Electrospun fibrillary scaffold for electrochemical cell biomarkers detection.

A novel scaffold for in situ electrochemical detection of cell biomarkers was developed using electrospun nanofibers and commercial adhesive polymeric membranes. The electrochemical sensing of cell biomarkers requires the cultivation of the cells on/near the (bio)sensor surface in a manner to preserve an appropriate electroactive available surface and to avoid the surface passivation and sensor damage. This can be achieved by employing biocompatible nanofiber meshes that allow the cells to have a normal behavior and do not alter the electrochemical detection. For a better mechanical stability and ease of handling, nylon 6/6 nanofibers were collected on commercial polymeric membranes, at an optimal fiber density, obtaining a double-layered platform. To demonstrate the functionality of the fabricated scaffold, the screening of cellular stress has been achieved integrating melanoma B16-F10 cells and the (bio)sensor components on the transducer whereas the melanin exocytosis was successfully quantified using a commercial electrode. Either directly on the surface of the (bio)sensor or spatially detached from it, the integration of cell cultures in biosensing platforms based on electrospun nanofibers represents a powerful bioanalytical tool able to provide real-time information about the biomarker release, enzyme activity or inhibition, and monitoring of various cellular events.

TiO2 Phase Ratio's Contribution to the Photocatalytic Activity.

Photocatalysis is one of the approaches for solving environmental issues derived from extremely harmful pollution caused by industrial dyes, medicine, and heavy metals. Titanium dioxide is among the most promising photocatalytic semiconductors; thus, in this work, TiO2 powders were prepared by a hydrothermal synthesis using titanium tetrachloride TiCl4 as a Ti source. The effect of the hydrochloric acid (HCl) concentration on TiO2 formation was analyzed, in which a thorough morpho-structural analysis was performed employing different analysis methods like XRD, Raman spectroscopy, SEM/TEM, and N2 physisorption. EPR spectroscopy was employed to characterize the paramagnetic defect centers and the photogeneration of reactive oxygen species. Photocatalytic properties were tested by photocatalytic degradation of the rhodamine B (RhB) dye under UV light irradiation and using a solar simulator. The pH value directly influenced the formation of the TiO2 phases; for less acidic conditions, the anatase phase of TiO2 crystallized, with a crystallite size of ≈9 nm. Promising results were observed for TiO2, which contained 76% rutile, showing a 96% degradation of RhB under the solar simulator and 91% under UV light after 90 min irradiation, and the best result showed that the sample with 67% of the anatase phase after 60 min irradiation under the solar simulator had a 99% degradation efficiency.

A Nanocomposite Sol-Gel Film Based on PbS Quantum Dots Embedded into an Amorphous Host Inorganic Matrix.

In this study, a sol-gel film based on lead sulfide (PbS) quantum dots incorporated into a host network was synthesized as a special nanostructured composite material with potential applications in temperature sensor systems. This work dealt with the optical, structural, and morphological properties of a representative PbS quantum dot (QD)-containing thin film belonging to the Al2O3-SiO2-P2O5 system. The film was prepared using the sol-gel method combined with the spin coating technique, starting from a precursor solution containing a suspension of PbS QDs in toluene with a narrow size distribution and coated on a glass substrate in a multilayer process, followed by annealing of each deposited layer. The size (approximately 10 nm) of the lead sulfide nanocrystallites was validated by XRD and by the quantum confinement effect based on the band gap value and by TEM results. The photoluminescence peak of 1505 nm was very close to that of the precursor PbS QD solution, which demonstrated that the synthesis route of the film preserved the optical emission characteristic of the PbS QDs. The photoluminescence of the lead sulfide QD-containing film in the near infrared domain demonstrates that this material is a promising candidate for future sensing applications in temperature monitoring.

Development and Characterization of Electrospun Composites Built on Polycaprolactone and Cerium-Containing Phases.

The current study reports on the fabrication of composite scaffolds based on polycaprolactone (PCL) and cerium (Ce)-containing powders, followed by their characterization from compositional, structural, morphological, optical and biological points of view. First, CeO2, Ce-doped calcium phosphates and Ce-substituted bioglass were synthesized by wet-chemistry methods (precipitation/coprecipitation and sol-gel) and subsequently loaded on PCL fibres processed by electrospinning. The powders were proven to be nanometric or micrometric, while the investigation of their phase composition showed that Ce was present as a dopant within the crystal lattice of the obtained calcium phosphates or as crystalline domains inside the glassy matrix. The best bioactivity was attained in the case of Ce-containing bioglass, while the most pronounced antibacterial effect was visible for Ce-doped calcium phosphates calcined at a lower temperature. The scaffolds were composed of either dimensionally homogeneous fibres or mixtures of fibres with a wide size distribution and beads of different shapes. In most cases, the increase in polymer concentration in the precursor solution ensured the achievement of more ordered fibre mats. The immersion in SBF for 28 days triggered an incipient degradation of PCL, evidenced mostly through cracks and gaps. In terms of biological properties, the composite scaffolds displayed a very good biocompatibility when tested with human osteoblast cells, with a superior response for the samples consisting of the polymer and Ce-doped calcium phosphates.

Organic Light-Emitting Diodes with Electrospun Electrodes for Double-Side Emissions.

Transparent conductive electrodes (TCE) obtained by the electrospinning method and gold covered were used as cathodes in the organic light-emitting diodes (OLEDs) to create double side-emission. The electro-active nanofibers of poly(methyl methacrylate) (PMMA) with diameters in the range of several hundreds of nanometers, were prepared through the electrospinning method. The nanofibers were coated with gold by sputtering deposition, maintaining optimal transparency and conductivity to increase the electroluminescence on both electrodes. Optical, structural, and electrical measurements of the as-prepared transparent electrodes have shown good transparency and higher electrical conductivity. In this study, two types of OLEDs consisting of indium tin oxide (ITO)/ poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS)/ Ir(III) complex (8-hydroxyquinolinat bis(2-phenylpyridyl) iridium-IrQ(ppy)2 20 wt% embedded in N, N'-Dicarbazolyl-4,4'-biphenyl (CBP) sandwich structure and either gold-covered PMMA electrospun nanoweb (OLED with electrospun cathode) were fabricated together with a similar structure containing thin film gold cathodes (OLED with thin film cathode). The luminance-current-voltage characteristics, the capacitance-voltage, and the electroluminescence properties of these OLEDs were investigated.

Microengineering Design for Advanced W-Based Bulk Materials with Improved Properties.

In fusion reactors, such as ITER or DEMO, the plasma used to generate nuclear reactions will reach temperatures that are an order of magnitude higher than in the Sun's core. Although the plasma is not supposed to be in contact with the reactor walls, a large amount of heat generated by electromagnetic radiation, electrons and ions being expelled from the plasma will reach the plasma-facing surface of the reactor. Especially for the divertor part, high heat fluxes of up to 20 MW/m2 are expected even in normal operating conditions. An improvement in the plasma-facing material (which is, in the case of ITER, pure Tungsten, W) is desired at least in terms of both a higher recrystallization temperature and a lower brittle-to-ductile transition temperature. In the present work, we discuss three microengineering routes based on inclusions of nanometric dispersions, which are proposed to improve the W properties, and present the microstructural and thermophysical properties of the resulting W-based composites with such dispersions. The materials' behavior after 6 MeV electron irradiation tests is also presented, and their further development is discussed.

Burdock-Derived Composites Based on Biogenic Gold, Silver Chloride and Zinc Oxide Particles as Green Multifunctional Platforms for Biomedical Applications and Environmental Protection.

Green nanotechnology is a rapidly growing field linked to using the principles of green chemistry to design novel nanomaterials with great potential in environmental and health protection. In this work, metal and semiconducting particles (AuNPs, AgClNPs, ZnO, AuZnO, AgClZnO, and AuAgClZnO) were phytosynthesized through a "green" bottom-up approach, using burdock (Arctium lappa L.) aqueous extract. The morphological (SEM/TEM), structural (XRD, SAED), compositional (EDS), optical (UV-Vis absorption and FTIR spectroscopy), photocatalytic, and bio-properties of the prepared composites were analyzed. The particle size was determined by SEM/TEM and by DLS measurements. The phytoparticles presented high and moderate physical stability, evaluated by zeta potential measurements. The investigation of photocatalytic activity of these composites, using Rhodamine B solutions' degradation under solar light irradiation in the presence of prepared powders, showed different degradation efficiencies. Bioevaluation of the obtained composites revealed the antioxidant and antibacterial properties. The tricomponent system AuAgClZnO showed the best antioxidant activity for capturing ROS and ABTS•+ radicals, and the best biocidal action against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa. The "green" developed composites can be considered potential adjuvants in biomedical (antioxidant or biocidal agents) or environmental (as antimicrobial agents and catalysts for degradation of water pollutants) applications.

Carbon Inks-Based Screen-Printed Electrodes for Qualitative Analysis of Amino Acids.

Due to the great significance of amino acids, a substantial number of research studies has been directed toward the development of effective and reliable platforms for their evaluation, detection, and identification. In order to support these studies, a new electrochemical platform based on PANI/ZnO nanowires' modified carbon inks screen-printed electrodes was developed for qualitative analysis of electroactive amino acids, with emphasis on tyrosine (Tyr) and tryptophan (Trp). A comparative investigation of the carbon ink before and after modification with the PANI/ZnO was performed by scanning electron microscopy and by Raman spectroscopy, confirming the presence of PANI and ZnO nanowires. Electrochemical investigations by cyclic voltammetry and electrochemical impedance spectroscopy have shown a higher charge-transfer rate constant, which is reflected into lower charge-transfer resistance and higher capacitance values for the PANI/ZnO modified ink when compared to the simple carbon screen-printed electrode. In order to demonstrate the electrochemical performances of the PANI/ZnO nanowires' modified carbon inks screen-printed electrodes for amino acids analysis, differential pulse voltammograms were obtained in individual and mixed solutions of electroactive amino acids. It has been shown that the PANI/ZnO nanowires' modified carbon inks screen-printed electrodes allowed for tyrosine and tryptophan a peak separation of more than 100 mV, enabling their screening and identification in mixed solutions, which is essential for the electrochemical analysis of proteins within the proteomics research field.

Influence of the Photodegradation of Azathioprine on DNA and Cells.

Azathioprine (AZA) is a pharmacologic immunosuppressive agent administrated in various conditions such as autoimmune disease or to prevent the rejection of organ transplantation. The mechanism of action is based on its biologically active metabolite 6-mercaptopurine (6-MP), which is converted, among others, into thioguanine nucleotides capable of incorporating into replicating DNA, which may act as a strong UV chromophore and trigger DNA oxidation. The interaction between azathioprine and DNA, before and after exposure to solar simulator radiation, was investigated using UV-vis spectrometry and differential pulse voltammetry at a glassy carbon electrode. The results indicated that the interaction of AZA with UV radiation was pH-dependent and occurred with the formation of several metabolites, which induced oxidative damage in DNA, and the formation of DNA-metabolite adducts. Moreover, the viability assays obtained for the L929 cell culture showed that both azathioprine and degraded azathioprine induced a decrease in cell proliferation.

Processing Effects on the Martensitic Transformation and Related Properties in the Ni55Fe18Nd2Ga25 Ferromagnetic Shape Memory Alloy.

The influence of processing on the martensitic transformation and related magnetic properties of the Ni55Fe18Nd2Ga25 ferromagnetic shape memory alloy, as bulk and ribbons prepared by the melt spinning method and subjected to different thermal treatments, is investigated. Structural, calorimetric, and magnetic characterizations are performed. Thermal treatment at 1173 K induces a decrease in both the Curie and the martensitic transformation temperatures, while a treatment at 673 K produces the structural ordering of the ribbons, hence an increase in TC. A maximum value of the magnetic entropy variation of -5.41 J/kgK was recorded at 310 K for the as quenched ribbons. The evaluation of the magnetoresistive effect shows a remarkable value of -13.5% at 275 K on the bulk sample, which is much higher than in the ribbons.

Nanostructured PbS-Doped Inorganic Film Synthesized by Sol-Gel Route.

IV-VI semiconductor quantum dots embedded into an inorganic matrix represent nanostructured composite materials with potential application in temperature sensor systems. This study explores the optical, structural, and morphological properties of a novel PbS quantum dots (QDs)-doped inorganic thin film belonging to the Al2O3-SiO2-P2O5 system. The film was synthesized by the sol-gel method, spin coating technique, starting from a precursor solution deposited on a glass substrate in a multilayer process, followed by drying of each deposited layer. Crystalline PbS QDs embedded in the inorganic vitreous host matrix formed a nanocomposite material. Specific investigations such as X-ray diffraction (XRD), optical absorbance in the ultraviolet (UV)-visible (Vis)-near infrared (NIR) domain, NIR luminescence, Raman spectroscopy, scanning electron microscopy-energy dispersive X-ray (SEM-EDX), and atomic force microscopy (AFM) were used to obtain a comprehensive characterization of the deposited film. The dimensions of the PbS nanocrystallite phase were corroborated by XRD, SEM-EDX, and AFM results. The luminescence band from 1400 nm follows the luminescence peak of the precursor solution and that of the dopant solution. The emission of the PbS-doped film in the NIR domain is a premise for potential application in temperature sensing systems.

Electrochemical Deposition of ZnO Nanowires on CVD-Graphene/Copper Substrates.

ZnO nanostructures were electrochemically synthesized on Cu and on chemical vapor deposited (CVD)-graphene/Cu electrodes. The deposition was performed at different electrode potentials ranging from -0.8 to -1.2 V, employing a zinc nitrate bath, and using voltametric and chronoamperometric techniques. The effects of the electrode nature and of the working electrode potential on the structural, morphological, and optical properties of the ZnO structures were investigated. It was found that all the samples crystallize in hexagonal wurtzite structure with a preferential orientation along the c-axis. Scanning electron microscopy (SEM) images confirm that the presence of a graphene covered electrode led to the formation of ZnO nanowires with a smaller diameter compared with the deposition directly on copper surface. The photoluminescence (PL) measurements revealed that the ZnO nanowires grown on graphene/Cu exhibit stronger emission compared to the nanowires grown on Cu. The obtained results add another possibility of tailoring the properties of such nanostructured films according to the specific functionality required.

Charge transport mechanisms in free-standing devices with electrospun electrodes.

Embedding electronic and optoelectronic devices in common, daily use objects is a fast developing field of research. New architectures are needed for migrating from the classic wafer- based substrates. Novel types of flexible PMMA/Au/Alq3/LiF/Al structures were obtained starting from electrospun polymer fibers. Thus, using an electrospinning process poly (methyl metacrylate) (PMMA) nanofibers were fabricated. A thin Au layer deposition rendered the fiber array conductive, this being further employed as the anode. The next steps consisted of the thermal evaporation of tris(8-hydroxyquinolinato) aluminum (Alq3) and aluminum deposition as the cathode. The Au covered PMMA nanofiber layer had a similar behavior with an indium tin oxide film i.e. low sheet resistance 10.6 Ω/sq and high transparency. The low electrode resistivities allow an electron drift mobility of about 10-6cm2V-1s-1at a low applied field, similar to the counterpart structures based on thin films. Concerning the relaxation processes in these structures, the Cole-Cole plots exhibit a slightly deformed semicircle, indicating a more complex equivalent circuit for the processes between metal electrodes and the active layer. This equivalent circuit includes reactance equivalent processes at the anode, cathode, in the active layer and most probably originates from the roughness of the metallic electrodes.

Investigations Regarding the Addition of ZnO and Li2O-TiO2 to Phosphate-Tellurite Glasses: Structural, Chemical, and Mechanical Properties.

Phosphate and tellurite glasses can be used in optics, optoelectronics, magneto-optics, and nuclear and medical fields. Two series of phosphate-tellurite glasses, (50-x)ZnO-10Al2O3-40P2O5-xTeO2 and (40-x)Li2O-10Al2O3-5TiO2-45P2O5-xTeO2 (x = 5, 10), were synthesized by a non-conventional wet-route, and the mechanical properties as key performance measures for their application in optoelectronics were investigated. X-ray Diffraction (XRD) measurements revealed the vitreous nature of the investigated materials. Instrumented indentation tests allowed the calculation of hardness (H) and Young's modulus (E) using the Oliver and Pharr model. The influence of increasing the TeO2 content, as well as the substitution of ZnO by Li2O-TiO2, on the variation of hardness, Young's modulus, penetration depth (PD), and fracture toughness (FT) was evaluated in both series. As a general trend, there is a decrease in the hardness and Young's modulus with increasing penetration depth. The addition of Li2O and TiO2 instead of ZnO leads to improved hardness and elastic modulus values. Regarding the H/E ratio, it was found that the samples with lower TeO2 content should be significantly more crack-resistant compared to the higher TeO2 content samples. The H3/E2 ratio, being lower than 0.01, revealed a poor resistance of these glasses to plastic deformation. At the same time, a decrease of the fracture toughness with increasing TeO2 content was noticed for each glass series. Based on dilatometry measurements, the thermal expansion coefficient as well as the characteristic temperatures of the glasses were measured. Field Emission Scanning Electron Microscopy-Energy Dispersive X-ray analysis (FESEM-EDX) revealed a uniform distribution of the elements in the bulk samples. The mechanical properties of these vitreous materials are important in relation to their application as magneto-optical Faraday rotators in laser cavities.

Microwave and Terahertz Properties of Spark-Plasma-Sintered Zr0.8Sn0.2TiO4 Ceramics.

Zr0.8Sn0.2TiO3 (ZST) powders synthesized by solid-state reaction were subject to processing by spark plasma sintering (SPS). A single-phase ceramic with a high relative density of 95.7% and 99.6% was obtained for sintering temperatures of 1150 °C and 1200 °C, respectively, and for a dwell time of 3 min. In order to reduce the oxygen vacancies, as-sintered discs were annealed in air at 1000 °C. The dielectric loss of the annealed samples, expressed by the Q × f product, measured in the microwave (MW) domain, varied between 35 THz and 50 THz. The intrinsic losses (Q × f ~ 60 THz) were derived by using terahertz time-domain spectroscopy (THz-TDS).

Correction: Zgura et al. Cytotoxicity, Antioxidant, Antibacterial, and Photocatalytic Activities of ZnO-CdS Powders. Materials 2020, 13, 182.

In the original publication [...].

Magnetic and Magnetostrictive Properties of Ni50Mn20Ga27Cu3 Rapidly Quenched Ribbons.

The influence of the rapid solidification technique and heat treatment on the martensitic transformation, magnetic properties, thermo- and magnetic induced strain and electrical resistivity is investigated for the Cu doped NiMnGa Heusler-based ferromagnetic shape memory ribbons. The martensitic transformation temperatures are unexpectedly low (below 90 K-which can be attributed to the disordered texture as well as to the uncertainty in the elements substituted by the Cu), preceded by a premartensitic transformation (starting at around 190 K). A thermal treatment slightly increases the transformation as well as the Curie temperatures. Additionally, the thermal treatment promotes a higher magnetization value of the austenite phase and a lower one in the martensite. The shift of the martensitic transformation temperatures induced by the applied magnetic field, quantified from thermo-magnetic and thermo-magnetic induced strain measurements, is measured to have a positive value of about 1 K/T, and is then used to calculate the transformation entropy of the ribbons. The magnetostriction measurements suggest a rotational mechanism in low fields for the thermal treated samples and a saturation tendency at higher magnetic fields, except for the temperatures close to the phase transition temperatures (saturation is not reached at 5 T), where a linear volume magnetostriction cannot be ruled out. Resistivity and magnetoresistance properties have also been measured for all the samples.

The Physico-Chemical Properties and Exploratory Real-Time Cell Analysis of Hydroxyapatite Nanopowders Substituted with Ce, Mg, Sr, and Zn (0.5-5 at.%).

Cation-substituted hydroxyapatite (HA), standalone or as a composite (blended with polymers or metals), is currently regarded as a noteworthy candidate material for bone repair/regeneration either in the form of powders, porous scaffolds or coatings for endo-osseous dental and orthopaedic implants. As a response to the numerous contradictions reported in literature, this work presents, in one study, the physico-chemical properties and the cytocompatibility response of single cation-doped (Ce, Mg, Sr or Zn) HA nanopowders in a wide concentration range (0.5-5 at.%). The modification of composition, morphology, and structure was multiparametrically monitored via energy dispersive X-ray, X-ray photoelectron, Fourier-transform infrared and micro-Raman spectroscopy methods, as well as by transmission electron microscopy and X-ray diffraction. From a compositional point of view, Ce and Sr were well-incorporated in HA, while slight and pronounced deviations were observed for Mg and Zn, respectively. The change of the lattice parameters, crystallite size, and substituting cation occupation factors either in the Ca(I) or Ca(II) sites were further determined. Sr produced the most important HA structural changes. The in vitro biological performance was evaluated by the (i) determination of leached therapeutic cations (by inductively coupled plasma mass spectrometry) and (ii) assessment of cell behaviour by both conventional assays (e.g., proliferation-3-(4,5-dimethyl thiazol-2-yl) 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium assay; cytotoxicity-lactate dehydrogenase release assay) and, for the first time, real-time cell analysis (RTCA). Three cell lines were employed: fibroblast, osteoblast, and endothelial. When monophasic, the substituted HA supported the cells' viability and proliferation without signs of toxicity. The RTCA results indicate the excellent adherence of cells. The study strived to offer a perspective on the behaviour of Ce-, Mg-, Sr-, or Zn-substituted HAs and to deliver a well-encompassing viewpoint on their effects. This can be highly important for the future development of such bioceramics, paving the road toward the identification of candidates with highly promising therapeutic effects.

Redox Mechanism of Azathioprine and Its Interaction with DNA.

The electrochemical behavior and the interaction of the immunosuppressive drug azathioprine (AZA) with deoxyribonucleic acid (DNA) were investigated using voltammetric techniques, mass spectrometry (MS), and scanning electron microscopy (SEM). The redox mechanism of AZA on glassy carbon (GC) was investigated using cyclic and differential pulse (DP) voltammetry. It was proven that the electroactive center of AZA is the nitro group and its reduction mechanism is a diffusion-controlled process, which occurs in consecutive steps with formation of electroactive products and involves the transfer of electrons and protons. A redox mechanism was proposed and the interaction of AZA with DNA was also investigated. Morphological characterization of the DNA film on the electrode surface before and after interaction with AZA was performed using scanning electron microscopy. An electrochemical DNA biosensor was employed to study the interactions between AZA and DNA with different concentrations, incubation times, and applied potential values. It was shown that the reduction of AZA molecules bound to the DNA layer induces structural changes of the DNA double strands and oxidative damage, which were recognized through the occurrence of the 8-oxo-deoxyguanosine oxidation peak. Mass spectrometry investigation of the DNA film before and after interaction with AZA also demonstrated the formation of AZA adducts with purine bases.

Fabrication of ZnO and TiO2 Nanotubes via Flexible Electro-Spun Nanofibers for Photocatalytic Applications.

Web-like architectures of ZnO and TiO2 nanotubes were fabricated based on a three-step process of templating polymer nanofibers produced by electrospinning (step 1). The electrospun polymer nanofibers were covered by radio-frequency magnetron sputtering with thin layers of semiconducting materials (step 2), with FESEM observations proving uniform deposits over their entire surface. ZnO or TiO2 nanotubes were obtained by subsequent calcination (step 3). XRD measurements proved that the nanotubes were of a single crystalline phase (wurtzite for ZnO and anatase for TiO2) and that no other crystalline phases appeared. No other elements were present in the composition of the nanotubes, confirmed by EDX measurements. Reflectance spectra and Tauc plots of Kubelka-Munk functions revealed that the band gaps of the nanotubes were lower than those of the bulk materials (3.05 eV for ZnO and 3.16 eV for TiO2). Photocatalytic performances for the degradation of Rhodamine B showed a large degradation efficiency, even for small quantities of nanotubes (0.5 mg/10 mL dye solution): ~55% for ZnO, and ~95% for TiO2.