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Chloroquine (CQ) is a first-choice drug against malaria and autoimmune diseases. It has been co-administered with zinc against SARS-CoV-2 and soon dismissed because of safety issues. The structural features of Zn-CQ complexes and the effect of CQ on zinc distribution in cells are poorly known. In this study, state-of-the-art computations combined with experiments were leveraged to solve the structural determinants of zinc-CQ interactions in solution and the solid state. NMR, ESI-MS, and X-ray absorption and diffraction methods were combined with ab initio molecular dynamics calculations to address the kinetic lability of this complex. Within the physiological pH range, CQ binds Zn2+ through the quinoline ring nitrogen, forming [Zn(CQH)Clx(H2O)3-x](3+)-x (x = 0, 1, 2, and 3) tetrahedral complexes. The Zn(CQH)Cl3 species is stable at neutral pH and at high chloride concentrations typical of the extracellular medium, but metal coordination is lost at a moderately low pH as in the lysosomal lumen. The pentacoordinate complex [Zn(CQH)(H2O)4]3+ may exist in the absence of chloride. This in vitro/in silico approach can be extended to other metal-targeting drugs and bioinorganic systems.

Rare-earth-basedCa9RE(PO4)7 (RE = Nd, Gd, Dy) materials were synthesized by solid-state reaction at T = 1200 °C. The obtained tricalcium phosphate (TCP) materials are efficient light emitters due to the presence of RE3+ ions, although these ions are present at high concentrations. Moreover, in these host structures,&nbsp, these ions can be used as optical probes to study their local environments. Thus, photoluminescence (PL) emission spectra of the powder samples clearly indicated, for Dy3+ and Gd3+ ions, the presence of the RE3+ ion in low-symmetry sites with some local structural disorder, and the spectra show the presence of vibrational features (in the case of Gd3+). For the Nd3+ phase, emission bands are present around 900, 1050, and 1330 nm, originating from the 4F3/2 level. In general, these RE-TCP samples are interesting luminescent materials in the visible (Dy), UV (Gd), and NIR (Nd) regions, due to weak concentration quenching even for high concentrations of the emitting ion.

The paper reports an investigation on whether valid results can be achieved in analyzing the structure of datasets although a large percentage of data is missing without replacement. Two types of confirmatory factor analysis (CFA) models were employed for this purpose: the missing data CFA model with an additional latent variable for representing the missing data and the semi-hierarchical CFA model that also includes the additional latent variable and reflects the hierarchical structure assumed to underlie the data. Whereas, the missing data CFA model assumes that the model is equally valid for all participants, the semi-hierarchical CFA model is implicitly specified differently for subgroups of participants with and without omissions. The comparison of these models with the regular one-factor model in investigating simulated binary data revealed that the modeling of missing data prevented negative effects of missing data on model fit. The investigation of the accuracy in estimating the factor loadings yielded the best results for the semi-hierarchical CFA model. The average estimated factor loadings for items with and without omissions showed the expected equal sizes. But even this model tended to underestimate the expected values.

The paper reports an investigation on whether valid results can be achieved in analyzing the structure of datasets although a large percentage of data is missing without replacement. Two types of confirmatory factor analysis (CFA) models were employed for this purpose: the missing data CFA model with an additional latent variable for representing the missing data and the semi-hierarchical CFA model that also includes the additional latent variable and reflects the hierarchical structure assumed to underlie the data. Whereas, the missing data CFA model assumes that the model is equally valid for all participants, the semi-hierarchical CFA model is implicitly specified differently for subgroups of participants with and without omissions. The comparison of these models with the regular one-factor model in investigating simulated binary data revealed that the modeling of missing data prevented negative effects of missing data on model fit. The investigation of the accuracy in estimating the factor loadings yielded the best results for the semi-hierarchical CFA model. The average estimated factor loadings for items with and without omissions showed the expected equal sizes. But even this model tended to underestimate the expected values.

Nickel ferrite nanoparticles (NiFe2O4) synthesized by chemical co-precipitation method, are added to poly(vinylidene fluoride-co-hexafluoroproplyene) (PVDF-HFP) in specific concentrations (1, 2, and 3 wt%) and the composite nanofibers are fabricated by electrospinning. Structural investigation and morphology of the synthesized NiFe2O4 magnetic nanoparticles reveal its spinel nature. The crystalline behavior in addition to the ferroelectric properties of NiFe2O4 enhance the interfacial interaction with the polymer chains and creates better dipole alignment and phase transformations within the nanocomposite. The nanocomposite with 1 wt% NiFe2O4 shows the maximum dielectric constant of 118 at 1 Hz frequency, which is about 24 times higher than that of the neat polymer. At the typical concentration of 2 wt% NiFe2O4 in PVDF-HFP, the nanocomposite is capable to generate an output voltage of 4 V suggesting the possible use of those flexible and magnetic polymer nanocomposites in designing piezoelectric devices. The structural performance, dielectric properties and the energy harvesting performance of the PVDF-HFP/NiFe2O4 nanocomposites are demonstrated here based on the filler and polymer characteristics. This publication was made possible by NPRP grant 6-282-2-119 from the Qatar National Research Fund (a member of Qatar Foundation). The statements made herein are solely the responsibility of the authors. Scopus

Nowadays, there is a very high importance of composite research and variety of their applications in the modern world. In that sense, we researched hollow glass capillaries filled with dissolved Grubbs catalyst (GC) and dicyclopentadiene (DCPD) were incorporated into a fiber-reinforced epoxy with the aim of improving the flow of healing agents to the crack site. The morphological investigation of the crack site was performed using field emission scanning electron microscopy (FESEM), showing the difference between the samples depending on the used solvent. The software analysis of sample photographs has been performed by calculating the fractured/healed surface area of the samples, revealing that approximately 20% of the volume was affected by the impact. Fourier transform infrared spectroscopy (FTIR) revealed that poly (dicyclopentadiene) (PDCPD) formed at the healed interface. However, the FTIR investigation of catalyst stability in different solvents showed structural changes in GC and partial deactivation. The mechanical tests of the samples showed that a recovery of 60% after 24 h at room temperature could be achieved through the use of a solvent and very low concentration of GC. The performed research results are a good base to develop the model for predicting the processes and morphology, with the goal to design the final mechanical and in the future, thermal, properties in advance. This opens a new direction for future research in the field of composite healing. © 2020 Elsevier B.V.

Different classes of foldamers, which are synthetic oligomers that adopt well-defined conformations in solution, have been the subject of extensive studies devoted to the elucidation of the forces driving their secondary structures and their potential as bioactive molecules. Regardless of the backbone type (peptidic or abiotic), the most important features of foldamers are the high stability, easy predictability and tunability of their folding, as well as the possibility to endow them with enhanced biological functions, with respect to their natural counterparts, by the correct choice of monomers. Foldamers have also recently started playing a starring role in the self-assembly of higher-order structures. In this review, selected articles will be analyzed to show the striking number of self-assemblies obtained for foldamers with different backbones, which will be analyzed in order of increasing complexity. Starting from the simplest self-associations in solution (e.g., dimers of β-strands or helices, bundles, interpenetrating double and multiple helices), the formation of monolayers, vesicles, fibers, and eventually nanostructured solid tridimensional morphologies will be subsequently described. The experimental techniques used in the structural investigation, and in the determination of the driving forces and mechanisms underlying the self-assemblies, will be systematically reported. Where applicable, examples of biomimetic self-assembled foldamers and their interactions with biological components will be described.

This work involves the design, fabrication and characterization of metamaterials based on meta-atoms and its assemblies. The aim is to tailor the optical properties that emerge from choosing material and geometry of their basic unit cells. The approach starts with the bottom-up preparation of nanoresonators, which consist in core-shell structures made of plasmonic nanoparticles covering a dielectric core. The coupling between the plasmonic units leads to new plasmon resonances that have a magnetic dipole character. The next step involves the meta-atoms organization on surfaces and the characterization of their structural and optical properties. Highly ordered monolayers and patterns of meta-atoms over large area were obtained via blade coating deposition. The samples are then characterized by spectral high-resolution interference microscopy, which provides information on the scattering intensity and the phase shift induced by the meta-atom. In this way, the scattering response of different meta-atoms is studied in an unprecedented manner.

The thermal behavior and occuring phase transitions of three sodalites, a permanganate-, a perrhenate and a mixed permanganate/perrhenate-sodalite are investigated. Below 300 K a loss of dynamic motion of the templating anions could be observed, causing a phase transition of perrhenate-sodalite. At elevated temperatures all sodalites show a phase transition to the fully expanded structure (P-43n to Pm-3n). At 900 K the permangante-sodalite shows a second phase transition to P23.Further a comprehensive study on cancrinites containing different divalent tetrahedral coordinated anions (XO4 2-; X = Mn, Cr, Se, Mo, W) and their effect on the thermal behavior is performed. Thirdly, a structural investigation of the one-dimensional disordered Intermediate phase is carried out. By correlating the lattice parameter c with the existing zeolite-cages and the chemical composition of the sample the structure of the intermediate phase could be modeled.

H. Klym thanks to the Ministry of Education and Science of Ukraine for support and Dr. P. Demchenko for the assistance in XRD experiments., Crystallization transformation in the 80GeSe2-20Ga2Se3 chalcogenide glasses caused by annealing at 380 °C during different duration (25, 50, 80 and 100 hours) are studied using X-ray diffraction and atomic force microscopy methods. It is established that GeGa4Se phase of low- and high-temperature modification, Ga2Se3 phase (α- and γ-modification) and GeSe2 phases are crystallized during this process. It is shown that annealing duration over 50 h does not lead to further internal structural crystallization, while annealing for 80 h result in processes of surface crystallization., Ministry of Education and Science of Ukraine; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART²

A multidisciplinary study, comprising geological, petrographical and geophysical methods, was carried out for the identification and the geometrical and volumetric assess of the main mineralized bodies (mixed sulphides, Zn-Pb and Fe-Cu) in the area of the Anti-Atlas chain, located at SW of the town of Sidi Flah (Ouarzazate, Morocco). The initial phase of exploration involved an extensive fieldwork (structural investigations and sampling) and a detailed survey for verifying the effectiveness and reliability of the Electrical Resistivity Method (ERT). Geological fieldworks and laboratory analyses played a fundamental role in identifying the resistivity anomalies and constraining tomographic results. Main issues we focused on are: i) mineralized bodies imaging according to the electrodic step; ii) consistency with geometry of mineralized bodies; iii) contrast of electrical resistivity between mineralized dykes and host rocks; iv) possible correlations between the type and amount of sulphides and electrical resistivity.

Within the general goal of reaching high operating temperature while maintaining strong requirements on infrared photodetector performances, the pressure on HgCdTe material quality is increasingly growing. In particular, careful attention is now being paid to stress and stress relaxation within HgCdTe photodiodes. While recent studies have focused on the lattice mismatch induced strain over areas in the order of the wafer, no experimental investigation has been able to resolve the strain at the micrometer level.The typical millimetric spatial resolution limit of standard diffraction can be overtaken using a focused synchrotron X-ray white beam. Indeed, by performing Laue microdiffraction measurements, we can map with a sub-micrometer resolution both the local deviatoric strain and lattice orientation. This thesis focuses on the analysis of etched trenches inside HgCdTe layers with variations on passivation and annealing steps. We are able to investigate a precise mapping around the etching and appreciate the local effects of the processing steps. Diffraction peak displacement mapping evidences bending of the crystal planes around etched trenches, with strong dependence upon the processing steps.Then, we focus on the relative position of all the peaks which are measured simultaneously. Assuming a bi-axial strain between layer and substrate, the slope of the peak relative displacement as a function of their position directly provides the strain value undergone by the material. Thus, we measure the strain through the entire sample with a precision of 3.10-5 and map it with a sub-micronic position precision.Finally, we show how the use of a three point calibrated bending set-up leads to the experimental determination of the plasticity threshold in HgCdTe/CdZnTe epitaxial structures together with the spatial distribution of the applied strain. The dynamics from elastic to plastic regime and the layer behavior once the plastic threshold is reached are investigated. Furthermore, the etching step creates abrupt edges inside the layer, leading to a modification of the strain field by concentrating it on the angles of the trench.; Dans le but d'atteindre une température de fonctionnement élevée tout en conservant de fortes exigences sur les performances des photodétecteurs infrarouges, la pression sur la qualité du matériau HgCdTe augmente de plus en plus. En particulier, une attention spéciale est maintenant portée aux contraintes et à leur relaxation des photodiodes HgCdTe. Bien que de récentes études se soient concentrées sur la déformation induite par un désaccord paramétrique sur des surfaces de la taille d'un plaque, aucune étude expérimentale n'a été capable de résoudre la déformation au niveau micrométrique.La limite de résolution spatiale millimétrique typique de la diffraction standard peut être dépassée en utilisant un faisceau synchrotron de rayons X focalisés. En effet, en effectuant des mesures de microdiffraction Laue, nous pouvons cartographier, avec une résolution submicronique, à la fois la contrainte déviatorique locale et l'orientation de la maille. Cette thèse se concentre sur l'analyse de tranchées gravées à l'intérieur des couches de HgCdTe avec des variations sur les étapes de passivation et de recuit. Nous sommes en mesure d'étudier une cartographie précise autour de la gravure et d'apprécier les effets locaux des étapes de traitement. La cartographie de déplacement des pics de diffraction montre la courbure des plans cristallins autour des tranchées gravées, avec une forte dépendance aux étapes technologiques.Ensuite, nous nous concentrons sur la position relative de tous les pics, qui sont mesurés simultanément. En supposant une contrainte bi-axiale entre la couche et le substrat, la pente du déplacement relatif du pic en fonction de leur position fournit directement la valeur de contrainte subie par le matériau. Ainsi, nous mesurons la déformation à travers l'ensemble de l'échantillon avec une précision de 3.10-5 et la cartographions avec une précision de position submicronique.Enfin, nous montrons comment l'utilisation d'un système de flexion 3 points conduit à la détermination expérimentale du seuil de plasticité dans les structures épitaxiées HgCdTe / CdZnTe ainsi qu'à la distribution spatiale de la contrainte appliquée. La dynamique du régime élastique au régime plastique et le comportement de la couche une fois que le seuil plastique est atteint sont étudiés. De plus, l'étape de gravure crée des bords abrupts à l'intérieur de la couche, conduisant à une modification du champ de contrainte en la concentrant sur les angles de la tranchée.

Within the general goal of reaching high operating temperature while maintaining strong requirements on infrared photodetector performances, the pressure on HgCdTe material quality is increasingly growing. In particular, careful attention is now being paid to stress and stress relaxation within HgCdTe photodiodes. While recent studies have focused on the lattice mismatch induced strain over areas in the order of the wafer, no experimental investigation has been able to resolve the strain at the micrometer level.The typical millimetric spatial resolution limit of standard diffraction can be overtaken using a focused synchrotron X-ray white beam. Indeed, by performing Laue microdiffraction measurements, we can map with a sub-micrometer resolution both the local deviatoric strain and lattice orientation. This thesis focuses on the analysis of etched trenches inside HgCdTe layers with variations on passivation and annealing steps. We are able to investigate a precise mapping around the etching and appreciate the local effects of the processing steps. Diffraction peak displacement mapping evidences bending of the crystal planes around etched trenches, with strong dependence upon the processing steps.Then, we focus on the relative position of all the peaks which are measured simultaneously. Assuming a bi-axial strain between layer and substrate, the slope of the peak relative displacement as a function of their position directly provides the strain value undergone by the material. Thus, we measure the strain through the entire sample with a precision of 3.10-5 and map it with a sub-micronic position precision.Finally, we show how the use of a three point calibrated bending set-up leads to the experimental determination of the plasticity threshold in HgCdTe/CdZnTe epitaxial structures together with the spatial distribution of the applied strain. The dynamics from elastic to plastic regime and the layer behavior once the plastic threshold is reached are investigated. Furthermore, the etching step creates abrupt edges inside the layer, leading to a modification of the strain field by concentrating it on the angles of the trench.; Dans le but d'atteindre une température de fonctionnement élevée tout en conservant de fortes exigences sur les performances des photodétecteurs infrarouges, la pression sur la qualité du matériau HgCdTe augmente de plus en plus. En particulier, une attention spéciale est maintenant portée aux contraintes et à leur relaxation des photodiodes HgCdTe. Bien que de récentes études se soient concentrées sur la déformation induite par un désaccord paramétrique sur des surfaces de la taille d'un plaque, aucune étude expérimentale n'a été capable de résoudre la déformation au niveau micrométrique.La limite de résolution spatiale millimétrique typique de la diffraction standard peut être dépassée en utilisant un faisceau synchrotron de rayons X focalisés. En effet, en effectuant des mesures de microdiffraction Laue, nous pouvons cartographier, avec une résolution submicronique, à la fois la contrainte déviatorique locale et l'orientation de la maille. Cette thèse se concentre sur l'analyse de tranchées gravées à l'intérieur des couches de HgCdTe avec des variations sur les étapes de passivation et de recuit. Nous sommes en mesure d'étudier une cartographie précise autour de la gravure et d'apprécier les effets locaux des étapes de traitement. La cartographie de déplacement des pics de diffraction montre la courbure des plans cristallins autour des tranchées gravées, avec une forte dépendance aux étapes technologiques.Ensuite, nous nous concentrons sur la position relative de tous les pics, qui sont mesurés simultanément. En supposant une contrainte bi-axiale entre la couche et le substrat, la pente du déplacement relatif du pic en fonction de leur position fournit directement la valeur de contrainte subie par le matériau. Ainsi, nous mesurons la déformation à travers l'ensemble de l'échantillon avec une précision de 3.10-5 et la cartographions avec une précision de position submicronique.Enfin, nous montrons comment l'utilisation d'un système de flexion 3 points conduit à la détermination expérimentale du seuil de plasticité dans les structures épitaxiées HgCdTe / CdZnTe ainsi qu'à la distribution spatiale de la contrainte appliquée. La dynamique du régime élastique au régime plastique et le comportement de la couche une fois que le seuil plastique est atteint sont étudiés. De plus, l'étape de gravure crée des bords abrupts à l'intérieur de la couche, conduisant à une modification du champ de contrainte en la concentrant sur les angles de la tranchée.

NASICON-type conductors based on LiGe2(PO4)3 are very promising lithium-conducting electrolytes for all-solid-state lithium-ion and lithium batteries. Al-doped LiGe2(PO4)3 solid electrolytes possessed higher conductivity (∼10-4 S/cm at room temperature) and stability versus metallic Li. In this paper, we present the structure study of Li1.5Al0.5Ge1.5(PO4)3 compound. Fast lithium-ion conductor Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte have been obtained through glass crystallization at 820 °C during 8 h. Structural positions occupied by atoms have been examined by solid state nuclear magnetic resonance experiments. 6Li, 7Li, 27Al и 31P NMR measurements have been performed at room temperature.

The strengthening mechanism based on the formation of precipitates (Guinier-Preston (GP) zones) during decomposition of a metastable supersaturated solid solution is stable and effective below temperatures, which are typically overcome in the piston region facing the combustion chamber. Therefore, pistons experience a progressive loss of strength due to over-aging during service. This contribution reports of a structural investigation on a eutectic AlSi12CuNiMg alloy before and after fatigue testing at high temperatures (up to 350 °C). Metallography, color etching, SEM and TEM are used to elucidate the following aspects: 1) the structural features of the alloy (dendrites of α−phase, primary Si particle size and distribution, morphology and distribution of intermetallic phases); 2) the evolution of the strengthening mechanism (GP zones) with high temperature exposure.

The CuxNi1−xFe2O4 (x = 0.0, 0.2, 0.5, 0.8, 1.0) nanoferrite powder were synthesized through chemical co-precipitation method using only (FeCl3, 6H2O), (NiCl2, 6H2O), (CuCl2, 4H2O), NaOH and acid oleic as raw materials. The synthesized powder was characterized by X-ray diffraction (XRD); it was used to determine the structural properties. The transmission electron microscopy and the scanning electron microscopy were used to determine the morphology and particle size. The Fourier Transform Infra-Red (FT-IR) spectroscopy is used to deduce the structural investigation and confirmation of ferrite. Raman spectroscopy is used to verify that we have synthesized CuxNi1−xFe2O4 and determines their phonon modes. The thermo gravimetric analysis findings allow the thermal cycle determination of samples whereas differential thermal analysis findings allow the phase transition temperature identification. The optical study UV–Visible is used to calculate the band gap energies. The vibrating sample magnetometer was used to obtain the hysteresis parameters. In conclude, the XRD confirmed the single phase spinel structure. The lattice constant increased with the increased copper contents. The size of nanoparticles decreased with the increased copper contents. The magnetic property of the CuxNi1−xFe2O4 shows remarkable changes with change of Cu2+.The variation of copper substitution has a significant influence on the optical, grain size and magnetic properties. The mean crystalline size of the synthesized ferrite was in the range of 14–43 nm., The present work was supported by the Research Funds of Electrochemistry, Materials and Environment Research Unit UREME (UR17ES45), Faculty of Sciences Gabes University, Tunisia and Structures, Properties and Modeling of Solids (SPMS) Laboratory, Ecole Centrale Paris, France.

The cellular form of the prion protein (PrPC) is a highly conserved glycoprotein mostly expressed in the central and peripheral nervous systems by different cell types in mammals. A misfolded, pathogenic isoform, denoted as prion, is related to a class of neurodegenerative diseases known as transmissible spongiform encephalopathy. PrPC function has not been unequivocally clarified, and it is rather defined as a pleiotropic protein likely acting as a dynamic cell surface scaffolding protein for the assembly of different signaling modules. Among the variety of PrPC protein interactors, the neuronal cell adhesion molecule (NCAM) has been studied in vivo, but the structural basis of this functional interaction is still a matter of debate. Here we focused on the structural determinants responsible for human PrPC (HuPrP) and NCAM interaction using stimulated emission depletion (STED) nanoscopy, SPR, and NMR spectroscopy approaches. PrPC co-localizes with NCAM in mouse hippocampal neurons, and this interaction is mainly mediated by the intrinsically disordered PrPC N-terminal tail, which binds with high affinity to the NCAM fibronectin type-3 domain. NMR structural investigations revealed surface-interacting epitopes governing the interaction between HuPrP N terminus and the second module of the NCAM fibronectin type-3 domain. Our data provided molecular details about the interaction between HuPrP and the NCAM fibronectin domain, and revealed a new role of PrPC N terminus as a dynamic and functional element responsible for protein-protein interaction.

Neste estudo, nanocarreadores lipidicos foram preparados a partir do triestearato de glicerila e oleo de ricino em diferentes proporcoes pela tecnica de difusao do solvente a quente. Estearato de PEG-660 ou Poloxamer 188 e lecitina de soja foram usados como surfactante e cossurfactante, respectivamente. Caracteristicas estruturais e fisico-quimicas das particulas foram investigadas por meio de espalhamento de luz dinâmico (DLS), calorimetria exploratoria diferencial (DSC), espalhamento de raios X a altos ângulos (WAXS), microscopia de forca atomica (AFM) e microscopia eletronica de transmissao (TEM e cryo-TEM). A analise por DLS indicou que particulas menores foram obtidas quando o lipidio liquido foi usado sozinho para obter as nanoemulsoes (NEs). Tecnicas microscopicas (TEM e cryo-TEM) mostraram que as NEs apresentaram formas esfericas, enquanto as nanoparticulas lipidicas solidas (NLSs) e os carreadores lipidicos nanoestruturados (CLNs) apresentaram formas mais complexas. As NLSs exibiram estrutura cristalina lamelar, enquanto os CLNs exibiram uma estrutura mista composta de fase cristalina lamelar em contato com compartimento oleoso. Estes experimentos contribuem para um melhor entendimento da capacidade de incorporacao e liberacao de farmacos destes nanocarreadores. In this study, drug delivery nanocarriers based on glyceryl tristearate and castor oil at different ratios were prepared by the hot solvent diffusion method. PEG 660-stearate or Poloxamer 188 and soybean lecithin were used as surfactant and co-surfactant, respectively. Structural and physicochemical characteristics of the particles were investigated by means of dynamic light scattering (DLS), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS), atomic force microscopy (AFM) and transmission electron microscopy (TEM and cryo-TEM). DLS data indicated that smaller particles were obtained when the liquid lipid was used alone to prepare nanoemulsions (NEs). TEM and cryo-TEM images showed that NEs presented spherical particles, whereas solid lipid nanoparticles (SLNs) and nanostructured lipid carriers (NLCs) presented more complex shapes. SLNs exhibited lamellar crystal structure, while NLCs displayed a hybrid structure composed of a lamellar crystalline phase in contact with a liquid oil compartment. These experiments contribute to a better understanding of the structure and release performance of these drug carrier systems.

Carbon nanotube (CNTs) derivatives are nowadays under thorough investigation as biomedically interesting materials. In this paper we describe a method for the preparation of water-soluble CNTs by condensation of the carboxylic groups introduced onto the carbon framework and the primary amine moieties inserted in the naturally occurring biopolymer hyaluronan (HA). The covalent conjugation between CNTs and HA should merge the biocompatibility and further processability of the HA chains with the well-known cellular penetration properties of the CNT derivatives to produce novel drug delivery platforms. In fact, thanks to the primary amino groups introduced in the HA chains, HA-CNT derivatives can be further covalently modified with model drugs like ibuprofen and methotrexate. We describe also the monitoring of all the CNT derivatization steps by diffusion-ordered NMR spectroscopy (DOSY), a technique that allows fast and reliable characterization of these novel derivatives.

Therapeutic vaccination with tumor antigens is a new approach in cancer treatment, which aims at inducing immune response while avoiding the side effects generally associated to many conventional therapies. To improve the efficacy of vaccines, suitable carriers may be used. Herein the insertion of a thioether analogue of GM3 lactone (SNeuAC-C14) into liposomes is reported. SNeuAC-C14 is a potential vaccine for the targeting of saccharide-based tumor epitopes. Different liposome formulations were designed to act as carriers and to generate recognition by tumor epitopes. The structural study of pure and loaded liposomes was carried out by synchrotron Small Angle X-ray Scattering and was complemented by Dynamic Light Scattering and Zeta potential measurements. This provided detailed information on relevant properties of the investigated host-guest structures and showed that the active unit of SNeuAC-C14, i.e. its spiro tricyclic moiety, was located in the polar head region of the liposome bilayer, which is an important requirement for recognition phenomena. Moreover, it was found that most of the SNeuAC-C14/liposome complexes were positively charged. The obtained results allow these systems to be considered as candidates to promote immunoresponse in tumor cells. © 2009 Elsevier B.V. All rights reserved.

A 13-step alkaline permanganate degradation of Bulgarian oil shale kerogen concentrate at ambient temperature was carried out. A high yield of oxidation products (90.1%) and a low yield of gaseous products (2.79%) were obtained. IR and (1)H NMR spectroscopic studies have shown that two significantly different types of high molecular products are present in kerogen. Further oxidation of these structures leads to the formation of low molecular aliphatic and aromatic acids, proven by gas chromotography (GC) and gas chromatography-mass spectrometry (GC-MS). The data obtained at these mild conditions allow us to acquire detailed information about the aromatic structures and polymethylene chain lengths in kerogen.The 5-step oxidation of the kerogen at 90 degrees C provides information about stable aromatic structures. Soluble and insoluble polyfunctional acids in acid medium have close molecular masses and spectral characteristics. The amount of benzene and naphthalene carboxylic acids is 11.3% of the organic matter of the oil shale. Publisher's Version Q2 WOS:000269733900003

cited By 0; Conference of 11th IEEE Nanotechnology Materials and Devices Conference, NMDC 2016 ; Conference Date: 9 October 2016 Through 12 October 2016; Conference Code:125383; International audience; We demonstrated the high throughput production of ultra-thin SiNWs by the innovative Inductively Coupled Plasma (ICP) approach. Our investigations revealed that the vast majority (∼95%) of the ICP produced SiNWs grew according to the Oxide Assisted Growth mechanism, and the 5% through the Vapor-Liquid-Solid mechanism. These SiNWs present an intriguing internal nanostructure, that provides a new kind of nanocomposite, where quantum confinement effects are expected. Indeed, an intense photoluminescence emission in the near infra-red was observed. These results prove the ICP as a genuinely bulk process, which can be exploited for large scale production of thin SiNWs to be integrated into attractive large-area and flexible optoelectronic devices.

In this work, we present in depth structural investigations of nanocomposite ZnO: Ge thin films by utilizing a state of the art grazing incidence small angle x-ray spectroscopy (GISAXS) technique. The samples have been deposited by sequential r.f. and d.c. sputtering of ZnO and Ge thin film layers, respectively, on single crystal Si(100) substrates. Transformation of Ge layers into Ge nanoparticles (Ge-np) has been initiated by ex-situ rapid thermal annealing of asprepared thin film samples at 600 °C for 30, 60, and 90 s under forming gas atmosphere. A special attention has been paid on the effects of reactive and nonreactive growth of ZnO layers on the structural evolution of Ge-np. GISAXS analyses have been performed via cylindrical and spherical form factor calculations for different nanostructure types. Variations of the size, shape, and distributions of both ZnO and Ge nanostructures have been determined. It has been realized that GISAXS results are not only remarkably consistent with the electron microscopy observations but also provide additional information on the large scale size and shape distribution of the nanostructured components. © 2016 Author(s).

cited By 18; International audience; Third-generation TiO2 photocatalysts were prepared by implantation of C+ ions into 110nm thick TiO2 films. An accurate structural investigation was performed by Rutherford backscattering spectrometry, secondary ion mass spectrometry, X-ray diffraction, Raman-luminescence spectroscopy, and UV/VIS optical characterization. The C doping locally modified the TiO2 pure films, lowering the band-gap energy from 3.3eV to a value of 1.8eV, making the material sensitive to visible light. The synthesized materials are photocatalytically active in the degradation of organic compounds in water under both UV and visible light irradiation, without the help of any additional thermal treatment. These results increase the understanding of the C-doped titanium dioxide, helpful for future environmental applications.

International audience; This work focuses on the structural and electrical characterization of La-Ni-O coatings deposited by reactive magnetron sputtering using Plasma Emission Monitoring (PEM) which allows high deposition rate. The optimal regulation setpoint for lanthanumdeposition is determined and then the current dissipated on the nickel target is adjusted to obtain the convenient La/Ni ratio to achieve the K2NiF4 structure. After an appropriate annealing treatment, all coatings exhibit crystalline structures that depend on the La/Ni ratio. Some cracks appear on samples deposited on alumina substrates depending to the argon flow rate and influence their electrical behavior.

International audience; A rational approach for the construction of multistranded artificial beta-sheets based not on hydrogen bonding, but on pi-pi aromatic stacking is presented. Using 4,6-dinitro,3,5-phenylenediamine units, rigid turns were designed that allow face-to-face pi-pi interactions between appended linear aromatic segments to be strong enough for folding in an organic solvent, but weak enough to prevent aggregation and precipitation. Solution and solid state studies on a series of turn units showed that the desired degree of rigidity, resulting from hindered bond rotation, could be fine tuned by the inclusion of additional methyl substituents on the aromatic rings. The high degree of preorganization afforded by these qualities further allowed the facile preparation of macrocyclic sheet structures from their non cyclic precursors. These macrocycles were shown to have slow internal dynamics and defined conforma-tional preferences. Using this background three and five-stranded artificial beta-sheets were synthesized and their folded conformations extensively characterized in solution by NMR. The solid state structures of the three and five-stranded sheets were also elucidated in the solid state by x-ray crystallography and confirmed intramolecular pi-pi aromatic stacking.

The preparation of highly porous piezoelectric materials offers a promising route to ultrasonic transducers with low acoustic impedancees suitable for ranging applications or gas flow measurements. Sol-gel derived lead titanate gel were dried at ambient pressure and under supercritical conditions. Electron microscopy, thermogravimetry and dilatometer measurements were made on samples of the prepared materials. Nitrogen adsorption experiments were performed to get information about the microstructure of gel samples that had been annealed for 1 h at temperatures between 110 and 550 deg C. A comprehensive model for the formation of lead titanate gels was established: primary particles are formed in the initial stage of hydrolysis and condense to yield secondary particles which are the building blocks for thr inorganic network of the wet gel. Solvent evaporation at ambient pressure leads to a complete breakdown of this hirarchy. the microstructural features of the alcogels are mainly conse rved throughout supercritical drying in carbon dioxide at 35 deg C, but shrinkage of secondary particles and their rearrangement result in a low mechanical stability of these aerogels. In contrast to the application of carbon dioxide, supercritical drying in isopropanol at 236 deg C promotes interparticle ripening and thus stabilization of the inorganic network. Under these conditions lead titanate aerogels with improved mechanical stability are obtained.

Transparent oxide semiconducting thin films based on mixed Ti-V oxides were prepared using a modified reactive magnetron sputtering method. Based on structural investigations performed with the help of x-ray diffraction and transmission electron microscopy analysis, two distinct regions in the prepared thin film have been observed: a nanocrystalline TiO2-V2O3-V2O5 mixed composition, and a thin layer consisting of amorphous phase and nanocystalline TiO2 phase deposited directly at the substrate. Optical measurements show excellent transmission in the visible spectral range of 73%, on average. Resistivity of the thin film was found at the order of 105 Ω cm at room temperature. The preparation of mixed Ti-V oxides provides a combination of high transparency and semiconducting properties.

The determination of the state of conservation of historic structures by optical techniques is still not used so widely as it ought to be, and this is clearly reflected also in national norms that make references only to well established techniques such us ultrasound, radar and sonic tests. However, the clear advantages of such techniques, and especially laser based ones like the Laser Doppler Vibrometry (LDV), are driving research in this direction; the most important feature of optical techniques is their non-invasiveness, so that they can be harmlessly employed on items characterized by delicate structures and precious surfaces. For the scope of this paper, LDV has been employed to acquire mechanical waves travelling in sample structures, in order to characterize the degree of connection among different parts of the structure and evaluate the presence and importance of defects. Different case studies will be presented, regarding both laboratory samples and real structures: as regards the field tests, investigations have been conducted in Schwäbisch Gmünd (Holy Cross Minster) and Berlin (Pergamon Museum), and the potential of LDV as a monitoring tool for short term structural evaluation will be also presented using sample walls installed at the University of Bologna.

Fe73.5Si13.5Cu1Nb3B9 and Fe77.2Si11.2Cu0.8Nb3.3B 7.5 nanocomposite materials consisting of nanocrystalline phase in an amorphous matrix were obtained by heat-treatment of their precursor amorphous ribbons. The influence of structural modifications induced during the heat-treatment on soft magnetic properties and magnetoimpedance (MI) effect have been studied. The structural investigations on both these ribbons revealed the presence of two phases, fine grained Fe3Si phase and a residual amorphous phase on heat-treatment. The maximum MI ratio obtained in the present study is 95 at f 4 MHz, for the optimized heat-treated Fe77.2Si 11.2Cu0.8Nb3.3B7.5 ribbon. This is ascribed to the increase in magnetic permeability and decrease in coercive force and intrinsic resistivity. Moreover, a maximum magnetic field sensitivity (?) of 8.3/Oe at f 2.5 MHz is obtained, for the optimized nanocrystalline Fe73.5Si13.5Cu1Nb3B9 ribbon. This suggests that tailoring of the nanocrystalline microstructures induced by optimum heat-treatment conditions can result in obtaining excellent combinations of the magnetic permeability and resistivity. Our results indicate that these Fe-based nanocrystalline materials can be ideally used for low magnetic field and high frequency sensor applications. � 2011 American Institute of Physics.

A new microfluidic sample-preparation system is presented for the structural investigation of proteins using small-angle X-ray scattering (SAXS) at synchrotrons. The system includes hardware and software features for precise fluidic control, sample mixing by diffusion, automated X-ray exposure control, UV absorbance measurements and automated data analysis. As little as 15 l of sample is required to perform a complete analysis cycle, including sample mixing, SAXS measurement, continuous UV absorbance measurements, and cleaning of the channels and X-ray cell with buffer. The complete analysis cycle can be performed in less than 3 min. Bovine serum albumin was used as a model protein to characterize the mixing efficiency and sample consumption of the system. The N2 fragment of an adaptor protein (p120-RasGAP) was used to demonstrate how the device can be used to survey the structural space of a protein by screening a wide set of conditions using high-throughput techniques. © 2011 International Union of Crystallography.

Thermally grown amorphous SiO2 was implanted at room temperature with heavy noble gases Kr and Xe in order to create cavities in the oxide and increase its porosity. The implantation energies were chosen in order to have the same implantation depth for both ions. Although both ions induce bubbles in amorphous SiO2, bubble size and spatial distribution depend upon the ion mass. Moreover, Xe implantation leads to the additional formation of "nanoclusters". Thermal stability of bubbles/cavities depends on the implanted ion. The nucleation of bubbles and nanoclusters in amorphous SiO2 is discussed in terms of ion mobility, gas-defect interactions, and chemical interaction. Bubble growth is shown to occur by a migration and coalescence process.

This thesis presents novel approaches for structural investigation of glucuronides using chemical derivatization in combination with liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MSn). Today, LC-ESI-MSn is the dominant technique for quantitative as well as qualitative analyses of metabolites, due to its high sensitivity and selectivity. However, for compounds without an easily ionizable group, e.g., steroids, the sensitivity is limited. In the work presented in this thesis, a derivatization procedure forming a basic oxime significantly increased the detection sensitivity for the altrenogest glucuronide. Furthermore, in structural evaluations of glucuronides, the limitation of LC-MSn becomes evident due to the initial neutral loss of 176 u, i.e. monodehydrated glucuronic acid, which often makes it impossible to elucidate the structures of the conjugates. To solve this problem, the main part of the work described in this thesis was devoted to chemical derivatization as a means of facilitating the determination of the site of conjugation. For the first time, the isomeric estriol glucuronides were evaluated using a combination of three reagents 2-chloro-1-methylpyridinium iodide (CMPI), 1-ethyl-3-(3-dimethyl- aminopropyl)-carbodiimide (EDC), and 2-picolylamine (PA). Interestingly, the derivatization gave a selective fragmentation pattern leading to differentiation of the isomers. Another derivatization reagent, 1,2-dimethylimidazole-4-sulfonyl chloride (DMISC), was also tested for the first time in structural investigations. The isomeric glucuronides of morphine, formoterol, and hydroxypropranolol were evaluated. They can all be conjugated in aliphatic as well as aromatic positions. DMISC was proven to be useful in two ways. Firstly, the morphine and formoterol glucuronides that contained a free phenol could be differentiated from those that were conjugated in the aromatic position based on different reactivity. Secondly, for the aromatic O-glucuronide of 4’-hydroxypropranolol, DMISC was proven to react with the amine. This product gave a different fragmentation pattern compared to the corresponding derivative of the aliphatic glucuronide.

The analysis of historical structures in need of preservation and restoration interventions is a very complex task due to the large uncertainties in the characterization of structural properties and detailing in view of the structural response. Moreover, the predictive performance of numerical analyses and simulations depend on the availability of information about the constructional properties of the architectural complex, crack patterns and active degradation phenomena. In particular, local changes in material properties or damage due to past events (such as earthquakes) can affect individual structural elements. They can be hardly detected as a result of the maintenance interventions carried out over the centuries and the possibility to carry out limited or even no destructive investigations due to the historical relevance of the structure. Thus, non-destructive investigations play a fundamental role in the assessment of historical structures minimizing, at the same time, the invasiveness of interventions. The present paper deals with an explanatory case study concerning the structural investigations carried out in view of the seismic assessment of an Italian historical monument, the Carthusian monastery of Trisulti in Collepardo, erected in 1204 under Pope Innocenzo HI. The relevance of the case study is due to the application, in combination, of different NDT methods, such as sonic tests, and active and passive infrared thermography, in order to characterize relevant masonry elements. Moreover, an advanced system for the in-situ nondestructive vibration-based estimation of the tensile loads in ancient tie-rods is described and the main results obtained from its application for the characterization of the tie-rods of the cloister are presented.

In the blue spectral region, GaN-based hetero-structures are most commonly applied in light-emitting diodes or laser-diodes. However, the incorporation of Si and Mg, which are most commonly used as n- and p-type dopant material respectively, induces a variety of defects, hence reducing the efficiency and lifetime of the devices. Thus, it is essential to investigate the interplay between dopant incorporation and defect formation. In this thesis, the incorporation of Mg and Si in GaN-films grown on (0001)-sapphire substrates is investigated in detail by applying several synchrotron radiation techniques.The segregational behavior of Si and Mg is investigated by x-ray-photoelectron-spectroscopy (XPS) and XPS-microscopy. For the first time, it is revealed that also Si segregates to the surface and stabilizes surface facets along high symmetry directions. Additionally, it is found that Mg also segregates to the crystal surface at concentrations far below the threshold condition for the formation of pyramidal defects.For the first time, the technique of x-ray standing waves (XSW), which allows to directly conclude on the crystal and defect structure on the atomic scale, is successfully applied to thick crystals with high defect density. In order to compensate for the high crystal mosaicity of GaN, which significantly reduces the accuracy of the XSW measurements, the experiments were performed in near backscattering geometry, as in this setup the intrinsic reflection width becomes large as compared to the tilt mosaicity. Influences of doped crystal material are suppressed by using a thick undoped high quality GaN-film for the formation of a standing wave field, which is used for the investigation of a thin doped film deposited on top. By performing the XSW measurements with probe signals of different surface sensitivity (fluorescence and photoelectrons) the incorporation behavior within the bulk crystal is compared to regions close to the surface.Recording photoelectron signals, non-dipole effects to the photoemission process need to be regarded. However, the non-dipole contributions of the Ga-2p-photoelectrons on the secondary yield can neither be calculated theoretically nor determined experimentally from the XSW photoelectron data, as the structural parameters, especially the coherent fraction, are not known exactly due to the high crystal mosaicity. Within this thesis a technique is suggested that allows to determine the non dipole contributions to the yield by comparing Auger electron and photoelectron secondary signals.The XSW-measurements on Si-doped samples reveal that Si is solely incorporated on substitutional Ga-sites both within the bulk crystal and close to the surface. In the bulk, Si is homogeneously distributed, distorting the crystal lattice in their vicinity. At the surface Si is preferentially incorporated at surface facets. The facet formation can be explained in terms of a strain relaxation mechanism induced by the Si lattice distortion.XSW measurements using Mg-KLL Auger electrons reveal that, with increasing dopant incorporation, Mg atoms progressively occupy non-substitutional sites. This is explained by Mg incorporation of Mg at the basal planes of rod-like inversion domains, which have been observed by scanning electron microscopy. Based on the XSW results, a structural model for the basal planar inversion domains is presented.

International Atomic Energy Agency

In order to discover new bioactive compounds from plant sources which could become new leads or new drugs, extracts should be submitted at the same time to chemical screening and to various biological or pharmacological targets. Metabolite profiling using hyphenated techniques such as LC/UV, LC/MS and more recently LC/NMR, quickly provides plenty of structural information, leading to a partial or a complete on-line de novo structure determination of the natural products of interest. As a complement to this approach, bioassays performed after LC/microfractionation of the extracts allow efficient localisation of the bioactive LC-peaks in the chromatograms. The combination of metabolite profiling and LC/bioassays provides the possibility of distinguishing between already known bioactive compounds (dereplication) and new molecules directly in crude plant extracts. Thus, the tedious isolation of compounds of low interest can be avoided and targeted isolation of new bioactive products or constituents presenting novel or unusual spectroscopic features can be undertaken. Several examples of rapid localisation of bioactive compounds, based on post-chromatographic bioautographic testing of LC/NMR microfractions and subsequent on-line identification will be illustrated. Application of hyphenated techniques for the efficient characterisation of labile constituents or constituents difficult to separate at the preparative scale will also be mentioned. The possibilities and limitations of LC/UV/NMR/MS and LC/bioassay as well as future development expected in this field will be discussed. (C) 2003 Elsevier Science B.V. All rights reserved.

Este trabalho objetivou investigar as principais unidades estruturais de ácidos húmicos obtidos do composto de resíduos sólidos urbano (AH-CRSU) e lodo de estação de tratamento de esgoto (AH-LETE) por meio da pirólise acoplada à cromatografia gasosa / espectrometria de massas. Os ácidos húmicos extraídos do lodo da estação de tratamento de esgotos apresentaram maior quantidade de mono e diaril ésteres de massa mais elevada. Os n-alcanos presentes nos AH-LETE revelaram-se de cadeia mais curta do que nos AH-CRSU. Foram incorporados na estrutura dos AH fragmentos de ftalatos, provavelmente em virtude da contaminação da matéria orgânica por plásticos. Os compostos aromáticos presentes nos AH-LETE originaram-se, principalmente, de derivados do naftaleno e derivados do benzeno com substituição por cadeias alifáticas maiores do que AH-CRSU. Os compostos nitrogenados presentes mostraram-se essencialmente heteroaromáticos e os oxigenados furanos substituídos originados da degradação de carboidratos. Os compostos oxiaromáticos predominantes foram fenóis substituídos. This research was conducted to investigate the principal structural units from humic acids obtained from urban waste compost (AH-CRSU) and sewage sludge (AH-LETE) by pyrolysis - gas chromatography / mass spectrometry. The humic acids from sewage sludge presented most mono and diaryl esters with higher mass. The n-alcans in AH-LETE showed a shorter chain than AH-CRSU. Phthalate fragments were incorporated into the humic acid structures, probably due to an organic matter contamination by plastics. The aromatic compounds in the AH-LETE originated mainly from naphtalene derivatives and benzene derivatives with alquil chain substitutives higher than AH-CRSU. The nitrogenated compounds were essentially heteroaromatic and the oxigenated compounds were substituted furans originated from carbohydrate degradation. The oxiaromatic compounds were substituted phenols.

The energy-dispersive X-ray reflectometry and turbidity measurements are used to investigate the kinetics of concanavalin A binding onto the distearoylphosphatidylcholine/distearoylphosphatidylethanolamine-maltobionamide (DSPC/DSPE-mal1) or distearoylphosphatidylcholine/distearoylphosphatidylethanolamine-maltotetrabionamide (DSPC/mal3) mixed monolayer at the air-water interface. The resulting adsorbed layer of this sugar-binding protein near the membrane with one or three hexoses in the lipid head-group is 3.9 nm or 9.7 nm thick, respectively. The different thicknesses of the adsorbed layer can be correlated with the diverse orientations of the adsorbed proteins. These lay flat on the surface containing DSPE-mal1 and `perpendicular' to the surface containing DSPE-mal3. The monolayer structure is little affected by concanavalin A binding, but the incorporation of sugar lipids decreases the chain tilt and the interfacial thickness marginally. The binding is quasi-exponential with the time constant between some minutes and several hours depending on the concanavalin A and vesicle concentrations in the bulk. The experimental resolution of the time-resolved measurements made with the laboratory-based instrument is 15 min and the spatial resolution is between 0.05 nm and 0.5 nm, depending on the electron contrast. It is estimated that the high-brilliance synchrotron X-ray source combined with the detection method outlined in this work, could permit the kinetic measurements on the time-scale of