Atomically isolated Sb(CN)3 on sp2-c-COFs with balanced hydrophilic and oleophilic sites for photocatalytic C-H activation.

Activation of carbon-hydrogen (C-H) bonds is of utmost importance for the synthesis of vital molecules. Toward achieving efficient photocatalytic C-H activation, our investigation revealed that incorporating hydrophilic C≡N-Sb(CN)3 sites into hydrophobic sp2 carbon-conjugated covalent organic frameworks (sp2-c-COFs) had a dual effect: It simultaneously enhanced charge separation and improved generation of polar reactive oxygen species. Detailed spectroscopy measurements and simulations showed that C≡N-Sb(CN)3 primarily functioned as water capture sites, which were not directly involved in photocatalysis. However, the potent interaction between water molecules and the Sb(CN)3-modified framework notably enhanced charge dynamics in hydrophobic sp2-c-COFs. The reactive species ·O2- and ·OH (ad) subsequently combined with benzyl radical, leading to the formation of benzaldehyde, benzyl alcohol, and lastly benzyl benzoate. Notably, the Sb(CN)3-modified sp2-c-COFs exhibited a 54-fold improvement in reaction rate as compared to pristine sp2-c-COFs, which achieved a remarkable 68% conversion rate for toluene and an 80% selectivity for benzyl benzoate.

Efficient Exciton Dissociation on Ceria Chelated Cerium-Based MOF Isogenous S-Scheme Photocatalyst for Acetaldehyde Purification.

Long-term exposure to low concentration indoor VOCs of acetaldehyde (CH3CHO) is harmful to human health. Thus, a novel isogenous heterojunction CeO2/Ce-MOF photocatalyst is synthesized via a one-step hydrothermal method for the effective elimination of CH3CHO in this work. This CeO2/Ce-MOF photocatalyst performs well in CH3CHO removal and achieves an apparent quantum efficiency of 7.15% at 420 nm, which presents ≈6.7 and 3.4 times superior to those generated by CeO2 and Ce-MOF, respectively. The enhanced efficiency is due to two main aspects including i) an effective photocarrier separation ability and the prolonged reaction lifetime of excitons play crucial roles and ii) the formation of an internal electric field (IEF) is sufficient to overcome the considerable exciton binding energy, and increases the exciton dissociation efficiency by up to 50.4%. Moreover, the reasonable pathways and mechanisms of CH3CHO degradation are determined by in situ DRIFTS analysis and simulated DFT calculations. Those results demonstrated that S-scheme heterojunction successfully increases the efficiency of harmful volatile organic compounds elimination, and it offers essential guidance for designing rare earth-based MOF photocatalysts.

Design and Fabrication of Biomass Derived Black Carbon Modified g-C3N4/FeIn2S4 Heterojunction as Highly Efficient Photocatalyst for Wastewater Treatment.

The environmental deterioration caused by dye wastewater discharge has received considerable attention in recent decades. One of the most promising approaches to addressing the aforementioned environmental issue is the development of photocatalysts with high solar energy consumption efficiency for the treatment of dye-contaminated water. In this study, a novel low-cost π-π biomass-derived black carbon modified g-C3N4 coupled FeIn2S4 composite (i.e., FeInS/BC-CN) photocatalyst is successfully designed and fabricated that reveals significantly improved photocatalytic performance for the degradation of Eosin Yellow (EY) dye in aqueous solution. Under dark and subsequent visible light irradiation, the amount optimized composite reveals 99% removal performance for EY dye, almost three-fold compared to that of the pristine FeInS and BC-CN counterparts. Further, it is confirmed by means of the electron spin resonance spectrometry, quenching experiments, and density functional theory (DFT) calculations, that the hydroxyl radicals (•OH) and superoxide radicals (•O2 -) are the dominant oxidation species involved in the degradation process of EY dye. In addition, a systematic photocatalytic degradation route is proposed based on the resultant degradation intermediates detectedduring liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis. This work provides an innovative idea for the development of advanced photocatalysts to mitigate water pollution.

Simultaneous Morphology and Band Structure Manipulation of BiOBr by Te Doping for Enhanced Photocatalytic Oxygen Evolution.

The photocatalytic oxygen evolution of bismuth oxybromide (BiOBr) is greatly hindered by its low visible-light response and high electron-hole recombination. Nonmetal doping can effectively alleviate these issues, leading to improvement in photocatalytic performance. Herein, Bi2Te3 was introduced as both the Te doping source and the morphology-control template to improve the photocatalytic performance of BiOBr. Appropriate amounts of Te are critical to maintain the ultrathin plate-like structure of BiOBr, whereas excessive Te results in the formation of a flower-like architecture. Oxygen evolution activity disclosed that a plate-like structure is essential for realizing higher performance owing to sufficient light utilization and efficient charge separation. An optimal oxygen evolution rate of 368.0 µmol h-1 g-1 was achieved for the Te-doped sample, which is 2.3-fold as that of the undoped BiOBr (158.9 µmol h-1 g-1). Theoretical calculations demonstrated that Te doping can induce impurity levels above the valence band of BiOBr, which slightly narrowed the band gap and strengthened the light absorption in the range of 400-800 nm. More importantly, Te dopants could act as shallow traps for confining the excited electrons, thus prolonging the carrier lifetime. This work provides a novel strategy to prepare highly efficient photocatalysts by simultaneously realizing morphology manipulation and nonmetal doping.

Methodological and reporting quality of systematic reviews on health effects of air pollutants were higher than extreme temperatures: a comparative study.

BACKGROUND: An increasing number of systematic reviews (SRs) in the environmental field have been published in recent years as a result of the global concern about the health impacts of air pollution and temperature. However, no study has assessed and compared the methodological and reporting quality of SRs on the health effects of air pollutants and extreme temperatures. This study aims to assess and compare the methodological and reporting quality of SRs on the health effects of ambient air pollutants and extreme temperatures. METHODS: PubMed, Embase, the Cumulative Index to Nursing and Allied Health Literature (CINAHL), Cochrane Library, Web of Science, and Epistemonikos databases were searched. Two researchers screened the literature and extracted information independently. The methodological quality of the SRs was assessed through A Measurement Tool to Assess Systematic Reviews 2 (AMSTAR 2). The reporting quality was assessed through Preferred Reporting Items of Systematic reviews and Meta-Analyses (PRISMA). RESULTS: We identified 405 SRs (286 for air pollution, 108 for temperature, and 11 for the synergistic effects). The methodological and reporting quality of the included SRs were suboptimal, with major deficiencies in protocol registration. The methodological quality of SRs of air pollutants was better than that of temperature, especially in terms of satisfactory explanations for any heterogeneity (69.6% v. 45.4%). The reporting quality of SRs of air pollution was better than temperature, however, adherence to the reporting of the assessment results of risk of bias in all SRs (53.5% v. 34.3%) was inadequate. CONCLUSIONS: Methodological and reporting quality of SRs on the health effect of air pollutants were higher than those of temperatures. However, deficiencies in protocol registration and the assessment of risk of bias remain an issue for both pollutants and temperatures. In addition, developing a risk-of-bias assessment tool applicable to the temperature field may improve the quality of SRs.

Exploring the Roles of Single Atom in Hydrogen Peroxide Photosynthesis.

This comprehensive review provides a deep exploration of the unique roles of single atom catalysts (SACs) in photocatalytic hydrogen peroxide (H2O2) production. SACs offer multiple benefits over traditional catalysts such as improved efficiency, selectivity, and flexibility due to their distinct electronic structure and unique properties. The review discusses the critical elements in the design of SACs, including the choice of metal atom, host material, and coordination environment, and how these elements impact the catalytic activity. The role of single atoms in photocatalytic H2O2 production is also analysed, focusing on enhancing light absorption and charge generation, improving the migration and separation of charge carriers, and lowering the energy barrier of adsorption and activation of reactants. Despite these advantages, several challenges, including H2O2 decomposition, stability of SACs, unclear mechanism, and low selectivity, need to be overcome. Looking towards the future, the review suggests promising research directions such as direct utilization of H2O2, high-throughput synthesis and screening, the creation of dual active sites, and employing density functional theory for investigating the mechanisms of SACs in H2O2 photosynthesis. This review provides valuable insights into the potential of single atom catalysts for advancing the field of photocatalytic H2O2 production.

Acetyl-CoA carboxylase Inhibition increases RPE cell fatty acid oxidation and limits apolipoprotein efflux.

Purpose: In age-related macular degeneration (AMD) and Sorsby's fundus dystrophy (SFD), lipid-rich deposits known as drusen accumulate under the retinal pigment epithelium (RPE). Drusen may contribute to photoreceptor and RPE degeneration in AMD and SFD. We hypothesize that stimulating ß-oxidation in RPE will reduce drusen accumulation. Inhibitors of acetyl-CoA carboxylase (ACC) stimulate ß-oxidation and diminish lipid accumulation in fatty liver disease. In this report we test the hypothesis that an ACC inhibitor, Firsocostat, limits the accumulation of lipid deposits in cultured RPE cells. Methods: We probed metabolism and cellular function in mouse RPE-choroid, human fetal- derived RPE cells, and induced pluripotent stem cell-derived RPE cells. We used 13 C6-glucose and 13 C16-palmitate to determine the effects of Firsocostat on glycolytic, Krebs cycle, and fatty acid metabolism. 13 C labeling of metabolites in these pathways were analyzed using gas chromatography-linked mass spectrometry. We quantified ApoE and VEGF release using enzyme-linked immunosorbent assays. Immunostaining of sectioned RPE was used to visualize ApoE deposits. RPE function was assessed by measuring the trans-epithelial electrical resistance (TEER). Results: ACC inhibition with Firsocostat increases fatty acid oxidation and remodels lipid composition, glycolytic metabolism, lipoprotein release, and enhances TEER. When human serum is used to induce sub-RPE lipoprotein accumulation, fewer lipoproteins accumulate with Firsocostat. In a culture model of Sorsby's fundus dystrophy, Firsocostat also stimulates fatty acid oxidation, improves morphology, and increases TEER. Conclusions: Firsocostat remodels intracellular metabolism and improves RPE resilience to serum-induced lipid deposition. This effect of ACC inhibition suggests that it could be an effective strategy for diminishing drusen accumulation in the eyes of patients with AMD.

Medium Depth Influences O2 Availability and Metabolism in Human RPE Cultures.

Purpose: Retinal pigment epithelium (RPE) oxidative metabolism is critical for normal retinal function and is often studied in cell culture systems. Here, we show that conventional culture media volumes dramatically impact O2 availability, limiting oxidative metabolism. We suggest optimal conditions to ensure cultured RPE is in a normoxic environment permissive to oxidative metabolism. Methods: We altered the availability of O2 to human primary and induced pluripotent stem cell-derived RPE cultures directly via a hypoxia chamber or indirectly via the amount of medium over cells. We measured oxygen consumption rates (OCRs), glucose consumption, lactate production, 13C6-glucose and 13C5-glutamine flux, hypoxia inducible factor 1α (HIF-1α) stability, intracellular lipid droplets after a lipid challenge, transepithelial electrical resistance, cell morphology, and pigmentation. Results: Medium volumes commonly employed during RPE culture limit diffusion of O2 to cells, triggering hypoxia, activating HIF-1α, limiting OCR, and dramatically altering cell metabolism, with only minor effects on typical markers of RPE health. Media volume effects on O2 availability decrease acetyl-CoA utilization, increase glycolysis and reductive carboxylation, and alter the size and number of intracellular lipid droplets under lipid-rich conditions. Conclusions: Despite having little impact on visible and typical markers of RPE culture health, media volume dramatically affects RPE physiology "under the hood." As RPE-centric diseases like age-related macular degeneration involve oxidative metabolism, RPE cultures need to be optimized to study such diseases. We provide guidelines for optimal RPE culture volumes that balance ample nutrient availability from larger media volumes with adequate O2 availability seen with smaller media volumes.

Developing Ni single-atom sites in carbon nitride for efficient photocatalytic H2O2 production.

Photocatalytic two-electron oxygen reduction to produce high-value hydrogen peroxide (H2O2) is gaining popularity as a promising avenue of research. However, structural evolution mechanisms of catalytically active sites in the entire photosynthetic H2O2 system remains unclear and seriously hinders the development of highly-active and stable H2O2 photocatalysts. Herein, we report a high-loading Ni single-atom photocatalyst for efficient H2O2 synthesis in pure water, achieving an apparent quantum yield of 10.9% at 420 nm and a solar-to-chemical conversion efficiency of 0.82%. Importantly, using in situ synchrotron X-ray absorption spectroscopy and Raman spectroscopy we directly observe that initial Ni-N3 sites dynamically transform into high-valent O1-Ni-N2 sites after O2 adsorption and further evolve to form a key *OOH intermediate before finally forming HOO-Ni-N2. Theoretical calculations and experiments further reveal that the evolution of the active sites structure reduces the formation energy barrier of *OOH and suppresses the O=O bond dissociation, leading to improved H2O2 production activity and selectivity.

Molecular Heptazine-Triazine Junction over Carbon Nitride Frameworks for Artificial Photosynthesis of Hydrogen Peroxide.

Revealing the photocatalytic mechanism between various junctions and catalytic activities has become a hotspot in photocatalytic systems. Herein, an internal molecular heptazine/triazine (H/T) junction in crystalline carbon nitride (HTCN) is constructed and devoted to selective two-electron oxygen reduction reaction (2e- ORR) for efficient hydrogen peroxide (H2 O2 ) production. In-situ X-ray diffraction spectra under various temperatures authenticate the successful formation of molecular H/T junction in HTCN during the calcining process rather than physically mixing. The increased surface photovoltage and transient photovoltage signals, and the decreased exciton binding energy undoubtably elucidate that an obvious increasement of carrier density and diffusion capability of photogenerated electrons are realized over HTCN. Additionally, the analyses of in situ photoirradiated Kelvin probe force microscopy and femto-second transient absorption spectra reveal the successful construction of the strong internal built-in-electric field and the existence of the majority of long-lived shallow trapped electrons associated with molecular H/T junction over HTCN, respectively. Benefiting from these, the photocatalytic results exhibit an incredible improvement (96.5-fold) for H2 O2 production. This novel work provides a comprehensive understanding of the long-lived reactive charges in molecular H/T junctions for strengthening the driving-force for photocatalytic H2 O2 production, which opens potential applications for enhancing PCN-based photocatalytic redox reactions.

Improved Lipofuscin Models and Quantification of Outer Segment Phagocytosis Capacity in Highly Polarized Human Retinal Pigment Epithelial Cultures.

The daily phagocytosis of photoreceptor outer segments by the retinal pigment epithelium (RPE) contributes to the accumulation of an intracellular aging pigment termed lipofuscin. The toxicity of lipofuscin is well established in Stargardt's disease, the most common inherited retinal degeneration, but is more controversial in age-related macular degeneration (AMD), the leading cause of irreversible blindness in the developed world. Determining lipofuscin toxicity in humans has been difficult, and animal models of Stargardt's have limited toxicity. Thus, in vitro models that mimic human RPE in vivo are needed to better understand lipofuscin generation, clearance, and toxicity. The majority of cell culture lipofuscin models to date have been in cell lines or have involved feeding RPE a single component of the complex lipofuscin mixture rather than fragments/tips of the entire photoreceptor outer segment, which generates a more complete and physiologic lipofuscin model. Described here is a method to induce the accumulation of lipofuscin-like material (termed undigestible autofluorescence material, or UAM) in highly differentiated primary human pre-natal RPE (hfRPE) and induced pluripotent stem cell (iPSC) derived RPE. UAM accumulated in cultures by repeated feedings of ultraviolet light-treated OS fragments taken up by the RPE via phagocytosis. The key ways that UAM approximates and differs from lipofuscin in vivo are also discussed. Accompanying this model of lipofuscin-like accumulation, imaging methods to distinguish the broad autofluorescence spectrum of UAM granules from concurrent antibody staining are introduced. Finally, to assess the impact of UAM on RPE phagocytosis capacity, a new method for quantifying outer segment fragment/tips uptake and breakdown has been introduced. Termed "Total Consumptive Capacity", this method overcomes potential misinterpretations of RPE phagocytosis capacity inherent in classic outer segment "pulse-chase" assays. The models and techniques introduced here can be used to study lipofuscin generation and clearance pathways and putative toxicity.

Medium depth influences O 2 availability and metabolism in cultured RPE cells.

PURPOSE: RPE oxidative metabolism is critical for normal retinal function and is often studied in cell culture systems. Here, we show that conventional culture media volumes dramatically impact O 2 availability, limiting oxidative metabolism. We suggest optimal conditions to ensure cultured RPE is in a normoxic environment permissive to oxidative metabolism. METHODS: We altered the availability of O 2 to human primary RPE cultures directly via a hypoxia chamber or indirectly via the amount of medium over cells. We measured oxygen consumption rates (OCR), glucose consumption, lactate production, 13 C-glucose flux, hypoxia inducible factor (HIF-1α) stability, intracellular lipid droplets after a lipid challenge, trans-epithelial electrical resistance, cell morphology, and pigmentation. RESULTS: Medium volumes commonly employed during RPE culture limit diffusion of O 2 to cells, triggering hypoxia, activating HIF-1α, limiting OCR, and dramatically altering cell metabolism, with only minor effects on typical markers of RPE health. Media volume effects on O 2 availability decrease acetyl-CoA utilization, increase glycolysis, and alter the size and number of intracellular lipid droplets under lipid-rich conditions. CONCLUSIONS: Despite having little impact on visible and typical markers of RPE culture health, media volume dramatically affects RPE physiology ″under the hood″. As RPE-centric diseases like age-related macular degeneration (AMD) involve oxidative metabolism, RPE cultures need to be optimized to study such diseases. We provide guidelines for optimal RPE culture volumes that balance ample nutrient availability from larger media volumes with adequate O 2 availability seen with smaller media volumes.

Modulating Hydrogen Adsorption via Charge Transfer at the Semiconductor-Metal Heterointerface for Highly Efficient Hydrogen Evolution Catalysis.

Designing and synthesizing highly efficient and stable electrocatalysts for hydrogen evolution reaction (HER) is important for realizing the hydrogen economy. Tuning the electronic structure of the electrocatalysts is essential to achieve optimal HER activity, and interfacial engineering is an effective strategy to induce electron transfer in a heterostructure interface to optimize HER kinetics. In this study, ultrafine RhP2 /Rh nanoparticles are synthesized with a well-defined semiconductor-metal heterointerface embedded in N,P co-doped graphene (RhP2 /Rh@NPG) via a one-step pyrolysis. RhP2 /Rh@NPG exhibits outstanding HER performances under all pH conditions. Electrochemical characterization and first principles density functional theory calculations reveal that the RhP2 /Rh heterointerface induces electron transfer from metallic Rh to semiconductive RhP2 , which increases the electron density on the Rh atoms in RhP2 and weakens the hydrogen adsorption on RhP2 , thereby accelerating the HER kinetics. Moreover, the interfacial electron transfer activates the dual-site synergistic effect of Rh and P of RhP2 in neutral and alkaline environments, thereby promoting reorganization of interfacial water molecules for faster HER kinetics.

Semi-heterogeneous photo-Cu-dual-catalytic cross-coupling reactions using polymeric carbon nitrides.

A merger of copper catalysis and semiconductor photocatalysis using polymeric carbon nitride (PCN) for multi-type cross-coupling reactions was developed. This dual-catalytic system enables mild C-H arylation, chalcogenation, and C-N cross-coupling reactions under visible light irradiation with a broad substrate scope. Good-to-excellent yields were obtained with appreciable site selectivity and functional group tolerance. Metal-free and low-cost PCN photocatalyst can easily be recovered and reused several times.

Multicarbons generation factory: CuO/Ni single atoms tandem catalyst for boosting the productivity of CO2 electrocatalysis.

Tandem electrocatalysis is an emerging concept for effective electrochemical CO2 reduction reaction (CO2RR) towards multicarbons (C2+). This decouples the multiple steps of CO2-to-C2+ into two steps of CO2-to-CO and CO-to-C2+ catalyzed by individual catalysts, to improve the Faradic efficiency (FE). However, due to the mass-transport limitation of CO from the generation site to the long-distance consumption site, such a strategy still remains challenge for high-rate production of C2+ products. Herein, we designed CuO/Ni single atoms tandem catalyst, which made the catalytic sites of Ni and Cu for independently catalyzing CO2-to-CO and CO-to-C2+ compactly neighbored, enabling the in-situ generation and rapid consumption of CO. The CuO/Ni SAs tandem catalyst achieved a particularly high partial current density of C2+ products (1220.8 mA/cm2), while still maintained outstanding C2+ products FE (81.4%) and excellent selectivities towards ethylene (FE 54.1%) and ethanol (FE 28.8%), enabling the profitable production of multicarbons by CO2RR.

Highly water-dispersible PCN nanosheets as light-controlled lysosome self-promoting escape type non-cationic gene carriers for tumor therapy.

The construction of non-viral gene delivery faces two major challenges: cytotoxicity caused by high cationic charge units and easy degradation by lysosomes. Herein, highly water-dispersible polymeric carbon nitride (PCN) nanosheets were utilized as the core to construct a light-controlled non-cationic gene delivery system with sufficient lysosomal escape ability. In this system, these nanosheets exhibited efficient DNA condensation, outstanding biocompatibility, transfection tracking, light responsiveness and high transfection efficiency. Once PCN-DNA was taken up by the tumor cells, the accumulated ROS generated by photosensitizers (PSs) under light irradiation would destroy the structure of lysosomes, promote the escape of PCN-DNA and increase the efficiency of gene transfection. Simultaneously, the gene transfection process could be tracked in real time through fluorescence imaging technology, which was conducive to investigate the transfection mechanism. In vitro and in vivo experiments further confirmed that PCN nanosheets loaded with the P53 gene were beneficial to the regeneration of the P53 apoptotic pathway, increased tumor sensitivity to PSs, and further induced tumor cell apoptosis. In summary, the highly water-dispersible PCN nanosheets were applied to light-controlled self-escaping gene delivery for the first time, and tumor gene therapy was successfully realized.

Types and Performances of Polymer Gels for Oil-Gas Drilling and Production: A Review.

Polymer gels with suitable viscoelasticity and deformability have been widely used for formation plugging and lost circulation control, profile control, and water shutoff. This article systematically reviews the research progress on the preparation principle, temperature resistance, salt resistance, and mechanical properties of the ground and in situ crosslinked polymer gels for oil-gas drilling and production engineering. Then, it comparatively analyzes the applicable conditions of the two types of polymer gel. To expand the application range of polymer gels in response to the harsh formation environments (e.g., high temperature and high salinity), we reviewed strategies for increasing the high temperature resistance, high salt resistance, and rheological/mechanical strengths of polymer gels. This article provides theoretical and technical references for developing and optimizing polymer gels suitable for oil-gas drilling and production.

Corrigendum: Application of One-Dimensional Nanomaterials in Catalysis at the Single-Molecule and Single-Particle Scale.

[This corrects the article DOI: 10.3389/fchem.2021.812287.].

Electro-exfoliated PdTe2 nanosheets for enhanced methanol electrooxidation performance in alkaline media.

Hydrogen-free cathodic exfoliation was utilized to obtain PdTe2 nanosheets (PTNS) with size 300 nm × 100 nm. Abundant highly exposed active sites and a strong electronic effect between Pd and Te endow PTNS with simultaneous superior methanol oxidation performance in alkaline media, which delivers a low onset potential, high mass and specific activity, and efficient CO elimination ability.

Vacancy-rich BiO2-x as a highly-efficient persulfate activator under near infrared irradiation for bacterial inactivation and mechanism study.

This study, for the first time, developed a novel defective BiO2-x based collaborating system, where the near-infrared light (NIR) irradiation (λ > 700 nm) initiated persulfate activation and photocatalytic bacterial inactivation simultaneously. Vacancy-rich BiO2-x nanoplates possessed impressive NIR absorption and firstly realized persulfate activation under NIR irradiation. In this collaborating system, on one hand, the persulfate can be transformed into sulfate radicals through light/heat activation mode directly, which would be enhanced by the presence of vacancy-rich BiO2-x owing to its outstanding light and heat absorption ability. On the other hand, the photogenerated electrons can further efficiently react with persulfate and form sufficient reactive sulfate radicals. The sulfate radicals, synergizing with other reactive species (O2-, h+, etc.), achieved a 7-log Escherichia coli inactivation within 40 min. The systematic investigation of inactivation mechanism revealed that the reactive species caused the dysfunction of cellular respiration, ATP synthesis and bacterial membrane, followed by the severely oxidative damage to the antioxidative SOD and CAT enzymes and the generation of carbonylated protein. The final leakage of DNA and RNA implied the lethal damage to the bacteria cells. This work provided a new insight into the persulfate associated NIR driven remediation technology of controlling microbial contaminants.