Safety evaluation of extracorporeal shockwave lithotripsy for pancreatic stones: Experience based on a large chronic pancreatitis cohort.

BACKGROUND: The safety of extracorporeal shock wave lithotripsy for pancreatic stones (P-ESWL) and adverse events were not evaluated and classified within large sample population. This study aimed to evaluate the safety and classify the adverse events of P-ESWL based on a large sample cohort. METHODS: This is an observational study based on the large prospective chronic pancreatitis (CP) cohort. Patients with painful pancreatic stones over 5 mm who underwent P-ESWL between March 2011 and June 2018 at Shanghai Changhai Hospital were included. Adverse events after P-ESWL including complications and transient adverse events (TAEs) were recorded. Risk factors of adverse events were analyzed through univariable and multivariable logistics regression analysis. Sensitivity analysis was conducted to test the stability of the study. RESULTS: Totally 2,071 patients underwent 5,002 sessions of P-ESWL were included. The overall complication rate and TAEs rate after all P-ESWL procedures were 5.2% and 20.9%. The complications and TAEs rate decreased obviously within the first 6 sessions. Several independent risk factors for adverse events after P-ESWL were identified. Sensitivity analysis suggested the stability of the results. CONCLUSIONS: P-ESWL is a safe treatment for pancreatic stones. Multiple P-ESWL sessions did not increase the complications and TAEs rate. ClincialTrials.gov number, NCT05916547.

Anchoring Metal-Nitrogen Sites on Porous Carbon Polyhedra with Highly Accessible Multichannels for Efficient Oxygen Reduction.

Transition metal-nitrogen-carbon complexes, featuring single metal atoms embedded in a nitrogen-doped carbon matrix, emerge as promising alternatives to traditional platinum-based catalysts, offering cost-effectiveness, abundance, and enhanced catalytic performance. This work introduces a novel method for the etching and doping of zeolitic imidazolate frameworks (ZIFs) with transition metals, creating a uniform distribution of secondary metal centers on ZIF surfaces. By disrupting the crystalline symmetry of ZIFs through synthetic defect engineering, we gain access to their entire internal volume, creating multichannel pathways. The absorption of metal ions is theoretically simulated, demonstrating their thermodynamically spontaneous nature. The selective removal of defect channels under Lewis acidic conditions, induced by metal ion alcoholysis/hydrolysis, facilitates the introduction of metal atoms into ZIF cavities. The resulting single-atom catalyst, after pyrolysis, features a three-dimensional (3D) multichannel structure, high surface area, and uniformly dispersed metal atoms within the N-doped carbon matrix, establishing it as an exceptional catalyst for the oxygen reduction reaction (ORR). Our findings highlight the potential of using metal etching in defect-engineered metal-organic frameworks (MOFs) for single-atom catalyst preparation, paving the way for the next generation of high-performance, cost-effective ORR catalysts in sustainable energy systems.

Difluorocarbene-Promoted O-O Bond Activation of Peroxy Acids for Electrophilic Carboxylation of Boronic Acids.

In this study, a difluorocarbene-promoted O-O bond activation of peroxy acids is developed through the insertion of difluorocarbene into O-H bond. This activation strategy in synergy with O-B coordination with boronic acids/ester greatly polarizes the O-O bond for in-situ generation of carboxylium species that reacts with the nucleophilic part of boronic acids in a concerted way to produce carboxylic esters. Good efficiency and functional group tolerance are demonstrated. Application of this method to the functionalization of a boronic acid drug used as HSL enzyme inhibitor produces smoothly the ester derivative. This difluorocarbene-mediated O-O bond activation strategy is conceptually different from traditional radical type methods, and is also complementary to conventional esterification methods with a distinct retro-synthetic disconnection.

"Hard" Emulsion-Induced Interface Super-Assembly: A General Strategy for Two-Dimensional Hierarchically Porous Metal-Organic Framework Nanoarchitectures.

Two-dimensional (2D) hierarchically porous metal-organic framework (MOF) nanoarchitectures with tailorable meso-/macropores hold great promise for enhancing mass transfer kinetics, augmenting accessible active sites, and thereby boosting performance in heterogeneous catalysis. However, achieving the general synthesis of 2D free-standing MOF nanosheets with controllable hierarchical porosity and thickness remains a challenging task. Herein, we present an ingenious "hard" emulsion-induced interface super-assembly strategy for preparing 2D hierarchically porous UiO-66-NH2 nanosheets with highly accessible pore channels, tunable meso-/macropore sizes, and adjustable thicknesses. The methodology relies on transforming the geometric shape of oil droplet templates within appropriate oil-in-water emulsions from conventional zero-dimensional (0D) "soft" liquid spheres to 2D "hard" solid sheets below the oil's melting/freezing point. Subsequent surfactant exchange on the surface of 2D "hard" emulsions facilitates the heterogeneous nucleation and interfacial super-assembly of in situ formed mesostructured MOF nanocomposites, serving as structural units, in a loosely packed manner to produce 2D MOF nanosheets with multimodal micro/meso-/macroporous systems. Importantly, this strategy can be extended to prepare other 2D hierarchically porous MOF nanosheets by altering metal-oxo clusters and organic ligands. Benefiting from fast mass transfer and highly accessible Lewis acidic sites, the resultant 2D hierarchically porous UiO-66-NH2 nanosheets deliver a fabulous catalytic yield of approximately 96% on the CO2 cycloaddition of glycidyl-2-methylphenyl ether, far exceeding the yield of approximately 29% achieved using conventional UiO-66-NH2 microporous crystals. This "hard" emulsion-induced interface super-assembly strategy paves a new path toward the rational construction of elaborate 2D nanoarchitecture of hierarchical MOFs with tailored physicochemical properties for diverse potential applications.

Copper/O2-Mediated Oxidative C-C Activation of Nitriles for Selective Acylation-Bromination of Anilines.

This study reports selective dual amino acylation and C-H bromination of aniline compounds enabled by Cu/O2 catalyst systems. This method involves crucial oxidation-induced C-CN bond cleavage of α-methylene nitriles to generate an acylcyanide intermediate that is facilely intercepted by anilines. After amino acylation, the Cu(II) precatalyst in combination with NBS generates Cu(III)-Br in situ that engages in selective electrophilic para- or ortho-C-H bromination. The substrate scope, mechanistic aspects, and late-stage functionalization of biologically active anilines are studied. This study shows the synthetic potential of oxidative C-CN bond activation of nitriles for the development of valuable reactions.

A de novo Mutation (p.Gln277X) of Cyclin D2 is Responsible for a Child with Megalencephaly-Polymicrogyria-Polydactyly-Hydrocephalus Syndrome.

Megalencephaly-polymicrogyria-polydactyly-hydrocephalus syndrome (MPPH), a type of overgrowth syndrome, is characterized by progressive megalencephaly, cortical brain malformations, and distal limb anomalies. Previous studies have revealed that the overactivity of the phosphatidylinositol 3-kinase-Protein kinase B pathway and the increased cyclin D2 (CCND2) expression were the main factors contributing to this disease. Here, we present the case of a patient who exhibited megalencephaly, polymicrogyria, abnormal neuronal migration, and developmental delay. Serum tandem mass spectrometry and chromosome examination did not detect any metabolic abnormalities or copy number variants. However, whole-exome sequencing and Sanger sequencing revealed a de novo nonsense mutation (NM_001759.3: c.829C>T; p.Gln277X) in the CCND2 gene of the patient. Bioinformatics analysis predicted that this mutation may disrupt the structure and surface charge of the CCND2 protein. This disruption could potentially prevent polyubiquitination of CCND2, leading to its resistance against degradation. Consequently, this could drive cell division and growth by altering the activity of key cell cycle regulatory nodes, ultimately contributing to the development of MPPH. This study not only presents a new case of MPPH and expands the mutation spectrum of CCND2 but also enhances our understanding of the mechanisms connecting CCND2 with overgrowth syndromes.

Electrochemical Knocking-Down of Zn Metal Clusters into Single Atoms.

Single Atoms Catalysts (SACs) have emerged as a class of highly promising heterogeneous catalysts, where the traditional bottom-up synthesis approaches often encounter considerable challenges in relation to aggregation issues and poor stability. Consequently, achieving densely dispersed atomic species in a reliable and efficient manner remains a key focus in the field. Herein, we report a new facile electrochemical knock-down strategy for the formation of SACs, whereby the metal Zn clusters are transformed into single atoms. While a defect-rich substrate plays a pivotal role in capturing and stabilizing isolated Zn atoms, the feasibility of this novel strategy is demonstrated through a comprehensive investigation, combining experimental and theoretical studies. Furthermore, when studied in exploring for potential applications, the material prepared shows a remarkable improvement of 58.21% for the Li+ storage and delivers a capacity over 300 Wh kg-1 after 500 cycles upon the transformation of Zn clusters into single atoms.

Perovskite Oxides Toward Oxygen Evolution Reaction: Intellectual Design Strategies, Properties and Perspectives.

Developing electrochemical energy storage and conversion devices (e.g., water splitting, regenerative fuel cells and rechargeable metal-air batteries) driven by intermittent renewable energy sources holds a great potential to facilitate global energy transition and alleviate the associated environmental issues. However, the involved kinetically sluggish oxygen evolution reaction (OER) severely limits the entire reaction efficiency, thus designing high-performance materials toward efficient OER is of prime significance to remove this obstacle. Among various materials, cost-effective perovskite oxides have drawn particular attention due to their desirable catalytic activity, excellent stability and large reserves. To date, substantial efforts have been dedicated with varying degrees of success to promoting OER on perovskite oxides, which have generated multiple reviews from various perspectives, e.g., electronic structure modulation and heteroatom doping and various applications. Nonetheless, the reviews that comprehensively and systematically focus on the latest intellectual design strategies of perovskite oxides toward efficient OER are quite limited. To bridge the gap, this review thus emphatically concentrates on this very topic with broader coverages, more comparative discussions and deeper insights into the synthetic modulation, doping, surface engineering, structure mutation and hybrids. More specifically, this review elucidates, in details, the underlying causality between the being-tuned physiochemical properties [e.g., electronic structure, metal-oxygen (M-O) bonding configuration, adsorption capacity of oxygenated species and electrical conductivity] of the intellectually designed perovskite oxides and the resulting OER performances, coupled with perspectives and potential challenges on future research. It is our sincere hope for this review to provide the scientific community with more insights for developing advanced perovskite oxides with high OER catalytic efficiency and further stimulate more exciting applications.

Dual Oxidation of Epoxides with a High-Valent Cu(III)-CF3 Compound and DMSO to Access 1,2-Diketones.

This study reports sequential dehydrogenation and transfer oxygenation of 1,2-diarylepoxides by high-valent phenCu(III)(CF3)3 and DMSO to produce 1,2-diketones. The Cu(III)-CF3 compound serves as a CF3 radical source to abstract the hydrogen atom of the epoxide ring. The resulting ether α-carbon radical undergoes ring-opening rearrangement to give a ketone α-carbon radical intermediate, which is oxygenated by DMSO with the release of Me2S. The combination of a Cu(III)-CF3 compound and DMSO may be exploited to develop other novel oxidation reactions.

Engineering FeCo Dual Sites on Tube-on-Plate Hollow Structure for Efficient Oxygen Electroreduction.

Atomically dispersed single-atom catalysts are intriguing catalysts in the field of electrocatalysis for nearly 100% exploitation of metal atoms. However, they are still far from practical usage due to the scaling relationship limit and metal loading limit. Generation of a diatomic complex would offer superior catalytic performance through the cooperation of two neighboring atoms as active sites. Herein, Fe/Co dual atomic sites embedded in a tube-on-plate hollow structure are designed and fabricated for an efficient electrochemical oxygen reduction reaction (ORR). The unique structure composed of ultrathin nanotube building blocks dramatically maximizes the surface area for copious active site exposure. Thanks to the synergetic interaction between Fe/Co pairs, the obtained FeCo/NC exhibits outstanding ORR activity and stability in alkaline media. Furthermore, density functional theory calculations have revealed that the remarkable activity is attributed to the electron-deficient Fe sites in FeCoN6. This work may pave the way for the innovative design of highly dispersed dual-site catalysts for broader applications in the realm of electrochemical catalysis.

Rejuvenation of aged graphite anodes from spent lithium-ion batteries via a facile surface treatment strategy.

In this study, we present a facile formic acid treatment to rejuvenate aged graphite anodes from spent lithium-ion batteries (LIBs) without damaging the electrode structure. This method effectively removes the interfacial blocking layer, improving capacity and rate performance. Our approach contributes to sustainable battery recycling strategies for spent graphite anodes in LIBs.

[Accumulation Characteristics and Influencing Factors of Heavy Metals in Cultivated Land Surface Soil in Lanzhou].

In this study, As, Cd, Cr, Hg, and Pb in the surface soil of cropland in Lanzhou were studied, and the combination of descriptive statistics, single-factor accumulation index, comprehensive accumulation index, geostatistical method, and a geographically weighted regression model (GWR) was used to investigate their accumulation status, spatial distribution, and influencing factors, in order to provide scientific basis for the precise control of heavy metal accumulation risk in the study area. The results showed that:①the single-factor accumulation index showed that the accumulation of Hg and Cd in the study area was the largest, followed by that of Pb and As, and that of Cr was the smallest; the comprehensive accumulation index showed that the accumulation rate of heavy metals was as high as 98.11%, of which 54.81% was mild accumulation and 43.30% was moderate and above accumulation. However, there was no heavy metal pollution in the surface soil of cultivated land in Lanzhou. ② Spatial autocorrelation analysis showed that there was no heavy metal pollution in the surface soil of Lanzhou, but there was accumulation in a few areas. The spatial autocorrelation analysis showed that the spatial autocorrelation of the Cr, Hg, and Pb single-factor accumulation indices was moderate, indicating that they were influenced by both random and structural factors; the spatial autocorrelation of the other two heavy metals was weak, indicating that they were mainly influenced by random factors, among which human factors were more influential. The Hg single-factor accumulation index was high in the middle and low in the fourth; the integrated accumulation index increased from northwest to southeast and decreased from the middle to both sides. ③ Geographically weighted regression (GWR) analysis showed that altitude, slope length, distance from rivers, soil organic matter (SOM) content, precipitation, air temperature, and surface temperature all showed positive driving effects, whereas the rest of the factors showed negative driving effects and significant spatial heterogeneity and instability (P<0.05). The magnitudes of the factor effects were in the order of soil characteristics>topographic characteristics>climate characteristics>location characteristics>socioeconomic characteristics>vegetation characteristics, with the largest contribution of SOM content, followed by that of altitude and air temperature, and the smallest of normalized difference vegetation index (NDVI) values. Compared with the other feature factors, the location feature factors had stronger spatial heterogeneity.

Direct formylation of phenols using difluorocarbene as a safe CO surrogate.

A convenient method to prepare aryl formates is reported herein that exploits difluorocarbene to serve as a CO surrogate. This reaction is proposed to occur through a sequential O-difluoromethylation of phenol, followed by α-C-F bond functionalization of the resulting aryl difluoromethyl ether intermediate by phenol or moisture through fluorosemiacetal or orthoformate intermediates. Late-stage modification of biologically and materially active compounds is demonstrated.

High-valent Cu(III)-CF3 compound-mediated esterification reaction.

Cu(III)-CF3 compounds are reported herein as novel coupling reagents to mediate ester synthesis from carboxyl acids and alcohols/phenols. Carboxylic acids are transformed to trifluoromethyl ester and acyl fluoride activated species that interact with each other. The broad substrate scope and late-stage application of this method are demonstrated. This study opens up new opportunities to develop interesting reactions using Cu(III)-CF3 compounds without transferring a CF3 group to the products.

Three-Component Coupling of Anilines, Amines, and Difluorocarbene to Access Formamidines.

A one-pot three-component reaction of two anilines (or one aniline and one alkylamine) and in situ-generated difluorocarbene is developed herein to enable efficient construction of formamidines. Crucial formimidoyl fluoride intermediate RN═CHF is proposed from the reaction of a primary aniline and difluorocarbene. Ensuing nucleophilic iminyl substitution of this intermediate with a second amine allows cross-condensation of the two amines to produce formamidines. When only one type of primary aniline is used as the substrate, the difluoromethylated homo-condensation products can also be produced under a 1:1 molar ratio of aniline/difluorocarbene. Intramolecular variant of this method allows concise synthesis of benzimidazoquinazolines and nitrogen-fused/spirocyclic compounds, showing the potential of this method in organic synthesis. More interesting reactions are anticipated by exploiting the reactivity of difluorocarbene and primary amines to isocyanides or the formimidoyl fluoride intermediates.

[Risk Assessment and Attribution Analysis of "Five Toxic" Heavy Metals in Cultivated Land in Lanzhou].

Heavy metals in cultivated soil may migrate and transform through the food chain to harm the ecological environment and human health. At present, the ecological environment and human health risks of heavy metals in cultivated soil in Lanzhou city remain unclear, which impacts the effective management and control of heavy metals. The potential ecological risk hazard index was used to evaluate the ecological environmental risks of As, Cd, Cr, Hg, and Pb in the surface soil of cultivated land in Lanzhou, and the health risk model proposed by USEPA and the recommended standard were used to evaluate their human health risk. The main factors influencing the spatial differentiation of human health risk were explored by using geographic detectors. The risk of heavy metals to the ecological environment of the cultivated land surface soil in the study area was mainly medium (65.25%), and small portions were low (13.80%) and high (20.95%). The low-risk areas were mainly located in the southeast of Yongdeng County, the middle and north of Yuzhong County, and the southwest of Gaolan County. Moderate risk areas were distributed in three counties and five districts. The high-risk areas were located in the north and southeast of Yongdeng County, the south of Chengguan District, the northeast of Qilihe, the east of Xigu District, and the middle of Yuzhong County. The non-carcinogenic and carcinogenic risks of five types of heavy metal exposure pathways were as follows:oral ingestion>skin contact>respiratory ingestion; generally speaking, children were at higher risk than adults. The non-carcinogenic risk in children was higher than that in adults; however, there was no such risk for local residents, as they were all less than 1. At the same time, the carcinogenic risk of As was greater than 1×10-5 (children 2.04×10-5) and less than 1×10-4 (adults 1.91×10-5), respectively. This indicated an acceptable medium risk to the local residents, and the risk to children was again greater than that to adults. Geographical detector analysis showed that average precipitation during the sampling season had the greatest impact on the spatial differentiation of human health risks of As and Cd, GDP had the greatest impact on the spatial differentiation of human health risks of Cr, and distance from the railway had the greatest impact on the spatial differentiation of human health risks of Hg and Pb. Interaction detection showed that all factors were enhanced by double factors. In addition to leading factors, other factors such as pH, slope, and altitude also enhanced the influence of leading factors on the spatial differentiation of heavy metal risk in cultivated soil.

Direct Arene Trifluoromethylation Enabled by a High-Valent CuIII -CF3 Compound.

Direct C-H trifluoromethylation of arenes and heteroarenes poses an important synthetic challenge that is highly desirable. High-valent CuIII -CF3 compounds have often been invoked in copper-mediated trifluoromethylation reactions, but the fundamental reactivity toward arenes is elusive. Herein, direct C-H trifluoromethylation of arenes/heteroarenes by a high-valent CuIII -CF3 compound is disclosed for the first time. The CuIII -CF3 compound serves CF3 radical and a CuII oxidant by homolytic cleavage of a CuIII -CF3 bond, which engage synergistically in a SE Ar type reaction with arenes. The presence of K2 S2 O8 co-oxidant can significantly improve the reaction yields. This reaction shows good efficiency, broad functional group tolerance, and the potential in late-stage functionalization. The reactivity of high-valent CuIII -CF3 compounds disclosed in this study represents an important progress in organofluorine and CuIII chemistry.

[Relationship between alien plant invasion and landscape matrix in the water-level fluctuating zone of the Three Gorges Reservoir, China.] / ä¸‰å³¡åº“åŒºæ¶ˆè½å¸¦å¤–æ¥æ¤ç‰©å ¥ä¾µä¸Žæ™¯è§‚åŸºè´¨ç»„æˆç»“æž„çš„å ³è”æ€§.

Invasive process of alien species is affected by not only the invaded habitats, but also the surrounding landscape matrix. Understanding the effects of landscape matrix on alien species is of great significance for controlling invasive alien species. We surveyed plant communities along the water-level fluctuating zone (WLFZ) of the Three Gorges Reservoir. Invasive status of alien plant species was evaluated. Totally 10 spatial scales of the surrounding landscape matrix in the scope of 2000 m (including WLFZ) were classified, and 14 landscape indices were applied to analyze the landscape matrix composition and configuration. Using the principal component analysis and correlation analysis, the effects of landscape matrix on the alien invasive plant species and associated scale effect were tested. Results showed that a total of 42 alien invasive plant species were found in the WLFZ, belonging to 17 families and 36 genera. Fuling was a dividing place to differentiate invasive species distribution. The number of the alien invasive species between Fuling and the Three Gorges Dam was found more than that between Fuling and Jiangjin. For the all scales (within 2000 m). The higher the landscape matrix fragmentation was, the more difficult the alien species invading. The higher landscape connectivity was, the easier the alien species invading. The effects of landscape matrix composition and configuration on the invasive plant diversity at large scales (1200-2000 m) was more significant than those at small scales (200-1000 m), in which landscape matrix composition and configuration at 1200-1400 m showed the strongest effect, demonstrating a significant spatial scale effect. Different invasive plant species showed the scale effects of landscape matrix composition and configuration. At all scales, Xanthium strumarium and Bidens frondosa showed weak correlations with landscape indices, but Bidens tripartita and Erigeron canadensis showed strong correlations. Landscape matrix was closely related to invasive plant species, and demonstrated a significant scale effect. The alien invasive plant species could be traced to the landscape matrix at large scales. Grassland and forest patches at the small scales could be used as the 'stepping stone' for the alien species transiting before they arrived at the WLFZ. In order to control alien plants in the WLFZ, land-use management and optimization should be strengthened at different scales of landscape matrix on the basis of enhancement of habitat management. A diversified comprehensive control for alien species should thus be taken into account.

Loading Single-Ni Atoms on Assembled Hollow N-Rich Carbon Plates for Efficient CO2 Electroreduction.

The rational design of catalysts' spatial structure is vitally important to boost catalytic performance through exposing the active sites, enhancing the mass transfer, and confining the reactants. Herein, a dual-linker zeolitic tetrazolate framework-engaged strategy is developed to construct assembled hollow plates (AHP) of N-rich carbon (NC), which is loaded with single-Ni atoms to form a highly efficient electrocatalyst (designated as Ni-NC(AHP)). In the carbonization process, the thermally unstable linker (5-aminotetrazole) serves as the self-sacrificial template and the other linker (2-methylimidazole) mainly serves as the carbon and nitrogen source to form hollow NC matrix. The formed Ni-NC(AHP) catalyst possesses enhanced mesoporosity and more available surface area, thus promoting mass transport and affording abundant accessible single-Ni sites. These features contribute to remarkable performance for electrochemical CO2 reduction with exceptionally high selectivity of nearly 100% towards CO in a wide potential range and dramatically enhanced CO partial current density.

Phosphorized CoNi2 S4 Yolk-Shell Spheres for Highly Efficient Hydrogen Production via Water and Urea Electrolysis.

Exploring earth-abundant electrocatalysts with excellent activity, robust stability, and multiple functions is crucial for electrolytic hydrogen generation. Porous phosphorized CoNi2 S4 yolk-shell spheres (P-CoNi2 S4 YSSs) were rationally designed and synthesized by a combined hydrothermal sulfidation and gas-phase phosphorization strategy. Benefiting from the strengthened Ni3+ /Ni2+ couple, enhanced electronic conductivity, and hollow structure, the P-CoNi2 S4 YSSs exhibit excellent activity and durability towards hydrogen/oxygen evolution and urea oxidation reactions in alkaline solution, affording low potentials of -0.135 V, 1.512 V, and 1.306 V (versus reversible hydrogen electrode) at 10 mA cm-2 , respectively. Remarkably, when used as the anode and cathode simultaneously, the P-CoNi2 S4 catalyst merely requires a cell voltage of 1.544 V in water splitting and 1.402 V in urea electrolysis to attain 10 mA cm-2 with excellent durability for 100 h, outperforming most of the reported nickel-based sulfides and even noble-metal-based electrocatalysts. This work promotes the application of sulfides in electrochemical hydrogen production and provides a feasible approach for urea-rich wastewater treatment.