A. Benedetti’s research while affiliated with Ca' Foscari University of Venice and other places

In recent years, Cr ³⁺ -activated phosphors have been attracting a lot of interest due to their unique optical features exploited for applications ranging from lasers to optical thermometry, near-infrared (NIR) emitting...

Herein we report new chiral luminescent Cs3Cu2Br5 needle-like microcrystals and the analysis of their optical properties and the effect of the ligand structure on the tranfer of chirality.

Piezoelectric materials are a class of compounds that is gaining increasing interest in various applications such as energy harvesting. During the last decade, lead-free ZnSnO3 perovskite ceramic has gained attention among the scientific community thanks to its unique symmetry-dependent and spontaneous polarization properties such as piezoelectricity and ferroelectricity. Nevertheless, only a few studies successfully prepared pure ZnSnO3, while most seem to mislead the product for its hydroxide precursor (ZnSn(OH)6) or a mixture of Zn2SnO4 and SnO2. In our work, we investigated the conversion of ZnSn(OH)6 at different temperatures (500, 600, 700, 750 and 800 °C) by X-ray powder diffraction analysis, and in-situ using synchrotron radiation up to 950 °C under ambient atmosphere and in a vacuum, to reproduce conventional reaction conditions. SEM and TEM have been used to understand the evolution of the particle shape and surface structure before and after the thermal treatments. Our results show the instability of the ZnSn(OH)6 phase, which converts into an amorphous structure at low temperature. Above 750 °C, the material segregates into Zn2SnO4 and SnO2, supporting the hypothesis that the thermal treatment of the hydroxide phase under typical conditions results in the formation of an oxide mixture rather than the phase pure ZnSnO3.

The design and development of effective luminescent thermal sensors have been driving technological progress in many different fields ranging from catalysis to biology and microelectronics, to name a few. The ratiometric concept of using the ratio between two luminescent emissions of lanthanide-doped phosphors allows overcoming some limitations resulting from the single emission-based thermometers. A fundamental requirement for the development of effective luminescent thermometers relies on efficient luminescence output, which is not always accessible. Therefore, alternative methods to probe the temperature in a reliable and simple way are still a challenge. Despite the conventional limits of using narrow band gap materials as hosts for lanthanoid ions, a smart design allows for the development of unusual phosphors with appealing properties. By taking advantage of the narrow band gap of Bi2O3 polymorphs, here we demonstrate the potential of the tetragonal Y-stabilized β-Bi2O3:Y³⁺,Nd³⁺ system as a multimodal thermometer combining the conventional Boltzmann thermometry based on Nd³⁺ together with the thermochromism of the host. With the aim of testing this new concept, the temperature dependence of the reflectance spectra was investigated. Moreover, from the application point of view, the chromaticity variations of the material described by means of simple thermometric parameters such as the ratio a*/b* and the hue angle hab are demonstrated to be particularly promising and already implemented in software commonly used worldwide. The results suggest the potential of the strategy of combining narrow band gap semiconductors with lanthanoid ions to design reliable and multimodal thermal sensors, paving the way to a new family of thermochromic and luminescent thermal sensors.

Chiral semiconductor quantum dots have recently received broad attention due to their promising application in several fields such as sensing and photonics. The extensive work in the last few years was focused on the observation of the chiroptical properties in binary Cd based systems. Herein, we report on the first evidence of ligand-induced chirality in silver indium sulfide semiconductor quantum dots. Ternary disulfide quantum dots are of great interest due to their remarkable optical properties and low toxicity. Non-stoichiometric silver indium sulfide quantum dots were produced via a room temperature coprecipitation in water, in the presence of cysteine as a capping agent. The obtained nanocrystals show a notable photoluminescence quantum yield of 0.24 in water dispersions. Several critical aspects of the nanocrystal growth and chemico-physical characterization, and the optimisation of the surface passivation by the chiral ligand in order to optimize the nanoparticle chirality are thoroughly investigated. Optical spectroscopy methods such as circular dichroism and luminescence as well as nuclear magnetic resonance techniques are exploited to analyze the coordination processes leading to the formation of the ligand-nanocrystal chiral interface. This study highlights the dynamic nature of the interaction between the nanocrystal surface and the chiral ligand and clarifies some fundamental aspects for the transfer and optimization of the chiroptical properties.

Cellulases are enzymes with great potential for converting biomass to biofuels for sustainable energy. However, their commercial use is limited by their costs and low reusability. Therefore, the scientific and industrial sectors are focusing on finding better strategies to reuse enzymes and improve their performance. In this work, cellulase from Aspergillus niger was immobilised through in situ entrapment and adsorption on bio-inspired silica (BIS) supports. To the best of our knowledge, this green effect strategy has never been applied for cellulase into BIS. In situ entrapment was performed during support synthesis, applying a one-pot approach at mild conditions (room temperature, pH 7, and water solvent), while adsorption was performed after support formation. The loading efficiency was investigated on different immobilisation systems by Bradford assay and FTIR. Bovine serum albumin (BSA) was chosen as a control to optimize cellulase loading. The residual activity of cellulase was analysed by the dinitro salicylic acid (DNS) method. Activity of 90% was observed for the entrapped enzyme, while activity of ~55% was observed for the adsorbed enzyme. Moreover, the supported enzyme systems were recycled five times to evaluate their reuse potential. The thermal and pH stability tests suggested that both entrapment and adsorption strategies can increase enzyme activity. The results highlight that the entrapment in BIS is a potentially useful strategy to easily immobilise enzymes, while preserving their stability and recycle potential.

A new instrumental neutron activation analysis (INAA) for the simultaneous determination of titanium (TiO2) and silica (SiO2) dioxide as UV-filters in sunscreens is described. Samples are encapsulated, neutron irradiated (30 s) and after a suitable decay (3 min), the induced ⁵¹Ti (T1/2 = 5.76 min) and ²⁹Al (T1/2 = 6.56 min) radionuclides are measured for the emitted γ-ray fingerprint. Three applications were carried out: (i) screening study (analysis of commercial sunscreens in combination with single particle inductively coupled plasma mass spectrometry (sp-ICP-MS); (ii) research study (development of innovative UV-filters such as titanium dioxide or bismuth titanate loaded inorganic mesoporous silica nanoparticles, MSN); (iii) validation study (intercalibration of a spectrochemical method (inductively coupled plasma optical emission spectrometry, ICP-OES). Collectively, the nuclear method appears a powerful tool adequate for quantifying TiO2 and SiO2 in the above studies. The limited accessibility at the nuclear reactor for neutron activation is probably one of the reasons why the excellent characteristics of the nuclear technique are not always fully known and exploited in the industrial and research chemical world.

The use of readily prepared bisphosphonic acids obtained in few steps through a thio‐Michael addition of commercially available thiols on tetraethyl vinylidenebisphosphonate enables the straightforward surface modification of amorphous mesoporous zirconia nanoparticles. Simple stirring of the zirconia nanoparticles in a buffered aqueous solution of the proper bisphosphonic acid leads to the surface functionalization of the nanoparticles with different kinds of functional groups, charge and hydrophobic properties. Formation of both chemisorbed and physisorbed layers of the bisphosphonic acid take place, observing after extensive washing a grafting density of 1.1 molecules/nm² with negligible release in neutral or acidic pH conditions, demonstrating stronger loading compared to monophosphonate derivatives. The modified nanoparticles were characterized by IR, XPS, ζ‐potential analysis to investigate the loading of the bisphosphonic acid, FE‐SEM to investigate the size and morphologies of the nanoparticles and ³¹P and ¹H MAS NMR to investigate the coordination motif of the phosphonate units on the surface. All these analytical techniques demonstrated the strong affinity of the bisphosphonic moiety for the Zr(IV) metal centers. The functionalization with bisphosphonic acids represents a straightforward covalent approach for tailoring the superficial properties of zirconia nanoparticles, much straightforward compared the classic use of trisalkoxysilane or trichlorosilane reagents typically employed for the functionalization of silica and metal oxide nanoparticles. Extension of the use of bisphosphonates to other metal oxide nanoparticles is advisable.