Andrea Lapini
Verified @unipr.it
Department of Chemistry, Life Science and Environmental Sustainability
Andrea Lapini received the master degree in Chemistry in 2005 from the University of Florence (110/110) and the PhD In Chemical Science from the Science Doctorate School of the University of Florence and the European Laboratory for Non-Linear Spectroscopy (LENS). During the PhD he developed a pronounced interest towards the usage of Coherent Ultrafast Spectroscopy to disentangle electronic and structural properties of simple and complex molecular systems. He spent the years between 2009 and 2017 as a pots-doctoral fellow @ LENS developing most of instrumentation nowadays employed to performed 2DIR and 2D-Visible spectroscopy. In 2018 Andrea got a permanent position as a researcher in the National Institute of Metrological Research (INRIM) in Turin, within the Advanced Material and Life Science division. In 2021 Andrea got a position as a Tenure-track Assistant Professor in Physical Chemistry at the Department of Chemistry, Life Science and Environmental Sustainability in Parma.
EDUCATION
Andrea Lapini received the master degree in Chemistry in 2005 from the University of Florence (110/110) and the PhD In Chemical Science from the Science Doctorate School of the University of Florence and the European Laboratory for Non-Linear Spectroscopy (LENS).
RESEARCH INTERESTS
Ultrafast Spectroscopy, Non Linear Microscopy, Non Linear Optics, regenerative medicine.
Scopus Publications
Scholar Citations
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Scopus Publications
Nerea Gonzalez‐Pato, Davide Blasi, Domna M. Nikolaidou, Francesco Bertocchi, Jesús Cerdá, Francesca Terenziani, Nora Ventosa, Juan Aragó, Andrea Lapini, Jaume Veciana,et al.
Wiley
AbstractNanothermometers are emerging probes as biomedical diagnostic tools. Especially appealing are nanoprobes using NIR light in the range of biological transparency window (BTW) since they have the advantages of a deeper penetration into biological tissues, better contrast, reduced phototoxicity and photobleaching. This article reports the preparation and characterization of organic nanoparticles (ONPs) doped with two polychlorinated trityl radicals (TTM and PTM), as well as studies of their electronic and optical properties. Such ONPs having inside isolated radical molecules and dimeric excimers, can be two‐photon excited showing optimal properties for temperature sensing. Remarkably, in TTM‐based ONPs the emission intensity of the isolated radical species is unaltered increasing temperature, while the excimer emission intensity decreases strongly being thereby able to monitor temperature changes with an excellent thermal absolute sensitivity of 0.6–3.7% K−1 in the temperature range of 278–328 K. The temperature dependence of the excimeric bands of ONPs are theoretically simulated by using electronic structure calculations and a vibronic Hamiltonian model. Finally, TTM‐doped ONPs as ratiometric NIR‐nanothermometers are tested with two‐photon excitationwith enucleated pig eye sclera, as a real tissue model, obtaining a similar temperature sensitivity as in aqueous suspensions, demonstrating their potential as NIR nanothermometers for bio applications.
Francesco Bertocchi, Danilo Marchetti, Sandra Doria, Mariangela di Donato, Cristina Sissa, Mauro Gemmi, Enrico Dalcanale, Roberta Pinalli, and Andrea Lapini
Wiley
AbstractThe current work focuses on the investigation of two functionalized naphthyridine derivatives, namely ODIN‐EtPh and ODIN‐But, to gain insights into the hydrogen bond‐assisted H‐aggregate formation and its impact on the optical properties of ODIN molecules. By employing a combination of X‐ray and electron crystallography, absorption and emission spectroscopy, time resolved fluorescence and ultrafast pump‐probe spectroscopy (visible and infrared) we unravel the correlation between the structure and light‐matter response, with a particular emphasis on the influence of the polarity of the surrounding environment. Our experimental results and simulations confirm that in polar and good hydrogen‐bond acceptor solvents (DMSO), the formation of dimers for ODIN derivatives is strongly inhibited. The presence of a phenyl group linked to the ureidic unit favors the folding of ODIN derivatives (forming an intramolecular hydrogen bond) leading to the stabilization of a charge‐transfer excited state which almost completely quenches its fluorescence emission. In solvents with a poor aptitude for forming hydrogen bonds, the formation of dimers is favored and gives rise to H aggregates, with a consequent considerable reduction in the fluorescence emission. The urea‐bound phenyl group furtherly stabilizes the dimers in chloroform.
Sara Catalini, Francesco Bagni, Stefano Cicchi, Mariangela Di Donato, Alessandro Iagatti, Andrea Lapini, Paolo Foggi, Caterina Petrillo, Alessandro Di Michele, Marco Paolantoni,et al.
Royal Society of Chemistry (RSC)
Self-aggregation of Boc-protected diphenylalanine towards the formation of architectures with morphology and structure highly dependent on the acetonitrile-water percentage.
Brunella Bardi, Davide Giavazzi, Elena Ferrari, Alessandro Iagatti, Mariangela Di Donato, D. K. Andrea Phan Huu, Francesco Di Maiolo, Cristina Sissa, Matteo Masino, Andrea Lapini,et al.
Royal Society of Chemistry (RSC)
The static and dynamic dielectric properties of amorphous matrices of interest for use in OLEDs are addressed via a careful experimental and theoretical analysis of Raman and time-resolved emission spectra of simple dyes dispersed in the matrix of interest.
Sara Venturi, Barbara Rossi, Mariagrazia Tortora, Renato Torre, Andrea Lapini, Paolo Foggi, Marco Paolantoni, and Sara Catalini
Elsevier BV
K. Swathi, Meleppatt Sujith, P. S. Divya, Merin Varghese P, Andrea Delledonne, D. K. Andrea Phan Huu, Francesco Di Maiolo, Francesca Terenziani, Andrea Lapini, Anna Painelli,et al.
Royal Society of Chemistry (RSC)
Highly symmetric multibranched phenyleneethynylenes exhibit intense fluorescence despite the presence of low-lying dark states. The inversion of the energy order of excited states is explained in terms of a novel phenomenon dubbed “symmetry swapping”.
Mattia Spedicati, Gerardina Ruocco, Alice Zoso, Leonardo Mortati, Andrea Lapini, Andrea Delledonne, Carla Divieto, Veronica Romano, Clotilde Castaldo, Franca Di Meglio,et al.
Frontiers Media SA
In vitro models of pathological cardiac tissue have attracted interest as predictive platforms for preclinical validation of therapies. However, models reproducing specific pathological features, such as cardiac fibrosis size (i.e., thickness and width) and stage of development are missing. This research was aimed at engineering 2D and 3D models of early-stage post-infarct fibrotic tissue (i.e., characterized by non-aligned tissue organization) on bioartificial scaffolds with biomimetic composition, design, and surface stiffness. 2D scaffolds with random nanofibrous structure and 3D scaffolds with 150 µm square-meshed architecture were fabricated from polycaprolactone, surface-grafted with gelatin by mussel-inspired approach and coated with cardiac extracellular matrix (ECM) by 3 weeks culture of human cardiac fibroblasts. Scaffold physicochemical properties were thoroughly investigated. AFM analysis of scaffolds in wet state, before cell culture, confirmed their close surface stiffness to human cardiac fibrotic tissue. Following 3 weeks culture, biomimetic biophysical and biochemical scaffold properties triggered the activation of myofibroblast phenotype. Upon decellularization, immunostaining, SEM and two-photon excitation fluorescence microscopy showed homogeneous decoration of both 2D and 3D scaffolds with cardiac ECM. The versatility of the approach was demonstrated by culturing ventricular or atrial cardiac fibroblasts on scaffolds, thus suggesting the possibility to use the same scaffold platforms to model both ventricular and atrial cardiac fibrosis. In the future, herein developed in vitro models of cardiac fibrotic tissue, reproducing specific pathological features, will be exploited for a fine preclinical tuning of therapies.
Jasper Deckers, Tom Cardeynaels, Sandra Doria, Nikolay Tumanov, Andrea Lapini, Anitha Ethirajan, Marcel Ameloot, Johan Wouters, Mariangela Di Donato, Benoît Champagne,et al.
Royal Society of Chemistry (RSC)
Rational, computationally guided, molecular design affords push–pull BODIPY photosensitizers with balanced brightness and phototoxicity for image-guided photodynamic therapy.
Alberto Mezzetti, Josefine Schnee, Andrea Lapini, and Mariangela Di Donato
Springer Science and Business Media LLC
Alberto Mezzetti, Josefine Schnee, Andrea Lapini, and Mariangela Di Donato
Springer Science and Business Media LLC
Time-resolved infrared (IR) spectroscopy is a widely used technique in the investigation of photoinduced reactions, given its capabilities of providing structural information about the presence of intermediates and the reaction mechanism. Despite the fact that it is used in several fields since the '80s, the communication between the different scientific communities (photochemists, photobiologists, etc.) has been to date quite limited. In some cases, this lack of communication happened-and still happens-even inside the same scientific community (for instance between specialists in ultrafast ps/fs IR and those in "fast" ns/µs/ms IR). Even more surprising is the difficulty of non-specialists to understand the potential of time-resolved IR spectroscopy, despite the fact that IR spectroscopy is normally taught to all chemistry and material science students, and to several biology and physics students. This tutorial review aims at helping to solve these issues, first by providing a comprehensive but reader-friendly overview of the different techniques, and second, by focusing on five "case studies" (from photobiology, gas-phase photocatalysis, photochemistry, semiconductors and metal-carbonyl complexes). We are confident that this approach can help the reader-whichever is its background-to understand the capabilities of time-resolved IR spectroscopy to study the mechanism of photoinduced reactions.
Sandra Doria, Mariangela Di Donato, Raffaele Borrelli, Maxim F. Gelin, Justin Caram, Marco Pagliai, Paolo Foggi, and Andrea Lapini
Royal Society of Chemistry (RSC)
Self-assembled ordered structures, such as H- or J-type molecular aggregates of organic chromophores, are extremely appealing materials for optoelectronic applications.
Chiara Calvagna, Andrea Lapini, Andrea Taschin, Samuele Fanetti, Marco Pagliai, Paolo Bartolini, Roberto Bini, Roberto Righini, and Renato Torre
Elsevier BV
Abstract The presence of ions induces perturbations in the water network, these structural and dynamic modifications can extent over space scales overcoming the local solvation shell: aqueous solutions of sodium perchlorate (NaClO4) are characterized by extended phenomena of structure breaking of the solvent network. The aim of the present work is the experimental investigation of the interplay between the local structural modifications induced by the perchlorate ions and the collective dynamical properties of the solvent. Ultrafast Optical Kerr Effect (OKE) and time resolved infrared absorption are the experimental techniques adopted: OKE is mostly sensitive to the collective properties of the sample, while transient IR provides access to local properties of the solvent. Classical Molecular Dynamics (MD) simulations support the analysis of the experimental results. All experiments and simulations are performed at room temperature, varying the concentrations (0-6 M) and varying the applied pressure (10-4 – 1.3 GPa). Experiments and computer simulations confirm that pressure and concentration have convergent effects on the water dynamics, due to the analogous modification of the short-range liquid structure that cancel some dynamical anomalies typical of pure water. Both local and collective dynamic observables point to structural properties as responsible for their peculiar pressure and concentration dependence.
Elena Ragnoni, Sara Catalini, Maurizio Becucci, Andrea Lapini, and Paolo Foggi
MDPI AG
In this work we report the linear and non-linear IR spectral response characterization of the CO bonds of PenicillinG sodium salt in D2O and in DMSO−d6 solutions. In order to better characterize the spectral IR features in the CO stretching region, broadband middle infrared pump-probe spectra are recorded. The role of hydrogen bonds in determining the inhomogeneous broadening and in tuning anharmonicity of the different types of oscillators is exploited. Narrow band pump experiments, at the three central frequencies of β−lactam, amide and carboxylate CO stretching modes, identify the couplings between the different types of CO oscillators opening the possibility to gather structural dynamic information. Our results show that the strongest coupling is between the β−lactam and the carboxylate CO vibrational modes.
Carla Divieto, Gabriele Barrera, Federica Celegato, Giancarlo D'Agostino, Marco Di Luzio, Marco Coïsson, Andrea Lapini, Leonardo Mortati, Massimo Zucco, Stefano Pavarelli,et al.
Frontiers Media SA
Effective interaction and accumulation of nanoparticles (NPs) within tumor cells is crucial for NP-assisted diagnostic and therapeutic biomedical applications. In this context, the shape and size features of NPs can severely influence the strength of adhesion between NPs and cell and the NP internalization mechanisms. This study proved the ability of the PT45 and A549 tumor cells to uptake and retain magnetic Au-coated Ni80Fe20 nanodisks (NDs) prepared by means of a bottom–up self-assembling nanolithography technique assisted by polystyrene nanospheres. The chosen geometrical parameters, i.e., diameter (≈650 nm) and thickness (≈30 nm), give rise to magnetic domain patterns arranged in vortex state at the magnetic remanence. PT45 and A549 cell lines were cultured in the presence of different concentrations of Au-coated Ni80Fe20 nanodisks, and their biocompatibility was evaluated by viability and proliferation tests. Electron microscopy techniques and a combined CARS (Coherent Anti-stokes Raman Scattering) and TPL (two-photon photoluminescence) microscopy allow localizing and distinguishing the NDs within or attached to the tumor cells, without any labeling. A quantitative measurement of ND amount retained within tumor cells as a function of ND concentrations was performed by the Instrumental Neutron Activation Analysis (INAA) characterization technique.
F. D’Amato, S. Viciani, A. Montori, A. Lapini, I. Fraboulet, and J. Poulleau
Elsevier BV
Abstract The quantitative detection of pollutants in industrial emissions, in particular the emissions of biomass burners, requires different types of analyzers. Optical devices are usually sensitive to the transparency and dirtiness of the exhaust gases, so optical measurements are normally carried out by extracting the samples from the stacks. This paper has a twofold aim. First, we will prove that the molecular composition of the exhaust mixture (in particular the concentration of water and carbon dioxide) can deeply affect the outcome of optical analyzers, depending on the adopted detection technique. This is a critical issue, in particular with a view to the necessity of providing suitable reference methods for monitoring biomass burners emissions. Second, we will show how it is possible to measure inside an artificial stack by using an optical multipass cell located across the gas flow, even at 140 °C, or in presence of soot.
Andrea Taschin, Paolo Bartolini, Samuele Fanetti, Andrea Lapini, Margherita Citroni, Roberto Righini, Roberto Bini, and Renato Torre
American Chemical Society (ACS)
Despite being water the most common and most widely studied substance in the world, it still presents unknown aspects. In particular, water shows several thermodynamic and dynamical anomalies in the liquid and supercooled metastable phases, whose nature is still hotly debated. Here we report measurements by Optical Kerr Effect on water as a function of pressure along two isotherms, at 273 K from 0.1 to 750 MPa and at 297 K from 0.1 MPa to 1350 MPa, reaching the supercooled metastable phase. The structural relaxation and the low frequency vibrational dynamics of water show a peculiar pressure dependence, similar to that of other dynamical properties. The data analysis suggests the presence in the water phase-diagram of a crossover area that divides two regions characterized by different dynamic regimes, which appear to be related to two liquid forms, one dominated by the high density water and the other by the low density water.
Amedeo Capobianco, Mariangela Di Donato, Tonino Caruso, Roberto Centore, Andrea Lapini, Carla Manfredi, Amalia Velardo, Sabato Volino, and Andrea Peluso
Elsevier BV
Abstract It is shown that 4-methyl-7-(4-hydroxyphenyl)-[1,2,4]-triazolo[3,2-c][1,2,4]triazole exhibits a rich photoinduced protolytic behavior: Forster cycle shows that the protonated nitrogen of the triazolo-triazole ring is a weak photoacid, with Δ pKa ≈ − 3 ; furthermore, at moderately basic pH its deprotonated monoanion exhibits a long distance water mediated phototautomerism, in which the hydroxyl group releases a proton to solvent and a basic nitrogen of the triazolo-triazole fused ring, different from that protonated in the neutral species, is protonated by the solvent.
Samuele Fanetti, Naomi Falsini, Paolo Bartolini, Margherita Citroni, Andrea Lapini, Andrea Taschin, and Roberto Bini
American Chemical Society (ACS)
Homogeneous melting of crystals is a complex multistep process involving the formation of transient states at temperatures considerably higher than the melting point. The nature and persistence of these metastable structures are intimately connected to the melting process and a precise definition of the temporal boundaries of these phenomena is not yet available. We set up a specifically designed experiment to probe by transient infrared absorption spectroscopy the entire dynamics, ranging from tens of picoseconds to microseconds, of superheating and melting of an ice crystal. In spite of a large excess of energy provided, only about 30% of the micrometric crystal liquefies in the first 20-25 ns because of the long persistence of the superheated metastable phase that extends for more than 100 ns. This behavior is ascribed to the population of low energy states that trap a large amount of energy favoring the formation of a metastable, likely plastic, ice phase.
Simona la Gatta, Francesco Milano, Gianluca M. Farinola, Angela Agostiano, Mariangela Di Donato, Andrea Lapini, Paolo Foggi, Massimo Trotta, and Roberta Ragni
Elsevier BV
The photosynthetic Reaction Center (RC) from the purple bacterium Rhodobacter sphaeroides has unique photoconversion capabilities, that can be exploited in assembly biohybrid devices for applications in solar energy conversion. Extending the absorption cross section of isolated RC through covalent functionalization with ad-hoc synthesized artificial antennas is a successful strategy to outperform the efficiency of the pristine photoenzyme under visible light excitation. Here we report a new heptamethine cyanine antenna that, upon covalent binding to RC, forms a biohybrid (hCyN7-RC) which, under white light excitation, has doubled photoconversion efficiency versus the bare photoenzyme. The artificial antenna hCyN7 successfully meets appropriate optical properties, i.e. peak position of absorption and emission maximum in the visible and NIR region respectively, large Stokes shift, and high fluorescence quantum yield, required for improving the efficiency of the biohybrid in the production of the charge-separated state in the RC. The kinetics of energy transfer and charge separation of hCyN7-RC studied via ultrafast visible and IR spectroscopies are here presented. The antenna transfers energy to RC chromophores within <10 ps and the rate of QA reduction is doubled compared to the native RC. These experiments further demonstrate hCyN7-RC, besides being an extremely efficient white light photoconverter, fully retains the charge separation mechanism and integrity of the native RC photoenzyme, thus allowing to envisage its suitability as biohybrid material in bioinspired systems for solar energy conversion.
Beatrice Gironi, Andrea Lapini, Elena Ragnoni, Chiara Calvagna, Marco Paolantoni, Assunta Morresi, and Paola Sassi
Royal Society of Chemistry (RSC)
The free volume distribution and the picosecond dynamics inside a model lipid membrane are explored in a wide temperature range and at different solvating conditions.
Andrea Lapini, Samuele Fanetti, Margherita Citroni, Roberto Bini, Charles-Olivier Gilbert, Simon Rondeau-Gagné, and Jean-Francois Morin
American Chemical Society (ACS)
Self-assembly of organic macrocycles has been exploited as a preliminary step in the synthesis of soluble and tailorable carbon-based nanostructures. Functionalized nanotubes have been prepared using, as core building blocks, nearly planar ring structures containing several alkyne units, exploiting the geometry achieved in the spontaneous preassembling step driven by π interaction. Covalent cross-linking between these units was achieved by thermal or photochemical activation with UV light. Here, we apply a moderate pressure in a sapphire anvil cell (1.0 GPa) to facilitate the preassembling and induce the cross-linking under pressure either with visible light, absorbed by two-photon absorption, or thermally. We observe a high yield of enhanced quality cross-linked nanotubes in a sample, showing, at ambient pressure, only side-chain decomposition. These results show that moderate pressures, easily achievable in large volume cells, are able to selectively favor topochemical reactions in such complex organic ...
Michael M. Lerch, Mariangela Di Donato, Adèle D. Laurent, Miroslav Medved', Alessandro Iagatti, Laura Bussotti, Andrea Lapini, Wybren Jan Buma, Paolo Foggi, Wiktor Szymański,et al.
Wiley
Abstract Donor–acceptor Stenhouse adducts (DASAs) are negative photochromes that switch with visible light and are highly promising for applications ranging from smart materials to biological systems. However, the strong solvent dependence of the photoswitching kinetics limits their application. The nature of the photoswitching mechanism in different solvents is key for addressing the solvatochromism of DASAs, but as yet has remained elusive. Here, we employ spectroscopic analyses and TD‐DFT calculations to reveal changing solvatochromic shifts and energies of the species involved in DASA photoswitching. Time‐resolved visible pump‐probe spectroscopy suggests that the primary photochemical step remains the same, irrespective of the polarity and protic nature of the solvent. Disentangling the different factors determining the solvent‐dependence of DASA photoswitching, presented here, is crucial for the rational development of applications in a wide range of different media.
Michael M. Lerch, Miroslav Medved′, Andrea Lapini, Adèle D. Laurent, Alessandro Iagatti, Laura Bussotti, Wiktor Szymański, Wybren Jan Buma, Paolo Foggi, Mariangela Di Donato,et al.
American Chemical Society (ACS)
Donor-acceptor Stenhouse adducts (DASAs) are a rapidly emerging class of visible light-activatable negative photochromes. They are closely related to (mero)cyanine dyes with the sole difference being a hydroxy group in the polyene chain. The presence or absence of the hydroxy group has far-reaching consequences for the photochemistry of the compound: cyanine dyes are widely used as fluorescent probes, whereas DASAs hold great promise for visible light-triggered photoswitching. Here we analyze the photophysical properties of a DASA lacking the hydroxy group. Ultrafast time-resolved pump-probe spectroscopy in both the visible and IR region show the occurrence of E-Z photoisomerization on a 20 ps time scale, similar to the photochemical behavior of DASAs, but on a slower time scale. In contrast to the parent DASA compounds, where the initial photoisomerization is constrained to a single position (next to the hydroxy group), 1H NMR in situ-irradiation studies at 213 K reveal that for nonhydroxy DASAs E-Z photoisomerization can take place at two different bonds, yielding two distinct isomers. These observations are supported by TD-DFT calculations, showing that in the excited state the hydroxy group (pre)selects the neighboring C2-C3 bond for isomerization. The TD-DFT analysis also explains the larger solvatochromic shift observed for the parent DASAs as compared to the nonhydroxy analogue, in terms of the dipole moment changes evoked upon excitation. Furthermore, computations provide helpful insights into the photoswitching energetics, indicating that without the hydroxy group the 4π-electrocyclization step is energetically forbidden. Our results establish the central role of the hydroxy group for DASA photoswitching and suggest that its introduction allows for tailoring photoisomerization pathways, presumably both through (steric) fixation via a hydrogen bond with the adjacent carbonyl group of the acceptor moiety, as well as through electronic effects on the polyene backbone. These insights are essential for the rational design of novel, improved DASA photoswitches and for a better understanding of the properties of both DASAs and cyanine dyes.
Sandra Doria, Andrea Lapini, Mariangela Di Donato, Roberto Righini, Nicolò Azzaroli, Alessandro Iagatti, Justin R. Caram, Timothy S. Sinclair, Lorenzo Cupellini, Sandro Jurinovich,et al.
Royal Society of Chemistry (RSC)
We aim to get insight the aggregation effect on the exciton behavior in phthalocyanine systems with coherent spectroscopy.
Mariangela Di Donato, Michael M. Lerch, Andrea Lapini, Adèle D. Laurent, Alessandro Iagatti, Laura Bussotti, Svante P. Ihrig, Miroslav Medved’, Denis Jacquemin, Wiktor Szymański,et al.
American Chemical Society (ACS)
Donor–acceptor Stenhouse adducts (DASAs) are negative photochromes that hold great promise for a variety of applications. Key to optimizing their switching properties is a detailed understanding of the photoswitching mechanism, which, as yet, is absent. Here we characterize the actinic step of DASA-photoswitching and its key intermediate, which was studied using a combination of ultrafast visible and IR pump–probe spectroscopies and TD-DFT calculations. Comparison of the time-resolved IR spectra with DFT computations allowed to unambiguously identify the structure of the intermediate, confirming that light absorption induces a sequential reaction path in which a Z–E photoisomerization of C2–C3 is followed by a rotation around C3–C4 and a subsequent thermal cyclization step. First and second-generation DASAs share a common photoisomerization mechanism in chlorinated solvents with notable differences in kinetics and lifetimes of the excited states. The photogenerated intermediate of the second-generation DASA was photo-accumulated at low temperature and probed with time-resolved spectroscopy, demonstrating the photoreversibility of the isomerization process. Taken together, these results provide a detailed picture of the DASA isomerization pathway on a molecular level.
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In 2020 the project Visco3DCell (development of a non-Invasive methodology to characterize Viscoelastic properties of 3D cell cultures) proposed by Andrea has been financed by the Cassa di Risparmio di Torino private foundation.