118 research outputs found

    Selective protein trapping within hybrid nanowells

    No full text
    Nanostructured surfaces offer a great deal in view of the control of biological processes at subcellular level. An innovative methodology has been developed to fabricate large-scale hexagonally close-packed arrays of polymer/gold nanowells of tunable diameter and depth, ranging between about 70 and 100 nm (diameter) and 15 and 40 nm (depth). Nanowell volumes down to 0.3 attolitres and nanowell densities as high as ∼109 wells per cm2 could also be demonstrated. The present paper investigates the main features of protein trapping processes within the obtained nanowell arrays. Selective protein trapping, also involving orientation and biofunctionality changes, appears to be induced by the nanoconfinement. Nanomorphology measurements and antibody preferential linkages are demonstrated for human serum albumin versus lysozyme, the first being efficiently trapped within the nanocavities and the second being preferentially deposited outside them. The selective protein-dependent trapping/untrapping within the nanowells is discussed in terms of the variation in the out-diffusion coefficients of the biomolecules entering the nanowells, either as a function of the matching/mismatching of the biomolecules and nanocavity dimensions, or, alternatively, owing to the drastic conformational changes due to nanoconfinement. In this case, the trapping of large and soft human serum albumin is privileged with respect to the small and hard lysozyme. Furthermore, the observed peculiar antibody response to the confined proteins is accounted for in terms of the enhancement of their biological response following the modified accessibility of the key epitopes, which in turn suggests drastic conformational changes

    Unravelling the Charge State of Oxygen Vacancies in ZrO2-x on the Basis of Synergistic Computational and Experimental Evidence

    No full text
    The functional properties of metal oxide semiconductors depend on intrinsic and extrinsic defects. The population of intrin-sic defects is strongly affected by the synthesis method and subsequent treatments of the material, while extrinsic defects can originate from suitable doping. Stoichiometric ZrO2 is a non-reducible oxide with a large band gap. Therefore, controlling and modulating its defect profile to induce energy states in the band gap is the sole possibility to make it a photocatalyst responsive to visible light. We report a method, based on low temperature sol-gel synthesis coupled with treatments per-formed in mild conditions, to obtain undoped visible light responsive ZrO2-x. The electronic structure of these materials is interpreted in relation to their oxygen vacancy defect population. On the basis of a wide set of experimental measurements (X-ray photoelectron, steady state and time-resolved photoluminescence, electron paramagnetic resonance and UV-visible dif-fuse reflectance spectroscopy) and supported by density functional theory calculations, we demonstrate, for the first time, the predominance of positively charged F-center oxygen vacancies that do not give rise to Zr3+ species

    Sustained normalization of cerebral blood-flow after iloprost therapy in a patient with neuropsychiatric systemic lupus erythematosus

    No full text
    We report the case of a 30-year-old caucasian woman affected by SLE who developed neurological symptoms (prosopagnosia and visual-spatial agnosia) after nine years of disease. Brain MRI showed no abnormalities while a brain SPECT scan showed diffuse uptake defects and hypoperfusion areas in the right and left frontal-parietal regions. At that time the patient was on hydroxychloroquine (400 mg/day) and oral prednisolone (0.5 mg/kg/day) as maintenance therapy. One year later the patient showed worsening of Raynaud’s phenomenon with digital dystrophic lesions and was therefore treated with an intravenous infusion of Iloprost (1.5 ng/kg/min per 6h/day for 10 days consecutively), while baseline treatment remained unchanged. One month later the patient showed a dramatic improvement in her cognitive function and subsequent SPECT scans showed the gradual disappearance of perfusion abnormalities. This first report of Iloprost treatment in CNS lupus suggests the potential therapeutic usefulness of this drug in patients with SLE and functional CNS involvement

    Probing the outermost layer of thin gold films by XPS and density functional theory

    No full text
    This work examines gold thin films of various thicknesses varying from 5 to over 100 nm along a 7 cm distance to investigate the effect on the surface sensitivity of the XPS Au4f signal. Increasing the relative intensity of the surface XPS signal can be useful for studying properties of the surface atoms in case of functionalized gold, and for shedding light on reactions occurring at the interface with the metal surface as well as adsorption geometry. The surface-to-bulk signal ratio increased with decreasing thickness for thicknesses greater than 15 nm. Below this value, the intensity of the surface signal decreased. The binding-energy shift of the surface component with respect to the bulk component was found to be in agreement with that calculated by density functional theory (DFT). The calculated shift was found to be essentially unaffected, whether or not final-state effects were included. KPFM was also performed to investigate correlations between the measured work function and the surface/bulk BE shift, revealing that the contact potential difference changes with thickness because of the influence of the substrate. Gradients were prepared by a novel evaporation method, by template stripping, and by photolithography, yielding stripes of increasing thickness in the same sample
    corecore