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    Effect of metal nanoparticles on the photophysical behaviour of dye–silica conjugates

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    Fluorescein has been covalently entrapped into 120 nm silica beads in order to measure the effect of plasmonic gold nanoparticles, having 25 nm diameter, on the radiative processes of the dye. Two distinct regimes of enhancement and quenching of fluorescein emission have been observed, depending on the concentration of the metal adsorbed on the silica surface and the overlap between the SPR and the fluorescein spectra. At particle concentrations below 5.0 x 10(13) nanoparticles mL(-1), the fluorescence of the dye is enhanced, and this effect is more pronounced when the excitation wavelength matches the maximum of the extinction spectrum of the gold nanoparticles. When the concentration of gold is further increased, quenching occurs and it has been attributed to the SPR shift following the aggregation of the gold colloids on the silica surface. The invariance of the fluorescence lifetimes during the whole process indicates that the mechanism of fluorophore-nanoparticle interaction is mainly based on changes in the absorption efficiency of the organic dye

    Driving the Interactions between Organic Nanoparticles and Phospolipidic Membranes by an Easy Treatment of the Surface Stabilizer

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    Polymer-stabilized perylene nanoparticles were prepd. through a solvent exchange method. The formation of the nanostructures in aq. soln. was confirmed by the appearance of a red-shifted emission attributable to the formation of excimerlike aggregates. The behavior of org. nanostructures in the presence of lipid vesicles was investigated through steadystate and time-resolved fluorescence measurements. When no further surface treatment is applied to the nanoparticles, changes in the decay times and emission spectra demonstrate that inside the lipid bilayers the nanoparticles redissolve into the monomeric form with a rate and efficiency detd. by the working temp. (above and below the transition temp. Tm of the phospholipid). On the other hand, when the stabilized shell is UV-cured to induce photo-crosslinking of the polymeric chains, the nanoparticle stability increases and their redissoln. in the membrane is prevented. Confocal fluorescence images support the data obtained in bulk. The results indicate that the prepd. nanostructures could be successfully used either as nanometric carriers for the delivery of poor water-sol. lipophilic compds. or as imaging tools depending on the rigidity/crosslinking degree of their polymeric stabilizer shell

    Hierarchical Assembly of Nanostructures to Decouple Fluorescence and Photothermal Effect

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    Hybrid nanoparticles are designed and produced by a two-step procedure with the aim to obtain optically controlled multifunctional nanomaterials. In particular, using a sol gel method in alcoholic/water media, silica particles doped with 9-aminoacridine molecules are prepared with a mean diameter of 31 nm, which preserves the fluorescent properties of the dye. In a second step, these nanoparticles are capped with a thin (7 nm-size) gold shell whose growth does not quench the emission of the dye as proven by steady-state and time-resolved fluorescence measurements. The careful choice of the organic dye and the control of the metal layer growth make possible to completely uncouple the fluorescence and the plasmon bands of gold. The selective photoexcitation of fluorescence or plasmon absorption, leading to heat release, has been tested on phospholipidic membranes loaded with the prepared hybrid particles. Under 400-nm irradiation fluorescence is activated, which is used to image the membranes; upon 650-nm irradiation only the gold layer absorbs and efficiently converts light into heat leading to a temperature increase of about 10 degrees C in the surrounding medium which is responsible for the alteration of the membrane architecture

    Silica nanoparticles assisted photodegradation of acridine orange in aqueous suspensions

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    tSilica nanostructured materials are often used as catalyst support but their catalytic role has not beendeeply investigated yet. In the present study, the photocatalytic degradation of acridine orange zincchloride double salt (AO) has been studied using silica nanoparticles (NPs) as catalysts. NPs of differentsize (55 and 146 nm) were prepared by a sol–gel procedure and their surface was modified with aminogroups to investigate the role of the chemical groups linked to the silica surface on the dye degradation.The silica nanomaterials were fully characterized by use of transmission electron microscopy (TEM), zetapotential measurements and UV–vis spectrophotometric methods.The photodegradation experiments were carried out irradiating at 313 or 490 nm for 50 min the aque-ous samples containing the dye and the silica NPs of 55 or 146 nm in diameter. The photocatalyticdegradation of the dye was determined from the decrease of its fluorescence intensity. AO fluorescenceintensity did not change when bare SiO2beads were used as catalysts, whereas an efficient decoloration(up to 58%) was achieved with amino functionalized NPs, with a photodegradation rate constant valueof 0.136 m−1. The data collected from the degradation experiments demonstrated that the functionalgroups on the silica surface have a fundamental role in the efficiency of the degradation processe

    Modelling the Optical Properties of Metal Nanoparticles: Analytical vs Finite Elements Simulation

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    Metal nanoparticles are an important research field for their broad and various application. The modeling of their chemical and physical properties is essential for the correct design of innovative materials. In this study the analytical simulation, based on the bare Mie theory, is directly compared with the measured absorbance spectra of gold colloids, prepared through a seed-mediated process. The goodness in the prediction of the particles dimension gives an indication on the level of precision of the model to simulate the optical behavior of the sample. Then, a discrete simulation is performed, which implements finite element analysis; a good level of agreement with the analytical model is obtained for single isolated nanoparticles, and additional properties like electromagnetic behavior of the particles is modeled. At last the discrete simulation is used to explore complex particle structures, whose analytical simulation is not possible, like dimer, nanoparticles chain and planar distribution. For these configurations, the electric field is analyzed, with particular attention to the best configuration for the field enhancement, and the trend of the absorption spectrum is studied as a function of the relative distance among the particles. The results indicate that the plasmon resonance shifts to the red when array of particles are considered since 10 and 30 nm shift has been observed for a chain of closely spaced nanoparticles and for a planar ordered nanoparticles, respectively
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