Reversible Supramolecular Noncovalent Self-Assembly Determines the Optical Properties and the Formation of Melanin-like Nanoparticles

The role of noncovalent supramolecular self-assembly in the formation of melanin-like NP, as well as the nature of the electronic transition at the basis of their unique optical properties, is strongly debated. Here we demonstrate that, during the first stage of formation of synthetic melanin, polydopamine (PDA), a small fraction of the molecular precursor dopamine (DA) is oxidized to quinone (Q) and a simple supramolecular charge-transfer (CT) adduct is formed thanks to the electron donor and electron acceptor properties of DA and Q, respectively. This adduct, also detectable by HPLC-MS, presents the broad absorption band in the red-NIR region typical of melanin-like materials. Importantly, its disaggregation upon dilution can be easily detected since it leads to the disappearance of the CT band, indicating the reversibility of the process. Moreover, the stability constant K of the CT adduct could be obtained using a simple association model

Fluorescent Carbon Dots from Food Industry By-Products for Cell Imaging

Herein, following a circular economy approach, we present the synthesis of luminescent carbon dots via the thermal treatment of chestnut and peanut shells, which are abundant carbon-rich food industry by-products. As-synthesized carbon dots have excellent water dispersibility thanks to their negative surface groups, good luminescence, and photo-stability. The excitation-emission behaviour as well as the surface functionalization of these carbon dots can be tuned by changing the carbon source (chestnuts or peanuts) and the dispersing medium (water or ammonium hydroxide solution). Preliminary in vitro biological data proved that the samples are not cytotoxic to fibroblasts and can act as luminescent probes for cellular imaging. In addition, these carbon dots have a pH-dependent luminescence and may, therefore, serve as cellular pH sensors. This work paves the way towards the development of more sustainable carbon dot production for biomedical applications

Effect of the embedment of carbon doped nanocomposites in a real matrix on the enhanced photocatalytic activity

Solar light can be used by semiconductor nanocrystals as a free and largely available source of energy to transform air pollutants into non-volatile less harmful chemicals. The efficiency of this process can be enhanced by doping the semiconductor with carbon-based materials, such as graphene. Nevertheless, such an increased activity has been reported (i) for nanocomposite photocatalysts produced on the research laboratory scale, (ii) analyzing their performance as self-standing photocatalysts and not after incorporation into “real” matrixes (e.g. building materials) and (iii) typically using model target pollutants instead of “real” hazardous ones. Here we describe the large-scale preparation of two series of carbon based photocatalysts starting from commercial materials and we demonstrate their superior photocatalytic activity in degrading important air pollutants as nitrogen oxides, compared to undoped photocatalysts. The photocatalytic activity was evaluated by NOx abatement adopting the continuous flow procedure and the apparatus reported in the Italian standard UNI 11,247. Best performing materials were incorporated into two different inorganic matrixes (cement and lime). In both cases, the superior photocatalytic performances were maintained. An improvement up to 42±7% of the photocatalytic activity was measured in the case of a cement sample for a carbon-doped photocatalyst with respect to bare TiO2 . The materials were characterized by UV-Vis spectroscopy, high resolution powder X-ray diffraction (HR-PXRD), high-resolution scanning electron microscopy (HR-SEM) energy-dispersive X-ray spectroscopy (EDS) and micro-Raman

An explainable model of host genetic interactions linked to COVID-19 severity

We employed a multifaceted computational strategy to identify the genetic factors contributing to increased risk of severe COVID-19 infection from a Whole Exome Sequencing (WES) dataset of a cohort of 2000 Italian patients. We coupled a stratified k-fold screening, to rank variants more associated with severity, with the training of multiple supervised classifiers, to predict severity based on screened features. Feature importance analysis from tree-based models allowed us to identify 16 variants with the highest support which, together with age and gender covariates, were found to be most predictive of COVID-19 severity. When tested on a follow-up cohort, our ensemble of models predicted severity with high accuracy (ACC = 81.88%; AUCROC = 96%; MCC = 61.55%). Our model recapitulated a vast literature of emerging molecular mechanisms and genetic factors linked to COVID-19 response and extends previous landmark Genome-Wide Association Studies (GWAS). It revealed a network of interplaying genetic signatures converging on established immune system and inflammatory processes linked to viral infection response. It also identified additional processes cross-talking with immune pathways, such as GPCR signaling, which might offer additional opportunities for therapeutic intervention and patient stratification. Publicly available PheWAS datasets revealed that several variants were significantly associated with phenotypic traits such as "Respiratory or thoracic disease", supporting their link with COVID-19 severity outcome.A multifaceted computational strategy identifies 16 genetic variants contributing to increased risk of severe COVID-19 infection from a Whole Exome Sequencing dataset of a cohort of Italian patients

The polymorphism L412F in TLR3 inhibits autophagy and is a marker of severe COVID-19 in males

The polymorphism L412F in TLR3 has been associated with several infectious diseases. However, the mechanism underlying this association is still unexplored. Here, we show that the L412F polymorphism in TLR3 is a marker of severity in COVID-19. This association increases in the sub-cohort of males. Impaired macroautophagy/autophagy and reduced TNF/TNFα production was demonstrated in HEK293 cells transfected with TLR3L412F-encoding plasmid and stimulated with specific agonist poly(I:C). A statistically significant reduced survival at 28 days was shown in L412F COVID-19 patients treated with the autophagy-inhibitor hydroxychloroquine (p = 0.038). An increased frequency of autoimmune disorders such as co-morbidity was found in L412F COVID-19 males with specific class II HLA haplotypes prone to autoantigen presentation. Our analyses indicate that L412F polymorphism makes males at risk of severe COVID-19 and provides a rationale for reinterpreting clinical trials considering autophagy pathways. Abbreviations: AP: autophagosome; AUC: area under the curve; BafA1: bafilomycin A1; COVID-19: coronavirus disease-2019; HCQ: hydroxychloroquine; RAP: rapamycin; ROC: receiver operating characteristic; SARS-CoV-2: severe acute respiratory syndrome coronavirus 2; TLR: toll like receptor; TNF/TNF-α: tumor necrosis factor

INPATT (Inorganic Photochemical pATTerning): Precipitation of calcium carbonate induced by light in a perspective of micropatterning application

INPATT is a Proof of Concept ERC (Horizon Europe) project aimed at developing the photo-induced precipitation of calcium minerals. The main idea behind the project is that light-controlled precipitation can be achieved using molecules that release functional moieties (as carbonate or phosphate groups), which subsequently precipitate in the presence of calcium ions. The absorbance of these cleavable molecules can be tuned to the preferred wavelength and therefore, these processes can be adapted to non-invasive conditions, using aqueous solutions, bio-compatible matrices, and a non-harmful irradiation wavelength. This dataset contains characterization analysis of light induced calcium carbonate precipitates, obtained by two main techniques. The first approach, based on a previous publication (Menichetti et al, 2021, DOI:10.1002/chem.202102321), aimed to the photo-precipitation of calcium carbonate by means of Ketoprofen as photoactive molecule which was optimized to obtain a fluid paste. Secondly, calcium carbonate photo-precipitation was investigated in presence of a photocurable polymeric resin

Melanin for Photoprotection and Hair Coloration in the Emerging Era of Nanocosmetics

Nanotechnology is revolutionizing fields of high social and economic impact. such as human health preservation, energy conversion and storage, environmental decontamination, and art restoration. However, the possible global-scale application of nanomaterials is raising increasing concerns, mostly related to the possible toxicity of materials at the nanoscale. The possibility of using nanomaterials in cosmetics, and hence in products aimed to be applied directly to the human body, even just externally, is strongly debated. Preoccupation arises especially from the consideration that nanomaterials are mostly of synthetic origin, and hence are often seen as “artificial” and their effects as unpredictable. Melanin, in this framework, is a unique material since in nature it plays important roles that specific cosmetics are aimed to cover, such as photoprotection and hair and skin coloration. Moreover, melanin is mostly present in nature in the form of nanoparticles, as is clearly observable in the ink of some animals, like cuttlefish. Moreover, artificial melanin nanoparticles share the same high biocompatibility of the natural ones and the same unique chemical and photochemical properties. Melanin is hence a natural nanocosmetic agent, but its actual application in cosmetics is still under development, also because of regulatory issues. Here, we critically discuss the most recent examples of the application of natural and biomimetic melanin to cosmetics and highlight the requirements and future steps that would improve melanin-based cosmetics in the view of future applications in the everyday market

Procédé assisté par la lumière pour la dissolution de carbonates de calcium cristallisés présents dans des oeuvres du patrimoine culturel

The invention relates to a process for dissolving crystalized carbonates present in Cultural Heritage Artworks comprising a step of mixing a solution comprising a photoacid generator or a mixture of a photoacid generator and a sensitizer with the crystalized calcium carbonate present in a cultural heritage artwork and a step of irradiating with light of wavelengths at which the photoacid generator or the sensitizer absorbs said light. Therefore, the present invention is of interest in the areas of restoration of cultural heritage artworks.Peer reviewedConsejo Superior de Investigaciones Científicas, Università di BolognaA1 Solicitud de patente con informe sobre el estado de la técnic

Procédé assisté par la lumière permettant de dissoudre des carbonates de calcium cristallisés présents dans des œuvres d'art de patrimoine culturel

[EN] The invention relates to a process for dissolving crystalized carbonates present in Cultural Heritage Artworks comprising a step of mixing a solution comprising a photoacid generator or a mixture of a photoacid generator and a sensitizer with the crystalized calcium carbonate present in a cultural heritage artwork and a step of irradiating with light of wavelengths at which the photoacid generator or the sensitizer absorbs said light. Therefore, the present invention is of interest in the areas of restoration of cultural heritage artworks.[FR] L'invention se rapporte à un procédé permettant de dissoudre des carbonates cristallisés présents dans des œuvres d'art de patrimoine culturel comprenant une étape consistant à mélanger une solution comprenant un générateur de photoacide ou un mélange d'un générateur de photoacide et d'un sensibilisateur avec le carbonate de calcium cristallisé présent dans une œuvre d'art de patrimoine culturel et une étape consistant à exposer à de la lumière de longueurs d'onde auxquelles le générateur de photoacide ou le sensibilisateur absorbe ladite lumière. Par conséquent, la présente invention présente un intérêt dans des secteurs de restauration d'œuvres d'art de patrimoine culturel.Peer reviewedConsejo Superior de Investigaciones Científicas, Università di BolognaA1 Solicitud de patente con informe sobre el estado de la técnic

Polydopamine-Based Nanoprobes Application in Optical Biosensing

Polydopamine (PDA), the synthetic counterpart of melanin, is a widely investigated bio-inspired material for its chemical and photophysical properties, and in the last few years, bio-application of PDA and PDA-based materials have had a dramatic increase. In this review, we described PDA application in optical biosensing, exploring its multiple roles as a nanomaterial. In optical sensing, PDA can not only be used for its intrinsic fluorescent and photoacoustic properties as a probe: in some cases, a sample optical signal can be derived by melanin generation in situ or it can be enhanced in another material thanks to PDA modification. The various possibilities of PDA use coupled with its biocompatibility will indeed widen even more its application in optical bioimaging