A chromium(II)-catalyzed reduction cross coupling reaction was reported.This reaction utilizes inexpensive and readily available chromium dichloride as a catalyst and 4,4'-di-tert-butyl-bipyridine as a ligand to a...A chromium(II)-catalyzed reduction cross coupling reaction was reported.This reaction utilizes inexpensive and readily available chromium dichloride as a catalyst and 4,4'-di-tert-butyl-bipyridine as a ligand to achieve reduction cross coupling between trifluoromethyl olefins and alkyl bromides under mild conditions,effectively synthesizing difluoroalkene derivatives.This reaction exhibits good substrate universality and is compatible with multiple important functional groups,providing a concise synthetic pathway for constructing conjugated difluoroalkenes containing allyl difluoromethylene structural units.Preliminary mechanistic experiments indicate that alkyl bromides first undergo a reduction process to generate corresponding alkyl radicals,followed by addition to trifluoromethyl olefins.After binding with Cr(II),they undergo aβ-fluorine elimination process to generate difluoroalkenes.展开更多
Chiral carbonyl compounds frequently occur in natural products and pharmaceuticals. Additionally, they serve as important intermediates in organic synthesis. Transition metal-catalyzed asymmetric carbonylative cross-c...Chiral carbonyl compounds frequently occur in natural products and pharmaceuticals. Additionally, they serve as important intermediates in organic synthesis. Transition metal-catalyzed asymmetric carbonylative cross-coupling reactions are among the most straightforward and effective methods for synthesizing chiral carbonyl compounds, including esters, amides, and ketones. The advances in asymmetric carbonylative cross-coupling reactions using various O-, N-, C-, and S-containing nucleophiles or electrophiles over the past decade are summarized.展开更多
Selective defluorinative functionalization of trifluoromethylarenes(ArCF3)to obtain the pharmaceutically commonα,α-difluorobenzylic motif is an attractive and elegant synthetic route.Over the past decade,although C(...Selective defluorinative functionalization of trifluoromethylarenes(ArCF3)to obtain the pharmaceutically commonα,α-difluorobenzylic motif is an attractive and elegant synthetic route.Over the past decade,although C(sp^(3))-F bonds functionalization have been greatly developed,catalytic cross-coupling of trifluoromethylarenes with C-H of terminal alkynes remains a challenge.Here,we report an approach to achieve Sonogashira-type cross-coupling of trifluoromethylarenes with terminal alkynes C(sp)-H bonds via photoredox and Cu/L dual catalysis.Tridentate anionic ligand is pivotal to realize this C-H sp-sp^(3) cross-coupling.Moreover,this unique catalytic system is also suitable for cross-coupling of C(sp^(3))-F bonds with azoles C(sp^(2))-H bonds.A series of trifluoromethylarenes,terminal alkynes and azoles with various functional groups are compatible with this protocol affording a variety of defluoroalkynylation or defluoroazolation products.Preliminary mechanistic studies indicated that deprotonated BINOL involved as a photocatalyst to activate ArCF3 rather than a ligand to the metal.展开更多
In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.The...In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions.Herein,we report a cobalt-catalyzed migratory carboncarbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl-and alkyl-functionalized cyclooctenes.Preliminary mechanistic studies suggest the oxidation-induced cisbicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction,which promotes the development of other diverse migratory cross-coupling of borate complexes.展开更多
The switchable cross-coupling of indoles and pyridotriazoles through carbene insertion at C_(2)-or C_(3)-positon has been developed in this paper.This highly site-selective C-H carbenoid functionalization is determine...The switchable cross-coupling of indoles and pyridotriazoles through carbene insertion at C_(2)-or C_(3)-positon has been developed in this paper.This highly site-selective C-H carbenoid functionalization is determined by both the Rh-catalyst species and auxiliary groups.[Cp∗RhCl_(2)]_(2) and coordinating pyrimidyl group direct the C-H carbenoid functionalization to occur at the C_(2)-position,while Rh2OAc4 and noncoordinating benzyl group lead the reaction to occur at the C_(3)-position of the indoles.This regioselective C−H functionalization strategy is of significant importance for the discovery of indole drugs.展开更多
An N-heterocyclic carbene(NHC)catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported andδ-lactone...An N-heterocyclic carbene(NHC)catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported andδ-lactones tolerated with stereogenic centers atβ-andγ-positions are obtained in moderate to high yields and with high enantioselectivities.Further computational studies explain that the radical crosscoupling step is the key to determining the enantioselectivity.Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control.DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.展开更多
A palladium catalytic system incorporating novel Fc-JosiPhos ligands enables efficient C–N bond formation with diverse(hetero)aryl halides under low palladium loading(0.1 mol%).We rationally designed novel ferrocenyl...A palladium catalytic system incorporating novel Fc-JosiPhos ligands enables efficient C–N bond formation with diverse(hetero)aryl halides under low palladium loading(0.1 mol%).We rationally designed novel ferrocenyl phosphine-derived JosiPhos ligands(L1–L3).These ligands incorporate a ferrocenyl group providing greater steric bulk than tert-butyl or cyclohexyl and superior electron donation to cyclohexyl,along with a tunable side chain.They delivered excellent yields in the catalytic coupling of challenging(hetero)aryl chlorides with hydrazine.The scalable synthesis of arylhydrazines(5mmol scale)and subsequent cyclization to pyrazoles(65%–91%yields)highlights their potential for industrial conversion.Furthermore,the modularity of this strategy supports late-stage pharmaceutical functionalization,exemplified by TRPC inhibitor intermediate.展开更多
The Pd-catalyzed Suzuki-Miyaura coupling reaction is a crucial tool for constructing C-C bonds.Currently,the organic solvents employed during reaction may cause serious environmental problems.Moreover,the low solubili...The Pd-catalyzed Suzuki-Miyaura coupling reaction is a crucial tool for constructing C-C bonds.Currently,the organic solvents employed during reaction may cause serious environmental problems.Moreover,the low solubility of inorganic bases in organic solvents leads to enormous mass transfer resistance.To address this issue,the Pickering droplets reactor stabilized by Pd/g-C_(3)N_(4)at substrate-water two-phase interface is reported.Benefiting from the hydrophobic conjugated framework and hydrophilic terminal groups,Pd/g-C_(3)N_(4)can configure stable Pickering emulsion without additional functionalization.The Pd loaded catalysts exhibits excellent performance(TOF=21852 h^(-1))for the Suzuki-Miyaura coupling reaction,which is deriving from unique electronic structure of g-C_(3)N_(4)and high interfacial area of emulsion.Moreover,there is no clear decrease in reactivity after six cycles(conversion>86%).In this study,the organic solvent was replaced by reaction substrate,and the high activity can be achieved for various halogenated aromatic hydrocarbons and their derivatives.展开更多
The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions,which is a powerful tool for pharmaceutical a...The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions,which is a powerful tool for pharmaceutical and fine chemical synthesis.Here,we report a PdNi single-atom alloy(SAA)catalyst in which isolated Pd single atoms are anchored onto the surface of Ni nanoparticles(NPs)applied for Suzuki coupling reactions and Heck coupling reactions.The 0.1%PdNi SAA exhibits extraordinary catalytic activity(reaction rate:17,032.25 mmol h^(-1)gPd^(-1))toward the Suzuki cross-coupling reaction between 4-bromoanisole and phenylboronic acid at 80℃for 1 h.The excellent activity is supposed to attribute to the 100 percent utilization rate of Pd atoms and the highly stable surface zero-valance Pd atoms,which provides abundant sites and electrons for the adsorption and fracture of the C-X(X=Cl,Br,I)bond.Moreover,our work demonstrates the excellent application prospect of SAAs for cross-coupling reactions.展开更多
In order to improve the trajectory tracking precision and reduce the synchronization error of a 6-DOF lightweight robot, nonlinear proportion-deviation （N-PD） cross-coupling synchronization control strategy based on...In order to improve the trajectory tracking precision and reduce the synchronization error of a 6-DOF lightweight robot, nonlinear proportion-deviation （N-PD） cross-coupling synchronization control strategy based on adjacent coupling error analysis is presented. The mathematical models of the robot, including kinematic model, dynamic model and spline trajectory planing, are established and verified. Since it is difficult to describe the real-time contour error of the robot for complex trajectory, the adjacent coupling error is analyzed to solve the problem. Combined with nonlinear control and coupling performance of the robot, N-PD cross-coupling synchronization controller is designed and validated by simulation analysis. A servo control experimental system which mainly consists of laser tracking system, the robot mechanical system and EtherCAT based servo control system is constructed. The synchronization error is significantly decreased and the maximum trajectory error is reduced from 0.33 mm to 0.1 mm. The effectiveness of the control algorithm is validated by the experimental results, thus the control strategy can improve the robot＇s trajectory tracking precision significantly.展开更多
The new energy power generation is becoming increasingly important in the power system.Such as photovoltaic power generation has become a research hotspot,however,due to the characteristics of light radiation changes,...The new energy power generation is becoming increasingly important in the power system.Such as photovoltaic power generation has become a research hotspot,however,due to the characteristics of light radiation changes,photovoltaic power generation is unstable and random,resulting in a low utilization rate and directly affecting the stability of the power grid.To solve this problem,this paper proposes a coordinated control strategy for a newenergy power generation system with a hybrid energy storage unit based on the lithium iron phosphate-supercapacitor hybrid energy storage unit.Firstly,the variational mode decomposition algorithm is used to separate the high and low frequencies of the power signal,which is conducive to the rapid and accurate suppression of the power fluctuation of the energy storage system.Secondly,the fuzzy control algorithm is introduced to balance the power between energy storage.In this paper,the actual data is used for simulation,and the simulation results show that the strategy realizes the effective suppression of the bus voltage fluctuation and the accurate control of the internal state of the energy storage unit,effectively avoiding problems such as overshoot and over-discharge,and can significantly improve the stability of the photovoltaic power generation systemand the stability of the Direct Current bus.It is of great significance to promote the development of collaborative control technology for photovoltaic hybrid energy storage units.展开更多
This paper presents the design of an asymmetrically variable wingtip anhedral angles morphing aircraft,inspired by biomimetic mechanisms,to enhance lateral maneuver capability.Firstly,we establish a lateral dynamic mo...This paper presents the design of an asymmetrically variable wingtip anhedral angles morphing aircraft,inspired by biomimetic mechanisms,to enhance lateral maneuver capability.Firstly,we establish a lateral dynamic model considering additional forces and moments resulting during the morphing process,and convert it into a Multiple Input Multiple Output(MIMO)virtual control system by importing virtual inputs.Secondly,a classical dynamics inversion controller is designed for the outer-loop system.A new Global Fast Terminal Incremental Sliding Mode Controller(NDO-GFTISMC)is proposed for the inner-loop system,in which an adaptive law is implemented to weaken control surface chattering,and a Nonlinear Disturbance Observer(NDO)is integrated to compensate for unknown disturbances.The whole control system is proven semiglobally uniformly ultimately bounded based on the multi-Lyapunov function method.Furthermore,we consider tracking errors and self-characteristics of actuators,a quadratic programmingbased dynamic control allocation law is designed,which allocates virtual control inputs to the asymmetrically deformed wingtip and rudder.Actuator dynamic models are incorporated to ensure physical realizability of designed allocation law.Finally,comparative experimental results validate the effectiveness of the designed control system and control allocation law.The NDO-GFTISMC features faster convergence,stronger robustness,and 81.25%and 75.0%reduction in maximum state tracking error under uncertainty compared to the Incremental Nonlinear Dynamic Inversion Controller based on NDO(NDO-INDI)and Incremental Sliding Mode Controller based on NDO(NDO-ISMC),respectively.The design of the morphing aircraft significantly enhances lateral maneuver capability,maintaining a substantial control margin during lateral maneuvering,reducing the burden of the rudder surface,and effectively solving the actuator saturation problem of traditional aircraft during lateral maneuvering.展开更多
This work proposes the application of an iterative learning model predictive control(ILMPC)approach based on an adaptive fault observer(FOBILMPC)for fault-tolerant control and trajectory tracking in air-breathing hype...This work proposes the application of an iterative learning model predictive control(ILMPC)approach based on an adaptive fault observer(FOBILMPC)for fault-tolerant control and trajectory tracking in air-breathing hypersonic vehicles.In order to increase the control amount,this online control legislation makes use of model predictive control(MPC)that is based on the concept of iterative learning control(ILC).By using offline data to decrease the linearized model’s faults,the strategy may effectively increase the robustness of the control system and guarantee that disturbances can be suppressed.An adaptive fault observer is created based on the suggested ILMPC approach in order to enhance overall fault tolerance by estimating and compensating for actuator disturbance and fault degree.During the derivation process,a linearized model of longitudinal dynamics is established.The suggested ILMPC approach is likely to be used in the design of hypersonic vehicle control systems since numerical simulations have demonstrated that it can decrease tracking error and speed up convergence when compared to the offline controller.展开更多
Model predictive control(MPC)has been deemed as an attractive control method in motor drives by virtue of its simple structure,convenient multi-objective optimization,and satisfactory dynamic performance.However,the s...Model predictive control(MPC)has been deemed as an attractive control method in motor drives by virtue of its simple structure,convenient multi-objective optimization,and satisfactory dynamic performance.However,the strong reliance on mathematical models seriously restrains its practical application.Therefore,improving the robustness of MPC has attained significant attentions in the last two decades,followed by which,model-free predictive control(MFPC)comes into existence.This article aims to reveal the current state of MFPC strategies for motor drives and give the categorization from the perspective of implementation.Based on this review,the principles of the reported MFPC strategies are introduced in detail,as well as the challenges encountered in technology realization.In addition,some of typical and important concepts are experimentally validated via case studies to evaluate the performance and highlight their features.Finally,the future trends of MFPC are discussed based on the current state and reported developments.展开更多
Cholesterol is a sterol with a four-membered ring structure and a single hydroxyl group attached to one of the rings. It is the active, raw form of cholesterol. Cholesteryl Ester is the inactive form in which choleste...Cholesterol is a sterol with a four-membered ring structure and a single hydroxyl group attached to one of the rings. It is the active, raw form of cholesterol. Cholesteryl Ester is the inactive form in which cholesterol is esterified to be transported to target organs. The newly developed process of making bulky esters from unprecedented tertiary alcohols is applied to synthesize cholesterol esters successfully. Although cholesterol is a secondary alcohol, it is a very bulky and interesting compound due to its immense application. Usually, specific enzymes catalyze cholesterol to cholesterol ester. This project aims to develop a cross-coupling chemistry process to synthesize cholesterol esters and see the broader application of those new cholesterol esters in chemical biology. The mixture of cholesterol, sodium tert-butoxide, aroyl chloride, the catalyst PdCl2 (dtbpf) complex, and the solvent 1,4-dioxane, when microwaved at 100˚C for 2 hours, works well for the formation of cross-coupling cholesterol ester products in good to high yields.展开更多
Purpose–This study aims to propose a cooperative adhesion control method for trains with multiple motors electric locomotives.The method is intended to optimize the output torque of each motor,maximize the utilizatio...Purpose–This study aims to propose a cooperative adhesion control method for trains with multiple motors electric locomotives.The method is intended to optimize the output torque of each motor,maximize the utilization of train adhesion within the total torque command,reduce the train skidding/sliding phenomenon and achieve optimal adhesion utilization for each axle,thus realizing the optimal allocation of the multi-motor electric locomotives.Design/methodology/approach–In this study,a model predictive control(MPC)-based cooperative maximum adhesion tracking control method for multi-motor electric locomotives is presented.Firstly,train traction system with multiple motors is constructed in accordance with Newton’s second law.These equations include the train dynamics equations,the axle dynamics equations,and the wheel-rail adhesion coefficient equations.Then,a new MPC-based multi-axle adhesion co-optimization method is put forward.This method calculates the optimal output torque through real-time iteration based on the known reference slip speed to achieve multi-axle co-optimization under different circumstances.Findings–This paper presents a MPC system designed for the cooperative control of multi-axle adhesion.The results indicate that the proposed control system is able to optimize the adhesion of multiple axles under numerous different conditions and achieve the optimal power distribution based on the reduction of train skidding/sliding.Originality/value–This study presents a novel cooperative adhesion tracking control scheme.It is designed for multi-motor electric locomotives,which has rarely been studied before.And simulations are carried out in different conditions,including variable surfaces and motor failing.展开更多
Patients with complete spinal cord injury retain the potential for volitional muscle activity in muscles located below the spinal injury level.However,because of prolonged inactivity,initial attempts to activate these...Patients with complete spinal cord injury retain the potential for volitional muscle activity in muscles located below the spinal injury level.However,because of prolonged inactivity,initial attempts to activate these muscles may not effectively engage any of the remaining neurons in the descending pathway.A previous study unexpectedly found that a brief clinical round of passive activity significantly increased volitional muscle activation,as measured by surface electromyography.In this study,we further explored the effect of passive activity on surface electromyographic signals during volitional control tasks among individuals with complete spinal cord injury.Eleven patients with chronic complete thoracic spinal cord injury were recruited.Surface electromyography data from eight major leg muscles were acquired and compared before and after the passive activity protocol.The results indicated that the passive activity led to an increased number of activated volitional muscles and an increased frequency of activation.Although the cumulative root mean square of surface electromyography amplitude for volitional control of movement showed a slight increase after passive activity,the difference was not statistically significant.These findings suggest that brief passive activity may enhance the ability to initiate volitional muscle activity during surface electromyography tasks and underscore the potential of passive activity for improving residual motor control among patients with motor complete spinal cord injury.展开更多
This study examines the adaptive boundary control problem of flexible marine riser with internal flow coupling.The dynamic model of the flexible marine riser system with internal flow coupling is derived using the Ham...This study examines the adaptive boundary control problem of flexible marine riser with internal flow coupling.The dynamic model of the flexible marine riser system with internal flow coupling is derived using the Hamiltonian principle.An analysis of internal flow’s influence on the vibration characteristics of flexible marine risers is conducted.Then,for the uncertain environmental disturbance,the adaptive fuzzy logic system is introduced to dynamically approximate the boundary disturbance,and a robust adaptive fuzzy boundary control is proposed.The uniform boundedness of the closed-loop system is proved based on Lyapunov theory.The well-posedness of the closed-loop system is proved by operator semigroup theory.The proposed control’s effectiveness is validated through comparison with existing control methods.展开更多
Dear Editor,This letter presents an improved repetitive controller(IRC) that uses a complex-coefficient filter to enhance the tracking performance of a system for periodic signals. Compared with the low-pass filter us...Dear Editor,This letter presents an improved repetitive controller(IRC) that uses a complex-coefficient filter to enhance the tracking performance of a system for periodic signals. Compared with the low-pass filter used in the conventional repetitive controller(CRC), the complex-coefficient filter causes less change in the phase and amplitude of a signal at the frequencies of the periodic signal, especially at the fundamental frequency, when the two filters have the same cutofffrequency.展开更多
文摘A chromium(II)-catalyzed reduction cross coupling reaction was reported.This reaction utilizes inexpensive and readily available chromium dichloride as a catalyst and 4,4'-di-tert-butyl-bipyridine as a ligand to achieve reduction cross coupling between trifluoromethyl olefins and alkyl bromides under mild conditions,effectively synthesizing difluoroalkene derivatives.This reaction exhibits good substrate universality and is compatible with multiple important functional groups,providing a concise synthetic pathway for constructing conjugated difluoroalkenes containing allyl difluoromethylene structural units.Preliminary mechanistic experiments indicate that alkyl bromides first undergo a reduction process to generate corresponding alkyl radicals,followed by addition to trifluoromethyl olefins.After binding with Cr(II),they undergo aβ-fluorine elimination process to generate difluoroalkenes.
文摘Chiral carbonyl compounds frequently occur in natural products and pharmaceuticals. Additionally, they serve as important intermediates in organic synthesis. Transition metal-catalyzed asymmetric carbonylative cross-coupling reactions are among the most straightforward and effective methods for synthesizing chiral carbonyl compounds, including esters, amides, and ketones. The advances in asymmetric carbonylative cross-coupling reactions using various O-, N-, C-, and S-containing nucleophiles or electrophiles over the past decade are summarized.
基金support of this work by the National Natural Science Foundation of China(Nos.22371307,21971267)the program for Guangdong Introducing Innovative and Entrepreneurial Teams(No.2017ZT07C069).
文摘Selective defluorinative functionalization of trifluoromethylarenes(ArCF3)to obtain the pharmaceutically commonα,α-difluorobenzylic motif is an attractive and elegant synthetic route.Over the past decade,although C(sp^(3))-F bonds functionalization have been greatly developed,catalytic cross-coupling of trifluoromethylarenes with C-H of terminal alkynes remains a challenge.Here,we report an approach to achieve Sonogashira-type cross-coupling of trifluoromethylarenes with terminal alkynes C(sp)-H bonds via photoredox and Cu/L dual catalysis.Tridentate anionic ligand is pivotal to realize this C-H sp-sp^(3) cross-coupling.Moreover,this unique catalytic system is also suitable for cross-coupling of C(sp^(3))-F bonds with azoles C(sp^(2))-H bonds.A series of trifluoromethylarenes,terminal alkynes and azoles with various functional groups are compatible with this protocol affording a variety of defluoroalkynylation or defluoroazolation products.Preliminary mechanistic studies indicated that deprotonated BINOL involved as a photocatalyst to activate ArCF3 rather than a ligand to the metal.
基金supported by the National Natural Science Foundation of China(No.22171046)the Hundred-Talent Project of Fujian(No.50021113)Fuzhou University(No.0480-00489503)。
文摘In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions.Herein,we report a cobalt-catalyzed migratory carboncarbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl-and alkyl-functionalized cyclooctenes.Preliminary mechanistic studies suggest the oxidation-induced cisbicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction,which promotes the development of other diverse migratory cross-coupling of borate complexes.
基金CAMS Innovation Fund for Medical Sciences(CIFMS)(Nos.2022-I2M-1-013,2022-I2M-1-014,2022-I2M-2-002).
文摘The switchable cross-coupling of indoles and pyridotriazoles through carbene insertion at C_(2)-or C_(3)-positon has been developed in this paper.This highly site-selective C-H carbenoid functionalization is determined by both the Rh-catalyst species and auxiliary groups.[Cp∗RhCl_(2)]_(2) and coordinating pyrimidyl group direct the C-H carbenoid functionalization to occur at the C_(2)-position,while Rh2OAc4 and noncoordinating benzyl group lead the reaction to occur at the C_(3)-position of the indoles.This regioselective C−H functionalization strategy is of significant importance for the discovery of indole drugs.
基金financial supports for this work are provided by the National Natural Science Foundation of China(Nos.21871160,21672121,22071130)。
文摘An N-heterocyclic carbene(NHC)catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported andδ-lactones tolerated with stereogenic centers atβ-andγ-positions are obtained in moderate to high yields and with high enantioselectivities.Further computational studies explain that the radical crosscoupling step is the key to determining the enantioselectivity.Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control.DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.
基金supported by the National Natural Science Foundation of China(2210829)We thank Analysis&Testing Laboratory for Life Sciences and Medicine of Air Force Medical University for HR MS analysis.
文摘A palladium catalytic system incorporating novel Fc-JosiPhos ligands enables efficient C–N bond formation with diverse(hetero)aryl halides under low palladium loading(0.1 mol%).We rationally designed novel ferrocenyl phosphine-derived JosiPhos ligands(L1–L3).These ligands incorporate a ferrocenyl group providing greater steric bulk than tert-butyl or cyclohexyl and superior electron donation to cyclohexyl,along with a tunable side chain.They delivered excellent yields in the catalytic coupling of challenging(hetero)aryl chlorides with hydrazine.The scalable synthesis of arylhydrazines(5mmol scale)and subsequent cyclization to pyrazoles(65%–91%yields)highlights their potential for industrial conversion.Furthermore,the modularity of this strategy supports late-stage pharmaceutical functionalization,exemplified by TRPC inhibitor intermediate.
基金the National Natural Science Foundation of China(22178243).
文摘The Pd-catalyzed Suzuki-Miyaura coupling reaction is a crucial tool for constructing C-C bonds.Currently,the organic solvents employed during reaction may cause serious environmental problems.Moreover,the low solubility of inorganic bases in organic solvents leads to enormous mass transfer resistance.To address this issue,the Pickering droplets reactor stabilized by Pd/g-C_(3)N_(4)at substrate-water two-phase interface is reported.Benefiting from the hydrophobic conjugated framework and hydrophilic terminal groups,Pd/g-C_(3)N_(4)can configure stable Pickering emulsion without additional functionalization.The Pd loaded catalysts exhibits excellent performance(TOF=21852 h^(-1))for the Suzuki-Miyaura coupling reaction,which is deriving from unique electronic structure of g-C_(3)N_(4)and high interfacial area of emulsion.Moreover,there is no clear decrease in reactivity after six cycles(conversion>86%).In this study,the organic solvent was replaced by reaction substrate,and the high activity can be achieved for various halogenated aromatic hydrocarbons and their derivatives.
基金supported by the financial aid from National Science and Technology Major Project of China(No.2021YFB3500700)National Natural Science Foundation of China(Nos.22020102003,22025506 and 22271274)Program of Science and Technology Development Plan of Jilin Province of China(Nos.20230101035JC and 20230101022JC)。
文摘The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions,which is a powerful tool for pharmaceutical and fine chemical synthesis.Here,we report a PdNi single-atom alloy(SAA)catalyst in which isolated Pd single atoms are anchored onto the surface of Ni nanoparticles(NPs)applied for Suzuki coupling reactions and Heck coupling reactions.The 0.1%PdNi SAA exhibits extraordinary catalytic activity(reaction rate:17,032.25 mmol h^(-1)gPd^(-1))toward the Suzuki cross-coupling reaction between 4-bromoanisole and phenylboronic acid at 80℃for 1 h.The excellent activity is supposed to attribute to the 100 percent utilization rate of Pd atoms and the highly stable surface zero-valance Pd atoms,which provides abundant sites and electrons for the adsorption and fracture of the C-X(X=Cl,Br,I)bond.Moreover,our work demonstrates the excellent application prospect of SAAs for cross-coupling reactions.
基金Project(2015AA043003)supported by National High-technology Research and Development Program of ChinaProject(GY2016ZB0068)supported by Application Technology Research and Development Program of Heilongjiang Province,ChinaProject(SKLR201301A03)supported by Self-planned Task of State Key Laboratory of Robotics and System(Harbin Institute of Technology),China
文摘In order to improve the trajectory tracking precision and reduce the synchronization error of a 6-DOF lightweight robot, nonlinear proportion-deviation （N-PD） cross-coupling synchronization control strategy based on adjacent coupling error analysis is presented. The mathematical models of the robot, including kinematic model, dynamic model and spline trajectory planing, are established and verified. Since it is difficult to describe the real-time contour error of the robot for complex trajectory, the adjacent coupling error is analyzed to solve the problem. Combined with nonlinear control and coupling performance of the robot, N-PD cross-coupling synchronization controller is designed and validated by simulation analysis. A servo control experimental system which mainly consists of laser tracking system, the robot mechanical system and EtherCAT based servo control system is constructed. The synchronization error is significantly decreased and the maximum trajectory error is reduced from 0.33 mm to 0.1 mm. The effectiveness of the control algorithm is validated by the experimental results, thus the control strategy can improve the robot＇s trajectory tracking precision significantly.
基金supported by the State Grid Corporation of China Science and Technology Project,grant number 52270723000900K.
文摘The new energy power generation is becoming increasingly important in the power system.Such as photovoltaic power generation has become a research hotspot,however,due to the characteristics of light radiation changes,photovoltaic power generation is unstable and random,resulting in a low utilization rate and directly affecting the stability of the power grid.To solve this problem,this paper proposes a coordinated control strategy for a newenergy power generation system with a hybrid energy storage unit based on the lithium iron phosphate-supercapacitor hybrid energy storage unit.Firstly,the variational mode decomposition algorithm is used to separate the high and low frequencies of the power signal,which is conducive to the rapid and accurate suppression of the power fluctuation of the energy storage system.Secondly,the fuzzy control algorithm is introduced to balance the power between energy storage.In this paper,the actual data is used for simulation,and the simulation results show that the strategy realizes the effective suppression of the bus voltage fluctuation and the accurate control of the internal state of the energy storage unit,effectively avoiding problems such as overshoot and over-discharge,and can significantly improve the stability of the photovoltaic power generation systemand the stability of the Direct Current bus.It is of great significance to promote the development of collaborative control technology for photovoltaic hybrid energy storage units.
基金supported by the National Natural Science Foundation of China(Nos.62103052 and No.52175214)。
文摘This paper presents the design of an asymmetrically variable wingtip anhedral angles morphing aircraft,inspired by biomimetic mechanisms,to enhance lateral maneuver capability.Firstly,we establish a lateral dynamic model considering additional forces and moments resulting during the morphing process,and convert it into a Multiple Input Multiple Output(MIMO)virtual control system by importing virtual inputs.Secondly,a classical dynamics inversion controller is designed for the outer-loop system.A new Global Fast Terminal Incremental Sliding Mode Controller(NDO-GFTISMC)is proposed for the inner-loop system,in which an adaptive law is implemented to weaken control surface chattering,and a Nonlinear Disturbance Observer(NDO)is integrated to compensate for unknown disturbances.The whole control system is proven semiglobally uniformly ultimately bounded based on the multi-Lyapunov function method.Furthermore,we consider tracking errors and self-characteristics of actuators,a quadratic programmingbased dynamic control allocation law is designed,which allocates virtual control inputs to the asymmetrically deformed wingtip and rudder.Actuator dynamic models are incorporated to ensure physical realizability of designed allocation law.Finally,comparative experimental results validate the effectiveness of the designed control system and control allocation law.The NDO-GFTISMC features faster convergence,stronger robustness,and 81.25%and 75.0%reduction in maximum state tracking error under uncertainty compared to the Incremental Nonlinear Dynamic Inversion Controller based on NDO(NDO-INDI)and Incremental Sliding Mode Controller based on NDO(NDO-ISMC),respectively.The design of the morphing aircraft significantly enhances lateral maneuver capability,maintaining a substantial control margin during lateral maneuvering,reducing the burden of the rudder surface,and effectively solving the actuator saturation problem of traditional aircraft during lateral maneuvering.
基金supported by the National Natural Science Foundation of China(12072090).
文摘This work proposes the application of an iterative learning model predictive control(ILMPC)approach based on an adaptive fault observer(FOBILMPC)for fault-tolerant control and trajectory tracking in air-breathing hypersonic vehicles.In order to increase the control amount,this online control legislation makes use of model predictive control(MPC)that is based on the concept of iterative learning control(ILC).By using offline data to decrease the linearized model’s faults,the strategy may effectively increase the robustness of the control system and guarantee that disturbances can be suppressed.An adaptive fault observer is created based on the suggested ILMPC approach in order to enhance overall fault tolerance by estimating and compensating for actuator disturbance and fault degree.During the derivation process,a linearized model of longitudinal dynamics is established.The suggested ILMPC approach is likely to be used in the design of hypersonic vehicle control systems since numerical simulations have demonstrated that it can decrease tracking error and speed up convergence when compared to the offline controller.
基金supported in part by the National Natural Science Foundation of China under Grant 52077002。
文摘Model predictive control(MPC)has been deemed as an attractive control method in motor drives by virtue of its simple structure,convenient multi-objective optimization,and satisfactory dynamic performance.However,the strong reliance on mathematical models seriously restrains its practical application.Therefore,improving the robustness of MPC has attained significant attentions in the last two decades,followed by which,model-free predictive control(MFPC)comes into existence.This article aims to reveal the current state of MFPC strategies for motor drives and give the categorization from the perspective of implementation.Based on this review,the principles of the reported MFPC strategies are introduced in detail,as well as the challenges encountered in technology realization.In addition,some of typical and important concepts are experimentally validated via case studies to evaluate the performance and highlight their features.Finally,the future trends of MFPC are discussed based on the current state and reported developments.
文摘Cholesterol is a sterol with a four-membered ring structure and a single hydroxyl group attached to one of the rings. It is the active, raw form of cholesterol. Cholesteryl Ester is the inactive form in which cholesterol is esterified to be transported to target organs. The newly developed process of making bulky esters from unprecedented tertiary alcohols is applied to synthesize cholesterol esters successfully. Although cholesterol is a secondary alcohol, it is a very bulky and interesting compound due to its immense application. Usually, specific enzymes catalyze cholesterol to cholesterol ester. This project aims to develop a cross-coupling chemistry process to synthesize cholesterol esters and see the broader application of those new cholesterol esters in chemical biology. The mixture of cholesterol, sodium tert-butoxide, aroyl chloride, the catalyst PdCl2 (dtbpf) complex, and the solvent 1,4-dioxane, when microwaved at 100˚C for 2 hours, works well for the formation of cross-coupling cholesterol ester products in good to high yields.
基金supported by Scientific Research Projects of China Association of Metros(CAMET-KY-2022039)State Key Laboratory of Traction and Control System of EMU and Locomotive(2023YJ386).
文摘Purpose–This study aims to propose a cooperative adhesion control method for trains with multiple motors electric locomotives.The method is intended to optimize the output torque of each motor,maximize the utilization of train adhesion within the total torque command,reduce the train skidding/sliding phenomenon and achieve optimal adhesion utilization for each axle,thus realizing the optimal allocation of the multi-motor electric locomotives.Design/methodology/approach–In this study,a model predictive control(MPC)-based cooperative maximum adhesion tracking control method for multi-motor electric locomotives is presented.Firstly,train traction system with multiple motors is constructed in accordance with Newton’s second law.These equations include the train dynamics equations,the axle dynamics equations,and the wheel-rail adhesion coefficient equations.Then,a new MPC-based multi-axle adhesion co-optimization method is put forward.This method calculates the optimal output torque through real-time iteration based on the known reference slip speed to achieve multi-axle co-optimization under different circumstances.Findings–This paper presents a MPC system designed for the cooperative control of multi-axle adhesion.The results indicate that the proposed control system is able to optimize the adhesion of multiple axles under numerous different conditions and achieve the optimal power distribution based on the reduction of train skidding/sliding.Originality/value–This study presents a novel cooperative adhesion tracking control scheme.It is designed for multi-motor electric locomotives,which has rarely been studied before.And simulations are carried out in different conditions,including variable surfaces and motor failing.
基金supported by the Fundamental Research Funds for Central Public Welfare Research Institute,No.2020CZ-5(to WS and GS)the National Natural Science Foundation of China,No.31970970(to JSR)Fundamental Research Funds for the Central Universities,No.YWF-23-YG-QB-010(to JSR)。
文摘Patients with complete spinal cord injury retain the potential for volitional muscle activity in muscles located below the spinal injury level.However,because of prolonged inactivity,initial attempts to activate these muscles may not effectively engage any of the remaining neurons in the descending pathway.A previous study unexpectedly found that a brief clinical round of passive activity significantly increased volitional muscle activation,as measured by surface electromyography.In this study,we further explored the effect of passive activity on surface electromyographic signals during volitional control tasks among individuals with complete spinal cord injury.Eleven patients with chronic complete thoracic spinal cord injury were recruited.Surface electromyography data from eight major leg muscles were acquired and compared before and after the passive activity protocol.The results indicated that the passive activity led to an increased number of activated volitional muscles and an increased frequency of activation.Although the cumulative root mean square of surface electromyography amplitude for volitional control of movement showed a slight increase after passive activity,the difference was not statistically significant.These findings suggest that brief passive activity may enhance the ability to initiate volitional muscle activity during surface electromyography tasks and underscore the potential of passive activity for improving residual motor control among patients with motor complete spinal cord injury.
基金financially supported by Sichuan Science and Technology Program(Grant No.2023NSFSC1980).
文摘This study examines the adaptive boundary control problem of flexible marine riser with internal flow coupling.The dynamic model of the flexible marine riser system with internal flow coupling is derived using the Hamiltonian principle.An analysis of internal flow’s influence on the vibration characteristics of flexible marine risers is conducted.Then,for the uncertain environmental disturbance,the adaptive fuzzy logic system is introduced to dynamically approximate the boundary disturbance,and a robust adaptive fuzzy boundary control is proposed.The uniform boundedness of the closed-loop system is proved based on Lyapunov theory.The well-posedness of the closed-loop system is proved by operator semigroup theory.The proposed control’s effectiveness is validated through comparison with existing control methods.
基金supported in part by the National Natural Science Foundation of China(61873348,6230 3266,62273200)JSPS(Japan Society for the Promotion of Science) KAKENHI(22H03998,23K25252)
文摘Dear Editor,This letter presents an improved repetitive controller(IRC) that uses a complex-coefficient filter to enhance the tracking performance of a system for periodic signals. Compared with the low-pass filter used in the conventional repetitive controller(CRC), the complex-coefficient filter causes less change in the phase and amplitude of a signal at the frequencies of the periodic signal, especially at the fundamental frequency, when the two filters have the same cutofffrequency.
