Sintering process of amorphous SiO2 nanoparticles investigated by AFM, IR and Raman techniques

We report an experimental investigation on the effects of thermal treatments at different temperatures (room— 1270 K) and for different duration (0–75 h) on amorphous silica nanoparticles (fumed silica) in powder tablet form. Three types of fumed silica are considered, comprising nearly spherical particles of 40 nm, 14 nmand 7 nm mean diameter. The experimental techniques used here are Raman and infrared absorption (IR) spectroscopy together with atomic force microscopy (AFM). Raman and IR spectra indicate that the structure of nanometer silica particles is significantly differentwith respect to that of a bulk silica glass. In particular, themain differences regard the positions of the IR band peaked at about 2260 cm−1, the Raman R-band peaked at about 440 cm−1 and the intensity of the D1 and the D2 Raman lines, related to the populations of 4- and 3-membered rings, respectively. Our data also indicate that, under thermal treatments, the structure of fumed silica samples is significantly changed, gradually relaxing towards that pertaining to ordinary bulk silica. These changes are interpreted here on the basis of the morphological information provided by the AFM measurements and assuming a two-shell structure for the fumed silica primary particles

Photoluminescence of Carbon Dots Embedded in a SiO2 Matrix

We synthetized carbon dots by a pyrolitic method, and studied their photoluminescence in aqueous environment and upon trapping in a solid matrix. To this aim, we devised a facile procedure allowing to embed the dots in amorphous SiO2, without the need of any pre-functionalization of the nanoparticles, and capable of yielding a brightly photoluminescent monolith. Experimental data reveal a remarkable similarity between the emission properties of carbon dots in water and in SiO2, suggesting that the chromophores responsible of the photoluminescence undergo only weak interactions with the environment. Time-resolved photoluminescence data reveal that the typical photoluminescence tunability of these dots mostly arises, in the present case, from the co-existence of two independent emission bands. These two signals have different emission peak positions (2.8-2.9 and 2.2-2.3 eV respectively) and decay lifetimes (7.0 and 9.0 ns respectively), while their intensity ratio is controlled by the excitation wavelength

Metal-organic framework-activated carbon composite materials for the removal of ammonia from contaminated airstreams

L.N.M and R.E.M wish to acknowledge the financial support from the EPSRC industrial CASE award (grant EP/N50936X/1). A.T and G.B would like to thank the financial support from the Fondo per il finanziamento delle attività base di ricerca (grant PJ-RIC-FFABR_2017).Metal-organic frameworks (MOFs) are a class of porous materials that show promise in the removal of Toxic Industrial Chemicals (TICs) from contaminated airstreams, though their development for this application has so far been hindered by issues of water stability and the wide availability and low cost of traditionally used activated carbons. Here a series of three MOF-activated carbon composite materials with different MOF to carbon ratios are prepared by growing STAM-17-OEt crystals inside the commercially available BPL activated carbon. The composite materials display excellent water stability and increased uptake of ammonia gas when compared to unimpregnated carbon. Such properties make these composites very promising in the fields of air purification and personal protective equipment.PostprintPeer reviewe

Properties of HO2• radicals induced by γ-ray irradiation in silica nanoparticles

We report an experimental investigation on the effects of γ-ray irradiation in several types of silica nanoparticles previously loaded with O2 molecules. They differ in specific surface and average diameter. By electron paramagnetic resonance (EPR) measurements we observe the generation of about 1018 HO2•/cm3 interstitial radicals. These radicals are induced by reaction of interstitial O2 molecules with radiolytic H atoms, as previously suggested for O2-loaded bulk a-SiO2 samples. However, at variance with respect to bulk materials, our experimental evidences suggest a different generation process of HO2• radical. In fact, by a detailed study of samples exposed to D2O, our results prove that radiolytic hydrogen atoms reacting with O2 to produce HO2• mainly arise from a radiation induced breaking of H2O molecules in the layers surrounding the nanoparticles or in the interstices. Also, by the correlation of HO2• paramagnetic centers concentration, determined by EPR measurements, and O2 Raman/PL signal we further considered the issue of the direct estimation of the O2 concentration in silica nanoparticles from Raman/PL spectra giving an independent conversion factor (the ratio between these latter two quantities), which is in good agreement with those previously proposed by other authors basing on optical measurements

Structure effects induced by high mechanical compaction of STAM-17-OEt MOF powders

Financial support by PJ-RIC-FFABR_2017 and the EPSRC grant EPSRC industrial CASE award (grant EP/N50936X/1) are acknowledged. The research programme Nanoporous materials (P1-0021) financially supported by Slovenian Research Agency (ARRS) is acknowledged as well.Metal-organic frameworks (MOFs) are promising materials for many potential applications, spacing from gas storage to catalysis. However, the powder form of which they are generally made is not suitable, mainly because of the low packing density. Powder compaction is therefore necessary, but also challenging because of their typical mechanical fragility. Indeed, generally, they undergo irreversibly damages upon densification processes, for example partially or totally loosing microporosity and catalytic activity. In this work, we deeply study the compaction effects on the flexible Cu(II)-based MOF STAM-17-OEt  (Cu(C10O5H8)1.6 H2O), whose chemical composition is close to that of HKUST-1, obtaining that it is, by contrast, extremely suitable for mechanical compaction processes with pressures up to 200 MPa, which increase its packing density, its catalytic activity, and preserve porosity, flexibility and water stability, characteristics of STAM-17-OEt. The results are supported by many experimental techniques including EPR spectroscopy, PXRD diffraction, CO2 isotherms studies and catalytic tests.Publisher PDFPeer reviewe

Fluorescent Carbon Nanodots as Sensors of Toxic Metal Ions and Pesticides

Carbon nanodots (CDs) are a new class of fluorescent carbon-based nanomaterials characterized by a plethora of morphologies and sizes. Among these, we can include two different types of CDs, namely, graphitic and diamond-like. This wide range of structures opens up the possibility to design different CDs, with tunable optical properties accordingly to the synthesis method and precursors used. We prepared two different CDs following a bottom-up approach by thermally induced decomposition of organic precursors (namely, citric acid and urea in different molar ratios), and using purification by Size Exclusion Chromatography (SEC). Obtained CDs were characterized by Raman, absorption and fluorescence (PL) spectroscopies to understand structural and optical properties, and by atomic force microscopy (AFM) to elucidate morphology. They feature graphitic and diamond-like carbon structures with highly efficient visible emissions. Their sensing towards Cd and Hg heavy metals has been tested by PL experiments. We found a PL quenching in the presence of concentrations of metal salts starting from 0.5 μM and a selectivity towards the interacting ions, depending on the CDs structure, enabling using them for sensing. Furthermore, preliminary experiments suggest that these dots can also be used in principle as sensors of common pesticides. Considering the advantages of carbon dots with respect to other nanomaterials, such as non-toxicity, low cost and ease of synthesis, we consider these results to be very promising in view of exploiting the optical response of carbon dots to fabricate in the near future a variety of pollutant-sensing devices

Fluorescent Boron Oxide Nanodisks as Biocompatible Multi-messenger Sensors for Ultrasensitive Ni2+^{2+} Detection

Boron-based nanocomposites are very promising for a wide range of technological applications, spanning from microelectronics to nanomedicine. A large variety of B-based nanomaterials has been already observed, such as borospherene, B nanotubes and nanoparticles, and boron nitride nanoparticles. However, their fabrication usually involves toxic precursors or leads to very low yields or small boron atom concentration. In this work, we report the synthesis of nanometric B$_{2}$O$_{3}$ nanodisks, a family of nanomaterials with a quasi-2D morphology capable of intense fluorescence in the visible range. Such as boron-based nanomaterial, which we synthesized by pulsed laser ablation of a boron target, is water-dispersible and nontoxic, and displays a highly crystalline structure. Moreover, its bright blue photoluminescence is highly sensitive and selective for the presence of Ni$^{2+}$ ions in solution, down to extremely small concentrations in the picomolar range. The results are very promising in view of the use of such novel B$_{2}$O$_{3}$ nanodisks as ultrasensitive multi-messenger Ni$^{2+}$ nanosensors

Streptomyces coelicolor Vesicles: Many Molecules To Be Delivered

Streptomyces coelicolor is a model organism for the study of Streptomyces, a genus of Gram-positive bacteria that undergoes a complex life cycle and produces a broad repertoire of bioactive metabolites and extracellular enzymes. This study investigated the production and characterization of membrane vesicles (MVs) in liquid cultures of S. coelicolor M145 from a structural and biochemical point of view; this was achieved by combining microscopic, physical and -omits analyses. Two main populations of MVs, with different sizes and cargos, were isolated and purified. S. coelicolor MV cargo was determined to be complex, containing different kinds of proteins and metabolites. In particular, a total of 166 proteins involved in cell metabolism/differentiation, molecular processing/transport, and stress response were identified in MVs, the latter functional class also being important for bacterial morpho-physiological differentiation. A subset of these proteins was protected from degradation following treatment of MVs with proteinase K, indicating their localization inside the vesicles. Moreover, S. coelicolor MVs contained an array of metabolites, such as antibiotics, vitamins, amino acids, and components of carbon metabolism. In conclusion, this analysis provides detailed information on S. coelicolor MVs under basal conditions and on their corresponding content, which may be useful in the near future to elucidate vesicle biogenesis and functions.IMPORTANCE Streptomycetes are widely distributed in nature and characterized by a complex life cycle that involves morphological differentiation. They are very relevant in industry because they produce about half of all clinically used antibiotics, as well as other important pharmaceutical products of natural origin. Streptomyces coelicolor is a model organism for the study of bacterial differentiation and bioactive molecule production. S. coelicolor produces extracellular vesicles that carry many molecules, such as proteins and metabolites, including antibiotics. The elucidation of S. coelicolor extracellular vesicle cargo will help us to understand different aspects of streptomycete physiology, such as cell communication during differentiation and response to environmental stimuli. Moreover, the capability of these vesicles for carrying different kinds of biomolecules opens up new biotechnological possibilities related to drug delivery. Indeed, decoding the molecular mechanisms involved in cargo selection may lead to the customization of extracellular vesicle content

The thin and medium filters of the EPIC camera on-board XMM-Newton: measured performance after more than 15 years of operation

After more than 15 years of operation of the EPIC camera on board the XMM-Newton X-ray observatory, we have reviewed the status of its Thin and Medium filters. We have selected a set of Thin and Medium back-up filters among those still available in the EPIC consortium and have started a program to investigate their status by different laboratory measurements including: UV/VIS transmission, Raman scattering, X-Ray Photoelectron Spectroscopy, and Atomic Force Microscopy. Furthermore, we have investigated the status of the EPIC flight filters by performing an analysis of the optical loading in the PN offset maps to gauge variations in the optical and UV transmission. We both investigated repeated observations of single optically bright targets and performed a statistical analysis of the extent of loading versus visual magnitude at different epochs. We report the results of the measurements conducted up to now. Most notably, we find no evidence for change in the UV/VIS transmission of the back-up filters in ground tests spanning a 2 year period and we find no evidence for change in the optical transmission of the thin filter of the EPIC-pn camera from 2002 to 2012. We point out some lessons learned for the development and calibration programs of filters for X-ray detectors in future Astronomy missions