Phototransformation of Vanillin in Artificial Snow by Direct Photolysis and Mediated by Nitrite.

The photodegradation of vanillin, as a proxy of methoxyphenols emitted by biomass burning, was investigated in artificial snow at 243 K and in liquid water at room temperature. Nitrite (NO2-) was used as a photosensitizer of reactive oxygen and nitrogen species under UVA light, because of its key photochemical role in snowpacks and atmospheric ice/waters. In snow and in the absence of NO2-, slow direct photolysis of vanillin was observed due to back-reactions taking place in the quasi-liquid layer at the ice-grain surface. The addition of NO2- made the photodegradation of vanillin faster, because of the important contribution of photoproduced reactive nitrogen species in vanillin phototransformation. These species triggered both nitration and oligomerization of vanillin in irradiated snow, as the identified vanillin by-products showed. Conversely, in liquid water, direct photolysis was the main photodegradation pathway of vanillin, even in the presence of NO2-, which had negligible effects on vanillin photodegradation. The results outline the different role of iced and liquid water in the photochemical fate of vanillin in different environmental compartments.

Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes.

In this paper, we present the synthetic potential of diarylmethylium tetrafluoroborates as catalysts for the visible light promoted hydrosulfonylation of unactivated alkenes. For the first time, these salts, which are bench stable and easily preparable on a multi-gram scale, were employed as organocatalysts. Interestingly, a catalyst loading of only 1 mol% allowed sulfone products to be efficiently obtained from good-to-excellent yields with high functional-group tolerance and scalability up to 15 mmol of alkene. The mechanistic study, both experimental and computational, presented here, revealed an alternative mechanism for the formation of the key sulfonyl radical. Indeed, the photoactive species was proved not to be the diarylcarbenium salt itself, but two intermediates, a stable S-C adduct and an ion couple, that were formed after its interaction with sodium benzenesulfinate. Upon absorbing light, the ion couple could reach an excited state with a charge-transfer character which gave the fundamental sulfonyl radical. A PCET (proton-coupled electron transfer) closes the catalytic cycle reforming the diarylcarbenium salt.

Rabbit IgG-imprinted nanoMIPs by solid phase synthesis: the effect of cross-linkers on their affinity and selectivity.

Solid phase synthesis (SPS) of molecularly imprinted nanopolymers (nanoMIPs) represents an innovative method to prepare nanomaterials with tailor-made molecular recognition properties towards peptides and proteins. The synthesis of nanoMIPs by SPS usually involves a pre-polymerization formulation, where the cross-linker is invariably N,N'-methylen-bis-acrylamide (BIS). To date, the effect of cross-linkers on the binding properties of nanoMIPs prepared using cross-linkers other than BIS has never been reported. In this work, in order to investigate the effect of different cross-linkers in protein-imprinted nanoMIPs prepared by SPS, alongside BIS we considered other similar cross-linkers: N,N'-ethylene dimethacrylamide (EDAM), N,O-bis-methacryloylethanolamine (NOBE), ethylene glycol dimethacrilate (EDMA) and glycerol dimethacrylate (GDMA), replacing BIS with them in pre-polymerization mixtures. The synthetized nanoMIPs were homogeneous, with a polydispersity index of 0.24-0.30 and a mean diameter of 129-169 nm in water. The binding properties of the nanoMIPs were measured via equilibrium partition experiments with the template, rabbit IgG (RIgG), and the selectivity was evaluated with respect to bovine IgG (BIgG), bovine serum albumin (BSA) and hen egg lysozyme (LZM). The experimental results show that all the cross-linkers, with the exception of EDMA, endowed nanoMIPs with high binding affinities for the template (BIS: 16.0 × 106 mol-1 L, EDAM: 8.8 × 106 mol-1 L, NOBE: 15.8 × 106 mol-1 L, and GDMA: 12.8 × 106 mol-1 L), medium to high imprinting factors (BIS: 12.3, EDAM: 5.5, NOBE: 7.2, and GDMA: 11.6) and good selectivity towards other proteins but markedly dependent on the structure of the cross-linker, confirming the importance of the latter in the SPS of imprinted nanopolymers.

Machine learning approach for elucidating and predicting the role of synthesis parameters on the shape and size of TiO2 nanoparticles.

In the present work a series of design rules are developed in order to tune the morphology of TiO2 nanoparticles through hydrothermal process. Through a careful experimental design, the influence of relevant process parameters on the synthesis outcome are studied, reaching to the develop predictive models by using Machine Learning methods. The models, after the validation and training, are able to predict with high accuracy the synthesis outcome in terms of nanoparticle size, polydispersity and aspect ratio. Furthermore, they are implemented by reverse engineering approach to do the inverse process, i.e. obtain the optimal synthesis parameters given a specific product characteristic. For the first time, it is presented a synthesis method that allows continuous and precise control of NPs morphology with the possibility to tune the aspect ratio over a large range from 1.4 (perfect truncated bipyramids) to 6 (elongated nanoparticles) and the length from 20 to 140 nm.

Polyethylene Glycol as Shape and Size Controller for the Hydrothermal Synthesis of SrTiO3 Cubes and Polyhedra.

Understanding the correlation between the morphological and functional properties of particulate materials is crucial across all fields of physical and natural sciences. This manuscript reports on the investigation of the effect of polyethylene glycol (PEG) employed as a capping agent in the synthesis of SrTiO3 crystals. The crucial influence of PEG on both the shape and size of the strontium titanate particles is revealed, highlighting the effect on the photocurrents measured under UV-Vis irradiation.

Degradation of nanoplastics in the environment: Reactivity and impact on atmospheric and surface waters.

Microplastics (MPs) and nanoplastics (NPs) are ubiquitous and contaminate soil, surface waters, atmospheric aerosol, precipitations, indoor and outdoor environments. However, the occurrence, transformation and fate of NPs in the environment are still unclear. In this work, polystyrene nanoparticles (PS-NPs) are used as a proxy of NPs to study their reactivity and potential impact on atmospheric and surface waters. In particular, the reactivity with hydroxyl radicals (OH) in the aqueous phase is investigated. For the first time, a reactivity constant for the reaction of NPs with OH is measured, strongly dependent on the exposed particle surface area of NPs. Degradation products (short chain carboxylic acids and aromatic compounds), obtained by direct and OH-mediated photolysis of PS-NPs suspensions, are identified by mass spectrometry. Irradiation of a PS-NPs suspension under natural sunlight for 1 year has shown the formation of formic acid and organic compounds similar to those found in riverine and cloud dissolved organic matter, which could contribute significantly to the dissolved organic matter in the aqueous phase.

Metabisulfite as an Unconventional Reagent for Green Oxidation of Emerging Contaminants Using an Iron-Based Catalyst.

In this work, contaminants of emerging concern were catalytically degraded in the homogeneous phase with the use of unconventional green reagents. Three reagents, namely, sulfite, metabisulfite, and persulfate, were tested and compared with conventional hydrogen peroxide in the degradation process activated by Fe-TAML. The latter is a biodegradable, homogeneous tetra-amido macrocyclic ligand catalyst containing iron(III). Metabisulfite showed the highest efficiency among the three tested reagents, and its reactivity was similar to that of H2O2. However, metabisulfite is a safer and cleaner reagent compared to H2O2. A comprehensive study of the activity of metabisulfite with Fe-TAML was carried out toward the oxidative degradation of eight contaminants of emerging concern. The catalytic process was tested at different pH values (7, 9, and 11). Metabisulfite showed the highest activity at pH 11, completely degrading some of the tested micropollutants, but in several cases, the system was active at pH 9 as well. In particular, metabisulfite showed the best efficiency toward phenolic compounds. A preliminary study on the reaction mechanism and the nature of the active species in the Fe-TAML/metabisulfite system was also conducted, highlighting that a high-valent iron-oxo species might be involved in the degradation pathways.

Photoelectrochemical Performance of the Ag(III)-Based Oxygen-Evolving Catalyst.

We report the electrosynthesis of a water oxidation catalyst based on Ag oxides (AgCat). The deposited AgCat is composed of mixed valence crystalline Ag oxides with the presence of particle aggregates whose size is ∼1 µm. This catalyst, coupled with TiO2 and hematite, and under photoelectrochemical conditions, substantially increases photocurrents in a wide range of applied potentials compared with bare and Co-Pi-modified photocatalysts. AgCat can sustain current densities comparable with other water oxidation catalysts. Dark bulk electrolysis demonstrated that AgCat is stable and can sustain high turnover number in operative conditions. Oxygen evolution from water occurs in mild conditions: pH = 2-13, room temperature and pressure, and moderate overpotentials (600 mV) compatible with the coupling with semiconducting oxides as sensitizers. Using hematite in sustained electrolysis O2 production is significant, both in the dark and under irradiation, after an initial slow induction time in which modification of surface species occurs.

Local Proton Source in Electrocatalytic CO2 Reduction with [Mn(bpy-R)(CO)3 Br] Complexes.

The electrochemical behavior of fac-[Mn(pdbpy)(CO)3 Br] (pdbpy=4-phenyl-6-(phenyl-2,6-diol)-2,2'-bipyridine) (1) in acetonitrile under Ar, and its catalytic performances for CO2 reduction with added water, 2,2,2-trifluoroethanol (TFE), and phenol are discussed in detail. Preparative-scale electrolysis experiments, carried out at -1.5 V versus the standard calomel electrode (SCE) in CO2 -saturated acetonitrile, reveal that the process selectivity is extremely sensitive to the acid strength, producing CO and formate in different faradaic yields. A detailed spectroelectrochemical (IR and UV/Vis) study under Ar and CO2 atmospheres shows that 1 undergoes fast solvolysis; however, dimer formation in acetonitrile is suppressed, resulting in an atypical reduction mechanism in comparison with other reported MnI catalysts. Spectroscopic evidence of Mn hydride formation supports the existence of different electrocatalytic CO2 reduction pathways. Furthermore, a comparative investigation performed on the new fac-[Mn(ptbpy)(CO)3 Br] (ptbpy=4-phenyl-6-(phenyl-3,4,5-triol)-2,2'-bipyridine) catalyst (2), bearing a bipyridyl derivative with OH groups in different positions to those in 1, provides complementary information about the role that the local proton source plays during the electrochemical reduction of CO2 .

A local proton source in a [Mn(bpy-R)(CO)3Br]-type redox catalyst enables CO2 reduction even in the absence of Brønsted acids.

The effect of a local proton source on the activity of a bromotricarbonyl Mn redox catalyst for CO2 reduction has been investigated. The electrochemical behaviour of the novel complex [fac-Mn(dhbpy)(CO)3Br] (dhbpy = 4-phenyl-6-(1,3-dihydroxybenzen-2-yl) 2,2'-bipyridine), containing two acidic OH groups in the proximity of the metal centre, under a CO2 atmosphere showed a sustained catalysis in homogeneous solution even in the absence of Brønsted acids.

Tuning TiO2 nanoparticle morphology in graphene-TiO2 hybrids by graphene surface modification.

We report the hydrothermal synthesis of graphene (GNP)-TiO2 nanoparticle (NP) hybrids using COOH and NH2 functionalized GNP as a shape controller. Anatase was the only TiO2 crystalline phase nucleated on the functionalized GNP, whereas traces of rutile were detected on unfunctionalized GNP. X-Ray Photoelectron spectroscopy (XPS) showed C-Ti bonds on all hybrids, thus confirming heterogeneous nucleation. GNP functionalization induced the nucleation of TiO2 NPs with specific shapes and crystalline facets exposed. COOH functionalization directed the synthesis of anatase truncated bipyramids, bonded to graphene sheets via the {101} facets, while NH2 functionalization induced the formation of belted truncated bipyramids, bonded to graphene via the {100} facets. Belted truncated bipyramids formed on unfunctionalized GNP too, however the NPs were more irregular and rounded. These effects were ascribed to pH variations in the proximity of the functionalized GNP sheets, due to the high density of COOH or NH2 groups. Because of the different reactivity of anatase {100} and {101} crystalline facets, we hypothesize that the hybrid materials will behave differently as photocatalysts, and that the COOH-GNP-TiO2 hybrids will be better photocatalysts for water splitting and H2 production.

Photocatalytic metamaterials: TiO2 inverse opals.

The study of the photocatalytic activity of TiO(2) inverse opals showed that these structures behave as metamaterials: their properties arise principally from the 3D periodic structure of the material and marginally from porosity, reflectivity and scattering.