Francesco Mura

Direct interaction of hydrophilic gold nanoparticles with dexamethasone drug: Loading and release study

Water-soluble gold nanoparticles functionalized by sodium 3-mercapto-1-propansulfonate (Au-3MPS) were synthesized with different Au/thiol molar ratios for their ability to interact with biomolecules. In particular, a synthetic glucocorticoid steroid, i.e. dexamethasone (DXM) was selected. Herein, the formation of the Au-3MPS/DXM bioconjugate is reported. Au-3MPS nanoparticles show a plasmon resonance at 520 nm, have a spherical morphology and average size of 7-10 nm. The total number of gold atoms was estimated to be about 10600, with a surface component of 8800 atoms and a number of thiol ligands of about 720, roughly one anchored thiol every 10 surface gold atoms. The drug-nanoparticle interaction occurs through the fluorine atom of DXM and Au(I) atoms on the gold nanoparticle surface. The 3MPS ligands closely pack apart each other to leave room for the DXM, that lies at the gold surface in an unusual, almost parallel feature. The loading efficiency of DXM on Au-3MPS was assessed in the range 70-80%, depending on the thiol content. Moreover, our studies confirmed the drug release of about 70% in 5 days. Thanks to their unique properties, i.e. high water solubility, small size and almost monodispersity, Au-3MPS display high potential in biotechnological and biomedical applications, mainly for the loading and release of water insoluble drugs.

Extracellular Matrix Molecular Remodeling in Human Liver Fibrosis Evolution

Chronic liver damage leads to pathological accumulation of ECM proteins (liver fibrosis). Comprehensive characterization of the human ECM molecular composition is essential for gaining insights into the mechanisms of liver disease. To date, studies of ECM remodeling in human liver diseases have been hampered by the unavailability of purified ECM. Here, we developed a decellularization method to purify ECM scaffolds from human liver tissues. Histological and electron microscopy analyses demonstrated that the ECM scaffolds, devoid of plasma and cellular components, preserved the three-dimensional ECM structure and zonal distribution of ECM components. This method has been then applied on 57 liver biopsies of HCV-infected patients at different stages of liver fibrosis according to METAVIR classification. Label-free nLC-MS/MS proteomics and computation biology were performed to analyze the ECM molecular composition in liver fibrosis progression, thus unveiling protein expression signatures specific for the HCV-related liver fibrotic stages. In particular, the ECM molecular composition of liver fibrosis was found to involve dynamic changes in matrix stiffness, flexibility and density related to the dysregulation of predominant collagen, elastic fibers and minor components with both structural and signaling properties. This study contributes to the understanding of the molecular bases underlying ECM remodeling in liver fibrosis and suggests new molecular targets for fibrolytic strategies.

Infrared properties of randomly oriented silver nanowires

We experimentally investigated the infrared properties of a set of randomly oriented silver nanowires films deposited onto glass substrate. Infrared emission of the obtained films was characterized in the long infrared range, i.e., 8–12 μm, by observing their temperature evolution under heating regime with a focal plane array infrared camera as well as a thermocouple. The obtained experimental results showed that the infrared emission from a mesh composed of silver nanowires might be tailored by opportunely assessing preparation condition, such as the metal filling factor. From the theoretical point of view, the real and imaginary part of the electrical permittivity components were retrieved from the calculations of effective permittivities of in-plane randomly oriented metallic wires, thus giving the refractive index and extinction coefficients for the four different silver nanowires meshes. Due to the correspondence between emissivity and absorbance, the experimental results are interpreted with the rec...

Network assembly of gold nanoparticles linked through fluorenyl dithiol bridges

Gold nanoparticles stabilized by two novel bifunctional fluorenyl thiols, generated in situ from 9,9-didodecyl-2,7-bis(acetylthio)fluorene (1) and 9,9-didodecyl-2,7-bis(acetylthiophenylethynyl)fluorene (2), exhibit bridged structures which self-assemble in parallel lines. The size, shape and structure of the AuNPs have been determined by means of dynamic light scattering (DLS), scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). AuNPs modified with fluorenyl thiol derivatives show diameters in the range of 3–7 nm. The linkage between the nanoparticles can be envisaged with the formation of dyads supported by TEM analysis and XPS measurements. Remarkably, investigation by scanning electron microscopy of the AuNP films revealed an ordered distribution of well-separated individual nanoparticles to form a 2D network. The formation of interconnected networks between AuNPs with different distances, depending on the nature of the thiol linkers (1) or (2), and the photoluminescence properties open perspectives for applications in optical devices and electronics.

Bdellovibrio bacteriovorus directly attacks Pseudomonas aeruginosa and Staphylococcus aureus Cystic fibrosis isolates

Bdellovibrio bacteriovorus is a predator bacterial species found in the environment and within the human gut, able to attack Gram-negative prey. Cystic fibrosis (CF) is a genetic disease which usually presents lung colonization by Pseudomonas aeruginosa or Staphylococcus aureus biofilms. Here, we investigated the predatory behavior of B. bacteriovorus against these two pathogenic species with: (1) broth culture; (2) “static” biofilms; (3) field emission scanning electron microscope (FESEM); (4) “flow” biofilms; (5) zymographic technique. We had the first evidence of B. bacteriovorus survival with a Gram-positive prey, revealing a direct cell-to-cell contact with S. aureus and a new “epibiotic” foraging strategy imaged with FESEM. Mean attaching time of HD100 to S. aureus cells was 185 s, while “static” and “flow” S. aureus biofilms were reduced by 74 (at 24 h) and 46% (at 20 h), respectively. Furthermore, zymograms showed a differential bacteriolytic activity exerted by the B. bacteriovorus lysates on P. aeruginosa and S. aureus. The dual foraging system against Gram-negative (periplasmic) and Gram-positive (epibiotic) prey could suggest the use of B. bacteriovorus as a “living antibiotic” in CF, even if further studies are required to simulate its in vivo predatory behavior.

New morphological, chemical, and structural data of woolly erionite-Na from Durkee, Oregon, U.S.A.

Abstract A detailed morphological, crystal-chemical, and structural characterization of erionite from the type locality of Durkee, Oregon, has been carried out by combining field emission scanning electron microscopy (FESEM) and laboratory parallel-beam transmission X‑ray powder diffraction (XRPD). According to the crystal-chemical formula (Na5.38K1.99Mg0.24)[Al7.66Si28.34O72.09]·29.83H2O, the sample has been classified as erionite-Na. The Rietveld refinement has indicated that the extraframework cations are located at three Ca1, Ca2, and Ca3 sites, the first one containing all available Mg. Moreover, the absence of the additional K2 site found in both dehydrated erionite and erionite-K has been demonstrated for this erionite sample. Furthermore, our results revealed the absence of Fe and Ca although previous investigations have reported the presence of a variable content of both these elements in erionite samples from Durkee. This is relevant information because it is well known from amphibole asbestos that Fe2+ has been claimed to be one of the causes of carcinogenesis by participating in Fenton chemistry and producing free radicals.

Glucose level determination with a multi-enzymatic cascade reaction in a functionalized glass chip

In this work we show the functionalization of the interior of microfluidic glass chips with poly(2-hydroxyethyl methacrylate) polymer brushes as anchors for co-immobilization of the enzymes glucose-oxidase and horseradish peroxidase. The formation of the brush layer and subsequent immobilization of these enzymes have been characterized on flat surfaces by atomic force microscopy and Fourier transform infrared spectroscopy, and studied inside glass chips by field emission scanning microscopy. Enzyme-functionalized glass chips have been applied for performing a multi-enzymatic cascade reaction for the fast (20 s) determination of glucose in human blood samples and the result is in excellent agreement with values obtained from the conventional hospital laboratory. The limit of detection of this bi-enzymatic method is 60 μM. With the advantages of high selectivity and reproducibility, this functionalization method can be used for improving the efficiency of glucose sensors.

Magneto-optical properties of wurtzite-phase InP nanowires

The possibility to grow in zincblende (ZB) and/or wurtzite (WZ) crystal phase widens the potential applications of semiconductor nanowires (NWs). This is particularly true in technologically relevant III-V compounds, such as GaAs, InAs, and InP, for which WZ is not available in bulk form. The WZ band structure of many III-V NWs has been widely studied. Yet, transport (that is, carrier effective mass) and spin (that is, carrier g-factor) properties are almost experimentally unknown. We address these issues in a well-characterized material: WZ indium phosphide. The value and anisotropy of the reduced mass (μ exc) and g-factor (g exc) of the band gap exciton are determined by photoluminescence measurements under intense magnetic fields (B, up to 28 T) applied along different crystallographic directions. μ exc is 14% greater in WZ NWs than in a ZB bulk reference and it is 6% greater in a plane containing the WZ ĉ axis than in a plane orthogonal to ĉ. The Zeeman splitting is markedly anisotropic with g exc = |ge| = 1.4 for B⊥ĉ (where ge is the electron g-factor) and g exc = |ge - gh,//| = 3.5 for B//ĉ (where gh,// is the hole g-factor). A noticeable B-induced circular dichroism of the emitted photons is found only for B//ĉ, as expected in WZ-phase materials.

Bandgap Energy of Wurtzite InAs Nanowires

InAs nanowires (NWs) have been grown on semi-insulating InAs (111)B substrates by metal-organic chemical vapor deposition catalyzed by 50, 100, and 150 nm-sized Au particles. The pure wurtzite (WZ) phase of these NWs has been attested by high-resolution transmission electron microscopy and selected area diffraction pattern measurements. Low temperature photoluminescence measurements have provided unambiguous and robust evidence of a well resolved, isolated peak at 0.477 eV, namely 59 meV higher than the band gap of ZB InAs. The WZ nature of this energy band has been demonstrated by high values of the polarization degree, measured in ensembles of NWs both as-grown and mechanically transferred onto Si and GaAs substrates, in agreement with the polarization selection rules for WZ crystals. The value of 0.477 eV found here for the bandgap energy of WZ InAs agrees well with theoretical calculations.

Graphene Meets Microbubbles: A Superior Contrast Agent for Photoacoustic Imaging

Coupling graphene with a soft polymer surface offers the possibility to build hybrid constructs with new electrical, optical, and mechanical properties. However, the low reactivity of graphene is a hurdle in the synthesis of such systems which is often bypassed by oxidizing its carbon planar structure. However, the defects introduced with this process jeopardize the properties of graphene. In this paper we present a different approach, applicable to many different polymer surfaces, which uses surfactant assisted ultrasonication to exfoliate, and simultaneously suspend, graphene in water in its intact form. Tethering pristine graphene sheets to the surfaces is accomplished by using suitable reactive functional groups of the surfactant scaffold. We focused on applying this approach to the fabrication of a hybrid system, made of pristine graphene tethered to poly(vinyl alcohol) based microbubbles (PVA MBs), designed for enhancing photoacoustic signals. Photoacoustic imaging (PAI) is a powerful preclinical diagnostic tool which provides real time images at a resolution of 40 μm. The leap toward clinical imaging has so far been hindered by the limited tissues penetration of near-infrared (NIR) pulsed laser radiation. Many academic and industrial research laboratories have met this challenge by designing devices, each with pros and cons, to enhance the photoacoustic (PA) signal. The major advantages of the hybrid graphene/PVA MBs construct, however, are (i) the preservation of graphene properties, (ii) biocompatibility, a consequence of the robust anchoring of pristine graphene to the bioinert surface of the PVA bubble, and (iii) a very good enhancement in a NIR spectral region of the PA signal, which does not overlap with the signals of PA active endogenous molecules such as hemoglobin.