Interfacial tuning in FeP/ZnIn2S4 Ohm heterojunction: Enhanced photocatalytic hydrogen production via Zn-P charge bridging.

Interfacial regulation is key to photocatalytic performance, yet modulating interfacial charge transfer in heterostructures remains challenging. Herein, a novel nanoflower-like FeP/ZnIn2S4 Ohm heterostructure is first designed, with Zn atoms in ZnIn2S4 (ZIS) acting as potential anchoring sites around P atoms, forming liganded Zn-P bonds. Combining 1D FeP nanowires and 2D ZIS nanosheets enhances the mobility of photogenerated electrons. The synergistic chain-type "electron pickup" mechanism of the Ohm heterojunction coupled with the Zn-P bond speeds up electron transport at the interface. The Ohm heterojunction initiates an internal electric field, creating a driving force to further transfer photogenerated electrons through the Zn-P rapid electron transport channel to FeP, which acts as a reservoir for active sites to release H2. The optimized FeP/ZIS demonstrates a remarkable H2 evolution rate at 4.36 mmol h-1 g-1, 3.6 times that of pristine ZIS. This work provides novel insights into optimizing photocarrier dynamics via interfacial microenvironment modulation.

Converting peracetic acid activation by Fe3O4 from nonradical to radical pathway via the incorporation of L-cysteine.

Recently, peracetic acid (PAA) based Fenton (-like) processes have received much attention in water treatment. However, these processes are limited by the sluggish Fe(III)/Fe(II) redox circulation efficiency. In this study, L-cysteine (L-Cys), an environmentally friendly electron donor, was applied to enhance the Fe3O4/PAA process for the sulfamethoxazole (SMX) abatement. Surprisingly, the L-Cys incorporation was found not only to enhance the SMX degradation rate constant by 3.2 times but also to switch the Fe(IV) dominated nonradical pathway into the •OH dominated radical pathway. Experiment and theoretical calculation result elucidated -NH2, -SH, and -COOH of L-Cys can increase Fe solubilization by binding to the Fe sites of Fe3O4, while -SH of L-Cys can promote the reduction of bounded/dissolved Fe(III). Similar SMX conversion pathways driven by the Fe3O4/PAA process with or without L-Cys were revealed. Excessive L-Cys or PAA, high pH and the coexisting HCO3-/H2PO4- exhibit inhibitory effects on SMX degradation, while Cl- and humic acid barely affect the SMX removal. This work advances the knowledge of the enhanced mechanism insights of L-Cys toward heterogeneous Fenton (-like) processes and provides experimental data for the efficient treatment of sulfonamide antibiotics in the water treatment.

Heterogeneous Fenton-like removal of tri(2-chloroisopropyl) phosphate by ilmenite (FeTiO3): Kinetic, degradation mechanism and toxic assessment.

Tri(2-chloroisopropyl) phosphate (TCPP), a common organophosphate flame retardant, was frequently detected in the environment and posed threats to human health. In this work, the main component of ilmenite FeTiO3 was synthesized by the sol-gel method and employed as the catalyst for the degradation of TCPP by activating persulfate (PS) under UV irradiation. The degradation processes were fitted by the pseudo-first-order kinetic. The kobs value in UV/FeTiO3/PS system was up to 0.0056 min-1 and much higher than that in UV/PS (0.0014 min-1), UV/FeTiO3 (0.0012 min-1) and FeTiO3/PS (0.0016 min-1) systems, demonstrating a distinct synergistic effect in TCPP removal. The degradation efficiency of TCPP increased with the increase of UV intensity, PS concentration and catalyst dosage, and with the decrease of pH. By quenching experiment and EPR analysis, ·OH was confirmed to be the dominant radical in the reaction of the UV/FeTiO3/PS system. The possible degradation pathways of TCPP were dechlorination, dealkylation, and further oxidation of alkyl groups based on the theoretical calculation of frontier molecular orbits. The toxicity of degradation intermediates evaluated by luminescence inhibition rate of photoluminescence was higher than TCPP. Thus, TCPP can be degraded in the UV/FeTiO3/PS system effectively at the premise of introducing controlling measures to reduce the toxicity of degradation intermediates.

Boosting the Quantum Yield of Oxygen-Doped g-C3N4 via a Metal-Azolate Framework-Enhanced Electron-Donating Strategy for Highly Sensitive Sulfadimethoxine Tracing.

Two of the most persistent challenges for the sensing applications of luminescent carbon nitride-based materials are poor quantum yields and aggregation-induced luminescence quenching in aqueous environments. Herein, a highly emissive oxygen-doped carbon nitride composite (OCNP@M7) was synthesized, with a metal-azolate framework (MAF-7) serving as a luminous booster. Both experimental studies and theoretical calculations suggest that the MAF-enhanced electron-donating effect dramatically promoted the electron density on the π-structure of oxygen-doped carbon nitride. In addition, the structural rigidity of MAF-7 effectively inhibits both aggregation and nonradiative energy dissipation. Consequently, OCNP@M7 exhibits strong and stable blue emission under UV light irradiation and an absolute quantum yield up to 95.2%, which is, as far as we know, the highest value among fluorescent carbon nitride materials in solution ever reported. OCNP@M7 could further function as a high-efficiency fluorescent probe for the sensitive detection of sulfadimethoxine residues in complex environments. It is anticipated that this strategy can be extended to fabricate various carbon nitride-based antibiotic monitoring systems with tailor-made functions.

Microplastics can selectively enrich intracellular and extracellular antibiotic resistant genes and shape different microbial communities in aquatic systems.

Microplastics (MPs), as emerging contaminants, are posing potential risks to environment, and animal and human health. The ubiquitous presence of MPs in natural ecosystems provides favorable platform to selectively adsorb antibiotic resistant genes (ARGs) and bacteria (ARB) and bacterial assemblages, especially in wastewater which is hotspot for MPs, ARGs and ARB. In this study, the selective capture of intracellular ARGs (iARGs), extracellular ARGs (eARGs), and bacterial assemblages by MPs with different materials (i.e. polyethylene, polyvinylchloride, and polyethylene terephthalate) and sizes (200 µm and 100 µm) was investigated. The results showed that iARGs (i.e. i-TetA, i-TetC, i-TetO, i-sul1), integron-integrase gene (intI1), and eARGs (i.e. e-TetA and e-blaTEM) were selectively enriched on MPs. Relative abundances of i-sul1, i-TetA, and intI1 were generally higher than that of i-TetC and i-TetO on all MPs. Moreover, MPs also have strong effects on the formation of microflora in wastewater, which resulted in different bacterial communities and functions in the wastewater and on the MPs. These findings suggested that MPs could affect the selective enrichment of ARB and ARGs in water environment.

Perylene diimide supermolecule (PDI) as a novel and highly efficient cocatalyst for photocatalytic degradation of tetracycline in water: A case study of PDI decorated graphitic carbon nitride/bismuth tungstate composite.

Employing perylene diimide supermolecule (PDI) as metal-free cocatalyst, a novel PDI/g-C3N4/Bi2WO6 (PCB) photocatalyst was constructed for the effective degradation of antibiotics. Both the photocatalytic activity and photostability of g-C3N4/Bi2WO6 (gCB) were further improved after loading PDI. Under simulated sunlight illumination, the apparent rate constant of tetracycline (TC) degradation by PCB reached 2.6 times that of gCB. The photocatalytic activity of PCB still kept over 80% after 4 cycle experiments, while gCB only remained around 21%. The superior activity of PCB was ascribed to the synergism between the extended visible light absorption range through the participation of PDI cocatalyst and facilitated gCB-to-PDI photoelectron transfer. TC would finally be transformed into non-toxic ring opening products and mineralized. This work demonstrated that PDI was an excellent metal-free cocatalyst and exhibited great potential to boost the activity of photocatalysts.

Enhanced directional quantum emission by tunable topological doubly resonant cavities.

How to utilize topological microcavities to control quantum emission is one of the ongoing research topics in the optical community. In this work, we investigate the emission of quantum emitters in a doubly-resonant topological Tamm microcavity, which can simultaneously achieve dual resonances at two arbitrary wavelengths according to the needs of practical application. To achieve the enhancement of quantum emission in such cavities, we have exploited the tunable doubly-resonant modes, in which one of resonant modes corresponds to the pump laser wavelength and the other one is located at the emission wavelength of quantum emitters. Both theoretical and experimental results demonstrate that the pump excitation and emission efficiencies of quantum emitters are greatly enhanced. The main physical mechanism can be explained by the doubly-resonant cavity temporal coupled-mode theory. Furthermore, we observe the faster emission rate and the higher efficiency of unidirectional quantum emission, which have promising applications in optical detection, sensing, filtering, and light-emitting devices.

Salt-resistant nanosensor for fast sulfadimethoxine tracing based on oxygen-doped g-C3N4 nanoplates.

A novel oxygen-doped g-C3N4 nanoplate (OCNP) structure that can serve as an efficient sulfadimethoxine (SDM) sensing platform has been developed. Taking advantage of its inherent oxygen-containing functional groups and 2D layered structure with π-conjugated system, OCNP exhibits effective radiative recombination of surface-confined electron-hole pairs and efficient π-π interaction with SDM. This causes rapid fluorescence response and thus ensures the fast and continuous monitoring of SDM. Based on the fluorescence experiments and band structure calculation, the mechanism of the SDM-induced quenching phenomenon was mainly elucidated as the photoinduced electron transfer process under a dynamic quenching mode. Under optimized conditions, the as-proposed nanosensor, which emitted strong fluorescence at 375 nm with an excitation wavelength at 255 nm, presents an excellent analytical performance toward SDM with a wide linear range from 3 to 60 µmol L-1 and a detection limit of 0.85 µmol L-1 (S/N = 3). In addition, this strategy exhibits satisfactory recovery varied from 94 to 103% with relative standard derivations (RSD) in the range 0.9 to 6.8% in real water samples. It also shows marked tolerability to a series of high concentrations of metals and inorganic salts. This strategy not only broadens the application of oxygen-doped g-C3N4 nanomaterial in antibiotic sensing field but also presents a promising potential for on-line contaminant tracing in complex environments.

Review on application of perylene diimide (PDI)-based materials in environment: Pollutant detection and degradation.

Environment pollution is getting serious and various poisonous contaminants with chemical durability, biotoxicity and bioaccumulation have been widespreadly discovered in municipal wastewaters and surface water. The detection and removal of pollutants show great significance for the protection of human health and other organisms. Due to its distinctive physical and chemical properties, perylene diimide (PDI) has received widespread attention from different research fields, especially in the area of environment. In this review, a comprehensive summary of the development of PDI-based materials in fluorescence detection and advanced oxidation technology for environment was introduced. Firstly, we chiefly presented the recent progress about the synthesis of PDI and PDI-based nanomaterials. Then, their application in fluorescence detection for environment was presented and categorized, principally including the detection of heavy metal ions, harmful anions and organic contaminants in the environment. In addition, the application of PDI and PDI-based materials in different advanced oxidation technologies for environment, such as photocatalysis, photoelectrocatalysis, Fenton and Fenton-like reaction and persulfate activation, was also summarized. At last, the challenges and future prospects of PDI-based materials in environmental applications were discussed. This review focuses on presenting the practical applications of PDI and PDI-based materials as fluorescent probes or catalysts (especially photocatalysts) in the detection of hazardous substances or catalytic elimination of organic contaminants. The contents are aimed at supplying the researchers with a deeper understanding of PDI and PDI-based materials and encouraging their further development in environmental applications.

Monoclinic dibismuth tetraoxide (m-Bi2O4) for piezocatalysis: new use for neglected materials.

Piezocatalysis is a promising approach for environmental pollutant removal. Monoclinic dibismuth tetraoxide (m-Bi2O4) was first applied to piezocatalyze organics under ultrasonic vibration. The built-in electric field with ultrasonic stress drives the separation of holes and electrons in m-Bi2O4. Its excellent piezocatalytic activity, reusability and chemical stability make m-Bi2O4 a new candidate of piezocatalysis.

Synthesis and application of magnetic materials-barium ferrite nanomaterial as an effective microwave catalyst for degradation of brilliant green.

In this work, magnetic separably barium ferrite nanomaterial (BaFeO) was synthesized via citrate acid assisted sol-gel combustion method. Subsequently, X-ray diffraction (XRD), scanning electron microscopy-energy dispersion spectroscopy (SEM-EDS), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM) were applied for its structural, morphological, and electromagnetic characterization. In addition, microwave (MW) absorption and thermal conversion test results indicated the BaFeO had electrothermal rather than magnetothermal conversion capacity. Meanwhile, the synthesized BaFeO showed satisfactory performance in both eliminating and mineralization of a typical triphenylmethane dye, brilliant green (BG), in MW-induced catalytic oxidation (MICO) process without extra oxidant addition. Besides, changes in element valence and content of BaFeO before and after MICO process investigated with XRD, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) showed its relatively stable properties. Furthermore, transition oxygen species involved in MICO process was deduced as lattice oxygen species. Then, the possible degradation pathway of BG was proposed as demethylation, open-loop of triphenylmethane, releasing one ring, formation of the benzene ring and the ultimate mineralization based on the degradation intermediates tentatively identified by gas chromatography mass spectrometry (GC/MS) and liquid chromatography mass spectrometry (LC/MS), respectively. Finally, ecotoxicity analysis by ecological structure activity relationships (ECOSAR) showed that both the acute and chronic toxicity of these intermediates were lower than that of parent BG. These findings are important regarding the development of efficient catalysts in MICO process for degradation of BG analogues in wastewater.

Highly efficient degradation of iohexol on a heterostructured graphene-analogue boron nitride coupled Bi2MoO6 photocatalyst under simulated sunlight.

Iohexol (IOH), as a typical iodinated X-ray contrast media (ICMs) with potential threat to human health, is difficult to be removed with the conventional wastewater treatment methods. In this work, new boron nitride coupled Bi2MoO6 layered microspheres (BN/Bi2MoO6) composites were applied to remove IOH from water via photocatalytic degradation. The degradation constant kapp of IOH over 3.5 wt% BN/Bi2MoO6 was 0.016 min-1, which was 3.2 times that of Bi2MoO6 (0.005 min-1). The degradation rate of IOH on 3.5 wt% BN/Bi2MoO6 reached 92% in 150 min. The enhanced photocatalytic activity of BN/Bi2MoO6 can be attributed to the heterojunction between BN and Bi2MoO6. The matched type-I band alignment heterojunction of two semiconductors prominently improved the charge separation. Based on the trapping experiments, holes and superoxide radicals were proved to be the main active species for photocatalytic IOH degradation. Besides, the degradation products of IOH were analyzed by LC-HRMS and the possible degradation mechanism of IOH was also proposed in this work.

Enhancing the performance of pollution degradation through secondary self-assembled composite supramolecular heterojunction photocatalyst BiOCl/PDI under visible light irradiation.

A novel n-n type inorganic/organic heterojunction of flaky-like BiOCl/PDI photocatalyst was constructed by water bath heating method. Meanwhile, a simple method - secondary self-assembly was used to prepare the BiOCl/PDI with a special band structure. The photocatalytic activities were evaluated by degrading aqueous organic pollutants under visible light (λ > 420 nm). The removal rates of 5 mg L-1 phenol (non-ionic type), methyl orange (MO, anionic type), rhodamine B (RhB, cationic type) and 10 mg L-1 RhB by secondary self-assembly BiOCl/PDI (BiOCl/PDI-2) were 8.0%, 3.4%, 27.8% and 78.9% higher than self-assembly BiOCl/PDI (BiOCl/PDI-1) under visible light (λ > 420 nm). The better photocatalytic activity for BiOCl/PDI-2 was attributed to the optimization of energy-band structures, which arose from different exposed surfaces, narrower interplanar spacing and stronger visible light absorption performance. Under acidic condition, BiOCl/PDI-2 showed a good photocatalytic activity, which was not affected by neutral ionic intensity and had good recycling properties. Moreover, the photocatalytic mechanism was explored by free radical capture test and electron paramagnetic resonance (EPR), and contribution of active species was calculated. The main active species of BiOCl/PDI-2 were ·O2-, 1O2 and h+. Our work may provide a route to design efficient inorganic/organic heterojunctions for organic pollutants degradation.

Bismuth Subcarbonate with Designer Defects for Broad-Spectrum Photocatalytic Nitrogen Fixation.

A facial hydrothermal method is applied to synthesize bismuth subcarbonate (Bi2O2CO3, BOC) with controllable defect density (named BOC- X) using sodium bismuthate (NaBiO3) and graphitic carbon nitride (GCN) as precursors. The defects of BOC- X may originate from the extremely slow decomposition of GCN during the hydrothermal process. The BOC- X with optimal defect density shows a photocatalytic nitrogen fixation amount of 957 µmol L-1 under simulated sunlight irradiation within 4 h, which is 9.4 times as high as that of pristine BOC. This superior photocatalytic performance of BOC- X is attributed to the surface defect sites. These defects in BOC- X contribute to a defect level in the forbidden band, which extends the light-harvest region of the photocatalyst from the ultraviolet to the visible-light region. Besides, surface defects prevent electron-hole recombination by accommodating photogenerated electrons in the defect level to promote the separation efficiency of charge carrier pairs. This work not only demonstrates a novel and scalable strategy to synthesize defective Bi2O2CO3 but also presents a new perspective for the synthesis of photocatalysts with controllable defect density.

Macroscopic urea-functionalized cadmium sulfide material with high visible-light photocatalytic activity for rewritable paper application.

A macroscopic urea-functionalized CdS (CdS-U) is synthesized for the first time. The CdS-U material is formed through the interaction between NH2/NH groups on urea and COO- groups on sodium oleate-capped CdS nanoparticles (CdS-So NPs). The CdS-U material exhibites excellent visible light photocatalytic activity and plasticity and has the potential to be produced as rewritable papers. It is convenience to produce a large-scale film by CdS-U. Letters can be written on the CdS-U film and disappear through a dissolution-irradiation process, and then the CdS-U film can be recycled by drying. This novel CdS-U material might be of interest and provide a new chance to advance the application of visible light photocatalyst on rewritable papers.

Inguinal and subinguinal micro-varicocelectomy, the optimal surgical management of varicocele: a meta-analysis.

Conventional meta-analyses have shown inconsistent results for the efficacy of various treatments of varicoceles. Therefore, we performed a multiple-treatment meta-analysis to assess the effectiveness and safety of 10 methods of varicocelectomy and embolization/sclerotherapy. We systematically reviewed 35 randomized controlled trials and observational studies, from 1966 to August 5, 2013, which compared any of the following treatments for varococeles: laparoscopic, retroperitoneal, open inguinal and subinguinal varicocelectomy, microsurgical subinguinal and inguinal varicocelectomy, percutaneous venous embolization, Tauber antegrade sclerotherapy, retrograde sclerotherapy and expectant therapy (no treatment). Inguinal and subinguinal microsurgery, open inguinal, laparoscopic varicocelectomy showed a significant advantage over expectant therapy in terms of pregnancy rates (odds ratio (OR): 3.48, 2.68, 2.92 and 2.90, respectively). Compared with retroperitoneal open surgery, inguinal microsurgery showed an improvement of sperm density (mean difference (MD): 10.60, 95% confidence interval (CI): 1.92-19.60) and sperm motility (MD: 9.09, 95% CI: 4.88-13.30). Subinguinal and inguinal microsurgery outperformed retroperitoneal open surgery in terms of recurrence (OR: 0.05, 0.06 respectively). Tauber antegrade sclerotherapy and subinguinal microsurgery were associated with the lowest risk of hydrocele formation. The odds of overall complication, compared with retroperitoneal open varicocelectomy, were lowest for inguinal microsurgery (OR = 0.07, 95% CI: 0.02-0.19), followed by subinguinal microsurgery (OR = 0.09, 95% CI: 0.02-0.19). Inguinal and subinguinal micro-varicocelectomy had the highest pregnancy rates, significant increases in sperm parameters, with low odds of complication. These results warrant additional properly conducted randomized controlled clinical studies with larger sample sizes.

Effects of preimplantation embryos on expressions of DNA methyltransferase 1 in mouse oviduct epithelial cells.

OBJECTIVE: To investigate the effects of mouse preimplantation embryos on the expressions of DNA methyltransferase 1(Dnmt1) of mouse oviduct epithelial cells. METHODS: The histological location of Dnmt1 protein was detected by immunohistochemical staining and the expression levels of Dnmt1 mRNA and protein in mouse oviduct were assayed by real-time reverse transcription-PCR(RT-PCR) and Western blotting in both pregnant and pseudopregnant mice at the 2-cell, 4-cell and 8-cell stages. RESULTS: The expressions of Dnmt1 protein were mainly located in the epithelial cells of mouse oviduct. It was found that during all three stages, the expression levels of Dnmt1 mRNA in the epithelial cells of the pregnant mice were significantly lower than those in the pseudopregnant mice (P< 0.05), and the level of Dnmt1 protein expression in the pregnant mice was significantly decreased as compared with that in pseudopregnant mice at the 4-cell stage. CONCLUSION: Expressions of both Dnmt1 mRNA and protein in the epithelial cells of mouse oviduct could be regulated by mouse preimplantation embryos, which might play an important role in the expression changes of some genes in oviduct epithelial cells during the preimplantation period.