Percutaneous endoscopic decompression for calcified thoracic disc herniation using a novel T rigid bendable burr.

BACKGROUND: The basic endoscopic instruments are not suitable for removing calcified or hard discs in patients with thoracic disc herniations (TDH). We describe a percutaneous endoscopic technique for the treatment of calcified TDH using an endoscopic drill system with a T rigid bendable burr. METHODS: Eleven patients (8 males, mean age 42.1 years) with single-segmental calcified TDH were treated with percutaneous endoscopic surgeries. RESULTS: Our technique using this endoscopic drill system with a T rigid bendable burr is safe and effective for the treatment of calcified TDH. CONCLUSIONS: Percutaneous endoscopic decompression using the T rigid bendable burr is a safe and reproducible surgical procedure for the treatment of calcified TDH.

Endoscopic cadaveric analysis of the origin of the ophthalmic artery.

PURPOSE: The ophthalmic artery is often involved in suprasellar and parasellar surgeries, but the anatomical structure where the ophthalmic artery originates has not been fully clarified from the perspective of an endoscopic endonasal approach (EEA). METHODS: A total of 10 fresh cadaveric heads (20 sides) were dissected through an EEA, and the origin of the bilateral ophthalmic arteries and their adjacent structures were observed from a ventral view. The origin of the ophthalmic artery in 50 healthy people was retrospectively studied on computed tomography angiography imaging. RESULTS: The ophthalmic artery originated from the intradural segment (75%), paraclinoid segment (15%), or parasellar segment (10%) of the internal carotid artery. The cross-sectional view of the internal carotid artery through the EEA showed that the ophthalmic artery originated from the middle 1/3 (75%) or medial 1/3 (25%) of the upper surface of the internal carotid artery. On computed tomography angiography, the ophthalmic artery originated from the middle 1/3 (77%) and medial 1/3 (22%) of the upper surface of the internal carotid artery. All ophthalmic arteries were near the level of the distal dural ring (DDR) of the internal carotid artery, that is, within 3 mm above or below the DDR. CONCLUSIONS: The ophthalmic artery usually originates in the middle 1/3 of the upper surface of the intradural segment of the internal carotid artery within 3 mm of the DDR. The ophthalmic artery can be protected to the utmost extent after its origin is identified through an EEA.

Selective removal of heavy metals by Zr-based MOFs in wastewater: New acid and amino functionalization strategy.

Zr-based metal-organic frameworks (MOFs) have been developed in recent years to treat heavy metals, e.g. hexavalent chromium Cr6+ pollution, which damages the surrounding ecosystem and threaten human health. This kind of MOF is stable and convenient to prepare, but has the disadvantage of low adsorption capacity, limiting its wide application. To this end, a novel formic acid and amino modified MOFs were prepared, referred to as Form-UiO-66-NH2. Due to the modification of formic acid, its specific surface area, pore size, and crystal size were effectively expanded, and the adsorption capacity of Cr6+ was significantly enhanced. Under optimal conditions, Form-UiO-66-NH2 exhibited an excellent adsorption capacity (338.98 mg/g), ∼10 times higher than that reported for unmodified Zr-based MOFs and most other adsorbents. An in-depth study on the photoelectronic properties and pH confirmed that the adsorption mechanism of Form-UiO-66-NH2 to Cr6+ was electrostatic adsorption. After modification, the improvement of Cr6+ adsorption capacity by Form-UiO-66-NH2 was attributed to the expansion of its specific surface area and the increase in its surface charge. The present study revealed an important finding that Form-UiO-66-NH2 elucidated selective adsorption to Cr6+ in mixed wastewater containing toxic heavy metal ions and common nonmetallic water quality factors. This research provided a new acid and amino functionalization perspective for improving the adsorption capacity of Zr-based MOF adsorbents while simultaneously demonstrating their pertinence to target contaminant adsorption.

Incorporating Oxygen Atoms in a SnS2 Atomic Layer to Simultaneously Stabilize Atomic Hydrogen and Accelerate the Generation of Hydroxyl Radicals for Water Decontamination.

Photoelectrocatalysis (PEC) is an efficient way to address various pollutants. Surface-adsorbed atomic hydrogen (H*) and hydroxyl radicals (•OH) play a key role in the PEC process. However, the instability of H* and low production of •OH considerably limit the PEC efficiency. In this study, we noted that incorporating oxygen atoms could regulate the behavior of H* by creating a locally favorable electron-rich state of S atoms in the SnS2 catalyst. The finely modulated H* led to a 12-fold decrease in the overpotential of H2O2 generation (H*-OOH*-H2O2-•OH) by decreasing the activation energy barrier of OOH* (rate-determining step). Considering density functional theory calculations, an H*-•OH redox pair suitable for a wide pH range (3-11) was successfully constructed based on the photocathode. The optimal SnS1.85O0.15 AL@TNA photocathode exhibited a ∼90% reduction in Cr(VI) in 10 min and ∼70% TOC removal of 4-nitrophenol, nearly 2- and 3-fold higher than that without oxygen incorporation. Electron spin resonance spectrometry and radical quenching experiments verified that H* and the derived •OH via 1-electron and 3-electron reduction were the main active species. Operando Raman spectroscopy confirmed that the stable SnO2 phase helped constantly activate the production of H* and •OH.

Effect of Early Normobaric Hyperoxia on Blast-Induced Traumatic Brain Injury in Rats.

Blast-induced traumatic brain injury (bTBI) is a leading cause of disability and mortality in soldiers during the conflicts in Iraq and Afghanistan. Although substantial clinical and animal studies have investigated the pathophysiology and treatments of bTBI, few effective therapies have been found, especially for the early rescue in the battlefield. The aim of this study is to evaluate neuroprotective effects of early normobaric hyperoxia (NBO) on bTBI. We established a rat model of bTBI caused by explosion in the cabin. It exhibited typical changes of mild bTBI, like impaired neurological function, brain edema, minor intracranial hemorrhage and neuron necrosis. The rats were divided into 4 groups (n = 12): Sham, Vehicle, hyperbaric oxygen (HBO) and NBO. Neurological function of the rats was assessed by the Neurological Severity Scores (NSS) at 24 h and 72 h after explosion. Serum interleukin-6 (IL-6), neuron specific enolase (NSE) and tau protein were measured at 24 h and 72 h after explosion. Brain water content was measured and Aquaporin-4 (AQP4) immunostaining was performed. Neuronal apoptosis was analyzed by TUNEL staining. NBO demonstrated curative effects on protecting the neurological function. Serum levels of NSE and tau protein were reduced at 24 h and 72 h after explosion. But the levels of IL-6 were not reduced significantly at both time points. Cerebral edema was alleviated. Simultaneously, AQP4 immunostaining of the hippocampus showed remarkably decreased expression after treatment. The number of apoptotic cells in hippocampus was also decreased. Compared with HBO, NBO is simple and convenient, and can be administered in remote areas. It may be a promising therapy for early rescue of bTBI in the battlefield.

UV-activated calcium peroxide system enables simultaneous organophosphorus degradation, phosphate recovery, and carbon fixation.

Advanced oxidation processes are a desirable technology for treatment of contaminants of emerging concern. Nevertheless, conventional advanced oxidation of organophosphorus compounds releases inorganic phosphate, posing downstream concerns related to eutrophication. For this reason, we evaluated the ultraviolet light-activated calcium peroxide (UV/CaO2) system for effective treatment of organophosphorus compounds and concurrent capture of the mineralization products, phosphate. The degradation mechanisms, reaction kinetics, and mineralizations were assessed to determine the overall efficiency and performance of the UV/CaO2 process. Knowledge gaps related to photocatalysis in the UV/CaO2 system were not only addressed, but also leveraged to identify unique advantages for removal of organophosphorus compounds and their degradation products. Experimental results confirmed that the UV/CaO2 system effectively mineralized organophosphorus compounds and recovered inorganic phosphate; additionally, collaborative carbon fixation performance of the system reveals the potential of carbon utilization. These outcomes were facilitated by the alkaline environment generated by CaO2. The recovered solids contained most of the phosphorus and carbon from the parent compounds. Ultimately, these findings provide transformative, new insights into the development and application of advanced oxidation processes that prevent downstream concerns related to mineralization products, especially inorganic phosphorus and carbon.

Enhanced water decontamination via photogenerated electron delocalization of π → π* and D-π-A synergistically.

Mixed-dimensional van der Waals heterojunctions (MD-vdWhs), known for exceptional electron transfer and charge separation capabilities, remain underexplored in photocatalysis. In this study, we leveraged the synergistic effect of intermolecular π â†’ π* and D-π-A dual channels to fabricate novel MD-vdWhs. Owing to the synergistic effect, it exhibits superior electron transfer and delocalization ability, thereby enhancing its photocatalytic performance. The Optimal photocatalyst can degrade 98.78 % of 20 mg/L tetracycline (TC) within 15 min. Additionally, we introduced a novel proof strategy for investigating the photoelectron transfer path, creatively demonstrating the synergistic dual channels effect, which can be attributed to the carbonyl density and light-excitation degree. Notably, even under low-power light sources, it achieved complete inactivation of Escherichia coli within just 7 mins, far surpassing current cutting-edge research. This theoretical framework holds promise for broader applications within related studies.

Enhancing interfacial electron transfer and photoelectrochemical kinetics for efficient water-treatment strategy through N-doped carbon dots modified PhC2Cu.

To improve the water environment quality, the development of an effective photocatalyst for pollutant removal was considered a promising strategy. The aim of the development of a novel photocatalyst PNC is pursued by modifying copper-phenylacetylide (PhC2Cu) with nitrogen-doped carbon quantum dots (N-CDs). Leading to a remarkable improvement in its light absorption capability, electron transfer efficiency and photoelectrochemical properties. Importantly, PNC possesses the characteristic of straightforward synthesis and demonstrates remarkable performance in the photodegradation of 99.87% sulfamethoxazole (SMX) within just 15 min, with a 3.95-fold increase in the photocatalytic rate. Analysis of the active substances revealed that 1O2, O2·-, and h+ are the generated active species by PNC. Active sites and degradation pathways of SMX were explored through density functional theory (DFT) calculations and intermediate analysis. Key evidence regarding the direction of electron transfer within the system was obtained through in-situ irradiated X-ray (ISI-XPS) techniques. This study deepened our understanding of the electron transfer characteristics of phenylacetylene copper and provided new insights for the modification of photocatalysts.

Degradation of sulfonamide antibiotic via UV/MgO2 system: kinetic, application, and mechanism.

In response to antibiotic residues in the water, a novel advanced oxidation technology based on MgO2 was used to remediate sulfamethazine (SMTZ) pollution in aquatic environments. Upon appropriate regulation, the remarkable removal efficiency of SMTZ was observed in a UV/MgO2 system, and the pseudo-first-order reaction constant reached 0.4074 min-1. In addition, the better performance of the UV/MgO2 system in a weak acid environment was discovered. During the removal of SMTZ, the pathways of SMTZ degradation were deduced, including nitration, ring opening, and group loss. In the mineralization exploration, the further removal of residual products of SMTZ by the UV/MgO2 system was visually demonstrated. The qualitative and quantitative researches as well as the roles of reactive species were valuated, which revealed the important role of ·O2-. Common co-existing substances in actual wastewater such as NO3- HA, Cl-, Fe2+, Co2+, and Mn2+ can slightly inhibit the degradation of SMTZ in the UV/MgO2 system. Finally, the capacity of efficient degradation of SMTZ in actual wastewater by the UV/MgO2 system was proved. The results indicated that the innovative UV/MgO2 system was of great practical application prospect in antibiotic residue wastewater remediation.

Insights into copper(I) phenylacetylide with in-situ transformation of oxygen and enhanced visible-light response for water decontamination: Cu-O bond promotes exciton dissociation and charge transfer.

The widespread contamination of hexavalent chromium (Cr(VI)), pharmaceuticals and personal care products (PPCPs), and dyes is a growing concern. necessitating the development of convenient and effective technologies for their removal. Copper(I) phenylacetylide (PhC2Cu) has emerged as a promising photocatalyst for environmental remediation. In this study, we introduced a functional Cu-O bond into PhC2Cu (referred to as OrPhC2Cu) by creatively converting the adsorbed oxygen on the surface of PhC2Cu into a Cu-O bond to enhance the efficiency of Cr(VI) photoreduction, PPCPs photodegradation, and dyes photodegradation through a facile vacuum activating method. The incorporation of the Cu-O bond optimized the electron structure of OrPhC2Cu, facilitating exciton dissociation and charge transfer. The exciton dissociation behavior and charge transfer mechanism were systematically investigated for the first time in the OrPhC2Cu system by photoelectrochemical tests, fluorescence and phosphorescence (PH) techniques, and density functional theory (DFT) calculations. Remarkably, the enhanced visible-light response of OrPhC2Cu improved photon utilization and significantly promoted the generation of reactive species (RSs), leading to the highly efficient Cr(VI) photoreduction (98.52% within 25 min) and sulfamethazine photodegradation (94.65% within 60 min), with 3.91 and 5.23 times higher activity compared to PhC2Cu. Additionally, the photocatalytic efficiency of OrPhC2Cu in degrading anionic dyes surpassed that of cationic dyes. The performance of the OrPhC2Cu system in treating electroplating effluent or natural water bodies suggests its potential for practical applications.

Whole-Exome Sequencing Revealed the Mutational Profiles of Primary Central Nervous System Lymphoma.

BACKGROUND: Primary central nervous system lymphoma (PCNSL) is a highly aggressive type of extranodal non-Hodgkin lymphoma, of which approximately 90% of the cases are diffuse large B-cell lymphoma (DLBCL). In recent years, the incidence of PCNSL has significantly increased in women and older men. Although advanced treatments such as high-dose methotrexate (HD-MTX) and targeted agents have been introduced, the prognosis of these patients remains poorer than those with other forms of non-Hodgkin's lymphoma. METHODS: Twelve cases of Chinese PCNSL were analyzed to detect their genetic alterations using whole-exome sequencing (WES). We identified 448 potential somatic single nucleotide variants (SNVs) with a median of 12 SNVs per PCNSL sample and 35 small indels with potentially protein-changing features in 9 PCNSL samples. RESULTS: We found that myeloid differentiation factor 88 (MYD88) had the highest mutation frequency, which affected the activity of the nuclear factor-κB (NF-κB) pathway. PCNSL samples with low-density lipoprotein receptor-related protein 1B (LRP1B) mutations had a higher mutation rate than samples with wild-type LRP1B. Polycystic kidney and hepatic disease 1 (PKHD1), the causal gene of autosomal recessive polycystic kidney disease (ARPKD), was identified in 2 PCNSL cases and exhibited missense mutations. Pathway analysis revealed enrichment in pathways associated with central carbon metabolism in cancer, renal cell carcinoma, nicotine addiction, bladder cancer, and long-term depression. CONCLUSIONS: WES revealed significantly mutated genes associated with the molecular mechanisms of PCNSL, which could serve as therapeutic targets to improve patient outcomes.

Leaf-like ionic covalent organic framework for the highly efficient and selective removal of non-steroidal anti-inflammatory drugs: Adsorption performance and mechanism insights.

In recent years, ionic covalent organic frameworks (iCOFs) have become popular for the removal of contaminants from water. Herein, we employed 2-hydroxybenzene-1,3,5-tricarbaldehyde (TFP) and 1,3-diaminoguanidine monohydrochloride (DgCl) to develop a novel leaf-like iCOF (TFP-DgCl) for the highly efficient and selective removal of non-steroidal anti-inflammatory drugs (NSAIDs). The uniformly distributed adsorption sites, suitable pore sizes, and functional groups (hydroxyl groups, guanidinium groups, and aromatic groups) of the TFP-DgCl endowed it with powerful and selective adsorption capacities for NSAIDs. Remarkably, the optimal leaf-like TFP-DgCl demonstrated an excellent maximum adsorption capacity (1100.08 mg/g) for diclofenac sodium (DCF), to the best of our knowledge, the largest adsorption capacity ever achieved for DCF. Further testing under varying environmental conditions such as pH, different types of anions, and multi-component systems confirmed the practical suitability of the TFP-DgCl. Moreover, the prepared TFP-DgCl exhibited exceptional reusability and stability through six adsorption-desorption cycles. Finally, the adsorption mechanisms of NSAIDs on leaf-like TFP-DgCl were confirmed as electrostatic interactions, hydrogen bonding, and π-π interactions. This work significantly supplements to our understanding of iCOFs and provides new insights into the removal of NSAIDs from wastewater.

Self-assembly construction of 1D carbon nitride nanotubes and cobalt-modified for superior photocatalytic degradation of sulfonamide antibiotics.

In the present work, a cobalt-doped carbon nitride nanotubes (Co-CNt) was synthesized via self-assembly process. Contributed to the narrow band gap, enlarged specific surface area and abundant active sites, Co-CNt has excellent photoelectric properties and superior performance than pristine CN in sulfisoxazole (SIZ) degradation under blue light irradiation, which achieved 100% removal within 40 min. Meanwhile, the system not only exhibited practical applicability by efficiently degrading SIZ, but also generating high levels of H2O2. Moreover, the Co-CNt/visible light system shows superior operability over a wide pH range, micro-concentration contaminants, various anions, water matrices and other sulfonamides with promising catalytic stability and applicability. The contribution of RSs in the degradation process were elucidated based on radical scavenging and spin-trapped tests, clarifying that O2·- and h+ majorly dominated the process. In addition, 4 probable degradation pathways of SIZ were provided and the generated intermediates' toxicity were evaluated. Overall, this study successfully synthesized a self-assembled 1D tubular photocatalyst with Co-doped and demonstrated the potential Co-CNt/visible light system for environmental remediation, providing a promising approach for the development of photocatalysis.

Carbon nitride nanotubes anchored with Cu(I) triggers peracetic acid activation with visible light for removal of antibiotic contaminants: Probing mechanisms of non-radical pathways and identifying active sites.

The peracetic acid (PAA)-activation process has attracted much attention in wastewater treatment. However, the low electron efficiency at the interface between heterogeneous catalysts and PAA has affected its practical application. For this study, we developed a carbon nitride hollow-nanotube catalysts with dispersed Cu(I) sites (Cu(I)-TCN) for the photocatalytic activation of PAA for antibiotics degradation. The obtained Cu(I)-TCN catalyst demonstrated an enhanced capacity for visible light harvesting along with increased charge transfer rates. Specifically, the developed Cu(I)-TCN/visible light/PAA system was able to completely remove antibiotics within 20 min, with a kinetic constant that was 25 times higher than a Cu(I)-TCN/visible light system, and 83 times higher than Cu(I)-TCN/PAA systems. Scavenging experiment and electron paramagnetic resonance (EPR) indicated that singlet oxygen was dominant reactive specie for sulfisoxazole (SIZ) removal. Besides, electrochemical tests and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy verified that the electron transfer efficiency of PAA activation was promoted due to the formation of inner-sphere interactions between PAA and Cu(I)-TCN, resulting in the quick removal of antibiotics. Further, after exposure to visible light, the Cu(I)-TCN excited photogenerated electrons which supplemented the electrons consumed in the reaction and drove the valence cycle of Cu ions. Overall, this research offered novel insights into the non-radical pathway for heterogeneous visible light-driven advanced oxidation processes and their potential for practical wastewater remediation.

Strategy for improvement of molecular oxygen activation capacity of PPECu by chlorine doping for water decontamination.

The activation of molecular oxygen and generation of reactive oxygen species (ROS) play important roles in the efficient removal of contaminants from aqueous ecosystems. Herein, using a simple and rapid solvothermal process, we developed a chlorine-doped phenylethynylcopper (Cl/PPECu) photocatalyst and applied it to visible light degradation of sulfamethazine (SMT) in aqueous media. The Cl/PPECu was optimized to have a 2.52 times higher steady-state concentration of O2•- (3.62 × 10-5 M) and a 28.87 times higher degradation rate constant (0.2252 min-1) for SMT compared to pure PPECu. Further, the effectiveness of Cl/PPECu in treating sulfonamide antibiotics (SAs) in real water systems was verified through an investigation involving natural water bodies, SAs, and ambient sunlight. The energy band structure, DFT calculation and correlation heat map indicated that the addition of chlorine modulated the local electronic structure of PPECu, leading to an improvement in the electron-hole separation, enhanced the O2 activation, and promoted the generation of ROSs. This study not only puts forward innovative ideas for the eco-compatible remediation of environmental pollution using PPECu, but also sheds new light on the activation of oxygen through elemental doping.

Simplified synthesis of direct Z-scheme Bi2WO6/PhC2Cu heterojunction that shows enhanced photocatalytic degradation of 2,4,6-TCP: Kinetic study and mechanistic insights.

For this work, we employed n-type Bi2WO6 and p-type PhC2Cu to formulate a direct Z-scheme Bi2WO6/PhC2Cu (PCBW) photocatalyst via simplified ultrasonic stirring technique. An optimal 0.6PCBW composite exhibited the capacity to rapidly photodegrade 2,4,6-TCP (98.6% in 120 min) under low-power blue LED light, which was 8.53 times and 12.53 times faster than for pristine PhC2Cu and Bi2WO6, respectively. Moreover, electron spin resonance (ESR), time-resolved PL spectra, and quantitative ROS tests indicated that the PCBW enhanced the separation capacity of photocarriers. It also more readily associated with dissolved oxygen in water to generate reactive oxygen species (ROS). Among them, the ability of PCBW to produce ·O2- in one hour was 12.07 times faster than for pure PhC2Cu. In addition, the H2O2 formation rate and apparent quantum efficiency of PCBW are 10.73 times that of PhC2Cu, which indicates that PCBW not only has excellent photocatalytic performance, but also has outstanding ROS production ability. Furthermore, Ag photodeposition, in situ X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations were utilized to determine the photogenerated electron migration paths in the PCBW, which systematically confirmed that Z-scheme heterojunction were successfully formed. Finally, based on the intermediate products, three potential 2,4,6-TCP degradation pathways were proposed.

Thin-wall hollow porous cystic-like graphitic carbon nitride with awakened n→π* electronic transitions and exceptional structural features for superior photocatalytic degradation of sulfamethoxazole.

Effective photoexcitation and carrier migration are the essential aspects to strengthen semiconductor-engaged redox reaction. Herein, a three-dimensional thin-wall hollow porous cystic-like g-C3N4 (HPCN) with curved layer edge was successfully fabricated via a non-template thermal-condensation strategy. The construction of unique distorted structure can evoke the hard-to-activate n→π* electronic transition to some extent, broadening the absorption spectrum to 800 nm. And benefiting from the multiple reflections of incident light, the effective photoactivation can be further achieved. Moreover, the thin-wall porous framework can shorten the diffusion distance and accelerate migration of photogenerated charge, favouring interfacial redox reactions. The optimized HPCN1.0 demonstrated an excellent photocatalytic degradation of SMX under blue-LED light irradiation, which was dramatically superior to that of pristine g-C3N4 (CN, 11.4 times). Ultimately, in consideration of reactions under several influencing factors with four different water samples, we demonstrated that the HPCN photocatalyst could be utilized far more productively for the elimination of SMX under real-world aqueous conditions. This work provides a straightforward approach for the removal of SMX and has immense potential to contribute to global scale environmental remediation.

Facile synthesis of direct Z-scheme UiO-66-NH2/PhC2Cu heterojunction with ultrahigh redox potential for enhanced photocatalytic Cr(VI) reduction and NOR degradation.

Z-scheme heterojunction-based photocatalysts typically have robust removal efficiencies for water contaminants. Herein, we employed p-type PhC2Cu and n-type UiO-66-NH2 to develop a direct Z-scheme UiO-66-NH2/PhC2Cu photocatalyst with an ultrahigh redox potential for Cr(VI) photoreduction and norfloxacin (NOR) photodegradation. Moreover, UV-vis diffuse reflectance, photoelectrochemical measurements, photoluminescence (PL) spectra and electron spin resonance (ESR) technique revealed that the UiO-66-NH2/PhC2Cu composite boosted light capturing capacities to promote photocatalytic efficiencies. Strikingly, the optimized UiO-66-NH2/PhC2Cu50 wt% rapidly reduced Cr(VI) (96.2%, 15 min) and degraded NOR (97.9%, 60 min) under low-power blue LED light. In addition, the UiO-66-NH2/PhC2Cu photocatalyst also exhibited favorable mineralization capacity (78.4%, 120 min). Benefitting from the enhanced interfacial electron transfer and ultrahigh redox potential of the Z-scheme heterojunction, the UiO-66-NH2/PhC2Cu photocatalyst greatly enhanced the separation efficacies of photogenerated carriers. This resulting abundance of active species (e.g., e-, h+, O2•-, and •OH) were generated to photo-reduce Cr(VI) and photo-oxidize NOR. Base on the identified intermediates, four degradation pathways of NOR were proposed. Finally, the Z-scheme mechanism were systematically confirmed through X-ray photoelectron spectroscopy (XPS), ESR, cyclic voltammetry (CV) tests, and photodeposition techniques.

Key role of Fe(VI)-activated Bi2WO6 in the photocatalytic oxidation of sulfonamides: Mediated electron transfer mechanism.

The widespread use of sulfonamides (SAs) in animals and human infections has raised significant concerns regarding their presence in ambient waterways and potential for inducing antimicrobial resistance. Herein, we report on the capacity of ferrate (VI) (FeVIO42-, Fe(VI)) to facilitate the photocatalytic degradation of sulfamethazine (SMT) via bismuth tungstate (Bi2WO6, BWO) under blue LED light (Vis/BWO/Fe(VI)) exposure, at rates that were 45-fold faster than BWO photocatalysis. Both the stepwise and time-series addition of Fe(VI) contributed to the degradation. Multiple lines of evidence confirmed that the common reactive species (RSs) in BWO-based photocatalytic systems and Fe(VI)-involved systems (e.g., •OH/h+, O2•-, 1O2 and Fe(V)/Fe(IV)) played subtle roles in our study system. Herein, for the first time, it was discovered that the precursor complex (BWO-Fe(V)/Fe(IV)* )) was the main contributor to induce electron transfer of SAs through the "conductive bridge" effect of BWO. The studied system was able to effectively degrade SMT in synthetic hydrolyzed urine (SHU) with low interference from background substances in water. This work not only offers a novel facilitation strategy for BWO, but also holds a great application prospect for contamination remediation in urine.

Effective stabilization of atomic hydrogen by Pd nanoparticles for rapid hexavalent chromium reduction and synchronous bisphenol A oxidation during the photoelectrocatalytic process.

Atomic hydrogen (H*) plays a vital role in the synchronous redox of metallic ions and organic molecules. However, H* is extremely unstable as it is easily converted to hydrogen. Herein, we designed a novel strategy for the effective stabilization of H* to enhance its utility. The synthesized Pd nanoparticles grown on the defective MoS2 (DMS) of TiO2 nanowire arrays (TNA) (TNA/DMS/Pd) photocathode exhibited rapid Cr(VI) reduction (~95% in 10 min) and bisphenol A (BPA) oxidation (~97% in 30 min), with the kinetic constants almost 24- and 6-fold higher than those of the TNA photocathode, respectively. This superior performances could be attributed to: (i) the generated interface heterojunctions between TNA and DMS boosted the separation efficiencies of photogenerated electrons, thereby supplying abundant valance electrons to lower the overpotential to create a suitable microenvironment for H* generation; (ii) the stabilization of H* by Pd nanoparticles resulted in a significant increase in the yield of hydroxyl radical (•OH). This research provides a new strategy for the effective utilization of H* toward rapid reduction of heavy metals and synchronous oxidation of the refractory organics.