Magnetothermal spider silk-based scaffolds for cartilage regeneration.

Developing biocompatible, magnetically controlled polymers is a multifunctional solution to many surgical complications. By combining nanoparticle technology with the latest advancements in polymer materials science, we created a multicomponent hybrid system comprised of a robust native spider silk-based matrix; a Mn0.9Zn0.1Fe2O4 nanoparticles coating to provide a controlled thermal trigger for drug release; and liposomes, which act as drug carriers. Fluorescent microscope images show that the dye loaded into the liposomes is released when the system is exposed to an alternating magnetic field due to heating of ferromagnetic nanoparticles, which had a low Curie temperature (40-46°Ð¡). The silk matrix also demonstrated outstanding biocompatibility, creating a favorable environment for human postnatal fibroblast cell adhesion, and paving the way for their directed growth. This paper describes a complex approach to cartilage regeneration by developing a spider silk-based scaffold with anatomical mechanical properties for controlled drug delivery in a multifunctional autologous matrix-induced chondrogenesis.

Stokes and Anti-Stokes Luminescent Rare-Earth-Doped Tantalum Oxide Nanoparticles.

Doping of nano- and microparticles of oxides with rare earth elements (REEs) is used to fine-tune their structural, optical, and electrochemical properties. On the way to establish the structure-property relationship, we dope tantalum oxide (Ta2O5) particles with REEs to study their effect on the oxide structure and luminescence. Ta2O5 is highly perspective in medicine, catalysis, and optics, but its crystal structure is insufficiently studied. Two synthesis approaches (sol-gel and solvothermal) were used to obtain powders with different textures. Experimental and theoretical studies of amorphous and crystallized tantalum oxide NPs by means of X-ray powder diffraction, Rietveld analysis, EXAFS/XANES spectroscopy, and density functional theory calculations were performed. All samples (doped and undoped) crystallized in orthorhombic phase with no admixtures. It was demonstrated that Ta2O5 is a promising wide-spectrum luminescent material: by combining REEs, both Stokes and anti-Stokes luminescence in the visible region were obtained. By means of optical absorption spectroscopy, it was shown that the prepared samples could be classified as wide band gap semiconductors.

Insight into the adsorptive removal of ibuprofen using porous carbonaceous materials: A review.

Over the last decade, the removal of pharmaceuticals from aquatic bodies has garnered substantial attention from the scientific community. Ibuprofen (IBP), a non-steroidal anti-inflammatory drug, is released into the environment in pharmaceutical waste as well as medical, hospital, and household effluents. Adsorption technology is a highly efficient approach to reduce the IBP in the aquatic environment, particularly at low IBP concentrations. Due to the exceptional surface properties of carbonaceous materials, they are considered ideal adsorbents for the IBP removal of, with high binding capacity. Given the importance of the topic, the adsorptive removal of IBP from effluent using various carbonaceous adsorbents, including activated carbon, biochar, graphene-based materials, and carbon nanostructures, has been compiled and critically reviewed. Furthermore, the adsorption behavior, binding mechanisms, the most effective parameters, thermodynamics, and regeneration methods as well as the cost analysis were comprehensively reviewed for modified and unmodified carbonaceous adsorbents. The compiled studies on the IBP adsorption shows that the IBP uptake of some carbon-based adsorbents is significantly than that of commercial activated carbons. In the future, much attention is needed for practical utilization and upscaling of the research findings to aid the management and sustainability of water resource.

Fluorescent Hybrid Material Based on Natural Spider Silk and Carbon Dots for Bioapplication.

Since the outcome of an operation largely depends on the quality of wound healing, it is one of the most challenging stages in surgery. Today, wound closure is mostly undertaken by means of a surgical suture. Good surgical sutures are biocompatible and biodegradable and possess excellent mechanical properties. Preferably, these sutures demonstrate optical activity for bacteria detection as there is a risk of surgical site infections. In this study, a solution, which fulfills all the requirements for manufacturing a multifunctional hybrid material, is proposed. In this work, a method for the in situ modification of spider silk with fluorescent carbon dots has been developed. The basic concept is the use of silk fibers as both the main framework for tissue regeneration and a carbon source during carbon dot synthesis. The resulting hybrid material exhibits strong photoluminescence in the red region of the spectrum (590 nm) when irradiated with blue light (480 nm). The proposed approach potentially allows for simultaneous wound closure and pathogen detection.

Nanostructured Temperature Indicator for Cold Chain Logistics.

Food, chemicals, agricultural products, drugs, and vaccines should be transported and stored within an appropriate low-temperature range, following cold chain logistics. Violations of the required temperature regime are generally reported by time-temperature indicators; however, current sensors do not cover a sufficiently broad low-temperature range and may lack thermal and photostability. Here, we report a nanostructured solvatochromic temperature indicator formed from cellulose nanocrystals decorated with carbon dots (C-dots). The indicator utilizes a strong nonlinear dependence of photoluminescence of C-dots on the composition of water/dimethyl sulfoxide (DMSO) solvent and a composition-dependent variation of the melting temperature of the water/DMSO mixture. Exceeding the temperature of the frozen mixed solvent above a designated threshold value results in solvent melting, flow, and impregnation of the nanostructured film, thus causing an irreversible change in the intensity and wavelength of photoluminescence emission of the film, which is reported both qualitatively and quantitatively. The indicator covers a temperature range from -68 to +19 °C and is cost-efficient, portable and photo- and thermostable.

Modulating Surface Properties of the Linothele fallax Spider Web by Solvent Treatment.

Linothele fallax (Mello-Leitão) (L. fallax) spider web, a potentially attractive tissue engineering material, was investigated using quantitative peak force measurement atomic force microscopy and scanning electron microscopy with energy dispersive spectroscopy both in its natural state and after treatment with solvents of different protein affinities, namely, water, ethanol, and dimethyl sulfoxide (DMSO). Native L. fallax silk threads are densely covered by globular objects, which constitute their inseparable parts. Depending on the solvent, treating L. fallax modifies its appearance. In the case of water and ethanol, the changes are minor. In contrast, DMSO practically removes the globules and fuses the threads into dense bands. Moreover, the solvent treatment influences the chemistry of the threads' surface, changing their adhesive and, therefore, biocompatibility and cell adhesion properties. On the other hand, the solvent-treated web materials' contact effect on different types of biological matter differs considerably. Protein-rich matter controls humidity better when wrapped in spider silk treated with more hydrophobic solvents. However, carbohydrate plant materials retain more moisture when wrapped in native spider silk. The extracts produced with the solvents were analyzed using nuclear magnetic resonance (NMR) and liquid chromatography-mass spectrometry techniques, revealing unsaturated fatty acids as representative adsorbed species, which may explain the mild antibacterial effect of the spider silk. The extracted metabolites were similar for the different solvents, meaning that the globules were not "dissolved" but "fused into" the threads themselves, being supposedly rolled-in knots of the protein chain.

Hafnium Oxide-Based Nanoplatform for Combined Chemoradiotherapy.

Recently, the combined therapy has become one of the main approaches in cancer treatment. Combining different approaches may provide a significant outcome by triggering several death mechanisms or causing increased damage of tumor cells without hurting healthy ones. The supramolecular nanoplatform based on a high-Z metal reported here is a suitable system for the targeted delivery of chemotherapeutic compounds, imaging, and an enhanced radiotherapy outcome. HfO2 nanoparticles coated with oleic acid and a monomethoxypoly(ethylene glycol)-poly(ε-caprolactone) copolymer shell (nanoplatform) are able to accumulate inside cancer cells and release doxorubicin (DOX) under specific conditions. Neither uncoated nor coated nanoparticles show any cytotoxicity in vitro. DOX loaded onto a nanoplatform demonstrates a lower IC50 value than pure DOX. X-ray irradiation of cancer cells loaded with a nanoplatform shows a higher death rate than that for cells without nanoparticles. These results provide an important foundation for the development of complex nanoscale systems for combined cancer treatment.

ClO2-Loaded Aerogels with Biocide Effect.

In this work, the mechanism of chlorine dioxide's (ClO2) interaction with aerogel surfaces is described for the first time. To determine the mechanism, three types of aerogels (namely, silica, titania, and zirconia composites) were synthesized and characterized using N2 sorption isotherm analysis, X-ray diffraction analysis, scanning electron microscopy, and X-ray photoelectron spectroscopy. The kinetics of the ClO2 interaction mechanism was investigated via ClO2-controlled sorption and desorption at different temperatures. The process was studied through the theoretical calculation of ClO2 interaction with the aerogel surface. The biocide efficiency of the as-synthesized ClO2-loaded aerogels on different bacteria strains was investigated, and efficient microorganism extermination was demonstrated. This system is a disinfectant that can find potential applications in various fields.

Application of extracted ß-glucan from oat for ß-carotene encapsulation.

ABSTRACT: The cell walls of cereals are rich sources of polysaccharide ß-glucan. In this study, the ß-glucan was extracted from oat bran using the hot-water extraction method and dried in a pure powder form. The concentration of the ß-glucan in the extract was determined using the l-cysteine sulfuric acid method. The results showed that the yield of ß-glucan using the hot-water extraction method is the highest compared to its yield achieved by enzymatic, acid, and alkaline methods. In this paper, the usage of the ß-glucan as a coating material for a water-insoluble carotenoid is considered. This study demonstrates for the first time the encapsulation of ß-carotene with modified octanoic acid ß-glucan. It implements to obtain a stable encapsulated polysaccharide-carotenoid system, which has been studied by a set of physicochemical methods and a cytotoxic analysis was performed on the HCT-116 cell line. The SEM image of the resulting encapsulated system is perfectly correlated with the DLS data, which has determined the size of MG capsules at 200 nm. The cytotoxic analysis demonstrates that the cell viability was more than 70%, which indicates its potential using in the food industry.

Native Spider Silk-Based Antimicrobial Hydrogels for Biomedical Applications.

Novel antimicrobial natural polymeric hybrid hydrogels based on hyaluronic acid (HA) and spider silk (Ss) were prepared using the chemical crosslinking method. The effects of the component ratios on the hydrogel characteristics were observed parallel to the primary physicochemical characterization of the hydrogels with scanning electron microscopic imaging, Fourier-transform infrared spectroscopy, and contact angle measurements, which confirmed the successful crosslinking, regular porous structure, exact composition, and hydrophilic properties of hyaluronic acid/spider silk-based hydrogels. Further characterizations of the hydrogels were performed with the swelling degree, enzymatic degradability, viscosity, conductivity, and shrinking ability tests. The hyaluronic acid/spider silk-based hydrogels do not show drastic cytotoxicity over human postnatal fibroblasts (HPF). Hydrogels show extraordinary antimicrobial ability on both gram-negative and gram-positive bacteria. These hydrogels could be an excellent alternative that aids in overcoming antimicrobial drug resistance, which is considered to be one of the major global problems in the biomedical industry. Hyaluronic acid/spider silk-based hydrogels are a promising material for collaborated antimicrobial and anti-inflammatory drug delivery systems for external use. The rheological properties of the hydrogels show shear-thinning properties, which suggest that the hydrogels could be applied in 3D printing, such as in the 3D printing of antimicrobial surgical meshes.

Tantalum oxide nanoparticles as an advanced platform for cancer diagnostics: a review and perspective.

The development of new safe and effective contrast agents (CAs) is a crucial factor to increase the effectiveness of computed tomography (CT). For now, tantalum oxide-based nanoparticles (TaOx NPs) are among the most promising CAs for CT due to their superior properties: high X-ray attenuation coefficient, excellent biocompatibility, and easily modifiable surface chemistry. Compared to the commercially available analogs (iodine-based CAs), TaOx NPs provide better contrast performance, long-circulation, and high safety profiles (reduced exposure of X-rays and CA dosage). Among the investigated nanoparticulate CAs they afford higher cost-effectiveness (Au, Pt, Lu). TaOx NPs can also be easily modified to include other imaging or therapeutic modalities. This review aims to summarize the current state-of-the-art knowledge in the field of tantalum oxide-based CAs used for single or multimodal imaging and theranostic purposes. The design specification of TaOx NPs in terms of size, surface functionalization, composition, and their influence on the contrast performance, toxicity, and pharmacokinetics are discussed. Finally, the future opportunities and challenges of TaOx NPs used as CT CAs are addressed.

Hybrid Spider Silk with Inorganic Nanomaterials.

High-performance functional biomaterials are becoming increasingly requested. Numerous natural and artificial polymers have already demonstrated their ability to serve as a basis for bio-composites. Spider silk offers a unique combination of desirable aspects such as biocompatibility, extraordinary mechanical properties, and tunable biodegradability, which are superior to those of most natural and engineered materials. Modifying spider silk with various inorganic nanomaterials with specific properties has led to the development of the hybrid materials with improved functionality. The purpose of using these inorganic nanomaterials is primarily due to their chemical nature, enhanced by large surface areas and quantum size phenomena. Functional properties of nanoparticles can be implemented to macro-scale components to produce silk-based hybrid materials, while spider silk fibers can serve as a matrix to combine the benefits of the functional components. Therefore, it is not surprising that hybrid materials based on spider silk and inorganic nanomaterials are considered extremely promising for potentially attractive applications in various fields, from optics and photonics to tissue regeneration. This review summarizes and discusses evidence of the use of various kinds of inorganic compounds in spider silk modification intended for a multitude of applications. It also provides an insight into approaches for obtaining hybrid silk-based materials via 3D printing.

Hybrid cellulose nanocrystal/magnetite glucose biosensors.

There exists a high demand for simple and affordable blood glucose monitoring methods. For this purpose, new generations of biosensors are being developed for possible in vivo or dermal use. We present (non)sulphated cellulose nanocrystal/magnetite thin films to act as dermal and oral glucose biosensors. The biocompatible (N-CNC)-Fe3O4 and (S-CNC)-Fe3O4 hybrid systems exhibit peroxidase-like activity, indicated by an almost instant color change when in the presence of glucose and ABTS. Both types of biosensors detect glucose concentrations as low as 5 mM (which corresponds to the level of glucose in biological fluids), with (S-CNC)-Fe3O4 being 1.5 - 2 times as sensitive as (N-CNC)-Fe3O4. Hybrid catalytic activity is more pronounced at room temperature and in acidic environments. The hybrids can therefore be used to determine glucose levels by using sweat and saliva - non-blood bodily secretions which tend to be slightly to moderately acidic and have relatively low glucose levels.

Surfactant-free tantalum oxide nanoparticles: synthesis, colloidal properties, and application as a contrast agent for computed tomography.

With the growing interest of the medical industry in biocompatible nanoparticles (NPs), the current synthetic methods should be adapted to appropriate demands (toxicity, scalability, etc.). Most applications require colloidal systems to be stable not only in water but also in vivo, which represents a major challenge. In this study, biocompatible Ta2O5 NPs were synthesized by a solvothermal method avoiding toxic reagents, and surfactant-free stable hydrosols were obtained and used for computed tomography (CT) imaging. The small hydrodynamic size (2 nm) and colloidal stability of primary NPs were studied by dynamic light scattering (DLS). The particles were characterized by X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Brunauer-Emmett-Teller analysis to confirm their structure and purity. To develop a stable hydrosol preparation protocol, the influence of pH and ultrasonication duration on the stability of Ta2O5 sols was analyzed by DLS and microelectrophoresis. To enhance the understanding of NP behavior in vivo, sol stability in conditions close to physiological (NaCl solutions) was studied in a pH range of 3-9. Hydrosols prepared by the proposed protocol were stable for at least 6 months and exhibited negligible cytotoxicity. Ta2O5 NPs also showed high CT contrast both in theoretical calculations and in vivo (rat gastrointestinal tract).

Hybrid Materials Based on Carbon Nanotubes and Nanofibers for Environmental Applications.

With the advances in material science, hybrid nanomaterials with unique mechanical, electrical, thermal and optical characteristics have been developed. Among them, hybrids based on filamentous forms of carbon, such as carbon nanotubes and carbon nanofibers, in combination with inorganic nanoparticles attract particular attention. Due to the structure and morphology, charge and energy transfer processes lead to synergistic effects that allow the use of less material with higher productivity. To clarify these issues, this review will summarize and discuss the relevant studies of the use of inorganic compounds of various chemical groups in modifying carbon nanomaterials for ecological applications.

Recent Advances in Development of Functional Spider Silk-Based Hybrid Materials.

Silkworm silk is mainly known as a luxurious textile. Spider silk is an alternative to silkworm silk fibers and has much more outstanding properties. Silk diversity ensures variation in its application in nature and industry. This review aims to provide a critical summary of up-to-date fabrication methods of spider silk-based organic-inorganic hybrid materials. This paper focuses on the relationship between the molecular structure of spider silk and its mechanical properties. Such knowledge is essential for understanding the innate properties of spider silk as it provides insight into the sophisticated assembly processes of silk proteins into the distinct polymers as a basis for novel products. In this context, we describe the development of spider silk-based hybrids using both natural and bioengineered spider silk proteins blended with inorganic nanoparticles. The following topics are also covered: the diversity of spider silk, its composition and architecture, the differences between silkworm silk and spider silk, and the biosynthesis of natural silk. Referencing biochemical data and processes, this paper outlines the existing challenges and future outcomes.

Magnetite Hydrosols with Positive and Negative Surface Charge of Nanoparticles: Stability and Effect on the Lifespan of Drosophila melanogaster.

This paper presents sols of uncoated and citric acid-coated Fe3O4 nanoparticles obtained by a combination of coprecipitation and sonochemistry methods. A stable concentrated CA-Fe3O4 sol synthesized by a combination of coprecipitation with an inconvenient Fe2+/Fe3+ ratio, modification with citric acid and US treatment was obtained for the first time. A comparative analysis of the composition and morphology of nanoparticles was performed. The sols are oppositely charged and behave as a typical ferrofluid. The citric acid-modified sol is aggregatively stable over wider ranges of pH and electrolyte concentration, but it becomes less stable with the temperature increase. DLVO calculations showed that steric repulsion forces are a vital factor contributing to increased aggregative stability in a modified Fe3O4 sol. The experiments have revealed the magneto-optical effect in a modified Fe3O4 sol with an electrolyte concentration of 0.025-0.075 M caused by a high potential barrier and a deep secondary minimum in pairwise interaction curves. The "pK spectroscopy" mathematical model to describe the potentiometric curves of synthesized magnetite sols was used for the first time. According to potentiometric titration, the ions of the electrolyte practically do not contribute to formation of a surface charge in modified Fe3O4 with a change in pH due to blocking the magnetite surface by citric acid molecules. Drosophila melanogaster was used as a model to show that Fe3O4 in chronic exposure has a low toxic effect.

Environmentally friendly Au@CNC hybrid systems as prospective humidity sensors.

Both cellulose nanocrystals and gold nanoparticles show immense potential for biological and chemical applications. Gold nanoparticles, which tend to aggregate, are hybridized with cellulose nanocrystals to form stable inorganic-organic hybrids in which nanocellulose acts as a green supporting material for the catalytically active gold nanoparticles. A green synthesis approach was taken, and hydrothermal treatment was used to reduce electrostatic repulsion between the gold nanoparticles and the cellulose nanocrystals to promote heteroaggregation instead of homoaggregation. AFM analysis showed hybrid films to be hygroscopic, suggesting that they would respond to changes in humidity. Laser diffraction and fluorescence quenching were used to determine how hybrid films respond to changes in humidity. Hybrid films were found to respond to changes in humidity quickly, reversibly, and autonomously, making them ideal for use as or in a humidity sensor. Gold nanoparticles were shown to enhance the hybrid response to ambient moisture, causing them to show a linear dependence on changes in humidity, making the hybrid controllable, highly sensitive, and a viable prospective material for humidity sensing applications.

Application of Immobilized Enzymes in Food Industry.

Enzymes are macromolecular biocatalysts, widely used in food industry. In applications, enzymes are often immobilized on inert and insoluble carriers, which increase their efficiency due to multiple reusability. The properties of immobilized enzymes depend on the immobilization method and the carrier type. The choice of the carrier usually concerns the biocompatibility, chemical and thermal stability, insolubility under reaction conditions, capability of easy regeneration and reusability, as well as cost efficiency. In this review, we provide an overview of various carriers for enzyme immobilization, with the primary focus on food industry.