A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented.The reaction is catalyzed by a ruthenium(II)...A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented.The reaction is catalyzed by a ruthenium(II)complex bearing a N-heterocyclic carbene nitrogen phosphine(CNP)ligand.The pronouncedα-donating capacity of the carbene within the CNP ligand of the catalyst plays a crucial role in stabilizing the catalytically active species.Additionally,the hemilability of the nitrogen facilitates the creation of coordination vacancies,which are essential for the activation of reaction substrate molecules.The synergistic interplay between these two functionalities markedly enhances catalytic efficiency.This catalytic system shows the significant catalytic activity and selectivity,along with a broad substrate adaptability.All substrates yield the target product in good to excellent yields with the maximum yield reaching 95%.Control experiments have substantiated that benzaldehyde and phenylmethanimine may serve as intermediates in the reaction,thereby reinforcing the role of benzylamine as both a hydrogen donor and a nitrogen source in the process.展开更多
Peptides play important roles in chemistry,medicinal chemistry and life science,due to their high efficiency and specificity,unusual biological and therapeutic properties.As naturally occurring peptides often face wit...Peptides play important roles in chemistry,medicinal chemistry and life science,due to their high efficiency and specificity,unusual biological and therapeutic properties.As naturally occurring peptides often face with their intrinsic limitations including metabolic instability and low membrane permeability,the strategies for synthesizing unnatural amino acids and peptides are explored.Among the methods for modifying amino acids and peptides,chemo-and site-selective approaches are preferred because of the ability to fine-tuning structural features.Recently,transition metal-catalyzed C–H activation has been employed for the functionalization of amino acids and peptides.Through domino C–H activation/annulation,a series of structurally complex and diverse amino acids and peptides is constructed.This review highlights recent advances in the synthesis of unnatural amino acids and peptides via transition metal-catalyzed C–H activation/annulation.展开更多
An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion ...An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion withα-bromoketone.This protocol showed good substrate compatibility as an array of structurally and electronically diverse thiazino[3,4-a]isoquinolines prepared efficiently in moderate to good yields.It is particularly emphasized that although this reaction exhibits moderate stereoselectivity,the two diastereomers can be separated by column chromatography,providing an important molecular diversity foundation for the screening and structural optimization of subsequent drug lead compounds,as well as a simple and efficient method for constructing complex nitrogen-containing and sulfur-containing heterocyclic compounds.It has potential application value in the fields of medicinal chemistry and organic synthesis.展开更多
A[3+4]annulation of α-substituted allenes and Schiff bases is reported.This methodology serves as a conduit for the construction of a series of biologically important benzazepine derivatives in good to excellent yiel...A[3+4]annulation of α-substituted allenes and Schiff bases is reported.This methodology serves as a conduit for the construction of a series of biologically important benzazepine derivatives in good to excellent yields under mild conditions by an unprecedented mode involving β’-carbon of α-substituted allenes and the proposed mechanism is supported by capturing the intermediate.Moreover,this class of benzazepine derivatives exhibited potential ability of cytotoxicity toward cancer cells.展开更多
Designing efficient,recyclable,and low-cost catalysts is crucial for the synthesis of quinoxaline derivatives.In this context,a novel N-stable Co_(2)P nano-catalyst(CoP@N–C-1.5)was developed using a templatesacrifici...Designing efficient,recyclable,and low-cost catalysts is crucial for the synthesis of quinoxaline derivatives.In this context,a novel N-stable Co_(2)P nano-catalyst(CoP@N–C-1.5)was developed using a templatesacrificial approach.The catalyst demonstrated a broad substrate scope and good functional group tolerance,achieving yields of up to 84%.Additionally,the catalyst exhibited reusability and can be recycled up to three times.The CoP@N–C-1.5 was characterized using X-ray powder diffraction(XRD),scanning electron microscopy(SEM),and transmission electron microscopy(TEM).The results indicated that the catalyst contained Co2P nanoparticles.The X-ray photoelectron spectroscopy(XPS)further confirms the presence of Co-P.Analysis of the characterization data and experimental results revealed that the active site of the catalyst comprises N-stable Co_(2)P nanoparticles.展开更多
Chromones serve as versatile heterocyclic scaffolds and are common core structural units in a variety of natural products and bioactive organic molecules.This area of research,at the forefront of organic synthesis,has...Chromones serve as versatile heterocyclic scaffolds and are common core structural units in a variety of natural products and bioactive organic molecules.This area of research,at the forefront of organic synthesis,has seen remarkable progress in recent years.Among the various synthetic methodologies for accessing chromone scaffolds,the tandem annulation of o-hydroxyaryl enaminones has emerged as a robust and practical strategy.This approach,through direct vinyl C-H bond functionalization of o-hydroxyaryl enaminones,enables the construction of structurally diverse chromones(including 3-substituted chromones,2-substituted chromones,and 2,3-disubstituted chromones)and their derivatives since mid-2019.In this review,we highlight recent advances in the synthesis of various types of chromones and their derivatives,achieved through tandem direct vinyl C-H activation and chromone annulation of o-hydroxyaryl enaminones.展开更多
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities,which attracted the attention of many chemists.Phosphine-catalyzed nucleophilic addition is one of the ...Polycyclic compounds are widely found in natural products and drug molecules with important biological activities,which attracted the attention of many chemists.Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy,mild reaction conditions and simplicity of operation.Allenolates,Morita−Baylis−Hillman(MBH)alcohols and their derivatives(MBHADs),electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations,which formed many phosphonium species such asβ-phosphonium enolates,β-phosphonium dienolates and vinyl phosphonium ylides as intermediates.This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations.Thus,a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates,MBH alcohols and MBHADs,electron-deficient olefins and alkynes are presented in Chapters 2-6,respectively.展开更多
A new oxidative N-heterocyclic carbene(NHC)-catalyzed high-order[7+3]annulation reaction ofγ-indolyl phenols as 1,7-dinucleophiles andα,β-alkynals with the aid of Sc(OTf)_(3)is reported,enabling the highly regiosel...A new oxidative N-heterocyclic carbene(NHC)-catalyzed high-order[7+3]annulation reaction ofγ-indolyl phenols as 1,7-dinucleophiles andα,β-alkynals with the aid of Sc(OTf)_(3)is reported,enabling the highly regioselective access to unprecedented polyarene-fused ten-membered lactams bearing a bridged aryl-aryl-indole scaffold in moderate to good yields.This protocol demonstrates a broad substrate scope,good compatibility with substituents and complete regioselectivity,providing an organocatalytic modular synthetic strategy for creating medium-sized lactams.展开更多
Fluorescent probes based on intramolecular charge transfer(ICT) have obvious advantages for accurate quantitative analysis.To obtain high-performance ratiometric probes requires distinct photophysical properties durin...Fluorescent probes based on intramolecular charge transfer(ICT) have obvious advantages for accurate quantitative analysis.To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process,which is closely related to their ICT characteristics.1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore.Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied,its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated.Herein,combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer(CT) is exhibited by the meta-amino substituted 1,8-naphthalimide(m-NH_(2)) compared to the para-amino substituted one(p-NH_(2)).The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation(m-NAc and p-NAc) can be attributed to the larger ICT and stronger-NH_(2) vibrations.This observation is further demonstrated by deuterium oxide experiments,viscosity experiments and quantum chemical calculations.The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed.This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics,and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.展开更多
Combining the advantages of high efficiency,low-pressure drop,and large throughput,the pore arrayenhanced tube-in-tube microchannel(PA-TMC) is a promising microreactor for industrial applications.However,most of the m...Combining the advantages of high efficiency,low-pressure drop,and large throughput,the pore arrayenhanced tube-in-tube microchannel(PA-TMC) is a promising microreactor for industrial applications.However,most of the mass transfer takes place in the upstream pore region,while the contribution of the downstream annulus is limited.In this work,helical wires were introduced into the annulus by adhering to the outer surface of the inner tube.Mixing behavior and mass transfer of liquid-liquid twophase flow in PA-TMC with different helical wires have been systematically studied by a combination of experiments and volume of fluid(VOF) method.The introduction of helical wires improves the overall volumetric mass transfer coefficient KLa by up to 133% and the mass transfer efficiency E by up to 117%.The simulation results show that the helical wire brings extra phase mixing regions and increases the specific interface area,while accelerating the fluid flow and expanding the area of enhanced turbulent dissipation rate.Influences of helical wires in various configurations are compared by the comprehensive index I concerning the pressure drop and mass transfer performance simultaneously and a new correlation between KLa and specific energy consumption φ is proposed.This research deepens the understanding of the mixing behavior and mass transfer in the PA-TMCs and provides practical experience for the process intensification of microchannel reactors.展开更多
Catalytic C–H activation-initiated annulation reactions have emerged as a versatile strategy for the efficient construction of diverse ring structural units and complex cyclic molecules in synthetic chemistry.Herein,...Catalytic C–H activation-initiated annulation reactions have emerged as a versatile strategy for the efficient construction of diverse ring structural units and complex cyclic molecules in synthetic chemistry.Herein,we describe a new Rh(Ⅲ)-catalyzed C–H activation-initiated transdiannulation reaction of N,Ndimethyl enaminones with gem-difluorocyclopropenes in the presence of H_(2)O,enabling a facile and oxygen transfer access to ring-fluorinated tricyclicγ-lactones with a 6-5 ring-junction tetrasubstituted stereocenter.This approach features bond-forming/annulation efficiency,good functional group tolerance and complete regioselectivity,which may include a complex process consisting of Rh(Ⅲ)-catalyzed C(sp2)–H activation,cyclic alkene insertion,defluorinated ring-opening of gem-difluorocyclopropane,intramolecular oxygen transfer,intramolecular cyclization and oxidative hydration.展开更多
Realizing efficient and controlled state transfers is necessary for implementing a wide range of classical and quantum information protocols.Recent studies have demonstrated that both asymmetric and symmetric state tr...Realizing efficient and controlled state transfers is necessary for implementing a wide range of classical and quantum information protocols.Recent studies have demonstrated that both asymmetric and symmetric state transfers can be achieved by encircling an exceptional point(EP)in non-Hermitian(NH)systems.However,the application of this phenomenon has been restricted to scenarios where an EP exists in single-qubit systems and is associated with a specific type of dissipation.In this work,we demonstrate efficient and controlled symmetric and asymmetric Bell-state transfers by modulating system parameters within a Jaynes-Cummings model while accounting for atomic spontaneous emission and cavity decay.The effective suppression of nonadiabatic transitions enables a symmetric exchange of Bell states irrespective of the encircling direction.Furthermore,we report a counterintuitive finding:the presence of an EP is not indispensable for implementing asymmetric state transfers in NH systems.We achieve perfect asymmetric Bell-state transfers even in the absence of an EP by dynamically orbiting around an approximate EP.Our work presents an approach to effectively and reliably manipulate entangled states with both symmetric and asymmetric characteristics,through dissipation engineering in NH systems.展开更多
Photocatalytic transfer hydrogenation using water as the proton source has emerged as an attractive and green approach for the catalytic reduction of unsaturated bonds.Herein,we report an oxygen-defective TiO_(2)-supp...Photocatalytic transfer hydrogenation using water as the proton source has emerged as an attractive and green approach for the catalytic reduction of unsaturated bonds.Herein,we report an oxygen-defective TiO_(2)-supported palladium catalyst(Pd-TiO_(2)-Ov)for efficient photocatalytic water-donating transfer hydrogenation of anethole towards 4-n-propylanisole in a high yield of 99.9%,which is significantly higher compared to the pristine TiO_(2)-supported palladium catalyst(Pd-TiO_(2),74%).The enhanced performance is ascribed to the presence of oxygen vacancies,which facilitate light absorption and suppress the recombination of photogenerated electron-hole pairs.Furthermore,the Pd-TiO_(2)-Ov is versatile in hydrogenating various alkene substrates including those with hydroxyl,ether,fluoride,and chloride functional groups in full conversion,thus offering a green method for transfer hydrogenation of alkenes.This study provides new insights and advances in current hydrogenation technology with water as the proton source.展开更多
Conventionally,foundations have been classified as shallow or deep in routine civil engineering practice.However,due to recent developments,two other approaches,semi-deep and ground modification foundations,are now av...Conventionally,foundations have been classified as shallow or deep in routine civil engineering practice.However,due to recent developments,two other approaches,semi-deep and ground modification foundations,are now available,complicating foundation categorization.Accordingly,a new concept for foundation categorization is introduced in this paper based on insights into the theory of structure analysis.Based on the form aspect,foundation systems can be categorized as one-dimensional(linear),two-dimensional(planar),and threedimensional(volumetric).Based on the load transfer aspect,foundations can also be categorized as vector-acting(piles),section or surface-acting(rafts and shells),and block-acting(piled rafts).As a step toward implementing this new categorization scheme,a database of 22 cases has been compiled,symbolizing novel introduced foundation systems.This compilation involves structures such as offshore jackets,high-rise buildings,towers and storages,and diverse geomaterials.Among them,a few have been selected for detailed evaluation,emphasizing influential factors in foundation selection,comprising superstructure,subsoil condition,foundation system,circumferential conditions,and supplementary considerations,that is,constructional and sustainability-based issues.Lessons learned from experience and these knowledge-based cases have described for foundation selection and implementation.Geotechnical and practical aspects with critical components have been realized as major performance assessment and comparison factors.Foundation systems have been compared and ranked using the improved analytic hierarchy process approach.Finally,four categories of buildings,from low-rise to towers and four prevailing levels of soil strength,from soft to very hard,have been considered to propose a perspective for building substructure implementation,adapted via relevant cases.Overall,the introduced categorization is recognized as an efficient algorithm for the experimentation of appropriate foundations for specific structures and subsoil conditions.展开更多
This study investigates the enhancement of convective heat transfer in a serpentine pipe using ferrofluid flow influenced by dual non-uniform magnetic sources.The primary objective is to improve thermal performance in...This study investigates the enhancement of convective heat transfer in a serpentine pipe using ferrofluid flow influenced by dual non-uniform magnetic sources.The primary objective is to improve thermal performance in compact cooling systems,such as those used in heat exchangers.A two-dimensional,steady-state Computational Fluid Dynamic(CFD)model is developed in ANSYS Fluent to simulate the behavior of an incompressible ferrofluid under applied constant heat flux and magnetic fields.The magnetic force is modeled using the Kelvin force,which acts on magnetized nanoparticles in response to spatially varying electromagnetic fields generated by two strategically positioned current-carrying wires.The effects of magnetic field strength,quantified by the magnetic number(Mn),on flow behavior and temperature distribution are thoroughly analyzed.The results indicate that increasing Mn leads to higher Nusselt numbers,demonstrating enhanced convective heat transfer.Secondary vortices induced by magnetic forcing improve fluid mixing,particularly in curved regions of the pipe.A mesh-independence study and model validation with benchmark data support the reliability of the numerical framework.This work highlights the potential of magnetic-field-assisted thermal control in energy-efficient cooling applications and provides a foundation for the further development of advanced ferrofluid-based heat transfer systems.展开更多
Cosmic-ray muon sources exhibit distinct scattering angle distributions when interacting with materials of different atomic numbers(Z values),facilitating the identification of various Z-class materials,particularly r...Cosmic-ray muon sources exhibit distinct scattering angle distributions when interacting with materials of different atomic numbers(Z values),facilitating the identification of various Z-class materials,particularly radioactive high-Z nuclear elements.Most traditional identification methods are based on complex statistical iterative reconstruction or simple trajectory approximation.Supervised machine learning methods offer some improvement but rely heavily on prior knowledge of the target materials,significantly limiting their practical applicability in detecting concealed materials.To the best of our knowledge,this is the first study to introduce transfer learning into muon tomography.We propose two lightweight neural network models for fine-tuning and adversarial transfer learning,utilizing muon scattering data of bare materials to predict the Z-class of materials coated by typical shieldings(e.g.,aluminum or polyethylene),simulating practical scenarios such as cargo inspection and arms control.By introducing a novel inverse cumulative distribution-based sampling method,more accurate scattering angle distributions could be obtained from the data,leading to an improvement of nearly 4% in prediction accuracy compared with the traditional random sampling-based training.When applied to coated materials with limited labeled or even unlabeled muon tomography data,the proposed method achieved an overall prediction accuracy exceeding 96%,with high-Z materials reaching nearly 99%.The simulation results indicate that transfer learning improves the prediction accuracy by approximately 10% compared to direct prediction without transfer.This study demonstrates the effectiveness of transfer learning in overcoming the physical challenges associated with limited labeled/unlabeled data and highlights the promising potential of transfer learning in the field of muon tomography.展开更多
Accurate assessment of seismic landslide susceptibility is crucial for disaster prevention and emergency decision-making.Although machine learning methods have been widely applied in this field,they exhibit a strong d...Accurate assessment of seismic landslide susceptibility is crucial for disaster prevention and emergency decision-making.Although machine learning methods have been widely applied in this field,they exhibit a strong dependence on large quantities of highquality samples,resulting in significantly low prediction accuracy of existing studies under data-scarce or crossregional prediction scenarios,which fail to meet practical application requirements.To address this issue,this study proposes an intelligent prediction model integrating transfer learning and a sampling optimization strategy,aiming to enhance the accuracy and applicability of seismic landslide susceptibility assessment.The model first improves the sample collection method through the sampling optimization strategy to enhance the precision and representativeness of training samples.This not only ensures the accuracy of origin area training but also further strengthens the model's predictive ability in the target area.Subsequently,it incorporates Transfer Component Analysis(TCA)to overcome the differences in environmental characteristics between the origin area and target area,and couples TCA with the Light GBM algorithm to construct the TCA-Light GBM model,realizing the assessment of seismic landslide susceptibility in sample-free areas.Validated through case studies of the Jiuzhaigou and Luding earthquakes,the results demonstrate that the proposed TCALight GBM transfer learning method exhibits excellent applicability in seismic landslide susceptibility prediction.After optimization with the TCA algorithm,the model's prediction performance in the target domain is significantly improved,with the AUC value increasing from 0.719 to 0.827,representing an increase of approximately 15.02%.This indicates that TCA technology can effectively alleviate the feature distribution discrepancy between the source domain and target domain,enhancing the model's generalization ability.The method is particularly suitable for scenarios with data scarcity and cross-regional prediction and can provide reliable technical support for the emergency response and risk prevention and control of seismic hazards.展开更多
In the era of materials genome engineering,data-driven machine learning has become a powerful tool for accelerating the re-search and development of metallic materials.However,the predictive accuracy and generalizatio...In the era of materials genome engineering,data-driven machine learning has become a powerful tool for accelerating the re-search and development of metallic materials.However,the predictive accuracy and generalization ability of traditional machine learning models are often limited by the scarcity and heterogeneity of available data,especially in small-sample scenarios.To address these chal-lenges,transfer learning has emerged as an effective strategy to leverage knowledge from related domains,thereby enhancing model per-formance with limited target data.This review systematically summarizes the fundamental concepts,methodologies,and representative applications of transfer learning in the prediction of metallic materials'properties.Transfer learning can be categorized into feature-based,instance-based,parameter-based,and knowledge-based methods.This work discusses their respective mechanisms,advantages,and limit-ations.Case studies demonstrate that transfer learning can significantly improve prediction accuracy,data efficiency,and model inter-pretability in tasks such as mechanical property prediction and alloy design.Furthermore,this work highlights emerging trends including hybrid,multi-task,meta,and adaptive transfer learning,which further expand the applicability of these techniques.Finally,this work out-lines future research directions,emphasizing the need for data standardization,algorithmic innovation,multimodal data fusion,and the in-tegration of physical principles to achieve robust,interpretable,and generalizable models.The perspectives presented aim to advance the intelligent design and discovery of metallic materials,promoting efficient knowledge transfer and collaborative innovation in materials science.展开更多
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry.Current methods for syn...The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry.Current methods for synthesizing thioesters primarily rely on the acylation of thiols,which produces substantial waste and requires malodorous,unstable sulfur sources.In this work,we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols,easily available alkenes and elemental sulfur under mild conditions.This protocol demonstrates broad applicability and high chemo-and regioselectivity for both primary alcohols and alkenes,highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.展开更多
The severe shuttle effect and sluggish reaction kinetics in room-temperature sodium-sulfur(RT Na-S)batteries have been major bottlenecks hindering their practical application.To overcome these challenges,a straightfor...The severe shuttle effect and sluggish reaction kinetics in room-temperature sodium-sulfur(RT Na-S)batteries have been major bottlenecks hindering their practical application.To overcome these challenges,a straightforward reduction approach was employed to design three bimetallic alloy nanoparticles(FeNi,FeCo,and NiCo)supported on multistage porous carbon substrates.Experimental and theoretical calculations reveal that the charge transfer within the alloy catalyst influences the position of its d-band center and its degree of hybridization with sodium polysulfides(NaPSs).An increased charge transfer leads to a shift of the alloy’s d-band center closer to the Fermi energy level,thereby enhancing its adsorption and catalytic capabilities.Among the three alloy compositions,the FeNi alloy exhibits the highest charge transfer.Consequently,the FeNi alloy demonstrates the superior electrochemical performance,achieving a high reversible specific capacity of 848.2 mA h g^(−1),with an average capacity degradation rate of only 0.037%per cycle over 1000 cycles at 1.2 C.The S/FeNi/NC cathode exhibits a low electrolyte-to-sulfur(E/S)ratio of 6.6µL mg^(−1),while maintaining a high reversible specific capacity of 568.1 mA h g^(−1).This offers valuable insights for the application of alloy catalysts in the S/FeNi/NC cathode of RT Na-S batteries.展开更多
文摘A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented.The reaction is catalyzed by a ruthenium(II)complex bearing a N-heterocyclic carbene nitrogen phosphine(CNP)ligand.The pronouncedα-donating capacity of the carbene within the CNP ligand of the catalyst plays a crucial role in stabilizing the catalytically active species.Additionally,the hemilability of the nitrogen facilitates the creation of coordination vacancies,which are essential for the activation of reaction substrate molecules.The synergistic interplay between these two functionalities markedly enhances catalytic efficiency.This catalytic system shows the significant catalytic activity and selectivity,along with a broad substrate adaptability.All substrates yield the target product in good to excellent yields with the maximum yield reaching 95%.Control experiments have substantiated that benzaldehyde and phenylmethanimine may serve as intermediates in the reaction,thereby reinforcing the role of benzylamine as both a hydrogen donor and a nitrogen source in the process.
基金supported by the Natural Science Foundation of Jiangsu Province(No.BK20220409)the National Natural Science Foundation of China(No.22401153)+2 种基金the FWO[Fund for Scientific Research-Flanders(Belgium)]for financial support(recipient Erik V.Van der Eycken)the Research Council of the KU Leuven(recipient Erik V.Van der Eycken)the support of the"RUDN University Strategic Academic Leadership Program"(recipient Erik V.Van der Eycken).
文摘Peptides play important roles in chemistry,medicinal chemistry and life science,due to their high efficiency and specificity,unusual biological and therapeutic properties.As naturally occurring peptides often face with their intrinsic limitations including metabolic instability and low membrane permeability,the strategies for synthesizing unnatural amino acids and peptides are explored.Among the methods for modifying amino acids and peptides,chemo-and site-selective approaches are preferred because of the ability to fine-tuning structural features.Recently,transition metal-catalyzed C–H activation has been employed for the functionalization of amino acids and peptides.Through domino C–H activation/annulation,a series of structurally complex and diverse amino acids and peptides is constructed.This review highlights recent advances in the synthesis of unnatural amino acids and peptides via transition metal-catalyzed C–H activation/annulation.
文摘An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion withα-bromoketone.This protocol showed good substrate compatibility as an array of structurally and electronically diverse thiazino[3,4-a]isoquinolines prepared efficiently in moderate to good yields.It is particularly emphasized that although this reaction exhibits moderate stereoselectivity,the two diastereomers can be separated by column chromatography,providing an important molecular diversity foundation for the screening and structural optimization of subsequent drug lead compounds,as well as a simple and efficient method for constructing complex nitrogen-containing and sulfur-containing heterocyclic compounds.It has potential application value in the fields of medicinal chemistry and organic synthesis.
基金financially supported by the National Natural Science Foundation of China(No.21572271).
文摘A[3+4]annulation of α-substituted allenes and Schiff bases is reported.This methodology serves as a conduit for the construction of a series of biologically important benzazepine derivatives in good to excellent yields under mild conditions by an unprecedented mode involving β’-carbon of α-substituted allenes and the proposed mechanism is supported by capturing the intermediate.Moreover,this class of benzazepine derivatives exhibited potential ability of cytotoxicity toward cancer cells.
基金support from the National Natural Science Foundation of China(Nos.22061017 and21862006)the Science and Technology program of Gansu Province(Nos.22YF7GG127 and 23JRRG0002)+1 种基金National innovative training program for college students(No.202310740015)the Open Project Funding of Hubei Key Laboratory of Processing and Application of Catalytic materials(No.202306004)。
文摘Designing efficient,recyclable,and low-cost catalysts is crucial for the synthesis of quinoxaline derivatives.In this context,a novel N-stable Co_(2)P nano-catalyst(CoP@N–C-1.5)was developed using a templatesacrificial approach.The catalyst demonstrated a broad substrate scope and good functional group tolerance,achieving yields of up to 84%.Additionally,the catalyst exhibited reusability and can be recycled up to three times.The CoP@N–C-1.5 was characterized using X-ray powder diffraction(XRD),scanning electron microscopy(SEM),and transmission electron microscopy(TEM).The results indicated that the catalyst contained Co2P nanoparticles.The X-ray photoelectron spectroscopy(XPS)further confirms the presence of Co-P.Analysis of the characterization data and experimental results revealed that the active site of the catalyst comprises N-stable Co_(2)P nanoparticles.
基金financially supported by National Natural Science Foundation of China(No.22161022).
文摘Chromones serve as versatile heterocyclic scaffolds and are common core structural units in a variety of natural products and bioactive organic molecules.This area of research,at the forefront of organic synthesis,has seen remarkable progress in recent years.Among the various synthetic methodologies for accessing chromone scaffolds,the tandem annulation of o-hydroxyaryl enaminones has emerged as a robust and practical strategy.This approach,through direct vinyl C-H bond functionalization of o-hydroxyaryl enaminones,enables the construction of structurally diverse chromones(including 3-substituted chromones,2-substituted chromones,and 2,3-disubstituted chromones)and their derivatives since mid-2019.In this review,we highlight recent advances in the synthesis of various types of chromones and their derivatives,achieved through tandem direct vinyl C-H activation and chromone annulation of o-hydroxyaryl enaminones.
基金the National Natural Science Foundation of China(Nos.22171147 and 21871148)for the financial support。
文摘Polycyclic compounds are widely found in natural products and drug molecules with important biological activities,which attracted the attention of many chemists.Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy,mild reaction conditions and simplicity of operation.Allenolates,Morita−Baylis−Hillman(MBH)alcohols and their derivatives(MBHADs),electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations,which formed many phosphonium species such asβ-phosphonium enolates,β-phosphonium dienolates and vinyl phosphonium ylides as intermediates.This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations.Thus,a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates,MBH alcohols and MBHADs,electron-deficient olefins and alkynes are presented in Chapters 2-6,respectively.
基金National Natural Science Foundation of China(Nos.21971090 and 22271123)the NSF of Jiangsu Province(No.BK20230201)+1 种基金the Natural Science Foundation of Jiangsu Education Committee(No.22KJB150024)the Natural Science Foundation of Jiangsu Normal University(No.21XSRX010)。
文摘A new oxidative N-heterocyclic carbene(NHC)-catalyzed high-order[7+3]annulation reaction ofγ-indolyl phenols as 1,7-dinucleophiles andα,β-alkynals with the aid of Sc(OTf)_(3)is reported,enabling the highly regioselective access to unprecedented polyarene-fused ten-membered lactams bearing a bridged aryl-aryl-indole scaffold in moderate to good yields.This protocol demonstrates a broad substrate scope,good compatibility with substituents and complete regioselectivity,providing an organocatalytic modular synthetic strategy for creating medium-sized lactams.
基金financially supported by National Key Research and Development Programs (Nos.2022YFD1700403 and 2023YFD1700303)National Natural Science Foundation of China (Nos.12274128 and 12250003)+2 种基金Shanghai Rising-Star Program (No.21QA1402600)the support of NYU-ECNU Center for Computational Chemistry at NYU Shanghaithe University of Bath and the Open Research Fund of the School of Chemistry and Chemical Engineering,Henan Normal University (No.2020ZD01) for support。
文摘Fluorescent probes based on intramolecular charge transfer(ICT) have obvious advantages for accurate quantitative analysis.To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process,which is closely related to their ICT characteristics.1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore.Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied,its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated.Herein,combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer(CT) is exhibited by the meta-amino substituted 1,8-naphthalimide(m-NH_(2)) compared to the para-amino substituted one(p-NH_(2)).The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation(m-NAc and p-NAc) can be attributed to the larger ICT and stronger-NH_(2) vibrations.This observation is further demonstrated by deuterium oxide experiments,viscosity experiments and quantum chemical calculations.The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed.This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics,and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
基金the National Natural Science Foundation of China(22208320)the Science and Technology Program of Henan Province(212102210044)The Henan Association for Science and Technology Youth Talent Support Program(2022HYTP026).
文摘Combining the advantages of high efficiency,low-pressure drop,and large throughput,the pore arrayenhanced tube-in-tube microchannel(PA-TMC) is a promising microreactor for industrial applications.However,most of the mass transfer takes place in the upstream pore region,while the contribution of the downstream annulus is limited.In this work,helical wires were introduced into the annulus by adhering to the outer surface of the inner tube.Mixing behavior and mass transfer of liquid-liquid twophase flow in PA-TMC with different helical wires have been systematically studied by a combination of experiments and volume of fluid(VOF) method.The introduction of helical wires improves the overall volumetric mass transfer coefficient KLa by up to 133% and the mass transfer efficiency E by up to 117%.The simulation results show that the helical wire brings extra phase mixing regions and increases the specific interface area,while accelerating the fluid flow and expanding the area of enhanced turbulent dissipation rate.Influences of helical wires in various configurations are compared by the comprehensive index I concerning the pressure drop and mass transfer performance simultaneously and a new correlation between KLa and specific energy consumption φ is proposed.This research deepens the understanding of the mixing behavior and mass transfer in the PA-TMCs and provides practical experience for the process intensification of microchannel reactors.
基金financial support from the schoollevel research projects of Yancheng Institute of Technology(No.xjr2020044)the National Natural Science Foundation of China(Nos.22101152,22271123 and 21971090)。
文摘Catalytic C–H activation-initiated annulation reactions have emerged as a versatile strategy for the efficient construction of diverse ring structural units and complex cyclic molecules in synthetic chemistry.Herein,we describe a new Rh(Ⅲ)-catalyzed C–H activation-initiated transdiannulation reaction of N,Ndimethyl enaminones with gem-difluorocyclopropenes in the presence of H_(2)O,enabling a facile and oxygen transfer access to ring-fluorinated tricyclicγ-lactones with a 6-5 ring-junction tetrasubstituted stereocenter.This approach features bond-forming/annulation efficiency,good functional group tolerance and complete regioselectivity,which may include a complex process consisting of Rh(Ⅲ)-catalyzed C(sp2)–H activation,cyclic alkene insertion,defluorinated ring-opening of gem-difluorocyclopropane,intramolecular oxygen transfer,intramolecular cyclization and oxidative hydration.
基金supported by the National Key Research and Development Program of China(Grant No.2024YFA1408900)the National Natural Science Foundation of China(Grant Nos.12264040,12374333,and U21A20436)+2 种基金the Jiangxi Natural Science Foundation(Grant Nos.20232BCJ23022 and 20252BAC240119)the Innovation Program for Quantum Science and Technology(Grant No.2021ZD0301705)the Jiangxi Province Key Laboratory of Applied Optical Technology(Grant No.2024SSY03051)。
文摘Realizing efficient and controlled state transfers is necessary for implementing a wide range of classical and quantum information protocols.Recent studies have demonstrated that both asymmetric and symmetric state transfers can be achieved by encircling an exceptional point(EP)in non-Hermitian(NH)systems.However,the application of this phenomenon has been restricted to scenarios where an EP exists in single-qubit systems and is associated with a specific type of dissipation.In this work,we demonstrate efficient and controlled symmetric and asymmetric Bell-state transfers by modulating system parameters within a Jaynes-Cummings model while accounting for atomic spontaneous emission and cavity decay.The effective suppression of nonadiabatic transitions enables a symmetric exchange of Bell states irrespective of the encircling direction.Furthermore,we report a counterintuitive finding:the presence of an EP is not indispensable for implementing asymmetric state transfers in NH systems.We achieve perfect asymmetric Bell-state transfers even in the absence of an EP by dynamically orbiting around an approximate EP.Our work presents an approach to effectively and reliably manipulate entangled states with both symmetric and asymmetric characteristics,through dissipation engineering in NH systems.
基金supported by the National Key Research and Development Program of China(2023YFD2200505)National Natural Science Foundation of China(22202105),Natural Science Foundation of Jiangsu Higher Education Institutions of China(21KJA150003)the Innovation and Entrepreneurship Team Program of Jiangsu Province(JSSCTD202345).
文摘Photocatalytic transfer hydrogenation using water as the proton source has emerged as an attractive and green approach for the catalytic reduction of unsaturated bonds.Herein,we report an oxygen-defective TiO_(2)-supported palladium catalyst(Pd-TiO_(2)-Ov)for efficient photocatalytic water-donating transfer hydrogenation of anethole towards 4-n-propylanisole in a high yield of 99.9%,which is significantly higher compared to the pristine TiO_(2)-supported palladium catalyst(Pd-TiO_(2),74%).The enhanced performance is ascribed to the presence of oxygen vacancies,which facilitate light absorption and suppress the recombination of photogenerated electron-hole pairs.Furthermore,the Pd-TiO_(2)-Ov is versatile in hydrogenating various alkene substrates including those with hydroxyl,ether,fluoride,and chloride functional groups in full conversion,thus offering a green method for transfer hydrogenation of alkenes.This study provides new insights and advances in current hydrogenation technology with water as the proton source.
文摘Conventionally,foundations have been classified as shallow or deep in routine civil engineering practice.However,due to recent developments,two other approaches,semi-deep and ground modification foundations,are now available,complicating foundation categorization.Accordingly,a new concept for foundation categorization is introduced in this paper based on insights into the theory of structure analysis.Based on the form aspect,foundation systems can be categorized as one-dimensional(linear),two-dimensional(planar),and threedimensional(volumetric).Based on the load transfer aspect,foundations can also be categorized as vector-acting(piles),section or surface-acting(rafts and shells),and block-acting(piled rafts).As a step toward implementing this new categorization scheme,a database of 22 cases has been compiled,symbolizing novel introduced foundation systems.This compilation involves structures such as offshore jackets,high-rise buildings,towers and storages,and diverse geomaterials.Among them,a few have been selected for detailed evaluation,emphasizing influential factors in foundation selection,comprising superstructure,subsoil condition,foundation system,circumferential conditions,and supplementary considerations,that is,constructional and sustainability-based issues.Lessons learned from experience and these knowledge-based cases have described for foundation selection and implementation.Geotechnical and practical aspects with critical components have been realized as major performance assessment and comparison factors.Foundation systems have been compared and ranked using the improved analytic hierarchy process approach.Finally,four categories of buildings,from low-rise to towers and four prevailing levels of soil strength,from soft to very hard,have been considered to propose a perspective for building substructure implementation,adapted via relevant cases.Overall,the introduced categorization is recognized as an efficient algorithm for the experimentation of appropriate foundations for specific structures and subsoil conditions.
文摘This study investigates the enhancement of convective heat transfer in a serpentine pipe using ferrofluid flow influenced by dual non-uniform magnetic sources.The primary objective is to improve thermal performance in compact cooling systems,such as those used in heat exchangers.A two-dimensional,steady-state Computational Fluid Dynamic(CFD)model is developed in ANSYS Fluent to simulate the behavior of an incompressible ferrofluid under applied constant heat flux and magnetic fields.The magnetic force is modeled using the Kelvin force,which acts on magnetized nanoparticles in response to spatially varying electromagnetic fields generated by two strategically positioned current-carrying wires.The effects of magnetic field strength,quantified by the magnetic number(Mn),on flow behavior and temperature distribution are thoroughly analyzed.The results indicate that increasing Mn leads to higher Nusselt numbers,demonstrating enhanced convective heat transfer.Secondary vortices induced by magnetic forcing improve fluid mixing,particularly in curved regions of the pipe.A mesh-independence study and model validation with benchmark data support the reliability of the numerical framework.This work highlights the potential of magnetic-field-assisted thermal control in energy-efficient cooling applications and provides a foundation for the further development of advanced ferrofluid-based heat transfer systems.
基金supported by the Research Program of State Key Laboratory of Heavy Ion Science and Technology,Institute of Modern Physics,Chinese Academy of Sciences(No.HIST2025CS06)the National Natural Science Foundation of China(Nos.12405402,12475106,12105327,and 12405337)the Guangdong Basic and Applied Basic Research Foundation,China(No.2023B1515120067)。
文摘Cosmic-ray muon sources exhibit distinct scattering angle distributions when interacting with materials of different atomic numbers(Z values),facilitating the identification of various Z-class materials,particularly radioactive high-Z nuclear elements.Most traditional identification methods are based on complex statistical iterative reconstruction or simple trajectory approximation.Supervised machine learning methods offer some improvement but rely heavily on prior knowledge of the target materials,significantly limiting their practical applicability in detecting concealed materials.To the best of our knowledge,this is the first study to introduce transfer learning into muon tomography.We propose two lightweight neural network models for fine-tuning and adversarial transfer learning,utilizing muon scattering data of bare materials to predict the Z-class of materials coated by typical shieldings(e.g.,aluminum or polyethylene),simulating practical scenarios such as cargo inspection and arms control.By introducing a novel inverse cumulative distribution-based sampling method,more accurate scattering angle distributions could be obtained from the data,leading to an improvement of nearly 4% in prediction accuracy compared with the traditional random sampling-based training.When applied to coated materials with limited labeled or even unlabeled muon tomography data,the proposed method achieved an overall prediction accuracy exceeding 96%,with high-Z materials reaching nearly 99%.The simulation results indicate that transfer learning improves the prediction accuracy by approximately 10% compared to direct prediction without transfer.This study demonstrates the effectiveness of transfer learning in overcoming the physical challenges associated with limited labeled/unlabeled data and highlights the promising potential of transfer learning in the field of muon tomography.
文摘Accurate assessment of seismic landslide susceptibility is crucial for disaster prevention and emergency decision-making.Although machine learning methods have been widely applied in this field,they exhibit a strong dependence on large quantities of highquality samples,resulting in significantly low prediction accuracy of existing studies under data-scarce or crossregional prediction scenarios,which fail to meet practical application requirements.To address this issue,this study proposes an intelligent prediction model integrating transfer learning and a sampling optimization strategy,aiming to enhance the accuracy and applicability of seismic landslide susceptibility assessment.The model first improves the sample collection method through the sampling optimization strategy to enhance the precision and representativeness of training samples.This not only ensures the accuracy of origin area training but also further strengthens the model's predictive ability in the target area.Subsequently,it incorporates Transfer Component Analysis(TCA)to overcome the differences in environmental characteristics between the origin area and target area,and couples TCA with the Light GBM algorithm to construct the TCA-Light GBM model,realizing the assessment of seismic landslide susceptibility in sample-free areas.Validated through case studies of the Jiuzhaigou and Luding earthquakes,the results demonstrate that the proposed TCALight GBM transfer learning method exhibits excellent applicability in seismic landslide susceptibility prediction.After optimization with the TCA algorithm,the model's prediction performance in the target domain is significantly improved,with the AUC value increasing from 0.719 to 0.827,representing an increase of approximately 15.02%.This indicates that TCA technology can effectively alleviate the feature distribution discrepancy between the source domain and target domain,enhancing the model's generalization ability.The method is particularly suitable for scenarios with data scarcity and cross-regional prediction and can provide reliable technical support for the emergency response and risk prevention and control of seismic hazards.
基金supported by the National NaturalScience Foundation of China(Nos.52301029 and 52274359)the Fundamental Research Funds for the CentralUniversities,China(No.06500165)+2 种基金the Guangdong Basicand Applied Basic Research Foundation,China(No.2022A1515140006)Young Elite Scientists Sponsorship Program by CAST(No.2023QNRC001)Beijing Young Elite Scientists Sponsorship Program by BMES,China.
文摘In the era of materials genome engineering,data-driven machine learning has become a powerful tool for accelerating the re-search and development of metallic materials.However,the predictive accuracy and generalization ability of traditional machine learning models are often limited by the scarcity and heterogeneity of available data,especially in small-sample scenarios.To address these chal-lenges,transfer learning has emerged as an effective strategy to leverage knowledge from related domains,thereby enhancing model per-formance with limited target data.This review systematically summarizes the fundamental concepts,methodologies,and representative applications of transfer learning in the prediction of metallic materials'properties.Transfer learning can be categorized into feature-based,instance-based,parameter-based,and knowledge-based methods.This work discusses their respective mechanisms,advantages,and limit-ations.Case studies demonstrate that transfer learning can significantly improve prediction accuracy,data efficiency,and model inter-pretability in tasks such as mechanical property prediction and alloy design.Furthermore,this work highlights emerging trends including hybrid,multi-task,meta,and adaptive transfer learning,which further expand the applicability of these techniques.Finally,this work out-lines future research directions,emphasizing the need for data standardization,algorithmic innovation,multimodal data fusion,and the in-tegration of physical principles to achieve robust,interpretable,and generalizable models.The perspectives presented aim to advance the intelligent design and discovery of metallic materials,promoting efficient knowledge transfer and collaborative innovation in materials science.
基金National Natural Science Foundation of China (Nos.22071185 and 22271224)the Fundamental Research Funds for the Central Universities (No.2042019kf0008)Wuhan University startup funding for financial support。
文摘The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry.Current methods for synthesizing thioesters primarily rely on the acylation of thiols,which produces substantial waste and requires malodorous,unstable sulfur sources.In this work,we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols,easily available alkenes and elemental sulfur under mild conditions.This protocol demonstrates broad applicability and high chemo-and regioselectivity for both primary alcohols and alkenes,highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
基金supported by Shaanxi Fundamental Science Research Project for Chemistry and Biology(23JHQ011)Natural Science Foundation of Shaanxi(2024JC-YBMS-115)Natural Science Basic Research Plan in Shaanxi Province of China(2025JC-YBMS-141)。
文摘The severe shuttle effect and sluggish reaction kinetics in room-temperature sodium-sulfur(RT Na-S)batteries have been major bottlenecks hindering their practical application.To overcome these challenges,a straightforward reduction approach was employed to design three bimetallic alloy nanoparticles(FeNi,FeCo,and NiCo)supported on multistage porous carbon substrates.Experimental and theoretical calculations reveal that the charge transfer within the alloy catalyst influences the position of its d-band center and its degree of hybridization with sodium polysulfides(NaPSs).An increased charge transfer leads to a shift of the alloy’s d-band center closer to the Fermi energy level,thereby enhancing its adsorption and catalytic capabilities.Among the three alloy compositions,the FeNi alloy exhibits the highest charge transfer.Consequently,the FeNi alloy demonstrates the superior electrochemical performance,achieving a high reversible specific capacity of 848.2 mA h g^(−1),with an average capacity degradation rate of only 0.037%per cycle over 1000 cycles at 1.2 C.The S/FeNi/NC cathode exhibits a low electrolyte-to-sulfur(E/S)ratio of 6.6µL mg^(−1),while maintaining a high reversible specific capacity of 568.1 mA h g^(−1).This offers valuable insights for the application of alloy catalysts in the S/FeNi/NC cathode of RT Na-S batteries.
