The potential of aerogels as catalysts for the synthesis of a relevant class of bis-heterocyclic compounds such as bis(indolyl)methanes was investigated. In particular, the studied catalyst was a nanocomposite aerogel based on nanocrystalline nickel ferrite (NiFeO) dispersed on amorphous porous silica aerogel obtained by two-step sol-gel synthesis followed by gel drying under supercritical conditions and calcination treatments. It was found that the NiFeO/SiO aerogel is an active catalyst for the selected reaction, enabling high conversions at room temperature, and it proved to be active for three repeated runs.
View Article and Find Full Text PDFThe emergence of SARS-CoV-2 variants requires close monitoring to prevent the reoccurrence of a new pandemic in the near future. The Omicron variant, in particular, is one of the fastest-spreading viruses, showing a high ability to infect people and evade neutralization by antibodies elicited upon infection or vaccination. Therefore, the search for broad-spectrum antivirals that can inhibit the infectious capacity of SARS-CoV-2 is still the focus of intense research.
View Article and Find Full Text PDFThe differences between bare carbon dots (CDs) and nitrogen-doped CDs synthesized from citric acid as a precursor are investigated, aiming at understanding the mechanisms of emission and the role of the doping atoms in shaping the optical properties. Despite their appealing emissive features, the origin of the peculiar excitation-dependent luminescence in doped CDs is still debated and intensively being examined. This study focuses on the identification of intrinsic and extrinsic emissive centers by using a multi-technique experimental approach and computational chemistry simulations.
View Article and Find Full Text PDFThe self-assembly reaction of the neutral dicyano-bis(1,10-phenanthroline) iron(II) complex with lanthanide ions (Ln = Eu(III), Gd(III), Er(III)) provided two different classes of heterometallic cyano-bridged 3-4 architectures depending on the nature of the counteranion, irrespective of the size of the 4 metal ion. Tetranuclear oligomers with a squared FeLn core were isolated when using nitrate salts, whereas unusual 1D polymeric chains were obtained when resorting to triflate salts under the same synthetic conditions. It is shown that the different structural motifs have a remarkable impact on the thermal stability and the optical properties of the compounds, which display a notable optical ipsochromism of the parent Fe(II) complex upon coordination with the Ln ion.
View Article and Find Full Text PDFIn this work, we unveil the fluorescence features of citric acid and urea-based Carbon Dots (CDs) through a photo-physical characterization of nanoparticles synthesized, under solvent-free and open-air conditions, within silica-ordered mesoporous silica, as a potential host for solid-state emitting hybrids. Compared to CDs synthesized without silica matrices and dispersed in water, silica-CD hybrids display a broader emission in the green range whose contribution can be increased by UV and blue laser irradiation. The analysis of hybrids synthesized within different silica (MCM-48 and SBA-15) calls for an active role of the matrix in directing the synthesis toward the formation of CDs with a larger content of graphitic N and imidic groups at the expense of N-pyridinic molecules.
View Article and Find Full Text PDFCarbon nanodots (CNDs) are the latest and most shining rising stars among photoluminescent (PL) nanomaterials. These carbon-based surface-passivated nanostructures compete with other related PL materials, including traditional semiconductor quantum dots and organic dyes, with a long list of benefits and emerging applications. Advantages of CNDs include tunable inherent optical properties and high photostability, rich possibilities for surface functionalization and doping, dispersibility, low toxicity, and viable synthesis (top-down and bottom-up) from organic materials.
View Article and Find Full Text PDFMagnetic scaffolds have been investigated as promising tools for the interstitial hyperthermia treatment of bone cancers, to control local recurrence by enhancing radio- and chemotherapy effectiveness. The potential of magnetic scaffolds motivates the development of production strategies enabling tunability of the resulting magnetic properties. Within this framework, deposition and drop-casting of magnetic nanoparticles on suitable scaffolds offer advantages such as ease of production and high loading, although these approaches are often associated with a non-uniform final spatial distribution of nanoparticles in the biomaterial.
View Article and Find Full Text PDFCarbonized polymer dots (CPDs), a peculiar type of carbon dots, show extremely high quantum yields, making them very attractive nanostructures for application in optics and biophotonics. The origin of the strong photoluminescence of CPDs resides in a complicated interplay of several radiative mechanisms. To understand the correlation between CPD processing and properties, the early stage formation of carbonized polymer dots has been studied.
View Article and Find Full Text PDFHighly fluorescent blue and green-emitting carbon dots have been designed to be integrated into sol-gel processing of hybrid organic-inorganic materials through surface modification with an organosilane, 3-(aminopropyl)triethoxysilane (APTES). The carbon dots have been synthesised using citric acid and urea as precursors; the intense fluorescence exhibited by the nanoparticles, among the highest reported in the scientific literature, has been stabilised against quenching by APTES. When the modification is carried out in an aqueous solution, it leads to the formation of silica around the C-dots and an increase of luminescence, but also to the formation of large clusters which do not allow the deposition of optically transparent films.
View Article and Find Full Text PDFContrast agents with a strong R dispersion have been shown to be effective in generating target-specific contrast in MRI. The utilization of this R field dependence requires the adaptation of an MRI scanner for fast field-cycling (FFC). Here, we present the first implementation and validation of FFC-MRI at a clinical field strength of 3 T.
View Article and Find Full Text PDFSamples of nickel cobaltite, a mixed oxide occurring in the spinel structure which is currently extensively investigated because of its prospective application as ferromagnetic, electrocatalytic, and cost-effective energy storage material were prepared in the form of nanocrystals stabilized in a highly porous silica aerogel and as unsupported nanoparticles. Nickel cobaltite nanocrystals with average size 4 nm are successfully grown for the first time into the silica aerogel provided that a controlled oxidation of the metal precursor phases is carried out, consisting in a reduction under H flow followed by mild oxidation in air. The investigation of the average oxidation state of the cations and of their distribution between the sites within the spinel structure, which is commonly described assuming the Ni cations are only located in the octahedral sites, has been carried out by X-ray absorption spectroscopy providing evidence for the first time that the unsupported nickel cobaltite sample has a Ni : Co molar ratio higher than the nominal ratio of 1 : 2 and a larger than expected average overall oxidation state of the cobalt and nickel cations.
View Article and Find Full Text PDFGold-iron oxide composites were obtained by reduction of an Au(III) precursor by an organic reductant (either potassium citrate or tiopronin) in a dispersion of preformed iron oxide ultrasmall magnetic (USM) nanoparticles. X-ray diffraction, transmission electron microscopy, chemical analysis and mid-infrared spectroscopy show the successful deposition of gold domains on the preformed magnetic nanoparticles, and the occurrence of either citrate or tiopronin as surface coating. The potential of the USM@Au nanoheterostructures as heat mediators for therapy through magnetic fluid hyperthermia was determined by calorimetric measurements under sample irradiation by an alternating magnetic field with intensity and frequency within the safe values for biomedical use.
View Article and Find Full Text PDFCopper-based nanoparticles, supported on either a silica aerogel or cubic mesostructured silicas obtained by using two different synthetic protocols, were used as catalysts for the water gas shift reaction. The obtained nanocomposites were thoroughly characterised before and after catalysis through nitrogen adsorption-desorption measurements at -196 °C, TEM, and wide- and low-angle XRD. The samples before catalysis contained nanoparticles of copper oxides (either CuO or Cu O), whereas the formation of metallic copper nanoparticles, constituting the active catalytic phase, was observed either by using pre-treatment in a reducing atmosphere or directly during the catalytic reaction owing to the presence of carbon monoxide.
View Article and Find Full Text PDFWe synthesize colloidal CdSe@CdS octapod nanocrystals decorated with Pt domains, resulting in a metal-semiconductor heterostructure. We devise a protocol to control the growth of Pt on the CdS surface, realizing both a selective tipping and a non-selective coverage. Ultrafast optical spectroscopy, particularly femtosecond transient absorption, is employed to correlate the dynamics of optical excitations with the nanocrystal morphology.
View Article and Find Full Text PDFThe optical properties of 7-hydroxy-4-methyl coumarin immobilized on polyethylene glycol support and dissolved in distilled water solution are compared with the optical properties of the dye dissolved in ethanol and discussed on the basis of the formation of different chemical species of the dye molecule. The presence of the polymeric support affects both the absorption and emission features of the coumarin by changing the chemical equilibrium among the different species typically observed at the ground and excited states. The optical properties of synthesized PEG-supported coumarins are able to warrant biomedical applications in water-based environment and enable us to gain insight into the photophysical activity of coumarins; in particular, the steric hindrance of the polymeric support inhibits, as expected, the formation of the tautomeric form of the compound in the excited state, a further proof of the single-step neutral to tautomer reaction in coumarins.
View Article and Find Full Text PDFMesoporous silica nanoparticles (MSNs) have been proposed as DNA and drug delivery carriers, as well as efficient tools for fluorescent cell tracking. The major limitation is that MSNs enter cells regardless of a target-specific functionalization. Here we show that non functionalized MSNs, synthesized using a PEG surfactant-based interfacial synthesis procedure, do not enter cells, while a highly specific, receptor mediated, cellular internalization of folic acid (FOL) grafted MSNs (MSN-FOL), occurs exclusively in folate receptor (FR) expressing cells.
View Article and Find Full Text PDFExtended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) techniques at both Fe and Mn K-edges were used to investigate the formation of MnFe(2)O(4) nanoparticles embedded in a silica aerogel matrix as a function of calcination temperature (at 450, 750 and 900 degrees C). Up to 450 degrees C, two separated highly-disordered phases of iron and manganese are present. With increasing the temperature (to 750 and 900 degrees C), the structure of aerogel nanoparticles becomes progressively similar to that of the spinel structure MnFe(2)O(4) (jacobsite).
View Article and Find Full Text PDFFeCo-SiO2 aerogel nanocomposites with different porosity were obtained using two different sol-gel procedures: the first involves a single acidic step and gives rise to relatively dense aerogels while the second procedure allows one to obtain highly porous aerogels using urea in the second step to promote fast gelation. Samples with different loading of FeCo equimolar alloy and with different Fe : Co ratios were prepared. The magnetic properties of all the nanocomposite aerogels were extensively studied as a function of porosity and composition.
View Article and Find Full Text PDFPbSe nanocrystals with rock-salt structure are grown on the tips of colloidal CdS and CdSe nanorods. The facets of wurtzite rods provide a substrate with various degrees of reactivity for the growth of PbSe. The presence of dangling Cd bonds may explain subtle differences between nonequivalent facets resulting in the selective nucleation of PbSe only on one of the two tips of each CdS rod.
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