Decomposition Process of Carboxylate MOF HKUST-1 Unveiled at the Atomic Scale Level

HKUST-1 is a metal-organic framework (MOF) which plays a significant role both in applicative and basic fields of research, thanks to its outstanding properties of adsorption and catalysis but also because it is a reference material for the study of many general properties of MOFs. Its metallic group comprises a pair of Cu2+ ions chelated by four carboxylate bridges, forming a structure known as paddle-wheel unit, which is the heart of the material. However, previous studies have well established that the paddle-wheel is incline to hydrolysis. In fact, the prolonged exposure of the material to moisture promotes the hydrolysis of Cu-O bonds in the paddle-wheels, so breaking the crystalline n…

Visible-ultraviolet vibronic emission of silica nanoparticles

We report the study of the visible-ultraviolet emission properties and the structural features of silica nanoparticles prepared through a laboratory sol-gel technique. Atomic force microscopy, Raman and Infrared investigations highlighted the 10 nm size, purity and porosity of the obtained nanoparticles. By using time resolved photoluminescence techniques in air and in a vacuum we were able to single out two contributions in the visible emission: the first, stable in both atmospheres, is a typical fast blue band centered around 2.8 eV; the second, only observed in a vacuum around the 3.0-3.5 eV range, is a vibrational progression with two phonon modes at 1370 cm(-1) and 360 cm(-1). By fully…

29Si Hyperfine structure of the E’_alfa center in amorphous silicon dioxide

We report a study by electron paramagnetic resonance on the E0 point defect in amorphous silicon dioxide (a-SiO2). Our experiments were performed on -ray irradiated oxygen-deficient materials and pointed out that the 29Si hyperfine structure of the E0 consists of a pair of lines split by 49 mT. On the basis of the experimental results, a microscopic model is proposed for the E0 center, consisting of a hole trapped in an oxygen vacancy with the unpaired electron sp3 orbital pointing away from the vacancy in a back-projected configuration and interacting with an extra oxygen atom of the a-SiO2 matrix.

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 nm and 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 different with respect to that of a bulk silica glass. In particular, the main differences regard the positions of the IR…

Effect of thermal annealing on the luminescence of defective ZnO nanoparticles synthesized by pulsed laser ablation in water

This work concerns ZnO nanoparticles (NPs), with sizes of tens of nm, produced by ablation with a pulsed Nd:YAG laser of a Zn plate in H2O. TEM images evidence the formation of nanoparticles with sizes of tens of nm. Moreover, HRTEM images and Raman spectra show that the distance between the crystalline planes and the vibrational modes are consistent with ZnO nanocrystal in wurtzite structure. Their optical properties are characterized by two emission bands both excited above the energy gap (3.4 eV): the first at 3.3 eV is associated with excitons recombination, the second at 2.2 eV is proposed to originate from a singly ionized oxygen vacancy. The green emission is independent of water pH,…

Effects of thermal treatments in controlled atmosphere on the Ce oxidation state in Ce-Ti-Eu doped SiO2 sol-gel glasses

We report an experimental study by optical absorption, photoluminescence and Raman spectroscopies of the modifications induced on Ce–Ti-Eu doped SiO2 glasses by thermal treatments in controlled atmosphere. Samples with Ce content varying up to 5,000 part per million by weight (ppm) and with Ti and Eu content fixed at 40 and 300 ppm respectively, have been investigated. The treatments were done in inert atmosphere of He and in O2 atmosphere at 390 C and 100 bar. Our experiments show that only Ce4? ions are affected by He treatments, whereas both Ce4? and Ce3? ions are affected by O2 treatments. The obtained results are interpreted on the basis of microstructural changes induced by the therma…

Fluorescent Boron Oxide Nanodisks as Biocompatible Multi-messenger Sensors for Ultrasensitive Ni$^{2+}$ 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 tar…

Luminescent silicon nanocrystals produced by near-infrared nanosecond pulsed laser ablation in water

Abstract We report the investigation of luminescent nanoparticles produced by ns pulsed Nd:YAG laser ablation of silicon in water. Combined characterization by AFM and IR techniques proves that these nanoparticles have a mean size of ∼3 nm and a core–shell structure consisting of a Si-nanocrystal surrounded by an oxide layer. Time resolved luminescence spectra evidence visible and UV emissions; a band around 1.9 eV originates from Si-nanocrystals, while two bands centered at 2.7 eV and 4.4 eV are associated with oxygen deficient centers in the SiO 2 shell.

Ge-doped silica nanoparticles: production and characterisation

Silica nanoparticles were produced from germanosilicate glasses by KrF laser irradiation. The samples were investigated by cathodoluminescence and scanning electron microscopy, providing the presence of nanoparticles with size from tens up to hundreds of nanometers. The emission of the Germanium lone pair center is preserved in the nanoparticles and atomic force microscopy revealed the presence of no spherical particles with a size smaller than ~4 nm. The absorption coefficient enhancement induced by Ge doping is reputed fundamental to facilitate the nanoparticles production. This procedure can be applied to other co-doped silica materials to tune the nanoparticles features.

Disclosing the emissive surface traps in green-emitting carbon nanodots

Abstract The bright photoluminescence of surface-functionalized carbon nanoparticles, known as carbon nanodots (CDs), has been studied for more than a decade because of its fundamental photo-physical interest and strong technological potential. However, the essential nature of the electronic states involved in their typical light emission remains very elusive. Here, we provide conclusive evidence that surface carboxylic moieties are the key to CD fluorescence. The synergy of nanosecond and femtosecond optical studies, cryogenic fluorescence, computational investigations and chemical engineering of a strategically chosen model CD system, allows to demonstrate that their visible-light transit…

Structure of amorphous SiO 2 nanoparticles probed through the E′ γ centers

We report an experimental investigation by electron paramagnetic resonance (EPR) spectroscopy on the properties of the E′ γ centers induced by β-ray irradiation in nanoparticles of amorphous SiO 2 (fumed silica) with mean diameters from 7 up to 40 nm. We found that the E′ γ centers are induced in all the fumed silica types in the dose range 4-400 kGy. They are characterized by an EPR line shape similar to that observed in common bulk silica materials independently on the particle diameter. Moreover, the E′ γ center concentration decreases on decreasing of the particle size for each given dose. Our findings are interpreted in terms of a shell-like model of nanoparticles in which it is assume…

Structural and CO [sub] 2 capture properties of ethylenediamine-modified HKUST-1 metal-organic framework

The high structural and compositional flexibility of metal–organic frameworks (MOFs) shows their great potential for CO2 capture and utilization in accordance with the environmental guidelines of low-carbon technology developments. HKUST-1 as one of the most intensively studied representatives of MOFs for such purposes excels because of its simplicity of production and high ability to tune its intrinsic properties by various functionalization processes. In the present work, ethylenediamine functionalization was performed for the first time in order to thoroughly investigate the amine sorption sites’ impact on the CO2 capture performance of HKUST-1. The placement of ethylenediamine moieties …

Structural properties of core and surface of silica nanoparticles investigated by Raman spectroscopy

We studied the experimental Raman spectra of various commercial silica nanoparticles of average diameter from 7 to 40 nm and specific surface from 50 to 380 m^2/g. We found that the peculiarities of the particles Raman spectra systematically depend on their specific surface. In detail, the peak position of the R band at about 440 cm ^-1 shifts towards high wavenumbers following an almost linear dependence on the specific surface. Similarly, the amplitudes of the D1 and D2 bands, at about 495 and 605 cm ^-1, respectively, increase linearly with the same quantity. Our results are interpreted in the frame of the shell model for the nanoparticles clarifying that the network of the core of the n…

Delocalized Nature of theEδ′Center in Amorphous Silicon Dioxide

We report an experimental study by electron paramagnetic resonance (EPR) of E(')(delta) point defect induced by gamma-ray irradiation in amorphous SiO2. We obtained an estimation of the intensity of the 10 mT doublet characterizing the EPR spectrum of such a defect arising from hyperfine interaction of the unpaired electron with a 29Si (I=1/2) nucleus. Moreover, determining the intensity ratio between this hyperfine doublet and the main resonance line of E(')(delta) center, we pointed out that the unpaired electron wave function of this center is actually delocalized over four nearly equivalent silicon atoms.

Structural modifications induced by electron irradiation in SiO2 glass: Local densification measurements

We report a study on the structural modifications induced in amorphous silicon dioxide (a-SiO2) by electron irradiation in the dose range from 1.2?103 to 5?106?kGy. This study has been performed by investigating the properties of the 29Si hyperfine structure of the E '? center by electron paramagnetic resonance (EPR) spectroscopy. Our data suggest that the structural modifications induced by irradiation take place through the nucleation of confined high-defective and densified regions statistically dispersed into the whole volume of the material. In addition, we have estimated that in the high dose limit (D?105?kGy) the degree of densification associated to the local (within the defective r…

Facile and novel synthesis of Graphene oxide/Silica nanohybrids with tunable properties

Experimental evidence for two different precursors of Eγ′ centers in silica

Abstract Electron paramagnetic resonance measurements of concentration and line shape of E γ ′ centers induced by γ ray irradiation are presented for natural and synthetic commercial silica with different OH contents. Synthetic materials with OH content >200 ppm by weight show one line shape for all investigated doses. In contrast, the other materials show a different line shape at low irradiation doses. Differences are also observed in the concentration growth of the E γ ′ centers in synthetic wet materials and in the other materials. The results are interpreted as evidence of two E γ ′ centers distinguishable by their line shape and having different precursors.

Modifications of optical absorption band of E'gamma center in silica

We report a study by electron paramagnetic resonance on the E0 point defect in amorphous silicon dioxide (a-SiO2). Our experiments were performed on -ray irradiated oxygen-deficient materials and pointed out that the 29Si hyperfine structure of the E0 consists of a pair of lines split by 49 mT. On the basis of the experimental results, a microscopic model is proposed for the E0 center, consisting of a hole trapped in an oxygen vacancy with the unpaired electron sp3 orbital pointing away from the vacancy in a back-projected configuration and interacting with an extra oxygen atom of the a-SiO2 matrix.

Substrate and atmosphere influence on oxygen p-doped graphene

Abstract The mechanisms responsible for p-type doping of substrate supported monolayer graphene (Gr) by thermal treatments in oxygen ambient have been investigated by micro-Raman spectroscopy, atomic force microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS), considering commonly employed dielectric substrates, such as SiO 2 and Al 2 O 3 thin films grown on Si. While a high p-type doping (∼10 13  cm −2 ) is observed for Gr on SiO 2 , no significant doping is found for Gr samples on the Al 2 O 3 substrate, suggesting a key role of the Gr/SiO 2 interface states in the trapping of oxygen responsible for the Gr p-type doping. Furthermore, we investigated the doping stability of Gr on SiO…

Raman and IR investigation of silica nanoparticles structure

Abstract In the present investigation we report experimental data regarding the Raman and Infra-Red (IR) absorption activities of commercial silica nanoparticles. We compared the data of the nanoparticles with the ones acquired in the same experimental conditions for commercial bulk silica. By this comparison we highlighted that the variability of the spectral features of the matrix related Raman and IR bands in the nanoparticles is above the one observed for the bulk systems before any treatments. Furthermore, by studying nanoparticles with different sizes (diameters from 40 to 7 nm) and applying the shell-model we can suggest that the core network of the nanoparticles is close to the one …

Characterization ofE′δand triplet point defects in oxygen-deficient amorphous silicon dioxide

We report an experimental study by electron paramagnetic resonance (EPR) of $\ensuremath{\gamma}$-ray irradiation induced point defects in oxygen deficient amorphous $\mathrm{Si}{\mathrm{O}}_{2}$ materials. We have found that three intrinsic ($\mathrm{E}^{\ensuremath{'}}{}_{\ensuremath{\gamma}}$, $\mathrm{E}^{\ensuremath{'}}{}_{\ensuremath{\delta}}$, and triplet) and one extrinsic $({[\mathrm{Al}{\mathrm{O}}_{4}]}^{0})$ paramagnetic centers are induced. All the paramagnetic defects but $\mathrm{E}^{\ensuremath{'}}{}_{\ensuremath{\gamma}}$ center are found to reach a concentration limit value for doses above ${10}^{3}\phantom{\rule{0.3em}{0ex}}\mathrm{kGy}$, suggesting a generation process f…

INTRINSIC PARAMAGNETIC CENTERS INDUCED IN GAMMA RAY IRRADIATED OXYGEN-DEFICIENT SILICA

Electron paramagnetic resonance investigation on the hyperfine structure of the E’_delta center in amorphous silicon dioxide

Synthesis of multi-color luminescent ZnO nanoparticles by ultra-short pulsed laser ablation

Abstract Crystalline ZnO nanoparticles (NPs) are synthesized by ultra-short femtosecond (fs) pulsed laser ablation (PLA) of a zinc plate in deionized water, and are investigated by optical absorption and time resolved luminescence spectra in combination with the morphology and structure analysis. The comparison with previous experiments based on short nanosecond (ns) PLA highlights that pulse duration is a crucial parameter to determine the size and the optical properties of ZnO NPs. While short PLA generates NPs with average size S ‾ of ~ 30 nm, ultrashort PLA allows to achieve much smaller NPs, S ‾ ⩽ 10  nm, that evidence weak quantum confinement effects on both the absorption edge and th…

Oxidation of silicon nanoparticles produced by ns laser ablation in liquids

The investigation of nanoparticles produced by ns pulsed Nd:YAG laser ablation of silicon in liquids is reported. Combined characterization by morphological and structural techniques shows that these nanoparticles have a mean diameter of ~3 nm and a core-shell structure consisting of a Si-nanocrystal surrounded by a layer of oxidized Si. Time resolved luminescence spectra evidence visible and UV emissions: a broad band around 1.9 eV originates from Si-nanocrystals, while two bands centered at 2.7 eV and 4.4 eV are associated with oxygen deficient centers in the SiO2 shell.

Carbon Nanodots as Functional Excipient to Develop Highly Stable and Smart PLGA Nanoparticles Useful in Cancer Theranostics

Theranostic systems have attracted considerable attention for their multifunctional approach to cancer. Among these, carbon nanodots (CDs) emerged as luminescent nanomaterials due to their exceptional chemical properties, synthetic ease, biocompatibility, and for their photothermal and fluorescent properties useful in cancer photothermal therapy. However, premature renal excretion due to the small size of these particles limits their biomedical application. To overcome these limitations, here, hybrid poly(lactic-co-glycolic acid) (PLGA-CDs) nanoparticles with suitable size distribution and stability have been developed. CDs were decisive in the preparation of polymeric nanoparticles, not on…

Experimental evidence of E’_gamma centers generation from oxygen vacancies in a-SiO2

Abstract We report on the thermal treatment effects in a γ-ray irradiated oxygen deficient amorphous silicon dioxide (a-SiO2) containing Al impurities. We observed that by thermal treatments the intensity of the 7.6 eV optical absorption band, associated to an oxygen deficient center, and the EPR signal amplitude of irradiation induced [AlO4]0 centers gradually decrease. During these thermal treatments, the E γ ′ centers concentration is found to increase in a correlated way to the decrease of the 7.6 eV absorption amplitude. These results are interpreted assuming an hole-transfer process from the [AlO4]0 centers to the diamagnetic oxygen vacancies, resulting in the generation of E γ ′ cent…

Electron paramagnetic resonance line shape investigation of the 29Si hyperfine doublet of the E’_gamma center in a-SiO2

Bright blue emission of synthesized silica nanoparticles conferred by surface defects

In-situ monitoring by Raman spectroscopy of the thermal doping of graphene and MoS2 in O-2-controlled atmosphere

The effects of temperature and atmosphere (air and O2) on the doping of monolayers of graphene (Gr) on SiO2 and Si substrates, and on the doping of MoS2 multilayer flakes transferred on the same substrates have been investigated. The investigations were carried out by in situ micro-Raman spectroscopy during thermal treatments up to 430 °C, and by atomic force microscopy (AFM). The spectral positions of the G and 2D Raman bands of Gr undergo only minor changes during treatment, while their amplitude and full width at half maximum (FWHM) vary as a function of the temperature and the used atmosphere. The thermal treatments in oxygen atmosphere show, in addition to a thermal effect, an effect a…

Optical and morphological properties of infrared emitting functionalized silica nanoparticles

Abstract The loading process of functionalized silica nanoparticles was investigated in order to obtain nanoparticles having functional groups on their surface and Near-Infrared (NIR) emission properties. The NIR emission induced by O 2 loading was studied in silica nanoparticles, produced by pyrogenic and microemulsion methods, with size ranging from 20 to 120 nm. Loading was carried out by thermal treatments in O 2 atmosphere up to 400 °C and 90 bar. The effects of the thermal treatments on the NIR emission and on the structural properties were studied by luminescence and Raman techniques, whereas the morphological features were investigated by Transmission Electron Microscopy and Atomic …

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 fluores…

Thermally Induced Structural Modification of Silica Nanoparticles Investigated by Raman and Infrared Absorption Spectroscopies

We report an experimental investigation by Raman and infrared (IR) absorption spectroscopies on the structural modifications induced by isochronal thermal treatments on amorphous SiO2 nanoparticles (fumed silica). In particular, three different commercial types of this material, characterized by particle mean diameters of 7, 14, and 40 nm, were subjected to thermal treatments from 100 up to 1000 °C. We found that some properties of fumed silica, such as the SiOSi mean bond angle, ring size distribution, and surface adsorbed water content, are drastically different from those of common bulk silica materials and intimately related to the particles' dimension. The SiOSi mean bond angle, probed…

Structural properties of core and surface of silica nanoparticles investigated by Raman spectroscopy

We studied the experimental Raman spectra of various commercial silica nanoparticles of average diameter from 7 to 40 nm and specific surface from 50 to 380 m2/g. We found that the peculiarities of the particles Raman spectra systematically depend on their specific surface. In detail, the peak position of the R band at about 440 cm−1 shifts towards high wavenumbers following an almost linear dependence on the specific surface. Similarly, the amplitudes of the D1 and D2 bands, at about 495 and 605 cm−1, respectively, increase linearly with the same quantity. Our results are interpreted in the frame of the shell model for the nanoparticles clarifying that the network of the core of the nanopa…

Near infrared emitting silica nanoparticles: O2 diffusion properties and excited state relaxation

A rapid and eco-friendly route to synthesize graphene-doped silica nanohybrids

International audience; In the present study, the possibility to synthesize graphene oxide (GO)-based nanohybrids with pure and O2-doped silica nanoparticles by a rapid and easy hydrothermal process has been explored. The nanohybrids were prepared by varying the type of silica nanoparticles (average diameter 7 nm or 40 nm) and the silica/GO weight ratio. All the materials were fully characterized by spectroscopic and morphological techniques.The experimental results revealed that it is possible to tune the characteristics of the obtained nanohybrids, such as morphology and amount of ester/ether linkages upon varying the preparation parameters, together with the nanosilica's typology and the…

Investigation on the ganaration process of HO2• radicals by γ-ray irradiation in O2-loaded fumed silica

Abstract We report an experimental investigation on the effects of γ-ray irradiation in three types of fumed silica previously loaded with O 2 molecules. Our data indicate that the main effect of irradiation in these systems is to generate a very large concentration of HO 2 interstitial radicals (about 10 18  molecules/cm 3 ). Furthermore, the number of generated HO 2 was found to be larger in the samples with higher O 2 contents before irradiation. This correlation suggests that HO 2 radicals are induced by reaction of interstitial O 2 molecules with radiolytic H atoms, as previously suggested for O 2 -loaded bulk amorphous silicon dioxide (a-SiO 2 or silica) samples. However, at variance …

Investigation by raman spectroscopy of the decomposition process of HKUST-1 upon exposure to air

We report an experimental investigation by Raman spectroscopy of the decomposition process of Metal-Organic Framework (MOF) HKUST-1 upon exposure to air moisture (T=300 K, 70% relative humidity). The data collected here are compared with the indications obtained from a model of the process of decomposition of this material proposed in literature. In agreement with that model, the reported Raman measurements indicate that for exposure times longer than 20 days relevant irreversible processes take place, which are related to the occurrence of the hydrolysis of Cu-O bonds. These processes induce small but detectable variations of the peak positions and intensities of the main Raman bands of th…

Optical absorption and electron paramagnetic resonance of the E’_alfa center in amorphous silicon dioxide

We report a combined study by optical absorption OA and electron paramagnetic resonance EPR spectroscopy on the E point defect in amorphous silicon dioxide a-SiO2. This defect has been studied in -ray irradiated and thermally treated oxygen-deficient a-SiO2 materials. Our results have pointed out that the E center is responsible for an OA Gaussian band peaked at 5.8 eV and having a full width at half maximum of 0.6 eV. The estimated oscillator strength of the related electronic transition is 0.14. Furthermore, we have found that this OA band is quite similar to that of the E center induced in the same materials, indicating that the related electronic transitions involve states highly locali…

Si29Hyperfine Structure of theE′αCenter in Amorphous Silicon Dioxide

We report a study by electron paramagnetic resonance on the $E^{\ensuremath{'}}{}_{\ensuremath{\alpha}}$ point defect in amorphous silicon dioxide ($a\mathrm{\text{\ensuremath{-}}}{\mathrm{SiO}}_{2}$). Our experiments were performed on $\ensuremath{\gamma}$-ray irradiated oxygen-deficient materials and pointed out that the $^{29}\mathrm{Si}$ hyperfine structure of the $E^{\ensuremath{'}}{}_{\ensuremath{\alpha}}$ consists of a pair of lines split by $\ensuremath{\sim}49\text{ }\text{ }\mathrm{mT}$. On the basis of the experimental results, a microscopic model is proposed for the $E^{\ensuremath{'}}{}_{\ensuremath{\alpha}}$ center, consisting of a hole trapped in an oxygen vacancy with the un…

Atomic force microscopy and Raman investigation on the sintering process of amorphous SiO2 nanoparticles

We report an experimental investigation on the sintering process induced in fumed silica powders by isochronal thermal treatments at T=1270 K. Three types of fumed silica are considered, consisting of amorphous SiO2 (a-SiO2) particles with mean diameters 7, 14, and 40 nm. The study is performed by atomic force microscopy (AFM), to follow the morphological changes, and by Raman scattering, to obtain information on the concomitant structural modifications. The former method indicates that the sintering process proceeds by aggregation of single particles into larger grains, whose sizes increase with the thermal treatment duration. Furthermore, for each fumed silica type considered, the quantit…

Optical absorption band at 5.8 eV associated with the E’_gamma centers in amorphous silicon dioxide: Optical absorption and EPR measurements

Line shape modifications induced by thermal treatment in the optical absorption and electron paramagnetic resonance EPR signals associated with the E center are experimentally investigated in various types of -irradiated amorphous silicon dioxide a-SiO2. The g values of the EPR main resonance line of the E center show a shift correlated with the peak energy variation of the absorption band at about 5.8 eV associated with this defect. These spectroscopic changes are proposed to originate from structural modifications of the defect environment. The correlation is theoretically explained considering that the spin-orbit interaction couples the g-tensor’s elements and the electronic energy level…

Oxidation of silicon nanoparticles produced by nanosecond laser ablation in liquids

We investigated nanoparticles produced by laser ablation of silicon in water by the fundamental harmonic (1064 nm) of a ns pulsed Nd:YAG. The silicon oxidation is evidenced by IR absorption features characteristic of amorphous SiO2 (silica). This oxide is highly defective and manifests a luminescence activity under UV excitation: two emission bands at 2.7 eV and 4.4 eV are associated with the twofold coordinated silicon, =SiO••.

Disentangling size effects and spectral inhomogeneity in carbon nanodots by ultrafast dynamical hole-burning.

Carbon nanodots (CDs) are a novel family of nanomaterials exhibiting unique optical properties. In particular, their bright and tunable fluorescence redefines the paradigm of carbon as a "black" material and is considered very appealing for many applications. While the field keeps growing, understanding CDs fundamental properties and relating them to their variable structures becomes more and more critical. Two crucial problems concern the effect of size on the electronic structure of CDs, and to what extent their optical properties are influenced by structural disorder. Furthermore, it remains largely unclear whether traditional concepts borrowed from the photo-physics of semiconductor qua…

IMPROVED STABILITY OF GRAPHENE OXIDE-SILICA NANOHYBRIDS AND RELATED POLYMER-BASED NANOCOMPOSITES

Although its promising properties make the graphene oxide (GO) very interesting as filler for polymer matrices, some problems related to its thermal stability in the region which ranges from 80 to 200 °C, are crucial for the possibility to melt process GO together with practically all the polymers [1,2]. Moreover, above 100 °C GO lamellae were found to become stacked. In this work, two different ways to preserve the GO structure and ensure its dispersion within different polymer matrices have been investigated and schematized in Fig. 1. Exfoliation plays a key-role in the achievement of good mechanical properties since it preserves the GO from both stacking phenomena. The capability of sili…

β-ray irradiation effects on silica nanoparticles

By electron paramagnetic resonance (EPR) measurements, we examine the amplitude of the signal typically due to a combination of NBOHC (Non Bridging Hole Center) and POR (Peroxy Radical) defects induced by β-ray irradiation (from 1.2 to 1200 MGy) in silica nanoparticles with diameter ranging from 7 to 20 nm. Our data indicate that the signal line-shapes recorded at different doses is quite independent from the particles sizes and from the dose. Furthermore, for each considered nanoparticles size, the concentration of defects is also almost constant with respect to dose, and it does not change significantly if measured after 2 or 9 months from the irradiation. By contrast, we observed that th…

EPR on Radiation-Induced Defects in SiO2

Continuous-wave electron paramagnetic resonance (EPR) spectroscopy has been the technique of choice for the studies of radiation-induced defects in silica (SiO2) for 60 years, and has recently been expanded to include more sophisticated techniques such as high-frequency EPR, pulse electron nuclear double resonance (ENDOR), and pulse electron spin echo envelope modulation (ESEEM) spectroscopy. Structural models of radiation-induced defects obtained from single-crystal EPR analyses of crystalline SiO2 (alfa-quartz) are often applicable to their respective analogues in amorphous silica (a-SiO2), although significant differences are common.

Luminescence activity of irradiated SiO2-clathrate Melanophlogite

Nitrogen-doped carbon dots embedded in a SiO2 monolith for solid-state fluorescent detection of Cu2+ ions

We describe the simple fabrication of SiO2 sol-gel monoliths embedding highly luminescent carbon nanodots (CDs) sensitive to metal ions. The pristine CDs we synthesize display an intense dual emission consisting in two fluorescence bands in the green and violet region, and we demonstrate that this photoluminescence is substantially unchanged when the dots are incorporated in the SiO2 matrix. The emission of these CDs is quenched by interactions with Cu2+ ions, which can be used to detect these ions with a detection limit of 1 μM. The chromophores remain accessible to diffusing Cu2+ ions even after embedding CDs in the sol-gel monolith, where their detection capabilities are preserved. Such …

Streptomyces coelicolor Vesicles: Many Molecules To Be Delivered

ABSTRACT 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 -omics 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 particul…

Structural and thermal stability of graphene oxide-silica nanoparticles nanocomposites

Abstract The investigation of the thermal stability up to 400 °C of Graphene Oxide (GO) and GO-silica nanoparticles (n-SiO2) composites prepared by direct mixture of GO and n-SiO2 is reported. Using Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy, Energy Dispersive X-ray analysis, Atomic Force Microscopy, Raman and Infrared absorption measurements a thorough characterization of the prepared materials is carried out. By deepening the changes induced in the 2D Raman spectral region of GO at about 2900 cm−1 the comprehension of an interplay, driven by the thermally induced changes of the material, between inter-valley and intra-valley vibrational transitions is elucidated. This …

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 carb…

Unveiled the Source of the Structural Instability of HKUST-1 Powders upon Mechanical Compaction: Definition of a Fully Preserving Tableting Method

Metal–organic frameworks (MOFs) are getting closer to finally being used in commercial applications. In order to maximize their packing density, mechanical strength, stability in reactive environme...

Photosensitivity of SiO2–Al and SiO2–Na glasses under ArF (193 nm) laser

Abstract Photosensitivity of SiO 2 –Al and SiO 2 –Na glass samples was probed by means of the induced optical absorption and luminescence as well as by electron spin-resonance (ESR) after irradiation with excimer-laser photons (ArF, 193 nm). Permanent visible darkening in the case of SiO 2 –Al and transient, life time about one hour, visible darkening in the case of SiO 2 –Na was found under irradiation at 290 K. No darkening was observed at 80 K for either kind of material. This investigation is dedicated to revealing the electronic processes responsible for photosensitivity at 290 and 80 K. The photosensitivity of both materials is related to impurity defects excited directly in the case …

E’_delta center in amorphous silicon dioxide: a potential probe for embedded silicon nanostructures

Graphene‐SiO2 Interaction from Composites to Doping

An overview of the interaction between monolayer graphene and SiO2 dielectric substrate is reported focusing on the effect this latter has on doping and strain induced by thermal treatments in controlled atmosphere. The disentanglement of strain and doping is highlighted and the comparison with another dielectric substrate of Al2O3 evidences the critical role that the substrate has in the electronic properties of graphene. The reported results pave the way for microelectronic devices based on graphene on dielectrics and for Fermi level tuning in composites of graphene and nanoparticles.

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

Abstract We report an experimental investigation on the effects of γ -ray irradiation in several types of silica nanoparticles previously loaded with O 2 molecules. They differ in specific surface and average diameter. By electron paramagnetic resonance (EPR) measurements we observe the generation of about 10 18 HO 2 • /cm 3 interstitial radicals. These radicals are induced by reaction of interstitial O 2 molecules with radiolytic H atoms, as previously suggested for O 2 -loaded bulk a-SiO 2 samples. However, at variance with respect to bulk materials, our experimental evidences suggest a different generation process of HO 2 • radical. In fact, by a detailed study of samples exposed to D 2 …

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 repea…

Electron Irradiation Effects on Single‐Layer MoS 2 Obtained by Gold‐Assisted Exfoliation

International audience; Mechanical exfoliation assisted by gold is applied to obtain good quality large lateral size single-layer MoS2. The effects of 2.5 MeV electron irradiation are investigated at room temperature on structural and electronic features by Raman and microluminescence spectroscopy. The exciton recombination emission in the direct bandgap of single-layer MoS2 is affected during irradiation starting from the minimum explored dose of 1 kGy. At higher doses, Raman bands show no relevant modifications whereas the exciton emission is quenched, suggesting that irradiation-induced point defects affect exciton dynamics.

Effects of Pressure, Thermal Treatment, and O2 Loading in MCM41, MSU-H, and MSU-F Mesoporous Silica Systems Probed by Raman Spectroscopy

We present a Raman study of the effects induced by pressure, thermal treatments, and O2 loading in MCM41, MSU-H, and MSU-F representative mesoporous silica. We compared the starting powders with the mechanically pressed tablets produced applying pressures of ∼0.2 and ∼0.45 GPa. The spectra of the three untreated tablets evidence that the main value of the Si-O-Si angle decreases and that in the MCM41 and the MSU-H Si-O-Si hydrolysis occurs, whereas such a process is absent or much less efficient in the MSU-F. Despite their different networks, the three powders tend to crystallize in cristobalite when treatments are at 1000 °C. The MCM41 and MSU-H tablets exhibit behavior similar to their st…

Multitechnique Analysis of the Hydration in Three Different Copper Paddle-Wheel Metal-Organic Frameworks

The structural instability in a humid environment of the majority of metal-organic frameworks (MOFs) is a challenging obstacle for their industrial-scale development. Recently, two water-resistant MOFs have been synthetized, STAM-1 and STAM-17-OEt. They both contain copper paddle wheels, like the well-known water-sensitive HKUST-1, but different organic linkers. The crystal lattice of both the MOFs undergoes a phase transition upon interaction with water molecules. Their unusual flexibility allows the controlled breaking of some interpaddle wheel Cu-O interactions in the so-called crumple zones, with a mechanism called hemilability, which is considered to have a crucial role for the stabili…

Isolation of the CH3˙ rotor in a thermally stable inert matrix: first characterization of the gradual transition from classical to quantum behaviour at low temperatures

International audience; Matrix isolation is a method which plays a key role in isolating and characterizing highly reactive molecularradicals. However, the isolation matrices, usually composed of noble gases or small diamagnetic molecules,are stable only at very low temperatures, as they begin to desegregate even above a few tens of Kelvin.Here we report on the successful isolation of CH3 radicals in the cages of a nearly inert clathrate–SiO2matrix. This host is found to exhibit a comparable inertness with respect to that of most conventionalnoble gas matrices but it is characterized by a peculiar thermal stability. The latter property is related to thecovalent nature of the host material a…

Structure of the FeBTC Metal–Organic Framework: A Model Based on the Local Environment Study

The local environment of iron in FeBTC, a metal organic framework commercially known as Basolite F300, is investigated combining XANES and EXAFS studies of the iron K-edge. The building block of the FeBTC can be described as an iron acetate moiety. Dehydration induces a change in the coordination of the first shell while preserving the network. We propose that the local structure around Fe atoms does not undergo a rearrangement, thus, leading to the formation of an open site. The analysis conveys that the FeBTC is a disordered network of locally ordered blocks.

EPR investigation on the polyamorphic transformation induced by electron irradiation in SiO2 glass

Photoluminescence properties of S2 molecule trapped in Melanophlogite

We studied the photoluminescence properties of a sample of SiO2-clathrate Melanophlogite, a crystalline microporous material which is found in nature as a rare mineral. Upon β irradiation, the material displays an intense light emission under near-UV illumination. We studied in detail this optical activity by steady-state and time-resolved photoluminescence measurements as a function of temperature. The spectroscopic properties we find can be ascribed to a population of quasi-free molecules trapped within each of the two different types of cage available in the structure of this clathrate, although the spectroscopic properties of the guest molecules are affected by their interactions with t…

Structural and luminescence properties of amorphous SiO2 nanoparticles

We report an experimental study on the photoluminescence band peaked at 2.7 eV (blue band) induced by thermal treatments in nanometric amorphous SiO 2. In particular the emission dependence on the nanometric particles size as a function of their mean diameter from 7 nm up to 40 nm is investigated. We found that the emission amplitude increases on decreasing the particle diameter, showing a strong correlation between the blue band and the nanometric nature of the particles. By Raman spectroscopy measurements it is evidenced that the SiO2 nanoparticles matrix is significantly affected by the reduction of size. Basing on the shell-like model, these findings are interpreted assuming that the de…

Sensing of Transition Metals by Top-Down Carbon Dots

Carbon quantum dots (CQDs) are a new class of carbon-rich materials with a range of unique optical and structural properties. They can be defined as carbon nanoparticles, with sizes in the range of 1–10 nm, displaying absorption and emission activities in the UV-VIS range. Depending on the structure, CQDs display a wide variability of properties, which provides the possibility of finely tuning them for several applications. The great advantages of CQDs are certainly the ease of synthesis, non-toxicity, and the strong interactions with the surrounding environment. Based on this, CQDs are especially promising as selective chemosensors. The present study reports on carbon quantum dots synthesi…

Light-Induced Formation of Pb3+Paramagnetic Species in Lead Halide Perovskites

Hybrid halide perovskites are soft materials processed at room temperature, revolutionary players in the photovoltaic field. Nowadays, investigation of the nature and role of defects is seen as one of the key challenges toward full comprehension of their behavior and achievement of high device stability under working conditions. We reveal the reversible generation, under illumination, of paramagnetic Pb3+ defects in CH3NH3PbI3, synthesized in ambient conditions, induced by the presence of Pb-O defects in the perovskite structure that may trap photogenerated holes, possibly mediated by the concomitant oxidation and migration of ions. According to the mechanism that we hypothesize, one charge…

Structural properties of the range-II- and range-III order in amorphous-SiO2 probed by electron paramagnetic resonance and Raman spectroscopy

In the present work we report an experimental investigation by electron paramagnetic resonance spectroscopy on the hyperfine structure of the E. point defect, probing the local arrangement of the network (range-II order), and by Raman spectroscopy on the D 1 and D 2 lines, probing mean features of the network (range-III order). Our studies, performed on a-SiO 2 samples thermally treated at 1000 °C in air for different time durations, show that changes of the hyperfine structure and of the D 1 and D 2 lines occur in a correlated way. These results give strong evidence that the range-II and range-III order properties are intimately related to each other and that these properties are determine…

Defect-related visible luminescence of silica nanoparticles

The high photon emissivity in the visible spectral range is one of the most relevant phenomena emerging from the reduction of silica down to nanoscale; hence it is promising for the development of optical nanotechnologies (down converter, probes, display). It is well accepted that the origin of this luminescence is related to the high specific surface (~100 m2/g) that favors the formation of optically active defects at the nanosilica surface. With the aim to clarify the role of specific luminescent defects, here we report a detailed study of spectral and decay features by time-resolved photoluminescence spectra under a visible-UV tunable laser excitation. Our study is carried out on differe…

The role of impurities in the irradiation induced densification of amorphous SiO(2).

In a recent work (Buscarino et al 2009 Phys. Rev. B 80 094202), by studying the properties of the (29)Si hyperfine structure of the E'(γ) point defect, we have proposed a model able to describe quantitatively the densification process taking place upon electron irradiation in amorphous SiO(2) (a-SiO(2)). In particular, we have shown that it proceeds heterogeneously, through the nucleation of confined densified regions statistically dispersed into the whole volume of the material. In the present experimental investigation, by using a similar approach on a wider set of materials, we explore how this process is influenced by impurities, such as OH and Cl, typically involved in relevant concent…

Aging of MCM41, MSU-H and MSU-F mesoporous systems investigated through the Raman spectroscopy

Here we report an experimental investigation, based on the Raman spectroscopy, on the aging of some mesoporous silica based systems. In details, we studied the aging in air of the MCM41, the MSU-H and the MSU-F materials by acquiring the Raman spectra of as received and of mechanically pressed, at 0.2 and 0.45 GPa, powders. Our data evidenced that the starting powders of the MCM41 and of the MSU-H undergo structural modification when they are exposed to the ambient atmosphere, such modification consisting in the decrease of the D2 Raman band (originated by the three member rings). At variance the powders of the MSU-F appear to be stable. Furthermore, by pressing the starting powders to prod…

Near-Infrared-Responsive Choline-Calix[4]arene-Gold Nanostructures for Potential Photothermal Cancer Treatment

The development of novel chemical approaches for the fabrication of gold nanostructures with localized surface plasmon resonance (LSPR) falling in the near-infrared (NIR) region is one challenging topic in nanomaterials science. Due to their optical and photothermal properties triggered by light excitation in the therapeutic window (λmax = 650-1300 nm), gold-based nanostructures are appealing candidates in anticancer nanomedicine. Here, we report a novel method to prepare water-dispersible gold nanostructures with NIR-LSPR (λmax = 600-1000 nm) properties. The gold nanostructures were achieved in a single step by an unconventional method using NADH as a reducing agent and an amphiphilic chol…

Nano-Oxides produced by ns laser ablation in liquids

Laser ablation in liquids was successfully applied to produce nanosized oxides from Si, Ti and Zn targets. The obtained colloidal solutions of nanoparticles were investigated by complementary techniques: AFM, IR and Raman spectroscopies; optical absorption and time resolved photoluminescence. The results demonstrate the production of SiO2, TiO2 and ZnO. The absorption and emission properties of these material have been also investigated and appear to be promising for optical applications.

Graphene oxide and Fumed silica graphene oxide nanocomposites modification by thermal treatments

In the present study we investigate post synthesis thermal treatments up to 400 °C of graphene oxide (GrO) prepared from commercial graphite and of GrO–silica nanocomposites prepared by a solution of commercial Fumed silica nanoparticles (average diameter 7 nm or 40 nm) and the GrO. The thermal treatments were carried out in air, vacuum or He atmosphere to highlight tunable changes. Two GrO batches with small differences in the D (~1350 cm–1) and G (~1580 cm–1) Raman bands have been employed to evaluate effects depending on preparation. Thermal effects have been monitored through the Raman spectroscopy focusing on D, G and 2D (2500–3500 cm–1) bands spectral ranges. The experiments evidenced…

Luminescence mechanisms of defective ZnO nanoparticles.

ZnO nanoparticles (NPs) synthesized by pulsed laser ablation (PLAL) of a zinc plate in deionized water were investigated by time-resolved photoluminescence (PL) and complementary techniques (TEM, AFM, μRaman). HRTEM images show that PLAL produces crystalline ZnO NPs in wurtzite structure with a slightly distorted lattice parameter a. Consistently, optical spectra show the typical absorption edge of wurtzite ZnO (Eg = 3.38 eV) and the related excitonic PL peaked at 3.32 eV with a subnanosecond lifetime. ZnO NPs display a further PL peaking at 2.2 eV related to defects, which shows a power law decay kinetics. Thermal annealing in O2 and in a He atmosphere produces a reduction of the A1(LO) Ra…

Structural organization of silanol and silicon hydride groups in the amorphous silicon dioxide network

We present a study on the effects of an isothermal annealing treatment on a-SiO 2 having a significant content of silanol hydride groups (Si-H). We examined the properties of the IR absorption bands of silanol (Si-OH) and silicon hydride groups as a function of the duration of the thermal treatment. We showed that the Si-OH and Si-H groups contents decrease in a linearly correlated way. The annealing dynamics suggest that the two species are close to each other in the amorphous network. We showed that the profile of the silanol groups absorption band is the same as that observed in other commercial a-SiO 2 materials, irrespectively of the concomitant presence of nearby Si-H groups, and, mor…

Piezoresistive Sensors from Bithiophene-fulleropyrrolidine Bisadducts Thin-Films

The phenomenon of piezoresistivity in materials is based on the separation of conductive domains triggered by mechanical strains, resulting in a variation of the electrical resistance.1 This property is at the core of sensors for wearable electronics, e-skins, human motion detectors and machine learning devices.2 Fundamental requirements include lightness, good transparency, high flexibility and sensitivity to tiny deformations. However, the fabrication of a system integrating all these features is challenging. Herein, we show a semitransparent piezoresistive sensor realized by an electropolymerized bithiophene‐fulleropyrrolidine bisadduct onto ITO/PET3 (see Figure 1a). The good outcome of …

Oxidation Processes in Sicilian Olive Oils Investigated by a Combination of Optical and EPR Spectroscopy

:  Extra virgin olive oil (EVOO) is recognized as one of the healthiest foods for its high content of antioxidants, which forestall and slow down radical formation. Free radical-initiated oxidation is considered one of the main causes of rancidity in fats and oils. As a consequence, reliable protocols for the investigation of oil oxidation based on selective, noninvasive, and fast methods are highly desirable. Here we report an experimental approach based on UV-Vis absorbance, steady-state fluorescence, and electron paramagnetic resonance (EPR) spectroscopy for studying oxidation processes induced by temperature for a period up to 35 d on Sicilian EVOO samples. We followed the decrease in β…

A two-component model for the 2260cm−1 infrared absorption band in electron irradiated amorphous SiO2

Abstract We report an experimental study by infrared absorption (IR) measurements focused on the effects of electron irradiation in the dose range from 1.2 × 10 3  kGy to 5 × 10 6  kGy on the intrinsic band peaked at 2260 cm − 1 in amorphous silicon dioxide (a-SiO 2 ) materials. This IR band is particularly relevant as it is assigned to an overtone of the strong asymmetric stretching vibration of Si–O–Si bridges and consequently it is intimately related to the Si–O–Si bond angle distribution. In a recent work we have shown that structural modifications induced by irradiation take place through the nucleation of confined high-defective and densified regions statistically dispersed into the w…

Effect of air on oxygen p-doped graphene on SiO2

Stability in ambient air or in vacuum-controlled atmosphere of molecular oxygen-induced p-type doping of graphene monolayer on SiO2 substrate on Si is investigated by micro-Raman spectroscopy and atomic force microscopy (AFM). The Raman 2D and G bands spectral positions and amplitude ratio are affected by the permanence in air atmosphere in a time scale of months whereas the vacuum safely maintains the doping effects determined through Raman bands. No morphological effects are induced by the doping and post-doping treatments. A reactivity of ambient molecular gas with stably trapped oxygen is suggested to induce the doping modification. (C) 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Determination of Geometry Arrangement of Copper Ions in HKUST-1 by XAFS During a Prolonged Exposure to Air

We present an experimental investigation focused on the local structural changes taking place around Cu2+ions in metal− organic framework (MOF) HKUST-1 for different times of exposure to air by XAFS (X-ray absorption fine structure). The analysis involves both XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) regions around the Cu K-edge. Starting from the paddle-wheel structures proposed in literature, a more detailed description of the geometrical environment of Cu2+ions has been found. In particular, the paddle-wheel structure of a fresh sample, which means a pristine HKUST-1 material with a single water molecule weakly adsorbed on each C…

Photoluminescence of Carbon Dots Embedded in a SiO2 Matrix

Abstract 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 tunab…

Investigation on the microscopic structure of E' center in amorphous silicon dioxide by electron paramagnetic resonance spectroscopy

The E′δ center is one of the most important paramagnetic point defects in amorphous silicon dioxide ( a-SiO 2) primarily for applications in the field of electronics. In fact, its appearance in the gate oxide of metal-oxide-semiconductor (MOS) structures seriously affects the proper work of many devices and, often, causes their definitive failure. In spite of its relevance, until now a definitive microscopic model of this point defect has not been established. In the present work we review our experimental investigation by electron paramagnetic resonance (EPR) on the E′δ center induced in γ-ray irradiated a-SiO 2. This study has driven us to the determination of the intensity ratio between…

Nanosystem for diagnosis and photothermal treatment of tumors

The invention relates to a nanosystem for the diagnosis, image-guided treatment of tumors and monitoring of the tumor microenvironment. The nanosystem is a contrast agent comprising a polymer shell based on a hyaluronic acid nanogel, super-parameg-netic iron oxide nanoparticles (SPIONs) and carbon nanoparticles (CDs).

Influence of oxide substrates on monolayer graphene doping process by thermal treatments in oxygen

Abstract The structural and the electronic properties of monolayer graphene made by chemical vapor deposition and transferred on various oxide substrates ( SiO 2 , Al 2 O 3 , and HfO 2 ) are investigated by Raman Spectroscopy and Atomic Force Microscopy in order to highlight the influence of the substrate on the features of p-doping obtained by O 2 thermal treatments. By varing the treatment temperature up to 400 °C, the distribution of the reaction sites of the substrates is evaluated. Their total concentration and the consequent highest doping available is determined and it is shown that this latter is linked to the water affinity of the substrate. Finally, by varing the exposure time to …

Si-rich sites embedded in a-SiO2 probed by electron paramagnetic resonance spectroscopy

Ethanol Controls the Self-Assembly and Mesoscopic Properties of Human Insulin Amyloid Spherulites.

Protein self-assembly into amyloid fibrils or highly hierarchical superstructures is closely linked to neurodegenerative pathologies as Alzheimer's and Parkinson's diseases. Moreover, protein assemblies also emerged as building blocks for bioinspired nanostructured materials. In both the above mentioned fields, the main challenge is to control the growth and properties of the final protein structure. This relies on a more fundamental understanding of how interactions between proteins can determine structures and functions of biomolecular aggregates. Here, we identify a striking effect of the hydration of the single human insulin molecule and solvent properties in controlling hydrophobicity/…

Ultrafast Interface Charge Separation in Carbon Nanodot-Nanotube Hybrids

Carbon dots are an emerging family of zero-dimensional nanocarbons behaving as tunable light harvesters and photoactivated charge donors. Coupling them to carbon nanotubes, which are well-known electron acceptors with excellent charge transport capabilities, is very promising for several applications. Here, we first devised a route to achieve the stable electrostatic binding of carbon dots to multi- or single-walled carbon nanotubes, as confirmed by several experimental observations. The photoluminescence of carbon dots is strongly quenched when they contact either semiconductive or conductive nanotubes, indicating a strong electronic coupling to both. Theoretical simulations predict a favo…

Controlling the oxidation processes of Zn nanoparticles produced by pulsed laser ablation in aqueous solution

We used online UV-VIS optical absorption and photoluminescence spectra, acquired during and after pulsed laser ablation of a Zinc plate in aqueous solution, to investigate the effect of the laser repetition rate and liquid environment on the oxidation processes of the produced nanoparticles. A transient Zn/ZnO core-shell structure was revealed by the coexistence of an absorption peak around 5.0 eV due to Zn surface plasmon resonance and of an edge at 3.4 eV coming from wurtzite ZnO. The growth kinetics of ZnO at the various repetition rates, selectively probed by the excitonic emission at 3.3 eV, began immediately at the onset of laser ablation and was largely independent of the repetition …

Polyamorphic transformation induced by electron irradiation ina-SiO2glass

We report a study by electron paramagnetic resonance of amorphous silicon dioxide $(a{\text{-SiO}}_{2})$ irradiated by 2.5 MeV electrons in the dose range from $1.2\ifmmode\times\else\texttimes\fi{}{10}^{3}$ to $5\ifmmode\times\else\texttimes\fi{}{10}^{6}\text{ }\text{kGy}$. By measuring the change in the splitting of the primary $^{29}\text{S}\text{i}$ hyperfine doublet of the ${E}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ centers we evidenced an irradiation induced local (around the defects) densification of $a{\text{-SiO}}_{2}$. Our data show that the local degree of densification of the materials is significantly higher than that obtained by mean density measurements, suggesting that the …

Photoinduced charge transfer from Carbon Dots to Graphene in solid composite

Abstract The emission in solid phase of Carbon Dots (CDs) deposited by drop-casting technique is investigated by means of micro-photoluminescence. Graphene and SiO2 are used as substrates, and the influence of their different nature – conductive or insulating – on the emission of CDs is highlighed. In particular, a systematic loss of efficiency in the emission of CDs on graphene is found, suggesting a CD-graphene interaction possibly due to a photoinduced electron transfer between the surface states of CDs and the conduction band of graphene. Finally, thanks to the negligible influence on CDs emission, SiO2 substrate is used as support to perform thermal processing of CDs in solid phase, sh…

Inhomogeneity Effects On Point Defects Studied By Photoluminescence Time Decay In SiO2.

Graphene p-Type Doping and Stability by Thermal Treatments in Molecular Oxygen Controlled Atmosphere

Doping and stability of monolayer low defect content graphene transferred on a silicon dioxide substrate on silicon are investigated by micro-Raman spectroscopy and atomic force microscopy (AFM) during thermal treatments in oxygen and vacuum controlled atmosphere. The exposure to molecular oxygen induces graphene changes as evidenced by a blue-shift of the G and 2D Raman bands, together with the decrease of I2D/IG intensity ratio, which are consistent with a high p-type doping (∼1013 cm-2) of graphene. The successive thermal treatment in vacuum does not affect the induced doping showing this latter stability. By investigating the temperature range 140-350 °C and the process time evolution, …

Optical absorption and electron paramagnetic resonance of theEα′center in amorphous silicon dioxide

We report a combined study by optical absorption (OA) and electron paramagnetic resonance (EPR) spectroscopy on the E{sub {alpha}}{sup '} point defect in amorphous silicon dioxide (a-SiO{sub 2}). This defect has been studied in {beta}-ray irradiated and thermally treated oxygen-deficient a-SiO{sub 2} materials. Our results have pointed out that the E{sub {alpha}}{sup '} center is responsible for an OA Gaussian band peaked at {approx}5.8 eV and having a full width at half maximum of {approx}0.6 eV. The estimated oscillator strength of the related electronic transition is {approx}0.14. Furthermore, we have found that this OA band is quite similar to that of the E{sub {gamma}}{sup '} center in…

Dynamic modification of Fermi energy in single-layer graphene by photoinduced electron transfer from carbon dots

Graphene (Gr)&mdash

Emissive titanium dioxide nanoparticles synthesized py pulsed laser ablation in liquid phase

The remarkable applications of TiO2 nanomaterials, including, e.g. photocatalysis and dye-sensitized solar cells, have inspired in the last two decades an extensive amount of research aimed at understanding the properties of these materials. Photoluminescence is scarcely used to probe the electronic properties of TiO2, because neither bulk or nanosized TiO2 commonly display room-temperature emission. In particular, the fundamental luminescence due to the recombination of the self-trapped exciton in anatase TiO2 is typically observed only at low temperatures. We report the synthesis of luminescent titanium dioxide nanoparticles (NPs) by pulsed laser ablation of titanium in aqueous solution. …

A Comparative Study of Top-Down and Bottom-Up Carbon Nanodots and Their Interaction with Mercury Ions

We report a study of carbon dots produced via bottom-up and top-down routes, carried out through a multi-technique approach based on steady-state fluorescence and absorption, time-resolved fluorescence spectroscopy, Raman spectroscopy, infrared spectroscopy, and atomic force microscopy. Our study focuses on a side-to-side comparison of the fundamental structural and optical properties of the two families of fluorescent nanoparticles, and on their interaction pathways with mercury ions, which we use as a probe of surface emissive chromophores. Comparison between the two families of carbon dots, and between carbon dots subjected to different functionalization procedures, readily identifies a …

Trifluoroethanol modulates α-synuclein amyloid-like aggregate formation, stability and dissolution

The conversion of proteins into amyloid fibrils and other amyloid-like aggregates is closely connected to the onset of a series of age-related pathologies. Upon changes in environmental conditions, amyloid-like aggregates may also undergo disassembly into oligomeric aggregates, the latter being recognized as key effectors in toxicity. This indicates new possible routes for in vivo accumulation of toxic species. In the light of the recognized implication of α-Synuclein (αSN) in Parkinson's disease, we present an experimental study on supramolecular assembly of αSN with a focus on stability and disassembly paths of such supramolecular aggregate species. Using spectroscopic techniques, two-pho…

Inkjet printing Ag nanoparticles for SERS hot spots

A novel inkjet printing based approach is developed for the fabrication of a customizable platform on glass substrates allowing for surface enhanced Raman spectroscopy (SERS) detection of analytes up to single hot spots generated by the spontaneous aggregation of Ag nanoparticles (Ag NPs) in pL scale droplets. After drying the printed droplets under ambient conditions, trace amounts of the analyte can be detected by SERS given the proximity to NP hot spots. By employing alizarin (10-5M) as a model system and scaling the ink droplet volume from 1 nL to 10 pL, the absolute quantity of hot spots has been derived in the printed droplets allowing detecting up to a few molecules in proximity to i…

Methyl Radical in Clathrate Silica Voids. The Peculiar Physisorption Features of the Guest-Host Molecular Dynamics Interaction.

EPR line shape simulations of CH3/SiO2 clathrates and comparison to CH3/N2O and CH3/SiO2 experiments reveal the motional conditions of the CH3 radical up to the unusual regime of its stability, the high-temperature diffusional regime, at 300 K. In the low-temperature region, the CH3 in clathrates is found to rotate around the in-plane axes even at as low temperatures as 3.8 K. However, nonrotating methyls performing only libration about the C2-axes as well as around the C3-axis are also found, proving the existence of special sites in the clathrate voids that begin to accumulate a significant fraction of methyl radicals at temperatures below approximately 7 K. A distinctive feature in the s…

Entrapping of O2 Molecules in Nanostructured Silica Probed by Photoluminescence

We studied the emission of the O2 molecules embedded in fumed silica (amorphous silicon dioxide) nanoparticles differing for diameters and specific surface. By using a 1064 nm laser as a source we recorded both the O2 emission and the Raman signal of silica. Our experimental data show that the O2 emission/Raman signal (at 800cm-1) ratio decreases with increasing the specific surface both for the as received and the loaded samples. By performing a thermal treatment (600 °C for 2h) we modified the structure and the water content of the smallest nanoparticles without observing any significant change in the O2 emission/Raman signal ratio. Our data are explained by a shell model showing that the…

Phase change and O2 loading in mesoporous silica MCM41, MSU-H and MSU-F

Bending Sensors Based on Thin Films of Semitransparent Bithiophene-Fulleropyrrolidine Bisadducts

In this study, a novel bithiophene‐fulleropyrrolidine bisadducts system (bis‐Th2PC 60 ) was synthesized and electropolymerized by chronoamperometry onto flexible ITO/PET substrates. The resulting semitransparent thin film was characterized by XPS, FT‐IR, cyclic voltammetry and optical techniques, confirming the good outcome of the electropolymerization process. AFM investigations permitted to highlight an inherent disordered granular morphology, in which the grain‐to‐grain separation depends upon the application of bending. The electrical resistance of the thin film was characterized as function of bending (in the range 0°‐90°), showing promising responsivity to low bending angles (10°‐30°)…

V Symposium SiO2 and Advanced Dielectrics

Modifications of optical absorption band of center in silica

Abstract We report an experimental study of the modifications induced by gamma ray irradiation and by thermal treatment of both the electron paramagnetic resonance (EPR) and the optical absorption spectra of the E γ ′ center in silica. Our data show that the main g-values of E γ ′ EPR signal change as a function of the irradiation dose together with a red shift of the peak position of the absorption band around 5.8 eV attributed to the same center. Changes in the opposite direction are observed in both signals after thermal treatments. The peak position change of the optical absorption band is in quantitative agreement with the g-values shift. This strict correlation is evidence for the exi…

β-C3N4 Nanocrystals: Carbon Dots with Extraordinary Morphological, Structural, and Optical Homogeneity

Carbon nanodots are known for their appealing optical properties, especially their intense fluorescence tunable in the visible range. However, they are often affected by considerable issues of optical and structural heterogeneity, which limit their optical performance and limit the practical possibility of applying these nanoparticles in several fields. Here we developed a synthesis method capable of producing a unique variety of carbon nanodots displaying an extremely high visible absorption strength (ε > 3 × 106 M(dot)−1 cm−1) and a high fluorescence quantum yield (73%). The high homogeneity of these dots reflects in many domains: morphological (narrow size distribution), structural (q…

Confined crystallization of a HKUST-1 metal–organic framework within mesostructured silica with enhanced structural resistance towards water

A HKUST-1 metal–organic framework was crystallized in the NH2-modified mesostructured silica FDU-12 in order to improve its structural stability upon water exposure. In-depth structural characterization studies of the designed composite confirmed successful formation of the MOF phase within the ordered spherical mesopores of the silica matrix. In spite of the confinement within the cavities, MOF exhibits full accessibility for the adsorbed gas molecules. In contrast to the bulk HKUST-1, which undergoes slow phase transition in a humid environment, the structural integrity of the HKUST-1 in the humid-protective matrix remains unchanged even after immersion and stirring in water at elevated t…

Thermally induced structural modifications and O2 trapping in highly porous silica nanoparticles

Abstract In this work we investigate by Raman spectroscopy the effect of isochronal (2 h) thermal treatments in air in the temperature range 200–1000 °C of amorphous silicon dioxide porous nanoparticles with diameters ranging from 5 up to 15 nm and specific surface 590–690 m2/g. Our results indicate that the amorphous structure changes similarly to other porous systems previously investigated, in fact superficial SiOH groups are removed, Si–O–Si linkages are created and the ring statistic is modified, furthermore these data evidence that the three membered rings do not contribute significantly to the Raman signal detected at about 495 cm−1. In addition, after annealing at 900 and 1000 °C we…

Structural inhomogeneity of Ge-doped amorphous SiO2 probed by photoluminescence lifetime measurements under synchrotron radiation.

We report a study of the photoluminescence (PL) time decay of the B-type center, characterized by an optical absorption band peaked at similar to 5.2 eV and two related PL bands peaked at similar to 3.2 eV and similar to 4.3 eV, in sol-gel Ge-doped a- SiO2 under excitation by synchrotron radiation. Measurements were carried out by excitation in UV and in vacuum-UV (VUV), and were performed in the temperature range from 8 K up to 300 K in order to isolate the effects of the intersystem-crossing process, proposed to link the two emission bands of the center. Repeating the time decay measurement at several emission energies falling inside the 4.3 eV band, we have observed a variation of the PL…

Electron paramagnetic resonance investigation on the hyperfine structure of the center in amorphous silicon dioxide

Abstract We report an experimental investigation by electron paramagnetic resonance (EPR) spectroscopy on the hyperfine structure of the E δ ′ center in γ-ray irradiated amorphous silicon dioxide materials. This study has driven us to the determination of the intensity ratio between the hyperfine doublet and the main resonance line of this point defect. This ratio was obtained for a variety of silica samples and compared with the analogous ratio obtained for the E γ ′ defect. The comparison definitively confirms that the electronic wave function involved in the E δ ′ center is actually delocalized over four nearly equivalent Si atoms.

Decagram-Scale Synthesis of Multicolor Carbon Nanodots: Self-Tracking Nanoheaters with Inherent and Selective Anticancer Properties

Carbon nanodots (CDs) are a new class of carbon-based nanoparticles endowed with photoluminescence, high specific surface area, and good photothermal conversion, which have spearheaded many breakthroughs in medicine, especially in drug delivery and cancer theranostics. However, the tight control of their structural, optical, and biological properties and the synthesis scale-up have been very difficult so far. Here, we report for the first time an efficient protocol for the one-step synthesis of decagram-scale quantities of N,S-doped CDs with a narrow size distribution, along with a single nanostructure multicolor emission, high near-infrared (NIR) photothermal conversion efficiency, and sel…

Wide range excitation of visible luminescence in nanosilica

The visible luminescence of nanometer-sized silica particles (7 nm mean diameter) was investigated using time resolved spectroscopy. This luminescence is characterized by a wide excitation in the visible and ultraviolet range. The emission spectrum is centred at 2.72 eV with a full width at half maximum of 0.70 eV when excited above 3.5 eV, whereas it progressively empties on the high energy side when excited below 3.5 eV. Moreover, the lifetime falls in the ns timescale and decreases on increasing the emission energy. These features are due to the exceptionally broad inhomogeneous distribution of the emitting centres peculiar to the silica nanoparticles. © 2010 Elsevier B.V. All rights res…

Optical absorption band at5.8eVassociated with theEγ′centers in amorphous silicon dioxide: Optical absorption and EPR measurements

Line shape modifications induced by thermal treatment in the optical absorption and electron paramagnetic resonance (EPR) signals associated with the ${E}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ center are experimentally investigated in various types of $\ensuremath{\gamma}$-irradiated amorphous silicon dioxide $(a\text{\ensuremath{-}}\mathrm{Si}{\mathrm{O}}_{2})$. The $g$ values of the EPR main resonance line of the ${E}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ center show a shift correlated with the peak energy variation of the absorption band at about $5.8\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ associated with this defect. These spectroscopic changes are proposed to originate from structu…

Preparation and photoactivity of samarium loaded anatase, brookite and rutile catalysts

Abstract Pure and samarium loaded anatase, brookite and rutile nanopowders were synthesized by thermohydrolysis of TiCl 4 . The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (SSA) determination, UV–vis diffuse reflectance spectroscopy (DRS), atomic force microscopy (AFM), contact angle (CA) measurements and photoluminescence (PL) spectroscopy. The photocatalytic activity of pure and Sm-loaded TiO 2 polymorphs was investigated by employing the photodegradation of 4-nitrophenol as probe reaction in a liquid-solid system. Loading with Sm resulted in an improvement of the photoreactivity of the three TiO 2 polymorphs. The benefi…

S29i attribution of the 1.3 mT hyperfine structure of the E′γ centers in amorphous SiO2

We report an experimental investigation by electron paramagnetic resonance of the doublet of lines split by ∼1.3 mT and centered on the E′γ; center resonance line in the spectrum of irradiated amorphous SiO2 . Commercial and sol-gel materials, some of which subjected to hydrogen-deuterium exchange, were investigated. Exposure to γ or Β rays at room temperature of the samples and subsequent thermal treatments were carried out to induce the defects and to study their thermal stability. In all the materials used the ratio between the signal of the E′γ centers and that of the 1.3 mT doublet is constant and independent of the OH and OD contents. Furthermore, the 1.3 mT doublet and the E′γ center…

Fluorescent nitrogen-rich carbon nanodots with an unexpected β-C3N4nanocrystalline structure

Carbon nanodots are a class of nanoparticles with variable structures and compositions which exhibit a range of useful optical and photochemical properties. Since nitrogen doping is commonly used to enhance the fluorescence properties of carbon nanodots, understanding how nitrogen affects their structure, electronic properties and fluorescence mechanism is important to fully unravel their potential. Here we use a multi-technique approach to study heavily nitrogen-doped carbon dots synthesized by a simple bottom-up approach and capable of bright and color-tunable fluorescence in the visible region. These experiments reveal a new variant of optically active carbonaceous dots, that is a nanocr…

Alpha and deuteron irradiation effects on silica nanoparticles

We present an experimental investigation focused on the effects of alpha and deuteron irradiation on different silica nanoparticles. The study has been devoted also to characterize the induced point defects and the eventual structural modifications to evaluate the effects of the different irradiation source in comparison with the bulk materials. After irradiation up to about 10^16 ions cm^-2, we performed electron paramagnetic resonance (EPR), photoluminescence (PL), infrared (IR) absorption, Raman, and atomic force microscopy (AFM) measurements. We found that the two types of irradiation qualitatively induce comparable effects. Furthermore, irradiation generates the socalled twofold coordi…

Electron paramagnetic resonance line shape investigation of the Si-29 hyperfine doublet of the E'γ center in a-SiO2

We report an experimental study by electron paramagnetic resonance (EPR) spectroscopy of the E′γ center and of its hyperfine structure, consisting in a pair of lines split by 42 mT. Our results show that two types of E′γ centers can be distinguished on the basis of the EPR line shapes of their main resonance line and hyperfine structure. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Fluorescence of carbon dots embedded in a SiO2 host matrix

Carbon dots (CD) are an emerging class of recently discovered carbonaceous nanomaterials, which have attracted a large interest because of their bright and characteristically “tunable” fluorescence, and their potential for suggestive applications. Despite quite an intense research, the fundamental properties of these systems are poorly understood and still lively debated. Here we report on a series of experiments on N-doped CDs prepared by thermal decomposition of citric acid and urea. We studied these CDs by steady-state and nanosecond time-resolved photoluminescence, optical absorption, infrared absorption and atomic force microscopy. CDs (3 nanometers-sized) are found to emit two co-exis…

Growth of paramagnetic defects by gamma rays irradiation in oxygen-deficient silica

Abstract We report an electron paramagnetic resonance (EPR) study of gamma rays irradiation effects on an oxygen-deficient silica obtained from fused quartz. We have found that three types of E′ centers, E α ′ , E γ ′ and E δ ′ , and a paramagnetic defect in a spin triplet state (S = 1) are induced. The EPR signals dependence on the microwave power have been investigated. The concentrations of these centers as a function of gamma ray irradiation show that for high dose a limit value is reached suggesting a generation process from precursors.

Atomic Force Microscopy and Spectroscopy

Atomic force microscopy (AFM) is probably the most celebrated technique falling into the family of experimental methods known as scanning probe microscopy. AFM is primarily designed to obtain the morphology of the surface of a solid material by using the force of interaction between an inert probe and the sample. The AFM microscope can generally be operated in many ways for morphology investigations, but they can be roughly classified into two main groups: static- and dynamic-deflection modes. Since atomic force microscopy makes use of tip-surface interaction to reconstruct the surface morphology of materials, it is of fundamental importance to fully understand the nature and properties of …

Monolayer graphene doping and strain dynamics induced by thermal treatments in controlled atmosphere

Time dynamics of doping and strain induced in single layer graphene by thermal treatments up to 300 degrees C in vacuum, nitrogen, carbon dioxide and oxygen controlled atmosphere are deeply studied by Raman spectroscopy and they are compared with its morphological evolution investigated by Atomic Force Microscopy. The reaction dynamics in oxygen treatments is determined down to a time scale of few minutes as well as that of dedoping process made by water vapor treatment. The interplay of strain modification and doping effects is separated. The strain is clarified to be strongly influenced by the cooling time. The doping removal is dominated by the water vapor, showing that the concentration…

Experimental evidence for two different precursors of E’γ centers in silica

Electron paramagnetic resonance measurements of concentration and line shape of centers induced by γ ray irradiation are presented for natural and synthetic commercial silica with different OH contents. Synthetic materials with OH content >200 ppm by weight show one line shape for all investigated doses. In contrast, the other materials show a different line shape at low irradiation doses. Differences are also observed in the concentration growth of the centers in synthetic wet materials and in the other materials. The results are interpreted as evidence of two centers distinguishable by their line shape and having different precursors.

Highly Homogeneous Biotinylated Carbon Nanodots: Red-Emitting Nanoheaters as Theranostic Agents toward Precision Cancer Medicine

Very recent red-emissive carbon nanodots (CDs) have shown potential as near-infrared converting tools to produce local heat useful in cancer theranostics. Besides, CDs seem very appealing for clinical applications combining hyperthermia, imaging, and drug delivery in a single platform capable of selectively targeting cancer cells. However, CDs still suffer from dramatic dot-to-dot variability issues such that a rational design of their structural, optical, and chemical characteristics for medical applications has been impossible so far. Herein, we report for the first time a simple and highly controllable layer-by-layer synthesis of biotin-decorated CDs with monodisperse size distribution, …

Status of the EPIC thin and medium filters on-board XMM-Newton after more than 10 years of operation I: laboratory measurements on back-up filters

After more than ten years of operation of the EPIC camera on board the X-ray observatory XMM-Newton, we have reviewed the status of its Thin and Medium filters by performing both laboratory measurements on back-up filters, and analysis of data collected in-flight. 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, X-ray transmission, RAMAN IR spectroscopy, X-Ray Photoelectron Spectroscopy, and Atomic Force Microscopy. We report the results of the measurements conducted up to now, and point out some lessons lear…

Streptomyces coelicolor extracellular vesicles

This study may reveal the importance of extracellular vesicles in the physiology of S. coelicolor and may also have important biotechnological implications.

Pressure-Dependent Tuning of Photoluminescence and Size Distribution of Carbon Nanodots for Theranostic Anticancer Applications

Carbon nanodots (CDs) have recently attracted attention in the field of nanomedicine because of the biocompatibility, cost-effective nature, high specific surface, good near infrared (NIR) photothermal conversion into heat and tunable fluorescence properties, which have paved the way toward incorporating use of CDs into innovative anticancer theranostic platforms. However, a reliable synthesis of CDs with established and controlled physiochemical proprieties is precluded owing to the lack of full manipulation of thermodynamic parameters during the synthesis, thus limiting their use in real world medical applications. Herein, we developed a robust solvothermal protocol which allow fine contr…

Synthesis of luminescent glass monoliths embedding water-soluble Carbon dots

Carbon dots (CD) are an emerging class of nanomaterials, currently motivating an intense scientific interest because of their bright and characteristically tunable fluorescence, and their possible applications such as sensors, lasers, imaging agents, white light emitting devices [1]. While most studies focused on CDs in liquid phase, a strong effort is being recently devoted to produce fluorescent solids embedding highly dispersed CDs. Many of these procedures are elaborate and require pre-functionalization of the dots [2]. Here we report a novel and very facile route to prepare glass monoliths containing CDs with no need of pre-functionalization of the dots. Our low-cost synthesis method p…

Properties of methyl radical trapped in amorphous SiO2 and in natural SiO2-clathrate Melanophlogite

Abstract We report an experimental investigation by electron paramagnetic resonance (EPR) on methyl radical (CH3 ) observed in γ-ray irradiated high-purity amorphous silicon dioxide (a-SiO2) and in a polycrystalline sample of Melanophlogite, a rare natural form of SiO2-clathrate. From the analysis of the EPR spectra we estimate the correlation time of the hindered rotational motion of CH3 molecules at T = 77 K in the two different materials. This physical quantity gives a quantitative measure of the freedom of motion of CH3 molecules trapped in the two solid systems, putting forward relevant information on the properties of the cavities/interstices in which the radicals are confined. In par…

Variability of the Si-O-Si angle in amorphous-SiO2 probed by electron paramagnetic resonance and Raman spectroscopy

We report an experimental investigation by electron paramagnetic resonance (EPR) and Raman spectroscopy on a variety of amorphous silicon dioxide materials. Our study by EPR have permitted us to point out that the splitting of the primary hyperfine doublet of the Eγ′ center shows a relevant sample-to-sample variability, changing from ∼41.8 to ∼42.6 mT in the set of materials we considered. The parallel study by Raman spectroscopy has enabled us to state that this variability is attributable to the different Si-O-Si angle characterizing the matrices of the different materials. © 2009 Elsevier B.V. All rights reserved.

Silica nanoparticle core structure examined by the E?Si? center 29Si strong hyperfine interaction

Abstract β-Ray irradiation up to 1.2 GGy was employed to induce E′Si γ defects and to study the structure of silica nanoparticles with diameters from 7 up to 20 nm. Defect concentration and their 29 Si strong hyperfine doublet were investigated through electron paramagnetic resonance measurements. Our data indicate that stable defects are located in the nanoparticle core. Furthermore, the E′Si γ hyperfine interaction evidences that the core structure is denser than bulk silica and independent from the particle size. Finally, we put in evidence that the core structure is stable and unaffected by the irradiation in the investigated dose range maintaining the specific features of nanoparticles.

The relevance of point defects in studying silica-based materials from bulk to nanosystems

The macroscopic properties of silica can be modified by the presence of local microscopic modifications at the scale of the basic molecular units (point defects). Such defects can be generated during the production of glass, devices, or by the environments where the latter have to operate, impacting on the devices’ performance. For these reasons, the identification of defects, their generation processes, and the knowledge of their electrical and optical features are relevant for microelectronics and optoelectronics. The aim of this manuscript is to report some examples of how defects can be generated, how they can impact device performance, and how a defect species or a physical phenomenon …

Hyperfine structure of the E'delta centre in amorphous silicon dioxide

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 processe…