TiO2-Alginate-Chitosan-Based Composites for Skin Tissue Engineering Applications.

The UV-B component of sunlight damages the DNA in skin cells, which can lead to skin cancer and premature aging. Therefore, it is necessary to use creams that also contain UV-active substances. Many sunscreens contain titanium dioxide due to its capacity to absorb UV-B wavelengths. In the present study, titan dioxide was introduced in alginate and chitosan-alginate hydrogel composites that are often involved as scaffold compositions in tissue engineering applications. Alginate and chitosan were chosen due to their important role in skin regeneration and skin protection. The composites were cross-linked with calcium ions and investigated using FT-IR, Raman, and UV-Vis spectroscopy. The stability of the obtained samples under solar irradiation for skin protection and regeneration was analyzed. Then, the hydrogel composites were assayed in vitro by immersing them in simulated body fluid and exposing them to solar simulator radiation for 10 min. The samples were found to be stable under solar light, and a thin apatite layer covered the surface of the sample with the two biopolymers and titanium dioxide. The in vitro cell viability assay suggested that the anatase phase in alginate and chitosan-alginate hydrogel composites have a positive impact.

The Impact of Ar or N2 Atmosphere on the Structure of Bi-Fe-Carbon Xerogel Based Composites as Electrode Material for Detection of Pb2+ and H2O2.

In this study, bismuth- and iron-embedded carbon xerogels (XG) were obtained using a modified resorcinol formaldehyde sol-gel synthesis method followed by additional enrichment with iron content. Pyrolysis treatment was performed at elevated temperatures under Ar or N2 atmosphere to obtain nanocomposites with different reduction yields (XGAr or XGN). The interest was focused on investigating the extent to which changes in the pyrolysis atmosphere of these nanocomposites impact the structure, morphology, and electrical properties of the material and consequently affect the electroanalytical performance. The structural and morphological particularities derived from X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) measurements revealed the formation of the nanocomposite phases, mostly metal/oxide components. The achieved performances for the two modified electrodes based on XG treated under Ar or N2 atmosphere clearly differ, as evidenced by the electroanalytical parameters determined from the detection of heavy metal cations (Pb2+) or the use of the square wave voltammetry (SWV) technique, biomarkers (H2O2), or amperometry. By correlating the differences obtained from electroanalytical measurements with those derived from morphological, structural, and surface data, a few utmost important aspects were identified. Pyrolysis under Ar atmosphere favors a significant increase in the α-Fe2O3 amount and H2O2 detection performance (sensitivity of 0.9 A/M and limit of detection of 0.17 µM) in comparison with pyrolysis under N2 (sensitivity of 0.5 A/M and limit of detection of 0.36 µM), while pyrolysis under N2 atmosphere leads to an increase in the metallic Bi amount and Pb2+ detection performance (sensitivity of 8.44 × 103 A/M and limit of detection of 33.05 pM) in comparison with pyrolysis under Ar (sensitivity of 6.47·103 A/M and limit of detection of 46.37 pM).

Ultrasensitive Electroanalytical Detection of Pb2+ and H2O2 Using Bi and Fe-Based Nanoparticles Embedded into Porous Carbon Xerogel-The Influence of Nanocomposite Pyrolysis Temperatures.

Multifunctional materials based on carbon xerogel (CX) with embedded bismuth (Bi) and iron (Fe) nanoparticles are tested for ultrasensitive amperometric detection of lead cation (Pb2+) and hydrogen peroxide (H2O2). The prepared CXBiFe-T nanocomposites were annealed at different pyrolysis temperatures (T, between 600 and 1050 °C) and characterized by X-ray diffraction (XRD), Raman spectroscopy, N2 adsorption, dynamic light scattering (DLS), and electron microscopies (SEM/EDX and TEM). Electrochemical impedance spectroscopy (EIS) and square wave anodic stripping voltammetry (SWV) performed at glassy carbon (GC) electrodes modified with chitosan (Chi)-CXBiFe-T evidenced that GC/Chi-CXBiFe-1050 electrodes exhibit excellent analytical behavior for Pb2+ and H2O2 amperometric detection: high sensitivity for Pb2+ (9.2·105 µA/µM) and outstanding limits of detection (97 fM, signal-to-noise ratio 3) for Pb2+, and remarkable for H2O2 (2.51 µM). The notable improvements were found to be favored by the increase in pyrolysis temperature. Multi-scale parameters such as (i) graphitization, densification of carbon support, and oxide nanoparticle reduction and purification were considered key aspects in the correlation between material properties and electrochemical response, followed by other effects such as (ii) average nanoparticle and Voronoi domain dimensions and (iii) average CXBiFe-T aggregate dimension.

The evaluation of the osteopromoting capabilities of composites based on biopolymers and gold/silver nanoparticles doped bioactive glasses on an experimental rat bone defect.

The most important concept behind using bone scaffolds is the biocompatibility of the material to avoid a local inflammatory response and must have the following properties: osteoinduction, osteoconductivity, angiogenesis, and mechanical support for cell growth. Gold nanoparticles/gold and silver nanoparticles -containing bioactive glasses in biopolymer composites have been used to enhance bone regeneration. These composites were testedin vitroon fibroblast and osteoblast cell lines using MTT tests, immunofluorescence, scanning electron microscopy analysis, andin vivoin an experimental bone defect in Sprague-Dawley rats. Both composites promoted adequate biological effects on human fibroblastic BJ (CRL 2522TM) cell lines and human osteoblastic cells isolated from the human patella in terms of cell proliferation, morphology, migration, and attachment. Most importantly, they did not cause cellular apoptosis and necrosis. According to the histological and immunohistochemical results, both composites were osteoinductive and promoted new bone formation at 60 d. Evidence from this study suggests that the small amount of silver content does not influence negatively thein vitroorin vivoresults. In addition, we obtained accurate results proving that the existence of apatite layer and proteins on the surface of the recovered composite, supports the validity ofin vitrobioactivity research.

Photoinhibitive Properties of α-MoO3 on Its Composites with TiO2, ZnO, BiOI, AgBr, and Cu2O.

Orthorhombic molybdenum trioxide (α-MoO3) is well known as a photocatalyst, adsorbent, and inhibitor during methyl orange photocatalytic degradation via TiO2. Therefore, besides the latter, other active photocatalysts, such as AgBr, ZnO, BiOI, and Cu2O, were assessed via the degradation of methyl orange and phenol in the presence of α-MoO3 using UV-A- and visible-light irradiation. Even though α-MoO3 could be used as a visible-light-driven photocatalyst, our results demonstrated that its presence in the reaction medium strongly inhibits the photocatalytic activity of TiO2, BiOI, Cu2O, and ZnO, while only the activity AgBr is not affected. Therefore, α-MoO3 might be an effective and stable inhibitor for photocatalytic processes to evaluate the newly explored photocatalysts. Quenching the photocatalytic reactions can offer information about the reaction mechanism. Moreover, the absence of photocatalytic inhibition suggests that besides photocatalytic processes, parallel reactions take place.

Anionic Polysaccharide Cryogels: Interaction and In Vitro Behavior of Alginate-Gum Arabic Composites.

In the present study, polysaccharide-based cryogels demonstrate their potential to mimic a synthetic extracellular matrix. Alginate-based cryogel composites with different gum arabic ratios were synthesized by an external ionic cross-linking protocol, and the interaction between the anionic polysaccharides was investigated. The structural features provided by FT-IR, Raman, and MAS NMR spectra analysis indicated that a chelation mechanism is the main process linking the two biopolymers. In addition, SEM investigations revealed a porous, interconnected, and well-defined structure suitable as a scaffold in tissue engineering. The in vitro tests confirmed the bioactive character of the cryogels through the development of the apatite layer on the surface of the samples after immersion in simulated body fluid, identifying the formation of a stable phase of calcium phosphate and a small amount of calcium oxalate. Cytotoxicity tests performed on fibroblast cells demonstrated the non-toxic effect of alginate-gum arabic cryogel composites. In addition, an increase in flexibility was noted for samples with a high gum arabic content, which determines an appropriate environment to promote tissue regeneration. The newly obtained biomaterials that exhibit all these properties can be successfully involved in the regeneration of soft tissues, wound management, or controlled drug release systems.

Insights into the Stability of Graphene Oxide Aqueous Dispersions.

Understanding graphene oxide's stability (or lack thereof) in liquid solvents is critical for fine-tuning the material's characteristics and its potential involvement in future applications. In this work, through the use of structural and surface investigations, the alteration of the structural and edge-surface properties of 2D graphene oxide nanosheets was monitored over a period of eight weeks by involving DLS, zeta potential, XRD, XPS, Raman and FT-IR spectroscopy techniques. The samples were synthesized as an aqueous suspension by an original modified Marcano-Tour method centred on the sono-chemical exfoliation of graphite. Based on the acquired experimental results and the available literature, a phenomenological explanation of the two underlying mechanisms responsible for the meta-stability of graphene oxide aqueous dispersions is proposed. It is based on the cleavage of the carbon bonds in the first 3-4 weeks, while the bonding of oxygen functional groups on the carbon lattice occurs, and the transformation of epoxide and hydroxyl groups into adsorbed water molecules in a process driven by the availability of hydrogen in graphene oxide nanosheets.

Thermal Evolution of C-Fe-Bi Nanocomposite System: From Nanoparticle Formation to Heterogeneous Graphitization Stage.

Carbon xerogel nanocomposites with integrated Bi and Fe particles (C­Bi­Fe) represent an interesting model of carbon nanostructures decorated with multifunctional nanoparticles (NPs) with applicability for electrochemical sensors and catalysts. The present study addresses the fundamental aspects of the catalyzed growth of nano-graphites in C­Bi­Fe systems, relevant in charge transport and thermo-chemical processes. The thermal evolution of a C­Bi­Fe xerogel is investigated using different pyrolysis treatments. At lower temperatures (~750°C), hybrid bismuth iron oxide (BFO) NPs are frequently observed, while graphitization manifests under more specific conditions such as higher temperatures (~1,050°C) and reduction yields. An in situ heating TEM experiment reveals graphitization activity between 800 and 900°C. NP motion is directly correlated with textural changes of the carbon support due to the catalyzed growth of graphitic nanoshells and nanofibers as confirmed by HR-TEM and electron tomography (ET) for the graphitized sample. An exponential growth model for the catalyst dynamics enables the approximation of activation energies as 0.68 and 0.29­0.34 eV during reduction and graphitization stages. The results suggest some similarities with the tip growth mechanism, while oxygen interference and the limited catalyst­feed gas interactions are considered as the main constraints to enhanced growth.

Bioactive Properties of Composites Based on Silicate Glasses and Different Silver and Gold Structures.

Using an ideal biomaterial to treat injured bones can accelerate the healing process and simultaneously exhibit antibacterial properties; thus protecting the patient from bacterial infections. Therefore, the aim of this work was to synthesize composites containing silicate-based bioactive glasses and different types of noble metal structures (i.e., AgI pyramids, AgIAu composites, Au nanocages, Au nanocages with added AgI). Bioactive glass was used as an osteoconductive bone substitute and Ag was used for its antibacterial character, while Au was included to accelerate the formation of new bone. To investigate the synergistic effects in these composites, two syntheses were carried out in two ways: AgIAu composites were added in either one step or AgI pyramids and Au nanocages were added separately. All composites showed good in vitro bioactivity. Transformation of AgI in bioactive glasses into Ag nanoparticles and other silver species resulted in good antibacterial behavior. It was observed that the Ag nanoparticles remained in the Au nanocages, which was also beneficial in terms of antibacterial properties. The presence of Au nanoparticles contributed to the composites achieving high cell viability. The most outstanding result was obtained by the consecutive addition of noble metals into the bioactive glasses, resulting in both a high antibacterial effect and good cell viability.

Rapid Synthesis Method of Ag3PO4 as Reusable Photocatalytically Active Semiconductor.

The widespread use of Ag3PO4 is not surprising when considering its higher photostability compared to other silver-based materials. The present work deals with the facile precipitation method of silver phosphate. The effects of four different phosphate sources (H3PO4, NaH2PO4, Na2HPO4, Na3PO4·12 H2O) and two different initial concentrations (0.1 M and 0.2 M) were investigated. As the basicity of different phosphate sources influences the purity of Ag3PO4, different products were obtained. Using H3PO4 did not lead to the formation of Ag3PO4, while applying NaH2PO4 resulted in Ag3PO4 and a low amount of pyrophosphate. The morphological and structural properties of the obtained samples were studied by X-ray diffractometry, diffuse reflectance spectroscopy, scanning electron microscopy, infrared spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic activity of the materials and the corresponding reaction kinetics were evaluated by the degradation of methyl orange (MO) under visible light. Their stability was investigated by reusability tests, photoluminescence measurements, and the recharacterization after degradation. The effect of as-deposited Ag nanoparticles was also highlighted on the photostability and the reusability of Ag3PO4. Although the deposited Ag nanoparticles suppressed the formation of holes and reduced the degradation of methyl orange, they did not reduce the performance of the photocatalyst.

Optimization Method of the Solvothermal Parameters Using Box-Behnken Experimental Design-The Case Study of ZnO Structural and Catalytic Tailoring.

ZnO photocatalysts were synthesized via solvothermal method and a reduced experimental design (Box-Behnken) was applied to investigate the influence of four parameters (temperature, duration, composition of the reaction mixture) upon the photocatalytic activity and the crystal structure of ZnO. The four parameters were correlated with photocatalytic degradation of methyl orange and the ratio of two crystallographic facets ((002) and (100)) using a quadratic model. The quadratic model shows good fit for both responses. The optimization experimental results validated the models. The ratio of the crystal facets shows similar variation as the photocatalytic activity of the samples. The water content of the solvent is the primary factor, which predominantly influence both responses. An explanation was proposed for the effect of the parameters and how the ratio of (002) and (100) crystal facets is influenced and its relation to the photocatalytic activity. The present research laconically describes a case study for an original experimental work, in order to serve as guideline to deal with such complicated subjects as quantifying influence of synthesis parameters upon the catalytic activity of the obtained ZnO.

Bioactive glass-biopolymers­gold nanoparticle based composites for tissue engineering applications.

Biomaterials based on bioactive glass with gold nanoparticle composites have many applications in tissue engineering due to their tissue regeneration and angiogenesis capacities. The objectives of the study were to develop new composites using bioactive glass with gold nanospheres (BGAuSP) and gold nanocages (BGAuIND), individually introduced in alginate-pullulan (Alg-Pll) polymer, to evaluate their biocompatibility potential, and to compare the obtained results with those achieved when ß-tricalcium phosphate-hydroxyapatite (ßTCP/HA) replaced the BG. The novel composites underwent structural and morphological characterization followed by in vitro viability testing on fibroblast and osteoblast cell lines. Additionally, the biomaterials were subcutaneously implanted in Sprague Dawley rats, for in vivo biocompatibility assessment during 3 separate time frames (14, 30 and 60 days). The biological effects were evaluated by histopathology and immunohistochemistry. The physical characterization revealed the cross-linking between polymers and glasses/ceramics and demonstrated a suitable thermal stability for sterilization processes. The in vitro assays demonstrated adequate form, pore size of composites ranging from few micrometers up to 100 µm, while the self-assembled apatite layer formed after simulated body fluid immersion confirmed the composites' bioactivity. Viability assays have highlighted optimal cellular proliferation and in vitro biocompatibility for all tested composites. Furthermore, based on the in vivo subcutaneous analyses the polymer composites with BGAuNP have shown excellent biocompatibility at 14, 30 and 60 days, exhibiting marked angiogenesis while, tissue proliferation was confirmed by high number of Vimentin positive cells, in comparison with the polymer composite that contains ßTCP/HA, which induced an inflammatory response represented by a foreign body reaction. The obtained results suggest promising, innovative, and biocompatible composites with bioactive properties for future soft tissue and bone engineering endeavours.

Poly(Vinyl Chloride) Spheres Coated with Graphene Oxide Sheets: From Synthesis to Optical Properties and Their Applications as Flame-Retardant Agents.

A new method to obtain poly(vinyl chloride) (PVC) spheres, which consists of an interaction between commercial PVC grains and hexyl ethyl cellulose and lauroyl peroxide at a temperature of 60 °C, is reported. The addition of the graphene oxide (GO) sheets dispersed in dimethylformamide to the reaction mixture leads to the generation of composites made of PVC spheres coated with GO sheets. Scanning electron microscopy studies have demonstrated that this method allows for the transformation of PVC grains with sizes between 75 and 227 µm into spheres with sizes varying from 0.7 to 3.5 µm when the GO concentration in the PVC/GO composite mass increases from 0.5 to 5 wt.%. Our studies of Raman scattering and FTIR spectroscopy highlight a series of changes that indicate the appearance of ClCH=CH-, CH2=CCl-, and/or -CH=CCl- units as a result of PVC partial dehydrogenation. New -COO- and C-OH bonds on the GO sheet surfaces are induced during the preparation of PVC spheres coated with GO sheets. A photoluminescence (PL) band with a maximum at 325 nm is reported to characterize the PVC spheres. A PVC PL quenching process is demonstrated to be induced by the increase in the concentration of the GO sheets in the PVC/GO composite mass. The perspectives regarding the use of this composite as a flame-retardant material are also reported.

The Effect of the Reducing Sugars in the Synthesis of Visible-Light-Active Copper(I) Oxide Photocatalyst.

In the present work, shape tailored Cu2O microparticles were synthesized by changing the nature of the reducing agent and studied subsequently. d-(+)-glucose, d-(+)-fructose, d-(+)xylose, d-(+)-galactose, and d-(+)-arabinose were chosen as reducing agents due to their different reducing abilities. The morpho-structural characteristics were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS), while their photocatalytic activity was evaluated by methyl orange degradation under visible light (120 min). The results show that the number of carbon atoms in the sugars affect the morphology and particle size (from 250 nm to 1.2 µm), and differences in their degree of crystallinity and photocatalytic activity were also found. The highest activity was observed when glucose was used as the reducing agent.

Gypsum Composite Boards Incorporating Phase Change Materials: A Review.

The purpose of this review is to provide an overview of the available gypsum based composite including various phase change materials employed to increase the thermal energy storage capacity of building materials. A wide range of materials such as n-alkane, saturated fatty acid, fatty acid esters etc are used as phase change materials. Adding carbonaceous material (carbon nanofibers, activated nanocarbon, graphite nanosheets etc.) to augment some properties is also a common practice. In addition, there are presented the methods of obtaining the nano/macro-composites together with some thermal characteristics of the newly prepared materials.

Preparation and Characterization of Carbon Xerogel Based Composites for Electrochemical Sensing and Photocatalytic Degradation.

In order to obtain a multifunctional nanocomposite material-for electrochemical sensors and photocatalytic applications, structures based on Bi, Fe and TiO2 were grown inside carbon xerogel supports (BiFeCX and BiFeCX-TiO2). First, a wet polymer containing Bi and Fe salts was obtained by following a modified resorcinol-formaldehyde based sol-gel route, followed by drying in ambient conditions, and pyrolysis under inert atmosphere. Then, through TiCl4 hydrolysis, TiO2 nanoparticles were deposited on the BiFeCX xerogel leading to BiFeCX-TiO2. The morphological and structural characterization of the investigated nanocomposites consisted in X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and N2 adsorption measurements, revealing porous carbon structures with embedded nanoparticles and the particularities driven by the pyrolysis and TiCl4 treatment. The new modified electrodes based on BiFeCX or BiFeCX-TiO2 nanocomposite materials, kept in a chitosan matrix (Chi) and deposited on a glassy carbon (GC) electrode surface (GC/Chi-BiFeCX or GC/Chi-BiFeCX-TiO2), were obtained and investigated for Pb(II) voltammetric detection and H2O2 amperometric detection. Moreover, the BiFeCX-TiO2 nanocomposite was tested for the photocatalytic degradation of methyl orange. The great potential of BiFeCX nanocomposite material for developing electrochemical sensors, or BiFeCX-TiO2 for sensors application and photocatalytic application was demonstrated.

The Impact of Composites with Silicate-Based Glasses and Gold Nanoparticles on Skin Wound Regeneration.

The silver content of the skin regeneration ointments can influence its regeneration process but in the meantime, it can take the benefit of the antibacterial properties of silver by avoiding the bacterial infection of an open wound. In the current study, the skin healing and regeneration capacity of bioactive glass with spherical gold nanocages (BGAuIND) in the Vaseline ointments were evaluated in vivo comparing the bioactive glass (BG)-Vaseline and bioactive glass with spherical gold (BGAuSP)-Vaseline ointments. Spherical gold nanocages are stabilized with silver and as a consequence the BGAuIND exhibits great antibacterial activity. Histological examination of the cutaneous tissue performed on day 8 indicates a more advanced regeneration process in rats treated with BGAuSP-Vaseline. The histopathological examination also confirms the results obtained after 11 days post-intervention, when the skin is completely regenerated at rats treated with BGAuSP-Vaseline compared with the others groups where the healing was incomplete. This result is also confirmed by the macroscopic images of the evolution of wounds healing. As expected, the silver content influences the wound healing process but after two weeks, for all of the post-interventional trials from the groups of rats, the skin healing was completely.

Shape tailoring of AgBr microstructures: effect of the cations of different bromide sources and applied surfactants.

Investigations regarding AgBr-based photocatalysts came to the center of attention due to their high photosensitivity. The present research focuses on the systematic investigation regarding the effect of different alkali metal cation radii and surfactants/capping agents applied during the synthesis of silver-halides. Their morpho-structural and optical properties were determined via X-ray diffractometry, diffuse reflectance spectroscopy, scanning electron microscopy, infrared spectroscopy, and contact angle measurements. The semiconductors' photocatalytic activities were investigated using methyl orange as the model contaminant under visible light irradiation. The correlation between the photocatalytic activity and the obtained optical and morpho-structural properties was analyzed using generalized linear models. Moreover, since the (photo)stability of Ag-based photoactive materials is a crucial issue, the stability of catalysts was also investigated after the degradation process. It was concluded that (i) the photoactivity of the samples could be fine-tuned using different precursors and surfactants, (ii) the as-obtained AgBr microcrystals were transformed into other Ag-containing composites during/after the degradation, and (iii) elemental bromide did not form during the degradation process. Thus, the proposed mechanisms in the literature (for the degradation of MO using AgBr) must be reconsidered.

New Insights into The Photoactivity of Shape-Tailored BiVO4 Semiconductors via Photocatalytic Degradation Reactions and Classical Reduction Processes.

In the present study, additive-free, pH-driven, hydrothermal crystallization was used to obtain shape-tailored monoclinic BiVO4 photocatalysts. The as-prepared BiVO4 products were systematically characterized, uncovering their crystallographic, morphologic and optical properties, while their applicability was verified in the visible light-driven photodegradation of oxalic acid and rhodamine B. Monoclinic clinobisvanite was obtained in most cases, with their band gap values located between 2.1 and 2.4 eV. The morphology varied from large, aggregated crystals, individual microcrystals to hierarchical microstructures. It was found that the degradation efficiency values obtained in the case of oxalic acid were directly related to the presence of (040) crystallographic plane, while the degradation of rhodamine B was partially independent by the presence of this structural feature. The importance of (040) crystallographic plane was also demonstrated via the reduction of Cu2+ to Cu, by analyzing the Raman spectra of the Cu containing samples, the mean primary crystallite size of Cu and Cu content. Furthermore, the presence of (040) crystallographic plane was directly proportional with the hydrodynamic properties of the powders as well.