Acids from fruits generate photoactive Fe-complexes, enhancing solar disinfection of water (SODIS): A systematic study of the novel "fruto-Fenton" process, effective over a wide pH range (4 - 9).

This study aimed to enhance solar disinfection (SODIS) by the photo-Fenton process, operated at natural pH, through the re-utilization of fruit wastes. For this purpose, pure organic acids present in fruits and alimentary wastes were tested and compared with synthetic complexing agents. Owing to solar light, complexes between iron and artificial or natural chelators can be regenerated through ligand-to-metal charge transfer (LMCT) during disinfection. The target complexes were photoactive under solar light, and the Fe:Ligand ratios for ex situ prepared iron complexes were assessed, achieving a balance between iron solubilization and competition with bacteria as a target for oxidizing species. In addition, waste extracts containing natural acidic ligands were an excellent raw material for our disinfection enhancement purposes. Indeed, lemon and orange juice or their peel infusions turned out to be more efficient than commercially available organic acids, leading to complete inactivation in less than 1 h by this novel "fruto-Fenton" process, i.e. in the presence of a fruit-derived ligand, Fe(II) and H2O2. Finally, its application in Lake Leman water and in situ complex generation led to effective bacterial inactivation, even in mildly alkaline surface waters. This work proposes interesting SODIS and fruit-mediated photo-Fenton enhancements for bacterial inactivation in resource-poor contexts and/or under the prism of circular economy.

Light-Induced Transformation of Virus-Like Particles on TiO2.

Titanium dioxide (TiO2) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO2 surface. The in situ GISAXS measurements under an N2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.

Diblock copolymer pattern protection by silver cluster reinforcement.

Pattern fabrication by self-assembly of diblock copolymers is of significant interest due to the simplicity in fabricating complex structures. In particular, polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP) is a fascinating base material as it forms an ordered micellar structure on silicon surfaces. In this work, silver (Ag) is applied using direct current magnetron sputter deposition and high-power impulse magnetron sputter deposition on an ordered micellar PS-b-P4VP layer. The fabricated hybrid materials are structurally analyzed by field emission scanning electron microscopy, atomic force microscopy, and grazing incidence small angle X-ray scattering. When applying simple aqueous posttreatment, the pattern is stable and reinforced by Ag clusters, making micellar PS-b-P4VP ordered layers ideal candidates for lithography.

Adsorption and Inactivation of SARS-CoV-2 on the Surface of Anatase TiO2(101).

We investigated the adsorption of severe acute respiratory syndrome corona virus 2 (SARS-CoV-2), the virus responsible for the current pandemic, on the surface of the model catalyst TiO2(101) using atomic force microscopy, transmission electron microscopy, fluorescence microscopy, and X-ray photoelectron spectroscopy, accompanied by density functional theory calculations. Three different methods were employed to inactivate the virus after it was loaded on the surface of TiO2(101): (i) ethanol, (ii) thermal, and (iii) UV treatments. Microscopic studies demonstrate that the denatured spike proteins and other proteins in the virus structure readsorb on the surface of TiO2 under thermal and UV treatments. The interaction of the virus with the surface of TiO2 was different for the thermally and UV treated samples compared to the sample inactivated via ethanol treatment. AFM and TEM results on the UV-treated sample suggested that the adsorbed viral particles undergo damage and photocatalytic oxidation at the surface of TiO2(101) which can affect the structural proteins of SARS-CoV-2 and denature the spike proteins in 30 min. The role of Pd nanoparticles (NPs) was investigated in the interaction between SARS-CoV-2 and TiO2(101). The presence of Pd NPs enhanced the adsorption of the virus due to the possible interaction of the spike protein with the NPs. This study is the first investigation of the interaction of SARS-CoV-2 with the surface of single crystalline TiO2(101) as a potential candidate for virus deactivation applications. Clarification of the interaction of the virus with the surface of semiconductor oxides will aid in obtaining a deeper understanding of the chemical processes involved in photoinactivation of microorganisms, which is important for the design of effective photocatalysts for air purification and self-cleaning materials.

Photocatalytic activation of peroxymonosulfate (PMS) by novel mesoporous Ag/ZnO@NiFe2O4 nanorods, inducing radical-mediated acetaminophen degradation under UVA irradiation.

A new mesoporous Ag/ZnO@NiFe2O4 nanorod was prepared by a facile, low-cost, and environmentally friendly strategy from a bimetallic Fe2Ni-MIL-88 metal organic framework (MOF), as an effective catalyst and peroxymonosulfate (PMS) photo-activator. The structural, morphological, optical, and magnetic properties, as well as the material composition were investigated by XRD, FE-SEM, EDX, HR-TEM, XPS, DRS, PL, EIS, VSM, N2 adsorption-desorption and ICP-AES analysis. 1.0% w/w loading of Ag nanoparticles on ZnO0.04@NiFe2O4 led to the best catalytic activity for PMS activation under UVA in acetaminophen (ACT) degradation. The maximum degradation efficiency for ACT was 100% within 15 min (at pH = 7.0), with a first-order rate constant of 0.368 min-1. The calculated quantum yield (1.3 × 10-3 molecule/photon) of the optimum catalyst was 2.05, and 5.63 times higher than its simple constituents, ZnO0.04@NiFe2O4 and NiFe2O4, respectively. Among the various inorganic ions, Cl- and HCO3- showed significant inhibition effect in 1.0%w/w Ag/ZnO0.04@NiFe2O4/PMS/UVA system, due to radical quenching effects. Based on scavenger experiments, HO• and SO4•- were the dominant reactive species in photocatalytic process coupled with PMS. Due to presence of the Fe3+/Fe2+, and Ni2+/Ni3+ reaction cycles in the as-made catalyst, the reaction rate of PMS activation was greatly enhanced. Moreover, the formation of a hetero-junction structure with NiFe2O4 and ZnO promoted the charge separation of the photo-generated electron/hole pairs. Finally, the major intermediates produced during the reaction were detected by LC-MS analysis, and a plausible mechanism for the photocatalytic degradation of ACT was proposed and discussed in detail.

An innovative, highly stable Ag/ZIF-67@GO nanocomposite with exceptional peroxymonosulfate (PMS) activation efficacy, for the destruction of chemical and microbiological contaminants under visible light.

In this work, Ag nanoparticles were loaded on ZIF-67 covered by graphene oxide (Ag/ZIF-67@GO), and its catalytic performance was studied for the heterogeneous activation of peroxymonosulfate (PMS) under visible-light. The catalyst surface morphology and structure were analyzed by FT-IR, XRD, XPS, DRS, FE-SEM, EDX, TEM, BET, ICP-AES and TGA analysis. The efficacy of PMS activation by the Ag/ZIF-67@GO under visible light was assessed by phenol degradation and E. coli inactivation. Phenol was completely degraded within 30 min by HO•, SO4•- and O2•- generated through the photocatalytic PMS activation. In addition, total E. coli inactivation was attained in 15 min that confirmed the highly efficient catalytic activation of PMS by the as-made nanocomposite under visible light. The reaction mechanism was elucidated and the importance of the generated reactive species followed the order of: HO• > SO4•- > O2•- > h+, implying a radical-pathway dominated process.