Au nanoparticles decorated nanographene oxide-based platform: Synthesis, functionalization and assessment of photothermal activity.

A novel hybrid nanocomposite formed of carboxylated Nano Graphene Oxide (c-NGO), highly densely decorated by monodisperse citrate-coated Au nanoparticles (c-NGO/Au NPs), is synthesized and thoroughly characterized for photothermal applications. A systematic investigation of the role played by the synthetic parameters on the Au NPs decoration of the c-NGO platform is performed, comprehensively studying spectroscopic and morphological characteristics of the achieved nanostructures, thus elucidating their still not univocally explained synthesis mechanism. Remarkably, the Au NPs coating density of the c-NGO sheets is much higher than state-of-the-art systems with analogous composition prepared with different approaches, along with a higher NPs size dispersion. A novel theoretical approach for estimating the average number of NPs per sheet, combining DLS and TEM results, is developed. The assessment of the c-NGO/Au NPs photothermal activity is performed under continuous wave (CW) laser irradiation, at 532 nm and 800 nm, before and after functionalization with PEG-SH. c-NGO/Au NPs composite behaves as efficient photothermal agent, with a light into heat conversion ability higher than that of the single components. The c-NGO/Au NPs compatibility for photothermal therapy is assessed by in vitro cell viability tests, which show no significant effects of c-NGO/Au NPs, as neat and PEGylated, on cell metabolic activity under the investigated conditions. These results demonstrate the great potential held by the prepared hybrid nanocomposite for photothermal conversion technologies, indicating it as particularly promising platform for photothermal ablation of cancer cells.

Oil-Dispersible Green-Emitting Carbon Dots: New Insights on a Facile and Efficient Synthesis.

Carbon dots (CDs) have been progressively attracting interest as novel environmentally friendly and cost-effective luminescent nanoparticles, for implementation in light-emitting devices, solar cells, photocatalytic devices and biosensors. Here, starting from a cost-effective bottom-up synthetic approach, based on a suitable amphiphilic molecule as carbon precursor, namely cetylpyridinium chloride (CPC), green-emitting CDs have been prepared at room temperature, upon treatment of CPC with concentrated NaOH solutions. The investigated method allows the obtaining, in one-pot, of both water-dispersible (W-CDs) and oil-dispersible green-emitting CDs (O-CDs). The study provides original insights into the chemical reactions involved in the process of the carbonization of CPC, proposing a reliable mechanism for the formation of the O-CDs in an aqueous system. The ability to discriminate the contribution of different species, including molecular fluorophores, allows one to properly single out the O-CDs emission. In addition, a mild heating of the reaction mixture, at 70 °C, has demonstrated the ability to dramatically decrease the very long reaction time (i.e. from tens of hours to days) at room temperature, allowing us to synthesize O-CDs in a few tens of minutes while preserving their morphological and optical properties.

Gold-Speckled SPION@SiO2 Nanoparticles Decorated with Thiocarbohydrates for ASGPR1 Targeting: Towards HCC Dual Mode Imaging Potential Applications.

Efforts are made to perform an early and accurate detection of hepatocellular carcinoma (HCC) by simultaneous exploiting multiple clinically non-invasive imaging modalities. Original nanostructures derived from the combination of different inorganic domains can be used as efficient contrast agents in multimodal imaging. Superparamagnetic iron oxide nanoparticles (SPIONs) and Au nanoparticles (NPs) possess well-established contrasting features in magnetic resonance imaging (MRI) and X-ray computed tomography (CT), respectively. HCC can be targeted by using specific carbohydrates able to recognize asialoglycoprotein receptor 1 (ASGPR1) overexpressed in hepatocytes. Here, two different thiocarbohydrate ligands were purposely designed and alternatively conjugated to the surface of Au-speckled silica-coated SPIONs NPs, to achieve two original nanostructures that could be potentially used for dual mode targeted imaging of HCC. The results indicated that the two thiocarbohydrate decorated nanostructures possess convenient plasmonic/superparamagnetic properties, well-controlled size and morphology and good selectivity for targeting ASGPR1 receptor.

Imaging modification of colon carcinoma cells exposed to lipid based nanovectors for drug delivery: a scanning electron microscopy investigation.

The adsorption at cell surfaces and cell internalization of two drug delivery lipid based nanovectors has been investigated by means of Field Emission Scanning Electron Microscopy (FE-SEM) operating at low beam voltage on two different colon carcinoma cell lines, CaCo-2 and CoLo-205, that were compared with the M14 melanoma cell line, as a reference. The cells were incubated with the investigated multifunctional nanovectors, based on liposomes and magnetic micelles loaded with 5-fluorouracil, as a chemotherapeutic agent, and a FE-SEM systematic investigation was performed, enabling a detailed imaging of any morphological changes of the drug exposed cells as a function of time. The results of the FE-SEM investigation were validated by MTS assay and immunofluorescence staining of the Ki-67 protein performed on the investigated cell lines at different times. The two nanoformulations resulted in a comparable effect on CaCo-2 and M14 cell lines, while for CoLo 205 cells, the liposomes provided an cytotoxic activity higher than that observed in the case of the micelles. The study highlighted the high potential of FE-SEM as a valuable complementary technique for imaging and monitoring in time the drug effects on the selected cells exposed to the two different nanoformulations.

Liposome-modified titanium surface: A strategy to locally deliver bioactive molecules.

Titanium and its alloys are widely employed materials for implants in orthopedic or dental surgery due to their mechanical properties, resistance to corrosion and osseointegration capability. However adverse reactions at the tissue/implant interface may occur, which limit the success of the osseointegration process. Therefore, different strategies have to be used to overcome these drawbacks. In this work, we developed two different liposome-based coatings on titanium surfaces as drug or bioactive molecule deposits for dental/orthopedic implant applications. The first one is a supported vesicular layer (SVL), obtained by liposome adhesion on passivated Ti surface, the second one is a covalently bonded vesicular layer (CBVL) grafted on properly functionalized Ti. Photoluminescence spectroscopy and atomic force microscopy investigations demonstrated the effective anchoring of intact liposomes in both systems. Cytotoxicity assays, performed after 48h, showed a MG63 cell viability higher than 75% and 70% on SVLs and CBVLs, respectively. Scanning electron microscopy investigation revealed numerous and spread MG63 cells after 48h on SVL modified Ti surface and a lower cell adhesion on samples coated with CBVL. The cellular uptake capability of liposome content was proved by fluorescence microscopy using carboxyfluorescein loaded SVLs and CBVLs. Finally, we demonstrated that these liposome-modified Ti surfaces were able to deliver a model bioactive molecule (phosphatidylserine) to adherent cells, confirming the potentiality of developed systems in bone related prosthetic applications.

Identification of ROS produced by photodynamic activity of chlorophyll/cyclodextrin inclusion complexes.

Photodynamic therapy (PDT) is a way of treating malignant tumors and hyperproliferative diseases. It is based on the use of photosensitizer, herein the chlorophyll a (chl a), and a light of an appropriate wavelength. The interaction of the photosensitizer (PS) with the light produces reactive oxygen species (ROS), powerful oxidizing agents, which cause critical damage to the tissue. To solubilize chl a in aqueous solution and to obtain it as monomer, we have used cyclodextrins, carriers which are able to interact with the pigment and form the inclusion complex. The aim of this study is to examine which types of ROS are formed by Chl a/cyclodextrin complexes in phosphate buffered solution and cell culture medium, using specific molecules, called primary acceptors, which react selectively with the reactive species. In fact the changes of the absorption and the emission spectra of these molecules after the illumination of the PS provide information on the specific ROS formation. The (1) O2 formation has been tested using chemical methods based on the use of Uric Acid (UA), 9,10-diphenilanthracene (DPA) and Singlet oxygen sensor green (SOSG) and by direct detection of Singlet Oxygen ((1) O2 ) luminescence decay at 1270 nm. Moreover, 2,7-dichlorofluorescin and ferricytochrome c (Cyt Fe(3+) ) have been used to detect the formation of hydrogen peroxide and superoxide radical anion, which reduces Fe(3+) of the ferricytochrome to Fe(2+) , respectively.

Phototoxicity and cytotoxicity of chlorophyll a/cyclodextrins complexes on Jurkat cells.

The aggregation status of chlorophyll a (Chl a) and the ability of four cyclodextrins, hydroxypropyl-beta-cyclodextrin (HP-beta-CD), hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD), heptakis(2,6-di-O-methyl)-beta-cyclodextrin (DIMEB), and heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TRIMEB), to solubilize the pigment in the complete cellular medium RPMI 1640 was estimated by means of UV-Vis absorption and static resonance light scattering (RLS) measurements. The results indicate that the pigment interacts with cyclodextrins in the cellular medium differently to that observed in water. The cytotoxic and phototoxic activity of these complexes towards human leukemia T-lymphocytes (Jurkat cells) was tested by means of experiments aimed to discriminate between the intrinsic toxicity and the toxicity induced by light. The overall data indicate that the HP-beta-CD is the cyclodextrins having the best characteristics to form with Chl a a potential supramolecular system for the photodynamic therapy.

Seeded growth of asymmetric binary nanocrystals made of a semiconductor TiO2 rodlike section and a magnetic gamma-Fe2O3 spherical domain.

Asymmetric binary nanocrystals (BNCs), comprising one c-axis elongated anatase TiO2 section and one gamma-Fe2O3 spherical domain attached together, are synthesized by heterogeneous nucleation of iron oxide onto the longitudinal facets of TiO2 nanorods in a ternary surfactant mixture. The topologically controlled composition of the BNCs is ascertained by a combination of powder X-ray diffraction, Raman and Mössbauer spectroscopy, high-angle annular dark-field imaging, and high-resolution transmission electron microscopy lattice fringe mapping, while their size-dependent magnetic behavior is demonstrated by ac susceptibility measurements. The heteroepitaxial growth proceeds through a mechanism never observed before for colloidal nanoheterostructures: the two domains share a restricted and locally curved junction region, which accommodates efficiently the interfacial strain and retards the formation of misfit dislocations. It is believed that these BNCs, which combine the properties of two technologically relevant oxide materials, can pave the way to reinforced applications in several fields of nanoscience, such as in photocatalysis, in malignant cell treatments, and in nanocrystal assembly.