Prediction of band edge potentials and reaction products in photocatalytic copper and iron sulfides.

The prediction of band edge potentials in photocatalytic materials is an important but challenging task. In contrast, bandgaps can be easily determined through absorption spectra. Here, we present two simple theoretical approaches for the determination of band edge potentials which are based on the electron negativity and work function of each constituent atom. We use these approaches to determine band edge potentials in semiconducting metallic oxides and sulfides, such as titanium dioxide (TiO2), chalcopyrite (CuFeS2), pyrite (FeS2), covellite (CuS), and chalcocite (Cu2S) with respect to an absolute scale (eV) and an electrochemical scale (V). Until now, there is little information on iron and copper sulfides referring to these thermodynamic parameters. TiO2 (Titania p25) was used as reference semiconductor to validate the calculation procedures using experimental values by X-ray diffraction analysis (XRD), diffuse reflectance spectrometry (DRS), and electron paramagnetic resonance spectroscopy (EPR). The production of key chemical species such as reactive oxygen species (ROS) and reactive sulfur species (RSS) has been theoretically and experimentally determined by EPR.

Copper concentrate dual-band joint classification using reflectance hyperspectral images in the VIS-NIR and SWIR bands.

A study on the classification of copper concentrates relevant to the copper refining industry is performed by means of reflectance hyperspectral images in the visible and near infrared (VIS-NIR) bands (400-1000 nm) and in the short-wave infrared (SWIR) (900-1700 nm) band. A total of 82 copper concentrate samples were press compacted into 13-mm-diameter pellets, and their mineralogical composition was characterized via quantitative evaluation of minerals and scanning electron microscopy. The most representative minerals contained in these pellets are bornite, chalcopyrite, covelline, enargite, and pyrite. Three databases (VIS-NIR, SWIR, and VIS-NIR-SWIR) containing a collection of average reflectance spectra computed from 9×9p i x e l neighborhoods in each pellet hyperspectral image are compiled to train the classification models. The classification models tested in this work are a linear discriminant classifier and two non-linear classifiers, a quadratic discriminant classifier, and a fine K-nearest neighbor classifier (FKNNC). The results obtained show that the joint use of VIS-NIR and SWIR bands allows for the accurate classification of similar copper concentrates that contain only minor differences in their mineralogical composition. Specifically, among the three tested classification models, the FKNNC performs the best in terms of overall classification accuracy, achieving 93.4% accuracy in the test set when only VIS-NIR data are used to construct the classification model, up to 80.5% using only SWIR data, and up to 97.6% using both VIS-NIR and SWIR bands together.

Role of the YehD fimbriae in the virulence-associated properties of enteroaggregative Escherichia coli.

The interaction of enteroaggregative Escherichia coli (EAEC) strains with the colonic gut mucosa is characterized by the ability of the bacteria to form robust biofilms, to bind mucin, and induce a local inflammatory response. These events are mediated by a repertoire of five different aggregative adherence fimbriae variants (AAF/I-V) typically encoded on virulence plasmids. In this study, we report the production in EAEC strains of a new YehD fimbriae (YDF), which is encoded by the chromosomal gene cluster yehABCD, also present in most E. coli strains. Immuno-labelling of EAEC strain 042 with anti-AAF/II and anti-YDF antibodies demonstrated the presence of both AAF/II and YDF on the bacterial surface. We investigated the role of YDF in cell adherence, biofilm formation, colonization of spinach leaves, and induction of pro-inflammatory cytokines release. To this aim, we constructed yehD deletion mutants in different EAEC backgrounds (strains 17-2, 042, 55989, C1010, 278-1, J7) each harbouring one of the five AAFs. The effect of the YDF mutation was strain dependent and AAF independent as the lack of YDF had a different impact on the phenotypes manifested by the different EAECs tested. Expression of the yehABCD operon in a E. coli K12 ORN172 showed that YDF is important for biofilm formation but not for adherence to HeLa cells. Lastly, screening of pro-inflammatory cytokines in supernatants of Caco-2 cells infected with EAEC strains 042 and J7 and their isogenic ΔyehD mutants showed that these mutants were significantly defective in release of IL-8 and TNF-α. This study contributes to the understanding of the complex and diverse mechanisms of adherence of EAEC strains and identifies a new potential target for preventive measures of gastrointestinal illness caused by EAEC and other E. coli pathogroups.

The Effect in Renal Function and Vascular Decongestion in Type 1 Cardiorenal Syndrome Treated with Two Strategies of Diuretics, a Pilot Randomized Trial.

AIM: The main treatment strategy in type 1 cardiorenal syndrome (CRS1) is vascular decongestion. It is probable that sequential blockage of the renal tubule with combined diuretics (CD) will obtain similar benefits compared with stepped-dose furosemide (SF). METHODS: In a pilot double-blind randomized controlled trial of CRS1 patients were allocated in a 1:1 fashion to SF or CD. The SF group received a continuous infusion of furosemide 100 mg during the first day, with daily incremental doses to 200 mg, 300 mg and 400 mg. The CD group received a combination of diuretics, including 4 consecutive days of oral chlorthalidone 50 mg, spironolactone 50 mg and infusion of furosemide 100 mg. The objectives were to assess renal function recovery and variables associated with vascular decongestion. RESULTS: From July 2017 to February 2020, 80 patients were randomized, 40 to the SF and 40 to the CD group. Groups were similar at baseline and had several very high-risk features. Their mean age was 59 ± 14.5 years, there were 37 men (46.2%). The primary endpoint occurred in 20% of the SF group and 15.2% of the DC group (p = 0.49). All secondary and exploratory endpoints were similar between groups. Adverse events occurred frequently (85%) with no differences between groups (p = 0.53). CONCLUSION: In patients with CRS1 and a high risk of resistance to diuretics, the use of CD compared to SF offers the same results in renal recovery, diuresis, vascular decongestion and adverse events, and it can be considered an alternative treatment. ClinicalTrials.gov with number NCT04393493 on 19/05/2020 retrospectively registered.

Conducting polymers/zinc oxide-based photocatalysts for environmental remediation: a review.

The accessibility to clean water is essential for humans, yet nearly 250 million people die yearly due to contamination by cholera, dysentery, arsenicosis, hepatitis A, polio, typhoid fever, schistosomiasis, malaria, and lead poisoning, according to the World Health Organization. Therefore, advanced materials and techniques are needed to remove contaminants. Here, we review nanohybrids combining conducting polymers and zinc oxide for the photocatalytic purification of waters, with focus on in situ polymerization, template synthesis, sol-gel method, and mixing of semiconductors. Advantages include less corrosion of zinc oxide, less charge recombination and more visible light absorption, up to 53%.

Clinical Manifestations, Mutational Analysis, and Immunological Phenotype in Patients with RAG1/2 Mutations: First Cases Series from Mexico and Description of Two Novel Mutations.

Mutations in recombinase activating genes 1 and 2 (RAG1/2) result in human severe combined immunodeficiency (SCID). The products of these genes are essential for V(D)J rearrangement of the antigen receptors during lymphocyte development. Mutations resulting in null-recombination activity in RAG1 or RAG2 are associated with the most severe clinical and immunological phenotypes, whereas patients with hypomorphic mutations may develop leaky SCID, including Omenn syndrome (OS). A group of previously unrecognized clinical phenotypes associated with granulomata and/or autoimmunity have been described as a consequence of hypomorphic mutations. Here, we present six patients from unrelated families with missense variants in RAG1 or RAG2. Phenotypes observed in these patients ranged from OS to severe mycobacterial infections and granulomatous disease. Moreover, we report the first evidence of two variants that had not been associated with immunodeficiency. This study represents the first case series of RAG1- or RAG2-deficient patients from Mexico and Latin America.

Multivariate approach to hydrogenated TiO2 photocatalytic activity under visible light.

The photocatalytic activity of hydrogenated TiO2 was evaluated in the photooxidation of methyl orange (MO). The hydrogenation of TiO2 was carried out by calcination of a mixture of TiO2 P-25 and NaBH4 , at 300 and 350°C for blue TiO2 and black TiO2 , respectively. An experimental design was made for the determination of the best reaction conditions for the oxidation of MO. The influence of catalyst dosage and pH on photocatalytic efficiency was optimized, and the degradation percentage of MO was the response factor. The photocatalytic reaction was performed using a Xenon lamp that simulates the solar light spectrum for the activation of the catalyst. It was determined that both blue and black TiO2 show the greatest activity at pH = 2 and 0.8 g/L of catalyst. Additionally, the positive influence of hydrogen peroxide in the photocatalytic activity of both hydrogenated catalysts was determined. In parallel, COD and TOC were also studied. PRACTITIONER POINTS: The extent of titania reduction by hydrogenation is dependent on the reaction time with sodium borohydride. The extent of titania reduction affects the photocatalytic activity in the oxidation of methyl orange. An excess of catalyst reduction inhibits the oxidation of the dye because of the increase of recombination points. The best reaction conditions were determined by multivariate optimization as pH 2 and 0.8 g L-1 of hydrogenated catalyst. The addition of hydrogen peroxide into the reaction system improves the oxidation yield attributed to their electron accepting capacity.

The CpxRA stress response system regulates virulence features of avian pathogenic Escherichia coli.

Avian pathogenic Escherichia coli (APEC) causes localized and systemic avian infections and is responsible for considerable economic losses in the poultry industry. This organism adheres and invades human and avian cells, however, the regulatory networks that dictate its virulence are largely unknown. The CpxRA two-component system is responsible for sensing and controlling outer-membrane stress and detecting misfolded proteins in the bacterial periplasmic space. CpxA is a membrane sensor kinase and CpxR is a cytoplasmic transcriptional regulator. In this study, we found that the CpxRA system regulates the virulence properties of APEC. Adherence, invasiveness, motility, production of type 1 fimbriae and biofilm were negatively affected in the ΔcpxA mutant indicating that the CpxA is required for full manifestation of these phenotypes. We also found that CpxR-P directly bound to the fimA promoter, locking the fimS region of type 1 fimbriae in the phase-OFF orientation. In addition, the absence of CpxA also reduced flagella production strongly suggesting that CpxRA regulates these two important surface organelles in APEC. This study provides compelling evidence of the role of the CpxRA two-component system in the regulation of virulence factors of avian pathogenic E. coli.

Living in poisoning environments: Invisible risks and human adaptation.

This article describes the hidden natural chemical contaminants present in a unique desert environment and their health consequences on ancient populations. Currently, millions of people are affected worldwide by toxic elements such as arsenic. Using data gathered from Atacama Desert mummies, we discuss long-term exposure and biocultural adaptation to toxic elements. The rivers that bring life to the Atacama Desert are paradoxically laden with arsenic and other minerals that are invisible and tasteless. High intake of these toxic elements results in severe health and behavioral problems, and even death. We demonstrate that Inca colonies, from Camarones 9 site, were significantly affected by chemical contaminants in their food and water. It appears however, some modern-day Andean populations resist the elevated levels of arsenic exposure as a result of positive selection mediated via the arsenic methyltransferase enzyme and display more tolerance to high chemical doses. This article further debate the effects of natural pollution and biocultural adaptation of past populations.

Prevalence of two Entamoeba gingivalis ST1 and ST2-kamaktli subtypes in the human oral cavity under various conditions.

Advances in molecular biology have facilitated analyses of the oral microbiome; however, the parasites role is poorly understood. Periodontal disease is a multifactorial process involving complex interactions among microorganisms, the host, and environmental factors. At present, the precise composition of the mouth parasites microbiota is unclear. Two protozoan species have been detected in the oral microbiota: Trichomonas tenax and Entamoeba gingivalis, and a new variant, E. gingivalis-ST2-kamaktli, was recently identified by us. In this study, both E. gingivalis and the new E. gingivalis-ST2-kamaktli variant were detected in the oral cavities of people with healthy periodontium, individuals undergoing orthodontic treatment, and patients with periodontal disease. In the group with healthy periodontium, the prevalence of E. gingivalis-ST1 was 48.6% and that of E. gingivalis-ST2-kamaktli 29.5%, with a combined prevalence of 54.3%. In patients undergoing orthodontics treatment, 81.2% carried both amoebas, with 47.5% having E. gingivalis-ST1 and 73.8% E. gingivalis-ST2-kamaktli. In people with periodontal disease, the prevalence of E. gingivalis-ST1 was 57.8%, and that of E. gingivalis-ST2-kamaktli 50.0%, with a combined prevalence of 73.5%; hence, E. gingivalis-ST1 and E gingivalis-ST2-kamaktli were detected in all three groups. The question arises, what are E. gingivalis-ST1 and E. gingivalis-ST2-kamaktli doing in the oral cavity? Although, the answer remains unclear, our results suggest that each amoeba subtype is genetically distinct, and they exhibit different patterns of infectious behavior. We hypothesize that E. gingivalis-ST1 and E. gingivalis-ST2-kamaktli may represent separate species. Our data contribute to better understanding of the roles of E. gingivalis-ST1 and E. gingivalis-ST2-kamaktli in the oral microbiota.

A new subtype of Entamoeba gingivalis: "E. gingivalis ST2, kamaktli variant".

Entamoeba gingivalis is a protozoan that resides in the oral cavity. Using molecular biology techniques, we identified a novel organism that shares the same ecological niche as E. gingivalis. To differentiate this organism from E. gingivalis, we named it "kamaktli variant." By sequencing the 18S-ITS1-5.8S-ITS2 rRNA region, we demonstrated that kamaktli variant is 89% identical to E. gingivalis. To elucidate the relationship between kamaktli variant and E. gingivalis, we performed a phylogenetic analysis. Both taxa clustered in the same clade with high support, indicating that the amoebas are closely related (98/99/1.00, maximum parsimony/maximum likelihood/MrBayes, respectively). Given this information, we propose that these molecular differences between kamaktli variant and E. gingivalis ST1 are sufficient to distinguish them as independent subtypes, and we name the new subtype "E. gingivalis ST2, kamaktli variant."

The expression of Longus type 4 pilus of enterotoxigenic Escherichia coli is regulated by LngR and LngS and by H-NS, CpxR and CRP global regulators.

Enterotoxigenic Escherichia coli produces a long type 4 pilus called Longus. The regulatory elements and the environmental signals controlling the expression of Longus-encoding genes are unknown. We identified two genes lngR and lngS in the Longus operon, whose predicted products share homology with transcriptional regulators. Isogenic lngR and lngS mutants were considerably affected in transcription of lngA pilin gene. The expression of lngA, lngR and lngS genes was optimally expressed at 37°C at pH 7.5. The presence of glucose and sodium chloride had a positive effect on Longus expression. The presence of divalent ions, particularly calcium, appears to be an important stimulus for Longus production. In addition, we studied H-NS, CpxR and CRP global regulators, on Longus expression. The response regulator CpxR appears to function as a positive regulator of lng genes as the cpxR mutant showed reduced levels of lngRSA expression. In contrast, H-NS and CRP function as negative regulators since expression of lngA was up-regulated in isogenic hns and crp mutants. H-NS and CRP were required for salt- and glucose-mediated regulation of Longus. Our data suggest the existence of a complex regulatory network controlling Longus expression, involving both local and global regulators in response to different environmental signals.

Homogeneous and heterogeneous degradation of caffeic acid using photocatalysis driven by UVA and solar light.

Waste water from the wine industry is characterized by a high concentration of dissolved organic matter and the presence of natural phenolic compounds with low biodegradability. High concentrations of phenolic compounds may cause environmental pollution and risks to human health. In this article caffeic acid (CA) was used as a model compound of wine effluent because it is refractory to the conventional wastewater treatments. The oxidation of caffeic acid in water solution (0.01 g L(-1)) by heterogeneous photocatalysis and photo-Fenton reaction was studied using UVA. The optimal conditions for each treatment were performed by multivariate experimental design. The optimal conditions for heterogeneous photocatalysis were pH 5.3 and 0.9 g L(-1) TiO2. In the case of photo-Fenton treatment, optimized variable were 82.4 µmol L(-1) of Fe(2+) and 558.6 µmol L(-1) of H2O2. The degradation profiles of CA were monitored by UV-Vis, HPLC, TOC and COD. To reach 90% of CA removal, 40 and 2 min of reaction, respectively, were required by heterogeneous and photo-Fenton processes, respectively. For comparison purposes, the reactions were also performed under solar light. The use of solar light does not change the efficiency of the photo-Fenton reaction, yet the performance of the heterogeneous process was significantly improved, reaching 90% of degradation in 15 min.

Urinary arsenic speciation profile in ethnic group of the Atacama desert (Chile) exposed to variable arsenic levels in drinking water.

Ethnic groups from the Atacama Desert (known as Atacameños) have been exposed to natural arsenic pollution for over 5000 years. This work presents an integral study that characterizes arsenic species in water used for human consumption. It also describes the metabolism and arsenic elimination through urine in a chronically exposed population in northern Chile. In this region, water contained total arsenic concentrations up to 1250 µg L(-1), which was almost exclusively As(V). It is also important that this water was ingested directly from natural water sources without any treatment. The ingested arsenic was extensively methylated. In urine 93% of the arsenic was found as methylated arsenic species, such as monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)]. The original ingested inorganic species [As(V)], represent less than 1% of the total urinary arsenic. Methylation activity among individuals can be assessed by measuring primary [inorganic As/methylated As] and secondary methylation [MMA/DMA] indexes. Both methylation indexes were 0.06, indicating a high biological converting capability of As(V) into MMA and then MMA into DMA, compared with the control population and other arsenic exposed populations previously reported.

Biodegradation of Tributyltin (TBT) by Extremophile Bacteria from Atacama Desert and Speciation of Tin By-products.

Biodegradation of tributyltin (TBT) by four tin resistant Gram negative bacteria isolated from extremely contaminated river sediments in the Atacama Desert in Chile was studied. Moraxella osloensis showed the greatest resistance and degradation capability of TBT, producing less toxic by-products, such as dibutyltin (DBT) and inorganic tin. In 7 days, approximately 80 % of TBT degradation was achieved, generating close to 20 % of DBT as degradation product. The degradation rate constant (k) was 0.022 [day(-1)] and TBT half-life (t1/2) in culture was 4.3 days. Debutylation is stated a probable mechanism of TBT degradation.

Oxidative degradation of sulfathiazole by Fenton and photo-Fenton reactions.

This article presents experimental results on 47 µmol L(-1) sulfathiazole (STZ) degradation by Fenton and photo-Fenton reactions using multivariate analysis. The optimal experimental conditions for reactions were obtained by Response Surface Methodology (RSM). In the case of the Fenton reactions there were 192 µmol L(-1) ferrous ions (Fe(II)) and 1856 µmol L(-1) hydrogen peroxide (H2O2), as compared with 157 µmol L(-1) (Fe(II)) and 1219 µmol L(-1) (H2O2) for photo-Fenton reactions. Under these conditions, around 90% of STZ degradation were achieved after 8 minutes treatment by Fenton and photo-Fenton reactions, respectively. Moreover, a marked difference was observed in the total organic carbon (TOC) removal after 60-min treatment, achieving 30% and 75% for the Fenton and photo-Fenton reactions, respectively. Acetic, maleic, succinic and oxamic acids could be identified as main Fenton oxidation intermediates. A similar pattern was found in the case of photo-Fenton reaction, including the presence of oxalic acid and ammonia at short periods of irradiation with UV-A. The calculated values of Average Oxidation State (AOS) corroborate the formation of oxidized products from the initial steps of the reaction.

Recent advancements in sustainable synthesis of zinc oxide nanoparticles using various plant extracts for environmental remediation.

The sustainable synthesis of zinc oxide nanoparticles (ZnO-NPs) using plant extracts has gained significant attention in recent years due to its eco-friendly nature and potential applications in numerous fields. This synthetic approach reduces the reliance on non-renewable resources and eliminates the need for hazardous chemicals, minimizing environmental pollution and human health risks. These ZnO-NPs can be used in environmental remediation applications, such as wastewater treatment or soil remediation, effectively removing pollutants and improving overall ecosystem health. These NPs possess a high surface area and band gap of 3.2 eV, can produce both OH° (hydroxide) and O2-° (superoxide) radicals for the generation of holes (h+) and electrons (e-), resulting in oxidation and reduction of the pollutants in their valence band (VB) and conduction band (CB) resulting in degradation of dyes (95-100% degradation of MB, MO, and RhB dyes), reduction and removal of heavy metal ions (Cu2+, Pb2+, Cr6+, etc.), degradation of pharmaceutical compounds (paracetamol, urea, fluoroquinolone (ciprofloxacin)) using photocatalysis. Here, we review an overview of various plant extracts used for the green synthesis of ZnO NPs and their potential applications in environmental remediation including photocatalysis, adsorption, and heavy metal remediation. This review summarizes the most recent studies and further research perspectives to explore their applications in various fields.

Phenylmercury degradation by heterogeneous photocatalysis assisted by UV-A light.

Photocatalytic degradation of phenylmercury was studied using TiO2 in aqueous suspension assisted by UV-A irradiation. Reaction conditions, such as pH and amount of TiO2 were set using a factorial design of experiments resulting in a greater influence of pH on phenylmercury degradation. Hg (II) reduction and simultaneous oxidation of aromatic group was observed. Optimum reaction conditions were obtained under nitrogen atmosphere at pH 10 and 0.35 g/L(-1) TiO2. Under these conditions almost 100% reduction of mercury was reached after 30 min UV irradiation. Total mercury reduction was achieved after 40 min reaction under saturated oxygen. Furthermore, phenol and diphenylmercury were identified as intermediate products of oxidation. It was observed that a major fraction of the reduced mercury was removed as metallic vapor by gas stripping, whereas a minor fraction was adsorbed on the catalyst surface, probably as Hg(OH)2. Under optimal conditions obtained by multivariable analysis, total mineralization of organic matter was achieved after about 60-min irradiation.