RESUMEN
Nanocellulose is not only a renewable material but also brings functions that are opening new technological opportunities. Here we discuss a special subset of this material, in its fibrillated form, which is produced by aerobic microorganisms, namely, bacterial nanocellulose (BNC). BNC offers distinct advantages over plant-derived counterparts, including high purity and high degree of polymerization as well as crystallinity, strength, and water-holding capacity, among others. More remarkably, beyond classical fermentative protocols, it is possible to grow BNC on non-planar interfaces, opening new possibilities in the assembly of advanced bottom-up structures. In this review, we discuss the recent advances in the area of BNC-based biofabrication of three-dimensional (3D) designs by following solid- and soft-material templating. These methods are shown as suitable platforms to achieve bioadaptive constructs comprising highly interlocked biofilms that can be tailored with precise control over nanoscale morphological features. BNC-based biofabrication opens applications that are not possible by using traditional manufacturing routes, including direct ink writing of hydrogels. This review emphasizes the critical contributions of microbiology, colloid and surface science, as well as additive manufacturing in achieving bioadaptive designs from living matter. The future impact of BNC biofabrication is expected to take advantage of material and energy integration, residue utilization, circularity and social latitudes. Leveraging existing infrastructure, the scaleup of biofabrication routes will contribute to a new generation of advanced materials rooted in exciting synergies that combine biology, chemistry, engineering and material sciences.
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Celulosa , Celulosa/química , Bacterias/metabolismo , Bacterias/química , Nanoestructuras/química , Biopelículas , Hidrogeles/químicaRESUMEN
Chitin, a fascinating biopolymer found in living organisms, fulfills current demands of availability, sustainability, biocompatibility, biodegradability, functionality, and renewability. A feature of chitin is its ability to structure into hierarchical assemblies, spanning the nano- and macroscales, imparting toughness and resistance (chemical, biological, among others) to multicomponent materials as well as adding adaptability, tunability, and versatility. Retaining the inherent structural characteristics of chitin and its colloidal features in dispersed media has been central to its use, considering it as a building block for the construction of emerging materials. Top-down chitin designs have been reported and differentiate from the traditional molecular-level, bottom-up synthesis and assembly for material development. Such topics are the focus of this Review, which also covers the origins and biological characteristics of chitin and their influence on the morphological and physical-chemical properties. We discuss recent achievements in the isolation, deconstruction, and fractionation of chitin nanostructures of varying axial aspects (nanofibrils and nanorods) along with methods for their modification and assembly into functional materials. We highlight the role of nanochitin in its native architecture and as a component of materials subjected to multiscale interactions, leading to highly dynamic and functional structures. We introduce the most recent advances in the applications of nanochitin-derived materials and industrialization efforts, following green manufacturing principles. Finally, we offer a critical perspective about the adoption of nanochitin in the context of advanced, sustainable materials.
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Quitina , Nanoestructuras , Biopolímeros , Quitina/química , Nanoestructuras/químicaRESUMEN
The effective regeneration of weight-bearing bone defects and critical-sized cartilage defects remains a significant clinical challenge. Traditional treatments such as autologous and allograft bone grafting have not been successful in achieving the desired outcomes, necessitating the need for innovative therapeutic approaches. Nucleic acids have attracted significant attention due to their ability to be designed to form discrete structures and programmed to perform specific functions at the nanoscale. The advantages of nucleic acid nanotechnology offer numerous opportunities for in-cell and in vivo applications, and hold great promise for advancing the field of biomaterials. In this review, the current abilities of nucleic acid nanotechnology to be applied in bone and cartilage regeneration are summarized and insights into the challenges and future directions for the development of this technology are provided.
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Ácidos Nucleicos , Nanotecnología , Cartílago , Regeneración Ósea , Materiales BiocompatiblesRESUMEN
The regeneration of weight-bearing bone defects and critical-sized cartilage defects remains a significant challenge. A wide range of nano-biomaterials are available for the treatment of bone/cartilage defects. However, their poor compatibility and biodegradability pose challenges to the practical applications of these nano-based biomaterials. Natural biomaterials inspired by the cell units (e.g., nucleic acids and proteins), have gained increasing attention in recent decades due to their versatile functionality, compatibility, biodegradability, and great potential for modification, combination, and hybridization. In the field of bone/cartilage regeneration, natural nano-based biomaterials have presented an unparalleled role in providing optimal cues and microenvironments for cell growth and differentiation. In this review, we systematically summarize the versatile building blocks inspired by the cell unit used as natural nano-based biomaterials in bone/cartilage regeneration, including nucleic acids, proteins, carbohydrates, lipids, and membranes. In addition, the opportunities and challenges of natural nano-based biomaterials for the future use of bone/cartilage regeneration are discussed.
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Cartílago , Ácidos Nucleicos , Materiales Biocompatibles/farmacología , Regeneración Ósea , Ciclo CelularRESUMEN
A core-satellite-structured surface molecularly imprinted polymer has been synthesized for the enrichment of 3-phenoxybenzaldehyde by pipette tip solid-phase extraction (SPE). In a typical sol-gel process, two silane reagents as functional monomers and 3-phenoxybenzoic acid as the dummy template, the surface imprinting layer was coated on the core-satellite silica microsphere, which formed the core-satellite-structured molecularly imprinted polymer (CSMIP). Compared to the silica-based core-shell ones, this CS-MIP exhibits a stunning surface area (142 m2 g-1) in micrometer size and also overcomes the aggregation trends of core-shell structure in nanoscale. Taking potassium permanganate solution as oxidizer and indicator, the adsorbed 3-phenoxybenzaldehyde can be a quantitatively determined through redox reaction after elution. The value of maximum adsorption capacity and imprinting factor of CS-MIP were calculated to be 87.5 µg mg-1 and 2.13, respectively. These CS-MIPs were packed into commercial pipette tip as the sorbent to concentrate 3-phenoxybenzaldehyde. Under the optimum condition, a liner relationship was achieved in the range 0.200 to 1.00 µg mL-1 and the limit of detection was 81 ng mL-1. Moreover, this customized SPE device exhibits good adsorption capability after six sequential adsorption-desorption cycles, and the high recovery range of 92.2~99.7% of spiked tap water assay demonstrated its potential application for real sample analysis. Graphical abstract Schematic presentation of core-satellite molecularly imprinted polymer preparation strategy and customized pipette tip solid-phase extraction device.
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Benzaldehídos/análisis , Polímeros Impresos Molecularmente/química , Extracción en Fase Sólida/métodos , Adsorción , Benzaldehídos/química , Benzaldehídos/aislamiento & purificación , Benzoatos/química , Colorimetría/métodos , Agua Potable/análisis , Impresión Molecular , Permanganato de Potasio/química , Extracción en Fase Sólida/instrumentación , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/aislamiento & purificaciónRESUMEN
Multiphase (emulsion) gels with internal phase fractions between 0.1 and 0.5 were formulated at low loadings of cellulose nanofibrils (CNF), alginate, and polylactide (PLA). Their properties (rheology and morphology) fitted those of inks used for direct ink writing (DIW). The effect of formulation and composition variables were elucidated after printing cubic scaffolds and other solid designs. The distinctive microstructures that were developed allowed high printing fidelity and displayed limited shrinkage after room temperature and freeze-drying (0 and 5% shrinkage in the out-of-plane and in-plane directions upon freeze-drying, respectively). The CNF added in the continuous phase was shown to be critical to achieve rheology control as an effective interfacial stabilizer and to ensure the printability of the ink toward high structural reliability. We found that the extent of shape retention of the dried scaffolds resulted from the tightly locked internal structure. The PLA that was initially added in the nonpolar or organic phase (0 to 12%) was randomly embedded in the entire scaffold, providing a strong resistance to shrinkage during the slow water evaporation at ambient temperature. No surface collapse or lateral deformation of the dried scaffolds occurred, indicating that the incorporation of PLA limited drying-induced shape failure. It also reduced compression strain by providing better CNF skeletal support, improving the mechanical strength. Upon rewetting, the combination of the hydrophilicity imparted by CNF and alginate together with the highly porous structure of the 3D material and the internal microchannels contributed to high water absorption via capillary and other phenomena (swelling % between â¼400 and 900%). However, no shape changes occurred compared to the initial 3D-printed shape. The swelling of the scaffolds correlated inversely with the PLA content in the precursor emulsion gel, providing a means to regulate the interaction with water given its low surface energy. Overall, the results demonstrate that by compatibilization of the CNF-based hydrophilic and the PLA-based hydrophobic components, it is possible to achieve shape control and retention upon 3D printing, opening the possibility of adopting low-solids inks for DIW into dry objects. The dryable CNF-based 3D structural materials absorb water while being able to support load (high elastic modulus) and maintain the shape upon hydration.
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Celulosa/análogos & derivados , Nanofibras/química , Impresión Tridimensional , Alginatos/química , Emulsiones/química , Geles/química , Interacciones Hidrofóbicas e Hidrofílicas , Poliésteres/químicaRESUMEN
We study the generation and decay of aqueous foams stabilized by sodium dodecyl sulfate (SDS) in the presence of unmodified cellulose nanofibrils (CNF). Together with the rheology of aqueous suspensions containing CNF and SDS, the interfacial/colloidal interactions are determined by quartz crystal microgravimetry with dissipation monitoring, surface plasmon resonance, and isothermal titration calorimetry. The results are used to explain the properties of the air/water interface (interfacial activity and dilatational moduli determined from oscillating air bubbles) and of the bulk (steady-state flow, oscillatory shear, and capillary thinning). These properties are finally correlated to the foamability and to the foam stability. The latter was studied as a function of time by monitoring the foam volume, the liquid fraction, and the bubble size distribution. The shear-thinning effect of CNF is found to facilitate foam formation at SDS concentrations above the critical micelle concentration (cSDS ≥ cmc). Compared with foams stabilized by pure SDS, the presence of CNF enhances the viscosity and elasticity of the continuous phase as well as of the air/water interface. The CNF-containing foams have higher liquid fractions, larger initial bubble sizes, and better stability. Due to charge screening effects caused by sodium counter ions and depletion attraction caused by SDS micelles, especially at high SDS concentrations, CNF forms aggregates in the Plateau borders and nodes of the foam, thus slowing down liquid drainage and bubble growth and improving foam stability. Overall, our findings advance the understanding of the role of CNF in foam generation and stabilization.
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Celulosa/química , Micelas , Nanofibras/química , Dodecil Sulfato de Sodio/química , Tensoactivos/químicaRESUMEN
We report on high-internal-phase, oil-in-water Pickering emulsions that are stable against coalescence during storage. Viscous, edible oil (sunflower) was emulsified by combining naturally derived cellulose nanocrystals (CNCs) and a food-grade, biobased cationic surfactant obtained from lauric acid and L-arginine (ethyl lauroyl arginate, LAE). The interactions between CNC and LAE were elucidated by isothermal titration calorimetry (ITC) and supplementary techniques. LAE adsorption on CNC surfaces and its effect on nanoparticle electrostatic stabilization, aggregation state, and emulsifying ability was studied and related to the properties of resultant oil-in-water emulsions. Pickering systems with tunable droplet diameter and stability against oil coalescence during long-term storage were controllably achieved depending on LAE loading. The underlying stabilization mechanism was found to depend on the type of complex formed, the LAE structures adsorbed on the cellulose nanoparticles (as unimer or as adsorbed admicelles), the presence of free LAE in the aqueous phase, and the equivalent alkane number of the oil phase (sunflower and dodecane oils were compared). The results extend the potential of CNC in the formulation of high-quality and edible Pickering emulsions. The functional properties imparted by LAE, a highly effective molecule against food pathogens and spoilage organisms, open new opportunities in food, cosmetics, and pharmaceutical applications, where the presence of CNC plays a critical role in achieving synergistic effects with LAE.
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Arginina/análogos & derivados , Celulosa/análogos & derivados , Emulsiones/química , Conservantes de Alimentos/química , Nanopartículas/química , Aceite de Girasol/química , Tensoactivos/química , Antiinfecciosos/química , Arginina/química , Electricidad EstáticaRESUMEN
Uniform poly(lactic acid)/cellulose nanocrystal (PLA/CNC) fibrous mats composed of either random or aligned fibers reinforced with up to 20 wt % CNCs were successfully produced by two different electrospinning processes. Various concentrations of CNCs could be stably dispersed in PLA solution prior to fiber manufacture. The microstructure of produced fibrous mats, regardless of random or aligned orientation, was transformed from smooth to nanoporous surface by changing CNC loading levels. Aligning process through secondary stretching during high-speed collection can also affect the porous structure of fibers. With the same CNC loading, fibrous mats produced with aligned fibers had higher degree of crystallinity than that of fibers with random structure. The thermal properties and mechanical performances of PLA/CNC fibrous mats can be enhanced, showing better enhancement effect of aligned fibrous structure. This results from a synergistic effect of the increased crystallinity of fibers, the efficient stress transfer from PLA to CNCs, and the ordered arrangement of electrospun fibers in the mats. This research paves a way for developing an electrospinning system that can manufacture high-performance CNC-enhanced PLA fibrous nanocomposites.
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Nanocompuestos/química , Nanofibras/química , Nanopartículas/química , Poliésteres/química , Nanocompuestos/ultraestructura , Nanofibras/ultraestructura , Nanopartículas/ultraestructuraRESUMEN
Cellulose nanofibrils (CNF) offer great prospects as a natural stabilizer of colloidal dispersions and complex fluids for application in food, pharma, and cosmetics. In this study, an ionic surfactant (sodium dodecyl sulfate, SDS) was used as emulsifier of oil-in-water and water-in-oil emulsions that were further costabilized by addition of CNF. The adsorption properties of SDS in both, CNF dispersions and emulsions, as well as the influence of composition (CNF and SDS concentration) and formulation (ionic strength, oil, and CNF types) on the phase behavior were elucidated and described in the framework of Windsor systems. At low salinity, the phase transition of emulsions containing CNF and SDS at low concentrations was controlled by molecular transfer in the oil-in-water system. Irregular droplets and "bi-continuous" morphologies were observed at medium and high salinity for systems containing high CNF and SDS concentrations. Water-in-oil emulsions were only possible at high salinity and SDS concentrations in the presence of small amounts of CNF. The results revealed some subtle differences in CNF interfacial activity, depending on the method used for their isolation via fiber deconstruction, either from microfluidization or aqueous counter collision. Overall, we propose that the control of emulsion morphology and stability by addition of CNF opens the possibility of developing environmentally friendly complex systems that display high stability and respond to ionic strength following the expectations of classical emulsion systems.
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Celulosa/química , Emulsiones/química , Nanofibras/química , Tensoactivos/química , Química Farmacéutica/métodos , Emulsionantes/química , Concentración Osmolar , Transición de Fase , Dodecil Sulfato de Sodio/química , Agua/químicaRESUMEN
Hair loss is characterized by the inability of hair follicles (HFs) to enter the telogen-anagen transition (TAT) and lack of de novo HFs. Current pharmaceutical therapies and surgical modalities have been largely limited to regulating hair regrowth efficiently without side effects and lacking treatment compliance. Here, this work proposes a materiobiomodulation therapy (MBMT), wherein polydopamine (PDA) nanoparticles with redox activity can be modulated to have a stoichiometric ROS (H2O2) donating ability. These nanoparticles can intracellularly deliver ROS with high-efficiency via the clathrin-dependent endocytosis process. Utilizing homozygote transgenic HyPerion (a genetically-encoded H2O2 biosensor) mice, this work also achieves in vivo dynamic monitoring of intracellular H2O2 elevation induced by ROS donators. Subcutaneous administration with ROS donators results in rapid onset of TAT and subsequent hair regrowth with a specific ROS "hormesis effect." Mechanistically, ROS activate ß-catenin-dependent Wnt signaling, upregulating hair follicle stem cell expression. This work further develops a microneedles patch for transdermal ROS delivery, demonstrating long-term, low-dose ROS release. Unlike photobiomodulation therapy (PBMT), MBMT requires no external stimuli, providing a convenient and efficient approach for clinical hair loss treatment. This material-HF communication implicates new avenues in HF-related diseases, achieving targeted ROS delivery with minimal side effects.
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Folículo Piloso , Indoles , Nanopartículas , Polímeros , Especies Reactivas de Oxígeno , Animales , Folículo Piloso/metabolismo , Folículo Piloso/efectos de los fármacos , Ratones , Indoles/química , Nanopartículas/química , Polímeros/química , Especies Reactivas de Oxígeno/metabolismo , Peróxido de Hidrógeno/metabolismo , Alopecia/terapia , Cabello/crecimiento & desarrollo , Cabello/efectos de los fármacos , Vía de Señalización Wnt/efectos de los fármacos , Humanos , Ratones TransgénicosRESUMEN
Despite the clinical prevalence of various bone defect repair materials, a full understanding of their influence on bone repair and regeneration remains elusive. This study focuses on poly(acrylamide) (PAAm) hydrogels, popular 2D model substrates, which have regulable mechanical properties within physiological. However, their bio-inert nature requires surface biofunctionalization to enhance cell-material interactions and facilitate the study of bone repair mechanisms. We utilized PAAm hydrogels of varying stiffness (18, 76 and 295 kPa), employed sulfosuccinimidyl-6-(4'-azido-2'-nitropheny-lamino) hexanoate (sulfo-SANPAH) and N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride/N-hydroxysuccinimidyl acrylate (EDC/NHS) as crosslinkers, and cultured macrophages, endothelial cells, and bone mesenchymal stem cells on these hydrogels. Our findings indicated that sulfo-SANPAH's crosslinking efficiency surpassed that of EDC/NHS, irrespective of pore size and stiffness. Importantly, we observed that the stiffness and surface biofunctionalization method of hydrogels significantly impacted cell adhesion and proliferation. The collagen-modified hydrogels by EDC/NHS strategy failed to support the normal biological behavior of bone mesenchymal stem cells and hindered endothelial cell spreading. In contrast, these modified hydrogels by the sulfo-SANPAH method showed good cytocompatibility with the three types of cells. This study underscores the critical role of appropriate conjugation strategies for PAAm hydrogels, providing valuable insights for hydrogel surface modification in bone repair and regeneration research.
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Resinas Acrílicas , Azidas , Regeneración Ósea , Células Endoteliales , Succinimidas , Hidrogeles/farmacologíaRESUMEN
Inspired by the self-recoverability ability of organisms, various self-healing materials have been developed. However, most reinforced fillers are faced with the problem that mechanical strength and self-healing efficiency of materials cannot be improved simultaneously. Here we first prepared new polysiloxane-polyurea (PDMS-PU) and used it as matrix resin to prepare cellulose nanofiber (CNF)/PDMS-PU composite materials with high mechanical properties. CNFs increased the tensile strength of PDMS-PU by 38.87 % and CNF/PDMS-PU composite materials maintained the great bending resistance, transparency and reprocessing properties of PDMS-PU. Moreover, the introduction of CNFs did not reduce the self-healing efficiency of PDMS-PU, and PDMS-PU containing disulfide bonds with CNF content of 1 % (CNF/PDMS-IPDI-S-1 %) with healing efficiency of 95.58 %, and the tensile strength after three recycling processing was still as high as 92.55 % of the original. CNFs reinforced PDMS-PU composite materials are expected to replace PDMS materials in advanced engineering fields that require high strength durability and good formability.
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Celulosa , Nanofibras , Celulosa/química , Siloxanos , Nanofibras/química , PolímerosRESUMEN
Macrophages play a crucial role in the complete processes of tissue repair and regeneration, and the activation of M2 polarization is an effective approach to provide a pro-regenerative immune microenvironment. Natural extracellular matrix (ECM) has the capability to modulate macrophage activities via its molecular, physical, and mechanical properties. Inspired by this, an ECM-mimetic hydrogel strategy to modulate macrophages via its dynamic structural characteristics and bioactive cell adhesion sites is proposed. The LZM-SC/SS hydrogel is in situ formed through the amidation reaction between lysozyme (LZM), 4-arm-PEG-SC, and 4-arm-PEG-SS, where LZM provides DGR tripeptide for cell adhesion, 4-arm-PEG-SS provides succinyl ester for dynamic hydrolysis, and 4-arm-PEG-SC balances the stability and dynamics of the network. In vitro and subcutaneous tests indicate the dynamic structural evolution and cell adhesion capacity promotes macrophage movement and M2 polarization synergistically. Comprehensive bioinformatic analysis further confirms the immunomodulatory ability, and reveals a significant correlation between M2 polarization and cell adhesion. A full-thickness wound model is employed to validate the induced M2 polarization, vessel development, and accelerated healing by LZM-SC/SS. This study represents a pioneering exploration of macrophage modulation by biomaterials' structures and components rather than drug or cytokines and provides new strategies to promote tissue repair and regeneration.
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Hidrogeles , Cicatrización de Heridas , Hidrogeles/química , Macrófagos/metabolismo , Materiales Biocompatibles/química , Matriz Extracelular/químicaRESUMEN
Cartilage defects are usually caused by acute trauma and chronic degeneration. However, it is still a great challenge to improve the repair of articular cartilage defects due to the limited self-regeneration capacity of such defects. Herein, a novel ROS-responsive in situ nanocomposite hydrogel loaded with kartogenin (KGN) and bone marrow-derived stem cells (BMSCs) was designed and constructed via the enzymatic reaction of fibrinogen and thrombin. Meanwhile, a ROS-responsive thioketal (TK)-based liposome was synthesized to load the chondrogenesis-inducing factor KGN, the bioenzyme thrombin and an ultrasound-sensitive agent PpIX. Under ultrasound stimulation, the TK-based liposome was destroyed, followed by in situ gelation of fibrinogen and thrombin. Moreover, sustained release of KGN was realized by regulating the ultrasound conditions. Importantly, ROS generation and KGN release within the microenvironment of the in situ fibrin hydrogel significantly promoted chondrogenic differentiation of BMSCs via the Smad5/mTOR signalling pathway and effectively improved cartilage regeneration in a rat articular cartilage defect model. Overall, the novel in situ nanocomposite hydrogel with ROS-controlled drug release has great potential for efficient cartilage repair.
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Cartílago Articular , Células Madre Mesenquimatosas , Ratas , Animales , Especies Reactivas de Oxígeno/metabolismo , Especies Reactivas de Oxígeno/farmacología , Liberación de Fármacos , Liposomas/metabolismo , Liposomas/farmacología , Nanogeles , Trombina/metabolismo , Trombina/farmacología , Células Madre Mesenquimatosas/metabolismo , Cartílago Articular/diagnóstico por imagen , Cartílago Articular/lesiones , Cartílago Articular/metabolismo , HidrogelesRESUMEN
Bone regeneration is a well-orchestrated process involving electrical, biochemical, and mechanical multiple physiological cues. Electrical signals play a vital role in the process of bone repair. The endogenous potential will spontaneously form on defect sites, guide the cell behaviors, and mediate bone healing when the bone fracture occurs. However, the mechanism on how the surface charges of implant potentially guides osteogenesis and osteoimmunology has not been clearly revealed yet. In this study, piezoelectric BaTiO3/ß-TCP (BTCP) ceramics are prepared by two-step sintering, and different surface charges are established by polarization. In addition, the cell osteogenesis and osteoimmunology of BMSCs and RAW264.7 on different surface charges were explored. The results showed that the piezoelectric constant d33 of BTCP was controllable by adjusting the sintering temperature and rate. The polarized BTCP with a negative surface charge (BTCP-) promoted protein adsorption and BMSC extracellular Ca2+ influx. The attachment, spreading, migration, and osteogenic differentiation of BMSCs were enhanced on BTCP-. Additionally, the polarized BTCP ceramics with a positive surface charge (BTCP+) significantly inhibited M1 polarization of macrophages, affecting the expression of the M1 marker in macrophages and changing secretion of proinflammatory cytokines. It in turn enhanced osteogenic differentiation of BMSCs, suggesting that positive surface charges could modulate the bone immunoregulatory properties and shift the immune microenvironment to one that favored osteogenesis. The result provides an alternative method of synergistically modulating cellular immunity and the osteogenesis function and enhancing the bone regeneration by fabricating piezoelectric biomaterials with electrical signals.
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Materiales Biocompatibles , Osteogénesis , Materiales Biocompatibles/farmacología , Fosfatos de Calcio/química , Diferenciación Celular , Citocinas , Propiedades de SuperficieRESUMEN
Polymeric micelle has emerged as an efficient implement to overcome the shortcomings of conventional cancer chemotherapy due to its superior solubility of hydrophobic drugs and less side effects of drugs. However, insufficient dilution resistance and ordinary therapeutic effect severely restrict the further translation of current drug-loaded polymeric micelles. Here, we showed that well-defined G-Fn (n = 5, 9, 13) polymeric micelles possessed excellent capabilities as a drug carrier in light of high drug loading content, high stability and precise drug release combined with wonderful endocytosis efficiency to tumors. The representative G-F13 exhibited an excellent dilution resistance, outstanding high drug loading content (22 wt%) and drug loading efficiency (82%), which might be attributed to the extremely low critical micelle concentration conferred by its special Gemini structure and the superhydrophobicity of the fluorocarbon chain. Furthermore, the "cross-linked" internal fluoride membrane consisted of the two chains of the Gemini structure made G-F13 stable even after 24 h of incubation in 10% fetal bovine serum (FBS). The camptothecin (CPT) release was selectively triggered by glutathione (GSH) and H2O2, reaching 75% and 85% after 24 h respectively, in which only 15% of drugs leak under physiological conditions. The CCK-8 assays of Hela cells showed that CPT-loaded G-F13 micelles had high cell compatibility (200 µg/mL, 93% cell viability, 48 h) and high cancer cytotoxicity (IC50 0.1 µg/mL). Notably, a tenfold lower dosage of loaded CPT had an higher tumor growth inhibition than the free CPT. This result was attributed to the combined treatment of fluorinated drug carriers were more likely to penetrate the cell membrane to enter tumor cells, the cytotoxicity of selenic acid generated after the oxidation of G-F13 and the large amounts of CPT after redox release. Excellent physical and chemical properties as well as good therapeutic effects reveal that G-F13 can act as a promising drug carrier to widely use in cancer chemotherapy.
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Micelas , Neoplasias , Camptotecina/química , Portadores de Fármacos/química , Liberación de Fármacos , Polímeros de Fluorocarbono , Células HeLa , Humanos , Peróxido de Hidrógeno , Neoplasias/tratamiento farmacológico , Oxidación-Reducción , Polímeros/metabolismoRESUMEN
The potential impact of microplastics (MPs) on health has caused great concern, and a toxicology platform that realistically reproduces the system behaviour is urgently needed to further explore and validate MP-related health issues. Herein, we introduce an optically assisted thrombus platform to reveal the interaction of MPs with the vascular system. The risk of accumulation has also been evaluated using a mouse model, and the effect of MPs on the properties of the thrombus are validated via in vitro experiments. The microfluidic system is endothelialized, and the regional tissue injury-induced thrombosis is then realized through optical irradiation. Whole blood is perfused with MPs, and the invasion process visualized and recorded. The mouse model shows a cumulative risk in the blood with continuous exposure to MPs (P-value < 0.0001). The on-chip results show that MP invasion leads to decreased binding of fibrin to platelets (P-value < 0.0001), which is consistent with the results of the in vitro experiments, and shows a high risk of thrombus shedding in real blood flow compared with normal thrombus. This work provides a new method to further reveal MP-related health risks.
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Trombosis , Contaminantes Químicos del Agua , Plaquetas/metabolismo , Humanos , Microfluídica , Microplásticos/toxicidad , Plásticos , Trombosis/inducido químicamente , Trombosis/metabolismo , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/metabolismo , Contaminantes Químicos del Agua/toxicidadRESUMEN
HYPOTHESIS: Nanocellulose and nanochitin are both biobased materials with complementary structures and properties. Both exhibit pH-dependent surface charges which are opposite in sign. Hence, it should be possible to manipulate them to form complexed structures via ionic bond formation at prescribed pH conditions. EXPERIMENT: Nanocellulose and nanochitin were mixed after exposure to acidic or neutral conditions to influence their ionization state. The heat of interaction during the introduction of nanochitin to nanocellulose was monitored via isothermal titration calorimetry. The strength and gel properties of the resulting structures were characterized via rheological measurement. FINDINGS: The resultant gel properties in the designed hybrid systems were found to depend directly on the charge state of the starting materials, which was dictated by pH adjustment. Different interparticle interactions including ionic attraction, hydrophobic associations, and physical entanglement were identified in the systems and the influence of each was elucidated for different conditions of pH, concentration, and ratio of nanochitin to nanocellulose. Hydrophobic associations between neutralized nanochitin particles were found to contribute strongly to increased elastic modulus values. Ionic complex formation was found to provide enhanced stability under broader pH conditions, while physical entanglement of cellulose nanofibers was a substantial thickening mechanism in all systems.
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Celulosa , Nanofibras , Reología , Concentración de Iones de Hidrógeno , Interacciones Hidrofóbicas e HidrofílicasRESUMEN
Recent developments in the area of plant-based hydrogels are introduced, especially those derived from wood as a widely available, multiscale, and hierarchical source of nanomaterials, as well as other cell wall elements. With water being fundamental in a hydrogel, water interactions, hydration, and swelling, all critically important in designing, processing, and achieving the desired properties of sustainable and functional hydrogels, are highlighted. A plant, by itself, is a form of a hydrogel, at least at given states of development, and for this reason phenomena such as fluid transport, diffusion, capillarity, and ionic effects are examined. These aspects are highly relevant not only to plants, especially lignified tissues, but also to the porous structures produced after removal of water (foams, sponges, cryogels, xerogels, and aerogels). Thus, a useful source of critical and comprehensive information is provided regarding the synthesis of hydrogels from plant materials (and especially wood nanostructures), and about the role of water, not only for processing but for developing hydrogel properties and uses.