Anthocyanins from blueberry ameliorated arsenic-induced memory impairment, oxidative stress, and mitochondrial-biosynthesis imbalance in rat hippocampal neurons.

In this study, blueberry anthocyanins extract (BAE) was used to investigate its protective effect on arsenic-induced rat hippocampal neurons damage. Arsenic exposure resulted in elevated levels of oxidative stress, decreased antioxidant capacity and increased apoptosis in rat hippocampal brain tissue and mitochondria. Immunohistochemical results showed that arsenic exposure also significantly decreased the expression of mitochondrial biosynthesis-related factors PGC-1α and TFAM. Treatment with BAE alleviated the decrease in antioxidant capacity, mitochondrial biogenesis related protein PGC-1α/NRF2/TFAM expression, and ATP production of arsenic induced hippocampal neurons in rats, and improved cognitive function in arsenic damaged rats. This study provides new insights into the detoxification effect of anthocyanins on the nervous system toxicity caused by metal exposure in the environment, indicating that anthocyanins may be a natural antioxidant against the nervous system toxicity caused by environmental metal exposure.

Intensifying Photocatalytic Baeyer-Villiger Oxidation of Ketones with the Introduction of Ru Metalloligands and Bimetallic Units in POM@MOF.

The synthesis of visible light-responsive and efficient photocatalysts toward green Baeyer-Villiger oxidation organic synthesis is of extraordinary significance. In this work, we have synthesized two examples of visible light responsive crystalline polyoxometalate@metal-organic framework materials Ru-NiMo and Ru-CoMo by introducing Ru metalloligands and {CdM3O12} bimetallic units (M = Ni or Co). This is the first report of metalloligand-modified polyoxometalate@metal-organic framework materials with bimetallic nodes, and the materials form a three-dimensional framework directly through coordination bonds between {CdM3O12} bimetallic units and metalloligands. In particular, Ru-NiMo can achieve efficient photocatalytic conversion of cyclohexanone to ε-caprolactone in yields as high as 95.5% under visible light excitation in the range of λ > 400 nm, achieving a turnover number and turnover frequency of 955 and 440 h-1, respectively, which are the best known photocatalysts for Baeyer-Villiger oxidation, while apparent quantum yield measured at 485 nm is 4.4%. Moreover, Ru-NiMo exhibited excellent structural stability and recyclability, producing a 90.8% yield after five cycles of recycling.

Feedback regulation of the isoprenoid pathway by SsdTPS overexpression has the potential to enhance plant tolerance to drought stress.

In order to maintain the dynamic physiological balance, plants are compelled to adjust their energy metabolism and signal transduction to cope with the abiotic stresses caused by complex and changeable environments. The diterpenoid natural compound and secondary metabolites, sclareol, derived from Salvia sclarea, has gained significant attention owing to its economic value as a spice material and diverse physiological activities. Here, we focused on the roles and regulatory mechanisms of the sclareol diterpene synthase gene SsdTPS in the resistance of S. sclarea to abiotic stresses. Our results suggested that abiotic stresses could induce the response and upregulation of SsdTPS expression and isoprenoid pathway in S. sclarea. Ectopic expression of SsdTPS conferred drought tolerance in transgenic Arabidopsis, compared with wild-type. Overexpression of SsdTPS enhanced the transcription of ABA signal transduction synthetic regulators and induced the positive feedback upregulating key regulatory genes in the MEP pathway, thereby promoting the increase of ABA content and improving drought tolerance in transgenic plants. In addition, SsdTPS-overexpressed transgenic Arabidopsis improved the responses of stomatal regulatory genes and ROS scavenging enzyme activities and gene expression to drought stress. This promoted the stomatal closure and ROS reduction, thus enhancing water retention capacity and reducing oxidative stress damage. These findings unveil the potentially positive role of SsdTPS in orchestrating multiple regulatory mechanisms and maintaining homeostasis for improved abiotic stress resistance in S. sclarea, providing a novel insight into strategies for promoting drought resistance and cultivating highly tolerant plants.

Integrated Transcriptome and Proteome Analysis Reveals the Regulatory Mechanism of Root Growth by Protein Disulfide Isomerase in Arabidopsis.

Protein disulfide isomerase (PDI, EC 5.3.4.1) is a thiol-disulfide oxidoreductase that plays a crucial role in catalyzing the oxidation and rearrangement of disulfides in substrate proteins. In plants, PDI is primarily involved in regulating seed germination and development, facilitating the oxidative folding of storage proteins in the endosperm, and also contributing to the formation of pollen. However, the role of PDI in root growth has not been previously studied. This research investigated the impact of PDI gene deficiency in plants by using 16F16 [2-(2-Chloroacetyl)-2,3,4,9-tetrahydro-1-methyl-1H-pyrido[3,4-b]indole-1-carboxylic acid methyl ester], a small-molecule inhibitor of PDI, to remove functional redundancy. The results showed that the growth of Arabidopsis roots was significantly inhibited when treated with 16F16. To further investigate the effects of 16F16 treatment, we conducted expression profiling of treated roots using RNA sequencing and a Tandem Mass Tag (TMT)-based quantitative proteomics approach at both the transcriptomic and proteomic levels. Our analysis revealed 994 differentially expressed genes (DEGs) at the transcript level, which were predominantly enriched in pathways associated with "phenylpropane biosynthesis", "plant hormone signal transduction", "plant-pathogen interaction" and "starch and sucrose metabolism" pathways. Additionally, we identified 120 differentially expressed proteins (DEPs) at the protein level. These proteins were mainly enriched in pathways such as "phenylpropanoid biosynthesis", "photosynthesis", "biosynthesis of various plant secondary metabolites", and "biosynthesis of secondary metabolites" pathways. The comprehensive transcriptome and proteome analyses revealed a regulatory network for root shortening in Arabidopsis seedlings under 16F16 treatment, mainly involving phenylpropane biosynthesis and plant hormone signal transduction pathways. This study enhances our understanding of the significant role of PDIs in Arabidopsis root growth and provides insights into the regulatory mechanisms of root shortening following 16F16 treatment.

Impact of SUSAN Denoising and ComBat Harmonization on Machine Learning Model Performance for Malignant Brain Neoplasms.

BACKGROUND AND PURPOSE: Feature variability in radiomics studies due to technical and magnet strength parameters is well known and may be addressed through various pre-processing methods. However, very few studies have evaluated downstream impact of variable pre-processing on model classification performance in a multi-class setting. We sought to evaluate the impact of SUSAN denoising and ComBat harmonization on model classification performance. MATERIALS AND METHODS: A total of 493 cases (410 internal and 83 external dataset) of glioblastoma (GB), intracranial metastatic disease (IMD) and primary CNS lymphoma (PCNSL) underwent semi-automated 3D-segmentation post baseline image processing (BIP) consisting of resampling, realignment, co-registration, skull stripping and image normalization. Post BIP, two sets were generated, one with and another without SUSAN denoising (SD). Radiomics features were extracted from both datasets and batch corrected to produce four datasets: (a) BIP, (b) BIP with SD, (c) BIP with ComBat and (d) BIP with both SD and ComBat harmonization. Performance was then summarized for models using a combination of six feature selection techniques and six machine learning models across four mask-sequence combinations with features derived from one-three (multi-parametric) MRI sequences. RESULTS: Most top performing models on the external test set used BIP+SD derived features. Overall, use of SD and ComBat harmonization led to a slight but generally consistent improvement in model performance on the external test set. CONCLUSIONS: The use of image pre-processing steps such as SD and ComBat harmonization may be more useful in a multiinstitutional setting and improve model generalizability. Models derived from only T1-CE images showed comparable performance to models derived from multiparametric MRI.

[Development of Wireless Wearable Sleep Monitoring System Based on EEG Signal].

A wireless wearable sleep monitoring system based on EEG signals is developed. The collected EEG signals are wirelessly sent to the PC or mobile phone Bluetooth APP for real-time display. The system is small in size, low in power consumption, and light in weight. It can be worn on the patient's forehead and is comfortable. It can be applied to home sleep monitoring scenarios and has good application value. The key performance indicators of the system are compared with the industry-related medical device measurement standards, and the measurement results are better than the special standards.

[Research Progress on End-Tidal Carbon Dioxide Detection Technology Based on Non-Dispersive Infrared Method].

The concentration of end-tidal carbon dioxide is one of the important indicators for evaluating whether the human respiratory system is normal. Accurately detecting of end-tidal carbon dioxide is of great significance in clinical practice. With the continuous promotion of the localization of end-tidal carbon dioxide monitoring technology, its application in clinical practice in China has become increasingly widespread in recent years. The study is based on the non-dispersive infrared method and comprehensively elaborates on the detection principle, gas sampling methods, key technologies, and technological progress of end-tidal carbon dioxide detection technology. It comprehensively introduces the current development status of this technology and provides reference for application promotion and further improvement.

A rhodium-catalyzed cascade C-H activation/annulation strategy for the expeditious assembly of pyrrolidinedione-fused 1,2-benzothiazines.

A cascade annulation strategy triggered by rhodium(III)-catalyzed C-H activation has been reported for the expeditious assembly of pyrrolidinedione-fused 1,2-benzothiazines from free NH-sulfoximines with maleimides under mild conditions. Without the need for inert atmosphere protection, a broad range of sulfoximines with maleimides were well tolerated, producing diverse fused-thiazine derivatives in moderate to good yields. Additionally, the late-stage transformation of the target product demonstrated the potential synthetic value of this protocol.

Genetic linkage map construction and QTL analysis for plant height in proso millet (Panicum miliaceum L.).

KEY MESSAGE: A genetic linkage map representing proso millet genome was constructed with SSR markers, and a major QTL corresponding to plant height was mapped on chromosome 14 of this map. Proso millet (Panicum miliaceum L.) has the lowest water requirements of all cultivated cereal crops. However, the lack of a genetic map and the paucity of genomic resources for this species have limited the utility of proso millet for detailed genetic studies and hampered genetic improvement programs. In this study, 97,317 simple sequence repeat (SSR) markers were developed based on the genome sequence of the proso millet landrace Longmi 4. Using some of these markers in conjunction with previously identified SSRs, an SSR-based linkage map for proso millet was successfully constructed using a large mapping population (316 F2 offspring). In total, 186 SSR markers were assigned to 18 linkage groups corresponding to the haploid chromosomes. The constructed map had a total length of 3033.42 centimorgan (cM) covering 78.17% of the assembled reference genome. The length of the 18 linkage groups ranged from 88.89 cM (Chr. 15) to 274.82 cM (Chr. 16), with an average size of 168.17 cM. To our knowledge, this is the first genetic linkage map for proso millet based on SSR markers. Plant height is one of the most important traits in crop improvement. A major QTL was repeatedly detected in different environments, explaining 8.70-24.50% of the plant height variations. A candidate gene affecting auxin biosynthesis and transport, and ROS homeostasis regulation was predicted. Thus, the linkage map and QTL analysis provided herein will promote the development of gene mining and molecular breeding in proso millet.

Photocatalytic Reduction of Nitrobenzene to Aniline by an Intriguing {Ru(C6H6)}-Based Heteropolytungstate.

In this paper, we have successfully synthesized a structurally novel heteropolytungstate via coordination of four {Ru(C6H6)} and trivacant {TeW9O33} clusters, formulated as Cs4Na2H2[Te2W20O72(H2O){(C6H6)Ru}4]·12H2O (1). Compound 1 inherited the strong absorption of [Ru(C6H6)Cl2]2 in the visible region and {TeW9O33} in the UV region, providing a good basis for photocatalysis. As expected, compound 1 showed good photocatalytic activity in the visible-light-driven reduction of nitrobenzene using N2H4·H2O as a reductant with a yield of 99.8%, a high turnover number (TON = 330), and a high turnover frequency (TOF = 24 h-1). The cyclic experiment of nitrobenzene reduction indicated that compound 1 was an effective and stable heterogeneous catalyst. Finally, the nitrobenzene reduction pathway was affirmed using condensation with azobenzene as a reaction intermediate based on control experiments.

Ginsenosides from Panax ginseng as potential therapeutic candidates for the treatment of inflammatory bowel disease.

BACKGROUND: Inflammatory bowel disease (IBD) is characterized by a chronic inflammation of the intestine, which significantly affects patients' quality of life. As a perennial plant with the homology of medicine and food, Panax ginseng is known for its substantial anti-inflammatory effects in various inflammatory disorders. Ginsenosides, the main bioactive compounds of P. ginseng, are recognized for their efficacy in ameliorating inflammation. PURPOSE: Over the past decade, approximately 150 studies have investigated the effects of P. ginseng and ginsenosides on IBD treatment and new issues have arisen. However, there has yet to be a comprehensive review assessing the potential roles of ginsenosides in IBD therapy. METHOD: This manuscript strictly adheres to the PRISMA guidelines, thereby guaranteeing systematic synthesis of data. The research articles referenced were sourced from major scientific databases, including Google Scholar, PubMed, and Web of Science. The search strategy employed keywords such as "ginsenoside", "IBD", "colitis", "UC", "inflammation", "gut microbiota", and "intestinal barrier". For image creation, Figdraw 2.0 was methodically employed. RESULTS: Treatment with various ginsenosides markedly alleviated clinical IBD symptoms. These compounds have been observed to restore intestinal epithelia, modulate cellular immunity, regulate gut microbiota, and suppress inflammatory signaling pathways. CONCLUSION: An increasing body of research supports the potential of ginsenosides in treating IBD. Ginsenosides have emerged as promising therapeutic agents for IBD, attributed to their remarkable efficacy, safety, and absence of side effects. Nevertheless, their limited bioavailability presents a substantial challenge. Thus, efforts to enhance the bioavailability of ginsenosides represent a crucial and promising direction for future IBD research.

Responses and resistance capacity of Solanum nigrum L. mediated by three ecological category earthworms in metal-[Cd-As-Cu-Pb]-contaminated soils of North China.

Earthworms play vital functions affecting plant growth and metal accumulation from downground to aboveground. Soil metal mobilization may be combined with use of earthworm and hyperaccumulator-Solanum nigrum to improve its remediation efficiency. Understanding the effects of specific-species earthworm belonging to different ecological categories on mechanisms underlying of S. nigrum is critical for metal-polluted remediation. However, seldom studies concerned earthworm-assisted phytoremediation of metal contaminated soil in Northern China. This study investigated the effects of earthworm (Eisenia fetida, Amynthas hupeiensis and Drawida gisti) on S. nigrum with exposure to uncontaminated and [Cd-As-Cu-Pb]-contaminated soil (referred to as S0 and S1) for 60 days, respectively. In S1 soil, A. hupeiensis (anecic) had stronger effects on growth and metal accumulation in the organs (root, stem, and leaf) of S. nigrum than D. gisti (endogeic) and E. fetida (epigeic), attributing to their ecological category. The BAF values of S. nigrum were generally ranking in Cd (0.66-5.13) > As (0.03-1.85) > Cu (0.03-0.06) > Pb (0.01-0.05); the BAFCd values were ranking in leaf (2.34-5.13) > root (1.96-4.14) > stem (0.66-1.33); BAFAs, BAFCu, and BAFPb were root (0.04-1.63) > stem (0.01-0.09) ≈ leaf (0.01-0.06). A. hupeiensis decreased the TF values of S. nigrum from the roots to the shoots. Co-effects of metal stress and earthworm activity on metal uptake by shoots suggested that A. hupeiensis increased the uptake of As, Cu, and Pb (by 56.3 %, 51.5 %, and 16.2 %, p < 0.05), but not Cd, which appeared to remain steady for prolonged durations. Alterations in the integrated biomarker response index version 2 (IBRv2) values demonstrated that A. hupeiensis (12.65) improved the resistance capacity (stimulated GSH, SnGS1, and SnCu-SOD) of S. nigrum under metal-containing conditions, compared with E. fetida and D. gisti (IBRv2 were 9.61 and 9.11). This study may provide insights into the patterns of 'soil-earthworm-plant system' on improving remediation efficiency of S. nigrum, from the perspective of earthworm ecological niche partitioning.

Effects of solution chemistry on dielectric barrier atmospheric non-thermal plasma for operative degradation of antiretroviral drug nevirapine.

The global prevalence of human immunodeficiency virus/acquired immunodeficiency syndrome (HIV/AIDS) has been an environmental menace. Tons of drug wastes from antiretroviral therapy are released into the environment annually. We, for the first time, employed the novel dielectric barrier atmospheric non-thermal plasma (DBANP) discharge, to mitigate the inadvertent pollution arising from the antiretroviral therapy. A 40-min treatment of nevirapine achieved >94 % (0.075 min-1) removal efficiency at discharge power of 63.5 W and plasma working gas of atmospheric air. Chemical probes confirmed •OH, ONOO- and eaq- as the dominant reactive species whilst further revealing the reaction acceleration role of NaNO3 and CCl4 which are known reaction terminators. The commonly coexisting inorganic anions potentiated nevirapine removal with over 98 % efficiency, achieving the highest rate constant of 0.148 min-1 in this study. Moreover, the initial solution pH (1.5-11.1) was no limiting factor either. The insensitivity of the DBANP discharge to actual water matrices was an eminent inference of its potential applicability in practical conditions. With reference to data obtained from the liquid chromatography-mass spectrometer analysis, nevirapine degradation pathway was proposed. A nucleophilic attack by ONOO- at the cyclopropyl group and •OH attack at the carbonyl carbon of the amide group, respectively, initiated nevirapine degradation process. It is anticipated that the findings herein, will provide new insights into antiretroviral drug waste management in environmental waters using the innovative and green non-thermal plasma process.

Green Nanopesticide: pH Response and Molybdenum Selenide Carrier with Photothermal Effect to Transport Prochloraz to Inhibit Sclerotinia Disease.

Accurate pesticide delivery is a key factor in improving pesticide utilization, which can effectively reduce the use of pesticides and environmental risks. In this study, we developed a nanocarrier preparation method which can be controlled by pH/near-infrared response. Mesoporous molybdenum selenide (MoSe2) with a high loading rate was used as the core, poly(acrylic acid) (PAA) with acid response was used as the shell, and prochloraz (Pro) was loaded to form a pH-/near-infrared-responsive core-shell nanosystem (Pro@MoSe2@PAA NPs, abbreviated as PMP). Sclerotinia sclerotiorum infection secretes oxalic acid, forming an acidic microenvironment. In an acidic environment, PMP could quickly release Pro, and the cumulative release amount of Pro at pH = 5.0 was 3.1 times higher than that at pH = 7.4, and the efficiency of releasing Pro in the acidic environment was significantly enhanced. In addition, the release rate of PMP under near-infrared light irradiation was also significantly improved, and the cumulative release of Pro under simulated sunlight was 2.35 times higher than that under no light. The contact angles of PMP droplets on rapeseeds were reduced by 31.2 and 13.9% compared to Pro and MoSe2, respectively, which proved that the nanosystems had good wettability. In addition, PMP shows excellent adhesion and resistance to simulated rain washout. In the plate antibacterial experiment, the inhibitory effect of 0.5 µg/mL PMP on S. sclerotiorum was as high as 75.2% after 6 days, which showed a higher bactericidal activity than Pro. More importantly, PMP shows excellent biocompatibility and safety to plants, microorganisms, and cells. In a word, PMP is a green nanopesticide with a dual response of pH/near-infrared light, which provides a new strategy for the sustainable development of agriculture.

Plant Growth-Promoting Rhizobacteria Are Key to Promoting the Growth and Furanocoumarin Synthesis of Angelica dahurica var. formosana under Low-Nitrogen Conditions.

Microbiomes are the most important members involved in the regulation of soil nitrogen metabolism. Beneficial interactions between plants and microbiomes contribute to improving the nitrogen utilization efficiency. In this study, we investigated the Apiaceae medicinal plant Angelica dahurica var. formosana. We found that under a low-nitrogen treatment, the abundance of carbon metabolites in the rhizosphere secretions of A. dahurica var. formosana significantly increased, thereby promoting the ratio of C to N in rhizosphere and nonrhizosphere soils, increasing carbon sequestration, and shaping the microbial community composition, thus promoting a higher yield and furanocoumarin synthesis. Confirmation through the construction of a synthetic microbial community and feedback experiments indicated that beneficial plant growth-promoting rhizobacteria play a crucial role in improving nitrogen utilization efficiency and selectively regulating the synthesis of target furanocoumarins under low nitrogen conditions. These findings may contribute additional theoretical evidence for understanding the mechanisms of interaction between medicinal plants and rhizosphere microorganisms.

Decreased transport of nano- and micro-plastics in the presence of low-molecular-weight organic acids in saturated quartz sand.

Low-molecular-weight organic acids (LMWOAs) and nano- and micro-plastics (NPs and MPs) are both widely distributed in terrestrial systems. To better understand the influence of LMWOAs on the transport of NPs and MPs, the effects of 0.5 mM citric- (CA), malic- (MA), and tartaric- (TA) acid on the transport of nano- (0.51 µm, PS NPs) and micro- (1.1 µm, PS MPs) polystyrene particles (2 mg L-1) in saturated quartz sand were investigated. All three LMWOAs decreased the transport of PS NPs and MPs, regardless of ionic composition or strength (0.1-10 mM NaCl and 0.1-1 mM CaCl2). Further investigation revealed that the interfacial interactions between PS-quartz sand surfaces and PS-PS were altered by LMWOAs. LMWOAs adsorbed to quartz sand surfaces could serve as new deposition sites, as evidenced by the decreased transport of PS NPs and MPs in quartz sand that was subjected to pre-equilibration with selected MA, the low inhibition of PS transport with low concentrations of LMWOAs (0.1 mM), and also the adsorption of LMWOAs onto quartz sand surfaces by batch experiments. Meanwhile, the adsorption of LMWOAs on PS, hydrodynamic measurement and visual TEM observation together clarified the slight aggregation of PS NPs and MPs in suspensions, inducing the subsequent decrease in transport. Among them, the adsorption of LMWOAs onto quartz sand surfaces was found to be the main factor dominating the decreased transport of both PS NPs and MPs in saturated quartz sand.

Effects of Land Use Type Transformation on the Structure and Diversity of Soil Bacterial Communities.

Soil microbiota are significantly influenced by their microenvironments. Therefore, to understand the impacts of various land use patterns on the diversity and composition of soil bacterial communities, this study focused on three typical land use types-NF (natural forest), AF (artificial forests), and FL (farmland)-in the Heilongjiang Central Station Black-billed Capercaillie National Nature Reserve, located in the southwestern part of Heihe City, Heilongjiang Province, China. Using high-throughput sequencing of the 16S rRNA gene, we examined the soil bacterial community structures in these different land use types and explored their correlation with soil environmental factors. The following were our main observations: (1) Significant variations in soil chemical properties among different land use patterns were observed. In artificial forests, total nitrogen (TN), alkali hydrolyzed nitrogen (AN), total phosphorus (TP), and available phosphorus (AP) were higher compared to farmland and significantly higher than those in natural forests. Furthermore, the organic carbon content (SOC) in natural forests was higher than in artificial forests and significantly higher than in farmland. (2) Comparative analysis using the Shannon and Simpson indices revealed that bacterial community diversity was higher in artificial forests than in natural forests, which was significantly higher than in farmland. (3) The effect of different land use types on soil bacterial community structure was not significant. The three land types were dominated by Proteobacteria, Acidobacteria, and Actinobacteria. Proteobacteria exhibited a higher relative abundance in farmland and artificial forests compared to natural forests, whereas Actinobacteria exhibited the lowest relative abundance in natural forests. (4) Redundancy analysis (RDA) revealed that SOC, TN, AN, and AP were key environmental factors influencing the microbial communities of soil. Collectively, our findings demonstrated that land use practices can significantly alter soil nutrient levels, thereby influencing the structure of bacterial communities.

Anisotropic Diffusion of Elongated Particles in Active Coherent Flows.

The study of particle diffusion, a classical conundrum in scientific inquiry, holds manifold implications for various real-world applications. Particularly within the domain of active flows, where the motion of self-propelled particles instigates fluid movement, extensive research has been dedicated to unraveling the dynamics of passive spherical particles. This scrutiny has unearthed intriguing phenomena, such as superdiffusion at brief temporal scales and conventional diffusion at longer intervals. In contrast to the spherical counterparts, anisotropic particles, which manifest directional variations, are prevalent in nature. Although anisotropic behavior in passive fluids has been subject to exploration, enigmatic aspects persist in comprehending the interplay of anisotropic particles within active flows. This research delves into the intricacies of anisotropic passive particle diffusion, exposing a notable escalation in translational and rotational diffusion coefficients, as well as the superdiffusion index, contingent upon bacterial concentration. Through a detailed examination of particle coordinates, the directional preference of particle diffusion is not solely dependent on the particle length, but rather determined by the ratio of the particle length to the associated length scale of the background flow field. These revelations accentuate the paramount importance of unraveling the nuances of anisotropic particle diffusion within the context of active flows. Such insights not only contribute to the fundamental understanding of particle dynamics, but also have potential implications for a spectrum of applications.

Tailored Exfoliation of Polymeric Carbon Nitride for Photocatalytic H2O2 Production and CH4 Valorization Mediated by O2 Activation.

The exfoliation of bulk C3N4 (BCN) into ultrathin layered structure is an effective strategy to boost photocatalytic efficiency by exposing interior active sites and accelerating charge separation and transportation. Herein, we report a novel nitrate anion intercalation-decomposition (NID) strategy that is effective in peeling off BCN into few-layer C3N4 (fl-CN) with tailored thickness down to bi-layer. This strategy only involves hydrothermal treatment of BCN in diluted HNO3 aqueous solution, followed by pyrolysis at various temperatures. The decomposition of the nitrate anions not only exfoliates BCN and changes the band structure, but also incorporates oxygen species onto fl-CN, which is conducive to O2 adsorption and hence relevant chemical processes. In photocatalytic O2 reduction under visible light irradiation, the H2O2 production rate over the optimal fl-CN-530 catalyst is 952 µmol g-1 h-1, which is 8.8 times that over BCN. More importantly, under full arc irradiation and in the absence of hole scavenger, CH4 can be photocatalytically oxidized by on-site formed H2O2 and active oxygen species to generate value-added C1 oxygenates with high selectivity of 99.2 % and record-high production rate of 1893 µmol g-1 h-1 among the metal-free C3N4-based photocatalysts.