In Vitro Antiviral Activity of Hyperbranched Poly-L-Lysine Modified by L-Arginine against Different SARS-CoV-2 Variants.

The emergence of SARS-CoV-2 variants requires close monitoring to prevent the reoccurrence of a new pandemic in the near future. The Omicron variant, in particular, is one of the fastest-spreading viruses, showing a high ability to infect people and evade neutralization by antibodies elicited upon infection or vaccination. Therefore, the search for broad-spectrum antivirals that can inhibit the infectious capacity of SARS-CoV-2 is still the focus of intense research. In the present work, hyperbranched poly-L-lysine nanopolymers, which have shown an excellent ability to block the original strain of SARS-CoV-2 infection, were modified with L-arginine. A thermal reaction at 240 °C catalyzed by boric acid yielded Lys-Arg hyperbranched nanopolymers. The ability of these nanopolymers to inhibit viral replication were assessed for the original, Delta, and Omicron strains of SARS-CoV-2 together with their cytotoxicity. A reliable indication of the safety profile and effectiveness of the various polymeric compositions in inhibiting or suppressing viral infection was obtained by the evaluation of the therapeutic index in an in vitro prevention model. The hyperbranched L-arginine-modified nanopolymers exhibited a twelve-fold greater therapeutic index when tested with the original strain. The nanopolymers could also effectively limit the replication of the Omicron strain in a cell culture.

Bidimensional SnSe2-Mesoporous Ordered Titania Heterostructures for Photocatalytically Activated Anti-Fingerprint Optically Transparent Layers.

The design of functional coatings for touchscreens and haptic interfaces is of paramount importance for smartphones, tablets, and computers. Among the functional properties, the ability to suppress or eliminate fingerprints from specific surfaces is one of the most critical. We produced photoactivated anti-fingerprint coatings by embedding 2D-SnSe2 nanoflakes in ordered mesoporous titania thin films. The SnSe2 nanostructures were produced by solvent-assisted sonication employing 1-Methyl-2-pyrrolidinone. The combination of SnSe2 and nanocrystalline anatase titania enables the formation of photoactivated heterostructures with an enhanced ability to remove fingerprints from their surface. These results were achieved through careful design of the heterostructure and controlled processing of the films by liquid phase deposition. The self-assembly process is unaffected by the addition of SnSe2, and the titania mesoporous films keep their three-dimensional pore organization. The coating layers show high optical transparency and a homogeneous distribution of SnSe2 within the matrix. An evaluation of photocatalytic activity was performed by observing the degradation of stearic acid and Rhodamine B layers deposited on the photoactive films as a function of radiation exposure time. FTIR and UV-Vis spectroscopies were used for the photodegradation tests. Additionally, infrared imaging was employed to assess the anti-fingerprinting property. The photodegradation process, following pseudo-first-order kinetics, shows a tremendous improvement over bare mesoporous titania films. Furthermore, exposure of the films to sunlight and UV light completely removes the fingerprints, opening the route to several self-cleaning applications.

Harnessing Molecular Fluorophores in the Carbon Dots Matrix: The Case of Safranin O.

The origin of fluorescence in carbon dots (C-dots) is still a puzzling phenomenon. The emission is, in most of the cases, due to molecular fluorophores formed in situ during the synthesis. The carbonization during C-dots processing does not allow, however, a fine control of the properties and makes finding the source of the fluorescence a challenging task. In this work, we present a strategy to embed a pre-formed fluorescent molecule, safranin O dye, into an amorphous carbonaceous dot obtained by citric acid carbonization. The dye is introduced in the melted solution of citric acid and after pyrolysis remains incorporated in a carbonaceous matrix to form red-emitting C-dots that are strongly resistant to photobleaching. Embedding dyes in amorphous C-dots represents an alternative method to optimize the emission in the whole visible spectrum.

Photobleaching and Recovery Kinetics of a Palette of Carbon Nanodots Probed by In Situ Optical Spectroscopy.

Carbon dots (CDs) are a family of fluorescent nanoparticles displaying a wide range of interesting properties, which make them attractive for potential applications in different fields like bioimaging, photocatalysis, and many others. However, despite many years of dedicated studies, wide variations exist in the literature concerning the reported photostability of CDs, and even the photoluminescence mechanism is still unclear. Furthermore, an increasing number of recent studies have highlighted the photobleaching (PB) of CDs under intense UV or visible light beams. PB phenomena need to be fully addressed to optimize practical uses of CDs and can also provide information on the fundamental mechanism underlying their fluorescence. Moreover, the lack of systematic studies comparing several types of CDs displaying different fluorescence properties represents another gap in the literature. In this study, we explored the optical properties of a full palette of CDs displaying a range from blue to red emissions, synthesized using different routes and varying precursors. We investigated the photostability of different CDs by observing in situ their time-resolved fluorescence degradation or optical absorption changes under equivalent experimental conditions and laser irradiation. The results about different PB kinetics clearly indicate that even CDs showing comparable emission properties may exhibit radically different resistances to PB, suggesting systematic connections between the resistance to PB, the characteristic spectral range of emission, and CD quantum yields. To exploit the PB dynamics as a powerful tool to investigate CD photophysics, we also carried out dedicated experiments in a partial illumination geometry, allowing us to analyze the recovery of the fluorescence due to diffusion. Based on the experimental results, we conclude that the nature of the CD fluorescence cannot be solely ascribable to small optically active molecules free diffusing in solution, contributing to shed light on one of the most debated issues in the photophysics of CDs.

Improving the Photocatalytic Activity of Mesoporous Titania Films through the Formation of WS2/TiO2 Nano-Heterostructures.

Heterostructures formed by anatase nanotitania and bidimensional semiconducting materials are expected to become the next-generation photocatalytic materials with an extended operating range and higher performances. The capability of fabricating optically transparent photocatalytic thin films is also a highly demanded technological issue, and increasing the performances of such devices would significantly impact several applications, from self-cleaning surfaces to photovoltaic systems. To improve the performances of such devices, WS2/TiO2 heterostructures obtained by incorporating two-dimensional transition metal dichalcogenides layers into titania mesoporous ordered thin films have been fabricated. The self-assembly process has been carefully controlled to avoid disruption of the order during film fabrication. WS2 nanosheets of different sizes have been exfoliated by sonication and incorporated in the mesoporous films via one-pot processing. The WS2 nanosheets result as well-dispersed within the titania anatase mesoporous film that retains a mesoporous ordered structure. An enhanced photocatalytic response due to an interparticle electron transfer effect has been observed. The structural characterization of the heterostructure has revealed a tight interplay between the matrix and nanosheets rather than a simple additive co-catalyst effect.

Highly Photostable Carbon Dots from Citric Acid for Bioimaging.

Bioimaging supported by nanoparticles requires low cost, highly emissive and photostable systems with low cytotoxicity. Carbon dots (C-dots) offer a possible solution, even if controlling their properties is not always straightforward, not to mention their potentially simple synthesis and the fact that they do not exhibit long-term photostability in general. In the present work, we synthesized two C-dots starting from citric acid and tris (hydroxymethyl)-aminomethane (tris) or arginine methyl ester dihydrochloride. Cellular uptake and bioimaging were tested in vitro using murine neuroblastoma and ovine fibroblast cells. The C-dots are highly biocompatible, and after 24 h of incubation with the cells, 100% viability was still observed. Furthermore, the C-dots synthesized using tris have an average dimension of 2 nm, a quantum yield of 37%, high photostability and a zeta potential (ζ) around -12 mV. These properties favor cellular uptake without damaging cells and allow for very effective bioimaging.

Comparative Evaluation of Graphene Nanostructures in GERS Platforms for Pesticide Detection.

Graphene-enhanced Raman scattering (GERS) produces enhancement of the Raman signal, which is based on chemical rather than electromagnetic mechanism such as in the surface-enhanced Raman scattering. Graphene oxide, amino- and guanidine-functionalized graphene oxide, exfoliated graphene, and commercial graphene nanoplatelets have been used to investigate the GERS response with the change of graphene properties. Different graphene nanostructures have been embedded into organic-inorganic microporous films to build a platform for the fast and sensitive detection of pesticides in water. The graphene nanostructures vary in the number of layers, lateral size, degree of oxidation, and surface functionalization. The GERS performances of the graphene nanostructures cast on silicon substrates and embedded in the nanocomposite films have been comparatively evaluated. After casting a few droplets of the pesticide aqueous solution on the graphene nanostructures, the Raman band enhancements of the analytes have been measured. In the nanocomposite films, the characteristic Raman bands originating from pesticides such as paraoxon, parathion, and glyphosate could be traced at concentrations below 10-7, 10-5, and 10-4 M, respectively. The results show that the surface functionalization reduces the GERS effect because it increases the ratio between the sp3 carbon and sp2 carbon. On the other hand, the comparison among different types of graphenes shows that the monolayers are more efficient than the few-layer nanostructures in enhancing the Raman signal.

Effective SARS-CoV-2 antiviral activity of hyperbranched polylysine nanopolymers.

The coronavirus pandemic (COVID-19) had spread rapidly since December 2019, when it was first identified in Wuhan, China. As of April 2021, more than 130 million cases have been confirmed, with more than 3 million deaths, making it one of the deadliest pandemics in history. Different approaches must be put in place to confront a new pandemic: community-based behaviours (i.e., isolation and social distancing), antiviral treatments, and vaccines. Although behaviour-based actions have produced significant benefits and several efficacious vaccines are now available, there is still an urgent need for treatment options. Remdesivir represents the first antiviral drug approved by the Food and Drug Administration for COVID-19 but has several limitations in terms of safety and treatment benefits. There is still a strong request for other effective, safe, and broad-spectrum antiviral systems in light of future emergent coronaviruses. Here, we describe a polymeric nanomaterial derived from L-lysine, with an antiviral activity against SARS-CoV-2 associated with a good safety profile in vitro. Nanoparticles of hyperbranched polylysine, synthesized by L-lysine's thermal polymerization catalyzed by boric acid, effectively inhibit the SARS-CoV-2 replication. The virucidal activity is associated with the charge and dimension of the nanomaterial, favouring the electrostatic interaction with the viral surface being only slightly larger than the virions' dimensions. Low-cost production and easiness of synthesis strongly support the further development of such innovative nanomaterials as a tool for potential treatments of COVID-19 and, in general, as broad-spectrum antivirals.

Real-time quantitative detection of styrene in atmosphere in presence of other volatile-organic compounds using a portable device.

Exposure to styrene is a major safety concern in the fibreglass processing industry. This compound is classified by the International Agency for Research on Cancer as a possible human carcinogen. Several types of analytical equipment exist for detecting volatile organic compounds (VOCs) in the atmosphere; however, most of them operate ex-situ or do not provide easy discrimination between different molecules. This work introduces an improved and portable method based on FTIR spectroscopy to analyse toxic gaseous substances in working sites down to a concentration of less than 4 ppm. Styrene and a combination of VOCs typically associated with it in industrial processes, such as acetone, ethanol, xylene and isopropanol, have been used to calibrate and test the methodology. The results demonstrate that the technique offers the possibility to discriminate between different gaseous compounds in the atmosphere with a high degree of confidence and obtain very accurate quantitative information on their concentration, down to the ppm level, even when different VOCs are present in a mixture.

Boron Nitride-Titania Mesoporous Film Heterostructures.

The fabrication of optically active heterostructures in the shape of mesostructured thin films is a highly challenging task. It requires an integrated process to allow in one-step incorporating the two-dimensional materials within the mesoporous ordered host without disrupting the pore organization. Hexagonal boron nitride (BN) nanosheets have been successfully introduced into titania mesoporous films using a template-assisted sol-gel synthesis and evaporation-induced self-assembly. Two types of BN sheets have been used, with and without defects, to investigate the role of defects in heterostructure properties. It has been found that the defects increase the ultraviolet radiation A (UVA) absorbance and enhance the photocatalytic response of the film. The BN sheets are optically transparent and do not exhibit any photocatalytic property but contribute to anatase crystallization via heterogeneous nucleation.

Polymerization-Driven Photoluminescence in Alkanolamine-Based C-Dots.

Carbonized polymer dots (CPDs), a peculiar type of carbon dots, show extremely high quantum yields, making them very attractive nanostructures for application in optics and biophotonics. The origin of the strong photoluminescence of CPDs resides in a complicated interplay of several radiative mechanisms. To understand the correlation between CPD processing and properties, the early stage formation of carbonized polymer dots has been studied. In the synthesis, citric acid monohydrate and 2-amino-2-(hydroxymethyl)propane-1,3-diol have been thermally degraded at 180 °C. The use of an oil bath instead of a more traditional hydrothermal reactor has allowed the CPD properties to be monitored at different reactions times. Transmission electron microscopy, time-resolved photoluminescence, nuclear magnetic resonance, infrared, and Raman spectroscopy have revealed the formation of polymeric species with amide and ester bonds. Quantum chemistry calculations have been employed to investigate the origin of CPD electronic transitions. At short reaction times, amorphous C-dots with 80 % quantum yield, have been obtained.

Silica-graphene porous nanocomposites for environmental remediation: A critical review.

With the increase of industrialization, there is an urgent need for developing technologies to detect and remove toxic pollutants from water bodies. The pollutants are often released to the environment due to the consumption of raw materials that are necessary for the production of technological goods (such as chemical and pharmaceutical compounds, metals, and alloys or foods). Amongst all the remediation techniques, adsorption is considered as one of the preferred techniques, due to its fast and efficient removal of contaminants. Novel materials, which are engineered for selective and responsive water remediation, have also recently revealed a strong potential in the detection of pollutants. Here, current trends of silica-graphene (SG) porous composites for the removal of oils, organic solvents, heavy metals, and dyes are reviewed in detail. Insights on the modifications of composites to enhance their sorption performance have been highlighted. In addition, the detection of pollutants using porous SG nanocomposites is also critically reviewed. Overall, SG composites reveal a strong potential as nanostructure materials with improved efficiency for environmental-based applications.

Classification of Unifloral Honeys from SARDINIA (Italy) by ATR-FTIR Spectroscopy and Random Forest.

Nowadays, the mislabeling of honey floral origin is a very common fraudulent practice. The scientific community is intensifying its efforts to provide the bodies responsible for controlling the authenticity of honey with fast and reliable analytical protocols. In this study, the classification of various monofloral honeys from Sardinia, Italy, was attempted by means of ATR-FTIR spectroscopy and random forest. Four different floral origins were considered: strawberry-tree (Arbutus Unedo L.), asphodel (Asphodelus microcarpus), thistle (Galactites tormentosa), and eucalyptus (Eucalyptus calmadulensis). Training a random forest on the infrared spectra allowed achieving an average accuracy of 87% in a cross-validation setting. The identification of the significant wavenumbers revealed the important role played by the region 1540-1175 cm-1 and, to a lesser extent, the region 1700-1600 cm-1. The contribution of the phenolic fraction was identified as the main responsible for this observation.

Reversible Aggregation of Molecular-Like Fluorophores Driven by Extreme pH in Carbon Dots.

The origin of carbon-dots (C-dots) fluorescence and its correlation with the dots structure still lack a comprehensive model. In particular, the core-shell model does not always fit with the experimental results, which, in some cases, suggest a molecular origin of the fluorescence. To gain a better insight, we have studied the response of molecular-like fluorophores contained in the C-dots at extreme pH conditions. Citric acid and urea have been employed to synthesize blue and green-emitting C-dots. They show a different emission as a function of the pH of the dispersing media. The photoluminescence has been attributed to molecular-like fluorophores: citrazinic acid and 4-hydroxy-1H-pyrrolo[3,4-c]-pyridine-1,3,6-(2H,5H)-trione. 3D and time-resolved photoluminescence, ultraviolet-visible (UV-vis) spectroscopy, and dynamic light scattering have been used to determine the aggregation state, quantum yield and emission properties of the C-dots. The dependence of the C-dots blue and green components on the chemical environment indicates that the origin of fluorescence is due to molecular-like fluorophores.

Anomalous Optical Properties of Citrazinic Acid under Extreme pH Conditions.

Citrazinic acid (CZA) is a weakly fluorescent molecular compound whose optical properties are dependent on aggregation states and chemical environment. This molecule and its derivatives have been recently identified as the source of the intense blue emission of carbon dots obtained from citric acid with a nitrogen source, such as ammonia or urea. Citrazinic acid has a strong tendency to aggregate and form tautomers whose optical properties are largely unexplored. At extreme acidic and basic pH values, we have observed an "anomalous" optical response of citrazinic acid, attributed to the formation of aggregates from the tautomers. We have characterized the molecule, both at pH = 1 and 14, using UV-vis, NMR, steady-state, and time-resolved fluorescence spectroscopy. At extremely low pH values, the protonation causes luminescence quenching and the appearance of new emissions. On the contrary, high pH values are responsible for deprotonation and splitting of the excitation spectra.

Integrating sol-gel and carbon dots chemistry for the fabrication of fluorescent hybrid organic-inorganic films.

Highly fluorescent blue and green-emitting carbon dots have been designed to be integrated into sol-gel processing of hybrid organic-inorganic materials through surface modification with an organosilane, 3-(aminopropyl)triethoxysilane (APTES). The carbon dots have been synthesised using citric acid and urea as precursors; the intense fluorescence exhibited by the nanoparticles, among the highest reported in the scientific literature, has been stabilised against quenching by APTES. When the modification is carried out in an aqueous solution, it leads to the formation of silica around the C-dots and an increase of luminescence, but also to the formation of large clusters which do not allow the deposition of optically transparent films. On the contrary, when the C-dots are modified in ethanol, the APTES improves the stability in the precursor sol even if any passivating thin silica shell does not form. Hybrid films containing APTES-functionalized C-dots are transparent with no traces of C-dots aggregation and show an intense luminescence in the blue and green range.

Fulleropyrrolidine-functionalized ceria nanoparticles as a tethered dual nanosystem with improved antioxidant properties.

Dual-tethered nanosystems which combine different properties at the nano scale represent a new fascinating frontier of research. In the present work, we present an example of a dual nanosystem designed to enhance the radical scavenging performances. Fulleropyrrolidine has been bonded to cerium oxide nanoparticles (nanoceria) to form a dual tethered system. Fulleropyrrolidine, bearing a silyl-alkoxide group, has been chemically bonded to the nanoceria surface, providing unprecedented antioxidant activity. This effect has been evaluated using an L929 mouse fibroblast cell line exposed to UV light. The fulleropyrrolidine molecules tethered to nanoceria enhance the radical scavenging properties of the oxide. At the same time, fulleropyrrolidine mitigates the potential toxicity of nanoceria at high doses. On the other hand, cerium oxide nanoparticles provide a strong hydrophilicity to the dual nanosystem, ensuring the administration in a cellular environment and preventing macroscopic aggregation of fulleropyrrolidine. The rational assembly of two different components in one nanosystem appears as a promising route for the development of "smarter" medical and cosmetic devices.

Modulating the Optical Properties of Citrazinic Acid through the Monomer-to-Dimer Transformation.

Understanding the luminescence of carbon dots is a highly challenging task because of the complex reactions involved in the synthesis process. Several by-products form at different reaction stages and become possible sources of emission. Citrazinic acid and its derivatives, in particular, have been identified as intermediates that give rise to blue fluorescence. Full comprehension of the optical properties of citrazinic acid itself is, however, still lacking. In particular, citrazinic acid has the property of forming different tautomers and aggregates such as dimers. However, the nature of these chemical species and the correlation with their relative optical properties have been only partially explored. In the present work, we have used a combination of spectroscopic techniques, UV-visible and fluorescence spectroscopy, time-resolved photoluminescence and computational simulation, to study the different species which citrazinic acid forms in water as a function of CZA molarity. A monomer-to-dimer transformation and a hypsochromic shift are observed with concentration. The monomer is in the keto structure and does not form other tautomers while the dimers are fluorescent J-type aggregates. The formation of aggregates strongly modulates the optical properties of citrazinic acid.

Boron oxynitride two-colour fluorescent dots and their incorporation in a hybrid organic-inorganic film.

Bottom-up synthesis of fluorescent boron-nitride based dots is a challenging task because an accurate design of the structure-properties relationship is, in general, difficult to achieve. Incorporation of the dots into a solid-state matrix is also another important target to develop light-emitting devices. Two-colour fluorescent boron oxynitride nanodots have been obtained by a bottom-up synthesis route and incorporated into a hybrid organic-inorganic film. A combination of different analytical techniques such as XPS, XRD, TEM, UV-Vis, TGA-DTA and fluorescence has been used to characterise the structure, composition and properties of the boron oxynitride dots. The presence of defects in the boron oxynitride structure is the source of the two-colour fluorescence. The BN dots thermal stability is limited to around 100 °C; higher temperatures induce condensation of the structure, which leads to a lower emission. Upon incorporation into a hybrid organic-inorganic film deposited by spin-coating, the boron oxynitride dots maintain their fluorescence and have shown to be highly compatible with the sol-gel chemistry.

Carbon Dots from Citric Acid and its Intermediates Formed by Thermal Decomposition.

Thermal decomposition of citric acid is one of the most common synthesis methods for fluorescent carbon dots; the reaction pathway is, however, quite complex and the details are still far from being understood. For instance, several intermediates form during the process and they also give rise to fluorescent species. In the present work, the formation of fluorescent C-dots from citric acid has been studied as a function of reaction time by coupling infrared analysis, X-ray photoelectron spectroscopy, liquid chromatography/mass spectroscopy (LC/MS) with the change of the optical properties, absorption and emission. The reaction intermediates, which have been identified at different stages, produce two main emissive species, in the green and blue, as also indicated by the decay time analysis. C-dots formed from the intermediates have also been synthesised by thermal decomposition, which gave an emission maximum around 450 nm. The citric acid C-dots in water show short temporal stability, but their functionalisation with 3-aminopropyltriethoxysilane reduces the quenching. The understanding of the citric acid thermal decomposition reaction is expected to improve the control and reproducibility of C-dots synthesis.