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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. Keywords: Ultrasmall, Silver, Ginger, Nanoparticles, Hydrocolloid, Microstructure

In this work we refer the properties of water solution of ciprofloxacin confined in single wall carbon nanotubes. Ciprofloxacin is well-known antibiotic applied against Gram-positive and Gram-negative bacteria. We study the influence of the size of nanotubes and their structure on interactions with the drug water solution. Analysis of Raman spectroscopy of the carbon nanotubes shows that the higher amorphousness of carbon nanotubes, which increase bio-capability of materials, is associated with their semiconductor’s properties. We used FT-IR spectroscopy to define the structure of confined ciprofloxacin, and we can assume what vibrations of functional group in the ciprofloxacin molecule have been suppressed by confining in the pores. ciprofloxacin, carbon nanotubes, drug delivery, raman spectroscopy, FT-IR.

This review presents the latest innovations and trends in the field of surface functionalization of various nanomaterials. The most recent protocols of smart materials fabrication as well as the main challenges which should be overcome in order to improve their final performance are discussed here. Particular attention has been paid to the properties improvement of polymer, silica, inorganic and hybrid nanomaterials and their potential for application in many fields, from industry, materials science, environmental protection to advanced biomedicine.

In granular thin films consisting of small particles of magnetic metal dispersed in nonmagnetic matrix both magnetization and magnetoresistance phenomena are directly related, and their relationship is very complex. This is due to the distribution of ferromagnetic grains in nonmagnetic metallic matrix and its mutual magnetic interactions. In this paper, we studied influence of CoxAg100-x film composition and thickness on film structure, magnetization and magnetoresistance. It has been found that the size of Co grains correlates with the sample thickness for the films with d = 20 nm, and the superparamagnetic state of Co granules is preserved up to x ≤ 55 at.%. However, thicker samples are superparamagnetic only up to x

This work aimed to study for the first time to our knowledge the influence of the structure of the dental flosses (DF) coated by hydroxyapatite nanoparticles (HAP NPs) on the biological performance of saliva probiotic bacteria (S. salivarius), and human dermal and osteoblast-like cells. We used three types of HAP@DF composites (based on two unwaxed dental flosses - “fluffy” and “smooth”, and one waxed “smooth”) with different morphologies. Obtained composites were characterized from the point of view of their structure, morphological characteristics, elemental and chemical composition. We observed that HAP NPs coated “smooth” dental flosses led to an increase of viability and proliferation of oral cavity probiotic bacteria (Streptococcus salivarius) and human cells (dermal fibroblasts and osteoblast-like). In contrast, the highest viability loss of probiotic bacteria (S. salivarius), fibroblasts, and osteoblast-like cells were observed for “fluffy” unwaxed dental flosses due to high cytotoxicity. Our studies showed that HAP NPs significantly improved the biological properties of “fluffy” dental floss. Pristine “smooth” DFs (waxed and unwaxed), as well as all HAP-coated DFs, induced acceptable biocompatibility toward selected human cells.

We report a novel room-temperature synthesis of selenium nanoparticles, which for the first time uses lignosulfonate as a stabilizer. Various lignosulfonates obtained both from hardwood and softwood were tested. Selenium oxide was used as the precursor of zero-valent selenium. Three different reducers were tested − sodium borohydride, hydrazine and ascorbic acid − and the latter proved most effective in terms of the particle size and stability of the final colloid. The lignosulfonate-stabilized selenium nanoparticles had a negative zeta potential, dependent on pH, which for some lignosulfonates reached −50 mV, indicating the excellent stability of the colloid. When spherical silica particles were introduced to the synthesis mixture, selenium nanoparticles were deposited on their surface. Additionally, star-like structures consisting of sharp selenium needles with silica cores were observed. After drying, the selenium-functionalized silica had a grey metallic hue. The method reported here is simple and cost-effective, and can be used for the preparation of large quantities of selenium colloids or the surface modification of other materials with selenium.

Titanium dioxide was synthesized in multistep process applying of AAO (Anode Aluminum Oxide) as a template. The TiO 2 nanowires were obtained by deposition of titanium precursors inside the pores of AAO membranes (non-hydrolytic sol-gel technique), calcined at 875 K with subsequent removal of alumina matrix by leaching it with phosphoric acid. During the AAO synthesis, it was proved that the electrical work can serve as the unified factor influencing the amount of formed AAO. The diameters of obtained titania nanowires were consequence of used AAO membranes. The higher density of titania elementary cell was observed for all synthesized nanostructures. It was confirmed by XRD and SAED measurements. The TiO 2 nanowires attached vertically to polymer disc (50 mm diameter) were used in photocatalytic decomposition of methyl orange. All nanomaterials showed ten times higher photocatalytic activity than P-25. High photoactivity of obtained material is related to external area of vertically aligned titania nanowires.

It has been long known that the physical encapsulation of oleic acid-capped iron oxide nanoparticles (OA–IONPs) with the cetyltrimethylammonium (CTA+) surfactant induces the formation of spherical iron oxide nanoparticle clusters (IONPCs). However, the behavior and functional properties of IONPCs in chemical reactions have been largely neglected and are still not well-understood. Herein, we report an unconventional ligand-exchange function of IONPCs activated when dispersed in an ethyl acetate/acetate buffer system. The ligand exchange can successfully transform hydrophobic OA–IONP building blocks of IONPCs into highly hydrophilic, acetate-capped iron oxide nanoparticles (Ac–IONPs). More importantly, we demonstrate that the addition of silica precursors (tetraethyl orthosilicate and 3-aminopropyltriethoxysilane) to the acetate/oleate ligand-exchange reaction of the IONPs induces the disassembly of the IONPCs into monodispersed iron oxide–acetate–silica core–shell–shell (IONPs@acetate@SiO2) nanoparticles. Our observations evidence that the formation of IONPs@acetate@SiO2 nanoparticles is initiated by a unique micellar fusion mechanism between the Pickering-type emulsions of IONPCs and nanoemulsions of silica precursors formed under ethyl acetate buffered conditions. A dynamic rearrangement of the CTA+–oleate bilayer on the IONPC surfaces is proposed to be responsible for the templating process of the silica shells around the individual IONPs. In comparison to previously reported methods in the literature, our work provides a much more detailed experimental evidence of the silica-coating mechanism in a nanoemulsion system. Overall, ethyl acetate is proven to be a very efficient agent for an effortless preparation of monodispersed IONPs@acetate@SiO2 and hydrophilic Ac–IONPs from IONPCs.

In this study ZnPc@TiO2 hybrid nanostructures, both nanoparticles and nanotubes, as potential photosensitizers for the photodynamic therapy, fluorescent bioimaging agents, as well as anti-cancer drug nanocarriers, were prepared via zinc phthalocyanine (ZnPc) deposition on TiO2. In order to provide the selectivity of prepared hybrid nanostructures towards cancer cells they were modified with folic acid molecules (FA). The efficient attachment of both ZnPc and FA molecules was confirmed with dynamic light scattering (DLS), zeta potential measurements and X-ray photoelectron spectroscopy (XPS). It was presented that ZnPc and FA attachment has a strong effect on fluorescence emission properties of TiO2 nanostructures, which can be further used for their simultaneous visualization upon cellular uptake. ZnPc@TiO2 and FA/ZnPc@TiO2 hybrid nanotubes were then employed as doxorubicin nanocarriers. It was demonstrated that doxorubicin can be easily loaded on these hybrid nanostructures via an electrostatic interaction and then released. In vitro cytotoxicity and photo-cytotoxic activity studies showed that prepared hybrid nanostructures were selectively targeting to cancer cells. Doxorubicin loaded hybrid nanostructures were significantly more cytotoxic than un-loaded ones and their cytotoxic effect was even more severe upon irradiation. The cellular uptake of prepared hybrid nanostructures and their localization in cells was monitored in vitro in 2D cell culture and tumor-like 3D multicellular culture environment with fluorescent confocal microscopy. These hybrid nanostructures preferentially penetrated into human cervical cancer cells (HeLa) than into normal fibroblasts (MSU-1.1) and were mainly localized within the cell cytoplasm. HeLa cells spheroids were also efficiently labelled by prepared hybrid nanostructures. Fluorescent imaging of Hela cells treated with doxorubicin loaded hybrid nanostructures showed that doxorubicin was effectively delivered into cells, released and evenly distributed in the cytoplasm. In conclusion, prepared hybrid nanostructures exhibit high potential as selective bioimaging agents next to their photodynamic activity and drug delivery ability.

Phase transformations of Al doped NbN nanocomposite coatings are studied in detail focusing on their microstructural evolution and phase composition. Several techniques such as XRD, SEM, HR-TEM, Nanoindentation and molecular dynamics simulation are employed in order to understand the phase evolution of the Nb-Al-N system. The nanocomposite structures were formed in the coatings, the roughness of the coatings decreased with increasing the Al concentration due to decreasing grain size. First-principles investigation of Nb-Al-N solid solutions was carried out to interpret film properties. It was found, that for small Al fractions, the solid solutions will form in agreement with our experimental results. The spinodal decomposition of Nb-Al-N solid solutions is supposed to be responsible for the formation of the nanocomosite structure observed in the deposited Nb-Al-N films.

Gd2(MoO4)3 (GMO) is a well-studied multiferroic material that exhibits full ferroelectric and ferroelastic behavior at room temperature. However, its difficult stabilization in thin films has prevented the study and exploitation of its multiferroic properties in different architectures. Here, we report on the study of GMO thin films deposited on Si(001) substrates by Pulsed Laser Deposition (PLD). The physicochemical properties of the films are discussed and studied. Results obtained by X-ray diffraction, X-ray photoelectron spectroscopy, high resolution transmission microscopy and second harmonic generation show that the orthorhombic (β′-GMO) multiferroic phase can be stabilized and homogenized by post deposition thermal reconstruction. Finally, the reconstruction process takes place via a complex surface mechanism with a clear leaf-like behavior.

Two polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers differing in molecular mass (49 and 78 kDa) but possessing the same PEO cylindrical morphology are examined to elucidate their molecular dynamics. Of particular interest here is the molecular motion of the PEO blocks involved in the rigid amorphous fraction (RAF). An analysis of complementary thermal calorimetry and X-ray scattering data confirms the presence of microphase-separated morphology as well as semicrystalline structure in each copolymer. Molecular motion within the copolymer systems is monitored by dielectric and nuclear magnetic resonance spectroscopies. The results reported herein reveal the existence of two local Arrhenius-type processes attributed to the noncooperative local motion of PEO segments involved in fully amorphous and rigid amorphous PEO microphases. In both systems, two structural relaxations governed by glass-transition phenomena are identified and assigned to cooperative segmental motion in the fully amorphous phase (the α process) and the RAF (the α

A heterojunction with excellent visible light response and stability based on titanium dioxide nanotubes (TiO2 NTs), bismuth sulfide quantum dots (Bi2S3 QDs), and platinum nanoparticles (Pt NPs) is proposed. Both Pt NPs (3.0 ± 0.2 nm) and Bi2S3 QDs (3.50 ± 0.20 nm) are well distributed on the (i) top parts, (ii) inner walls, and (iii) outer walls of the TiO2 NTs. Visible-light-induced photoreaction was initialized by excitation of narrow band gap Bi2S3 QDs, followed by electron injection to the conduction band of TiO2, while Pt NPs acted as electron traps, enhacing O2–• generation. Phenol in the aqueous phase and toluene in the gas phase were efficiently degraded over Bi2S3–Pt NTs, even for wavelengths longer than 455 and 465 nm, respectively, while no degradation of model compounds was observed over pristine TiO2 NTs under the same irradiation conditions. Photocatalytic tests of phenol degradation in the presence of scavengers revealed that superoxide radicals were responsible for the visible-light degra...

Superparamagnetic behavior in aqueously well dispersible magnetite core-shell Fe3O4@SiO2 nanoparticles is presented. The magnetic properties of core-shell nanoparticles were measured with use of the DC, AC magnetometry and EPR spectroscopy. Particles where characterized by HR-TEM and Raman spectroscopy, showing a crystalline magnetic core of 11.5 ± 0.12 nm and an amorphous silica shell of 22 ± 1.5 nm in thickness. The DC, AC magnetic measurements confirmed the superparamagnetic nature of nanoparticles, additionally the EPR studies performed at much higher frequency than DC, AC magnetometry (9 GHz) have confirmed the paramagnetic nature of the nanoparticles. Our results show the excellent magnetic behavior of the particles with a clear magnetite structure, which are desirable properties for environmental remediation and biomedical applications.

Nanoparticles (NP) string formations on self-assembled copolymeric substrates has been observed. These ”thread of beads” like structures develop via simple colloidal droplet evaporation during meniscus rim withdrawal on polystyrene-block-poly(ethylene oxide) (PS-PEO) copolymer surfaces. It is shown that the process is triggered by the presence of the substrate impurities, which lead to NP aggregate formations serving as string initiation sites. The growth mechanism of these linear structures seems to be capillarity-driven. Moreover, there is an exceptional alignment coupling between NP strips and the block copolymer (BC) domains observed. BC directed NP assembly stems from a gold nanocrystal surface functionalization, which introduces selective affinity for one particular type of BC domain. The presented results reveal a potential fabrication method of NP wires characterized by remarkably low width and thickness comparable with the size of the individual constituent NP.

Carbon nanotubes and a number of other carbon nanomaterials have a tendency to aggregate, which often resulted in difficulties of dispersion of these nanomaterials in aqueous solutions. The ability of dicationic (gemini) surfactants to disperse multiwall carbon nanotubes in water and the dynamic processes taking place at the water–multiwall carbon nanotubes (MWCTs) interface are studied. Stable dispersions of multiwall carbon nanotubes with selected gemini surfactants (1,1′-(1,6-hexanediyl)bis(3-alkyloxymethylimidazolium) dichlorides) were prepared and characterized by nuclear magnetic relaxation dispersion (NMRD), NMR diffusometry, scanning and transmission electron microscopy, and Fourier transform infrared spectroscopy. The addition of multiwall carbon nanotubes to aqueous solutions of studied gemini surfactants leads to significant paramagnetic enhancement of the spin–lattice relaxation processes, which gets more pronounced with increasing concentration of well-dispersed MWNTs in water. The dominant r...

The main aim of this research was the synthesis of the multimodal hybrid ZnO@Gd 2 O 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 2 O 3 nanostructures are polydispersed with size 30–100 nm. NMR (Nuclear Magnetic Resonance) studies of ZnO@Gd 2 O 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 2 O 3 nanostructures could be good contrast agents, useful for magnetic resonance imaging.

Though the cytotoxic properties of magnetite nanoparticles (NPs) are rather well investigated and known to be dose dependent and rather low, surface functionalization can drastically change their properties. To determine whether the cytotoxicity of magnetite/Ag/antibiotic NPs may be associated, among other things, with iron, silver and antibiotic release, this study investigates the release profiles and cytotoxicity of magnetite/Ag/rifampicin and magnetite/Ag/doxycycline NPs compares it similar profiles from magnetite, magnetite/Ag NPs and antibiotics. It was established that the studied NPs released not only water-soluble substances, such as antibiotics, but also poorly-soluble ones, such as iron and silver. The deposition of silver on the magnetite surface promotes the release of iron by the formation of a galvanic couple. Antibiotic adsorbed on the magnetite/Ag surface plays a dual role in the galvanic corrosion processes: as a corrosion inhibitor for iron oxides and as a corrosion promoter for silver. Magnetite/Ag/rifampicin and magnetite/Ag/doxycycline. NPs were found to have greater cytotoxicity towards the HEK293T cell line than magnetite NPs. These results were attributed to the combined toxic action of the released iron, silver ions and antibiotics. Intensive and simultaneous release of the NP components caused cell stress and suppressed their growth.

Sulfanyl porphyrazine with isophthaloxyalkyl substituents was metallated with copper(II), cobalt(II) and iron(II) metal ions. New macrocycles were characterized using MS, UV–Vis and NMR spectroscopy. Compounds were carefully purified by column chromatography and their purity was analyzed by HPLC. According to the voltammetric analysis data, the copper(II), cobalt(II) and iron(II) sulfanyl porphyrazine complexes exhibited good electrochemical reversibility. Well-defined metal ion centered redox processes were observed for cobalt(II) and iron(II) derivatives. These compounds were considered as the electrocatalytically active complexes and immobilized by π-π stacking forces within the matrix of electrochemically reduced graphene oxide. The porphyrazine-graphene hybrids revealed stronger electrocatalytic performance than their separately analyzed counterparts. The electrocatalytic properties of the investigated materials were attributed to the contributions from both the reduced graphene oxide conducting matrix, and the faradaic reactions provided by porphyrazine metal complex immobilized on the electrodes. In the presence of 1 mM of l -cysteine or hydrogen peroxide, the electrocatalytic oxidation coupled with higher catalytic current with reduced overpotential, was observed at the glassy carbon/reduced graphene oxide modified electrode. It was found that the glassy carbon/reduced graphene oxide/porphyrazine electrodes can assay l -cysteine in the linear range between 1.0 and 660 μM (LOD of 0.79 μM) and hydrogen peroxide in the linear range between 4.5 and 460 μM (LOD of 4.0 μM). The formation of the metalled porphyrazine/reduced graphene oxide hybrid is a valuable strategy in obtaining synergetic effects between the redox active macrocyclic complex and a highly conducting carbon support which has potential value for the development of advanced electrodes for electrocatalytic applications.

The synthesis and physicochemical properties of a novel diazepinoporphyrazine possessing G1-dendrimeric substituents are presented. Initially, diaminomaleonitrile was condensed with 1,3-bis-(4-hydroxyphenyl)-1,3-propanedione to give a novel 1,4-diazepine-2,3-dicarbonitrile derivative which was subjected to an alkylation reaction with 3,5-bis(benzyloxy)benzylbromide furnishing a 1,4-diazepine-2,3-dicarbonitrile derivative with bulky substituents. Subsequent macrocyclization led to the desired diazepinoporphyrazine with conjugated, hyperbranched G1-dendrimeric substituents, which was characterized by MS MALDI and NMR. The potential photosensitizing activity of the novel porphyrazine was evaluated by measuring its ability to generate singlet oxygen. This measurement was performed with and without addition of the anti-aggregation agent tetramethylamonium fluoride to determine the role of the monomeric form in singlet oxygen generation.

The molecular dynamics of an ionic liquid (IL) composed of a 1-ethyl-3-methylimidazolium cation and a triflate (trifluoromethanesulfonate) anion, abbreviated as [Emim][TfO], were studied by NMR spectroscopy. By measuring the temperature-dependent high-field 1H and 19F spin-lattice relaxation (SLR) rates, the frequency-dependent 1H and 19F SLR dispersion curves using fast-field-cycling relaxometry, and the temperature-dependent 1H and 19F diffusion constants, and by utilizing the fact that the primary NMR-active nucleus on the Emim cation is 1H, whereas on the TfO anion it is 19F, the cationic and anionic dynamics were studied separately. A single theoretical relaxation model successfully reproduced all the experimental data of both types of resonant nuclei by fitting all the data simultaneously with the same set of fit parameters. Upon cooling, [Emim][TfO] exhibited a supercooled liquid phase between TSL = 256 K and the crystallization temperature TCr ≈ 227–222 K, as confirmed by differential scanning calorimetry (DSC) experiments. Theoretical analysis revealed that within the liquid and the supercooled liquid states of [Emim][TfO], the 1H and 19F relaxation rates are affected by both the rotational and translational diffusional processes with no discontinuous change at TSL. While the rotational diffusion is well described as an Arrhenius thermally activated process, the translational diffusion undergoes strong freezing dynamics that are well described by the Vogel–Fulcher model assuming a freezing temperature of T0 = 157 K. The existence of the supercooled liquid region in the [Emim][TfO] IL should be taken into account when using this IL for a specific application.

Pyrazinoporphyrazines and tribenzopyrazinoporphyrazines were synthesized and studied towards their potential applications in photodynamic therapy. The macrocycles were obtained via Linstead macrocyclization with good yields. The expansion of the porphyrazine periphery with hyperbranched aryl substituents was beneficial in terms of purification and isolation of compounds, effectively hampering their aggregation tendency in different concentrations. The obtained macrocycles were assessed for their singlet oxygen generation quantum yields and revealed far better efficacies for tribenzopyrazinoporphyrazines than pyrazinoporphyrazines. A comparison of the crystal packing of two 2,3-dicyanopyrazine derivatives revealed that the recurring motif of the supramolecular architecture is a dimer formed by π–π stacking interactions between aromatic pyrazine and phenyl rings of the inversion center related molecules.

Organic compounds designed to serve as stable dendrimer cores were developed. A series of aminosugar and amino polyol containing G0 dendrimers were synthesized. The reaction mixture composition was checked by MALDI TOF mass spectrometry, while that of purified products – by 1H and 13C NMR combined with 2D NMR spectroscopy as well as MALDI TOF MSMS mass spectra. Mass spectrometric fragmentation experiments were performed in positive ion mode in order to determine common fragmentation patterns of [M+H]+ ions.

This article reports on the thorough characterization of structural-phase transformation in amorphous TiAlBSiN coating after high temperature annealing at 900 °C in ambient air. The influence of annealing on the tribo-mechanical behavior of the coating at nano and micro scale was also examined. The research included multiple experimental techniques, i.e. AFM, SEM, TEM, HR-TEM, EDS, XPS and Raman spectroscopy. Experiments showed that the amorphous phase of the TiAlBSiN coating undergoes a structural transformation, evidenced in the changes of parameters such as topological and chemical short-range order after the post-deposition annealing at 900 °C in air. The observed structural transformation, leads to a phase separation with the formation of a three dimensional nc-TiAl 3 /a-SiBN(O) nanocomposite structure. The relative increase of hardness, reduced elastic modulus, H/Er ratio and H 2 /E 3 r ratio after high temperature treatment of TiAlBSiN coatings is also reported. The complex interdependency between chemistry, morphology and relative composition of the amorphous TiAlBSiN coating phase, during the high temperature treatment, with the respective change of the tribo-mechanical characteristics, are evidence of the improvement of the coating properties in response to the environmental conditions and high temperature. This work contributes particularly to the development and understanding of flexible nanocomposite protective coatings and their changes at high temperature of operation.

In the present investigation, TiO 2 modified with a different geometry and size of gold particles, such as nanospheres (NSPs), nanostars (NSTs) and nanorods (NRs), were prepared by the immobilization method. The effect of the gold shape, size and TiO 2 matrix type (TiO 2 microspheres or rutile TIO-6_TiO 2 ) were systematically investigated. The obtained photocatalysts were thoroughly characterized by UV–vis diffuse-reflectance spectroscopy (DRS), BET surface area measurements, scanning electron microscopy (SEM), scanning transmission microscopy (TEM), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity under visible light (λ > 420 nm) has been estimated in phenol degradation reaction in an aqueous phase. The significantly high photocatalytic activity under visible light irradiate as demonstrated by the TiO 2 sample modified by spheres of gold. The average rate of phenol decomposition was 1.9 μmol dm −3 min −1 and was three-times higher compared to the pristine TiO 2 amorphous microspheres. On the other hand the photocatalytic activity was relatively lower and was 0.38 and 0.27 μmol dm −3 min −1 for nanorods and nanostars deposited on the amorphous form of TiO 2 microspheres, respectively. The visible light activity decreased in following order: (NSPs)> (NRs)> (NSTs). The obtained photocatalytic efficiency of samples was ascribed to the geometry and the size effect of the enhanced and the possible mechanism for this was discussed in detail. Furthermore, in this work we show the effect of calcination temperature on the structure of gold NPs, NRs and NSs before and after modification on the morphology and photocatalytic activity of Au-TiO 2 .

We report on the synthesis, physico-chemical properties of magnesium sulfanyl porphyrazine derivatives with peripheral hyperbranched groups and their deposition on the multi-walled carbon nanotube surface. Sulfanyl porphyrazines containing bulky and dendrimeric peripheral benzyloxy units, mers, up to their second generation, were synthesized and characterized using MS, UV–Vis, FT-IR, NMR spectroscopy and HPLC. The morphology of the hybrid nanostructures was researched using SEM and AFM microscopy. Their potential for biomedicine and technology was assessed in an electrochemical study. The electrodes modified with dendrimeric sulfanyl porphyrazine/multiwalled carbon nanotube hybrids were utilized for electrocatalytic determination of hydrogen peroxide, which is an important compound generated in many enzymatic reactions. The strong synergistic effect between two nanostructural components, namely multi-walled carbon nanotubes and dendrimeric porphyrazines was evaluated in the electrochemical study. In the result a significant enhancement of electrochemical properties of the modified electrode was observed. The reversible redox couples derived from porphyrazine ring–based electron transfer were responsible for the improvement of the electrocatalytic response of the modified electrode toward hydrogen peroxide reduction. According to the electrochemical results, multi-walled carbon nanotube - dendrimeric porphyrazine hybrids deposited on the surface of glassy carbon electrode constitute a valuable material for enzyme–free biosensor development.

In this study we examine multiwall carbon nanotube (MWCNT) based nanosystems i.e. aligned MWCNT matrices, as potential scaffolds for cell growth and tissue engineering. We present the effect of samples purification and surface modification on the viability, adhesiveness and morphology of human normal gingival fibroblasts (HGF-1) and human osteosarcoma (U2OS) cell lines. We employ spectroscopic and analytical techniques (Scanning Electron Microscopy, Thermal Gravimetric Analysis, Atomic Force Microscopy, Raman and Fourier Transform Infrared Absorption Spectroscopy and Confocal Microscopy) in order to characterize the obtained structures. Furthermore, we analyze the expression level of selected cell adhesion-related genes by the quantitative real-time (qRT-PCR) method and the cell viability for MWCNT powders. We show that the surface structure of MWCNTs carpets contributes to the adhesion of cells. Additionally, we report the increased expression level of integrin, talin and fibronectin, proteins which are involved in cell attachment. We speculate that carbon nanotube based materials can be consider as potential candidates for biomedical purposes and as a biocompatible scaffold for cell growth.

An important subgroup within the porphyrazine (Pz) family constitutes seco-porphyrazines, in the chemical structure of which one pyrrole unit is opened in the oxidative process. So far, there are only limited data on N-seco- and C-seco-Pzs. Here, the synthesis of a novel member of the Pzs seco-family, represented by an S-seco-tribenzoporphyrazine analogue, 22,23-bis(4-(3,5-dibutoxycarbonylphenoxy)butylsulfanyl)tribenzo[b,g,l]-22,23-dioxo-22,23-seco-porphyrazinato magnesium(II), is reported, with moderate 34% yield. The new derivative was characterized using NMR spectroscopy, UV–Vis spectroscopy, and mass spectrometry. In the photochemical study performed following the indirect chemical method with 1,3-diphenylisobenzofuran, S-seco-Pz revealed a high singlet oxygen quantum yield of 0.27 in DMF. Potential photocytotoxicity of S-seco-Pz was assessed in vitro on three cancer cell lines – two oral squamous cell carcinoma cell lines derived from the tongue (CAL 27, HSC-3) and human cervical epithelial adenocarcinoma cells (HeLa). In the biological study, the macrocycle was tested in its free form and after loading into liposomes. It is worth noting that S-seco-Pz was found to be non-toxic in the dark, with cell viability levels over 80%. The photocytotoxic IC50 values for free S-seco-Pz were 0.61, 0.18, and 4.1 µM for CAL 27, HSC-3 and HeLa cells, respectively. Four different liposomal compositions were analyzed, and the cationic liposomes revealed the highest photokilling efficacy, with the IC50 values for CAL 27, HSC-3, and HeLa cells at 0.24, 0.25, and 0.31 µM, respectively. The results of the photocytotoxicity study indicate that the new S-seco-tribenzoporphyrazine can be considered as a potential photosensitizer in photodynamic therapy of cancer, along with the developed cationic liposomal nanocarrier.

A pressing challenge in engineering devices with topological insulators (TIs) is that electron transport is dominated by the bulk conductance, and so dissipationless surface states account for only a small fraction of the conductance. Enhancing the surface-to-volume ratio is a common method to enhance the relative contribution of such states. In thin films with reduced thickness, the confinement results in symmetry-breaking and is critical for the experimental observation of topologically protected surface states. We employ micro-Raman and tip-enhanced Raman spectroscopy to examine three different mechanisms of symmetry breaking in Bi2Te3 TI thin films: surface plasmon generation, charge transfer, and application of a periodic strain potential. These mechanisms are facilitated by semiconducting and insulating substrates that modify the electronic and mechanical conditions at the sample surface and alter the long-range interactions between Bi2Te3 and the substrate. We confirm the symmetry breaking in Bi2Te3 via the emergence of the Raman-forbidden $${{\boldsymbol{A}}}_{{\bf{1}}{\boldsymbol{u}}}^{{\bf{2}}}$$ A 1 u 2 mode. Our results suggest that topological surface states can exist at the Bi2Te3/substrate interface, which is in a good agreement with previous theoretical results predicting the tunability of the vertical location of helical surface states in TI/substrate heterostructures.

The authors regret that few mistakes were made in the original publication by Mrówczyński et al [...]

Here we report on the structural and tribo-mechanical characterization of epitaxial single-crystalline Ti2AlC MAX phase thin films, grown by means of electron beam physical vapor deposition at relatively low temperature (700°C). The growth of phase pure Ti2AlC at a relatively lower temperature when compared to other PVD methods was achieved utilizing a relatively low deposition rate and layer-by-layer deposition technique. The epitaxial growth is evidenced through the combination of XRD, HR-TEM and Raman spectroscopy measurements. The nanomechanical and micro-scale tribological properties of the Ti2AlC thin films were studied by means of nanoindentation and nanoscratch tests. The growth temperature of phase pure single-crystalline Ti2AlC MAX phase thin films was reduced to 700°C utilizing the low-rate layer-by-layer PVD technique.

Multilayer CrN/MoN transition metal nitride coatings were studied in this research. Films were deposited by vacuum arc deposition (Arc-PVD) from Cr and Mo cathodes in nitrogen atmosphere p = 0.4 Pa. Three series of samples with different values of negative bias voltage (−20, −150, and −300 V) applied to the surface were fabricated. Each series has samples with 11, 22, 44, 88, 180 and 354 layers while total thickness was maintained with the same value. Samples were studied by scanning electron microscopy (SEM) on cross-sections and coatings surface, energy-dispersive X-ray spectroscopy (EDS), electron backscatter diffraction (EBSD), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), micro-indentation. Two main cubic phases of γ-Mo N and cubic CrN were detected. It was observed that the crystal growth orientation changes while the negative bias voltage of the substrate decreases. The maximum values of hardness (38–42 GPa) among the studied samples were obtained for coatings with a minimal individual layer thickness of 20 nm deposited at U = −20 V. N 2 b, FCT - Sumy State University(0116U002621). Foundation of Science and Technology (FCT) of Portugal [references NORTE-01- 0145-FEDER-022096, SFRH/BD/129614/2017], Network of Extreme Conditions Laboratories (NECL) and by Ukrainian state budget programs [No. 0116U006816, 0118U003579 and 0116U002621]. Partial support by COST Action CA15102 is also greatly appreciated

Many bacteria become progressively more resistant to antibiotics and it remains a challenging task to control their overall levels. Polymers combined with active biomolecules come to the forefront for the design of antibacterial materials that can address this encounter. In this work, we investigated the photo-crosslinking approach of UV-sensitive benzophenone molecule (BP) with polyvinylpyrrolidone (PVP) polymer within electrospun fibres. The BP and PVP solutions allowed fabricating polymer mats that were subsequently functionalised with antibacterial lysozyme. The physical properties of the crosslinked electrospun fibres were investigated by scanning electron microscopy and atomic force microscopy. The average diameter of the obtained fibres decreased from 290 ± 50 nm to 270 ± 70 nm upon the addition of the crosslinking molecules and then to 240 ± 80 nm and 180 ± 90 nm after subsequent crosslinking reaction at an increasing time: 3 and 5 h, respectively. The peak force quantitative nanomechanical mapping (PF-QNM) indicated the increase of DMT modulus of obtained cross-linked fibres from 4.1 ± 0.8 GPa to 7.2 ± 0.5 GPa. Furthermore, the successful crosslinking reaction of PVP and BP solution into hydrogels was investigated in terms of examining photo-crosslinking mechanism and was confirmed by rheology, Raman, Fourier transform infrared and nuclear magnetic resonance. Finally, lysozyme was successfully encapsulated within cross-linked PVP-BP hydrogels and these were successfully electrospun into mats which were found to be as effective antibacterial agents as pure lysozyme molecules. The dissolution rate of photo cross-linked PVP mats was observed to increase in comparison to pure PVP electrospun mats which opened a potential route for their use as antibacterial, on-demand, dissolvable coatings for various biomedical applications., Graphical Abstract

Nanocomposites based on block copolymer (BCP) and gold nanoparticles (NPs) filler were measured in terms of their structure and polymer chain molecular dynamics. NPs were functionalized in order to gain selective affinity to one specific type of BCP domain. BCP directed NPs assembly was monitored using atomic force microscopy. Thin nanocomposite films were fabricated via spin-coating technique, annealed and subsequently subjected to reactive ion etching in order to expose inorganic NPs location within the BCP matrix. Selective NPs incorporation was confirmed. Furthermore, interesting NPs distribution in quasi-2D crystallites was revealed. Spectroscopic methods (nuclear magnetic resonance and dielectric spectroscopy) enabled investigation of polymer chain reorientations and estimation of the impact of nano-filler on polymer dynamics. Nanocomposite crystallinity was assessed via thermal analysis and supported by spectroscopic techniques.

The growing incidence of cancer is a problem for modern medicine, since the therapeutic efficacy of applied modalities is still not satisfactory in terms of patients&rsquo, survival rates, especially in the case of patients with brain tumors. The destructive influence of chemotherapy and radiotherapy on healthy cells reduces the chances of full recovery. With the development of nanotechnology, new ideas on cancer therapy, including brain tumors, have emerged. Photothermal therapy (PTT) is one of these. It utilizes nanoparticles (NPs) that can convert the light, preferably in the near-infrared (NIR) region, into heat. In this paper, we report the use of nanodiamonds (NDs) conjugated with biomimetic polydopamine (PDA) and indocyanine green (ICG) for glioblastoma cancer PTT therapy. The obtained materials were thoroughly analyzed in terms of their PTT effectiveness, as well as their physicochemical properties. The performed research demonstrated that NDs@PDA@ICG can be successfully applied in the photothermal therapy of glioblastoma for PTT and exhibited high photothermal conversion efficiency &eta, above 40%, which is almost 10 times higher than in case of bare NDs. In regard to our results, our material was found to lead to a better therapeutic outcome and higher eradication of glioblastoma cells, as demonstrated in vitro.

Glioblastoma multiforme (GBM) is the most common type of malignant gliomas, characterized by genetic instability, intratumoral histopathological variability and unpredictable clinical behavior. Disappointing results in the treatment of gliomas with surgery, radiation and chemotherapy have fueled a search for new therapeutic targets and treatment modalities. Here we report new approach towards RNA interference therapy of glioblastoma multiforme based on the magnetic nanoparticles delivery of the double-stranded RNA (dsRNA) with homological sequences to mRNA of tenascin-C (TN-C), named ATN-RNA. The obtained nanocomposite consisted of polyethyleneimine (PEI) coated magnetic nanoparticles conjugated to the dsRNA show high efficiency in ATN-RNA delivery, resulting not only in significant TN-C expression level suppressesion, but also impairing the tumor cells migration. Moreover, synthesized nanomaterials show high contrast properties in magnetic resonance imaging (MRI) and low cytotoxicity combining with lack of induction of interferon response. We believe that the present work is a successful combination of effective, functional, non-immunostimulatory dsRNA delivery system based on magnetic nanoparticles with high potential for further application in GBM therapy.

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. Graphical abstractᅟ Electronic supplementary material The online version of this article (10.1007/s11051-018-4416-y) contains supplementary material, which is available to authorized users.

Alkylation reaction of dimercaptomaleonitrile disodium salt with N-(2-bromoethyl)phthalimide in N,N-dimethylformamide, and potassium carbonate led to novel maleonitrile derivative. This compound was used in the Linstead tetramerization reaction in n-butanol in the presence of magnesium n-butoxide towards magnesium(II) sulfanyl porphyrazine with phthalimide peripheral substituents. Its demetallation and subsequent zinc(II) ion insertion led to zinc(II) sulfanyl porphyrazine derivative. All obtained compounds were thoroughly characterized using UV–vis, MS, and 1H and 13C NMR spectroscopy. The purity of macrocycles was assessed using HPLC. Novel symmetrical porphyrazines were found to generate singlet oxygen in N,N-dimethylformamide and dimethyl sulfoxide in low yields. The highest, over 4% yield of singlet oxygen generation, was noted for zinc(II) porphyrazine derivative in DMSO. In the biological study, the cytotoxicities and photocytotoxicities of symmetrical sulfanyl porphyrazines with phthalimide peripheral substituents were compared with lately obtained unsymmetrical sulfanyl tribenzoporphyrazine, 22,23-bis[3,5-bis(3,5- dimethoxybenzyloxy)benzylsulfanyl]tribenzo[b,g,l]porphyrazinato magnesium(II). The in vitro study was performed on androgen-sensitive human prostate adenocarcinoma (LNCaP) and human prostate cancer (PC3) cell lines using MTT assay. The data obtained for liposomal formulations containing sulfanyl porphyrazines with phthalimide substituents indicated their low and light-independent cytotoxicity against cancer cells. On the contrary, the sulfanyl tribenzoporphyrazine was studied in its free form and after incorporation in liposomes. In the free form it revealed moderate photocytotoxicity against both cancer cell lines with IC50 values of 7.71 μM and 8.82 μM for LNCaP and PC3 cells, respectively. Moreover, the liposomal DOTAP : POPC formulation containing sulfanyl tribenzoporphyrazine revealed over 10-fold higher effectiveness reaching the IC50 up to 0.52 μM against LNCaP cancer cells in comparison to its free form. On the contrary, liposomal PG formulation of sulfanyl tribenzoporphyrazine was found to be inactive on the human cancer cells.

Photocatalytic hydrogen (H2) production on zinc sulfide (ZnS) still remains unsatisfactory because of the fast charge carrier recombination through direct-bandgap and photocorrosion by oxidative holes at the valence band. Here we report on a strongly coupled heterojunction photocatalyst (ZnS/PDA) comprising by a ZnS nanorod and ultrathin polydopamine (PDA). The ZnS/PDA exhibits H2 production rate of 2162.5 μmol h−1 g−1, and 78.7 % of this initial photoactivity is sustained after consecutive running for 24 h. A double staggered heterostructure by interfacial zinc oxysulfide and 1 nm-thick PDA layer gives rise to the effective separation, transport, and tunneling of charge carriers for robust H2 production without the trade-off between photocatalytic stability and activity. We anticipate that the present ZnS/PDA can be exploitable in other catalytic applications, such as disinfection of bacteria and air purification. Furthermore, easy modification of optoelectronic properties by PDA will be applicable to a wide range of materials.

Egg-shaped nanoparticles with a core–shell morphology were synthesized by thermal decomposition of an iron oleate complex. XRD and M(T) magnetic measurements confirmed the presence of FeO (wustite) and Fe3O4 (magnetite) phases in the nanoparticles. Oxidation of FeO to Fe3O4 was found to be the mechanism for the shell formation. As-made nanoparticles exhibited high values of exchange bias at 2 K. Oxidation led to decrease of exchange field from 2880 Oe (in as-made sample) to 330 Oe (in oxidized sample). At temperatures higher than the Neel temperature of FeO (200 K) there was no exchange bias. An interesting observation was made showing the exchange field to be higher than the coercive field at temperatures close to magnetite's Verwey transition.

Due to their unique microphase structure copolymer systems have become important potential candidates for nanolitographic purposes. In order to properly design copolymeric templates a complete characterization of the phase separated system is required. Due to the fact that structural analysis of organic compounds remains demanding, especially when it comes to nanometer scale features such as interfacial spaces, there are very often at least two complementary experimental techniques employed to fully characterize observed morphologies. In this work diblock copolymers of poly (styrene)-b-poly (ethylene oxide) (PS-PEO) with three different molecular weights were investigated. Two different experimental methods were used: nuclear magnetic resonance spectroscopy (NMR) and atomic force microscopy (AFM). AFM topographic images of self-assembled polymer films enabled estimation of average interdomain distances, whereas the NMR spin diffusion experiment provided structural parameters related to stiff PS domains and interfacial space thickness. An application of two complementary methods enabled complete description of the studied morphologies and revealed substantial differences in polymer chain mobility between two distinct phases.

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.

The structural and mechanical properties of NbN and Nb-Si-N films have been investigated both experimentally and theoretically, in their as-deposited and annealed states. The films were deposited using magnetron sputtering at substrate bias (U B ) between 0 and −70 V. While NbN films were found to crystallize in the cubic δ-NbN structure, Nb-Si-N films with Si content of 11–13 at% consisted of a two-phases nanocomposite structure where δ-NbN nanocrystals were embedded in SiN x amorphous matrix. Films deposited at U B =0 V were highly (001)-textured. Application of substrate bias potential led to a depletion of light atoms, and caused a grain size refinement concomitantly with the increase of (111) preferred orientations in both films. The maximum hardness was 28 GPa and 32 GPa for NbN and Nb-Si-N films, respectively. NbN and Nb-Si-N films deposited at U B =−70 V exhibited compressive stress of −3 and −4 GPa, respectively. After vacuum annealing, a decrease in the stress-free lattice parameter was observed for both films, and attributed to alteration of film composition. To obtain insights on interface properties and related mechanical and thermal stability of Nb-Si-N nanocomposite films, first principles molecular dynamics simulations of NbN/SiN x heterostructures with different structures (cubic and hexagonal) and atomic configurations were carried out. All the hexagonal heterostructures were found to be dynamically stable and weakly dependent on temperature. Calculation of the tensile strain-stress curves showed that the values of ideal tensile strength for the δ -NbN(111)- and e-NbN(001)-based heterostructures with coherent interfaces and Si 3 N 4 –like Si 2 N 3 interfaces were the highest with values in the range 36–65 GPa, but lower than corresponding values of bulk NbN compound. This suggests that hardness enhancement is likely due to inhibition of dislocation glide at the grain boundary rather than interfacial strengthening due to Si-N chemical bonding.

Bifunctional nanostructures based on ZnO nanoparticles (NPs) with controlled Gd 2 O 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 2 O 3 shell leads to an increase of the ZnO particles size up to 80–160 nm and the formation the Gd 2 O 3 shell with size of 2–4 nm. The dependence of the phase composition, luminescent and magnetic properties on Gd 2 O 3 content are also discussed.