Practical and regioselective halonitrooxylation of olefins to access ß-halonitrates.

Organic nitrates, as effective donors of the signaling molecule nitric oxide, are widely applied in the pharmaceutical industry. However, practical and efficient methods for accessing organic nitrates are still scarce, and achieving high regiocontrol in unactivated alkene difunctionalization remains challenging. Here we present a simple and practical method for highly regioselective halonitrooxylation of unactivated alkenes. The approach utilizes TMSX (X: Cl, Br, or I) and oxybis(aryl-λ3-iodanediyl) dinitrates (OAIDN) as sources of halogen and nitrooxy groups, with 0.5 mol % FeCl3 as the catalyst. Remarkably, high regioselectivity in the halonitrooxylation of aromatic alkenes can be achieved even without any catalyst. This protocol features easy scalability and excellent functional group compatibility, providing a range of ß-halonitrates (127 examples, up to 99% yield, up to >20:1 rr). Notably, 2-iodoethyl nitrate, a potent synthon derived from ethylene, reacts smoothly with a variety of functional units to incorporate the nitrooxy group into the desired molecules.

Cold-hot Janus electrochemical aptamer-based sensor for calibration-free determination of biomolecules.

Real-time, high-frequency measurements of pharmaceuticals, metabolites, exogenous antigens, and other biomolecules in biological samples can provide critical information for health management and clinical diagnosis. Electrochemical aptamer-based (EAB) sensor is a promising analytical technique capable of achieving these goals. However, the issues of insufficient sensitivity, frequent calibration and lack of adapted portable electrochemical device limit its practical application in immediate detection. In response we have fabricated an on-chip-integrated, cold-hot Janus EAB (J-EAB) sensor based on the thermoelectric coolers (TECs). Attributed to the Peltier effect, the enhanced/suppressed current response can be generated simultaneously on cold/hot sides of the J-EAB sensor. The ratio of the current responses on the cold and hot sides was used as the detection signal, enabling rapid on-site, calibration-free determination of small molecules (procaine) as well as macromolecules (SARS-CoV-2 spike protein) in single step, with detection limits of 1 µM and 10 nM, respectively. We have further demonstrated that the J-EAB sensor is effective in improving the ease and usability of the actual detection process, and is expected to provide a universal, low-cost, fast and easy potential analytical tool for other clinically important biomarkers, drugs or pharmaceutical small molecules.

Electron Delocalization Disentangles Activity-Selectivity Trade-Off of Transition Metal Phosphide Catalysts in Oxidative Desulfurization.

Breaking the activity-selectivity trade-off has been a long-standing challenge in catalysis. Here, we proposed a nanoheterostructure engineering strategy to overcome the trade-off in metal phosphide catalysts for the oxidative desulfurization (ODS) of fuels. Experimental and theoretical results demonstrated that electron delocalization was the key driver to simultaneously achieve high activity and high selectivity for the molybdenum phosphide (MoP)/tungsten phosphide (WP) nanoheterostructure catalyst. The electron delocalization not only promoted the catalytic pathway transition from predominant radicals to singlet oxygens in H2O2 activation but also simultaneously optimized the adsorption of reactants and intermediates on Mo and W sites. The presence of such dual-enhanced active sites ideally compensated for the loss of activity due to the nonradical catalytic pathway, consequently disentangling the activity-selectivity trade-off. The resulting catalyst (MoWP2/C) unprecedentedly achieved 100% removal of thiophenic compounds from real diesel at an initial concentration of 2676 ppm of sulfur with a high turnover frequency (TOF) of 105.4 h-1 and a minimal O/S ratio of 4. This work provides fundamental insight into the structure-activity-selectivity relationships of heterogeneous catalysts and may inspire the development of high-performance catalysts for ODS and other catalytic fields.

Room-Temperature Self-Healing and Recyclable Self-Crosslinked Isosorbide-Based Adhesive Bioelastomer.

Recently, renewable bio-based materials have received more and more attention due to environmental issues such as global warming and ecosystem destruction. In the present work, a series of isosorbide-based bioelastomers poly(isosorbide carbonate-co-butanediol aliphatic esters)s (PICBAs) are synthesized by a facile and economical two-step melt polycondensation. Due to the slightly self-crosslinking reaction of isosorbide, PICBAs exhibit excellent tensile strength and self-healing ability, the mechanical properties of PICBAs can recover over 95% after 48 h under room temperature. In addition, PICBAs can stick different substances, such as glass, rubber, plastic, and stones, and show better adhesive performance than 3M commercially available double-sided tape. Consequently, isosorbide-based bioelastomers PICBAs are of great potential to be used as environmentally friendly pressure-sensitive adhesives (PSA) in the future.

Fasting blood glucose as a screening measure for late-onset gestational diabetes in the third trimester.

OBJECTIVE: To investigate the positive rate of late-onset gestational diabetes mellitus (GDM) by additional fasting blood glucose (FBG) screening at 32-34 gestational weeks (GW) and analyse the perinatal outcomes of late-onset GDM after standard treatment. DESIGN: An Prospective cohort study. SETTING: Single centre in China. POPULATION: 1130 singleton pregnancies with negative GDM screening in their first and second trimester. METHODS: Additional FBG testing was performed at 32-34 GW. Pregnancies with FBG ≥5.1 mmol/L were diagnosed as GDM and received standardized treatment. Perinatal outcomes were collected and compared. MAIN OUTCOME MEASURES: Diagnosis of late-onset GDM, obstetric and neonatal outcomes. RESULTS: 6.3% (71/1130) of participants had FBG values ≥5.1 mmol/L and were diagnosed with late-onset GDM. Sixty-five (91.5%) were treated by dietary therapy and 6 (8.5%) by insulin therapy. The perinatal outcomes of full-term delivery were compared. The incidence of macrosomia (22.7% vs. 5.1%, adjusted odds ratio (aOR) 5.51, 95% confidence interval (CI) 1.83-16.61, p = 0.002) and NICU transferring (18.3% vs. 10.1%, aOR 1.94, 95% CI 1.01-3.74, p = 0.046) was significantly higher in late-onset GDM group than that in FBG <5.1 mmol/L group. Elevated FBG was associated with overweight or obesity during pregnancy (54.9% vs. 34.9%, OR 2.27, 95% CI 1.40-3.68, p = 0.001). CONCLUSIONS: 6.3% of singleton pregnancies with normal GDM screening results in the first and second trimester were found to have late-onset GDM by additional FBG screening at 32-34 GW, and their risk of macrosomia during a full-term pregnancy remains significantly higher after standard treatment.

Therapeutic effects and mechanisms of fecal microbiota transplantation on EAE partly through HPA axis-mediated neuroendocrine regulation.

Background: The pathogenesis of multiple sclerosis (MS) may be closely related to immune regulation and inflammatory cytokines induced by specific flora. Repairing the intestinal flora may alter the immune response in MS patients, thus opening up novel approaches for the treatment of MS. Objective: We aimed to test the therapeutic effect of fecal microbiota transplantation (FMT) on experimental autoimmune encephalomyelitis (EAE) and the characteristics of intestinal microbiota composition changes, explore the potential mechanisms of FMT treatment. Methods: EAE animals were treated with FMT, with the therapeutic effects were evaluated by observing neurological scores and measuring serum levels of cortisol, IL-17, and TLR-2. Fecal microbiome 16S rRNA sequencing was used to profile changes in microbiota composition, and adrenalectomy pretreatment was used to test whether FMT effects were dependent on HPA axis function. Results: FMT improved neurological function and reduced serum IL-17 to levels that were close to the control group. FMT reestablished intestinal homeostasis by altering the structure of the intestinal flora, increasing the abundance of beneficial flora, and regulating intestinal metabolites. We found that the therapeutic effects of FMT depended partly on the efferent function of the HPA axis; surgical disruption of the HPA axis altered the abundance and diversity of the intestinal flora. Conclusion: FMT showed a neuroprotective effect on EAE by increasing the abundance of the beneficial flora, rebuilding intestinal homeostasis, reducing IL-17 and cortisol serum levels, and promoting serum TLR-2; the therapeutic effect of FMT on EAE is partly dependent on the HPA axis.

Stepwise extraction of lithium and potassium and recovery of fluoride from aluminum electrolyte wastes through calcification roasting-two-stage leaching.

Aluminum electrolyte is a necessity for aluminum reduction cells; however, its stock is rising every year due to several factors, resulting in the accumulation of solid waste. Currently, it has become a favorable material for the resources of lithium, potassium, and fluoride. In this study, the calcification roasting-two-stage leaching process was introduced to extract lithium and potassium separately from aluminum electrolyte wastes, and the fluoride in the form of CaF2 was recycled. The separation behaviors of lithium and potassium under different conditions were investigated systematically. XRD and SEM-EDS were used to elucidate the phase evolution of the whole process. During calcification roasting-water leaching, the extraction efficiency of potassium was 98.7% under the most suitable roasting parameters, at which the lithium extraction efficiency was 6.6%. The mechanism analysis indicates that CaO combines with fluoride to form CaF2, while Li-containing and K-containing fluorides were transformed into water-insoluble LiAlO2 phase and water-soluble KAlO2 phase, respectively, thereby achieving the separation of two elements by water leaching. In the second acid-leaching stage, the extraction efficiency of lithium was 98.8% from water-leached residue under the most suitable leaching conditions, and CaF2 was obtained with a purity of 98.1%. The present process can provide an environmentally friendly and promising method to recycle aluminum electrolyte wastes and achieve resource utilization.

Biodegradable poly(lactic acid) blocked polyurethane/carbon nanotubes coated cotton fabric prepared by ultrasonic-assisted inkjet printing for high performance strain sensors.

In order to fulfill the demands for degradability, a broad working range, and heightened sensitivity in flexible sensors, biodegradable polyurethane (BTPU) was synthesized and combined with CNTs to produce BTPU/CNTs coated cotton fabric using an ultrasonic-assisted inkjet printing process. The synthesized BTPU displayed a capacity for degradation in a phosphate buffered saline solution, resulting in a weight loss of 25 % after 12 weeks of degradation. The BTPU/CNTs coated cotton fabric sensor achieved an extensive strain sensing range of 0-137.5 %, characterized by high linearity and a notable sensitivity (gauge factor (GF) of 126.8). Notably, it demonstrated a low strain detection limit (1 %), rapid response (within 280 ms), and robust durability, enabling precise monitoring of both large and subtle human body movements such as finger, wrist, neck, and knee bending, as well as swallowing. Moreover, the BTPU/CNTs coated cotton fabric exhibited favorable biocompatibility with human epidermis, enabling potential applications as wearable skin-contact sensors. This work provides insight into the development of degradable and high sensing performance sensors suitable for applications in electronic skins and health monitoring devices.

Electrospun radially oriented berberine-PHBV nanofiber dressing patches for accelerating diabetic wound healing.

A dressing patch made of radially oriented poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanofibers was successfully manufactured with a modified electrospinning strategy. The as-electrospun PHBV radially oriented nanofiber dressing patch exhibited uniform and bead-free nanofibrous morphology and innovative radially oriented arrangement, which was demonstrated to possess obviously improved mechanical property, increased surface hydrophilicity and enhanced biological properties compared to the PHBV nanofiber dressing patch control with traditionally randomly oriented pattern. Interestingly, it was found that the radially oriented pattern could induce the cell migration from the periphery to the center along the radially oriented nanofibers in a rapid manner. To further improve the biofunction of PHBV radially oriented nanofiber dressing patch, berberine (Beri, an isoquinoline alkaloid) with two different concentrations were encapsulated into PHBV nanofibers during electrospinning, which were found to present a sustained drug release behavior for nearly one month. Importantly, the addition of Beri could impart the dressing patch with excellent anti-inflammatory property by significantly inhibiting the secretion of pro-inflammatory factors of M1 macrophages, and also showed an additive influence on promoting the proliferation of human dermal fibroblasts (HDFs), as well as inhibiting the growth of E. coli, S. aureus and C. albicans, compared with the Beri-free dressing patch. In the animal studies, the electrospun PHBV radially oriented nanofiber dressing patch loading with high Beri content was found to obviously accelerate the healing process of diabetic mouse full-thickness skin wound with shortened healing time (100% wound closure rate after 18 days' treatment) and improved healing quality (improved collagen deposition, enhanced re-epithelialization and neovascularization and increased hair follicles). In all, this study reported an innovative therapeutic strategy integrating the excellent physical cues of electrospun PHBV radially oriented nanofiber dressing patch with the multiple biological cues of Beri for the effective treatment of hard-to-heal diabetic wounds.

Enantioselective copper-catalyzed azidation/click cascade reaction for access to chiral 1,2,3-triazoles.

Chiral 1,2,3-triazoles are highly attractive motifs in various fields. However, achieving catalytic asymmetric click reactions of azides and alkynes for chiral triazole synthesis remains a significant challenge, mainly due to the limited catalytic systems and substrate scope. Herein, we report an enantioselective azidation/click cascade reaction of N-propargyl-ß-ketoamides with a readily available and potent azido transfer reagent via copper catalysis, which affords a variety of chiral 1,2,3-triazoles with up to 99% yield and 95% ee under mild conditions. Notably, chiral 1,5-disubstituted triazoles that have not been accessed by previous asymmetric click reactions are also prepared with good functional group tolerance.

Therapeutic Potentials of Medicinal Leech in Chinese Medicine.

The use of medicinal leeches in clinical therapy has been employed for a long time, as it was originally recognized for exerting antithrombin effects. These effects were due to the ability of the leech to continuously suck blood while attached to human skin. According to Chinese Pharmacopoei, leeches used in traditional Chinese medicine mainly consist of Whitmania pigra Whitman, Hirudo nipponia Whitman, and Whitmania acranulata, but the latter two species are relatively scarce. The main constituents of leeches are protein and peptide macromolecules. They can be categorized into two categories based on their pharmacological effects. One group consists of active ingredients that directly target the coagulation system, such as hirudin, heparin, and histamine, which are widely known. The other group comprises protease inhibitor components like Decorsin and Hementin. Among these, hirudin secreted by the salivary glands of the leech is the most potent thrombin inhibitor and served as the sole remedy for preventing blood clotting until the discovery of heparin. Additionally, leeches play a significant role in various traditional Chinese medicine formulations. In recent decades, medicinal leeches have been applied in fields including anti-inflammatory treatment, cardiovascular disease management, antitumor treatment, and many other medical conditions. In this review, we present a comprehensive overview of the historical journey and medicinal applications of leeches in various medical conditions, emphasizing their pharmaceutical significance within traditional Chinese medicine. This review offers valuable insights for exploring additional therapeutic opportunities involving the use of leeches in various diseases and elucidating their underlying mechanisms for future research.

Four new polyketides from an endophytic fungus Talaromyces muroii.

In our continuous work on the isolation of endophytes, the endophytic fungal strain YIMF00209 was obtained from the roots of Gmelina arborea, which is an ethnic medicinal plant mainly distributed in Southeast Asia. The fermentation extracts of the strain exhibited significant antimicrobial activities against Staphylococcus aureus, Fusarium solani, and Escherichia coli. Based on morphological characteristics and phylogenetic analysis, it was identified as Talaromyces muroii. Four new polyketides, talaromurolides A-D (1-4), along with 26 known compounds (5-30), were isolated from the culture broth of the strain in two different media. Their structures were identified based on HRESIMS, NMR, and CD spectral data. Among them, compounds 2, 4-6, 19, 22, 24, 27, 28, and 30 were isolated from the fermentation broth in CYM medium; compounds 1, 3, 7-18, 20, 21, 23, 25, 26, and 29 were obtained from the fermentation broth in PDB medium; and compounds 2, 5, and 30 were existed in both two media. Compounds 6-9, 12, 16, 20, 21, 23, 25, and 29 were obtained from the genus Talaromyces for the first time. The antimicrobial activities of several compounds were assayed against six pathogens. Compound 1 exhibited inhibitory activities against S. aureus, E. coli, Candida albicans, Salmonella typhimurium, and Botrytis cinerea with MIC value of 64 µg/mL. Compound 25 exhibited antibacterial activity against E. coli with MIC value of 32 µg/mL.

TransEBUS: The interpretation of endobronchial ultrasound image using hybrid transformer for differentiating malignant and benign mediastinal lesions.

The purpose of this study is to establish a deep learning automatic assistance diagnosis system for benign and malignant classification of mediastinal lesions in endobronchial ultrasound (EBUS) images. EBUS images are in the form of video and contain multiple imaging modes. Different imaging modes and different frames can reflect the different characteristics of lesions. Compared with previous studies, the proposed model can efficiently extract and integrate the spatiotemporal relationships between different modes and does not require manual selection of representative frames. In recent years, Vision Transformer has received much attention in the field of computer vision. Combined with convolutional neural networks, hybrid transformers can also perform well on small datasets. This study designed a novel deep learning architecture based on hybrid transformer called TransEBUS. By adding learnable parameters in the temporal dimension, TransEBUS was able to extract spatiotemporal features from insufficient data. In addition, we designed a two-stream module to integrate information from three different imaging modes of EBUS. Furthermore, we applied contrastive learning when training TransEBUS, enabling it to learn discriminative representation of benign and malignant mediastinal lesions. The results show that TransEBUS achieved a diagnostic accuracy of 82% and an area under the curve of 0.8812 in the test dataset, outperforming other methods. It also shows that several models can improve performance by incorporating two-stream module. Our proposed system has shown its potential to help physicians distinguishing benign and malignant mediastinal lesions, thereby ensuring the accuracy of EBUS examination.

Dynamics of land cover changes and carbon emissions driven by large dams in China.

The recent surge in dam construction has sparked debates regarding their contribution to carbon neutrality and food security, focusing on trade-offs between production benefits and ecological drawbacks. However, how dams affect carbon emissions and land cover changes, including their spatial differentiations, remains unclear. We quantified spatiotemporal variations in carbon emissions and storage of 137 large dams in China from 1992 to 2020, resulting from land cover change in potentially affected areas. We observed a lesser increase in carbon emissions and a more pronounced increase in carbon storage driven by forest conservation and regeneration within dam-affected areas compared to unaffected areas. Additionally, we noticed an increased grain yield in nearby areas potentially due to increased water availability. Our findings highlight the importance of considering land cover change when assessing carbon neutrality or grain yield at regional and national scales. This study provides useful insights into optimizing dam locations to mitigate future carbon emissions effectively.

MbEOMT1 regulates methyleugenol biosynthesis in Melaleuca bracteata F. Muell.

Methyleugenol, a bioactive compound in the phenylpropene family, undergoes its final and crucial biosynthetic transformation when eugenol O-methyltransferase (EOMT) converts eugenol into methyleugenol. While Melaleuca bracteata F. Muell essential oil is particularly rich in methyleugenol, it contains only trace amounts of its precursor, eugenol. This suggests that the EOMT enzyme in M. bracteata is highly efficient, although it has not yet been characterized. In this study, we isolated and identified an EOMT gene from M. bracteata, termed MbEOMT1, which is primarily expressed in the flowers and leaves and is inducible by methyl jasmonate (MeJA). Subcellular localization of MbEOMT1 in the cytoplasm was detected. Through transient overexpression experiments, we found that MbEOMT1 significantly elevates the concentration of methyleugenol in M. bracteata leaves. Conversely, silencing of MbEOMT1 via virus-induced gene silencing led to a marked reduction in methyleugenol levels. Our in vitro enzymatic assays further confirmed that MbEOMT1 specifically catalyzes the methylation of eugenol. Collectively, these findings establish that the MbEOMT1 gene is critical for methyleugenol biosynthesis in M. bracteata. This study enriches the understanding of phenylpropene biosynthesis and suggests that MbEOMT1 could serve as a valuable catalyst for generating bioactive compounds in the future.

Exploring the diversity, bioactivity of endophytes, and metabolome in Synsepalum dulcificum.

Synsepalum dulcificum exhibits high edible and medicinal value; however, there have been no reports on the exploration of its endophyte resources. Here, we conducted analyses encompassing plant metabolomics, microbial diversity, and the biological activities of endophytic metabolites in S. dulcificum. High-throughput sequencing identified 4,913 endophytic fungal amplicon sequence variants (ASVs) and 1,703 endophytic bacterial ASVs from the roots, stems, leaves, flowers, and fruits of S. dulcificum. Fungi were classified into 5 phyla, 24 classes, 75 orders, 170 families, and 313 genera, while bacteria belonged to 21 phyla, 47 classes, 93 orders, 145 families, and 232 genera. Furthermore, there were significant differences in the composition and content of metabolites in different tissues of S. dulcificum. Spearman's correlation analysis of the differential metabolites and endophytes revealed that the community composition of the endophytes correlated with plant-rich metabolites. The internal transcribed spacer sequences of 105 isolates were determined, and phylogenetic analyses revealed that these fungi were distributed into three phyla (Ascomycota, Basidiomycota, and Mucoromycota) and 20 genera. Moreover, 16S rDNA sequencing of 46 bacteria revealed they were distributed in 16 genera in three phyla: Actinobacteria, Proteobacteria, and Firmicutes. The antimicrobial activities (filter paper method) and antioxidant activity (DPPH and ABTS assays) of crude extracts obtained from 68 fungal and 20 bacterial strains cultured in different media were evaluated. Additionally, the α-glucosidase inhibitory activity of the fungal extracts was examined. The results showed that 88.6% of the strains exhibited antimicrobial activity, 55.7% exhibited antioxidant activity, and 85% of the fungi exhibited α-glucosidase inhibitory activity. The research suggested that the endophytes of S. dulcificum are highly diverse and have the potential to produce bioactive metabolites, providing abundant species resources for developing antibiotics, antioxidants and hypoglycemic drugs.

3-O-Methyl-D-Glucose Blunts Cold Ischemia Damage in Kidney via Inhibiting Ferroptosis.

BACKGROUND: The glucose derivative 3-O-methyl-D-glucose (OMG) is used as a cryoprotectant in freezing cells. However, its protective role and the related mechanism in static cold storage (CS) of organs are unknown. The present study aimed to investigate the effect of OMG on cod ischemia damage in cold preservation of donor kidney. METHODS: Pretreatment of OMG on kidney was performed in an isolated renal cold storage model in rats. LDH activity in renal efflux was used to evaluate the cellular damage. Indicators including iron levels, mitochondrial damage, MDA level, and cellular apoptosis were measured. Kidney quality was assessed via a kidney transplantation (KTx) model in rats. The grafted animals were followed up for 7 days. Ischemia reperfusion (I/R) injury and inflammatory response were assessed by biochemical and histological analyses. RESULTS: OMG pretreatment alleviated prolonged CS-induced renal damage as evidenced by reduced LDH activities and tubular apoptosis. Kidney with pCS has significantly increased iron, MDA, and TUNEL+ cells, implying the increased ferroptosis, which has been partly inhibited by OMG. OMG pretreatment has improved the renal function (p <0.05) and prolonged the 7-day survival of the grafting recipients after KTx, as compared to the control group. OMG has significantly decreased inflammation and tubular damage after KTx, as evidenced by CD3-positive cells and TUNEL-positive cells. CONCLUSION: Our study demonstrated that OMG protected kidney against the prolonged cold ischemia-caused injuries through inhibiting ferroptosis. Our results suggested that OMG might have potential clinical application in cold preservation of donor kidney.

Chemical structure of hydrocarbons significantly affects removal performance and microbial responses in gas biotrickling filters.

The control of emissions of short-chain hydrocarbons with different structures is critical for the petrochemical industry. Herein, three two-carbon-containing (C2) hydrocarbons, ethane, ethylene, and acetylene, were chosen as pollutants to study the effects of chemical structure of hydrocarbons on removal performance and microbial responses in biotrickling filters. Results showed that the removal efficiency (RE) of C2 hydrocarbons followed the sequence of acetylene > ethane > ethylene. When the inlet loading rate was 30 g/(m3·h) and the empty bed residence time was 60 s, the RE of ethane, ethylene, and acetylene was 57 ± 4.0 %, 49 ± 1.0 %, and 84 ± 2.7 %, respectively. The high water solubility resulted in the high removal of C2 hydrocarbons, while a low surface tension enhanced the removal of C2 hydrocarbons. Additionally, the microbial community, enzyme activity, and extracellular properties of microorganisms also contributed to the difference in C2 hydrocarbon removal. These results could be referred for the effective control of light hydrocarbon emissions.

Spatiotemporal decoupling between impervious surface areas and ecosystem services.

Impervious surface area, due to its high energy storage and low permeability, hinders the cycles of material and energy between soil and atmosphere, thus affecting the sustainable supply of ecosystem services. It is of great practical significance to explore the influence of impervious surface areas on ecosystem services for territorial spatial planning and ecological construction projects. Correlation analysis and decoupling are used to explore the spatiotemporal variation and interaction between impervious surface areas and six ecosystem services in Hangzhou Bay from 1996 to 2018. The results show that different abundance levels of impervious surface areas are negatively correlated with ecosystem services, and with the increase of the impervious surface areas, the correlation coefficients with ecosystem services gradually decrease; there are mostly weak decoupling (79.2%) and strong decoupling (11.9%) between impervious surface areas and ecosystem services from 2007 to 2018, and the central areas that have achieved urbanization are mostly dominated by strong and weak decoupling, while the peripheral areas of the central cities are dominated by expansive recoupling and expansive connection. These results indicate that the loss of ecosystem services can be mitigated with the continuous advancement of urbanization and the enhancement of land use intensification. Finally, based on the aforementioned results, differentiated control suggestions are proposed, in order to provide insights for the sustainability of the urbanization of Hangzhou Bay and other cities with similar characteristics around the world.

Cobalt doping amount determines dominant reactive species in peroxymonosulfate activation via porous carbon catalysts co-doped by cobalt and nitrogen.

Switching the reaction routes in peroxymonosulfate (PMS)-based advanced oxidation processes have attracted much attention but remain challenging. Herein, a series of Co-N/C catalysts with different compositions and structures were prepared by using bimetallic zeolitic imidazolate frameworks based on ZIF-8 and ZIF-67 (xZn/Co-ZIFs). Results show that Co doping amount could mediate the transformation of the activation pathway of PMS over Co-N/C. When Co doping amount was less than 10%, the constructed xCo-N/C/PMS system (x ≤ 10%) was singlet oxygen-dominated reaction; however further increasing Co doping amount would lead to the generation and coexistence of sulfate radicals and high-valent cobalt, besides singlet oxygen. Furthermore, the nitrogen-coordinated Co (Co-NX) sites could serve as main catalytically active sites to generate singlet oxygen. While excess Co doping amount caused the formation of Co nanoparticles from which leached Co ions were responsible for the generation of sulfate radicals and high-valent cobalt. Compared to undoped N/C, Co doping could significantly enhance the catalytic performance. The 0.5% Co-N/C could achieve the optimum degradation (0.488 min-1) and mineralization abilities (78.4%) of sulfamethoxazole among the investigated Co-N/C catalysts, which was superior to most of previously reported catalysts. In addition, the application prospects of the two systems in different environmental scenarios (pH, inorganic anions and natural organic matter) were assessed and showed different degradation behaviors. This study provides a strategy to regulate the reactive species in PMS-based advanced oxidation process.