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The use of hexagonal boron nitride (h-BN) as a material for hydrogen storage is attributed to its ability to accommodate atomic and molecular hydrogen. However, the low diffusion barrier of molecular hydrogen within the h-BN structure does not fully explain the long-term stability of hydrogen bubbles observed in experimental work [L. He, H. Wang, L. Chen, X. Wang, H. Xie, C. Jiang, C. Li, K. Elibol, J. Meyer, K. Watanabe, T. Taniguchi, Z. Wu, W. Wang, Z. Ni, X. Miao, C. Zhang, D. Zhang, H. Wang and X. Xie, Nat. Commun., 2019, 10, 2815, https://doi.org/10.1038/s41467-019-10660-9]. Another unresolved inquiry is the method by which hydrogen infiltrates the h-BN layer in a perpendicular direction. In this study, we conducted a comprehensive examination of several aspects that can impact the permeation of hydrogen in the h-BN structure. We employed DFT within the rPBE (DFT-D3(0)) functional to suggest a process for the penetration of atomic hydrogen through the h-BN sheet along the normal direction by sequential hydrogen passivation.

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Novel nanomaterials used for wound healing should have many beneficial properties, including high biological and antibacterial activity. Immobilization of proteins can stimulate cell migration and viability, and implanted Ag ions provide an antimicrobial effect. However, the ion implantation method, often used to introduce a bactericidal element into the surface, can lead to the degradation of vital proteins. To analyze the surface structure of nanofibers coated with a layer of plasma COOH polymer, fibronectin/gentamicin, and implanted with Ag ions, a new X-ray photoelectron spectroscopy (XPS) fitting method is used for the first time, allowing for a quantitative assessment of surface biomolecules. The results demonstrated noticeable changes in the composition of fibronectin- and gentamicin-modified nanofibers upon the introduction of Ag ions. Approximately 60% of the surface chemistry has changed, mainly due to an increase in hydrocarbon content and the introduction of up to 0.3 at.% Ag. Despite the significant degradation of fibronectin molecules, the biological activity of Ag-implanted nanofibers remained high, which is explained by the positive effect of Ag ions inducing the generation of reactive oxygen species. The PCL nanofibers with immobilized gentamicin and implanted silver ions exhibited very significant antipathogen activity to a wide range of Gram-positive and Gram-negative strains. Thus, the results of this work not only make a significant contribution to the development of new hybrid fiber materials for wound dressings but also demonstrate the capabilities of a new XPS fitting methodology for quantitative analysis of surface-related proteins and antibiotics.

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The objective of this research was to develop an environment-friendly and scalable method for the production of self-sanitizing electrospun nanofibers. This was achieved by immobilizing silver nanoparticles (Ag NPs) onto plasma-treated surfaces of biodegradable polycaprolactone (PCL) nanofibers. The plasma deposited polymer layer containing carboxyl groups played a critical role in providing a uniform distribution of Ag NPs on the nanofiber surface. Ag ions were absorbed by electrostatic interaction and then reduced under the action of UV-light. The concentration and release of Ag ions were analyzed using the EDXS/XPS and ICP AES methods, respectively. Although high levels of Ag ions were detected after 3 h of immersion in water, the material retained a sufficient amount of silver nanoparticles on the surface (~2.3 vs. 3.5 at.% as determined by XPS), and the release rate subsequently decreased over the next 69 h. The antipathogenic properties of PCL-Ag were tested against gram-negative and gram-positive bacteria, fungi, and biofilm formation. The results showed that the PCL-Ag nanofibers exhibit significant antimicrobial activity against a wide range of microorganisms, including those that cause human infections. The incorporation of Ag NPs into PCL nanofibers resulted in a self-sanitizing material that can be used in variety of applications, including wound dressings, water treatment, and air filtration. The development of a simple, scalable, and environmentally friendly method for the fabrication of these nanofibers is essential to ensure their widespread use in various industries. The ability to control the concentration and release rate of Ag ions in the PCL nanofibers will be critical to optimize their efficacy while minimizing their potential toxicity to human cells and the environment.

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Diabetic foot ulcers (DFU) are a common complication of Type 2 Diabetes Mellitus (T2DM). Development of bioactive wound healing covers is an important task in medicine. The use of autologous platelet-rich plasma (PRP) consisting of growth factors, cytokines and components of extracellular matrix is a perspective approach for DFU treatment, but we previously found that some T2DM PRP samples have a toxic effect on mesenchymal stem cells (MSCs) in vitro. Here, we covalently immobilized T2DM PRP proteins on polycaprolactone (PCL) nanofibers, and the growth of endothelial cells on the PCL-COOH-PRP was investigated. Additionally, the level of NO reflecting the cytotoxic effects of PRP, angiogenin, and VEGF levels were measured in T2DM PRP samples. The results showed that the application of PCL-COOH-PRP nanofibers allows to remove the cytotoxicity of T2DM PRP and to improve endothelial cell adhesion and proliferative activity. We showed that the origin of T2DM PRP (the level of PRP toxicity or presence/absence of DFU) does not influence the efficiency of cell growth on PCL-COOH-PRP, and on the level of angiogenin, vascular epidermal growth factor (VEGF) in PRP itself.

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Platelet-rich Plasma (PRP) is an ensemble of growth factors, extracellular matrix components, and proteoglycans that are naturally balanced in the human body. In this study, the immobilization and release of PRP component nanofiber surfaces modified by plasma treatment in a gas discharge have been investigated for the first time. The plasma-treated polycaprolactone (PCL) nanofibers were utilized as substrates for the immobilization of PRP, and the amount of PRP immobilized was assessed by fitting a specific X-ray Photoelectron Spectroscopy (XPS) curve to the elemental composition changes. The release of PRP was then revealed by measuring the XPS after soaking nanofibers containing immobilized PRP in buffers of varying pHs (4.8; 7.4; 8.1). Our investigations have proven that the immobilized PRP would continue to cover approximately fifty percent of the surface after eight days.

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The spread of bacterial, fungal, and viral diseases by airborne aerosol flows poses a serious threat to human health, so the development of highly effective antibacterial, antifungal and antiviral filters to protect the respiratory system is in great demand. In this study, we developed ZnO-modified polycaprolactone nanofibers (PCL-ZnO) by treating the nanofiber surface with plasma in a gaseous mixture of Ar/CO2/C2H4 followed by the deposition of ZnO nanoparticles (NPs). The structure and chemical composition of the composite fibers were characterized by SEM, TEM, EDX, FTIR, and XPS methods. We demonstrated high material stability. The mats were tested against Gram-positive and Gram-negative pathogenic bacteria and pathogenic fungi and demonstrated high antibacterial and antifungal activity.

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The use of nanoparticles (NPs) to modify the surface of cotton fabric is a promising approach to endowing the material with a set of desirable characteristics that can significantly expand the functionality, wear comfort, and service life of textile products. Herein, two approaches to modifying the surface of hexagonal boron nitride (h-BN) NPs with a hollow core and a smooth surface by treatment with maleic anhydride (MA) and diethylene triamine (DETA) were studied. The DETA and MA absorption on the surface of h-BN and the interaction of surface-modified h-NPs with cellulose as the main component of cotton were modeled using density functional theory with the extended Perdew-Burke-Ernzerhof functional. Theoretical modeling showed that the use of DETA as a binder agent can increase the adhesion strength of BN NPs to textile fabric due to the simultaneous hydrogen bonds with cellulose and BN. Due to the difference in zeta potentials (-38.4 vs -25.8 eV), MA-modified h-BN NPs form a stable suspension, while DETA-modified BN NPs tend to agglomerate. Cotton fabric coated with surface-modified NPs exhibits an excellent wash resistance and high hydrophobicity with a water contact angle of 135° (BN-MA) and 146° (BN-DETA). Compared to the original textile material, treatment with MA- and DETA-modified h-BN NPs increases heat resistance by 10% (BN-MA fabric) and 15% (BN-DETA fabric). Cotton fabrics coated with DETA- and MA-modified BN NPs show enhanced antibacterial activity against Escherichia coli U20 and Staphylococcus aureus strains and completely prevent the formation of an E. coli biofilm. The obtained results are important for the further development of fabrics for sports and medical clothing as well as wound dressings.

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Currently, new nanomaterials for high-capacity lithium-ion batteries (LIBs) and sodium- ion batteries (SIBs) are urgently needed. Materials combining porous structure (such as representatives of metal-organic frameworks) and the ability to operate both with lithium and sodium (such as transition-metal dichalcogenides) are of particular interest. Our work reports the computational modelling of a new A'-MoS2 structure and its application in LIBs and SIBs. The A'-MoS2 monolayer was dynamically stable and exhibited semiconducting properties with an indirect band gap of 0.74 eV. A large surface area, together with the presence of pores resulted in a high capacity of the A'-MoS2 equal to ~391 mAg-1 at maximum filling for both Li and Na atoms. High adsorption energies and small values of diffusion barriers indicate that the A'-MoS2 is promising in the application of anode material in LIBs and SIBs.

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The role of plasma functionalization of multi-walled carbon nanotubes (MWCNTs) for room-temperature ammonia gas sensors was investigated. Plasma functionalization of MWCNTs with maleic anhydride was carried out at various durations. The active material of the gas sensor was investigated by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was shown that the formation of functional groups on the surface of carbon nanotubes led to an increase in the ammonia sensor response by two to four times. The increase in functionalization duration induced the rise of O/C from 0.28 to 0.335, an increase in sensor resistance, and the distortion of the shape of the I-V curves.

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The treatment of produced water, associated with oil & gas production, is envisioned to gain more significant attention in the coming years due to increasing energy demand and growing interests to promote sustainable developments. This review presents innovative practical solutions for oil/water separation, desalination, and purification of polluted water sources using a combination of porous membranes and plasma treatment technologies. Both these technologies can be used to treat produced water separately, but their combination results in a significant synergistic impact. The membranes functionalized by plasma show a remarkable increase in their efficiency characterized by enhanced oil rejection capability and reusability, while plasma treatment of water combined with membranes and/or adsorbents could be used to soften water and achieve high purity.

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This study focused on the synthesis and characterization of pure curdlan-chitosan foams (CUR/CS), as well as foams containing Ag nanoparticles (CUR/CS/Ag), and their effect on the skin repair of diabetic mice (II type). The layer of antibacterial superabsorbent foam provides good oxygenation, prevents bacterial infection, and absorbs exudate, forming a soft gel (moist environment). These foams were prepared from a mixture of hydrolyzed curdlan and chitosan by lyophilization. To enhance the antibacterial properties, an AgNO3 solution was added to the curdlan/chitosan mixture during the polymerization and was then reduced by UV irradiation. The membranes were further investigated for their structure and composition using optical microscopy, scanning electron microscopy, energy-dispersive spectroscopy, FT-IR spectroscopy, and XPS analysis and modeling. In vivo tests demonstrated that CUR/CS/Ag significantly boosted the regeneration process compared with pure CUR/CS and the untreated control.

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Novel magnetic gas sensors are characterized by extremely high efficiency and low energy consumption, therefore, a search for a two-dimensional material suitable for room temperature magnetic gas sensors is a critical task for modern materials scientists. Here, we computationally discovered a novel ultrathin two-dimensional antiferromagnet V3S4, which, in addition to stability and remarkable electronic properties, demonstrates a great potential to be applied in magnetic gas sensing devices. Quantum-mechanical calculations within the DFT + U approach show the antiferromagnetic ground state of V3S4, which exhibits semiconducting electronic properties with a band gap of 0.36 eV. A study of electronic and magnetic response to the adsorption of various gas agents showed pronounced changes in properties with respect to the adsorption of NH3, NO2, O2, and NO molecules on the surface. The calculated energies of adsorption of these molecules were -1.25, -0.91, -0.59, and -0.93 eV, respectively. Obtained results showed the prospective for V3S4 to be used as effective sensing materials to detect NO2 and NO, for their capture, and for catalytic applications in which it is required to lower the dissociation energy of O2, for example, in oxygen reduction reactions. The sensing and reducing of NO2 and NO have great importance for improving environmental protection and sustainable development.

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The COVID-19 pandemic has raised the problem of efficient, low-cost materials enabling the effective protection of people from viruses transmitted through the air or via surfaces. Nanofibers can be a great candidate for efficient air filtration due to their structure, although they cannot protect from viruses. In this work, we prepared a wide range of nanofibrous biodegradable samples containing Ag (up to 0.6 at.%) and Cu (up to 20.4 at.%) exhibiting various wettability. By adjusting the magnetron current (0.3 A) and implanter voltage (5 kV), the deposition of TiO2 and Ag+ implantation into PCL/PEO nanofibers was optimized in order to achieve implantation of Ag+ without damaging the nanofibrous structure of the PCL/PEO. The optimal conditions to implant silver were achieved for the PCL-Ti0.3-Ag-5kV sample. The coating of PCL nanofibers by a Cu layer was successfully realized by magnetron sputtering. The antiviral activity evaluated by widely used methodology involving the cultivation of VeroE6 cells was the highest for PCL-Cu and PCL-COOH, where the VeroE6 viability was 73.1 and 68.1%, respectively, which is significantly higher compared to SARS-CoV-2 samples without self-sanitizing (42.8%). Interestingly, the samples with implanted silver and TiO2 exhibited no antiviral effect. This difference between Cu and Ag containing nanofibers might be related to the different concentrations of ions released from the samples: 80 µg/L/day for Cu2+ versus 15 µg/L/day for Ag+. The high antiviral activity of PCL-Cu opens up an exciting opportunity to prepare low-cost self-sanitizing surfaces for anti-SARS-CoV-2 protection and can be essential for air filtration application and facemasks. The rough cost estimation for the production of a biodegradable nanohybrid PCL-Cu facemask revealed ~$0.28/piece, and the business case for the production of these facemasks would be highly positive, with an Internal Rate of Return of 34%.

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Copper-coated nanofibrous materials are desirable for catalysis, electrochemistry, sensing, and biomedical use. The preparation of copper or copper-coated nanofibers can be pretty challenging, requiring many chemical steps that we eliminated in our robust approach, where for the first time, Cu was deposited by magnetron sputtering onto temperature-sensitive polymer nanofibers. For the first time, the large-scale modeling of PCL films irradiation by molecular dynamics simulation was performed and allowed to predict the ions penetration depth and tune the deposition conditions. The Cu-coated polycaprolactone (PCL) nanofibers were thoroughly characterized and tested as antibacterial agents for various Gram-positive and Gram-negative bacteria. Fast release of Cu2+ ions (concentration up to 3.4 µg/mL) led to significant suppression of E. coli and S. aureus colonies but was insufficient against S. typhimurium and Ps. aeruginosa. The effect of Cu layer oxidation upon contact with liquid media was investigated by X-ray photoelectron spectroscopy revealing that, after two hours, 55% of Cu atoms are in form of CuO or Cu(OH)2. The Cu-coated nanofibers will be great candidates for wound dressings thanks to an interesting synergistic effect: on the one hand, the rapid release of copper ions kills bacteria, while on the other hand, it stimulates the regeneration with the activation of immune cells. Indeed, copper ions are necessary for the bacteriostatic action of cells of the immune system. The reactive CO2/C2H4 plasma polymers deposited onto PCL-Cu nanofibers can be applied to grafting of viable proteins, peptides, or drugs, and it further explores the versatility of developed nanofibers for biomedical applications use.

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In recent years, bacteria inactivation during their direct physical contact with surface nanotopography has become one of the promising strategies for fighting infection. Contact-killing ability has been reported for several nanostructured surfaces, e.g., black silicon, carbon nanotubes, zinc oxide nanorods, and copper oxide nanosheets. Herein, we demonstrate that Gram-negative antibiotic-resistant Escherichia coli (E. coli) bacteria are killed as a result of their physical destruction while contacting nanostructured h-BN surfaces. BN films, made of spherical nanoparticles formed by numerous nanosheets and nanoneedles with a thickness <15 nm, have been obtained through a reaction of ammonia with amorphous boron. The contact-killing bactericidal effect of BN nanostructures has been compared with a toxic effect of gentamicin released from them. For a wider protection against bacterial and fungal infection, the films have been saturated with a mixture of gentamicin and amphotericin B. Such BN films demonstrate a high antibiotic/antimycotic agent loading capacity and a fast initial and sustained release of therapeutic agents for 170-260 h depending on the loaded dose. The pristine BN films possess high antibacterial activity against E. coli K-261 strain at their initial concentration of 104 cells/mL, attaining >99% inactivation of colony forming units after 24 h, same as gentamicin-loaded (150 µg/cm2) BN sample. The BN films loaded with a mixture of gentamicin (150 and 300 µg/cm2) and amphotericin B (100 µg/cm2) effectively inhibit the growth of E. coli K-261 and Neurospora crassa strains. During immersion in the normal saline solution, the BN film generates reactive oxygen species (ROS), which can lead to accelerated oxidative stress at the site of physical cell damage. The obtained results are valuable for further development of nanostructured surfaces having contact killing, ROS, and biocide release abilities.

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Biodegradable composite nanofibers were electrospun from poly(ε-caprolactone) (PCL) and poly(ethylene oxide) (PEO) mixtures dissolved in acetic and formic acids. The variation of PCL:PEO concentration in the polymer blend, from 5:95 to 75:25, revealed the tunability of the hydrolytic stability and mechanical properties of the nanofibrous mats. The degradation rate of PCL/PEO nanofibers can be increased compared to pure PCL, and the mechanical properties can be improved compared to pure PEO. Although PCL and PEO have been previously reported as immiscible, the electrospinning into nanofibers having restricted dimensions (250-450 nm) led to a microscopically mixed PCL/PEO blend. However, the hydrolytic stability and tensile tests revealed the segregation of PCL into few-nanometers-thin fibrils in the PEO matrix of each nanofiber. A synergy phenomenon of increased stiffness appeared for the high concentration of PCL in PCL/PEO nanofibrous mats. The pure PCL and PEO mats had a Young's modulus of about 12 MPa, but the mats made of high concentration PCL in PCL/PEO solution exhibited 2.5-fold higher values. The increase in the PEO content led to faster degradation of mats in water and up to a 20-fold decrease in the nanofibers' ductility. The surface of the PCL/PEO nanofibers was functionalized by an amine plasma polymer thin film that is known to increase the hydrophilicity and attach proteins efficiently to the surface. The combination of different PCL/PEO blends and amine plasma polymer coating enabled us to tune the surface functionality, the hydrolytic stability, and the mechanical properties of biodegradable nanofibrous mats.

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The immobilization of viable proteins is an important step in engineering efficient scaffolds for regenerative medicine. For example, angiogenin, a vascular growth factor, can be considered a neurotrophic factor, influencing the neurogenesis, viability, and migration of neurons. Angiogenin shows an exceptional combination of angiogenic, neurotrophic, neuroprotective, antibacterial, and antioxidant activities. Therefore, this protein is a promising molecule that can be immobilized on carriers used for tissue engineering, particularly for diseases that are complicated by neurotrophic and vascular disorders. Another highly important and viable protein is apoliprotein A1. Nevertheless, the immobilization of these proteins onto promising biodegradable nanofibers has not been tested before. In this work, we carefully studied the immobilization of human recombinant angiogenin and apoliprotein A1 onto plasma-coated nanofibers. We developed a new methodology for the quantification of the protein density of these proteins using X-ray photoelectron spectroscopy (XPS) and modeled the XPS data for angiogenin and apoliprotein A1 (Apo-A1). These findings were also confirmed by the analysis of immobilized Apo-A1 using fluorescent microscopy. The presented methodology was validated by the analysis of fibronectin on the surface of plasma-coated poly(ε-caprolactone) (PCL) nanofibers. This methodology can be expanded for other proteins and it should help to quantify the density of proteins on surfaces using routine XPS data treatment.

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Due to their good mechanical stability compared to gelatin, collagen or polyethylene glycol nanofibers and slow degradation rate, biodegradable poly-ε-caprolactone (PCL) nanofibers are promising material as scaffolds for bone and soft-tissue engineering. Here, PCL nanofibers were prepared by the electrospinning method and then subjected to surface functionalization aimed at improving their biocompatibility and bioactivity. For surface modification, two approaches were used: (i) COOH-containing polymer was deposited on the PCL surface using atmospheric pressure plasma copolymerization of CO2 and C2H4, and (ii) PCL nanofibers were coated with multifunctional bioactive nanostructured TiCaPCON film by magnetron sputtering of TiC-CaO-Ti3POx target. To evaluate bone regeneration ability in vitro, the surface-modified PCL nanofibers were immersed in simulated body fluid (SBF, 1×) for 21 days. The results obtained indicate different osteoblastic and epithelial cell response depending on the modification method. The TiCaPCON-coated PCL nanofibers exhibited enhanced adhesion and proliferation of MC3T3-E1 cells, promoted the formation of Ca-based mineralized layer in SBF and, therefore, can be considered as promising material for bone tissue regeneration. The PCL-COOH nanofibers demonstrated improved adhesion and proliferation of IAR-2 cells, which shows their high potential for skin reparation and wound dressing.

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A new low-pressure plasma-based approach to activate the surface of BN nanoparticles (BNNPs) in order to facilitate the attachment of folate acid (FA) molecules for cancer-specific therapy is described. Plasma treatment of BNNPs (BNNPsPT) was performed in a radiofrequency plasma reactor using ethylene and carbon dioxide monomers. The carboxyl groups deposited on the surface of BNNPsPT were activated by N,N'-dicyclohexylcarbodiimide (DCC) and participated in the condensation reaction with ethylene diamine (EDA) to form a thin amino-containing layer (EDA-BNNPPT). Then, the DCC-activated FA was covalently bonded with BNNPsPT by a chemical reaction between amino groups of EDA-BNNPsPT and carboxyl groups of FA. Density functional theory calculations showed that the pre-activation of FA by DCC is required for grafting of the FA to the EDA-BNNPsPT. It was also demonstrated that after FA immobilization, the electronic characteristics of the pteridine ring remain unchanged, indicating that the targeting properties of the FA/EDA-BNNPsPT nanohybrids are preserved.

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A rapid increase in the number of antibiotic-resistant bacteria urgently requires the development of new more effective yet safe materials to fight infection. Herein, we uncovered the contribution of different metal nanoparticles (NPs) (Pt, Fe, and their combination) homogeneously distributed over the surface of nanostructured TiCaPCON films in the total antibacterial activity toward eight types of clinically isolated bacterial strains (Escherichia coli K261, Klebsiella pneumoniae B1079k/17-3, Acinetobacter baumannii B1280A/17, Staphylococcus aureus no. 839, Staphylococcus epidermidis i5189-1, Enterococcus faecium Ya-235: VanA, E. faecium I-237: VanA, and E. coli U20) taking into account various factors that can affect bacterial mechanisms: surface chemistry and phase composition, wettability, ion release, generation of reactive oxygen species (ROS), potential difference and polarity change between NPs and the surrounding matrix, formation of microgalvanic couples on the sample surfaces, and contribution of a passive oxide layer, formed on the surface of films, to general kinetics of the NP dissolution. The results indicated that metal ion implantation and subsequent annealing significantly changed the chemistry of the TiCaPCON film surface. This, in turn, greatly affected the shedding of ions, ROS formation, potential difference between film components, and antibacterial activity. The presence of NPs was critical for ROS generation under UV or daylight irradiation. By eliminating the potential contribution of ions and ROS, we have shown that bacteria can be killed using direct microgalvanic interactions. The possibility of charge redistribution at the interfaces between Pt NPs and TiO2 (anatase and rutile), TiC, TiN, and TiCN components was demonstrated using density functional theory calculations. The TiCaPCON-supported Pt and Fe NPs were not toxic for lymphocytes and had no effect on the ability of lymphocytes to activate in response to a mitogen. This study provides new insights into understanding and designing of antibacterial yet biologically safe surfaces.

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