3.92, which is close to the isoelectric point of BSA. Colloidal probes were prepared by modification of the AFM probes with the nanofibers, and the nanofiber coating on the AFM tip was for the first time confirmed through fluorescence labeling and confocal optical sectioning. We have found that the wet-state normalized adhesion force is approximately 17.87 ± 8.58 pN/nm for the carboxylated cellulose nanofibers (TOCNF) and about 11.70 ± 2.97 pN/nm for the phosphorylated ones (PCNF) at the studied pH. Moreover, the adsorbed protein partially unfolded at the cellulose interface due to the secondary structure's loss of intramolecular hydrogen bonds. We demonstrate that nanocellulose colloidal probes can be used as a sensitive tool to reveal interactions with BSA at nano and molecular scales and under in situ conditions. RMD simulations helped to gain a molecular- and atomistic-level understanding of the differences between these findings. In the case of PCNF, partially solvated metal ions, preferentially bound to the phosphates, reduced the direct protein-cellulose connections. This understanding can lead to significant advancements in the development of cellulose-based antifouling surfaces and provide crucial insights for expanding the pH range of use and suggesting appropriate recalibrations.
Asunto(s)
Celulosa , Microscopía de Fuerza Atómica , Simulación de Dinámica Molecular , Nanofibras , Albúmina Sérica Bovina , Albúmina Sérica Bovina/química , Celulosa/química , Nanofibras/química , Animales , Bovinos , Microscopía de Fuerza Atómica/métodos , Agua/química , Enlace de Hidrógeno , Coloides/química , Concentración de Iones de Hidrógeno , AdsorciónRESUMEN
There are various biomaterials, but none fulfills all requirements. Cellulose biopolymers have advanced biomedicine to satisfy high market demand and circumvent many ecological concerns. This review aims to present an overview of cellulose knowledge and technical biomedical applications such as antibacterial agents, antifouling, wound healing, drug delivery, tissue engineering, and bone regeneration. It includes an extensive bibliography of recent research findings from fundamental and applied investigations. Cellulose-based materials are tailorable to obtain suitable chemical, mechanical, and physical properties required for biomedical applications. The chemical structure of cellulose allows modifications and simple conjugation with several materials, including nanoparticles, without tedious efforts. They render the applications cheap, biocompatible, biodegradable, and easy to shape and process.
Asunto(s)
Celulosa , Nanoestructuras , Materiales Biocompatibles/química , Celulosa/química , Sistemas de Liberación de Medicamentos , Ingeniería de TejidosRESUMEN
Bio-based and patient-specific three-dimensional (3D) scaffolds can present next generation strategies for bone tissue engineering (BTE) to treat critical bone size defects. In the present study, a composite filament of poly lactic acid (PLA) and 45S5 bioglass (BG) were used to 3D print scaffolds intended for bone tissue regeneration. The thermally induced phase separation (TIPS) technique was used to produce composite spheres that were extruded into a continuous filament to 3D print a variety of composite scaffolds. These scaffolds were analyzed for their macro- and microstructures, mechanical properties, in vitro cytotoxicity and in vivo biocompatibility. The results show that the BG particles were homogeneously distributed within the PLA matrix and contributed to an 80% increase in the mechanical strength of the scaffolds. The in vitro cytotoxicity analysis of PLA-BG scaffolds using L929 mouse fibroblast cells confirmed their biocompatibility. During the in vivo studies, the population of the cells showed an elevated level of macrophages and active fibroblasts that are involved in collagen extracellular matrix synthesis. This study demonstrates successful processing of PLA-BG 3D-printed composite scaffolds and their potential as an implant material with a tunable pore structure and mechanical properties for regenerative bone tissue engineering.
Asunto(s)
Ingeniería de Tejidos , Andamios del Tejido , Ratones , Animales , Ingeniería de Tejidos/métodos , Andamios del Tejido/química , Poliésteres/farmacología , Poliésteres/química , Regeneración Ósea , Impresión TridimensionalRESUMEN
A strategy is devised to synthesize zwitterionic acetylated cellulose nanofibrils (CNF). The strategy included acetylation, periodate oxidation, Schiff base reaction, borohydride reduction, and a quaternary ammonium reaction. Acetylation was performed in glacial acetic acid with a short reaction time of 90 min, yielding, on average, mono-acetylated CNF with hydroxyl groups available for further modification. The products from each step were characterized by FTIR spectroscopy, ζ-potential, SEM-EDS, AFM, and titration to track and verify the structural changes along the sequential modification route.
Asunto(s)
Celulosa/síntesis química , Técnicas de Química Sintética , Nanofibras/química , Ácido Acético/química , Acetilación , Borohidruros/química , Celulosa/análogos & derivados , Humanos , Nanofibras/ultraestructura , Oxidación-Reducción , Compuestos de Amonio Cuaternario/química , Bases de Schiff/químicaRESUMEN
Double cross-linked interpenetrating polymer network (IPN) hydrogels of sodium alginate and gelatin (SA/G) reinforced with 50 wt % cellulose nanocrystals (CNC) have been prepared via the freeze-drying process. The IPNs were designed to incorporate CNC with carboxyl surface groups as a part of the network contribute to the structural integrity and mechanical stability of the hydrogel. Structural morphology studies of the hydrogels showed a three-dimensional (3D) network of interconnected pores with diameters in the range of 10-192 µm and hierarchical pores with a nanostructured pore wall roughness, which has potential benefits for cell adhesion. Significant improvements in the tensile strength and strain were achieved in 98% RH at 37 °C for CNC cross-linked IPNs. The high porosity of the scaffolds (>93%), high phosphate buffered saline (PBS) uptake, and cytocompatibility toward mesenchymal stem cells (MSCs) are confirmed and considered beneficial for use as a substitute for cartilage.
Asunto(s)
Celulosa/química , Hidrogel de Polietilenoglicol-Dimetacrilato/química , Nanopartículas/química , Ingeniería de Tejidos , Alginatos/química , Alginatos/farmacología , Cartílago/efectos de los fármacos , Cartílago/crecimiento & desarrollo , Adhesión Celular/efectos de los fármacos , Celulosa/farmacología , Enanismo , Facies , Gelatina/química , Gelatina/farmacología , Ácido Glucurónico/química , Ácido Glucurónico/farmacología , Ácidos Hexurónicos/química , Ácidos Hexurónicos/farmacología , Humanos , Hidrogel de Polietilenoglicol-Dimetacrilato/farmacología , Microcefalia , Polímeros/química , Polímeros/farmacología , Resistencia a la Tracción/efectos de los fármacosRESUMEN
The aim of this study was to develop a fundamental understanding of the adsorption behavior of metal ions on cellulose surfaces using experimental techniques supported by computational modeling, taking Ag(I) as an example. Force interactions among three types of cellulose microspheres (native cellulose and its derivatives with sulfate and phosphate groups) and the silica surface in AgNO3 solution were studied with atomic force microscopy (AFM) using the colloidal probe technique. The adhesion force between phosphate cellulose microspheres (PCM) and the silica surface in the aqueous AgNO3 medium increased significantly with increasing pH while the adhesion force slightly decreased for sulfate cellulose microspheres (SCM), and no clear adhesion force was observed for native cellulose microspheres (CM). The stronger adhesion enhancement for the PCM system is mainly attributed to the electrostatic attraction between Ag(I) and the negative silica surface. The observed force trends were in good agreement with the measured zeta potentials. The scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) analyses confirmed the presence of silver on the surface of cellulose microspheres after adsorption. This study showed that PCM with a high content of phosphate groups exhibited a larger amount of adsorbed Ag(I) than CM and SCM and possible clustering of Ag(I) to nanoparticles. The presence of the phosphate group and a wavenumber shift of the P-OH vibration caused by the adsorption of silver ions on the phosphate groups were further confirmed with computational studies using density functional theory (DFT), which gives support to the above findings regarding the adsorption and clustering of Ag(I) on the cellulose surface decorated with phosphate groups as well as IR spectra.
RESUMEN
Integrating polypyrrole-cellulose nanocrystal-based composites with glucose oxidase (GOx) as a new sensing regime was investigated. Polypyrrole-cellulose nanocrystal (PPy-CNC)-based composite as a novel immobilization membrane with unique physicochemical properties was found to enhance biosensor performance. Field emission scanning electron microscopy (FESEM) images showed that fibers were nanosized and porous, which is appropriate for accommodating enzymes and increasing electron transfer kinetics. The voltammetric results showed that the native structure and biocatalytic activity of GOx immobilized on the PPy-CNC nanocomposite remained and exhibited a high sensitivity (ca. 0.73 µA·mM(-1)), with a high dynamic response ranging from 1.0 to 20 mM glucose. The modified glucose biosensor exhibits a limit of detection (LOD) of (50 ± 10) µM and also excludes interfering species, such as ascorbic acid, uric acid, and cholesterol, which makes this sensor suitable for glucose determination in real samples. This sensor displays an acceptable reproducibility and stability over time. The current response was maintained over 95% of the initial value after 17 days, and the current difference measurement obtained using different electrodes provided a relative standard deviation (RSD) of 4.47%.
Asunto(s)
Técnicas Biosensibles , Celulosa/farmacología , Glucosa Oxidasa/metabolismo , Glucosa/análisis , Técnicas Biosensibles/instrumentación , Técnicas Biosensibles/métodos , Celulosa/química , Sinergismo Farmacológico , Electrodos , Enzimas Inmovilizadas/química , Enzimas Inmovilizadas/metabolismo , Glucosa/metabolismo , Glucosa Oxidasa/química , Límite de Detección , Nanocompuestos/química , Nanopartículas/química , Polímeros/química , Pirroles/químicaRESUMEN
Sabu Thomas, Maya John and Aji Mathew introduce the Nanoscale Advances themed issue on Bionanocomposites.
RESUMEN
The upcycling of discarded garments can help to mitigate the environmental impact of the textile industry. Here, we fabricated hybrid anisotropic foams having cellulose nanocrystals (CNCs), which were isolated from discarded cotton textiles and had varied surface chemistries as structural components, in combination with xanthan gum (XG) as a physical crosslinker of the dispersion used for foam preparation. All CNCs had crystallinity indices above 85 %, zeta potential values below -40 mV at 1 mM NaCl, and true densities ranging from 1.61 to 1.67 g·cm-3. Quartz crystal microbalance with dissipation (QCM-D) measurements indicated weak interactions between CNC and XG, while rheology measurements showed that highly charged CNCs caused the XG chains to change from an extended to a helicoidal conformation, resulting in changes the in viscoelastic properties of the dispersions. The inclusion of XG significantly enhanced the compression mechanical properties of the freeze-casted foams without compromising their thermal properties, anisotropy, or degree of alignment. CNC-XG foams maintained structural integrity even after exposure to high humidity (91 %) and temperatures (100 °C) and displayed very low radial thermal conductivities. This research provides a viable avenue for upcycling cotton-based clothing waste into high-performance materials.
RESUMEN
Biopolymer-based functional materials are essential for reducing the carbon footprint and providing high-quality lightweight materials suitable for packaging and thermal insulation. Here, cellulose nanocrystals (CNCs) were efficiently upcycled from post-consumer cotton clothing by TEMPO-mediated oxidation and HCl hydrolysis with a yield of 62% and combined with wood cellulose nanofibrils (CNFs) to produce anisotropic foams by unidirectional freeze-casting followed by freeze drying (FD) or supercritical-drying (SCD). Unidirectional freeze-casting resulted in foams with aligned macropores irrespective of the drying method, but the particle packing in the foam wall was significantly affected by how the ice was removed. The FD foams showed tightly packed and aligned CNC and CNF particles while the SCD foams displayed a more network-like structure in the foam walls. The SCD compared to FD foams had more pores smaller than 300 nm and higher specific surface area but they were more susceptible to moisture-induced shrinkage, especially at relative humidities (RH) > 50%. The FD and SCD foams displayed low radial thermal conductivity, and the FD foams displayed a higher mechanical strength and stiffness in compression in the direction of the aligned particles. Better understanding how drying influences the structural, thermal, mechanical and moisture-related properties of foams based on repurposed cotton is important for the development of sustainable nanostructured materials for various applications.
RESUMEN
Although cellulose derivatives are widely applied in high-tech materials, the relation between their force responses and their surface chemical properties in a biological environment as a function of pH is unknown. Here, interaction forces of surface modified cellulose nanocrystals (CNCs), lignin residual cellulose nanocrystals (LCNCs), and 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanofibres (TCNFs) with OSO3-, COO- and lignin chemical groups were measured using in situ peak force quantitative nanomechanical mapping and force spectroscopy in salt solution at two pH values. We found that the forces acting between the tip and CNC or LCNC are steric dominated showing long range and slow decay as a result of their low surface charge density. High Mw lignin contributed to the increased repulsion range for LCNCs compared to CNCs. The repulsion measured for TCNFs at the very short range was electrostatic force dominating showing a steep decay attributed to its high surface charge density. In the case of TCNFs, electrostatic double layer force was also evidenced by the attraction measured at secondary minima. In all the three cases the electro steric interactions are pH dependent. Dissipation maps verified that the force behavior for each material was related to structural conformation restriction of the groups at compression. The slow decayed repulsion of CNCs or LCNCs is related to a weak restriction of conformational change due to small surface groups or high molecular weight bound polymers forming flat layers, whereas the steep repulsion of TCNFs is attributed to a strong conformation restriction of carboxylic groups occurred by forming extended structure. Our results suggest that the force responses of the materials were dominated by surface charges and structural differences. TCNFs showed superior nanomechanical and repulsion properties over CNCs or LCNCs at neutral pH.
Asunto(s)
Lignina , Nanopartículas , Lignina/química , Celulosa/química , Polímeros/química , Nanopartículas/química , Análisis EspectralRESUMEN
Metal-organic frameworks (MOFs) have advanced several technologies. However, it is difficult to market MOFs without processing them into a commercialized structure, causing an unnecessary delay in the material's use. Herein, three-dimensional (3D) printing of cellulose/leaf-like zeolitic imidazolate frameworks (ZIF-L), denoted as CelloZIF-L, is reported via direct ink writing (DIW, robocasting). Formulating CelloZIF-L into 3D objects can dramatically affect the material's properties and, consequently, its adsorption efficiency. The 3D printing process of CelloZIF-L is simple and can be applied via direct printing into a solution of calcium chloride. The synthesis procedure enables the formation of CelloZIF-L with a ZIF content of 84%. 3D printing enables the integration of macroscopic assembly with microscopic properties, i.e., the formation of the hierarchical structure of CelloZIF-L with different shapes, such as cubes and filaments, with 84% loading of ZIF-L. The materials adsorb carbon dioxide (CO2) and heavy metals. 3D CelloZIF-L exhibited a CO2 adsorption capacity of 0.64-1.15 mmol g-1 at 1 bar (0 °C). The materials showed Cu2+ adsorption capacities of 389.8 ± 14-554.8 ± 15 mg g-1. They displayed selectivities of 86.8%, 6.7%, 2.4%, 0.93%, 0.61%, and 0.19% toward Fe3+, Al3+, Co2+, Cu2+, Na+, and Ca2+, respectively. The simple 3D printing procedure and the high adsorption efficiencies reveal the promising potential of our materials for industrial applications.
RESUMEN
The development of porous organic polymers, specifically covalent organic frameworks (COFs), has facilitated the advancement of numerous applications. Nevertheless, the limited availability of COFs solely in powder form imposes constraints on their potential applications. Furthermore, it is worth noting that COFs tend to undergo aggregation, leading to a decrease in the number of active sites available within the material. This work presents a comprehensive methodology for the transformation of a COF into three-dimensional (3D) scaffolds using the technique of 3D printing. As part of the 3D printing process, a composite material called CelloCOF was created by combining cellulose nanofibrils (CNF), sodium alginate, and COF materials (i.e., COF-1 and COF-2). The intervention successfully mitigated the agglomeration of the COF nanoparticles, resulting in the creation of abundant active sites that can be effectively utilized for adsorption purposes. The method of 3D printing can be described as a simple and basic procedure that can be adapted to accommodate hierarchical porous materials with distinct micro- and macropore regimes. This technology demonstrates versatility in its use across a range of COF materials. The adsorption capacities of 3D CelloCOF materials were evaluated for three different adsorbates: carbon dioxide (CO2), heavy metal ions, and perfluorooctanesulfonic acid (PFOS). The results showed that the materials exhibited adsorption capabilities of 19.9, 7.4-34, and 118.5-410.8 mg/g for CO2, PFOS, and heavy metals, respectively. The adsorption properties of the material were found to be outstanding, exhibiting a high degree of recyclability and exceptional selectivity. Based on our research findings, it is conceivable that the utilization of custom-designed composites based on COFs could present new opportunities in the realm of water and air purification.
RESUMEN
Biobased adsorbents and membranes offer advantages related to resource efficiency, safety, and fast kinetics but have challenges related to their reusability and water flux. Nanocellulose/alginate composite hydrogel beads were successfully prepared with a diameter of about 3-4 mm and porosity as high as 99%. The beads were further modified with in situ TEMPO-mediated oxidation to functionalize the hydroxyl groups of cellulose and facilitate the removal of cationic pollutants from aqueous samples at low pressure, driven by electrostatic interactions. The increased number of carboxyl groups in the bead matrix improved the removal efficiency of the adsorbent without compromising the water throughput rate; being as high as 17 000 L h-1 m-2 bar-1. The absorptivity of the beads was evaluated with UV-vis for the removal of the dye Methylene Blue (91% removal) from spiked water and energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) elemental analyses for the removal of Cd2+ from industrial mining effluents. The modified beads showed a 3-fold increase in ion adsorption and pose as excellent candidates for the manufacturing of three-dimensional (3-D) column filters for large-volume, high flux water treatment under atmospheric pressure.
RESUMEN
Thermosetting polymeric materials have advantageous properties and are therefore used in numerous applications. In this study, it was hypothesized and ultimately shown that thermosets could be derived from comparably sustainable sub-components. A two-step procedure to produce a thermoset comprising of Kraft lignin (KL) and the cross-linker adipic acid (AdA) was developed. The cross-linking was activated by means of an acetylating agent comprising isopropenyl acetate (IPA) to form a cross-linking mixture (CLM). The cross-linking was confirmed by FTIR and solid-state NMR spectroscopy, and the esterification reactions were further studied using model compounds. When the KL lignin was mixed with the CLM, partial esterification occurred to yield a homogeneous viscous liquid that could easily be poured into a mold, as the first step in the procedure. Without any additions, the mold was heated and the material transformed into a thermoset by reaction of the two carboxylic acid-derivatives of AdA and KL in the second step.
Asunto(s)
Adipatos , Lignina , Calor , Lignina/química , ViscosidadRESUMEN
Whatman® cellulosic filter paper was used as a substrate for the synthesis of two zeolitic imidazolate frameworks (ZIFs); ZIF-8 and ZIF-67 with and without 2,2,6,6-tetramethyl-1-piperidine oxoammonium salt (TEMPO)-oxidized cellulose nanofibril (TOCNF). All synthesis procedures take place at room temperature via a one-pot procedure. The synthesis steps were followed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transforms infrared (FT-IR). Data indicated the formation of metal oxide that converted to a pure phase of ZIFs after the addition of the organic linker i.e. 2-methyl imidazole (Hmim). The materials were characterized using XRD, FT-IR, SEM, energy dispersive X-ray (EDX), nitrogen adsorption-desorption isotherms, and X-ray photoelectron microscope (XPS). Data analysis confirms the synthesis of ZIFs into Whatman® filter paper. The materials were used for the reduction of pollutants such as 4-nitrophenol (4-NP) compound to 4-aminophenol (4-AP). The materials exhibit high potential for water treatment and may open new exploration for hybrid materials consisting of cellulose and ZIFs.
RESUMEN
In this study, we present a facile, one-step method for the manufacturing of all-cellulose, layered membranes containing cellulose nanocrystals (CNC), TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidized cellulose nanofibers (TO-CNF), or zwitterionic polymer grafted cellulose nanocrystals (CNC-g-PCysMA) as functional entities in combination with cellulose fibers and commercial grade microfibrillated cellulose. The presence of active sites such as hydroxyl, carbonyl, thioethers, and amines, gave the membranes high adsorption capacities for the metal ions Au (III), Co (II), and Fe (III), as well as the cationic organic dye methylene blue (MB). Furthermore, the membranes served as excellent metal-free catalysts for the decolorization of dyes via hydrogenation. A 3-fold increase of the hydrogenation efficiency for cationic dyes such as rhodamine B (RhB) and methylene blue was obtained in the presence of membranes compared to NaBH4 alone. Water-based processing, the abundance of the component materials, and the multifunctional characteristics of the membranes ensure their potential as excellent candidates for water purification systems.
Asunto(s)
Celulosa/química , Nanofibras/química , Nanopartículas/química , Purificación del Agua/métodos , Adsorción , Catálisis , Celulosa Oxidada/química , Colorantes/química , Óxidos N-Cíclicos/química , Humanos , Hidrogenación , Iones/química , Membranas/química , Metales/química , Azul de Metileno/química , Polímeros/química , Agua/químicaRESUMEN
This article presents a comparative study of the surface characteristics and water purification performance of commercially available cellulose nonwoven fabrics modified, via cast coating, with different nano-dimensioned bio-based carbohydrate polymers, viz. cellulose nanocrystals (CNC), TEMPO-oxidized cellulose nanofibers (T-CNF), and chitin nanocrystals (ChNC). The surface-modified nonwoven fabrics showed an improvement in wettability, surface charge modification, and a slight decrease of maximum pore size. The modification improved the water permeance in most of the cases, enhanced the particle separation performance in a wide range of sizes, upgraded the mechanical properties in dry conditions, and showed abiotic antifouling capability against proteins. In addition, T-CNF and ChNC coatings proved to be harmful to the bacteria colonizing on the membranes. This simple surface impregnation approach based on green nanotechnology resulted in highly efficient and fully bio-based high-flux water filtration membranes based on commercially available nonwoven fabrics, with distinct performance for particle rejection, antifouling and antibacterial properties.
RESUMEN
High flux, monolithic water purification filters based on polylactic acid (PLA) functionalised with fish scale extracted hydroxyapatite (HAp) were prepared by solvent-assisted blending and thermally induced phase separation (TIPS), followed by twin-screw extrusion into filaments and processed via three-dimensional (3D) printing. The printed filters with consistent pore geometry and channel interconnectivity as well as homogenous distribution of HAp in the PLA matrix showed adsorption capabilities towards heavy metals i.e. cadmium (Cd) and lead (Pb) with maximum adsorption capacity of 112.1 mg gHAp -1 and 360.5 mg gHAp -1 for the metal salt of Pb and Cd, respectively. The adsorption was found to be driven by a combination of ion exchange, dissolution and precipitation on HAp and surface complexation.
RESUMEN
Nanocellulose isolation from lignocellulose is a tedious and expensive process with high energy and harsh chemical requirements, primarily due to the recalcitrance of the substrate, which otherwise would have been cost-effective due to its abundance. Replacing the chemical steps with biocatalytic processes offers opportunities to solve this bottleneck to a certain extent due to the enzymes substrate specificity and mild reaction chemistry. In this work, we demonstrate the isolation of sulphate-free nanocellulose from organosolv pretreated birch biomass using different glycosyl-hydrolases, along with accessory oxidative enzymes including a lytic polysaccharide monooxygenase (LPMO). The suggested process produced colloidal nanocellulose suspensions (ζ-potential -19.4 mV) with particles of 7-20 nm diameter, high carboxylate content and improved thermostability (To = 301 °C, Tmax = 337 °C). Nanocelluloses were subjected to post-modification using LPMOs of different regioselectivity. The sample from chemical route was the least favorable for LPMO to enhance the carboxylate content, while that from the C1-specific LPMO treatment showed the highest increase in carboxylate content.