Preparación de recubrimientos microestructurados de TiO2 por proyección térmica para su utilización como fotoánodos. Tratamiento fotoelectrocatalítico de agua contaminada con un colorante azoico

Se ha sintetizado por proyección térmica un recubrimiento microestructurado de TiO2 sobre un sustrato metálico conductor (acero) con el fin de utilizarlo para eliminar un contaminante orgánico tóxico y recalcitrante en aguas (el colorante azoico Naranja Ácido 7). Se ha realizado una caracterización estructural para elucidar las fases de TiO2 del polvo utilizado en la síntesis del depósito y en el recubrimiento obtenido mediante XRD. También se obtuvieron micrografías de SEM para visualizar la superficie obtenida. La caracterización del depósito de TiO2 se completó con la determinación de porosidad, microrugosidad, microdureza y la fuerza de adhesión. Con ello se comprobó la estabilidad mecánica del sistema para su uso en fotoelectrocatálisis. Se estudió la posible aplicabilidad del recubrimiento realizado en el tratamiento fotoelectrocatalítico de un agua contaminada con Naranja Ácido 7, producto no degradable por tratamientos físico-químicos y biológicos convencionales. Se realizaron los experimentos bajo luz solar considerando variables como la densidad de corriente aplicada, el pH de las disoluciones y la concentración del colorante azoico. Se evaluó la eficiencia del proceso fotoelectrocatalítico mediante la eliminación del color y del carbón orgánico total de la disolución. Se identificaron los intermedios de oxidación y se siguió la cinética de degradación del compuesto por cromatografía de HPLC. Tras el estudio completo se logró la obtención de un fotoánodo con excelentes propiedades tanto mecánicas como de estabilidad al paso de corrientes anódica. Gracias al fotoánodo de TiO2 se consiguió decolorar completamente la solución de Naranja Ácido 7 mediante las condiciones optimizadas del tratamiento de fotoelectrocatálisis solar

Photocatalytic treatment of natural waters. Reality or hype? The case of cyanotoxins remediation

This review compiles recent advances and challenges in the photocatalytic treatment of natural water by analyzing the remediation of cyanotoxins. The review frames the treatment need based on the occurrence, geographical distribution, and legislation of cyanotoxins in drinking water while highlighting the underestimated global risk of cyanotoxins. Next, the fundamental principles of photocatalytic treatment for remediating cyanotoxins and the complex degradation pathway for the most widespread cyanotoxins are presented. The state-of-the-art and recent advances on photocatalytic treatment processes are critically discussed, especially the modification strategies involving TiO2 and the primary operational conditions that determine the scalability and integration of photocatalytic reactors. The relevance of light sources and light delivery strategies are shown, with emphasis on novel biomimicry materials design. Thereafter, the seldomly-addressed role of water-matrix components is thoroughly and critically explored by including natural organic matter and inorganic species to provide future directions in designing highly efficient strategies and scalable reactors

A ceramic electrode of ZrO2-Y2O3 for the generation of oxidant species in anodic oxidation. Assessment of the treatment of Acid Blue 29 dye in sulfate and chloride media

A micron-sized powder of 7% mol Y2O3 stabilized ZrO2 (YSZ) was used to deposit a ceramic coating onto Ti substrate by atmospheric plasma spray. The novel YSZ ceramic presented a dense structure with cubic crystalline structure. The as-synthesized YSZ ceramic as stable anode, coupled to a stainless-steel cathode, was assessed for the anodic oxidation of Acid Blue 29 diazo dye solutions in sulfate and chloride media. The decolorization of these solutions in acidic conditions was clearly faster with chloride as electrolyte, since the generated active chlorine HClO from anodic oxidation of Clwas more powerful oxidant than ¿OH formed from water discharge at the 7YSZ surface in sulfate medium. In alkaline conditions, the loss of color was drastically reduced because of the conversion of HClO into the weaker oxidant ClO, as well as the loss of oxidation power of ¿OH, partially compensated by the increasing oxidation ability of SO4¿formed from anodic oxidation of SO42ion. The effect of other experimental variables such as current density, as well as the concentration of each electrolyte and the dye, was examined. The best experimental conditions at pH 7.0 were found for 0.050 M of electrolyte at 20 and 10 mA cm-2 using sulfate and chloride media, respectively. In contrast, lower mineralization was achieved in chloride medium because of the formation of very recalcitrant and persistent chloro-derivatives that decelerated the mineralization process. In sulfate medium, NH4+, NO3and, to much lesser extent, NO2ions were released during mineralization, whereas tartaric, maleic, acetic and oxalic acids remained in the final solution

Scaling up photoelectrocatalytic reactors: A TiO2 nanotube-coated disc compound reactor effectively degrades acetaminophen

Multiple discs coated with hierarchically-organized TiO2 anatase nanotubes served as photoelectrodes in a novel annular photoelectrocatalytic reactor. Electrochemical characterization showed light irradiation enhanced the current response due to photogeneration of charge carriers. The pharmaceutical acetaminophen was used as a representative water micropollutant. The photoelectrocatalysis pseudo-first-order rate constant for acetaminophen was seven orders of magnitude greater than electrocatalytic treatment. Compared against photocatalysis alone, our photoelectrocatalytic reactor at <8 V reduced by two fold, the electric energy per order (EEO; kWh m-3 order-1 for 90% pollutant degradation). Applying a cell potential higher than 8 V detrimentally increased EEO. Acetaminophen was degraded across a range of initial concentrations, but absorbance at higher concentration diminished photon transport, resulting in higher EEO. Extended photoelectrocatalytic reactor operation degraded acetaminophen, which was accompanied by 53% mineralization based upon total organic carbon measurements. This proof of concept for our photoelectrocatalytic reactor demonstrated a strategy to increase photo-active surface area in annular reactors

Photoelectrocatalytic degradation of 2,4-dichlorophenol in a TiO2 nanotube-coated disc flow reactor

Photoelectrocatalytic (PEC) water treatment is a promising technology for organic pollution abatement. Much of the prior research focused on material discovery and optimization. However, challenges exist in scaling-up PEC processes and are associated with designing reactors with effective light irradiation on electrode surfaces and, simultaneously, efficient electrode configurations. We design and demonstrate key reactor design principles, which influence reaction mechanisms, for a reactor using a TiO2 nanotube-coated disc flow reactor. Degradation of organochlorinated 2,4-dichlorophenol was studied as representative carcinogenic micropollutant. The synergistic photoelectrocatalytic process showed 5-fold faster degradation kinetics than solely electrocatalytic treatment or a greater than 2-fold enhancement over photocatalysis alone. Applicability of photoelectrocatalytic treatment was demonstrated over a wide range of micropollutant concentrations with almost complete abatement even at concentrations up to 25 mg L-1 of 2,4-dichlorophenol. Mechanistically, the increase in applied current density efficiency for degradation of 2,4-dichlorophenol was due to stabilization of charge carriers and higher oxidants production rates in the PEC system. Carboxylic acids were identified as the main by-products formed from cleavage of the phenolic ring moieties in 2,4-dichlorophenol. However, very importantly we achieved dehalogenation photoelectrocatalysis with evidence of chlorine heteroatoms released as innocuous chloride anions. Overall, this research demonstrates the importance of PEC reactor design and how properly orientated TiO2 nanotube-coated disc flow reactors leverage both novel material designs and reactor architectures to achieve pollutant degradation

Portable point-of-use photoelectrocatalytic device provides rapid water disinfection

Portable water purification devices are needed to provide safe drinking water in rural communities, developing communities with low quality centralized water distribution, and military or recreational applications. Filtration, ultraviolet light, or chemical additives provide a spectrum of alternatives to remove pathogens from water. For the first time, we design, fabricate and demonstrate the performance of a small portable photoelectric point-of-use device, and document its performance on pathogen inactivation. The device utilizes a commercial teacup from which TiO2 nanotube photoanodes were produced in-situ and, with a small rechargeable battery powered 365 nm light emitting diode, was able to achieve 5-log inactivation of Escherichia coli in 10 s and 2.6-log of Legionella in 60 s of treatment in model water samples. Treatment of natural water achieved a 1-log bacteria inactivation after 30 s due to matrix effects. The electro-photocatalytic disinfection reactor in a kup (e-DRINK) can provide a feasible and affordable solution to ensure access to clean water. More broadly, this work demonstrates the potential for illumination to improve the efficiency of electrocatalytic surfaces

In-Host HEV Quasispecies Evolution Shows the Limits of Mutagenic Antiviral Treatments

Deep sequencing; Mutagens; QuasispeciesSeqüenciació profunda; Mutàgens; QuasiespècieSecuenciación profunda; Mutágenos; CuasiespecieHere, we report the in-host hepatitis E virus (HEV) quasispecies evolution in a chronically infected patient who was treated with three different regimens of ribavirin (RBV) for nearly 6 years. Sequential plasma samples were collected at different time points and subjected to RNA extraction and deep sequencing using the MiSeq Illumina platforms. Specifically, we RT-PCR amplified a single amplicon from the core region located in the open-reading frame 2 (ORF2). At the nucleotide level (genotype), our analysis showed an increase in the number of rare haplotypes and a drastic reduction in the frequency of the master (most represented) sequence during the period when the virus was found to be insensitive to RBV treatment. Contrarily, at the amino acid level (phenotype), our study revealed conservation of the amino acids, which is represented by a high prevalence of the master sequence. Our findings suggest that using mutagenic antivirals concomitant with high viral loads can lead to the selection and proliferation of a rich set of synonymous haplotypes that express the same phenotype. This can also lead to the selection and proliferation of conservative substitutions that express fitness-enhanced phenotypes. These results have important clinical implications, as they suggest that using mutagenic agents as a monotherapy treatment regimen in the absence of sufficiently effective viral inhibitors can result in diversification and proliferation of a highly diverse quasispecies resistant to further treatment. Therefore, such approaches should be avoided whenever possible.This study was partially supported by Plan Estratègic de Recerca i Innovació en Salut (PERIS)—Direcció General de Recerca i Innovació en Salut (DGRIS), Catalan Health Ministry, Generalitat de Catalunya; Centro para el Desarrollo Tecnológico Industrial (CDTI) from the Spanish Ministry of Economy and Business, grant number IDI-20200297, Grant PID2021-126447OB-I00 funded by MCIN/AEI/10.13039/501100011033 and by ERDF A way of making Europe; Projects PI19/00301 and PI22/00258 funded by Instituto de Salud Carlos III (ISCIII) and cofounded by the European Union; and Gilead’s biomedical research project GLD21/00006. S.C.-C has received support from Spanish Ministry of Education, grant FPU21/04150. M.I.-L. received the support of a fellowship from the “la Caixa” Foundation (ID 100010434), whose code is “LCF/BQ/DR23/12000020”

The frequency of defective genomes in Omicron differs from that of the Alpha, Beta and Delta variants

Evolution; Genetics; Molecular biologyEvolució; Genètica; Biologia molecularEvolución; Genética; Biología molecularThe SARS-CoV-2 Omicron variant emerged showing higher transmissibility and possibly higher resistance to current COVID-19 vaccines than other variants dominating the global pandemic. In March 2020 we performed a study in clinical samples, where we found that a portion of genomes in the SARS-CoV-2 viral population accumulated deletions immediately before the S1/S2 cleavage site (furin-like cleavage site, PRRAR/S) of the spike gene, generating a frameshift and appearance of a premature stop codon. The main aim of this study was to determine the frequency of defective deletions in prevalent variants from the first to sixth pandemic waves in our setting and discuss whether the differences observed might support epidemiological proposals. The complete SARS-CoV-2 spike gene was deeply studied by next-generation sequencing using the MiSeq platform. More than 90 million reads were obtained from respiratory swab specimens of 78 COVID-19 patients with mild infection caused by the predominant variants circulating in the Barcelona city area during the six pandemic waves: B.1.5, B.1.1, B.1.177, Alpha, Beta, Delta, and Omicron. The frequency of defective genomes found in variants dominating the first and second waves was similar to that seen in Omicron, but differed from the frequencies seen in the Alpha, Beta and Delta variants. The changing pattern of mutations seen in the various SARS-CoV-2 variants driving the pandemic waves over time can affect viral transmission and immune escape. Here we discuss the putative biological effects of defective deletions naturally occurring before the S1/S2 cleavage site during adaption of the virus to human infection.This study was partially supported by Pla Estratègic de Recerca i Innovació en Salut (PERIS) – Direcció General de Recerca i Innovació en Salut (DGRIS), Catalan Health Ministry, Generalitat de Catalunya; the Spanish Network for the Research in Infectious Diseases (REIPI RD16/0016/0003) from the European Regional Development Fund (ERDF); Centro para el Desarrollo Tecnológico Industrial (CDTI) from the Spanish Ministry of Economy and Business, grant number IDI-20200297; Grant PI19/00301 from Instituto de Salud Carlos III cofinanced by the European Regional Development Fund (ERDF), and Gilead’s biomedical research project GLD21/00006. We gratefully acknowledge the authors, originating and submitting laboratories of the sequences from GISAID’s EpiCov Database on which this research is based

Characteristics of 24 SARS-CoV-2-Sequenced Reinfection Cases in a Tertiary Hospital in Spain

SARS-CoV-2; Clinical features; ReinfectionSARS-CoV-2; Características clínicas; ReinfecciónSARS-CoV-2; Característiques clíniques; ReinfeccióBackground: Since the emergence of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the main concern is whether reinfections are possible, and which are the associated risk factors. This study aims to describe the clinical and molecular characteristics of 24 sequence-confirmed reinfection SARS-CoV-2 cases over 1 year in Barcelona (Catalonia, Spain). Methods: Patients with > 45 days between two positive PCR tests regardless of symptoms and negative tests between episodes were initially considered as suspected reinfection cases from November 2020 to May 2021. Whole-genome sequencing (WGS) was performed to confirm genetic differences between consensus sequences and for phylogenetic studies based on PANGOLIN nomenclature. Reinfections were confirmed by the number of mutations, change in lineage, or epidemiological criteria. Results: From 39 reported suspected reinfection cases, complete viral genomes could be sequenced from both episodes of 24 patients, all were confirmed as true reinfections. With a median age of 44 years (interquartile range [IQR] 32–65), 66% were women and 58% were healthcare workers (HCWs). The median days between episodes were 122 (IQR 72–199), occurring one-third within 3 months. Reinfection episodes were frequently asymptomatic and less severe than primary infections. The absence of seroconversion was associated with symptomatic reinfections. Only one case was reinfected with a variant of concern (VOC). Conclusion: Severe acute respiratory syndrome coronavirus 2 reinfections can occur in a shorter time than previously reported and are mainly found in immunocompetent patients. Surveillance through WGS is useful to identify viral mutations associated with immune evasion.This research was supported by CIBER -Consorcio Centro de Investigación Biomédica en Red- (CB 2021), Instituto de Salud Carlos III, Ministerio de Ciencia e Innovación and Unión Europea – NextGenerationEU

A year living with SARS-CoV-2: an epidemiological overview of viral lineage circulation by whole-genome sequencing in Barcelona city (Catalonia, Spain)

Catalonia; SARS-CoV-2; Molecular epidemiologyCataluña; SARS-CoV-2; Epidemiología molecularCatalunya; SARS-CoV-2; Epidemiologia molecularHerein, we describe the genetic diversity of circulating SARS-CoV-2 viruses by whole-genome sequencing (WGS) in Barcelona city (Catalonia, Spain) throughout the first four pandemic waves. From weeks 11/2020–24/2021, SARS-CoV-2-positive respiratory samples were randomly selected per clinical setting (80% from primary care or 20% from the hospital), age group, and week. WGS was performed following the ARTICv3 protocol on MiSeq or NextSeq2000 Illumina platforms. Nearly complete consensus sequences were used for genetic characterization based on GISAID and PANGOLIN nomenclatures. From 2475 samples, 2166 (87%) were fully sequenced (78% from primary care and 22% from hospital settings). Multiple genetic lineages were co-circulating, but four were predominant at different periods. While B.1.5 (50.68%) and B.1.1 (32.88%) were the major lineages during the first pandemic wave, B.1.177 (66.85%) and B.1.1.7 (83.80%) were predominant during the second, third, and fourth waves, respectively. Almost all (96.4%) were carrying D614G mutation in the S protein, with additional mutations that define lineages or variants. But some mutations of concern, such as E484K from B.1.351 and P.1 lineages are currently under monitoring, together with those observed in the receptor-binding domain or N-terminal domain, such as L452R and T478K from B.1.617.2 lineage. The fact that a predominant lineage was observed in each pandemic wave suggests advantageous properties over other contemporary co-circulating variants. This genetic variability should be monitored, especially when a massive vaccination campaign is ongoing because the potential selection and emergence of novel antigenic SARS-CoV-2 strains related to immunological escapement events.This work was supported by Spanish Network for the Research in Infectious Diseases: [Grant Number REIPI RD16/0016/0003]; Centro para el Desarrollo Tecnológico Industrial (CDTI) from the Spanish Ministry of Economy and Business [Grant Number IDI-20200297]; Direcció General de Recerca i Innovació en Salut (DGRIS); European Development Regional Fund (ERDF) “A way to achieve Europe” by Spanish Network for Research in Infectious Diseases [REIPI RD16/0016/0003]