Advances in the Toxicity Assessment of Silver Nanoparticles Derived from a Sphagnum fallax Extract for Monolayers and Spheroids.

The production of nanomaterials through environmentally friendly methods is a top priority in the sustainable development of nanotechnology. This paper presents data on the synthesis of silver nanoparticles using an aqueous extract of Sphagnum fallax moss at room temperature. The morphology, stability, and size of the nanoparticles were analyzed using various techniques, including transmission electron microscopy, Doppler laser velocimetry, and UV-vis spectroscopy. In addition, Fourier transform infrared spectroscopy was used to analyze the presence of moss metabolites on the surface of nanomaterials. The effects of different concentrations of citrate-stabilized and moss extract-stabilized silver nanoparticles on cell viability, necrosis induction, and cell impedance were compared. The internalization of silver nanoparticles into both monolayers and three-dimensional cells spheroids was evaluated using dark-field microscopy and hyperspectral imaging. An eco-friendly method for the synthesis of silver nanoparticles at room temperature is proposed, which makes it possible to obtain spherical nanoparticles of 20-30 nm in size with high bioavailability and that have potential applications in various areas of human life.

Micropatterning of biologically derived surfaces with functional clay nanotubes.

Micropatterning of biological surfaces performed via assembly of nano-blocks is an efficient design method for functional materials with complex organic-inorganic architecture. Halloysite clay nanotubes with high aspect ratios and empty lumens have attracted widespread interest for aligned biocompatible composite production. Here, we give our vision of advances in interfacial self-assembly techniques for these natural nanotubes. Highly ordered micropatterns of halloysite, such as coffee rings, regular strips, and concentric circles, can be obtained through high-temperature evaporation-induced self-assembly in a confined space and shear-force brush-induced orientation. Assembly of these clay nanotubes on biological surfaces, including the coating of human or animal hair, wool, and cotton, was generalized with the indication of common features. Halloysite-coated microfibers promise new approaches in cotton and hair dyeing, medical hemostasis, and flame-retardant tissue applications. An interfacial halloysite assembly on oil microdroplets (Pickering emulsion) and its core-shell structure (functionalization with quantum dots) was described in comparison with microfiber nanoclay coatings. In addition to being abundantly available in nature, halloysite is also biosafe, which makes its spontaneous surface micropatterning prospective for high-performance materials, and it is a promising technique with potential for an industrial scale-up.

This international group of authors unites researchers who pioneered halloysite clay nanotubes for biomaterials, and discloses a new strategy for this nanoclay composite design through interfacial architecture. These results confirm Dr. K. Ariga concept of nanoarchitectonics, and demonstrate promising applications. Assembly of the clay nanotubes on biosurfaces, including the coating of human or animal hair, wool, and cotton, was generalized for the process optimization. Halloysite-coated microfibers promise new approaches in cotton and hair dyeing, and medical hemostasis and flame-retardant tissue applications. Related techniques of interfacial halloysite assembly on oil microdroplets (Pickering emulsion) and its quantum dots core­shell structure for cell imaging are also described. Contrary to many other synthetic nanomaterials, described natural halloysite nanotubes are environmentally safe and abundantly available, thus allowing for scale up of the suggested functional biocomposites.

Architectural design of core-shell nanotube systems based on aluminosilicate clay.

A nanoarchitectural approach to the design of functional nanomaterials based on natural aluminosilicate nanotubes and their catalysis, and practical applications are described in this paper. We focused on the buildup of hybrid core-shell systems with metallic or organic molecules encased in aluminosilicate walls, and nanotube templates for structured silica and zeolite preparation. The basis for such an architectural design is a unique Al2O3/SiO2 dual chemistry of 50 nm diameter halloysite tubes. Their structure and site dependent properties are well combined with biocompatibility, environmental safety, and abundant availability, which makes the described functional systems scalable for industrial applications. In these organic/ceramic hetero systems, we outline drug, dye and chemical inhibitor loading inside the clay nanotubes, accomplished with their silane or amphiphile molecule surface modifications. For metal-ceramic tubule composites, we detailed the encapsulation of 2-5 nm Au, Ru, Pt, and Ag particles, Ni and Co oxides, NiMo, and quantum dots of CdZn sulfides into the lumens or their attachment at the outside surface. These metal-clay core-shell nanosystems show high catalytic efficiency with increased mechanical and temperature stabilities. The combination of halloysite nanotubes with mesoporous MCM-41 silica allowed for a synergetic enhancement of catalysis properties. Finally, we outlined the clay nanotubes' self-assembly into organized arrays with orientation and ordering similar to nematic liquid crystals, and these systems are applicable for life-related applications, such as petroleum spill bioremediation, antimicrobial protection, wound healing, and human hair coloring.

Prokaryotic and eukaryotic toxicity of halloysite decorated with photoactive nanoparticles.

The development of new approaches to treat the growing antibiotic resistance of pathogenic bacterial species is an important task to ensure the future safety of society. Utilization of irradiation of different wavelengths together with nanostructured materials based on metal containing nanoparticles may result in synergetic antibacterial effects. In this paper we aim to show the main conceptions of light-assisted bacteria deactivation techniques and prospects of application of natural clay nanotubes as a carrier for scalable photoactive antibacterial nanomaterials. Halloysite aluminosilicate nanotubes (ca 50 nm diameter, ca. 1.0 µm length) are safe and biocompatible natural materials produced in tons. Their application as a template or a carrier for metal nanoparticles, QDs and organic compounds has already found application in biomedical research, cosmetics, polymers, coatings, catalysis and related applications. Here, we show the toxicity of halloysite decorated with photoactive nanoparticles on prokaryotic and eukaryotic cells. The formation of light active nanostructured materials with this clay as the base is a promising tool for solving the problem of the antibiotic resistance of microorganisms.

Photoinduced Antibacterial Activity and Cytotoxicity of CdS Stabilized on Mesoporous Aluminosilicates and Silicates.

Inactivation of bacteria under the influence of visible light in presence of nanostructured materials is an alternative approach to overcome the serious problem of the growing resistance of pathogenic bacteria to antibiotics. Cadmium sulfide quantum dots are superefficient photocatalytic material suitable for visible light transformation. In this work, CdS nanoparticles with size of less than 10 nm (QDs) were synthesized on the surface of natural and synthetic mesoporous aluminosilicates and silicates (halloysite nanotubes, MCM-41, MCM-41/Halloysite, SBA-15). Materials containing 5-7 wt.% of CdS were characterized and tested as agents for photocatalytic bacteria degradation of Gram-positive S. aureus and Gram-negative E. coli with multiple antibiotic resistance. Eukaryotic cell viability tests were also conducted on the model cancer cells A 459. We found that the carrier affects prokaryotic and eukaryotic toxicity of CdS quantum dots. CdS/MCM-41/HNTs were assumed to be less toxic to eukaryotic cells and possess the most prominent photocatalytic antibacterial efficiency. Under visible light irradiation, it induced 100% bacterial growth inhibition at the concentration of 125 µg/mL and the bacteriostatic effect at the concentration of 63 µg/mL. CdS/MCM-41/HNTs showed 100% E. coli growth inhibition in the concentration of 1000 µg/mL under visible light irradiation.

Natural aluminosilicate nanotubes loaded with RuCo as nanoreactors for Fischer-Tropsch synthesis.

Following nanoarchitectural approach, mesoporous halloysite nanotubes with internal surface composed of alumina were loaded with 5-6 nm RuCo nanoparticles by sequential loading/reduction procedure. Ruthenium nanoclusters were loaded inside clay tube by microwave-assisted method followed by cobalt ions electrostatic attraction to ruthenium during wetness impregnation step. Developed nanoreactors with bimetallic RuCo nanoparticles were investigated as catalysts for the Fischer-Tropsch process. The catalyst with 14.3 wt.% of Co and 0.15 wt.% of Ru showed high activity (СO conversion reached 24.6%), low selectivity to methane (11.9%), CO2 (0.3%), selectivity to C5+ hydrocarbons of 79.1% and chain growth index (α) = 0.853. Proposed nanoreactors showed better selectivity to target products combined with high activity in comparison to the similar bimetallic systems supported on synthetic porous materials. It was shown that reducing agent (NaBH4 or H2) used to obtain Ru nanoclusters at first synthesis step played a very important role in the reducibility and selectivity of resulting RuCo catalysts.

Biodistribution of Quantum Dots-Labelled Halloysite Nanotubes: A Caenorhabditis elegans In Vivo Study.

Halloysite is a promising building block in nanoarchitectonics of functional materials, especially in the development of novel biomaterials and smart coatings. Understanding the behavior of materials produced using halloysite nanotubes within living organisms is essential for their safe applications. In this study, quantum dots of different compositions were synthesized on the surface of modified clay nanotubes, and the biodistribution of this hybrid material was monitored within Caenorhabditis elegans nematodes. The influence of the modification agent as well as the particles' composition on physicochemical properties of hybrid nanomaterials was investigated. Several microscopy techniques, such as fluorescence and dark-field microscopy, were compared in monitoring the distribution of nanomaterials in nematodes' organisms. The effects of QDs-halloysite composites on the nematodes' life cycle were investigated in vivo. Our fluorescent hybrid probes induced no acute toxic effects in model organisms. The stable fluorescence and low toxicity towards the organisms suggest that the proposed synthesis procedure yields safe nanoarchitectonic materials that will be helpful in monitoring the behavior of nanomaterials inside living cells and organisms.

Clay Nanotube Immobilization on Animal Hair for Sustained Anti-Lice Protection.

Topical administration of drugs is required for the treatment of parasitic diseases and insect infestations; therefore, fabrication of nanoscale drug carriers for effective insecticide topical delivery is needed. Here we report the enhanced immobilization of halloysite tubule nanoclay onto semiaquatic capybaras which have hydrophobic hair surfaces as compared to their close relatives, land-dwelling guinea pigs, and other agricultural livestock. The hair surface of mammals varies in hydrophobicity having a cortex surrounded by cuticles. Spontaneous 1-2 µm thick halloysite hair coverages on the semi-aquatic rodent capybara, non-aquatic rodent guinea pig, and farm goats were compared. The best coating was found for capybara due to the elevated 5 wt% wax content. As a result, we suggest hair pretreatment with diluted wax for enhanced nanoclay adsorption. The formation of a stable goat hair coverage with a 2-3 µm halloysite layer loaded with permethrin insecticide allowed for long-lasting anti-parasitic protection, enduring multiple rain wettings and washings. We expect that our technology will find applications in animal parasitosis protection and may be extended to prolonged human anti-lice treatment.

Ru/CdS Quantum Dots Templated on Clay Nanotubes as Visible-Light-Active Photocatalysts: Optimization of S/Cd Ratio and Ru Content.

A nanoarchitectural approach based on in situ formation of quantum dots (QDs) within/outside clay nanotubes was developed. Efficient and stable photocatalysts active under visible light were achieved with ruthenium-doped cadmium sulfide QDs templated on the surface of azine-modified halloysite nanotubes. The catalytic activity was tested in the hydrogen evolution reaction in aqueous electrolyte solutions under visible light. Ru doping enhanced the photocatalytic activity of CdS QDs thanks to better light absorption and electron-hole pair separation due to formation of a metal/semiconductor heterojunction. The S/Cd ratio was the major factor for the formation of stable nanoparticles on the surface of the azine-modified clay. A quantum yield of 9.3 % was reached by using Ru/CdS/halloysite containing 5.2 wt % of Cd doped with 0.1 wt % of Ru and an S/Cd ratio of unity. In vivo and in vitro studies on the CdS/halloysite hybrid demonstrated the absence of toxic effects in eukaryotic cells and nematodes in short-term tests, and thus they are promising photosensitive materials for multiple applications.

Ruthenium-Loaded Halloysite Nanotubes as Mesocatalysts for Fischer-Tropsch Synthesis.

Halloysite aluminosilicate nanotubes loaded with ruthenium particles were used as reactors for Fischer-Tropsch synthesis. To load ruthenium inside clay, selective modification of the external surface with ethylenediaminetetraacetic acid, urea, or acetone azine was performed. Reduction of materials in a flow of hydrogen at 400 °C resulted in catalysts loaded with 2 wt.% of 3.5 nm Ru particles, densely packed inside the tubes. Catalysts were characterized by N2-adsorption, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray fluorescence, and X-ray diffraction analysis. We concluded that the total acidity and specific morphology of reactors were the major factors influencing activity and selectivity toward CH4, C2-4, and C5+ hydrocarbons in the Fischer-Tropsch process. Use of ethylenediaminetetraacetic acid for ruthenium binding gave a methanation catalyst with ca. 50% selectivity to methane and C2-4. Urea-modified halloysite resulted in the Ru-nanoreactors with high selectivity to valuable C5+ hydrocarbons containing few olefins and a high number of heavy fractions (α = 0.87). Modification with acetone azine gave the slightly higher CO conversion rate close to 19% and highest selectivity in C5+ products. Using a halloysite tube with a 10-20-nm lumen decreased the diffusion limitation and helped to produce high-molecular-weight hydrocarbons. The extremely small C2-C4 fraction obtained from the urea- and azine-modified sample was not reachable for non-templated Ru-nanoparticles. Dense packing of Ru nanoparticles increased the contact time of olefins and their reabsorption, producing higher amounts of C5+ hydrocarbons. Loading of Ru inside the nanoclay increased the particle stability and prevented their aggregation under reaction conditions.

Development of Marine Antifouling Epoxy Coating Enhanced with Clay Nanotubes.

An antifouling epoxy resin doped with natural clay nanotubes that are loaded with biocide or silver allowed extended protection against the proliferation of marine microorganisms. Compared to the 2-3 months of protection with antifoulant dichlorooctylisothiazolone (DCOIT) directly admixed into epoxy resin, the DCOIT release time of the halloysite formulations was extended to 12 months by incorporating biocide-loaded nanoclay in the polymer matrix. The protective properties of the epoxy-halloysite nanocomposites showed much less adhesion and proliferation of marine bacteria Vibrio natriegens on the resin surface after a two-month exposure to seawater than the coating formulations directly doped with non-encapsulated DCOIT. The coating formulation protection efficiency was further confirmed by twelve-month shallow field tests in the South China Sea. Replacing 2 wt.% biocide in the traditional formula with DCOIT-loaded natural environmentally friendly halloysite clay drastically improved the antifouling properties of the epoxy coating, promising scalable applications in protective marine coating. The antifouling property of epoxy resin was enhanced with silver particles synthesized on halloysite nanotubes. A natural mixture of MnO particles and halloysite could also be used as a nonbiocide additive to marine coating. The short-term White Sea water test of epoxy coating with 5% of Ag-halloysite composite of MnO-halloysite natural mixture showed no visible fouling.

Antimicrobial Applications of Clay Nanotube-Based Composites.

Halloysite nanotubes with different outer surface/inner lumen chemistry (SiO2/Al2O3) are natural objects with a 50 nm diameter hollow cylindrical structure, which are able to carry functional compounds both inside and outside. They are promising for biological applications where their drug loading capacity combined with a low toxicity ensures the safe interaction of these nanomaterials with living cells. In this paper, the antimicrobial properties of the clay nanotube-based composites are reviewed, including applications in microbe-resistant biocidal textile, paints, filters, and medical formulations (wound dressings, drug delivery systems, antiseptic sprays, and tissue engineering scaffolds). Though halloysite-based antimicrobial materials have been widely investigated, their application in medicine needs clinical studies. This review suggests the scalable antimicrobial nano/micro composites based on natural tubule clays and outlines research and development perspectives in the field.

Templated self-assembly of ordered mesoporous silica on clay nanotubes.

A novel self-assembly strategy of ordered silica arrays on halloysite clay nanotubes allows us to obtain mesoporous MCM-41 materials with enhanced thermal and mechanical stability. The formation of a structured mesoporous silica phase on halloysite is based on the assembly of cationic amphiphilic molecules onto a negative nanotube surface. The resulting MCM-41/halloysite composite demonstrated thermal and mechanical stability up to 1100 °C and 500 MPa showing great potential for application of mesoporous materials as industrial catalyst carriers and adsorbents.

Interfacial Self-Assembly in Halloysite Nanotube Composites.

A self-assembly of clay nanotubes in functional arrays for the production of organized organic/inorganic heterostructures is described. These 50-nm-diameter natural alumosilicate nanotubes are biocompatible. Halloysite allows for 10-20 wt % chemical/drug loading into the inner lumen, and it gives an extended release for days and months (anticorrosion, self-healing, flame-retardant, antifouling, and antibacterial composites). The structured surfaces of the oriented nanotube micropatterns enhance interactions with biological cells, improving their capture and inducing differentiation in stem cells. An encapsulation of the cells with halloysite enables control of their growth and proliferation. This approach was also developed for spill petroleum bioremediation as a synergistic process with Pickering oil emulsification. We produced 2-5-nm-diameter particles (Au, Ag, Pt, Co, Ru, Cu-Ni, Fe3O4, ZrO2, and CdS) selectively inside or outside the aluminosilicate clay nanotubes. The catalytic hydrogenation of benzene and phenol, hydrogen production, impacts of the metal core-shell architecture, the metal particle size, and the seeding density were optimized for high-efficiency processes, exceeding the competitive industrial formulations. These core-shell mesocatalysts are based on a safe and cheap natural clay nanomaterial and may be scaled up for industrial applications.

Fluorescence and Cytotoxicity of Cadmium Sulfide Quantum Dots Stabilized on Clay Nanotubes.

Quantum dots (QD) are widely used for cellular labeling due to enhanced brightness, resistance to photobleaching, and multicolor light emissions. CdS and CdxZn1-xS nanoparticles with sizes of 6⁻8 nm were synthesized via a ligand assisted technique inside and outside of 50 nm diameter halloysite clay nanotubes (QD were immobilized on the tube's surface). The halloysite⁻QD composites were tested by labeling human skin fibroblasts and prostate cancer cells. In human cell cultures, halloysite⁻QD systems were internalized by living cells, and demonstrated intense and stable fluorescence combined with pronounced nanotube light scattering. The best signal stability was observed for QD that were synthesized externally on the amino-grafted halloysite. The best cell viability was observed for CdxZn1-xS QD immobilized onto the azine-grafted halloysite. The possibility to use QD clay nanotube core-shell nanoarchitectures for the intracellular labeling was demonstrated. A pronounced scattering and fluorescence by halloysite⁻QD systems allows for their promising usage as markers for biomedical applications.

Nanoparticles Formed onto/into Halloysite Clay Tubules: Architectural Synthesis and Applications.

Nanoparticles, being objects with high surface area are prone to agglomeration. Immobilization onto solid supports is a promising method to increase their stability and it allows for scalable industrial applications, such as metal nanoparticles adsorbed to mesoporous ceramic carriers. Tubular nanoclay - halloysite - can be an efficient solid support, enabling the fast and practical architectural (inside / outside) synthesis of stable metal nanoparticles. The obtained halloysite-nanoparticle composites can be employed as advanced catalysts, ion-conducting membrane modifiers, inorganic pigments, and optical markers for biomedical studies. Here, we discuss the possibilities to synthesize halloysite decorated with metal, metal chalcogenide, and carbon nanoparticles, and to use these materials in various fields, especially in catalysis and petroleum refinery.

Rapid and Controlled In Situ Growth of Noble Metal Nanostructures within Halloysite Clay Nanotubes.

A rapid (≤2 min) and high-yield low-temperature synthesis has been developed for the in situ growth of gold nanoparticles (NPs) with controlled sizes in the interior of halloysite nanotubes (HNTs). A combination of HAuCl4 in ethanol/toluene, oleic acid, and oleylamine surfactants and ascorbic acid reducing agent with mild heating (55 °C) readily lead to the growth of targeted nanostructures. The sizes of Au NPs are tuned mainly by adjusting nucleation and growth rates. Further modification of the process, through an increase in ascorbic acid, allows for the formation of nanorods (NRs)/nanowires within the HNTs. This approach is not limited to gold-a modified version of this synthetic strategy can also be applied to the formation of Ag NPs and NRs within the clay nanotubes. The ability to readily grow such core-shell nanosystems is important to their further development as nanoreactors and active catalysts. NPs within the tube interior can further be manipulated by the electron beam. Growth of Au and Ag could be achieved under a converged electron beam suggesting that both Au@HNT and Ag@HNT systems can be used for the fundamental studies of NP growth/attachment.

Investigation of the ozonation products of natural complex mixtures using Fourier transform ion cyclotron resonance mass spectrometry.

Natural complex mixtures such as oil and dissolved organic matter play an important role in the economy and in the global carbon cycle. One of the most promising approaches for the investigation of the chemical structure of such substances is the combination of the high-resolution mass spectrometry and selective chemical reactions. Here, we report the investigation of the ozonation products of natural complex mixtures using Fourier transform ion cyclotron resonance mass spectrometry. Ozonation of crude oil results in the appearance of the new compounds with high content (up to 9 atom) of oxygen. Isotopic exchange reaction showed that those oxygen stem from the carbonyl groups. Ozonation of the dissolved organic matter leads to the destruction of the substance and shift towards the region of the saturated compounds.

Formation of metal clusters in halloysite clay nanotubes.

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 µm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube's central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube's wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.