Sequential anaerobic and electro-Fenton processes mediated by W and Mo oxides for degradation/mineralization of azo dye methyl orange in photo assisted microbial fuel cells

The intensification of the degradation and mineralization of the azo dye methyl orange (MO) in contaminated water with simultaneous production of renewable electrical energy was achieved in photo-assisted microbial fuel cells (MFCs) operated sequentially under anaerobic - aerobic processes, in the presence of Fe(III) and W and Mo oxides catalytic species. In this novel process, the W and Mo oxides deposited on the graphite felt cathodes accelerated electron transfer and the reductive decolorization of MO. Simultaneously, the mineralization of MO and intermediate products was intensified by the production of hydroxyl radicals (HO[rad]) produced by (i) the photoreduction of Fe(III) to Fe(II), and by (ii) the reaction of the photochemically and electrochemically produced Fe(II) with hydrogen peroxide, which was produced in-situ during the aerobic stage. Under anaerobic conditions, the reductive decolorization of MO was driven by cathodic electrons, while the partial oxidation of the intermediates proceeded through holes oxidation, producing N,N-dimethyl-p-phenylenediamine. In contrast, under aerobic conditions superoxide radicals (O2[rad]−) were predominant to HO[rad], forming 4-hydroxy-N,N-dimethylaniline. In the presence of Fe(III) and under aerobic conditions, the oxidation of the intermediate products driven by HO[rad] superseded that of O2[rad]−, yielding phenol and amines, via the oxidation of 4-hydroxy-N,N-dimethylaniline and N,N-dimethyl-p-phenylenediamine. These sequential anaerobic and electro-Fenton processes led to the production of benzene and significantly faster oxidation reactions, compared to either the anaerobic or the aerobic operation in the presence of Fe(III). Complete degradation and mineralization (96.8 ± 3.5%) of MO (20 mg/L) with simultaneous electricity production (0.0002 kW h/kg MO) was therefore achieved with sequential anaerobic (20 min) - aerobic (100 min) operation in the presence of Fe(III) (10 mg/L). This study demonstrates an alternative and environmentally benign approach for efficient remediation of azo dye contaminated water with simultaneous production of renewable energy

Impact of Fe(III) as an effective electron-shuttle mediator for enhanced Cr(VI) reduction in microbial fuel cells: Reduction of diffusional resistances and cathode overpotentials

© 2016 Elsevier B.V.The role of Fe(III) was investigated as an electron-shuttle mediator to enhance the reduction rate of the toxic heavy metal hexavalent chromium (Cr(VI)) in wastewaters, using microbial fuel cells (MFCs). The direct reduction of chromate (CrO4−) and dichromate (Cr2O72−) anions in MFCs was hampered by the electrical repulsion between the negatively charged cathode and Cr(VI) functional groups. In contrast, in the presence of Fe(III), the conversion of Cr(VI) and the cathodic coulombic efficiency in the MFCs were 65.6% and 81.7%, respectively, 1.6 times and 1.4 folds as those recorded in the absence of Fe(III). Multiple analytical approaches, including linear sweep voltammetry, Tafel plot, cyclic voltammetry, electrochemical impedance spectroscopy and kinetic calculations demonstrated that the complete reduction of Cr(VI) occurred through an indirect mechanism mediated by Fe(III). The direct reduction of Cr(VI) with cathode electrons in the presence of Fe(III) was insignificant. Fe(III) played a critical role in decreasing both the diffusional resistance of Cr(VI) species and the overpotential for Cr(VI) reduction. This study demonstrated that the reduction of Cr(VI) in MFCs was effective in the presence of Fe(III), providing an alternative and environmentally benign approach for efficient remediation of Cr(VI) contaminated sites with simultaneous production of renewable energy

Intensified degradation and mineralization of antibiotic metronidazole in photo-assisted microbial fuel cells with Mo-W catalytic cathodes under anaerobic or aerobic conditions in the presence of Fe(III)

A novel strategy to intensify the degradation and mineralization of the antibiotic drug metronidazole (MNZ) in water with simultaneous production of renewable electrical energy was achieved in photo-assisted microbial fuel cells (MFCs). In this system Mo and W catalytic species immobilized onto a graphite felt cathode intensified the cathodic reduction of MNZ under anaerobic conditions and the oxidation of MNZ under aerobic conditions. The aerobic oxidation process was further accelerated in the presence of Fe(III), realizing a combined photo-assisted MFCs and Fenton-MFCs process. The highest rates of MNZ degradation (94.5 ± 1.4%; 75.6 ± 1.1 mg/L/h) and mineralization (89.5 ± 1.1%; 71.6 ± 0.9 mg/L/h), and power production (251 mW/m2; 0.015 kWh/m3; 0.22 kWh/kg COD) were achieved at a Mo/W loading of 0.18 mg/cm2with a Mo/W ratio of 0.17:1.0, in the presence of 10 mg/L of Fe(III) and at an incident photon flux of 23.3 mW/cm2. Photo-generated holes were directly involved into the oxidation of MNZ under anaerobic conditions. Conversely, under aerobic conditions, the photo-generated electrons favored the production of O2[rad]−over [rad]OH, while in the presence of Fe(III), [rad]OH was predominant over O2[rad]−, explaining the intensification of the MNZ mineralization observed. This study demonstrates an alternative and environmentally benign approach for the intensification of the removal of the antibiotic MNZ in water and possibly other contaminants of emerging concern by combining photo-assisted MFCs and Fenton-MFCs in a single process with simultaneous production of renewable electrical energy

Wider. Bigger. Greater. Neo-Palladian country houses as representations of power struggle, globalization and "Britishness" in the United Kingdom of the 1750s

Neo-Palladianism in the United Kingdom followed a clear formula when it was first introduced in the 1720s: small and compact villas, a central portico and references to the Villa Emo or La Rotonda. This concept changed significantly till the 1750s: wings were added, the complexes became wider and references became more diverse. The early 18th century was also a time of change for the political and social situation in the United Kingdom. The Hanoverians took over the throne from the Stuarts in 1714 and the Whigs governed the country for almost three decades. At the same time the world had become more global thanks to colonization and Britain was constantly in conflict with continental Europe. This meant that the collective identity of the British elite had to be newly created. This thesis discusses how Neo-Palladian country houses on the English countryside were used to create this new collective identity of the British elite in the 1750s

Table1_Comprehensive analysis of cuproptosis-related lncRNAs model in tumor immune microenvironment and prognostic value of cervical cancer.DOCX

Cervical cancer (CC) is the fourth leading gynecological malignancy in females worldwide. Cuproptosis, a form of cell death induced by copper, elicits a novel therapeutic strategy in anticancer therapy. Nonetheless, the effects of cuproptosis-related lncRNAs in CC remain unclear. Therefore, we aim to investigate cuproptosis-related lncRNAs, develop a risk model for prognostic prediction, and elucidate the immunological profile of CC. Transcription profiles and clinical follow-up data of CC were retrieved from The Cancer Genome Atlas (TCGA) database. Afterward, the risk model was built by distinguishing prognostic cuproptosis-related lncRNAs using the least absolute shrinkage and selection operator (LASSO) Cox regression. The correctness of the risk model was validated, and a nomogram was established followed by tumor immune microenvironment analysis. Tumor immune dysfunction and exclusion (TIDE) scores were used to assess immunotherapy response, and anticancer pharmaceutical half-maximal inhibitory concentration (IC50) prediction was performed for potential chemotherapy medicines. Finally, through coexpression analysis, 199 cuproptosis-related lncRNAs were collected. A unique risk model was generated using 6 selected prognostic cuproptosis-related lncRNAs. The risk score performed a reliable independent prediction of CC survival with higher diagnostic effectiveness compared to generic clinical characteristics. Immunological cell infiltration investigation indicated that the risk model was substantially linked with CC patients’ immunology, and the low-risk patients had lower TIDE scores and increased checkpoint expression, suggesting a stronger immunotherapy response. Besides, the high-risk group exhibited distinct sensitivity to anticancer medications. The immune-related progression was connected to the differentially expressed genes (DEGs) between risk groups. Generally, the risk model comprised 6 cuproptosis-related lncRNAs that may help predict CC patients’ overall survival, indicate immunocyte infiltration, and identify individualized treatment.</p

Infrared Spectra of NgBeS (Ng = Ne, Ar, Kr, Xe) and BeS₂ in Noble-Gas Matrices

Laser-ablated beryllium atom has been codeposited at 4 K with hydrogen sulfide in excess noble gas matrices. Four noble-gas compounds NgBeS (Ng = Ne, Ar, Kr, Xe) and the BeS₂ molecule are identified on the basis of the S-34 isotopic substitution, DFT and CCSD­(T) theoretical predictions, and a comparison of noble-gas substitution. The agreement between the experimental and calculated vibrational frequencies supports the identification of these molecules. The dissociation energies are calculated at 1.6, 12.6, 10.7, and 13.4 kcal/mol for NeBeS, ArBeS, KrBeS, and XeBeS, respectively, at the CCSD­(T) level. The BeS Lewis acid molecule favors strong chemical binding between the Be and Ng atoms

Image2_Comprehensive analysis of cuproptosis-related lncRNAs model in tumor immune microenvironment and prognostic value of cervical cancer.PNG

Cervical cancer (CC) is the fourth leading gynecological malignancy in females worldwide. Cuproptosis, a form of cell death induced by copper, elicits a novel therapeutic strategy in anticancer therapy. Nonetheless, the effects of cuproptosis-related lncRNAs in CC remain unclear. Therefore, we aim to investigate cuproptosis-related lncRNAs, develop a risk model for prognostic prediction, and elucidate the immunological profile of CC. Transcription profiles and clinical follow-up data of CC were retrieved from The Cancer Genome Atlas (TCGA) database. Afterward, the risk model was built by distinguishing prognostic cuproptosis-related lncRNAs using the least absolute shrinkage and selection operator (LASSO) Cox regression. The correctness of the risk model was validated, and a nomogram was established followed by tumor immune microenvironment analysis. Tumor immune dysfunction and exclusion (TIDE) scores were used to assess immunotherapy response, and anticancer pharmaceutical half-maximal inhibitory concentration (IC50) prediction was performed for potential chemotherapy medicines. Finally, through coexpression analysis, 199 cuproptosis-related lncRNAs were collected. A unique risk model was generated using 6 selected prognostic cuproptosis-related lncRNAs. The risk score performed a reliable independent prediction of CC survival with higher diagnostic effectiveness compared to generic clinical characteristics. Immunological cell infiltration investigation indicated that the risk model was substantially linked with CC patients’ immunology, and the low-risk patients had lower TIDE scores and increased checkpoint expression, suggesting a stronger immunotherapy response. Besides, the high-risk group exhibited distinct sensitivity to anticancer medications. The immune-related progression was connected to the differentially expressed genes (DEGs) between risk groups. Generally, the risk model comprised 6 cuproptosis-related lncRNAs that may help predict CC patients’ overall survival, indicate immunocyte infiltration, and identify individualized treatment.</p

Image3_Comprehensive analysis of cuproptosis-related lncRNAs model in tumor immune microenvironment and prognostic value of cervical cancer.PNG

Cervical cancer (CC) is the fourth leading gynecological malignancy in females worldwide. Cuproptosis, a form of cell death induced by copper, elicits a novel therapeutic strategy in anticancer therapy. Nonetheless, the effects of cuproptosis-related lncRNAs in CC remain unclear. Therefore, we aim to investigate cuproptosis-related lncRNAs, develop a risk model for prognostic prediction, and elucidate the immunological profile of CC. Transcription profiles and clinical follow-up data of CC were retrieved from The Cancer Genome Atlas (TCGA) database. Afterward, the risk model was built by distinguishing prognostic cuproptosis-related lncRNAs using the least absolute shrinkage and selection operator (LASSO) Cox regression. The correctness of the risk model was validated, and a nomogram was established followed by tumor immune microenvironment analysis. Tumor immune dysfunction and exclusion (TIDE) scores were used to assess immunotherapy response, and anticancer pharmaceutical half-maximal inhibitory concentration (IC50) prediction was performed for potential chemotherapy medicines. Finally, through coexpression analysis, 199 cuproptosis-related lncRNAs were collected. A unique risk model was generated using 6 selected prognostic cuproptosis-related lncRNAs. The risk score performed a reliable independent prediction of CC survival with higher diagnostic effectiveness compared to generic clinical characteristics. Immunological cell infiltration investigation indicated that the risk model was substantially linked with CC patients’ immunology, and the low-risk patients had lower TIDE scores and increased checkpoint expression, suggesting a stronger immunotherapy response. Besides, the high-risk group exhibited distinct sensitivity to anticancer medications. The immune-related progression was connected to the differentially expressed genes (DEGs) between risk groups. Generally, the risk model comprised 6 cuproptosis-related lncRNAs that may help predict CC patients’ overall survival, indicate immunocyte infiltration, and identify individualized treatment.</p

Overcoming the Limiting Step of Fe₂O₃ Reduction via in Situ Sulfide Modification

Iron-based alkaline batteries are extremely attractive due to iron’s environmental friendliness, and low cost. The parasitic reaction of H₂ evolution and the poor electrical conductivity of the discharge products are among the major barriers for the commercialization of these batteries. In this paper, we first show that O^2– diffusion inside the solid Fe₂O₃ particles is the rate-limiting step in the reduction reaction. In situ sulfide modified Fe₂O₃, which has a core–shell structure verified by SEM, XRD and XPS analysis, has excellent electrical and ionic conductivity. The functional mechanism of sulfide in the reaction was identified as in the potential region around −1.071 V (vs Hg/HgO), the outside layer of Fe₂O₃ was reduced to amorphous FeS, which has good electrical conductivity and enlarges the electrochemical reaction interface. O^2– diffusion inside the Fe₂O₃ particle is still the rate-limiting step. In the potential region around −1.15 V (vs Hg/HgO), amorphous FeS ages to FeS (pyrrhotite), FeS₂ (marcasite), and FeS_0.9 (mackinawite), which have high electrical conductivity. FeS_0.9 can also introduce vacancies into Fe₂O₃ particles, which can greatly enhance O^2– diffusion and the ionic conductivity, and the surface reaction is the rate-limiting step. In summary, after in situ sulfide modification, the ohmic overpotential and ion diffusion overpotential for Fe₂O₃ reduction were significantly reduced. The reduction reaction rate increases 26 times and the discharge capacity of Fe₂O₃ electrode increases 78 times after sulfide modification

Image1_Comprehensive analysis of cuproptosis-related lncRNAs model in tumor immune microenvironment and prognostic value of cervical cancer.JPEG

Cervical cancer (CC) is the fourth leading gynecological malignancy in females worldwide. Cuproptosis, a form of cell death induced by copper, elicits a novel therapeutic strategy in anticancer therapy. Nonetheless, the effects of cuproptosis-related lncRNAs in CC remain unclear. Therefore, we aim to investigate cuproptosis-related lncRNAs, develop a risk model for prognostic prediction, and elucidate the immunological profile of CC. Transcription profiles and clinical follow-up data of CC were retrieved from The Cancer Genome Atlas (TCGA) database. Afterward, the risk model was built by distinguishing prognostic cuproptosis-related lncRNAs using the least absolute shrinkage and selection operator (LASSO) Cox regression. The correctness of the risk model was validated, and a nomogram was established followed by tumor immune microenvironment analysis. Tumor immune dysfunction and exclusion (TIDE) scores were used to assess immunotherapy response, and anticancer pharmaceutical half-maximal inhibitory concentration (IC50) prediction was performed for potential chemotherapy medicines. Finally, through coexpression analysis, 199 cuproptosis-related lncRNAs were collected. A unique risk model was generated using 6 selected prognostic cuproptosis-related lncRNAs. The risk score performed a reliable independent prediction of CC survival with higher diagnostic effectiveness compared to generic clinical characteristics. Immunological cell infiltration investigation indicated that the risk model was substantially linked with CC patients’ immunology, and the low-risk patients had lower TIDE scores and increased checkpoint expression, suggesting a stronger immunotherapy response. Besides, the high-risk group exhibited distinct sensitivity to anticancer medications. The immune-related progression was connected to the differentially expressed genes (DEGs) between risk groups. Generally, the risk model comprised 6 cuproptosis-related lncRNAs that may help predict CC patients’ overall survival, indicate immunocyte infiltration, and identify individualized treatment.</p