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Seeing the atomic configuration of single organic nanoparticles at a sub-Å spatial resolution by transmission electron microscopy has been so far prevented by the high sensitivity of soft matter to radiation damage. This difficulty is related to the need to irradiate the particle with a total dose of a few electrons/Å2, not compatible with the electron beam density necessary to search the low-contrast nanoparticle, to control its drift, finely adjust the electron-optical conditions and particle orientation, and finally acquire an effective atomic-resolution image. On the other hand, the capability to study individual pristine nanoparticles, such as proteins, active pharmaceutical ingredients, and polymers, with peculiar sensitivity to the variation in the local structure, defects, and strain, would provide advancements in many fields, including materials science, medicine, biology, and pharmacology. Here, we report the direct sub-ångström-resolution imaging at room temperature of pristine unstained crystalline polymer-based nanoparticles. This result is obtained by combining low-dose in-line electron holography and phase-contrast imaging on state-of-the-art equipment, providing an effective tool for the quantitative sub-ångström imaging of soft matter.
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The realization of electron microscopy facilities all over the world has experienced a paramount increase in the last decades. This means huge investments of public and private money due to the high costs of equipment, but also for maintenance and running costs. The proper design of a transmission electron microscopy facility is mandatory to fully use the advanced performances of modern equipment, capable of atomic resolution imaging and spectroscopies, and it is a prerequisite to conceive new methodologies for future advances of the knowledge. Nonetheless, even today, in too many cases around the world, the realization of the environment hosting the equipment is not appropriate and negatively influences the scientific quality of the results during the life of the infrastructure, practically vanishing the investment made. In this study, the key issues related to the realization of an advanced electron microscopy infrastructure are analyzed based on personal experience of more than thirty years, and on the literature.
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Crystal engineering has exclusively focused on the development of advanced materials based on small organic molecules. We now demonstrate how the cocrystallization of a polymer yields a material with significantly enhanced thermal stability but equivalent mechanical flexibility. Isomorphous replacement of one of the cocrystal components enables the formation of solid solutions with melting points that can be readily fine-tuned over a usefully wide temperature range. The results of this study credibly extend the scope of crystal engineering and cocrystallization from small molecules to polymers.
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Transmission Electron Microscopy (TEM) owes its success to the capability to investigate fundamental aspects of nature, answering the human need of knowledge necessary to understand unknown mechanisms and to find new solutions in a variety of fields like physics, biology, medicine, engineering, or chemistry [...].
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In this paper, for the first time it is shown how in-line holography in Transmission Electron Microscopy (TEM) enables the study of radiation-sensitive nanoparticles of organic and inorganic materials providing high-contrast holograms of single nanoparticles, while illuminating specimens with a density of current as low as 1-2 e-Å-2s-1. This provides a powerful method for true single-particle atomic resolution imaging and opens up new perspectives for the study of soft matter in biology and materials science. The approach is not limited to a particular class of TEM specimens, such as homogenous samples or samples specially designed for a particular TEM experiment, but has better application in the study of those specimens with differences in shape, chemical composition, crystallography, and orientation, which cannot be currently addressed at atomic resolution.
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The paper focuses on the development of electron coherent diffraction imaging in transmission electron microscopy, made in the, approximately, last ten years in our collaborative research group, to study the properties of materials at atomic resolution, overcoming the limitations due to the aberrations of the electron lenses and obtaining atomic resolution images, in which the distribution of the maxima is directly related to the specimen atomic potentials projected onto the microscope image detector. Here, it is shown how augmented coherent diffraction imaging makes it possible to achieve quantitative atomic resolution maps of the specimen atomic species, even in the presence of low atomic number atoms within a crystal matrix containing heavy atoms. This aim is achieved by: (i) tailoring the experimental set-up, (ii) improving the experimental data by properly treating parasitic diffused intensities to maximize the measure of the significant information, (iii) developing efficient methods to merge the information acquired in both direct and reciprocal spaces, (iv) treating the dynamical diffused intensities to accurately measure the specimen projected potentials, (v) improving the phase retrieval algorithms to better explore the space of solutions. Finally, some of the future perspectives of coherent diffraction imaging in a transmission electron microscope are given.
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BACKGROUND: The combination of Au-metallic-NPs and CNTs are a new class of hybrid nanomaterials for the development of electrochemical biosensor. Concentration of Au(nanoparticles [NPs]) in the electrochemical biosensor is crucial for the efficient charge transfer between the Au-NPs-MWCNTs modified electrode and electrolytic solution. METHODS: In this work, the charge transfer kinetics in the glassy carbon electrode (GCE) modified with Au(NPs)-multiwalled carbon nanotube (MWCNT) nanohybrid with varied concentrations of Au(NPs) in the range 40-100 nM was studied using electrochemical impedance spectroscopy (EIS). Field emission scanning electron microscopy and transmission electron microscopy confirmed the attachment of Au(NPs) on the surface of MWCNTs. RESULTS: The cyclic voltammetry and EIS results showed that the charge transfer mechanism was diffusion controlled and the rate of charge transfer was dependent on the concentration of Au(NPs) in the nanohybrid. The formation of spherical diffusion zone, which was dependent on the concentration of Au(NPs) in nanohybrids, was attributed to result in 3 times the increase in the charge transfer rate ks, 5 times increase in mass transfer, and 5% (9%) increase in Ipa (Ipc) observed in cyclic voltammetry in 80 nM Au(NP) nanohybrid-modified GCE from MWCNT-modified GCE. The work was extended to probe the effect of charge transfer rates at various concentrations of Au(NPs) in the nanohybrid-modified electrodes in the presence of Escherichia coli. The cyclic voltammetry results clearly showed the best results for 80 nM Au(NPs) in nanohybrid electrode. CONCLUSION: The present study suggested that the formation of spherical diffusion zone in nanohybrid-modified electrodes is critical for the enhanced electrochemical biosensing applications.
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Técnicas Biossensoriais/instrumentação , Espectroscopia Dielétrica/instrumentação , Nanopartículas Metálicas/química , Nanotubos de Carbono/química , Técnicas Biossensoriais/métodos , Espectroscopia Dielétrica/métodos , Difusão , Eletrodos , Ferrocianetos/química , Ouro/química , Microscopia Eletrônica de TransmissãoRESUMO
Well-defined sized (5-10 nm) metallic iron nanoparticles (NPs) with body-centered cubic structure encapsulated inside the tip of millimeter-long vertically aligned carbon nanotubes (VACNTs) of uniform length have been investigated with high-resolution transmission electron microscopy and soft X-ray spectroscopy techniques. Surface-sensitive and chemically-selective measurements have been used to evaluate the magnetic properties of the encapsulated NPs. The encapsulated Fe NPs display magnetic remanence up to room temperature, low coercivity, high chemical stability and no significant anisotropy. Our surface-sensitive measurements combined with the specific morphology of the studied VACNTs allow us to pinpoint the contribution of the surface oxidized or hydroxidized iron catalysts present at the VACNT-substrate interface.
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We performed reproducible atomic resolution Transmission Electron Microscopy and Wide Angle X-ray Scanning Microscopy experiments studying for the first time the nanoscale properties of a pristine fiber taken from the Turin Shroud. We found evidence of biologic nanoparticles of creatinine bounded with small nanoparticles of iron oxide. The kind, size and distribution of the iron oxide nanoparticles cannot be dye for painting but are ferrihydrate cores of ferritin. The consistent bound of ferritin iron to creatinine occurs in human organism in case of a severe polytrauma. Our results point out that at the nanoscale a scenario of violence is recorded in the funeral fabric and suggest an explanation for some contradictory results so far published.
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Antropologia Forense , Religião e Medicina , Compostos Férricos/análise , Humanos , Microscopia Eletrônica de Transmissão , NanopartículasRESUMO
Coherent Diffractive Imaging is a lensless technique that allows imaging of matter at a spatial resolution not limited by lens aberrations. This technique exploits the measured diffraction pattern of a coherent beam scattered by periodic and non-periodic objects to retrieve spatial information. The diffracted intensity, for weak-scattering objects, is proportional to the modulus of the Fourier Transform of the object scattering function. Any phase information, needed to retrieve its scattering function, has to be retrieved by means of suitable algorithms. Here we present a new approach, based on a memetic algorithm, i.e. a hybrid genetic algorithm, to face the phase problem, which exploits the synergy of deterministic and stochastic optimization methods. The new approach has been tested on simulated data and applied to the phasing of transmission electron microscopy coherent electron diffraction data of a SrTiO3 sample. We have been able to quantitatively retrieve the projected atomic potential, and also image the oxygen columns, which are not directly visible in the relevant high-resolution transmission electron microscopy images. Our approach proves to be a new powerful tool for the study of matter at atomic resolution and opens new perspectives in those applications in which effective phase retrieval is necessary.
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The aims of our experiment were to evaluate the uptake and translocation of cerium and titanium oxide nanoparticles and to verify their effects on the growth cycle of barley (Hordeum vulgare L.). Barley plants were grown to physiological maturity in soil enriched with either 0, 500 or 1000 mg · kg(-1) cerium oxide nanoparticles (nCeO2) or titanium oxide nanoparticles (nTiO2) and their combination. The growth cycle of nCeO2 and nTiO2 treated plants was about 10 days longer than the controls. In nCeO2 treated plants the number of tillers, leaf area and the number of spikes per plant were reduced respectively by 35.5%, 28.3% and 30% (p ≤ 0.05). nTiO2 stimulated plant growth and compensated for the adverse effects of nCeO2. Concentrations of Ce and Ti in aboveground plant fractions were minute. The fate of nanomaterials within the plant tissues was different. Crystalline nTiO2 aggregates were detected within the leaf tissues of barley, whereas nCeO2 was not present in the form of nanoclusters.
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Cério/toxicidade , Hordeum/efeitos dos fármacos , Hordeum/crescimento & desenvolvimento , Folhas de Planta/efeitos dos fármacos , Fenômenos Fisiológicos Vegetais , Titânio/toxicidade , Poluentes Químicos da Água/efeitos adversos , Grão Comestível/crescimento & desenvolvimento , Nanopartículas/toxicidade , Folhas de Planta/crescimento & desenvolvimentoRESUMO
An iron-molybdenum alloy powder was extensively deformed by high energy milling, so to refine the bcc iron domain size to nanometer scale (~10 nm) and introduce a strong inhomogeneous strain. Both features contribute to comparable degree to the diffraction peak profile broadening, so that size and strain contributions can be easily separated by exploiting their different dependence on the diffraction angle. To assess the reliability of Line Profile Analysis, results were compared with evidence from other techniques, including scanning and transmission electron microscopy and X-ray small angle scattering. Results confirm the extent of the size broadening effect, whereas molecular dynamics simulations provide insight into the origin of the local atomic, inhomogeneous strain, pointing out the role of dislocations, domain boundaries and interactions among crystalline domains.
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We report on the unprecedented direct observation of spin-polarization transfer across colloidal magneto-plasmonic Au@Fe-oxide core@shell nanocrystal heterostructures. A magnetic moment is induced into the Au domain when the magnetic shell contains a reduced Fe-oxide phase in direct contact with the noble metal. An increased hole density in the Au states suggested occurrence of a charge-transfer process concomitant to the magnetization transfer. The angular to spin magnetic moment ratio, m(orb)/m(spin), for the Au 5d states, which was found to be equal to 0.38, appeared to be unusually large when compared to previous findings. A mechanism relying on direct hybridization between the Au and Fe states at the core/shell interface is proposed to account for the observed transfer of the magnetic moment.
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Coloides/química , Compostos Férricos/química , Ouro/química , Nanopartículas Metálicas/química , Ressonância de Plasmônio de Superfície/métodos , Campos Magnéticos , Teste de Materiais , Marcadores de SpinRESUMO
In the present research a salt of vincamine, a poorly bioavailable indole alkaloid derived from the leaves of Vinca minor L., was synthesized in the solid state by means of a mechanochemical process employing citric acid as a reagent. The mechanochemical process was adopted as a solvent-free alternative to classical citrate synthetic route that involves the use of solvents. Since the mechanochemical salification is little studied to date and presents the disadvantage of offering a low yield, in this work, the influence of three process and formulation variables on the percentage of vincamine citrate was studied. In particular, the time of mechanical treatment (in planetary mill Fritsch P5) and the amount of citric acid were varied in order to evaluate their effect on the yield of the process, and the introduction of a solid solvent, a common pharmaceutical excipient (sodium carboxymethylcellulose, NaCMC), was considered. Due to the complexity of the resulting samples' matrix, an appropriate experimental design was employed to project the experimental trials and the influence of the three variables on the experimental response was estimated with the help of a statistical analysis. The experimental response, that is, the yield of the process corresponding to the percentage of vincamine in the protonated form, was unconventionally calculated by means of X-ray photoelectron spectroscopy analysis (XPS). Out of 16 samples, the one with the highest yield was the coground sample containing vincamine and citric acid in a 1:2 molar ratio, treated for 60 min in the presence of NaCMC. Under the above conditions the salification reaction was completed highlighting the importance of a proper selection of process and formulation variables of the mechanochemical salification, and emphasizing the crucial role of the solid solvent in facilitating the salification. The second step of the research encompassed the characterization of the citrate salt obtained by solid excipient assisted mechanochemical salification (SEAMS) in comparison with the vincamine citrate obtained by classical synthetic route. The samples were characterized by, besides XPS, high resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRPD), in vitro solubilization kinetics and in vivo oral pilot study in rats. Finally, in order to monitor over time possible disproportionation phenomena, stability studies have been performed by repeating XPS analysis after 8 months. As expected, the the SEAMS-vincamine salt consisted of particles both crystalline and amorphous. The solubilization kinetics was superior to the corresponding salt probably thanks to the favorable presence of the hydrophilic excipient although the two salts were bioequivalent in rats after oral administration. Furthermore, no evidence of disporportionation phenomena in the SEAMS-vincamine salt was found after storage. In conclusion, in the case of forming salts of poorly soluble drugs, the SEAMS process may be an interesting alternative to both classical synthetic routes, eliminating the need for solvent removal, and simple neat mechanochemical salification, overcoming the problem of limited process yield.
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Ácido Cítrico/química , Vincamina/química , Animais , Disponibilidade Biológica , Química Farmacêutica/métodos , Estabilidade de Medicamentos , Excipientes/química , Cinética , Tamanho da Partícula , Espectroscopia Fotoeletrônica/métodos , Projetos Piloto , Ratos , Ratos Sprague-Dawley , Sais/química , Solubilidade , Solventes/química , Vincamina/administração & dosagem , Vincamina/sangue , Vincamina/farmacocinética , Difração de Raios X/métodosRESUMO
Electron diffractive imaging (EDI) relies on combining information from the high-resolution transmission electron microscopy image of an isolated kinematically diffracting nano-particle with the corresponding nano-electron diffraction pattern. Phase-retrieval algorithms allow one to derive the phase, lost in the acquisition of the diffraction pattern, to visualize the actual atomic projected potential within the specimen at sub-ångström resolution, overcoming limitations due to the electron lens aberrations. Here the approach is generalized to study extended crystalline specimens. The new technique has been called keyhole electron diffractive imaging (KEDI) because it aims to investigate nano-regions of extended specimens at sub-ångström resolution by properly confining the illuminated area. Some basic issues of retrieving phase information from the EDI/KEDI measured diffracted amplitudes are discussed. By using the generalized Shannon sampling theorem it is shown that whenever suitable oversampling conditions are satisfied, EDI/KEDI diffraction patterns can contain enough information to lead to reliable phase retrieval of the unknown specimen electrostatic potential. Hence, the KEDI method has been demonstrated by simulations and experiments performed on an Si crystal cross section in the [112] zone-axis orientation, achieving a resolution of 71 pm.
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TiO(2) anatase thin films grown by pulsed laser deposition are investigated by high resolution transmission electron microscopy and high angle annular dark field scanning transmission electron microscopy. The analyses provide evidence of a peculiar growth mode of anatase on LaAlO(3) and SrTiO(3) characterized by the formation of an epitaxial layer at the film/substrate interface, due to cationic diffusion from the substrate into the film region. Pure TiO(2) anatase growth occurs in both specimens above a critical thickness of about 20 nm. The microstructural and chemical characterization of the samples is presented and discussed in the framework of oxide interface engineering.
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A colloidal crystal-splitting growth regime has been accessed, in which TiO(2) 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 Ti(5)O(5) 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 TiO(2) 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.
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Corantes/química , Nanopartículas/química , Energia Solar , Titânio/química , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
High-resolution imaging of low-atomic-number chemical elements using electron microscopy is challenging and may require the use of high doses of electrons. Electron diffractive imaging, which creates real-space images using diffraction intensities and phase retrieval methods, could overcome such issues, although it is also subject to limitations. Here, we show that a combination of electron diffractive imaging and high-resolution transmission electron microscopy can image individual TiO(2) nanocrystals with a resolution of 70 pm while exposing the specimen to a low dose of electrons. Our approach, which does not require spherical and chromatic aberration correction, can reveal the location of light atoms (oxygen) in the crystal lattice. We find that the unit cell in nanoscale TiO(2) is subtly different to that in the corresponding bulk.
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A colloidal nonaqueous approach to semiconductor-magnetic hybrid nanocrystals (HNCs) with selectable heterodimer topologies and tunable geometric parameters is demonstrated. Brookite TiO(2) nanorods, distinguished by a curved shape-tapered profile with richly faceted terminations, are exploited as substrate seeds onto which a single spherical domain of inverse spinel iron oxide can be epitaxially grown at either one apex or any location along their longitudinal sidewalls in a hot surfactant environment. The topologically controlled arrangement of the component material lattices, the crystallographic relationships holding between them, and strain distribution across individual heterostructures have been studied by combining X-ray diffraction and absorption techniques with high-resolution transmission electron microscopy investigations. Supported by such structural knowledge, the synthetic achievements are interpreted within the frame of various mechanistic models offering complementary views of HNC formation. The different HNC architectures are concluded to be almost equivalent in terms of surface-interface energy balance associated with their formation. HNC topology selection is rationalized on the basis of a diffusion-limited mechanism allowing iron oxide heterogeneous nucleation and growth on the TiO(2) nanorods to switch from a thermodynamically controlled to a kinetically overdriven deposition regime, in which the anisotropic reactivity offered by the uniquely structured seeds is accentuated under high spatially inhomogeneous monomer fluxes. Finally, the multifunctional capabilities of the heterostructures are highlighted through illustration of their magnetic and photocatalytic properties, which have been found to diverge from those otherwise exhibited by their individual material components and physical mixture counterparts.
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The action of dopamine on the aggregation of the unstructured alpha-synuclein (alpha-syn) protein may be linked to the pathogenesis of Parkinson's disease. Dopamine and its oxidation derivatives may inhibit alpha-syn aggregation by non-covalent binding. Exploiting this fact, we applied an integrated computational and experimental approach to find alternative ligands that might modulate the fibrillization of alpha-syn. Ligands structurally and electrostatically similar to dopamine were screened from an established library. Five analogs were selected for in vitro experimentation from the similarity ranked list of analogs. Molecular dynamics simulations showed they were, like dopamine, binding non-covalently to alpha-syn and, although much weaker than dopamine, they shared some of its binding properties. In vitro fibrillization assays were performed on these five dopamine analogs. Consistent with our predictions, analyses by atomic force and transmission electron microscopy revealed that all of the selected ligands affected the aggregation process, albeit to a varying and lesser extent than dopamine, used as the control ligand. The in silico/in vitro approach presented here emerges as a possible strategy for identifying ligands interfering with such a complex process as the fibrillization of an unstructured protein.