The direct difunctionalization of alkenes, a cheap and abundant feedstock, represents one of the most attractive strategies for increasing molecular complexity in synthetic organic chemistry. In ...contrast with the 1,2‐difunctionalization of alkenes, recent advances showcase alkene 1,n‐difunctionalizations (n≠2) involving metal migration is an emerging and rapidly growing area of research. This promising strategy not only opens a novel avenue for future development of alkene transformations, but also significantly expands upon the bond disconnections available in modern organic synthesis. This Minireview summarizes recent progress in the migratory difunctionalization of alkenes, with an emphasis on the driving force for metal migration.
Driving force: The difunctionalization of alkenes involving metal migration provides access to a new class of products that are not readily synthesized by other methods. This Minireview summarizes recent advances in the field, with an emphasis on the driving force for metal migration.
The Catellani reaction is known as a powerful strategy for the expeditious synthesis of highly substituted arenes and benzo‐fused rings, which are usually difficult to access through traditional ...cross‐coupling strategies. It utilizes the synergistic interplay of palladium and norbornene catalysis to facilitate sequential ortho C−H functionalization and ipso termination of aryl halides in a single operation. In classical Catellani‐type reactions, aryl halides are mainly used as the substrates, and a Pd0 catalyst is required to initiate the reaction. Nevertheless, recent advances showcase that Catellani‐type reactions can also be initiated by a PdII catalyst with different starting materials instead of aryl halides via different reaction mechanisms and under different conditions. This emerging concept of PdII/norbornene cooperative catalysis has significantly advanced Catellani‐type reactions, thus enabling future developments of this field. In this Minireview, PdII‐initiated Catellani‐type reactions and their application in the synthesis of bioactive molecules are summarized.
Cooperative solutions: Palladium(II)‐initiated norbornene (NBE)‐mediated cooperative catalysis has enabled significant developments of the Catellani reaction. These advances and their application in the synthesis of bioactive molecules are summarized in this Minireview.
Chiral tetrahydrocarbazoles (THCs) are prevalent in numerous natural indole alkaloids as well as synthetic pharmaceuticals, and exhibit a broad spectrum of bioactivities. As such, the development of ...efficient synthetic methodologies for the synthesis of chiral THCs is of substantial interest. The advent of asymmetric catalysis provides a powerful platform to assemble chiral THC motifs and great efforts have been devoted to this field over the past decades. In this feature article, we summarise recent advances in catalytic asymmetric synthesis of THCs, with particular emphases on reaction types and reaction mechanism.
A novel Z-scheme system of CeO2–Ag/AgBr heterostructure photocatalyst exhibits excellent ability to eliminate ciprofloxacin under visible light irradiation.
Display omitted
•Novel Z-scheme ...CeO2–Ag/AgBr photocatalysts were prepared.•Superior photocatalytic activity for the degradation of ciprofloxacin (CIP) refractory pollutants was obtained.•The factors affecting the photocatalytic performance were investigated.•A plausible degradation pathway for CIP was proposed.•A Z-scheme photocatalytic mechanism was proposed.
In this study, CeO2–Ag/AgBr composite photocatalysts with a Z-scheme configuration were fabricated by in situ interspersal of AgBr on CeO2 and subsequent photoreduction process. The CeO2–Ag/AgBr composites exhibited enhanced photocatalytic activity for the photodegradation of ciprofloxacin (CIP) under visible light irradiation. The effects of initial CIP concentration and various inorganic salts were investigated in detail. Three-dimensional excitation–emission matrix fluorescence spectra were used to further monitor the CIP molecule degradation. Plausible degradation pathways for CIP were proposed based on LC-MS instruments. Photoluminescence, electrochemical impedance spectroscopy, and photocurrent tests indicated the rapid transfer and migration of electrons–holes can be achieved in this ternary photocatalytic system. The enhanced photocatalytic performances of CeO2–Ag/AgBr could be credited to the accelerated interfacial charge transfer process and the improved separation of the photogenerated electron–hole pairs. The existence of a small amount of metallic Ag is conducive to the formation of a stable Z-scheme photocatalytic system. This work would pave the route for the design of novel Z-scheme photocatalytic systems for application in solar-to-fuel conversion and photocatalytic water treatment.
The robustness of carbon nanomaterials and their potential for ultrahigh permeability has drawn substantial interest for separation processes. However, graphene oxide membranes (GOms) have ...demonstrated limited viability due to instabilities in their microstructure that lead to failure under cross-flow conditions and applied hydraulic pressure. Here we present a highly stable and ultrapermeable zeolitic imidazolate framework-8 (ZIF-8)-nanocrystal-hybridized GOm that is prepared by ice templating and subsequent in situ crystallization of ZIF-8 at the nanosheet edges. The selective growth of ZIF-8 in the microporous defects enlarges the interlayer spacings while also imparting mechanical integrity to the laminate framework, thus producing a stable microstructure capable of maintaining a water permeability of 60 l m
h
bar
(30-fold higher than GOm) for 180 h. Furthermore, the mitigation of microporous defects via ZIF-8 growth increased the permselectivity of methyl blue molecules sixfold. Low-field nuclear magnetic resonance was employed to characterize the porous structure of our membranes and confirm the tailored growth of ZIF-8. Our technique for tuning the membrane microstructure opens opportunities for developing next-generation nanofiltration membranes.
Blockchain technology, with its decentralization, traceability, and immutability, offers promising solutions across various sectors, including education. This study explores the application of ...blockchain in enhancing the security and personalization of educational resource sharing within university physical education (PE). We ensure secure resource sharing by developing a blockchain-based model for PE resource distribution and refining the consensus algorithm. Our research involved a 10-week experiment with 80 university students, measuring changes in psychological factors (e.g., anxiety, depression) and physiological parameters (e.g., lung capacity). Results indicated a notable improvement in students’ psychological well-being, with anxiety and depression levels dropping by an average of 15%, and a significant enhancement in physiological health, evidenced by an average increase in lung capacity of 2.11±1.00 ml/kg. These findings underscore the potential of blockchain technology to elevate university PE teaching practices and positively impact student health, highlighting its significant applicability and future potential in educational contexts.
Display omitted
•Novel direct Z-scheme AgI/Bi4V2O11 photocatalysts were prepared.•A superior photocatalytic activity for the degradation of SMZ refractory pollutants.•A plausible degradation pathway ...for SMZ was proposed.•The fabrication Z-scheme heterostructure play a central role in promoting charge separation and active radical generation.
Z-scheme heterojunction can not only promote the separation of photogenerated carriers, but also retain the strong redox potential of the system, which would greatly improve the photocatalytic performance of catalyst. Herein, a Z-scheme AgI/Bi4V2O11 heterojunction photocatalyst was prepared by a hydrothermal process combined with in situ coprecipitation process. Multiple techniques were employed to investigate the morphology, composition, chemical and electronic properties of the as-prepared samples. The obtained Z-scheme AgI/Bi4V2O11 heterojunction photocatalyst exhibited remarkably enhanced photocatalytic performance towards sulfamethazine (SMZ) degradation under visible light irradiation. Especially, the 20 wt% AgI/Bi4V2O11 composites exhibited the highest photocatalytic activity for sulfamethazine (SMZ) degradation and 91.47% SMZ would be eliminated within 60 min. In comparison with NO3− and SO42−, the presence of Cl− and HCO3− presented more obviously inhibition effects on SMZ degradation. The possible degradation pathways of SMZ were speculated by identifying degradation intermediates. O2−, h+ and OH all involved in the photocatalytic degradation SMZ. The highly enhanced photocatalytic performance might be attributed to form Z-scheme junction between AgI and BVO, which are conducive to the efficient charges separation and maintain high redox potential. This work enriches Bi4V2O11-based Z-scheme heterojunction photocatalytic system and provides a reference for the preparation of effective Z-scheme junction photocatalysts.
Reported is a modular one‐step three‐component synthesis of tetrahydroisoquinolines using a Catellani strategy. This process exploits aziridines as the alkylating reagents, through ...palladium/norbornene cooperative catalysis, to enable a Catellani/Heck/aza‐Michael addition cascade. This mild, chemoselective, and scalable protocol has broad substrate scope (43 examples, up to 90 % yield). The most striking feature of this protocol is the excellent regioselectivity and diastereoselectivity observed for 2‐alkyl‐ and 2‐aryl‐substituted aziridines to access 1,3‐cis‐substituted and 1,4‐cis‐substituted tetrahydroisoquinolines, respectively. Moreover, this is a versatile process with high step and atom economy.
A modular synthesis of tetrahydroisoquinolines was developed. Aziridines act as the alkylating reagents to enable a Catellani/Heck/aza‐Michael addition cascade by palladium/norbornene (NBE) cooperative catalysis. This mild, chemoselective, and scalable protocol is compatible with a wide range of readily available aryl iodides, aziridines, and olefins. Excellent regio‐ and diastereoselectivities are observed for 1,3‐cis‐substituted and 1,4‐cis‐substituted tetrahydroisoquinolines.
Background Prosthesis-related complications, after knee reconstruction with endoprosthesis during operation for tumors around the knee, remain an unresolved problem which necessitate a revision or ...even an amputational surgery. The purpose of the current study was to identify significant risk factors associated with implant failure, and establish a novel model to predict survival of the prosthesis in patients operated with endoprostheses for tumor around knee. Methods We retrospectively reviewed the clinical database of our institution for patients who underwent knee reconstruction due to tumors. A total of 203 patients were included, including 123 males (60.6%) and 80 (39.4%) females, ranging in age from 14 to 77 years (mean: 34.3 + or - 17.3 years). The cohort was randomly divided into training (n = 156) and validation (n = 47) samples. Univariable COX analysis was used for initially identifying potential independent predictors of prosthesis survival with the training group (p < 0.150). Multivariate COX proportional hazard model was selected to identify final significant prognostic factors. Using these significant predictors, a graphic nomogram, and an online dynamic nomogram were generated for predicting the prosthetic survival. C-index and calibration curve were used for evaluate the discrimination ability and accuracy of the novel model, both in the training and validation groups. Results The 1-, 5-, and 10-year prosthetic survival rates were 94.0, 90.8, and 83.0% in training sample, and 96.7, 85.8, and 76.9% in validation sample, respectively. Anatomic sites, length of resection and length of prosthetic stem were independently associated with the prosthetic failure according to multivariate COX regression model (p<0.05). Using these three significant predictors, a graphical nomogram and an online dynamic nomogram model were generated. The C-indexes in training and validation groups were 0.717 and 0.726 respectively, demonstrating favourable discrimination ability of the novel model. And the calibration curve at each time point showed favorable consistency between the predicted and actual survival rates in training and validation samples. Conclusions The length of resection, anatomical location of tumor, and length of prosthetic stem were significantly associated with prosthetic survival in patients operated for tumor around knee. A user-friendly novel online model model, with favorable discrimination ability and accuracy, was generated to help surgeons predict the survival of the prosthesis. Keywords: Limb salvage, Prognostic factor, Tumor endoprostheses, Nomogram
Display omitted
•The formation of Schottky barrier in MONC-3 can inhibit the backflow of electrons.•MONC-3 can convert the absorbed light energy into local high temperature.•Photodynamic and ...photothermal effects synergistically lead to bacterial death.•DFT calculation clarifies the charge transfer mechanism in Schottky heterojunction.
Developing green and highly efficient water disinfection technique is of great importance to public health. Herein, a near-infrared (NIR) light-triggerable thermo-sensitive defective molybdenum oxide-nitrogen doped carbon (MoO3-x/NCNs) composite was fabricated and applied to water disinfection. With the synergy of photodynamic and photothermal effects, the MoO3-x/NCNs achieve a rapid and effective inactivation of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) as compared to photocatalytic treatment or thermal catalytic alone. Particularly, MONC-3 with optimal ratio can completely inactivate 7.6 log of E. coli and S. aureus within 60 min and 100 min, respectively. The MONC-3 hybrid exhibits efficient charge separation and migration ability due to the formation of Schottky heterojunction, resulting in the highly enhanced O2− (11.34 × 10−10 M) generation activity. Meanwhile, excellent NIR light absorption and photothermal conversion efficiency (52.6%) of MONC-3 can generate local high temperature to promote photocatalytic reaction rate and destruct the bacterial integrity. The monitoring of cell damage process confirmed the irreversible death of bacteria. Based on density functional theory (DFT) calculation, the antibacterial mechanism and Schottky effect were clarified. This work provides new insights for constructing a water disinfection strategy based on plasma-induced photothermal synergy catalysis.
PDF
