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Davide Altamura
Ruolo
III livello - Ricercatore
Organizzazione
Consiglio Nazionale delle Ricerche
Dipartimento
Non Disponibile
Area Scientifica
AREA 03 - Scienze chimiche
Settore Scientifico Disciplinare
CHIM/02 - Chimica Fisica
Settore ERC 1° livello
PE - PHYSICAL SCIENCES AND ENGINEERING
Settore ERC 2° livello
PE5 Synthetic Chemistry and Materials: Materials synthesis, structure-properties relations, functional and advanced materials, molecular architecture, organic chemistry
Settore ERC 3° livello
PE5_1 Structural properties of materials
Diamond is considered as a very promising material for the development of devices for radiation detection. Unlike other conventional photoconductive detectors diamond-based devices should provide high discrimination between UV and visible radiation. In this work we present the electro-optical properties of devices based on randomly oriented diamond films, synthesized in a microwave plasma enhanced chemical vapor deposition reactor. A comparative study on devices with coplanar interdigitated Cr/Au electrodes (with different interelectrode pitches) made of films grown simultaneously on intrinsic and p-doped silicon (100) substrates has been performed. The chemical-structural, morphological, electrical and optical properties of ROD films have been studied. In particular, the optical response has been measured in air using a Xe flash lamp coupled with an optical quartz fiber and a properly tailored front-end electronics based on a charge sensitive amplifier. Experimental results gave indications on how the device performances are dependent on the two types of employed substrates.
The properties of nanoscale materials vary with the size and shape of the building blocks, which can be measured by (grazing-incidence) small-angle X-ray scattering along with the mutual positions of the nanoparticles. The accuracy in the determination of such parameters is dependent on the signal-to-noise ratio of the X-ray scattering pattern and on the visibility of the interference fringes. Here, a first-generation-synchrotron-class X-ray laboratory microsource was used in combination with a new restoration algorithm to probe nanoscale-assembled superstructures. The proposed algorithm, based on a maximum likelihood approach, allows one to deconvolve the beam-divergence effects from data and to restore, at least partially, missing data cut away by the beam stopper. It is shown that the combination of a superbright X-ray laboratory microsource with the data-restoring method allows a virtual enhancement of the instrument brilliance, improving signal-to-noise ratio and fringe visibility and reaching levels of performance comparable to third-generation synchrotron radiation beamlines.
The paper shows how a table top superbright microfocus laboratory X-ray source and an innovative restoring-data algorithm, used in combination, allow to analyze the super molecular structure of soft matter by means of Small Angle X-ray Scattering ex-situ experiments. The proposed theoretical approach is aimed to restore diffraction features from SAXS profiles collected from low scattering biomaterials or soft tissues, and therefore to deal with extremely noisy diffraction SAXS profiles/maps. As biological test cases we inspected: i) residues of exosomes' drops from healthy epithelial colon cell line and colorectal cancer cells; ii) collagen/human elastin artificial scaffolds developed for vascular tissue engineering applications; iii) apoferritin protein in solution. Our results show how this combination can provide morphological/structural nanoscale information to characterize new artificial biomaterials and/or to get insight into the transition between healthy and pathological tissues during the progression of a disease, or to morphologically characterize nanoscale proteins, based on SAXS data collected in a room-sized laboratory.
Conjugated polymers are complex multichromophore systems, with emission properties strongly dependent on the electronic energy transfer through active subunits. Although the packing of the conjugated chains in the solid state is known to be a key factor to tailor the electronic energy transfer and the resulting optical properties, most of the current solution-based processing methods do not allow for effectively controlling the molecular order, thus making the full unveiling of energy transfer mechanisms very complex. Here we report on conjugated polymer fibers with tailored internal molecular order, leading to a significant enhancement of the emission quantum yield. Steady state and femtosecond time-resolved polarized spectroscopies evidence that excitation is directed toward those chromophores oriented along the fiber axis, on a typical time scale of picoseconds. These aligned and more extended chromophores, resulting from the high stretching rate and electric field applied during the fiber spinning process, lead to improved emission properties. Conjugated polymer fibers are relevant to develop optoelectronic plastic devices with enhanced and anisotropic properties.
The ability of peptides to self-assemble represents a valuable tool for the development of biomaterialsof biotechnological and/or biomedical interest. Diphenylalanine homodimer (FF) and its analogues areamong the most promising systems in this field. The longest Phe-based building block hithertocharacterized is pentaphenylalanine (F5). We studied the aggregation propensity and the structural/morphological features of assemblies of zwitterionic hexaphenylalanine H+-F6-O and of three variantscharacterized by different charged states of the terminal ends (Ac-F6-Amide, H+-F6-Amide and Ac-F6-O).As previously observed for PEGylated hexaphenylalanine (PEG8-F6), all F6 variants show a strong tendencyto form b-rich assemblies in which the structural motif is constituted by antiparallel b-strands in thecross-b framework. Extensive replica exchange molecular dynamics simulations carried out on a pairs ofF6 peptides indicate that the antiparallel b-structure of the final assemblies is likely dictated by thepreferred association modes of the individual chains in the very early stages of the aggregation process.Our data suggest that even very small F6 peptides are properly pre-organized and prone to the build-upof the final assembly.
In this chapter, we will focus on a specific X-ray-based technique among those employed in surface science and which is especially suitable for the study of self-assembled nanocrystals: Grazing Incidence Small Angle X-ray Scattering (GISAXS). We will first introduce the main field of investigation considered herein, with basic notions of X-ray scattering from surfaces, and then address basic concepts about GISAXS. Finally, we will describe a few relevant examples of studies, of nanostructured architectures, through ex situ and in situ experiments of grazing incidence X-ray scattering. This manuscript is focused on the former, showing that they can be performed by using laboratory instruments. In situ investigations still need synchrotron radiation sources in most cases; therefore, only a few examples selected from the literature are reported here, for the sake of completeness. The experiments described are mainly performed in the small angle range, providing information on the size and shape of nanocrystals, together with their spatial arrangement. Both 2D and 3D architectures are considered. In particular, GISAXS measurements of 2D superlattices of nano-octapods, performed both at a third generation synchrotron beamline and with a table-top set-up, are compared; the employed table-top set-up is described in a dedicated paragraph. Further examples of grazing incidence studies as performed by the authors with a table-top set-up are reported: a GISAXS study of 3D iron oxide nanocrystal superlattices, showing the importance of modelling in order to obtain structural information from data; a combined small/wide angle scattering (GISAXS/GIWAXS) study of 3D PbS nanocrystal superlattices; and a GIWAXS study of P3HT nanofibres, showing how the ordering at the molecular and atomic length scales can be obtained by exploring different angular ranges in the same grazing incidence geometry. Finally, selected examples of in situ GISAXS studies, performed with synchrotron radiation sources, are described.
Suitable postsynthesis surface modification of lead-chalcogenide quantum dots (QDs) is crucial to enable their integration in photovoltaic devices. Here we exploit arenethiolate anions to completely replace pristine oleate ligands on PbS QDs in the solution phase, thus preserving the colloidal stability of QDs and allowing their solution-based processability into photoconductive thin films. Complete QD surface modification relies on the stronger acidic character of arenethiols compared to that of alkanethiols and is demonstrated by FTIR and UVvisNIR absorption spectroscopy analyses, which provide quantitative evaluation of stoichiometry and thermodynamic stability of the resulting system. Arenethiolate ligands induce a noticeable reduction of the optical band gap of PbS QDs, which is described and explained by charge transfer interactions occurring at the organic/inorganic interface that relax exciton confinement, and a large increase of QD molar absorption coefficient, achieved through the conjugated moiety of the replacing ligands. In addition, surface modification in the solution phase promotes switching of the symmetry of PbS QD self-assembled superlattices from hexagonal to cubic close packing, which is accompanied by further reduction of the optical band gap, ascribed to inter-QD exciton delocalization and dielectric effects, together with a drastic improvement of the charge transport properties in PbS QD solids. As a result, smooth dense-packed thin films of arenethiolate-capped PbS QDs can be integrated in heterojunction solar cells via a single solution-processing step. Such single PbS QD layers exhibit abated cracking upon thermal or chemical postdeposition treatment, and the corresponding devices generate remarkable photocurrent densities and overall efficiencies, thus representing an effective strategy toward low-cost processing for QD-based photovoltaics.
Excitation of lattice vibrations in nanostructured anatase TiO2 frequently occurs at energy values differingfrom that found for the corresponding bulk phase. Particularly, investigations have long aimed at establishinga correlation between the low-frequency Eg(1) mode and the mean crystallite size on the basis of phononconfinementmodels. Here, we report a detailed Raman study, supported by X-ray diffraction analyses, onanatase TiO2 nanocrystals with rod-shaped morphology and variable geometric parameters, prepared by colloidalwet-chemical routes. By examining the anomalous shifts of the Eg(1) mode in the spectra of surfactantcappednanorods and in those of corresponding organic-free derivatives (obtained by a suitable thermal oxidativetreatment), an insight into the impact of exposed facets and of the coherent crystalline domain size onRaman-active lattice vibrational modes has been gained. Our investigation offers a ground for clarifying thecurrent lack of consensus as to the applicability of phonon-confinement models for drawing information on thesize of surface-functionalized TiO2 nanocrystals upon analysis of their Raman features.
The dynamism of proteins is central to their function, and several proteins have beendescribed as flexible, as consisting of multiple domains joined by flexible linkers, and even asintrinsically disordered. Several techniques exist to study protein structures, but small angle X-rayscattering (SAXS) has proven to be particularly powerful for the quantitative analysis of such flexiblesystems. In the present report, we have used SAXS in combination with X-ray crystallographyto highlight their usefulness at characterizing flexible proteins, using as examples two proteinsinvolved in different steps of ribosome biogenesis. The yeast BRCA2 and CDKN1A-interactig protein,Bcp1, is a chaperone for Rpl23 of unknown structure. We showed that it consists of a rigid, slightlyelongated protein, with a secondary structure comprising a mixture of alpha helices and beta sheets.As an example of a flexible molecule, we studied the SBDS (Shwachman-Bodian-Diamond Syndrome)protein that is involved in the cytoplasmic maturation of the 60S subunit and constitutes the mutatedtarget in the Shwachman-Diamond Syndrome. In solution, this protein coexists in an ensemble ofthree main conformations, with the N- and C-terminal ends adopting different orientations withrespect to the central domain. The structure observed in the protein crystal corresponds to an average of those predicted by the SAXS flexibility analysis.
The evolution from solvated precursors to hybrid halide perovskite films dictates most of the photophysicaland optoelectronic properties of the final polycrystalline material. Specifically, the complex equilibria andthe importantly different solubilities of lead iodide (PbI2) and methylammonium iodide (MAI) induceinhomogeneous crystal growth, often leading to a defect dense film showing non-optimaloptoelectronic properties and intrinsic instability. Here, we explore a supramolecular approach based onthe use of cyclodextrins (CDs) to modify the underlying solution chemistry. The peculiar phenomenondemonstrated is a tunable complexation between different CDs and MA+ cations concurrent to an out ofcage PbI2 intercalation. Notably, the first report of a connection between the solvation equilibria of thetwo perovskite precursors identified the optimal conditions in terms of CD cavity size and polarity andthose translate to a neat enhancement of PbI2 solubility in the reaction media, leading to an equilibration3 of the availability of the precursors in solution. The macroscopic result of this is an improved nucleationprocess, leading to a perovskite material with higher crystallinity, better optical properties and improvedmoisture resistance. Remarkably, the use of CDs presents a great potential for a wide range of devicerelatedapplications, as well as for the development of tailored composite materials.
Scanning small and wide angle X-ray scattering (scanning SWAXS) experiments were performed on healthy and pathologic human bone sections. Via crystallographic tools the data were transformed into quantitative images and as such compared with circularly polarized light (CPL) microscopy images. SWAXS and CPL images allowed extracting information of the mineral nanocrystalline phase embedded, with and without preferred orientation, in the collagen fibrils, mapping local changes at sub-osteon resolution. This favorable combination has been applied for the first time to biopsies of dwarfism syndrome and Paget's disease to shed light onto the cortical structure of natural bone in healthy and pathologic sections.
ZnO thin films, prepared using a printing-compatible sol-gel method involving a thermal treatmentbelow 400 °C, are proposed as active layers in water-gated thin-film transistors (WG-TFTs). Thethin-film structure and surface morphology reveal the presence of contiguous ZnO crystalline(hexagonal wurtzite) with isotropic nano-grains as large as 10nm characterized by a preferentialorientation along the a-axis. The TFT devices are gated through a droplet of deionized waterby means of electrodes characterized by different work functions. The high capacitance ofthe electrolyte allowed operation below 0.5V. While the Ni, Pd, Au and Pt gate electrodes areelectrochemically stable in the inspected potential range, electrochemical activity is revealed for theW one. Such an occurrence leads to an increase of capacitance (and current), which is ascribed to ahigh output current from the dissolution of a lower capacitance W-oxide layer. The environmentalstability of the ZnO WG-TFTs is quite good over a period of five months
The aim of this work was to investigate the structural features of type I collagen isoforms and collagen-based films at atomic and molecular scales, in order to evaluate whether and to what extent different protocols of slurry synthesis may change the protein structure and the final properties of the developed scaffolds. Wide Angle X-ray Scattering data on raw materials demonstrated the preferential orientation of collagen molecules in equine tendon-derived collagens, while randomly oriented molecules were found in bovine skin collagens, together with a lower crystalline degree, analyzed by the assessment of FWHM (Full Width at Half Maximum), and a certain degree of salt contamination. WAXS and FT-IR (Fourier Transform Infrared) analyses on bovine collagen-based films, showed that mechanical homogenization of slurry in acidic solution was the treatment ensuring a high content of super-organization of collagen into triple helices and a high crystalline domain into the material. In vitro tests on rat Schwannoma cells showed that Schwann cell differentiation into myelinating cells was dependent on the specific collagen film being used, and was found to be stimulated in case of homogenization-treated samples. Finally DHT/EDC crosslinking treatment was shown to affect mechanical stiffness of films depending on collagen source and processing conditions.
Hybrid halide perovskite solar cells generally show differences in the power output depending on the voltage sweep direction, an undesired phenomenon termed hysteresis. Although the causes of this behavior have not yet been univocally determined, commonly, hysteresis heavily affects solar cells based on flat TiO2 as electron extracting layer. Herein, it is shown how perovskite material quality has a preeminent impact on hysteresis, and how combined deposition and post-deposition engineered manufacturing could lead to highly efficient and hysteresis-less solar cells, notwithstanding a planar TiO2-based layout. This methodology relies on solvent engineering during the casting process, leading to an ultra-flat, uniform, and thick film ensuring an optimal interface connection with the charge-extracting layer combined with post-deposition thermal and vacuum treatments, which merge the crystalline domains and cure the defects at the grain boundaries. This method allows obtaining perovskite active layer with superior optical properties, explaining the ideal device behavior and performances, therefore, a simple optimization of perovskite processing conditions can efficiently stem hysteresis targeting different device layouts. Power conversion efficiency of 15.4% and reduced hysteresis are achieved.
In this work, the use of unconventional reference materials to determine experimentally the Cliff-Lorimer factor for EDS quantitative analysis with a TEM is checked by means of an alternative experimental procedure. The k-factor is determined by the extrapolation method based on pure elements, by measuring the normalized X-ray intensities emitted by thin films of pure gold and pure silver of different thickness, accurately measured by X-ray reflectivity. The goal of this work is to confirm the value of the k-factor previously obtained by the use of unconventional reference materials consisting of a bi-layer of pure gold on pure silver. The current result is in accordance with the previous one when considering their error bars, however, their relative difference is about 13 %, probably due to some uncertainties in mass thickness measurements. The mass thickness measurement of the layers of pure elements needs to be performed by different methods in order to reduce its uncertainty.
Organic capped Au nanoparticles (NPs) and PbS quantum dots (QDs), synthesized with high control on size and size distribution, were used as building blocks for fabricating solid crystals by solvent evaporation. The superlattice formation process for the two types of nano-objects was investigated as a function of concentration by means of electron microscopy and X-ray techniques. The effect of building block composition, size, geometry, and concentration and the role of the organic coordinating molecules was related to the degree of order in the superlattices. A convenient combination of different complementary X-ray techniques, namely in situ and ex situ GISAXS and GIWAXS, allowed elucidating the most reliable signatures of the superlattices at various stages of the self-assembly process, since their early stage of formation and up to few months of aging. Significantly different assembly behaviour was assessed for the two types of NPs, clearly explained on the basis of their chemical composition, ultimately reflecting on the assembling process and on the final structure characteristics.
A colloidal crystal-splitting growth regime has been accessed, in which TiO2 nanocrystals, selectively trapped in the metastable anatase phase, can evolve to anisotropic shapes with tunable hyperbranched topologies over a broad size interval. The synthetic strategy relies on a nonaqueous sol-gel route involving programmed activation of aminolysis and pyrolysis of titanium carboxylate complexes in hot surfactant media via a simple multi-injection reactant delivery technique. Detailed investigations indicate that the branched objects initially formed upon the aminolysis reaction possess a strained monocrystalline skeleton, while their corresponding larger derivatives grown in the subsequent pyrolysis stage accommodate additional arms crystallographically decoupled from the lattice underneath. The complex evolution of the nanoarchitectures is rationalized within the frame of complementary mechanistic arguments. Thermodynamic pathways, determined by the shape-directing effect of the anatase structure and free-energy changes accompanying branching and anisotropic development, are considered to interplay with kinetic processes, related to diffusion-limited, spatially inhomogeneous monomer fluxes, lattice symmetry breaking at transient Ti5O5 domains, and surfactant-induced stabilization. Finally, as a proof of functionality, the fabrication of dye-sensitized solar cells based on thin-film photoelectrodes that incorporate networked branched nanocrystals with intact crystal structure and geometric features is demonstrated. An energy conversion efficiency of 6.2% has been achieved with standard device configuration, which significantly overcomes the best performance ever approached with previously documented prototypes of split TiO2 nanostructures. Analysis of the relevant photovoltaic parameters reveals that the utilized branched building blocks indeed offer light-harvesting and charge-collecting properties that can overwhelm detrimental electron losses due to recombination and trapping events.
We exploit TiO2 surface functionalization as a tool to induce the crystallization process of CH3NH3PbI3xClxperovskite thin films resulting in a reduction of the degree of orientation of the (110) crystallographic planes.Notably, the variation of the film crystalline orientational order does not affect the photovoltaicperformances of the perovskite-based devices, whose efficiency remains mostly unchanged. Ourfindings suggest that other factors are more significant in determining the device efficiency, such as thenon-homogenous coverage of the TiO2 surface causing charge recombination at the organic/TiO2interface, defect distribution on the perovskite bulk and at the interfaces, and transport in the organic orTiO2 layer. This observation represents a step towards the comprehension of the perovskite filmpeculiarities influencing the photovoltaic efficiency for high performance devices.
SnO2 nanocrystals were prepared by precipitation in dodecylamine at 100°C, then they were reacted with vanadium chloromethoxide in oleic acid at 250°C. The resulting materials were heat-treated at various temperatures up to 650°C for thermal stabilization, chemical purification and for studying the overall structural transformations. From the crossed use of various characterization techniques, it emerged that the as-prepared materials were constituted by cassiterite SnO2 nanocrystals with a surface modified by isolated V(IV) oxide species. After heat-treatment at 400°C, the SnO2 nanocrystals were wrapped by layers composed of vanadium oxide (IV-V mixed oxidation state) and carbon residuals. After heating at 500°C, only SnO2 cassiterite nanocrystals were obtained, with a mean size of 2.8nm and wrapped by only V2O5-like species. The samples heat-treated at 500°C were tested as RhB photodegradation catalysts. At 10-7M concentration, all RhB was degraded within 1h of reaction, at a much faster rate than all pure SnO2 materials reported until now.
Biosystems integration into an organic field-effect transistor (OFET)structure is achieved by spin coating phospholipid or protein layersbetween the gate dielectric and the organic semiconductor. Anarchitecture directly interfacing supported biological layers to theOFET channel is proposed and, strikingly, both the electronic propertiesand the biointerlayer functionality are fully retained. Theplatform bench tests involved OFETs integrating phospholipids andbacteriorhodopsin exposed to 1-5% anesthetic doses that revealdrug-induced changes in the lipid membrane. This result challengesthe current anesthetic action model relying on the so far providedevidence that doses much higher than clinically relevant ones(2.4%) do not alter lipid bilayers' structure significantly. Furthermore,a streptavidin embedding OFET shows label-free biotin electronicdetection at 10 parts-per-trillion concentration level, reachingstate-of-the-art fluorescent assay performances. These examplesshow how the proposed bioelectronic platform, besides resultingin extremely performing biosensors, can open insights into biologicallyrelevant phenomena involving membrane weak interfacialmodifications.
Bovine cornea was studied with scanning small-angle X-ray scattering (SAXS) microscopy, by using both synchrotron radiation and a microfocus laboratory source. A combination of statistical (adaptive binning and canonical correlation analysis) and crystallographic (pair distribution function analysis) approaches allowed inspection of the collagen lateral packing of the supramolecular structure. Results reveal (i) a decrease of the interfibrillar distance and of the shell thickness around the fibrils from the periphery to the center of the cornea, (ii) a uniform fibril diameter across the explored area, and (iii) a distorted quasi-hexagonal arrangement of the collagen fibrils. The results are in agreement with existing literature. The overlap between laboratory and synchrotron-radiation data opens new perspectives for further studies on collagen-based/engineered tissues by the SAXS microscopy technique at laboratory-scale facilities.Bovine cornea was studied with scanning small-angle X-ray scattering microscopy, by using both synchrotron radiation and a microfocus laboratory source. The supramolecular structure of the collagen fibers is explored thanks to the combination of statistical (adaptive binning and canonical correlation analysis) and crystallographic (pair distribution function analysis) approaches.
We use ultrafast transient absorption microscopy to map the effect of structural disorder on the photophysical properties within a micrometer-sized crystal of methylammonium lead iodide (CH3NH3PbI3) perovskite. We reveal a spatial inhomogeneity of the structural and photophysical behavior on the submicrometer scale induced by a local distortion of the crystal lattice, which affects the electron hole correlation over the hundreds of nanometers length scale.
Hybrid halide perovskites are soft materials processed at room temperature, revolutionary players in the photovoltaic field. Nowadays, investigation of the nature and roleof defects is seen as one of the key challenges toward full comprehension of their behavior and achievement of high device stability under working conditions. We reveal the reversible generation, under illumination, of paramagnetic Pb3+ defects in CH3NH3PbI3, synthesized in ambient conditions, induced by the presence of Pb-O defects in the perovskite structure that may trap photogenerated holes, possibly mediated by the concomitant oxidation and migration of ions. According to the mechanism thatwe hypothesize, one charge is trapped for each paramagnetic center generated; thus, it does not contribute to the photocurrent,potentially limiting the solar cell performance. Our study, based on combined experimental/theoretical approach, reveals the dynamic evolution of the perovskite characteristics under illumination that needs to be considered when investigating the material physical-chemical properties.
Nanocrystal superlattices are attracting significant interest due to novel and peculiar collective properties arising from the interactions of the nanocrystals forming the superlattice. A large variety of superlattice structures can be obtained, involving one or more types of nanocrystals, with different sizes and concentrations. Engineering of the superlattice properties relies on accurate structural and morphological characterization, able to provide not only a fundamental feedback for synthesis procedures, but also relevant insight into their structural properties for possible applications. Electron microscopy and X-ray based techniques are complementary approaches for nanoscale structural imaging, which however become challenging in the presence of building blocks only a few nanometers in size. Here, a structure solution for a three-dimensional (3D) self-assembly of PbS nanocrystals with bimodal size distribution is obtained, by exploiting small-angle X-ray diffraction, transmission electron microscopy, crystallographic procedures, and geometric constraints. In particular, analysis of small-angle X-ray diffraction data, based on the Patterson function and on the single crystal model, is shown to provide relevant information on the 3D superlattice structure as well as on particle size, the scattering signal being sensitive to particles as small as 1.5 nm. The combined approach here proposed is thus demonstrated to effectively overcome important resolution limitations in the imaging of superlattices including small nanocrystals.
In this work, we report on the microstructural and morphological characterization of III-V semiconductor nanowires (NWs) epitaxially grown on (111)B-GaAs substrates by Au-catalyst assisted metalorganic vapor phase epitaxy. As-grown dense (10 8-10 9 cm -2) arrays of few-micron long vertically-aligned (i.e. parallel to the ?111? crystallographic axis) GaAs, Al xGa 1-xAs and core-shell GaAs-Al xGa 1-xAs NWs were investigated, carrying out HRXRD measurements on different (hkl) reflections and by recording reciprocal space maps (RSMs) around the materials (111) reciprocal lattice points (relps). We show that NW diffraction peaks are visible in the RSM by means of characteristic halos. In the case of GaAs NWs, the halo is located at the (111) relp indicating that the NWs are grown along the ?111? direction and parallel to the ?111? axis of the GaAs substrate. On the contrary, for Al xGa 1-xAs NWs or intentional core-shell GaAs-Al xGa 1-xAs NWs the halo is displaced (along the momentum transfer normal to the surface, Q z) with respect to the GaAs (111) relp due to the elastic lattice strain associated with the compositional variation, e.g. the Al molar fraction in the Al xGa 1-xAs alloy, within the nanostructures.
For the final step of the maturation of the ribosome, the nascent 40S and 60S subunits are exported from the nucleus to the cell cytoplasm. To prevent premature association of these ribosomal subunits, eukaryotic initiation factor 6 (eIF6) binds the 60S subunit within the nucleus. Its release in the cytoplasm requires the interaction of EFL1 and SDBS proteins. In Shwachman-Diamond syndrome (SDS), a defective SDBS protein prevents eIF6 eviction, inhibiting its recycle to the nucleus and subsequent formation of the active 80S ribosome. Objective This study aims to identify the molecular basis of an SDS-like disease, manifested by pancytopenia, exocrine pancreatic insufficiency and skeletal abnormalities in six patients from three unrelated families. Methods Whole exome analysis was used for mutation identification. Fluorescence microscopy studies assessed the localisation of Tif6-GFP, the yeast eIF6 homologue, in yeast WT and mutant cells. Human and yeast EFL1 proteins, WT and mutants, were expressed in Saccharomyces cerevisiae BCY123 strain, and circular dichroism and small-angle X-ray scattering were used to assess the folding and flexibility of these proteins. Green malachite colorimetric assay was performed to determine the GTPase activity of WT and Efl1 mutants. Results Four patients were homozygous for p.R1095Q variant and two patients were homozygous for p.M882K variant in EFL1. Residue R1095 and M882 are conserved across species. Neither the GTPase activity of the mutant proteins nor its activation by the SDBD protein or the 60S ribosomal subunit were affected. Complementation of efl1? yeast cells with the EFL1 mutants rescued the slow growth phenotype. Nonetheless, Tif6-GFP was relocalised to the cytoplasm in mutant yeast cells in contrast to its nuclear localisation in WT cells. Conclusions Mutations in EFL1 clinically manifest as SDS-like phenotype. Similar to the molecular pathology of SDS, mutant EFL1 proteins do not promote the release of cytoplasmic Tif6 from the 60S subunit, likely preventing the formation of mature ribosomes.
PbS colloidal nanocrystal (NC) assemblies with monomodal and bimodal size distribution have been fabricated by slow evaporation of solvent on silicon substrates. The interparticle distances of the assembled structures have been carefully defined, both in the plane and in the z direction, perpendicular to the substrate, thanks to the combination of small and wide-angle X-ray diffraction and TEM measurements. The spectroscopic characteristics of PbS NCs, both in solution and organized in a superlattice, have been investigated by steady-state and time-resolved photoluminescence measurements. The optical results reveal the occurrence of a Forster resonant energy transfer (FRET) mechanism between closed-packed neighboring PbS NCs. The occurrence of FRET is dependent on NC assembly geometry, and thus on their interparticle distance, suggesting that only when NCs are close enough, as in the close-packed arrangement of the monomodal assembly, the energy transfer can be promoted. In bimodal assemblies, the energy transfer between large and small NCs is negligible, due to the low spectral overlap between the emission and absorption bands of the different sized nanoparticles and to the large interparticle distance. Moreover, recombination lifetimes on the microsecond time scale have been observed and explained in terms of dielectric screening effect, in agreement with previous findings on lead chalcogenide NC optical properties.
Research on composite materials is facing, among others, the challenging task of incorporating nanocrystals, and their superstructures, in polymer matrices. Electron microscopy can typically image nanometre-scale structures embedded in thin polymer films, but not in films that are micron size thick. Here, X-ray Ptychography was used to visualize, with a resolution of a few tens of nanometers, how CdSe/CdS octapod-shaped nanocrystals self-assemble in polystyrene films of 24 ± 4 ?m, providing a unique means for non-destructive investigation of nanoparticles distribution and organization in thick polymer films.
The nanoscale structural order of air-dried rat-tail tendon is investigated using small-angle X-ray scattering (SAXS). SAXS fiber diffraction patterns were collected with a superbright laboratory microsource at XMI-LAB [Altamura, Lassandro, Vittoria, De Caro, Siliqi, Ladisa & Giannini (2012). J. Appl. Cryst. 45, 869-873] for increasing integration times (up to 10 h) and a novel algorithm was used to estimate and subtract background, and to deconvolve the beam-divergence effects. Once the algorithm is applied, the peak visibility improves considerably and reciprocal space information up to the 22nd diffraction order is retrieved (q = 0.21 angstrom(-1), d = 29 angstrom) for an 8-10 h integration time. The gain in the visibility is already significant for patterns collected for 0.5 h, at least on the more intense peaks. This demonstrates the viability of detecting structural changes on a molecular/nanoscale level in tissues with state-of-the-art laboratory sources and also the technical feasibility to adopt SAXS fiber diffraction as a future potential clinical indicator for disease.
Films obtained by casting, starting from conventional emulsions (CE), nanoemulsions (NE) or their gels, whichled to different structures, with the aim of explore the relationship between structure and physical properties,were prepared. Sodium caseinate was used as the matrix, glycerol as plasticizer, glucono-delta-lactone asacidulant to form the gels, and TiO2 nanoparticles as reinforcement to improve physical behavior. Structuralcharacterization was performed by SAXS and WAXS (Small and Wide Angle X-ray Scattering, respectively),combined with confocal and scanning electron microscopy. The results demonstrate that the incorporation of thelipid phase does not notably modify the mechanical properties of the films compared to solution films. Filmsfrom NE were more stable against oil release than those from CE. Incorporation of TiO2 improved mechanicalproperties as measured by dynamical mechanical analysis (DMA) and uniaxial tensile tests. TiO2 macroscopicspatial distribution homogeneity and the nanostructure character of NE films were confirmed by mapping the qdependentscattering intensity in scanning SAXS experiments. SAXS microscopies indicated a higher intrinsichomogeneity of NE films compared to CE films, independently of the TiO2 load. NE-films containing structureswith smaller and more homogeneously distributed building blocks showed greater potential for food applicationsthan the films prepared from sodium caseinate solutions, which are the best known films.
Nowadays, there is strong interest in the development of smart inorganic nanostructured materials as tools for targeted delivery in cancer cells. We proposed a novel synthetic procedure of calcium carbonate nanocrystals (NCs) and their use as drug delivery systems, studying the physical chemical properties and the in vitro interaction with two model cancer cells.Pure and thermodynamically stable CaCO3 NCs in calcite phase were synthesized by a readily and feasible method, easily scalable, that allows the control of NCs shape and size without any surfactant use. CaCO3 NCs were extensively investigated by Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS), X-ray Diffraction (XRD), Raman spectroscopy and Brunauer-Emmett-Teller analysis (BET). To deeper investigate their possible use as nanovectors for drug cancer therapies, CaCO3 NCs biocompatibility (by MTT assay), cell interaction and internalization were studied in in vitro experiments on HeLa and MCF7 cell lines. Confocal and transmission electron microscopies were used to monitor and evaluate NCs-cell interaction and cellular uptake.Data here reported demonstrated that synthesized NCs readily penetrate HeLa and MCF7 cells. NCs preferentially localize inside the cytoplasm, but were also found into mitochondria, nucleus and lysosomes. This study suggests that synthesized CaCO3 NCs are good candidates as effective intracellular therapeutic delivery system.
Osteoarthritis (OA), among other bone pathologies, is expected to determine supramolecular changes at the level of the mineralized collagen fiber. In a proof-of-principle study, bone biopsies were collected from six coxarthritis-affected patients, aged 62-87 years, during hip prosthesis implant surgery, sliced down to 100 mm-thick tissues, and investigated using scanning small-angle and wide-angle X-ray scattering (SAXS and WAXS) transmission microscopy. A multimodal imaging evaluation of the SAXS and WAXS data, combined with principal component and canonical correlation analyses, allowed the transformation of the raw data into microscopy images and inspection of the nanoscale structure of the mineralized collagen fibers across mm 2 tissue areas. The combined scanning SAXS and WAXS microscopy is shown to be a suitable choice for characterizing and quantifying the nanostructural properties of collagen over extended areas. The results suggest the existence of a correlation between age and cross-linking-induced rigidity of collagen fibers.
This study is aimed at investigating the structure of a scaffold made of bovine gelatin and hydroxyapatite for bone tissue engineering purposes. In particular, the detailed characterization of such a material has a great relevance because of its application in the healing process of the osteochondral defect that consists of a damage of cartilage and injury of the adjacent subchondral bone, significantly compromising millions of patient's quality of life. Two different techniques exploiting X-ray radiation, with table-top setups, are used: microtomography (micro-CT) and microdiffraction. Micro-CT characterizes the microstructure in the three dimensions at the micrometer scale spatial resolution, whereas microdiffraction provides combined structural/morphological information at the atomic and nanoscale, in two dimensional microscopy images with a hundred micrometer spatial resolution. The combination of these two techniques allowed an appropriate structural characterization for the purpose of validating the engineering approach used for the realization of the hydroxyapatite gradient across the scaffold, with properties close to the natural model.
In this paper, a method to synthesize anatase TiO2 nanorods by hydrolysis of titanium(IV) isopropoxide(TTIP) in the presence of benzyl alcohol and acetic acid at 210 °C was tested. The novelty of the presentapproach relies on the evaluation of the shape-controlled synthesis of anatase TiO2 nanocrystals via amicrowave-solvothermal method in 45 min. The different TiO2 nanocrystals were obtained by tuningthe TTIP/acetic acid ratio under optimized synthetic conditions and were characterized in detail by X-raydiffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), micro Raman(together with microphotoluminescence) and FT-IR spectroscopies. The acetic acid coordinated on thenanocrystal surface was removed by the reduction of its carboxyl group via a "super-hydride reaction",and the photocatalytic activity of bare TiO2 nanocrystals, under visible light irradiation, was alsoevaluated: the best performing TiO2 anatase nanocrystals exhibited a discrete photoactivity, completelydegrading Rhodamine B solution in five hours.
The integration of colloidal nanocrystals with polymers adds optoelectronicfunctionalities to flexible and mechanically robust organic films. Inparticular, self-assembled structures of nanocrystals in polymers can actas functional components enhancing, for instance, transport or opticalproperties of the hybrid material. This study presents Cu2Te hexagonalnanodisks that assemble into ribbons with a face-to-face configuration inpoly(3-hexylthiophene-2,5-diyl) through a controlled solvent evaporationprocess. The ribbons form weaving patterns that create 3D networksfully embedded in the thin polymer film at high nanodisk concentration.The photoresponse of these composite films measured in a layeredvertical geometry demonstrates increased photocurrent with increasingnanocrystal loading. This study attributes this behavior to the presenceof networks of Cu2Te nanodisks that form a bulk heterojunction with thesemiconducting polymer, which improves exciton dissociation and theoverall photoelectric response.
OFETs based on new solution-processed ester functionalized 9,10-ter-anthrylene-ethynylenes show a mobility increase of four orders of magnitude, leading to mobilities as high as 4.9 x 10(-2) cm(2) V(-1) s(-1) if the deposited film is annealed before contact deposition. The behavior is ascribed to an increase in film order at the dielectric/semiconductor interface as revealed by X-ray studies.
Titania anatase nanocrystals were prepared by solgel solvothermal synthesis in oleic acid at 2508C, and modified by co-reaction with Mo chloroalkoxide, aimed at investigatingthe effects on gas-sensing properties induced by tailored nanocrystals surface modification with ultra-thin layers of MoOx species. For the lowest Mo concentration, only anatasenanocrystals were obtained, surface modified by a disordered ultra-thin layer of mainly octahedral MoVI oxide species.For larger Mo concentrations, early MoO2 phase segregation occurred. Upon heat treatment up to 5008C, the sample with the lowest Mo concentration did not featureany Mo oxide phase segregation, and the surface Mo layer was converted to dense octahedral MoVI oxide. At larger Mo concentrations all segregated MoO2 was converted to MoO3. The two different materials typologies, depending on the Mo concentration, were used for processing gas-sensing devicesand tested toward acetone and carbon monoxide, which gave a greatly enhanced response, for all Mo concentrations, to acetone (two orders of magnitude) and carbonmonoxide with respect to pure TiO2. For the lowest Mo concentration, dye-sensitized solar cells were also prepared to investigate the influence of anatase surface modification onthe electrical transport properties, which showed that the charge transport mainly occurred in the ultra-thin MoOx surface layer.
Peptides containing aromatic residues are known to give spontaneous phenomena of supramolecular organization into ordered nanostructures (NSs). Here we studied the structural behavior and the optoelectronic properties of new biocompatible materials obtained by self-assembling of a series of hexaphenylalanines (F6) modified at the N-terminus with a PEG chain of different length. PEG12-F6, PEG18-F6 and PEG24-F6 peptides were synthesized by coupling sequentially two, three or four units of amino-carboxy PEG6 blocks, each one containing six ethoxylic repetitions. Changes in length and composition of the PEG chain were found able to modulate the structural organization of phenylalanine based nanostructures. An increase in the self-aggregation tendency with longer PEG is observed; while, independently from PEG length, the peptide NSs display cross-beta like secondary structure with an antiparallel beta-strand arrangement. WAXS/GIWAXS diffraction patterns indicate a progressive decrease of the fiber order along the series. All the PEG-F6 derivatives present blue photoluminescent (PL) emission at 460 nm, while the adduct with longest PEG (PEG24-F6) shows an additional green emission at 530 nm.
Organic field-effect transistors including a functional biorecognition interlayer, sandwiched between the dielectric and the organic semiconductor layers, have been recently proposed as ultrasensitive label-free biosensors capable to detect a target molecule in the low pM concentration range. The morphology and the structure of the stacked bilayer formed by the protein biointerlayer and the overlying organic semiconductor is here investigated for different protein deposition methods. X-ray scattering techniques and scanning electron microscopy allow us to gather key relevant information on the interface structure and to assess target analyte molecules capability to percolate through the semiconducting layer reaching the protein deposit lying underneath. Correlations between the structural and morphological data and the device analytical performances are established allowing us to gather relevant details on the sensing mechanism and further improving sensor performances, in particular in terms of sensitivity and selectivity. © 2014 American Chemical Society.
Ribosome biogenesis is closely linked to the cell growth and proliferation. Dysregulation of this process causes several diseases collectively known as ribosomopathies. One of them is the Shwachman-Diamond Syndrome, and the SBDS protein mutated in this disease participates with EFL1 in the cytoplasmic maturation of the 60S subunit. Recently, we have shown that the interaction of EFL1 with SBDS resulted in a decrease of the Michaelis-Menten constant (KM) for GTP and thus SBDS acts as a GEF for EFL1 (1). Subsequent studies demonstrated that SBDS greatly debilitates the interaction of EFL1 with GDP without altering that for GTP. The interaction of EFL1 alone or in complex with SBDS to guanine nucleotides is followed by a conformational rearrangement. Understanding the molecular strategy used by SBDS to disrupt the binding of EFL1 for GDP and the associated conformational changes will be key to understand their mode of action and alterations occurring in the disease. The structure of the GTPase EFL1 is not known and its crystallization has been unsuccessful at least in our hands. In this study, we aim to show the conformational changes resulting from the interactions between EFL1 and its binding partners, the SBDS protein and the guanine nucleotides using SAXS technique (2, 3). SAXS will provide structural information of the proteins and their conformational changes (4). For the SAXS data analysis we have built models of EFL1 using by EF-2 as homology template and of SBDS using the crystal structures of the archaea orthologues.
SUNBIM (supramolecular and submolecular nano- and biomaterials X-rayimaging) is a suite of integrated programs which, through a user-friendlygraphical user interface, are optimized to perform the following: (i) q-scalecalibration and two-dimensional ! one-dimensional folding on small- andwide-angle X-ray scattering (SAXS/WAXS) and grazing-incidence SAXS/WAXS (GISAXS/GIWAXS) data, also including possible eccentricity correctionsfor WAXS/GIWAXS data; (ii) background evaluation and subtraction,denoising, and deconvolution of the primary beam angular divergence onSAXS/GISAXS profiles; (iii) indexing of two-dimensional GISAXS frames andextraction of one-dimensional GISAXS profiles along specific cuts; (iv) scanningmicroscopy in absorption and SAXS contrast. The latter includes collection oftransmission and SAXS data, respectively, in a mesh across a mm2 area,organization of the as-collected data into a single composite image oftransmission values or two-dimensional SAXS frames, analysis of the composeddata to derive the absorption map and/or the spatial distribution, andorientation of nanoscale structures over the scanned area.
Nanocrystalline diamond (NCD) coatings with thickness of about 3 um were grown on silicon substrates at four deposition temperatures ranging from 653 to 884 degrees C in CH4/H2/Ar microwave plasmas. The morphology, structure, chemical composition and mechanical and surface properties were studied by means of Atomic Force Microscopy (AFM), X-Ray Diffraction (XRD), Raman spectroscopy, nanoindentation and Water Contact Angle (WCA) techniques. The different deposition temperatures used enabled to modulate the chemical, structural and mechanical NCD properties, in particular the grain size and the shape. The characterization measurements revealed a relatively smooth surface morphology with a variable grain size, which affected the incorporated hydrogen amount and the sp(2) carbon content, and, as a consequence, the mechanical properties. Specifically, the hydrogen content decreased by increasing the grain size, whereas the sp(2) carbon content increased. The highest values of hardness (121 +/- 25 GPa) and elastic modulus (1036 +/- 163 GPa) were achieved in NCD film grown at the lowest value of deposition temperature, which favored the formation of elongated nanocrystallites characterized by improved hydrophobic surface properties. (C) 2014 Elsevier B.V. All rights reserved.
Drops of exosome dispersions from healthy epithelial colon cell line and colorectal cancer cells were dried on a superhydrophobic PMMA substrate. The residues were studied by small- and wide-angle X-ray scattering using both a synchrotron radiation micrometric beam and a high-flux table-top X-ray source. Structural differences between healthy and cancerous cells were detected in the lamellar lattices of the exosome macro-aggregates.
Suitable post-synthesis surface modification of lead-chalcogenide quantum dots (QDs) is crucial to enable their integration in photovoltaic devices. We have developed a solution-phase ligand exchange strategy that exploits arenethiolate anions to replace the pristine oleate ligands on PbS QDs, while preserving the long-term colloidal stability of QDs and allowing their solution-based processability into photoconductive thin-films. Complete QD surface modification is demonstrated by IR spectroscopy analysis, whereas UV-Vis-NIR Absorption Spectroscopy provides quantitative evaluation of stoichiometry and thermodynamic stability of the resulting system. Arenethiolate ligands permit to reduce the inter-particle distance in PbS QD solids, leading to a drastic improvement of the photoinduced charge transport properties. Therefore, smooth dense-packed thin-films of arenethiolate-capped PbS QDs obtained via a single solution-processing step are integrated in heterojunction solar cells: such devices generate remarkable photocurrent densities (14 mA cm(-2)) and overall efficiencies (1.85%), which are outstanding for a single PbS QD layer. Solution-phase surface modification of QDs thus represents an effective intermediate step towards low-cost processing for all-inorganic and hybrid organic/inorganic QD-based photovoltaics.
XTOP 2018 - the 14th Biennial Conference on High-Resolution X-Ray Diffraction and ImagingBari, 3rd -7th September 2018TABLE-TOP SCANNING SAXS/WAXS MICROSCOPY OF ENGINEERED NANO/BIO-MATERIALSD. Altamura1,*, S.G. Pastore1, D. Siliqi1, M. Ladisa1, F. Scattarella1, A. Terzi1, and C. Giannini11 CNR-Istituto di Cristallografia, Via Amendola 122/O, 70126 Bari, Italy*e-mail: (davide.altamura@ic.cnr.it)INTRODUCTION: Simultaneous SAXS/WAXS data collection allows to directly relate atomic and nano- scale structures at each point on the sample. Synchrotron beamlines typically exploit an off-axis detector for WAXS, although this prevents the collection of diffraction rings over the full azimuthal range, or scanning is performed twice to collect the full scattering signal at small (SAXS) and wide (WAXS) angles. Despite the excellent data quality, a possible drawback can be some information loss and/or mismatch between SAXS and WAXS maps due to sample structural evolution (spontaneous, due to drying, radiation damage, drifts). A different approach, also available in table-top facilities, exploits an image plate detector with central hole, to collect the average 2D WAXS signal along with a spatially resolved SAXS map, and/or single SAXS/WAXS patterns from selected sample points.EXPERIMENTAL: A Rigaku synchrotron-class micro-source, coupled to a SAXS/WAXS camera, allows for double length scale diffraction microscopy with 70?200 ?m spatial resolution1.RESULTS AND DISCUSSION: Even though a scattering component from sample local structure can be partially smeared out in the integrated average, the spatially resolved SAXS/Absorption map can help in discriminating and localizing micro- and nano-scale components (e.g. CaS and HA, respectively, in the Figure), through the following simultaneous SAXS/WAXS signal collection from selected regions of interest. Once the correspondence of SAXS/WAXS features is assessed, the 2D SAXS/Absorption map can be used for qualitative structural mapping, quantitative estimation of concentration gradients (e.g. HA nanocrystals across the scaffold in the Figure)1, or statistical quantitative information can be extracted by averaging the normalized SAXS intensity in selected q-ranges, for comparative studies on nanoparticle abundance (e.g. oil nanodroplets in films made from emulsions)2, among others.CONCLUSIONS:The simultaneous SAXS/WAXS-integrated full pattern collection allows for double length scale description of the real-time status of the sample, with 2D spatial resolution, without loss of intensity or possibly information in case of preferred orientations, and is feasible with laboratory equipment.REFERENCES:1. D. Altamura, S. G. Pastore, M. G. Raucci, D. Siliqi, F. De Pascalis, M. Nacucchi, L. Ambrosio, and C. Giannini. ACS Appl. Mater. Interfaces (2016), 8, 8728-8736.2. Juan M. Montes de Oca-Ávalosa, D. Altamura, Roberto J. Candal, F. Scattarella, D. Siliqi, C. Giannini, M. Lidia Herrera. Relationship between nano/mi
Au nanoparticles (NPs) self-assembled by means of a simple solvent evaporation strategy in a two-dimensional (2D) superlattice with a highly controlled geometry and extending over micrometers squared when drop cast onto a suitably functionalized silicon substrate. The assembly procedure was defined by carefully monitoring experimental parameters, namely, dispersing solvent, deposition temperature, Au NP concentration, and chemistry of supporting substrate. The investigated parameters were demonstrated to play a significant role on the delicate energetic balance of the mutual NPs as well as NP-substrate interactions, ultimately directing the NP assembly. Remarkably, substrate surface chemistry revealed to be decisive to control the extent of the organization. Scanning electron microscopy demonstrated that the 2D superlattice extends uniformly over hundreds of square micrometers. Grazing-incidence small-angle X-ray scattering investigation validated the Au NP organization in crystalline domains and confirmed the role played by the surface chemistry of the substrate onto the 2D lattice assembly. Finally, preliminary spectroscopic ellipsometry investigation allowed extraction of optical constants of NP assemblies. The localized surface plasmon resonance modes of the NP assemblies were studied through a combined analysis of reflection, transmission, and ellipsometric data that demonstrated that the plasmonic properties of the Au NP assemblies strongly depend on the substrate, which was found to influence NP ordering and near-field interactions between NPs. © 2014 American Chemical Society.
The detailed action mechanism of volatile general anesthetics is still unknown despite their effect has been clinically exploited for more than a century. Long ago it was also assessed that the potency of an anesthetic molecule well correlates with its lipophilicity and phospholipids were eventually identified as mediators. As yet, the direct effect of volatile anesthetics at physiological relevant concentrations on membranes is still under scrutiny. Organic field-effect transistors (OFETs) integrating a phospholipid (PL) functional bio inter-layer (FBI) are here proposed for the electronic detection of archetypal volatile anesthetic molecules such as diethyl ether and halothane. This technology allows to directly interface a PL layer to an electronic transistor channel, and directly probe subtle changes occurring in the bio-layer. Repeatable responses of PL FBI-OFET to anesthetics are produced in a concentration range that reaches few percent, namely the clinically relevant regime. The PL FBI-OFET is also shown to deliver a comparably weaker response to a non-anesthetic volatile molecule such as acetone. © 2012 Elsevier B.V.
During recent decades innovative nanomaterials have been extensively studied, aiming at both investigating the structure-property relationship and discovering new properties, in order to achieve relevant improvements in current state-of-the art materials. Lately, controlled growth and/or assembly of nanostructures into hierarchical and complex architectures have played a key role in engineering novel functionalized materials. Since the structural characterization of such materials is a fundamental step, here we discuss X-ray scattering/diffraction techniques to analyze inorganic nanomaterials under different conditions: dispersed in solutions, dried in powders, embedded in matrix, and deposited onto surfaces or underneath them.
A first-generation-synchrotron-class X-ray laboratory microsource, coupled to a three-pinhole camera, is presented. It allows (i) small- and wide-angle X-ray scattering images to be acquired simultaneously, and (ii) scanning small- and wide-angle X-ray scattering microscopy to be carried out. As representative applications, the structural complexity of a biological natural material (human bone biopsy) and of a metamaterial (colloidal nanocrystal assembly) are inspected at different length scales, studying the atomic/molecular ordering by (grazing-incidence) wide-angle X-ray scattering and the morphological/structural conformation by (grazing-incidence) small-angle X-ray scattering. In particular, the grazing-incidence measurement geometries are needed for inspecting materials lying on top of surfaces or buried underneath surfaces.
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