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.

Gelatin/carboxymethyl chitosan/aloe juice hydrogels with skin-like endurance and quick recovery: Preparation, characterization, and properties.

Gelatin-based hydrogels have gained considerable attention due to their resemblance to the extracellular matrix and hydrophilic three-dimensional network structure. Apart from providing an air-permeable and moist environment, these hydrogels optimize the inflammatory microenvironment of the wounds. These properties make gelatin-based hydrogels highly competitive in the field of wound dressings. In this study, a series of composite hydrogels were prepared using gelatin (Gel) and carboxymethyl chitosan (CMCh) as primary materials, glutaraldehyde as a crosslinker, and aloe vera juice as an anti-inflammatory component. The properties of the hydrogel, including its rheological properties, microscopic structures, mechanical properties, swelling ratios, thermal stability, antibacterial properties, and biocompatibility, were investigated. The results demonstrate that the gelatin-based hydrogels exhibit good elasticity and rapid self-healing ability. The hydrogels exhibited slight shear behavior, which is advantageous for skin care applications. Furthermore, the inclusion of aloe vera juice into the hydrogel resulted in a dense structure, improved mechanical properties and enhanced swelling ratio. The Gel/CMCh/Aloe hydrogels tolerate a compressive strength similar to that of human skin. Moreover, the hydrogels displayed excellent cytocompatibility with HFF-1 cells, and exhibited antibacterial activity against E. coli and S. aureus. Lomefloxacin was used as a model drug to study the releasing behavior of the Gel/CMCh/aloe hydrogels. The results showed that the drug was released rapidly at the initial stage, and could continue to be released for 12 h, the maximum releasing rate exceeded 20 %. These findings suggest that the gelatin-based hydrogels hold great promise as effective wound dressings.

Nanoarchitectonics in Materials Science: Method for Everything in Materials Science.

The history of mankind has been accompanied by the development of materials science [...].

Polyurethane/n-Octadecane Phase-Change Microcapsules via Emulsion Interfacial Polymerization: The Effect of Paraffin Loading on Capsule Shell Formation and Latent Heat Storage Properties.

Organic phase-change materials (PCMs) hold promise in developing advanced thermoregulation and responsive energy systems owing to their high latent heat capacity and thermal reliability. However, organic PCMs are prone to leakages in the liquid state and, thus, are hardly applicable in their pristine form. Herein, we encapsulated organic PCM n-Octadecane into polyurethane capsules via polymerization of commercially available polymethylene polyphenylene isocyanate and polyethylene glycol at the interface oil-in-water emulsion and studied how various n-Octadecane feeding affected the shell formation, capsule structure, and latent heat storage properties. The successful shell polymerization and encapsulation of n-Octadecane dissolved in the oil core was verified by confocal microscopy and Fourier-transform infrared spectroscopy. The mean capsule size varied from 9.4 to 16.7 µm while the shell was found to reduce in thickness from 460 to 220 nm as the n-Octadecane feeding increased. Conversely, the latent heat storage capacity increased from 50 to 132 J/g corresponding to the growth in actual n-Octadecane content from 25% to 67% as revealed by differential scanning calorimetry. The actual n-Octadecane content increased non-linearly along with the n-Octadecane feeding and reached a plateau at 66-67% corresponded to 3.44-3.69 core-to-monomer ratio. Finally, the capsules with the reasonable combination of structural and thermal properties were evaluated as a thermoregulating additive to a commercially available paint.

Whole Genome Sequencing of the Novel Probiotic Strain Lactiplantibacillus plantarum FCa3L.

Lactiplantibacillus plantarum is best known for its significant adaptive potential and ability to colonize different ecological niches. Different strains of L. plantarum are widely used as probiotics. To characterize the probiotic potential of the novel L. plantarum FCa3L strain isolated from fermented cabbage, we sequenced its whole genome using the Illumina MiSeq platform. This bacterial isolate had a circular chromosome of 3,365,929 bp with 44.3% GC content and a cyclic phage phiX174 of 5386 bp with 44.7% GC content. The results of in vitro studies showed that FCa3L was comparable with the reference probiotic strain L. plantarum 8PA3 in terms of acid and bile tolerance, adhesiveness, H2O2 production, and acidification rate. The strain 8PA3 possessed higher antioxidant activity, while FCa3L demonstrated superior antibacterial properties. The antibiotic resistance of FCa3L was more relevant to the probiotic strain than that of 8PA3, although a number of silent antibiotic resistance genes were identified in its genome. Genomic evidence to support adhesive and antibacterial properties, biosynthesis of bioactive metabolites, and safety of FCa3L was also presented. Thus, this study confirmed the safety and probiotic properties of L. plantarum FCa3L via complete genome and phenotype analysis, suggesting its potential as a probiotic, although further in vivo investigations are still necessary.

Fireproof Nanocomposite Polyurethane Foams: A Review.

First introduced in 1954, polyurethane foams rapidly became popular because of light weight, high chemical stability, and outstanding sound and thermal insulation properties. Currently, polyurethane foam is widely applied in industrial and household products. Despite tremendous progress in the development of various formulations of versatile foams, their use is hindered due to high flammability. Fire retardant additives can be introduced into polyurethane foams to enhance their fireproof properties. Nanoscale materials employed as fire-retardant components of polyurethane foams have the potential to overcome this problem. Here, we review the recent (last 5 years) progress that has been made in polyurethane foam modification using nanomaterials to enhance its flame retardance. Different groups of nanomaterials and approaches for incorporating them into foam structures are covered. Special attention is given to the synergetic effects of nanomaterials with other flame-retardant additives.

A lipid membrane supported on an artificial extracellular matrix made of polyelectrolyte multilayers: towards nanoarchitectonics at the cellular interface.

To implement a specific function, cells recognize multiple physical and chemical cues and exhibit molecular responses at their interfaces - the boundary regions between the cell lipid-based membrane and the surrounding extracellular matrix (ECM). Mimicking the cellular external microenvironment presents a big challenge in nanoarchitectonics due to the complexity of the ECM and lipid membrane fragility. This study reports an approach for the assembly of a lipid bilayer, mimicking the cellular membrane, placed on top of a polyelectrolyte multilayer cushion made of hyaluronic acid and poly-L-lysine - a nanostructured biomaterial, which represents a 3D artificial ECM. Model proteins, lysozyme and α-lactalbumin, (which have similar molecular masses but carry opposite net charges) have been employed as soluble signalling molecules to probe their interaction with these hybrids. The formation of a lipid bilayer and the intermolecular interactions in the hybrid structure are monitored using a quartz crystal microbalance and confocal fluorescence microscopy. Electrostatic interactions between poly-L-lysine and the externally added proteins govern the transport of proteins into the hybrid. Designed ECM-cell mimicking hybrids open up new avenues for modelling a broad range of cell membranes and ECM and their associated phenomena, which can be used as a tool for synthetic biology and drug screening.

Probing nanoplastics derived from polypropylene face masks with hyperspectral dark-field microscopy.

The high worldwide consumption of cheap plastic goods has already resulted in a serious environmental plastic pollution, exacerbated by piling of disposed personal protective equipment because of the recent outbreak of COVID-19. The aim of this study was to assess the feasibility of dark-field hyperspectral microscopy in the 400-1000 wavelength range for detection of nanoplastics derived from weathered polypropylene masks. A surgical mask was separated to layers and exposed to UV radiation (254 nm) for 192 h. Oxidative degradation of the polypropylene was evidenced by ATR FT-IR analysis. UV treatment for 192 h resulted in generation of differently shaped micro- and nano-sized particles, visualized by dark-field microscopy. The presence of nanoparticles was confirmed by AFM studies. The hyperspectral profiles (400-1000 nm) were collected after every 48 h of the UV treatment. The distinct hyperspectral features faded after prolonged UV exposure, but the assignment of some particles to either blue or white layers of mask could still be made based on spectral characteristics.

Antibiotic Susceptibility Testing with Raman Biosensing.

Antibiotics guard us against bacterial infections and are among the most commonly used medicines. The immediate consequence of their large-scale production and prescription is the development of antibiotic resistance. Therefore, rapid detection of antibiotic susceptibility is required for efficient antimicrobial therapy. One of the promising methods for rapid antibiotic susceptibility testing is Raman spectroscopy. Raman spectroscopy combines fast and contactless acquisition of spectra with good selectivity towards bacterial cells. The antibiotic-induced changes in bacterial cell physiology are detected as distinct features in Raman spectra and can be associated with antibiotic susceptibility. Therefore, the Raman-based approach may be beneficial in designing therapy against multidrug-resistant infections. The surface-enhanced Raman spectroscopy (SERS) and resonance Raman spectroscopy (RRS) additionally provide excellent sensitivity. In this review, we present an analysis of the Raman spectroscopy-based optical biosensing approaches aimed at antibiotic susceptibility testing.

Keratin/alginate hybrid hydrogels filled with halloysite clay nanotubes for protective treatment of human hair.

Keratin/alginate hydrogels filled with halloysite nanotubes (HNTs) have been tested for the protective coating of human hair. Preliminary studies have been conducted on the aqueous colloidal systems and the corresponding hydrogels obtained by using Ca2+ ions as crosslinkers. Firstly, we have investigated the colloidal properties of keratin/alginate/HNTs dispersions to explore the specific interactions occurring between the biomacromolecules and the nanotubes. Then, the rheological properties of the hydrogels have been studied highlighting that the keratin/alginate interactions and the subsequent addition of HNTs facilitate the biopolymer crosslinking. Finally, human hair samples have been treated with the hydrogel systems by the dipping procedure. The protection efficiency of the hydrogels has been evaluated by studying the tensile properties of hair fibers exposed to UV irradiation. In conclusion, keratin/alginate hydrogel filled with halloysite represents a promising formulation for hair protective treatments due to the peculiar structural and rheological characteristics.

Identification of micro- and nanoplastics released from medical masks using hyperspectral imaging and deep learning.

Apart from other severe consequences, the COVID-19 pandemic has inflicted a surge in personal protective equipment usage, some of which, such as medical masks, have a short effective protection time. Their misdisposition and subsequent natural degradation make them huge sources of micro- and nanoplastic particles. To better understand the consequences of the direct influence of microplastic pollution on biota, there is an urgent need to develop a reliable and high-throughput analytical tool for sub-micrometre plastic identification and visualisation in environmental and biological samples. This study evaluated the application of a combined technique based on dark-field enhanced microscopy and hyperspectral imaging augmented with deep learning data analysis for the visualisation, detection and identification of microplastic particles released from commercially available medical masks after 192 hours of UV-C irradiation. The analysis was performed using a separated blue-coloured spunbond outer layer and white-coloured meltblown interlayer that allowed us to assess the influence of the structure and pigmentation of intact and UV-exposed samples on classification performance. Microscopy revealed strong fragmentation of both layers and the formation of microparticles and fibres of various shapes after UV exposure. Based on the spectral signatures of both layers, it was possible to identify intact materials using a convolutional neural network successfully. However, the further classification of UV-exposed samples demonstrated that the spectral characteristics of samples in the visible to near-infrared range are disrupted, causing a decreased performance of the CNN. Despite this, the application of a deep learning algorithm in hyperspectral analysis outperformed the conventional spectral angle mapper technique in classifying both intact and UV-exposed samples, confirming the potential of the proposed approach in secondary microplastic analysis.

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.

Coronas of micro/nano plastics: a key determinant in their risk assessments.

As an emerging pollutant in the life cycle of plastic products, micro/nanoplastics (M/NPs) are increasingly being released into the natural environment. Substantial concerns have been raised regarding the environmental and health impacts of M/NPs. Although diverse M/NPs have been detected in natural environment, most of them display two similar features, i.e.,high surface area and strong binding affinity, which enable extensive interactions between M/NPs and surrounding substances. This results in the formation of coronas, including eco-coronas and bio-coronas, on the plastic surface in different media. In real exposure scenarios, corona formation on M/NPs is inevitable and often displays variable and complex structures. The surface coronas have been found to impact the transportation, uptake, distribution, biotransformation and toxicity of particulates. Different from conventional toxins, packages on M/NPs rather than bare particles are more dangerous. We, therefore, recommend seriously consideration of the role of surface coronas in safety assessments. This review summarizes recent progress on the eco-coronas and bio-coronas of M/NPs, and further discusses the analytical methods to interpret corona structures, highlights the impacts of the corona on toxicity and provides future perspectives.

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.

Probing Diffusive Dynamics of Natural Tubule Nanoclays with Machine Learning.

Reproducibility of the experimental results and object of study itself is one of the basic principles in science. But what if the object characterized by technologically important properties is natural and cannot be artificially reproduced one-to-one in the laboratory? The situation becomes even more complicated when we are interested in exploring stochastic properties of a natural system and only a limited set of noisy experimental data is available. In this paper we address these problems by exploring diffusive motion of some natural clays, halloysite and sepiolite, in a liquid environment. By using a combination of dark-field microscopy and machine learning algorithms, a quantitative theoretical characterization of the nanotubes' rotational diffusive dynamics is performed. Scanning the experimental video with the gradient boosting tree method, we can trace time dependence of the diffusion coefficient and probe different regimes of nonequilibrium rotational dynamics that are due to contacts with surfaces and other experimental imperfections. The method we propose is of general nature and can be applied to explore diffusive dynamics of various biological systems in real time.

DNA/Magnetic Nanoparticles Composite to Attenuate Glass Surface Nanotopography for Enhanced Mesenchymal Stem Cell Differentiation.

Mesenchymal stem cells (MSCs) have extensive pluripotent potential to differentiate into various cell types, and thus they are an important tool for regenerative medicine and biomedical research. In this work, the differentiation of hTERT-transduced adipose-derived MSCs (hMSCs) into chondrocytes, adipocytes and osteoblasts on substrates with nanotopography generated by magnetic iron oxide nanoparticles (MNPs) and DNA was investigated. Citrate-stabilized MNPs were synthesized by the chemical co-precipitation method and sized around 10 nm according to microscopy studies. It was shown that MNPs@DNA coatings induced chondrogenesis and osteogenesis in hTERT-transduced MSCs. The cells had normal morphology and distribution of actin filaments. An increase in the concentration of magnetic nanoparticles resulted in a higher surface roughness and reduced the adhesion of cells to the substrate. A glass substrate modified with magnetic nanoparticles and DNA induced active chondrogenesis of hTERT-transduced MSC in a twice-diluted differentiation-inducing growth medium, suggesting the possible use of nanostructured MNPs@DNA coatings to obtain differentiated cells at a reduced level of growth factors.

Nanomechanical Atomic Force Microscopy to Probe Cellular Microplastics Uptake and Distribution.

The concerns regarding microplastics and nanoplastics pollution stimulate studies on the uptake and biodistribution of these emerging pollutants in vitro. Atomic force microscopy in nanomechanical PeakForce Tapping mode was used here to visualise the uptake and distribution of polystyrene spherical microplastics in human skin fibroblast. Particles down to 500 nm were imaged in whole fixed cells, the nanomechanical characterization allowed for differentiation between internalized and surface attached plastics. This study opens new avenues in microplastics toxicity research.

Label-free identification of microplastics in human cells: dark-field microscopy and deep learning study.

The development of an automatic method of identifying microplastic particles within live cells and organisms is crucial for high-throughput analysis of their biodistribution in toxicity studies. State-of-the-art technique in the data analysis tasks is the application of deep learning algorithms. Here, we propose the approach of polystyrene microparticle classification differing only in pigmentation using enhanced dark-field microscopy and a residual neural network (ResNet). The dataset consisting of 11,528 particle images has been collected to train and evaluate the neural network model. Human skin fibroblasts treated with microplastics were used as a model to study the ability of ResNet for classifying particles in a realistic biological experiment. As a result, the accuracy of the obtained classification algorithm achieved up to 93% in cell samples, indicating that the technique proposed will be a potent alternative to time-consuming spectral-based methods in microplastic toxicity research.

Sequence Does Not Matter: The Biomedical Applications of DNA-Based Coatings and Cores.

Biomedical applications of DNA are diverse but are usually associated with specific recognition of target nucleotide sequences or proteins and with gene delivery for therapeutic or biotechnological purposes. However, other aspects of DNA functionalities, like its nontoxicity, biodegradability, polyelectrolyte nature, stability, thermo-responsivity and charge transfer ability that are rather independent of its sequence, have recently become highly appreciated in material science and biomedicine. Whereas the latest achievements in structural DNA nanotechnology associated with DNA sequence recognition and Watson-Crick base pairing between complementary nucleotides are regularly reviewed, the recent uses of DNA as a raw material in biomedicine have not been summarized. This review paper describes the main biomedical applications of DNA that do not involve any synthesis or extraction of oligo- or polynucleotides with specified sequences. These sequence-independent applications currently include some types of drug delivery systems, biocompatible coatings, fire retardant and antimicrobial coatings and biosensors. The reinforcement of DNA properties by DNA complexation with nanoparticles is also described as a field of further research.