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The aim of this work was to develop new method for the production of chitosan/agarose (CHN/A) film that could serve as a potential artificial skin substitute for regenerative medicine applications. Within this new production method, the concentrations of biomaterial components (chitosan in CH3COOH and agarose in NaOH) were optimized to provide neutralization of the resultant mixture up to pH approx. 6.0 without uncontrolled precipitation (gelation) of chitosan constituent. Produced thin film was subjected to comprehensive evaluation of its biomedical potential by determination of mechanical, physicochemical, and biological properties. It was demonstrated that the developed CHN/A film reveals slightly acidic pH of 5.98 known to support skin regeneration, high exudate absorption capacity, and is prone to biodegradation in simulated enzymatic wound environment. Performed tensile test proved high elastic deformations of the film (Young's modulus = 0.02 MPa, elongation at break = 23%) in a wet state, which would allow suitable stretching after application at the wound site. Moreover, novel biomaterial is non-toxic and supports fibroblast growth on its surface. Based on the obtained results it may be concluded that the produced CHN/A film possesses all necessary features of the artificial skin substitute.

Composite structures exhibiting a periodic arrangement of building blocks can be found in natural systems at different length scales. Recreating such systems in artificial composites using the principles of self-assembly has been a great challenge, especially for 1D microscale systems. Here, we present a purposely designed composite material consisting of gold nanoparticles and a nematic liquid crystal matrix that has the ability to self-create a periodic structure in the form of a one-dimensional photonic lattice through a phase separation process occurring in a confined space. Our strategy is based on the use of a thermoswitchable medium that reversibly and quickly responds to both heating and cooling. We find that the period of the structure is strongly related to the size of the confining space. We believe that our findings will allow us to not only better understand the phase separation process in multicomponent soft/colloid mixtures with useful optical properties but also improve our understanding of the precise assembly of advanced materials into one-dimensional periodic systems, with prospective applications in future photonic technologies.

The reaction of monolayer graphene with aryl diazonium salts is a popular approach for functionalizing graphene under ambient conditions. We here apply interference reflection microscopy (IRM), a label-free optical technique, to study the in situ reaction dynamics of the representative diazonium reaction of graphene with 4-nitrobenzenediazonium tetrafluoroborate (4-NBD) at high spatiotemporal resolution and further correlate results with atomic force microscopy, Raman spectroscopy, and infrared scattering scanning near-field optical microscopy. Interestingly, we find the reaction to be significantly promoted by a low (0.5 W/cm2) level of blue visible light, whereas at the same intensity level, red light has negligible effects on reaction rate. We further report rich spatial heterogeneities for the reaction, including enhanced reactivity at graphene edges and an unexpected flake-to-flake variation in reaction rate. Moreover, we demonstrate direct photopatterning for the 4-NBD functionalization, achieving 400 nm patterning resolution.

Composite, helical nanostructures formed using cooperative interactions of liquid crystals and Au nanoparticles were studied using a scanning transmission electron microscopy (STEM) mode. The investigated helical assemblies exhibit long-range hierarchical order across length scales, as a result of the crystallization (freezing) directed growth mechanism of nanoparticle-coated twisted nanoribbons and their ability to form organized bundles. Here, STEM methods were used to reproduce the 3D structure of the Au nanoparticle double helix.

Modern bone tissue engineering is based on the use of implants in the form of biomaterials, which are used as scaffolds for osteoprogenitor or stem cells. The task of the scaffolds is to temporarily sustain the function, proliferation and differentiation of bone tissue to enable its regeneration. The aim of this work is to use the macro ATR-FTIR spectroscopic imaging for analysis of the ceramic-based biomaterial (chitosan/β-1,3-glucan/hydroxyapatite). Specifically, during long-term culture of mesenchymal cells derived from adipose tissue (ADSCs) and bone marrow (BMDSCs) on the surface of scaffold. Infrared spectroscopy allows the acquisition of information on both the organic and inorganic parts of the tested composite. This innovative spectroscopic approach proved to be very suitable for studying the formation of new bone tissue and ECM components, sample staining and demineralization are not required and consequently the approach is rapid and cost-effective. The novelty of this study focuses on the innovatory use of ATR-FTIR imaging to evaluate the molecular structure and maturity of collagen as well as mineral matrix formation and crystallization in the context of bone regenerative medicine. Our research has shown that the biomaterial investigated on this work facilitates the formation of valid bone ECM of the stem cells types studied, as a result of the synthesis of type I collagen and mineral content deposition. Nevertheless, ADSC cells have been proven to produce a greater amount of collagen with a lower content of helical secondary structures, at the same time showing a higher mineralization intensity compared to BMDSC cells. Considering the above results, it could be stated that the developed scaffold is a promising material for biomedical applications, including modification of bone implants to increase their biocompatibility.

Under ambient conditions, the behavior of a solid surface is often dominated by a molecularly thin adsorbed layer (adlayer) of small molecules. Here we develop an optical approach to unveil the nanoscale structure and composition of small-molecule adlayers on glass surfaces through spectrally resolved super-resolution microscopy. By recording the images and emission spectra of millions of individual solvatochromic molecules that turn fluorescent in the adlayer phase, we obtain ~30 nm spatial resolution and achieve concurrent measurement of local polarity. This allows us to establish that the adlayer dimensionality gradually increases through a sequence of 0D (nanodroplets), 1D (nano-lines), and 2D (films) for liquids of increasing polarity. Moreover, we find that in adlayers, a solution of two miscible liquids spontaneously demixes into nanodroplets of different compositions that correlate strongly with droplet size and location. We thus reveal unexpectedly rich structural and compositional behaviors of surface adlayers at the nanoscale., Characterization of adsorbed molecular layers on surfaces is the key to wide-ranging applications, but elucidating the structure and composition of such adlayers remains challenging. Here the authors develop an approach to unveil the nanoscale structure and composition of adlayers through spectrally resolved super-resolution microscopy.

The potential of rising two-dimensional materials, such as graphene, can be substantially expanded through chemistry. However, it has been a challenge to study how chemical reactions of two-dimensional materials progress. Existing techniques offer limited signal contrast and/or spatial-temporal resolution and are difficult to apply to in situ studies. Here we employ an optical approach, namely interference reflection microscopy, to quantitatively monitor the redox reaction dynamics of graphene and graphene oxide (GO) in situ with diffraction-limited (∼300 nm) spatial resolution and video-rate time resolution. Remarkably, we found that the oxidation kinetics of graphene is characterized by a seeded, autocatalytic process that gives rise to unique, wave-like propagation of reaction in two dimensions. The reaction is initially slow and confined to highly localized, nanoscale hot spots associated with structural defects, but then self-accelerates while propagating outward, hence flower-like, micrometer-sized reaction patterns over the entire sample. In contrast, the reduction of GO is spatially homogeneous and temporally pseudo-first-order, and through in situ data, we further identify pH as a key reaction parameter.

Highly reactive bioceramics deprive culture medium of Ca 2+ ions which is lethal to the cells in vitro . The aim of this work was to demonstrate that new method for HA/glucan scaffold fabrication, involving calcium as a cross-linker for β-1,3-glucan gel, may support cell survival in vitro when highly reactive bioceramics are the component of the biomaterial. Two composites made of highly reactive hydroxyapatite (HA) and β-1,3-glucan were prepared basing on 2 different methods. Then, ion reactivity of the materials and cell behaviour on their surfaces were compared. Obtained results proved that new method for HA/β-1,3-glucan fabrication protects against Ca 2+ uptake by reactive HA supporting osteoblast growth in vitro .

Low-temperature atmospheric pressure plasma was demonstrated to have an ability to generate different reactive oxygen and nitrogen species (RONS), showing wide biological actions. Within this study, mesoporous silica nanoparticles (NPs) and FexOy/NPs catalysts were produced and embedded in the polysaccharide matrix of chitosan/curdlan/hydroxyapatite biomaterial. Then, basic physicochemical and structural characterization of the NPs and biomaterials was performed. The primary aim of this work was to evaluate the impact of the combined action of cold nitrogen plasma and the materials produced on proliferation and osteogenic differentiation of human adipose tissue-derived mesenchymal stem cells (ADSCs), which were seeded onto the bone scaffolds containing NPs or FexOy/NPs catalysts. Incorporation of catalysts into the structure of the biomaterial was expected to enhance the formation of plasma-induced RONS, thereby improving stem cell behavior. The results obtained clearly demonstrated that short-time (16s) exposure of ADSCs to nitrogen plasma accelerated proliferation of cells grown on the biomaterial containing FexOy/NPs catalysts and increased osteocalcin production by the cells cultured on the scaffold containing pure NPs. Plasma activation of FexOy/NPs-loaded biomaterial resulted in the formation of appropriate amounts of oxygen-based reactive species that had positive impact on stem cell proliferation and at the same time did not negatively affect their osteogenic differentiation. Therefore, plasma-activated FexOy/NPs-loaded biomaterial is characterized by improved biocompatibility and has great clinical potential to be used in regenerative medicine applications to improve bone healing process.

International audience; In this article, we show how advanced hierarchical structures of topological defects in the so-called smectic oily streaks can be used to sequentially transfer their geometrical features to gold nanospheres. We use two kinds of topological defects, 1D dislocations and 2D ribbon-like topological defects. The large trapping efficiency of the smectic dislocation cores not only surpasses that of the elastically distorted zones around the cores but also the one of the 2D ribbon-like topological defect. This enables the formation of a large number of aligned NP chains, within the dislocation cores that can be quasi-fully filled without any significant aggregation outside the cores. When the NP concentration is large enough to entirely fill the dislocation cores, the LC confinement varies from 1D to 2D. We demonstrate that the 2D topological defect cores induce a confinement that leads to planar hexagonal networks of NPs. We then draw the phase diagram driven by NP concentration, associated with the sequential confinements induced by these two kinds of topological defects. Owing to the excellent large-scale order of these defect cores, not only the NP chains but also the NP hexagonal networks can be oriented along the desired direction, suggesting a possible new route for the creation of either 1D or 2D highly anisotropic NP networks. In addition, these results open rich perspectives based on the possible creation of coexisting NP assemblies of different kinds, localized in different confining areas of a same smectic film that would thus interact thanks to their proximity but also would interact via the surrounding soft matter matrix.

The availability of helical assemblies of plasmonic nanoparticles with precisely controlled and tunable structures can play a key role in the future development of chiral plasmonics and metamaterials. Here, a strategy to efficiently yield helical structures based on the cooperative interactions of liquid crystals and gold nanoparticles in thin films is developed. These nanocomposites exhibit exceptional long-range hierarchical order across length scales, which results from the growth mechanism of nanoparticle-coated twisted nanoribbons and their ability to form organized bundles. The helical assembly formation is governed by the presence of rationally functionalized nanoparticles. Importantly, the thickness of the achieved nanocomposites can be reversibly reconfigured owing to the polymorphic nature of the liquid crystal. The versatility of the proposed approach is demonstrated by preparing helices assembled from nanoparticles of different geometries and dimensions (spherical and rod-like). The described strategy may become an enabling technology for structuring nanoparticle assemblies with high precision and fabricating optically active materials.

Robust synthesis of large-scale self-assembled nanostructures with long-range organization and a prominent response to external stimuli is critical to their application in functional plasmonics. Here, the first example of a material made of liquid crystalline nanoparticles which exhibits UV-light responsive surface plasmon resonance in a condensed state is presented. To obtain the material, metal cores are grafted with two types of organic ligands. A promesogenic derivative softens the system and induces rich liquid crystal phase polymorphism. Second, an azobenzene derivative endows nanoparticles with photoresponsive properties. It is shown that nanoparticles covered with a mixture of these ligands assemble into long-range ordered structures which exhibit a novel dual-responsivity. The structure and plasmonic properties of the assemblies can be controlled by a change in temperature as well as by UV-light irradiation. These results present an efficient way to obtain bulk quantities of self-assembled nanostructured materials with stability that is unattainable by alternative methods such as matrix-assisted or DNA-mediated organization.

In this work, we report a study of two thermotropic liquid crystalline samples showing a not common mesophase behavior. The samples, namely a di-benzyloxy biphenyl derivative labelled 9/2 RS/RS, and a bimesogenic liquid crystal labelled L1, show a direct transition between two isotropic phases followed, at lower temperatures, by the optically isotropic, 3D structured, cubic phase. These systems have been investigated by means of 1H NMR diffusometry and 1H NMR relaxometry in order to characterize their isotropic&ndash, isotropic&rsquo, &ndash, cubic mesophase behavior, mainly on the dynamic point of view. In particular, the temperature trend of the self-diffusion coefficients measured for both samples allowed us to significantly distinguish between the two isotropic phases, while the temperature dependence of the 1H spin-lattice relaxation time (T1) did not show significant discontinuities at the isotropic&ndash, phase transition. A preliminary analysis of the frequency-dependence of 1H T1 at different temperatures gives information about the main motional processes active in the isotropic mesophases.

Effective management of chronic wounds with excessive exudate may be challenging for medical doctors. Over the years, there has been an increasing interest in the engineering of biomaterials, focusing on the development of polymer-based wound dressings to accelerate the healing of exuding wounds. The aim of this study was to use curdlan, which is known to support wound healing, as a base for the production of superabsorbent hybrid biomaterials (curdlan/agarose and curdlan/chitosan) with the intended use as wound dressings for highly exuding wound management. To evaluate the biomedical potential of the fabricated curdlan-based biomaterials, they were subjected to a comprehensive assessment of their microstructural, physicochemical, and biological properties. The obtained results showed that foam-like biomaterials with highly porous structure (66–77%) transform into soft gel after contact with the wound fluid, acting as typical hydrocolloid dressings. Novel biomaterials have the superabsorbent ability (1 g of the biomaterial absorbs approx. 15 ml of exudate) with horizontal wicking direction while keeping dry edges, and show water vapor transmission rate of approx. 1700–1800 g/m2/day which is recommended for optimal wound healing. Moreover, they are stable in the presence of collagenases, but prone to biodegradation in lysozyme solution (simulated infected wound environment). Importantly, the developed biomaterials are non-toxic and their surface hinders fibroblast attachment, which is essential during dressing changes to avoid damage to newly formed tissues in the wound bed. All mentioned features make the developed biomaterials promising candidates to be used as the wound dressings for the management of chronic wounds with moderate to high exudate.

There are many modern wound dressings that have promising properties for repairing skin damage. However, due to various types of wounds and the problems they cause, there is still a great demand for new, effective healing strategies. The aim of this study was to create superabsorbent wound dressing made of marine-derived polysaccharides (agarose and chitosan) using the freeze-drying method. The secondary goal was its comprehensive evaluation for potential use as an external superabsorbent bandage for wounds with high exudation. Due to the well-known positive effect of ascorbic acid (vitamin C) on the healing process, biomaterial enriched with vitamin C was prepared and compared to the variant without the addition of ascorbic acid. It was shown that the produced foam-like wound dressing had a very porous structure, which was characterized by hydrophilicity, allowing a large amount of human fluids to be absorbed. According to in vitro tests on human fibroblasts, biomaterial was nontoxic and supportive to cell proliferation. Vitamin C-enriched dressing also had the ability to significantly reduce matrix metalloproteinase-2 production and to promote platelet-derived growth factor-BB synthesis by fibroblasts, which is desired during chronic wound treatment. The material has features of the eco-friendly wound care product since it was made of naturally-derived polysaccharides and was proved to be biodegradable. Importantly, despite degradable character, it was stable in the chronic and infected wound microenvironment, maintaining high integrity after 8-week incubation in the enzymatic solutions containing lysozyme and collagenases. The obtained results clearly showed that developed biomaterial possesses all necessary features of the external dressing for the management of exudate from both acute and chronic non-healing wounds.

Permanent orthopedic/dental implants should reveal good osseointegration, which is defined as an ability of the biomaterial to form a direct connection with the surrounding host bone tissue after its implantation into the living organism. Currently, biomaterial osseointegration is confirmed exclusively with the use of in vivo animal tests. This study presents for the first time ex vivo determination of osseointegration process using human trabecular bone explant that was drilled and filled with the chitosan/curdlan/hydroxyapatite biomaterial, followed by its long-term culture under in vitro conditions. Within this study, it was clearly proved that tested biomaterial allows for the formation of the connection with bone explant since osteoblasts, having ability to produce bone extracellular matrix (type I collagen, fibronectin), were detected at a bone-implant interface by confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). Importantly, in this research it was demonstrated by Live/Dead staining and CLSM imaging that human bone explants may stay alive for a long period of time (at least approx. 50 days) during their culture under in vitro conditions. Therefore, ex vivo bone explant, which is a heterogeneous tissue containing many different cell types, may serve as an excellent model to test biomaterial osseointegration during comparative and preliminary studies, reducing animal tests which is compatible with the principles of ‘3Rs’, aiming to Replace, Reduce and Refine the use of animals wherever possible.

Achieving remotely controlled, reversibly reconfigurable assemblies of plasmonic nanoparticles is a prerequisite for the development of future photonic technologies. Here, we obtained a series of gold-nanoparticle-based materials which exhibit long-range order, and which are controlled with light or thermal stimuli. The influence of the metallic core size and organic shell composition on the switchability is considered, with emphasis on achieving light-responsive behavior at room temperature and high yield production of nanoparticles. The latter translates to a wide size distribution of metallic cores but does not prevent their assembly into various, switchable 3D and 2D long-range ordered structures. These results provide clear guidelines as to the impact of size, size distribution, and organic shell composition on self-assembly, thus enhancing the smart design process of multi-responsive nanomaterials in a condensed state, hardly attainable by other self-assembly methods which usually require solvents.

Cellular uptake of nanoparticles (NPs) depends on the nature of the nanobio system including the solid nanocomponents ( e. g., physicochemical properties of NPs), nanobio interfaces ( e. g., protein corona composition), and the cellular characteristics ( e. g., cell type). In this study, we document the role of sex in cellular uptake of NPs as an "overlooked" factor in nanobio interface investigations. We demonstrate that cell sex leads to differences in NP uptake between male and female human amniotic stem cells (hAMSCs), with greater uptake by female cells. hAMSCs are one of the earliest sources of somatic stem cells. The experiments were replicated with primary fibroblasts isolated from the salivary gland of adult male and female donors of similar ages, and again the extent of NP uptake was altered by cell sex. However, in contrast to hAMSCs, uptake was greater in male cells. We also found out that female versus male amniotic stem cells exhibited different responses to reprogramming into induced pluripotent stem cells (iPSCs) by the Yamanaka factors. Thus, future studies should consider the effect of sex on the nanobio interactions to optimize clinical translation of NPs and iPSC biology and to help researchers to better design and produce safe and efficient therapeutic sex-specific NPs.

In this work we studied a newly reported class of nonlinear effects observed in 5CB liquid crystals doped with gold nanoparticles (GNPs). The size of the GNP was determined by direct TEM imaging and by X-ray scattering of the diluted NP solution. GNPs was coated by thiols with the ratio of mesogenic to n-alkyl thiols varying from 1:2 to 1:1. The research involved comparing properties of both undoped and doped 5CB (nematic LC) by infiltrating LC cell and microholes of the photonic crystal fiber (PCF) separately. In our experiment the PCF fiber type LMA-10 made by NKT Photonics as host material has been used.

The discovery and rise of graphene were historically enabled by its ∼10% optical contrast on specialized substrates like oxide-capped silicon. However, substantially lower contrast is obtained on transparent substrates. Moreover, it remains difficult to visualize nanoscale defects in graphene, including voids, cracks, wrinkles, and multilayers, on most device substrates. We report the use of interference reflection microscopy (IRM), a facile, label-free optical microscopy method originated in cell biology, to directly visualize graphene on transparent inorganic and polymer substrates at 30-40% image contrast per graphene layer. Our noninvasive approach overcomes typical challenges associated with transparent substrates, including insulating and rough surfaces, enables unambiguous identification of local graphene layer numbers and reveals nanoscale structures and defects with outstanding contrast and throughput. We thus demonstrate in situ monitoring of nanoscale defects in graphene, including the generation of nanocracks under uniaxial strain, at up to 4× video rate.