[en] Bifunctional nanostructures based on ZnO nanoparticles (NPs) with controlled Gd_2O_3 shell thicknesses were obtained by simple low-temperature methods (sol–gel technique and seed deposition method). The morphology, nanostructure, phase and chemical composition as well as luminescent and magnetic properties of the obtained core–shell nanostructures were investigated by transmission electron microscopy (HRTEM), energy dispersive x-ray spectroscopy (EDS), x-ray diffraction (XRD) techniques, optical spectroscopy, and SQUID magnetometer. As-obtained ZnO NPs are highly monodispersed and crystalline with mean particles size distribution of about 7 nm. Modification of the ZnO NPs surface by Gd_2O_3 shell leads to an increase of the ZnO particles size up to 80–160 nm and the formation the Gd_2O_3 shell with size of 2–4 nm. The dependence of the phase composition, luminescent and magnetic properties on Gd_2O_3 content are also discussed. - Highlights: • The bifunctional ZnO@Gd_2O_3 nanostructures were obtained by sol–gel technique. • ZnO@Gd_2O_3 have intensive luminescence in the visible range under 325 nm excitation. • Gd"3"+ content allows to control paramagnetic properties of the ZnO@Gd_2O_3. • ZnO@Gd_2O_3 nanostructures are potential objects for application in medicine.

[en] Highlights: • The multimodal ZnO@Gd_2O_3 nanostructures were obtained by wet chemistry methods. • FA and Dox have been effectively bonded onto the ZnO nanoparticles surface. • Functionalized ZnO@Gd_2O_3 NPs are good contrast agents, useful for MR imaging. - Abstract: The main aim of this research was the synthesis of the multimodal hybrid ZnO@Gd_2O_3 nanostructures as prospective contrast agent for Magnetic Resonance Imaging (MRI) for bio-medical applications. The nanoparticles surface was functionalized by organosilicon compounds (OSC) then, by folic acid (FA) as targeting agent and doxorubicin (Dox) as chemotherapeutic agent. Doxorubicin and folic acid were attached to the nanoparticles surface by amino groups as well as due to attractive physical interactions. The morphology and crystallography of the nanostructures were studied by HRTEM and SAXS techniques. After ZnO nanoparticles surface modification by Gd"3"+ and annealing at 900 °C, ZnO@Gd_2O_3 nanostructures are polydispersed with size 30–100 nm. NMR (Nuclear Magnetic Resonance) studies of ZnO@Gd_2O_3 were performed on fractionated particles with size up to 50 nm. Fourier transform infrared spectroscopy (FTIR), UV–vis spectroscopy, zeta-potential measurements and energy dispersive X-ray analysis (EDX) showed that functional groups have been effectively bonded onto the nanoparticles surface. The high adsorption capacity of folic acid (up to 20%) and doxorubicin (up to 40%) on nanoparticles was reached upon 15 min of adsorption process in a temperature-dependent manner. The nuclear magnetic resonance (NMR) relaxation measurements confirmed that the obtained ZnO@Gd_2O_3 nanostructures could be good contrast agents, useful for magnetic resonance imaging.

[en] In this investigation, the fabrication of porous core/shell nanostructures consisting of copper (core) and copper-gold nanoalloy (shell) for medical applications is presented. As a core triangular-shaped copper nanoparticles were used. The porous bimetallic nanoshell was prepared via galvanic reaction in the presence of oil-in water emulsion. It was proved that porous nanoalloy layer can be prepared at pH 7 and in the presence 0.1% and 0.5% oil-in water emulsion. The porous structure fabrication was mainly determined by volume fraction of hexadecane to acetone in the oil-in water emulsion and Zeta-potential of emulsion droplets (pH of emulsion). The influence of emulsion droplets size before galvanic reaction on porous structure preparation was negligible. It was found that doxorubicin could be easily introduced and released from porous core/shell nanostructures, due to spontaneous adsorption on the copper-gold nanoporous surface. The in vitro test showed that cytotoxic effect was more prominent once the doxorubicin was adsorbed on the porous copper-gold nanocarriers. It was demonstrated, that doxorubicin-loaded copper-gold nanostructures caused inhibition cell proliferation and viability of cancer cells, in a concentration-dependent manner. The results indicates that presented coper-gold nanocarrier have potential to be used in targeted cancer therapy, due to its porous structure and cytotoxic effect in cancer cells. - Highlights: • Porous copper-gold nanostructure as a cytostatic drug carrier was prepared. • Kinetics and thermodynamics of drug adsorption were studied. • DOX-loaded copper-gold nanoparticles showed a pH-controlled release rate. • DOX-loaded copper-gold NPs caused inhibition cell proliferation of cancer cells. • The Cu-Au NPs could serve as a theranostic platform for biomedical applications.

[en] Zinc oxide (ZnO) is a wide-bandgap semiconductor material with applications in a variety of fields such as electronics, optoelectronic and solar cells. However, much of these applications demand a reproducible, reliable and controllable synthesis method that takes special care of their functional properties. In this work ZnO and Cu-doped ZnO nanowires are obtained by an optimized hydrothermal method, following the promising results which ZnO nanostructures have shown in the past few years. The morphology of as-prepared and copper-doped ZnO nanostructures is investigated by means of scanning electron microscopy and high resolution transmission electron microscopy. X-ray diffraction is used to study the impact of doping on the crystalline structure of the wires. Furthermore, the mechanical properties (nanoindentation) and the functional properties (absorption and photoluminescence measurements) of ZnO nanostructures are examined in order to assess their applicability in photovoltaics, piezoelectric and hybrids nanodevices. This work shows a strong correlation between growing conditions, morphology, doping and mechanical as well as optical properties of ZnO nanowires. (paper)

[en] A graphene oxide (GO), reduced graphene oxide (RGO) and poly(3,4-ethylenedioxytiophene)-reduced graphene oxide (PEDOT-RGO composite) gas sensors were successfully fabricated using an electrodeposition method. The electrodeposition was carried out in aqueous GO dispersions. In order to obtain RGO and PEDOT-RGO, the electrochemical reduction of GO and PEDOT-GO was carried out in 0.1 M KCl at constant potential of  −0.85 V. The GO, RGO and PEDOT-RGO composites were characterized by scanning and high resolution transmission electron microscopies with electron energy loss spectroscopy, Fourier-transform infrared and Raman spectroscopies. In this work the effect of GO electrochemical reduction process was discussed. The effects of the humidity and sensing response of GO, RGO and PEDOT-RGO to different gases were investigated. It was found out the PEDOT-RGO response to NO₂ was much higher than to the other analyzed gases. The influence of the operating temperature on the gas sensing response was compared. The role of the polymer and RGO in PEDOT-RGO composite has been indicated. The results are discussed in light of recent literature on graphene sensors. (paper)

[en] Magnetite nanoparticles (NPs) decorated with silver (magnetite/Ag) are intensively investigated due to their application in the biomedical field. We demonstrate that the increase of silver content on the surface of nanoparticles improves the adsorptivity of antibiotic rifampicin as well as antibacterial properties. The use of ginger extract allowed to improve the silver nucleation on the magnetite surface that resulted in an increase of silver content. Physicochemical and functional characterization of magnetite/Ag NPs was performed. Our results show that 5%–10% of silver content in magnetite/Ag NPs is already sufficient for antimicrobial properties against Streptococcus salivarius and Staphylococcus aureus . The rifampicin molecules on the magnetite/Ag NPs surface made the spectrum of antimicrobial activity wider. Cytotoxicity evaluation of the magnetite/Ag/rifampicin NPs showed no harmful action towards normal human fibroblasts, whereas the effect on human embryonic kidney cell viability was time and dose dependent. (paper)

[en] Although number of stimuli-responsive drug delivery systems based on mesoporous silica nanoparticles (MSNs) have been developed, the simultaneous real-time monitoring of carrier in order to guarantee proper drug targeting still remains as a challenge. GQDs-MSNs nanocomposite nanoparticles composed of graphene quantum dots (GQDs) and MSNs are proposed as efficient doxorubicin delivery and fluorescent imaging agent, allowing to monitor intracellular localization of a carrier and drug diffusion route from the carrier.

Graphene quantum dots (average diameter 3.65 ± 0.81 nm) as a fluorescent agent were chemically immobilized onto mesoporous silica nanoparticles (average diameter 44.08 ± 7.18 nm) and loaded with doxorubicin. The structure, morphology, chemical composition, and optical properties as well as drug release behavior of doxorubicin (DOX)-loaded GQDs-MSNs were investigated. Then, the in vitro cytotoxicity, cellular uptake, and intracellular localization studies were carried out. Prepared GQDs-MSNs form stable suspensions exhibiting excitation-dependent photoluminescence (PL) behavior. These nanocomposite nanoparticles can be easily DOX-loaded and show pH- and temperature-dependent release behavior. Cytotoxicity studies proved that GQDs-MSNs nanocomposite nanoparticles are nontoxic; however, when loaded with drug, they enable the therapeutic activity of DOX via its active delivery and release. GQDs-MSNs owing to their fluorescent properties and efficient in vitro cellular internalization via caveolae/lipid raft-dependent endocytosis show a high potential for the optical imaging, including the simultaneous real-time optical tracking of the loaded drug during its delivery and release.

.

[en] Highlights: • Self-organizing Ag and iron oxide nanoparticles were produced in one-step synthesis using ginger extract; • Self-organizing nanoparticles combine fluorescence and bactericidal properties with contrasting of magnetic resonance image; • Highly-ordered hierarchical microstructure is formed by self-organizing ultrasmall iron oxide and Ag nanoparticles; • Ginger polysaccharides and water molecules impact the microstructure forming by ultrasmall iron oxide and Ag nanoparticles; • Fluorescent emittance of self-organizing iron oxide and Ag nanoparticles depends on microstructure elements that they form. Multimodal nanoparticles (NPs) that may be used for therapies and diagnostics is the most promising trend for efficient therapy. We demonstrate that nanocomposite based on self-organizing silver and ultrasmall magnetic iron oxide NPs (MAg) produced in one-step synthesis revealed unique combination of fluorescence, bactericidal, fungicidal properties and have a potential as magnetic resonance imaging (MRI) contrast agent. Using the green chemistry approach, ginger (Zingiber officinale) rhizome extract was applied as capping agent for MAg synthesis, providing also additional fluorescent properties of NPs and inducing hydrocolloids structuring. The MAg were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive microanalysis (EDS), fluorescence microscopy, cryo-SEM, dynamic light scattering (DLS) techniques, Fourier transform infrared (FTIR) and ultraviolet–visible (UV–Vis) spectroscopies. MAg dispersions in water and some biological media are very stable which is important for biomedical application. The existence of microstructure in MAg hydrocolloids was proved. The hierarchical character and high ordering of this microstructure were discovered and its level-by-level building blocks were investigated. The microstructure was found to be responsible for fluorescence emittance of MAg hydrocolloids. The properties as well as potential application of the MAg hydrocolloids is yet to be discovered.

[en] Highlights: • Nanolaminate thin films of Al₂O₃/TiO₂ with different bilayer density were prepared by ALD method. • A new multidimensional reconstruction method was implemented to analyze the nanomechanical response of the samples. • Mechanical response of the nanolaminates showed to be improved by layer thickness and follow the behavior of a nanocomposite coating. • The method implemented allows the reconstruction of 4D mechanical data at the nanoscale. A novel method of nanomechanical testing of multilayered Al₂O₃/TiO₂ nanolaminates was implemented by the nanoindentation technique. The indentation data were reconstructed and filtered by a statistical analysis algorithm and presented as a function of the penetration depth of the indenter. Results show the increment of mechanical properties on the laminates as a function of the amorphous interfaces of the individual layers and the effective control of the wear rate of the structures for further applications. The results presented show both important insights on the mechanical behavior of nanolaminates and the further applicability of the reconstruction model for error reduction on mechanical testing of nanolaminate samples.

[en] Highlights: • Multilayer TiN/ZrN films were deposited using sequential vacuum-arc deposition of Ti and Zr targets in nitrogen atmosphere; • Several samples were annealed in air at the temperature 700 °C; • First-principles calculations of TiN(111), ZrN(111) structures and TiN(111)/ZrN(111) multilayer were carried out; • All deposited samples were highly polycrystalline with quite large 20–25 nm crystals; • The nanohardness and elastic modulus of non-annealed coatings reached 42 GPa and 348 GPa, respectively; • Deposited coatings demonstrate good wear and oxidation resistance; - Abstract: Nanoscale multilayered TiN/ZrN films were deposited using sequential vacuum-arc deposition of Ti and Zr targets in a nitrogen atmosphere. Studies of film's properties were carried out using various modern methods of analysis, such as XRD, STEM, HRTEM, SIMS combined with results of nanoindentation and tribological tests. To interpret the mechanical properties of the deposited multilayer films first-principles calculations of TiN(111), ZrN(111) structures and TiN(111)/ZrN(111) multilayer were carried out. To study the influence of thermal annealing, several samples were annealed in air at the temperature 700 °C. All deposited samples were highly polycrystalline with quite large 20–25 nm crystals. The crystalline planes were very ordinated and demonstrated an excellent coordinated growth. The nanohardness and elastic modulus of non-annealed coatings reached 42 GPa and 348 GPa, respectively. Annealing in air at the temperature 700 °C led to partial oxidation of the multilayered coatings, however hardness of the non-oxidized part of the coatings remained as high, as for initial coatings. All deposited coatings demonstrate good wear resistance.