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In a theoretical study of gas adsorption on carbon nanotubes (CNTs), we conduct a series of ab initio simulations for a “gas–single-wall carbon nanotube” system for gases of particular practical interest: He and NO. The obtained values of adsorption energy reveal preferable localization sites of absorbed He atoms as well as their dependency on the adsorption distances. A significant effect of NO adsorption on CNT electronic properties is demonstrated. The effect of the presence of a vacancy on the adsorption nature is analyzed. It is shown that under the influence of vacancy formation the CNT structure undergoes reconstruction that enables chemisorption of NO molecules.

Novel sugar-sensing, soluble in aqueous media, boronic acid derivatives designed for easy analysis through MALDI mass spectrometry have been synthesized in a high yield through a mild and efficient procedure. The synthesized compounds are based on formylphenylboronic acids, which can bind through the formyl group with acid hydrazides to form the respective hydrazones. As hydrazide substrates, Girard reagents T and P were chosen, which possess precharged ammonium and pyridinium moieties, respectively. Nuclear magnetic resonance spectroscopy (1H, 13C, HSQC, HMBC, and NOESY) and mass spectrometry were employed to study their structure, conformational equilibrium and interaction with selected sugars and other diols. Our study shows that the ammonioacetohydrazones of formylphenylboronic acids are present in DMSO solution in the form of cis/trans amide conformers and the effectiveness of their interaction with sugars depends on the situation of the substituent in relation to the boronic acid group. Introducing an ionic group to the receptor molecule improves the sensitivity for conjugate detection when analyzed by MS with matrix-assisted laser desorption/ionization (MALDI) in the positive-ion mode.

In this study Fe-doped TiO2 (0.35 to 3.50 wt% Fe) nanotubes (NTs) were prepared as the potential photosensitizer for near-visible light driven photodynamic therapy (PDT) against cervical cancer cells (HeLa). Characterization of the prepared nanotubes by X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the successful incorporation of Fe3+ as a dopant into the TiO2 matrix, which was mainly composed of an anatase phase, while elemental mapping using energy dispersive X-ray spectroscopy (EDX) showed homogenous distribution of the dopant ions in TiO2 for both low and high doping levels. UV-Vis studies showed that Fe doping in TiO2 increases the light absorption within the visible range, particularly in the case of 0.70 and 1.40 wt% Fe–TiO2 and provides additional energy levels within the band gap, which promotes the photo-excited charge transport towards the conduction band. Photo-cytotoxic activity of the prepared Fe-doped TiO2 NTs was investigated in vitro against cervical cancer cells (HeLa) and compared with human normal fibroblasts (GM07492). Fe-doped TiO2 NTs exhibited no or lower dark cytotoxicity than un-doped TiO2 NTs, which confirms their superior biocompatibility. Under the near-visible light irradiation (∼405 nm) Fe-doped TiO2 NTs showed higher photo-cytotoxic efficiency than un-doped TiO2 NTs, which was found to be dependent on the NTs concentration, but not on the incubation time of cells after near-visible light irradiation. The highest activity was observed for 0.70 and 1.40 wt% Fe–TiO2 NTs. Fluorescent labeling of treated HeLa cells showed distinct morphological changes, particularly in the perimitochondrial area suggesting a mitochondria-involved apoptosis of cells, but also the nuclei and cytoskeleton were subject to Fe–TiO2 NTs induced photo-damage. Apoptosis of PDT treated HeLa cells was also confirmed using ethidium homodimer (EthD-1).

Metallic nanoparticles, in particular gold nanoparticles (AuNPs), offer a wide spectrum of applications in biomedicine. A crucial issue is their cytotoxicity, which depends greatly on various factors, including morphology of nanoparticles. Because metallic nanoparticles have an effect on cell membrane integrity, their shape and size may affect the viability of cells, due to their different geometries as well as physical and chemical interactions with cell membranes. Variations in the size and shape of gold nanoparticles may indicate particular nanoparticle morphologies that provide strong cytotoxicity effects. Synthesis of different sized and shaped bare AuNPs was performed with spherical (~ 10 nm), nanoflowers (~ 370 nm), nanorods (~ 41 nm), nanoprisms (~ 160 nm) and nanostars (~ 240 nm) morphologies. These nanostructures were characterized and interacting with cancer (HeLa) and normal (HEK293T) cell lines and cell viability tests were performed by WST-1 tests and fluorescent live/dead cell imaging experiments. It was shown that various shapes and sizes of gold nanostructures may affect the viability of the cells. Gold nanospheres and nanorods proved to be more toxic than star, flower and prism gold nanostructures. This may be attributed to their small size and aggregation process. This is the first report concerning a comparison of cytotoxic profile in vitro with a wide spectrum of bare AuNPs morphology. The findings show their possible use in biomedical applications.

For more flexibility of environmental perception by artificial intelligence it is needed to exist the supporting software modules, which will be able to automate the creation of specific language syntax and to make a further analysis for relevant decisions based on semantic functions. According of our proposed approach, of which implementation it is possible to create the couples of formal rules of given sentences (in case of natural languages) or statements (in case of special languages) by helping of computer vision, speech recognition or editable text conversion system for further automatic improvement. In other words, we have developed an approach, by which it can be achieved to significantly improve the training process automation of artificial intelligence, which as a result will give us a higher level of self-developing skills independently from us (from users). At the base of our approach we have developed a software demo version, which includes the algorithm and software code for the entire above mentioned component's implementation (computer vision, speech recognition and editable text conversion system). The program has the ability to work in a multi - stream mode and simultaneously create a syntax based on receiving information from several sources.

Oxygenation is one of the most important physiological parameters of biological systems. Low oxygen concentration (hypoxia) is associated with various pathophysiological processes in different organs. Hypoxia is of special importance in tumor therapy, causing poor response to treatment. Triaryl methyl (TAM) derivative radicals are commonly used in electron paramagnetic resonance (EPR) as sensors for quantitative spatial tissue oxygen mapping. They are also known as magnetic resonance imaging (MRI) contrast agents and fluorescence imaging compounds. We report the properties of the TAM radical tris(2,3,5,6-tetrachloro-4-carboxy-phenyl)methyl, (PTMTC), a potential multimodal (EPR/fluorescence) marker. PTMTC was spectrally analyzed using EPR and characterized by estimation of its sensitivity to the oxygen in liquid environment suitable for intravenous injection (1 mM PBS, pH = 7.4). Further, fluorescent emission of the radical was measured using the same solvent and its quantum yield was estimated. An in vitro cytotoxicity examination was conducted in two cancer cell lines, HT-29 (colorectal adenocarcinoma) and FaDu (squamous cell carcinoma) and followed by uptake studies. The stability of the radical in different solutions (PBS pH = 7.4, cell media used for HT-29 and FaDu cells culturing and cytotoxicity procedure, full rat blood and blood plasma) was determined. Finally, a primary toxicity test of PTMTC was carried out in mice. Results of spectral studies confirmed the multimodal properties of PTMTC. PTMTC was demonstrated to be not absorbed by cancer cells and did not interfere with luciferin-luciferase based assays. Also in vitro and in vivo tests showed that it was non-toxic and can be freely administrated till doses of 250 mg/kg BW via both i.v. and i.p. injections. This work illustrated that PTMTC is a perfect candidate for multimodal (EPR/fluorescence) contrast agent in preclinical studies.

Dielectric and infrared spectroscopies were employed to study inter- and intramolecular glass-transition dynamics in the series of hyperbranched polyesters of the second, third, and fourth generati...

We report on the effect of organic acid capping on the behavior of magnetite nanoparticles. The nanoparticles of magnetite were obtained using microwave activated process, and the magnetic properties as well as the electron magnetic resonance behavior were studied for the Fe3O4 nanoparticles capped with alginic acid. The capped nanoparticles exhibit improved crystalline structure of the surface which leads to an enhanced magnetization. The saturation magnetization Ms increases to ~75% of the bulk magnetization. The improved structure also facilitates quantization of spin-wave spectrum in the finite size nanoparticles and this in turn is responsible for unconventional behavior at low temperatures. In magnetic resonance these anomalies are manifested as an unusual increase in the resonant field Hr(T) and also as a maximum of the spectroscopic splitting geff parameter at low temperatures. The unconventional behavior of the nanoparticles also leads to pronounced upturn of magnetization at low temperatures and a deviation from the Bloch law M(T) T^3/2., Comment: 9 pages, 13 figures

The paper presents results of a systematic NMR studies on fluorinated phenylboronic acids. All possible derivatives were studied. The experimental (1)H, (13)C, (19)F, (11)B, and (17)O spectral data were compared with the results of theoretical calculations. The relation between the calculated natural bond orbital parameters and spectral data (chemical shifts and coupling constants) is discussed. The first examples of (10)B/(11)B isotopic effect on the (19)F spectra and (4)JFO scalar coupling in organic compounds are reported.

In this study, the oxidation of multiwalled carbon nanotubes (MWCNTs) sonicated and/or refluxed in acids (H2SO4/HNO3) was investigated using a combination of high-resolution transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and ab initio computational methods. Sonication of the sample has the strongest effect, leading to the highest concentration of defects and carboxyl groups on the walls. Substantial correlations between treatment protocols, CNT size, and the types of chemical moieties are observed. Finally, based on experimental and computational results, we suggest the mechanism of the oxidation process for attaching the functional groups on the sidewalls.

We report on the preparation method of nanocrystalline titanium dioxide modified with platinum by using nanosecond laser ablation in liquid (LAL). Titania in the form of anatase crystals has been prepared in a two-stage process. Initially, irradiation by laser beam of a titanium metal plate fixed in a glass container filled with deionized water was conducted. After that, the ablation process was continued, with the use of a platinum target placed in a freshly obtained titania colloid. In this work, characterization of the obtained nanoparticles, based on spectroscopic techniques – Raman, X-ray photoelectron and UV-vis reflectance spectroscopy – is given. High resolution transmission electron microscopy was used to describe particle morphology. On the basis of photocatalytic studies we observed the rate of degradation process of methylene blue (MB) (a model organic pollution) in the presence of Pt modified titania in comparison to pure TiO2 – as a reference case. Physical and chemical mechanisms of the formation of platinum modified titania are also discussed here. Stable colloidal suspensions containing Pt modified titanium dioxide crystalline anatase particles show an almost perfect spherical shape with diameters ranging from 5 to 30 nm. The TiO2 nanoparticles decorated with platinum exhibit much higher (up to 30%) photocatalytic activity towards the degradation of MB under UV illumination than pure titania.

The chemical composition of nanoparticles (NPs) may be so designed as to provide measurability for numerous imaging techniques in order to achieve synergistic advantages. Innovative and unique structure of the core/shell ZnO@Gd

The transmembrane (TM) proteins are gateways for molecular transport across the cell membrane that are often selected as potential targets for drug design. The bilitranslocase (BTL) protein facilitates the uptake of various anions, such as bilirubin, from the blood into the liver cells. As previously established, there are four hydrophobic transmembrane segments (TM1&ndash, TM4), which constitute the structure of the transmembrane channel of the BTL protein. In our previous studies, the 3D high-resolution structure of the TM2 and TM3 transmembrane fragments of the BTL in sodium dodecyl sulfate (SDS) micellar media were solved using Nuclear Magnetic Resonance (NMR) spectroscopy and molecular dynamics simulations (MD). The high-resolution 3D structure of the fourth transmembrane region (TM4) of the BTL was evaluated using NMR spectroscopy in two different micellar media, anionic SDS and zwitterionic DPC (dodecylphosphocholine). The presented experimental data revealed the existence of an &alpha, helical conformation in the central part of the TM4 in both micellar media. In the case of SDS surfactant, the &alpha, helical conformation is observed for the Pro258&ndash, Asn269 region. The use of the zwitterionic DPC micelle leads to the formation of an amphipathic &alpha, helix, which is characterized by the extension of the central &alpha, helix in the TM4 fragment to Phe257&ndash, Thr271. The complex character of the dynamic processes in the TM4 peptide within both surfactants was analyzed based on the relaxation data acquired on 15 N and 31 P isotopes. Contrary to previously published and present observations in the SDS micelle, the zwitterionic DPC environment leads to intensive low-frequency molecular dynamic processes in the TM4 fragment.

The nuclear magnetic resonance (NMR) and dielectric spectroscopy (DS) methods were used to investigate the segmental and global dynamics in lamellar microphase separated poly(styrene-b-isoprene) (SI) diblock copolymer. For the first time, the susceptibility representation of the NMR relaxation data is applied to the analysis of the molecular dynamics in complex polymer systems like the diblock copolymer. This approach in combination with the frequency-temperature superposition (FTS) allows one to compare directly the NMR and DS data in an extended frequency range providing a unique comprehensive picture of various relaxation processes present in the system studied. The findings of these investigations include structural relaxations of the polyisoprene (PI) and the polystyrene (PS) blocks, a normal mode relaxation of the PI block, and an extra low frequency interfacial relaxation. Special attention has been devoted to influence of the copolymer morphology on the segmental and global dynamics in PI.

The NanoTech Poland is an annual international conference with a strong scientific agenda focused on nanotechnology in energy, environment, and biomedicine. The Nanotech Poland 2018 was held at the NanoBioMedical Centre and Department of Physics at Adam Mickiewicz University in Poznań from June 6th to June 9th. The aim of NanoTech Poland 2018 was to bring together the scientific community’s principal investigators, scientists, researchers, analysts, clinicians, policy makers, industry experts, and well-established and budding entrepreneurs to discuss the present and future perspectives in nanotechnology and nanoscience research and development. This year, the 1st Symposium on Polydopamine was held on June 6th. This forum was dedicated to the application of polydopamine and related catechol materials in a variety of research fields, both at the nano- and macroscale. The symposium gathered leading scientists from this important research field from top universities and institutions that have been involved in the research revolved around polydopamine. With over 200 national and international participants, NanoTech Poland 2018 and the 1st Symposium on Polydopamine provided a forum to present and discuss the latest scientific news from the field of nanotechnology with a strong interdisciplinary aspect and bioinspired materials.

Polyurethane PEO-based hydrogels have a broad range of biomedical applicability. They are attractive for drug-controlled delivery systems, surgical implants and wound healing dressings. In this study, a PEO based polyurethane hydrogels containing Cloisite® 30B, an organically modified clay mineral, was synthesized. Structure of nanocomposite hydrogels was determined using XRD technique. Its molecular dynamics was studied by means of NMR spectroscopy, DMA and DSC analysis. The mechanical properties and thermal stability of the systems were improved by incorporation of clay and controlled by varying the clay content in polymeric matrix. Molecular dynamics of polymer chains depends on interaction of Cloisite® 30B nanoparticles with soft segments of polyurethanes. The characteristic nanosize effect is observed.

This paper presents comprehensive studies on the molecular dynamics of a pharmaceutically important substance, posaconazole. In order to characterize relaxation dynamics in the supercooled liquid and glassy states, dielectric and mechanical spectroscopies were applied. Dielectric data have indicated multiple relaxation processes that appear above and below the glass transition temperature Tg (τα=100 s) of posaconazole. From the curvature of the dielectric log10(τα) versus inverse of temperature dependence, we determine so-called "fragility", being a very popular parameter for classifying the structural dynamics of supercooled liquids and polymers. From the calculations, we get m=150, which means that is one of the most fragile glass-forming liquids. In this paper, the relaxation dynamics of supercooled posaconazole extracted from the dielectric response function was also confronted with shear-mechanical relaxation. Finally, we have also presented a direct comparison of the fragility and the number of dynamically correlated molecules Nc determined from dynamic calorimetry curves and dielectric and mechanical spectroscopies, showing a clear deviation in the picture of glass-transition dynamics generated by calorimetric and spectroscopic techniques.

Electrochemically mediated atom transfer radical polymerization (eATRP) was investigated for synthesis of star polymers using macroinitiators (MIs), achieving high star yield with low Cu catalyst loading (∼100 ppm, w/w). The arm first method, using MIs, is one of the most robust procedures for star polymer synthesis. During the polymerization, MIs can react with cross-linkers (divinyl or multivinyl compounds) for initial chain extension followed by the cross-linking reaction. The MIs can be transformed to arms of the star, and the cross-linker can form the star core. In this study, poly(ethylene oxide) (PEO, Mn = 2000) based MIs (PEO MIs) were prepared, and the chain-end functionalities were confirmed by 1H NMR analysis. The ATRP functionalized PEO MIs were then used for the star synthesis by reacting with ethylene glycol diacrylate cross-linkers. Various experimental conditions were conducted for optimizing star formation, including MI concentration, MI to cross-linker molar ratio, and applied potential ...

Molecular dynamics of miktoarm star copolymers consisting of poly(n-butyl acrylate) PBA and polyethylene oxide (PEO) arms was studied by means of Broadband Dielectric Spectroscopy (BDS) and Nuclear Magnetic Resonance (NMR) methods. The spectroscopic studies were performed for three types of copolymers differing in the composition, namely materials containing 76%, 46% and 16% molar fraction of PBA arms. The local processes, described by the Arrhenius law (e.g. the anisotropic rotation of methyl groups and the anisotropic local motions in the PEO chain), were observed for the studied systems below the glass transition temperature. It was found that the investigated PBA/PEO miktoarm star copolymers are characterized by single glass transition, which may result from similar values of glass transition temperatures of the PBA and PEO polymers. The segmental dynamics in the studied systems was quantitatively described by using the Vogel-Fulcher-Tammann (VFT) relation applied to combined NMR and BDS data. Moreover, above the glass transition temperature the interfacial polarization and conductivity phenomena were detected with the BDS method for all systems under study.

Water status and diffusion transport were studied in the roots of yellow lupine ( Lupinus luteus L., cv. Juno) treated for 48 h with two selected concentrations of Pb(NO 3 ) 2 : 150 mg l −1 , which inhibited root growth by about 50% (medium stress intensity), as well as 350 mg l −1 , which almost entirely suppressed root elongation (severe stress intensity). Relative water content (RWC), which characterizes the degree of root water saturation, slightly increased at the lower lead concentration and remained unchanged at the higher lead dose. Ultrastructure analyses under a transmission electron microscope revealed that plasmolysis was not evoked by lead in the apical part of the meristem. Moreover, direct observation of meristem cells using Nomarsky optics indicated enhanced vacuolization in the presence of both lead concentrations. These data suggest that the water status of the roots was not affected by the metal. Due to the fact that proline is involved in the maintenance of turgor in the cells, the metabolism of this amino acid was investigated. In the roots, the activity of enzymes involved in proline synthesis, such as pyrroline-5-carboxylate synthetase (P5CS) and ornithine aminotransferase (OAT), increased at 150 mg l −1 Pb 2+ ; nevertheless, proline content was diminished at the lower lead concentration. This effect is likely the result of proline degradation by proline dehydrogenase (PDH), since the activity of this enzyme increased at the lower lead dose. On the other hand, in the presence of 350 mg l −1 Pb 2+ , a low level of proline was correlated with a decrease in the activity of P5CS and OAT, as well as unchanged PDH activity in lupine roots. These data may imply that enzymatic synthesis of proline was strongly damaged by the metal ions. The low level of proline in both experimental variants suggests that proline accumulation is inessential to maintaining the osmotic uptake of water into root cells. NMR spectroscopy showed that exposition of lupine seedlings to lead caused a deceleration in water transport in the roots due to a reduction in the water transfer rate across the membranes (transmembrane transfer) and vacuoles continuum, as well as water diffusion along the root apoplast. Fluorescence staining and immunogold labeling showed the presence of callose strands in cell walls and/or in the vicinity of them. In lead-treated lupine roots, callose was mainly localized in the parenchyma cortex placed lengthwise to the vascular cylinder. Callose deposits in the cell walls may reduce vacuolar transport, as well as increase cell wall resistance to water flow. Deceleration of diffusional water movement to the vascular system, may in turn, influence the rate of long-distance water transport to aerial parts of the plant.

In this study ZnPc@TiO

Producción Científica, The capability of a phthalocyanine-based voltammetric electronic tongue to analyze strong alcoholic beverages has been evaluated and compared with the performance of spectroscopic techniques coupled to chemometrics. Nalewka Polish liqueurs prepared from five apple varieties have been used as a model of strong liqueurs. Principal Component Analysis has demonstrated that the best discrimination between liqueurs prepared from different apple varieties is achieved using the e-tongue and UV-Vis spectroscopy. Raman spectra coupled to chemometrics have not been efficient in discriminating liqueurs. The calculated Euclidean distances and the k-Nearest Neighbors algorithm (kNN) confirmed these results. The main advantage of the e-tongue is that, using PLS-1, good correlations have been found simultaneously with the phenolic content measured by the Folin–Ciocalteu method (R2 of 0.97 in calibration and R2 of 0.93 in validation) and also with the density, a marker of the alcoholic content method (R2 of 0.93 in calibration and R2 of 0.88 in validation). UV-Vis coupled with chemometrics has shown good correlations only with the phenolic content (R2 of 0.99 in calibration and R2 of 0.99 in validation) but correlations with the alcoholic content were low. Raman coupled with chemometrics has shown good correlations only with density (R2 of 0.96 in calibration and R2 of 0.85 in validation). In summary, from the three holistic methods evaluated to analyze strong alcoholic liqueurs, the voltammetric electronic tongue using phthalocyanines as sensing elements is superior to Raman or UV-Vis techniques because it shows an excellent discrimination capability and remarkable correlations with both antioxidant capacity and alcoholic content—the most important parameters to be measured in this type of liqueurs., Fondo Social Europeo (projects POKL.04.01.01-00-368/09 and POKL04.03.00-00-238/12), Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (project AGL2015-67482-R), Junta de Castilla y León (project VA-032U13 and grant BOCYL-D-24112015-9)

Current paper presents the results of investigating of multifunctional Ti-Si-N coatings. Ti-Si-N coatings have been deposited using CAVD method with the aim of studying their chemical, physical, structural and mechanical properties. Coatings of Ti-Si-N were modified by high-intensity ion implantation using copper ions with dose D = 2 × 1017 ions/cm2 and energy E = 60 keV. The results demonstrated that ion implantation has effect on grain size, hardness, and Young modulus of the Ti-Si-N coating.

Coatings Nb-Al-N were deposited on a silicon substrate under argon and nitrogen by magnetron sputtering at a substrate temperature of 350 °C and a constant current of 250 mA at the aluminum cathode. The analysis of the dependence chemical composition, morphology, structure and mechanical properties of the annealing temperature were performed for different series of coatings. Coatings demonstrated high thermal stability after annealing to 1000 °C.

We simulate selective $A1BA2\text{\ensuremath{-}}A$ and $A1BA2\text{\ensuremath{-}}B$ triblock solutions (that is, mixtures of the $A1BA2$ triblock with a solvent of either type $A$ or type $B$) using a lattice Monte Carlo method. Although the simulated triblock chains are compositionally symmetric in terms of the $A$ to $B$ volume ratio, the $A1$ block is significantly shorter than the $A2$ block. For the pure $A1BA2$ melt the phase behavior is relatively well known, including the existence and stability of the recently discovered interstitial micelles which were found at the very strong segregation limit. In this paper, we investigate the stability of the interstitial micelles as a function of triblock volume fraction in a selective solvent of either type $A$ or type $B$. The main finding of this paper is that adding a selective solvent of type $A$ shifts the stability of the interstitial micelles into significantly higher temperatures which may provide a pathway towards experimental studies of interstitial micelles in real triblock solutions. We also find that adding selective solvents to the $A1BA2$ melt gives rise to a variety of nonlamellar nanostructures for temperatures and compositions at which the interstitial micelles are stable.

Previous studies on preferences of phoretic deutonymphs of Uropodina for attachment sites have shown that they frequently select smooth and hydrophobic surfaces. The aim of our study was to provide the detailed morphological and topographical characteristics of beetle body surfaces to which deutonymphs frequently attach and to verify how the presence of setae and surface sculpture affects deutonymph attachment. The study was conducted on Uropoda orbicularis (Müller, 1776) and its common beetle carriers: Aphodius prodromus (Brahm, 1790), Aphodius fimetarius (Linnaeus, 1758), Onthophagus nuchicornis (Linnaeus, 1758) and Margarinotus carbonarius (Hoffmann, 1803). Morphology and topography of elytra, femora, propygidia and pygidia of beetles were analysed mainly using SEM methods supported with CLSM and AFM techniques. The hypothesis that deutonymphs may attach to surfaces covered with setae, if seta density is low enough not to disturb mite movement, was tested. The study revealed that deutonymphs attach to surfaces of various types as follows: (i) smooth, (ii) hairy, i.e., covered with setae, (iii) flat and (iv) sculptured. Smooth body parts and body parts covered with setae of low density were most frequently and intensively occupied with deutonymphs. Surfaces of high seta density were avoided by mites. Within elytra of Aphodius beetles, deutonymphs definitely preferred flat surfaces of elytral intervals. On the contrary, densely punctuated propygidium and pygidium in M. carbonarius were heavily infested with deutonymphs. We conclude that carrier surface morphology and topography are important for Uropodina deutonymph attachment, but these two factors cannot fully explain the observed relation.

International audience; In this paper, iRGD peptide-mediated quantum dots (QDs) delivery was studied. In the first step,dodecanethiol-capped CuInZnxS2 x (ZCIS) QDs were prepared and subsequently transferred into water using a standard and facile ligand exchange approach involving 3-mercaptopropionic acid (MPA). ZCIS@MPA nanocrystals possess a photoluminescence quantum yield (PL QY) of 25%, a PL emission centered at ca. 640 nm and low distributions in size and shape. Next, the iRGD peptide was electrostatically associated to ZCIS@MPA QDs. After cytotoxicity evaluation, the tumor-targeting and penetrating activities of the iRGD/QD assembly were investigated by confocal microscopy. The experiments performed on various cancer cell lines revealed a high penetration ability of the assembly, while the bare QDs were not internalized. Additionally, imaging experiments were conducted on three-dimensional multicellular tumor spheroids in order to mimic the tumor microenvironment in vivo. iRGD/QD assemblies were found to be evenly distributed throughout the whole HeLa spheroid contrary to normal cells where they were not present. Therefore, iRGD/QD assemblies have a great potential to be used as targeted imaging agentsand/or nanocarriers specific to cancer cells.

Structural and optical properties of TiO2 ALD coated silicon nanostructures were investigated. The morphology and chemical composition of TiO2 coated silicon nanopillars and porous silicon were studied by using methods of scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). Optical characteristics were studied using measurements of reflectance and luminescence spectra. Detailed analysis of morphological features and photoluminescence mechanisms were provided. Peculiarities of reflectance spectra were discussed. It was shown the possible application of these structures as antireflectance coatings.

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.

Sulfanyl porphyrazines substituted at their periphery with different dendrimeric moieties up to their first generation were synthesized and characterized by photochemical and biological methods. The presence of a dendrimeric periphery enhanced the spectral properties of the porphyrazines studied. The singlet-oxygen-generation quantum yield of the obtained macrocycles ranged from 0.02 to 0.20 and was strongly dependent on the symmetry of the compounds and the terminal groups of the dendritic outer shell. The in vitro biological effects of three most promising tribenzoporphyrazines were examined; the results indicated their potential as photosensitizers for photodynamic therapy (PDT) against two oral squamous cell carcinoma cell lines derived from the tongue. The highest photocytotoxicity was found for sulfanyl tribenzoporphyrazine that possessed 4-[3,5-di(hydroxymethyl)phenoxy]butyl substituents with nanomolar IC50 values at 10 and 42 nm against CAL 27 and HSC-3 cell lines, respectively.

International audience; Zinc Oxide (ZnO) and graphene (G) have been extensively studied because of their unique physical properties. Here, Graphene-Zinc Oxide (G/ZnO) nanolaminates were fabricated, respectively, by chemical vapor deposition and low temperature atomic layer deposition technique. The number of obtained G/ZnO layers was tuned from 1 to 11 with a total thickness of 100 nm for all prepared nanolaminates. The structure, optical properties and interaction between G and ZnO were studied by X-ray methods, TEM, AFM, Raman and optical spectroscopy. The obtained results were interpreted and analysed taking into account strain and charge effects of graphene in G/ZnO nanostructures. We demonstrate that the bottom graphene used as a substrate stimulated the formation of ZnO crystalline structure. n-doping of graphene caused by charge transfer from ZnO to graphene has been detected by blue-shift of G-band of Raman spectra of the nanolaminates. ZnO photoluminescence intensity was found to be dependent on the number of graphene layers in G/ZnO nanolaminate. n-doping of graphene could be tailored by controlling the construction of the G/ZnO nanolaminates for variety of applications such as, for example, selective adsorption of the target molecules on graphene surface. Thus, G/ZnO nanolaminates may find applications in optical, bio-and chemical sensors.

International audience; Nanolaminates are new class of promising nanomaterials with outstanding properties. Here we explored on the tuning of structural properties and the enhancement of electronic and optical properties of 1D PAN ZnO/Al2O3 nanolaminates designed by atomic layer deposition (ALD) and electrospinning. The influence of ZnO/Al2O3 bilayer thicknesses on the fundamental properties of 1D PAN ZnO/Al2O3 nanolaminates has been investigated. Due to the quantum confinement effect, the shift of XPS peaks to higher energies has been observed. Work function of Al2O3 was mostly independent of the bilayers number, whereas the ZnO work function decreased with an increase of the bilayer number. Photoluminescence of the 1D PAN ZnO/Al2O3 nanolaminates corresponded to emission bands in ZnO nanolayers. Due to quantum confinement and surface band bending, no excitonic peaks were observed. The defect emission band was affected by the band bending and defect concentration. The enhanced photoluminescence of the 1D PAN ZnO/Al2O3 nanolaminates allows applications in optical (bio)sensing field

In the present work, multifunctional Ti-Si-N coatings have been deposited using CAVD method with the aim of studying their chemical, physical, structural and mechanical properties. Coatings of Ti-Si-N were modified by high-intensity ion implantation using copper ions with dose D = 2 × 1017 ions/cm2 and energy E = 60 keV. The results demonstrated that ion implantation has an effect on the grain size, hardness, and Young modulus of the Ti-Si-N coating. Additionally, the effect of Cu implantation on the bioactive properties of coatings was investigated by contact antimicrobial essay. The results show a high release of Cu ions in the cultivation liquid and the low efficiency of the

Morphology and NMR self-diffusion of two miktoarm star copolymers differing in fraction of poly(n-butyl acrylate) and poly(ethylene oxide) (PBA and PEO) arms were under investigation. Structural characteristics of copolymers was obtained on the basis of Small Angle X-Ray Scattering (SAXS) investigations. The phase separated nanoscale morphology of the miktoarm star copolymer with a high fraction of PEO arms was confirmed by Scanning Probe Microscopy (SPM) studies. The modified Avrami approach was used to obtain the information on the non-isothermal crystallization kinetics of the studied systems. It was observed that the crystallization in the system with a higher content of PBA, occurring at higher undercooling, was characterized by a higher crystallization rate. It was also found that increase in PBA arms fraction leads to the reduction in the size of PEO domains. The activation energy of the crystallization process, estimated with Kissinger's method, is lower for miktoarm star copolymer with higher PBA content, which results from facilitation of the transport of PEO chains in the direction of the growing crystal due to the presence of mobile PBA arms. The self-diffusion studies of miktoarm star copolymers melts, carried out with the Pulsed-Gradient STimulated-Echo (PGSTE) Nuclear Magnetic Resonance (NMR) technique, reveals the existence of at least two types of diffusion mechanisms in these systems.

A series of polyurethane nanocomposites were synthesized from thermoplastic polyurethanes (with different hard segment ratios) and two types of organically modified montmorillonites (OMMT) – Cloisite® 10A and Cloisite® 20A. The thermal behavior was examined by non-isothermal thermogravimetry (TG, DTG), Differential Scanning Calorimetry (DSC) and Dynamic-Mechanical Thermal Analysis (DMTA). The results of X-ray analyses showed that the OMMT produced the intercalated polyurethane nanocomposites. It has been proven that the thermal stability and tensile properties of these new systems were higher when the organoclay was present within the polymer matrix. Moreover, these properties depend on both the OMMT loading and the type of gallery cations of the organically modified montmorillonites.

Structural behavior of miktoarm star polymers comprising poly(butyl acrylate) (PBA) and poly(ethylene oxide) (PEO) arms was studied by means of Differential Scanning Calorimetry (DSC), Wide Angle X-Ray Scattering (WAXS), Polarized Optical Microscopy (POM) and Fourier Transform Infrared Spectroscopy (FTIR) methods. The aim of this study was to correlate changes in the composition of the arms of the PBA/PEO miktoarm star polymers with their structures. As a consequence of increasing PBA content, the decrease in crystallinity of the studied PBA/PEO heteroarm star copolymers was observed. Regardless of the copolymer composition, fraction of oxyethylene units in the crystalline PEO phase was similar in all investigated systems. The POM images showed spherulitic morphology of the materials having low PBA content, while an increase in PBA arms fraction leads to the formation of less ordered structures. The analysis of FTIR vibrational spectrum indicates helical conformation of PEO chains in the crystalline phase. Isothermal crystallization studies carried out using the FTIR technique suggest the existence of isolated domains in the nanoscopic scale of investigated materials.

Spin–lattice relaxation time constants, T1, were studied for low-molecular-weight linear and grafted polydimethylsiloxane over a wide temperature and frequency range. Quantitative evaluations of proton T1 measurements indicated two relaxation processes: anisotropic rotation of methyl groups around the Si–C bond (low temperature process) and motions of the PDMS side-chains connected with the glass transition (high temperature process). Additional analyses of the T1 relaxation dispersion profiles revealed specific local segment fluctuation times, which are characteristic of the coherent motions in the grafted polymer chains.

The frequency dependence of spin–lattice relaxation times measured by means of Fast Field Cycling (FFC) Relaxometry and spin locking on and off-resonance NMR techniques were used to study the molecular dynamics of poly(ethylene oxide) polymer in the confined and bulk phases of PEO/MMT nanocomposite systems. The Rouse model, the renormalized Rouse formalism and the concept of reptation were applied to describe the polymer behavior in the samples studied. The polymer dynamics was found to depend on the molecular weight of the polymer intercalated in the clay structure. Analysis of the NMR T 1 ( ν ) profiles allowed discrimination of the molecular dynamics of polymer chains at different locations in the nanocomposite structure. Two components of the T 1 spin–lattice relaxation times were indicated for low molecular weight PEO polymers using the FFC method. The longer one was connected with the bulk polymer, whereas the shorter one was attributed to the intercalated polymer fraction. Analysis of the correlation times indicated that polymer confined in montmorillonite galleries is more rigid than that in the bulk phase. To determine the two phases of the polymer for the high molecular weights polymers, additional methods were applied: spin locking, off-resonance NMR techniques and inversion-recovery experiment at a static magnetic field.

Rheological and dielectric behavior of linear PDMS and alkyl-modified PDMS melts has been studied. Molecular dynamics of linear PDMS, being a model of grafted polydimethylsiloxanes studied, has been examined carefully with particular attention paid to its ability to form the semicrystalline phase. Random incorporation of alkyl groups into PDMS chain has been shown to prevent the polymer crystallization. The glass transition temperature of the grafted PDMS changes proportionally to the modifier content. Both techniques allow characterization of the main α-relaxation, which is related to the glass transition and exhibits similar behavior in all systems. This relaxation is discussed in terms of the Vogel–Fulcher–Tammann–Hesse (VFTH) approach. The fragility of grafted PDMS materials was found to be higher as compared to the linear polymer. The analysis of the rheological data shows the existence of additional slow relaxation, which has been interpreted as the polymer chain motion.

Aqueous suspension of a mixture of 1,2-dimyrilstoyl-sn-glycero-3-phosphocholine (DMPC) and (dodecyloxymethyl)dodecydimethylammonium (DDMDDAC) has been investigated by Fourier transform infrared spectroscopy (FTIR), small angle scattering of synchrotron radiation (SAXS) and dielectric spectroscopy (DS). The introduction of surfactant to DMPC water solution probably induces formation of discoidal (bicellar) phase, as revealed by SAXS studies. The presence of the surfactant has been found to decrease the main phase transition temperature, i.e., from rippled gel to liquid crystalline phase, as indicated by the DS and FTIR results. The small steps in the real part of dielectric permittivity plot vs. temperature can be related to the: planar gel to rippled gel ( L β ′ → P β ′ ) and rippled gel–liquid crystal ( P β ′ → Lα) phase transitions, which is supported by the temperature dependencies of the symmetric and anti-symmetric CH2 band frequencies from FTIR measurements.

Molecular dynamics of polyisoprene, polystyrene and poly(styrene-b-isoprene) diblock copolymer has been studied by means of broadband dielectric and magnetic resonance spectroscopies. The measurements of dielectric permittivity as well as NMR second moment, spin–lattice relaxation times T 1 and T 1 ρ in wide range of temperature were performed. It was found that the copolymer exhibits all motions observed in the neat components i.e., three motions connected with polyisoprene blocks (segmental, normal-mode and methyl group rotation) and one (segmental) related to polystyrene blocks. The mutual interaction between polystyrene and polyisoprene chains leads to stiffening of polyisoprene blocks and loosening of polystyrene structure. The polyisoprene segmental and normal-mode motions were analyzed in terms of the Havriliak–Negami model and Vogel–Fulcher–Tamman (VFT) relation. Based on NMR spin-diffusion experiment the size of polystyrene domains in copolymer was evaluated and accounts to 9 nm.

Dynamic mechanical studies of molecular dynamics have been performed for two ethylene–norbornene copolymers. The analysis of data indicates the existence of three relaxation processes: a primary (α) and two secondary (β and γ) ones. It was found that the secondary processes β and γ are connected with the local motions of ethylene and norbornene groups, respectively and that their rates follow the Arrhenius relation. Moreover, the β process was recognized as the Johari–Goldstein process acting as the precursor of the cooperative structural α-relaxation. Contrary to γ and β processes, the motional rate of α-one follows the Vogel–Fulcher–Tammann equation indicating the cooperative nature of motions involved in this process. An increase in norbornene content in copolymer slows down the molecular dynamics of both norbornene fragments and whole chains, and in consequence shifts these relaxation processes into higher temperatures. Using the Havriliak–Negami formalism the motional parameters for the processes mentioned above were estimated.

Diffusion-weighted magnetic resonance imaging (DW MRI) was applied to the lyotropic lamellar phase of the dodecylammonium chloride/water system (DDACl/H(2)O). In the course of employing a well-known medical imaging method, namely, diffusion tensor imaging (DTI), the system morphology was assessed accurately in the most straightforward way by two-dimensional visualization of eigenvectors associated with planar distribution of effective diffusion tensors throughout the whole slice with 40 microm in-plane resolution. Long-range order was observed in the studied lamellar phase, and morphology was best described by a combination of three- and one-dimensional diffusion.

The (1)H NMR Fast Field Cycling relaxometry was applied to study the molecular dynamics of the human protein HC (alpha (1)-microglobulin), its hydration and aggregation in solution state. The (1)H NMRD data have revealed the complex nature of the water/protein HC system resulting from the co-existence of monomer and dimer forms of the protein in solution as well as the presence of oligosaccharides linked to the polypeptide chain. A comparison of the average correlation time values obtained from the model-free fits with the values predicted on the basis of hydrodynamic tau (r) theory, suggests that the dynamics in solution state is governed mainly by the dimer form of the protein HC (the dominant contribution to the water proton-spin lattice relaxation comes from exchanging protons from the surface of the dimer). The existence of small number of oligomeric forms of the protein HC in solutions is postulated because of the two-step shape of water proton spin-lattice relaxation rate dispersion profiles.