A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-...A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.展开更多
Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions.Herein,we investigated the cascade hydrolysis and intramolecula...Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions.Herein,we investigated the cascade hydrolysis and intramolecular cyclization reactions of three vips with varying lengths within the well-defined nanocavities of cavitands in aqueous solution.Driven by hydrophobic effect,these vips were encapsulated within the dimeric capsules,adopting distinct conformations and orientations due to spatial constraints.Specifically,the shorter vip maintained an extended linear geometry,whereas the longer vips adopted a folded binding mode.Upon initiating the reaction,the terminal residue of the shorter vip displayed lower reactivity,while the longer vips,preorganized within the cavity,underwent efficient cyclization,resulting in significant differences in reaction kinetics.Furthermore,electrostatic potential fields played a critical role in modulating reaction rates,with the positively charged cavitand accelerating the reaction more efficiently compared to its negatively charged counterpart,likely due to stabilization of the anionic transition state.This study provides an effective strategy for designing enzymemimetic nanoreactors through the utilization of well-defined nanospaces.展开更多
The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis.However,examples of asymmetric Meinwald rearrangements are quite scarce,and these reactions have so far been limited to the...The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis.However,examples of asymmetric Meinwald rearrangements are quite scarce,and these reactions have so far been limited to the use of chiral Br?nsted acids as catalysts.Here,we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction,allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities.Thus,this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement,but also constitutes the first example of asymmetric formal monocarbon insertion into C-O bond of ester.Moreover,theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.展开更多
An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite(K_(2)S_(2)O_(5))as a connector is developed for the synthesis of various lactam-substi...An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite(K_(2)S_(2)O_(5))as a connector is developed for the synthesis of various lactam-substituted alkyl sulfones.Notably,this process does not require a metal catalyst or metal powder reductant,highlighting its environmentally friendly features.The reaction demonstrates outstanding substrate adaptability and a high tolerance towards diverse functional groups.Furthermore,the biologically active molecules and commercially available drugs with a late-stage modification are also highly compatible with this transformation.Mechanistic studies revealed that the reaction proceeds through a single-step process involving intramolecular radical cyclization,"SO_(2)"insertion,and external alkyl incorporation.展开更多
The evolutionarily conserved mitogen-activated protein kinase(MAPK)cascades relay extracellular signals into cells,triggering a variety of cellular responses.We previously revealed NtMPK4 as a positive regulator of ni...The evolutionarily conserved mitogen-activated protein kinase(MAPK)cascades relay extracellular signals into cells,triggering a variety of cellular responses.We previously revealed NtMPK4 as a positive regulator of nicotine biosynthesis;however,its upstream regulation remains unclear.Here,we characterized a MAPK cascade,comprising NtMEKK1b,NtMPKK2a,and NtMPK4,that promotes nicotine biosynthesis.This signaling module transduces external cues,including jasmonate and pathogen elicitors such as flg22,into post-translational modifications that enhance transcriptional activity and pathway gene expression.NtMPKK2a physically interacts with and phosphorylates NtMPK4 in vivo,confirming its role as an upstream kinase.RNAi-mediated silencing of NtMPKK2a significantly reduced the expression of nicotine pathway genes and decreased nicotine accumulation,whereas induced-overexpression of NtMPKK2a upregulated nicotine pathway genes and increased nicotine contents in tobacco hairy roots.Overexpression of NtMPKK2a in tobacco cells enhanced the transactivation activity of a NIC2-locus Ethylene Response Factor NtERF221 on Putrescine N-methyltransferase(NtPMT)promotor,further supporting its role in promoting nicotine biosynthesis.Furthermore,we identified NtMEKK1b,a tobacco MEKK that interacts with NtMAPKK2a in yeast cells.Knock-down of NtMEKK1b in transgenic tobacco plants attenuated the expression of nicotine pathway genes and reduced nicotine contents,whereas induced-overexpression of NtMEKK1b upregulated gene expression and nicotine accumulation.Our findings uncover a previously uncharacterized MAPK cascade module,NtMEKK1b-NtMPKK2a-NtMPK4,that regulates nicotine biosynthesis,highlighting the importance of posttranslational regulation in nicotine biosynthesis.展开更多
Nickel-catalyzed reductive cross-coupling(RCC)reactions between alkenes and alkyl electrophiles are undoubtedly the attractive approaches to new functionalized heterocycles.However,the alkylation reagents are still ra...Nickel-catalyzed reductive cross-coupling(RCC)reactions between alkenes and alkyl electrophiles are undoubtedly the attractive approaches to new functionalized heterocycles.However,the alkylation reagents are still rather limited for the arylalkylation of tethered alkenes via RCC reactions.Thus,developing more robust methods to access heterocycles from stable and readily available starting materials under RCC conditions is still highly challenging and desirable.A new nickelcatalyzed reductive arylalkylation of tethered alkenes with cyclosulfonium salts as C(sp^(3))electrophiles to access the sulfurcontaining oxindoles is developed.This tandem ring-opening/cyclization/reductive coupling protocol enables the efficient construction of various oxindoles bearing all-carbon quaternary centers under mild conditions with broad functional group tolerance.Notably,many drug derivatives are readily functionalized using the developed protocol.展开更多
One of the main issues in designing optimum tapered cascades for uranium enrichment for annual fuel production in a power reactor is whether to employ large(fat)or small(thin)cascades.What will be the permissible and ...One of the main issues in designing optimum tapered cascades for uranium enrichment for annual fuel production in a power reactor is whether to employ large(fat)or small(thin)cascades.What will be the permissible and optimal ranges of the number of machines that can be used in a cascade?For the first time,the permissible and optimal ranges of the number of gas centrifuges that can be utilized in a cascade were investigated using two types of centrifuges,and the performance of small and large tapered cascades was discussed.The particle swarm optimization algorithm(PSO)has been used to optimize tapered cascades.The results show:(1)For the first centrifuge,41 cascades(91≤n≤4897)and for the second centrifuge,49 cascades(18≤n≤3839)with small and large sizes can be used in enrichment facilities,and the best cascade for them has 530(with 23 stages)and 39(with 7 stages)centrifuges,respectively.(2)For both centrifuges,when 600≤n(number of centrifuges=n),the large cascade performance changes are relatively insignificant.(3)For both types of gas centrifuges,the annual los s of separation power in enrichment facilities is approximately 1.25%-4.82%of the total separation work required.展开更多
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity,characterized by a 5-5-6-5tetracyclic carbon skeleton formed by mangicdiene synthase Fg MS.Two proposed mechanisms for mangicdiene formation inv...Mangicol-type sesterterpenoids possess potent anti-inflammatory activity,characterized by a 5-5-6-5tetracyclic carbon skeleton formed by mangicdiene synthase Fg MS.Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization(path a) or C2-C10 cyclization(path b) after the C10carbocation formation,but neither has been experimentally validated.Here,we have identified a second mangicdiene synthase Man D,which is derived from Fusarium sp.JNU-XJ070152-01 and shares high amino acid sequence identity with Fg MS.Through heterologous expression of man D in Aspergillus oryzae NSAR1,we observed production not only of mangicdiene(1) and variecoltetraene(2),previously identified by expression of Fg MS in Escherichia coli,but also two novel sesterterpene skeletons fusadiene(3)and fusatriene(4).The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b,thus experimentally confirming that mangicdiene is built via path b for the first time,consistent with previous density functional theory(DFT) calculation results.展开更多
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report ph...Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission,which is constructed by cucurbit[7]uril(CB[7]),cyanostilbene derivative(DAC)and Laponite XLG(LP)via supramolecular cascade assembly.Compared with the free vip molecule DAC,the confinement of macrocycle CB[7]achieve effective near-infrared fluorescence in the aqueous phase from scratch,and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC,which not only result in a substantial enhancement of the fluorescence intensity,but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states.Further,8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt(HPTS)is introduced in the cascade assembly to fabricated photocontrollable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer,which is successfully employed in reversible multiple information encryption.展开更多
Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmemb...Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.展开更多
During sending-end faults in the hybrid cascaded HVDC(HC-HVDC)system,the transient voltage drop characteristics under the interaction of the AC/DC hybrid system remain unclear,and the reactive power support provided b...During sending-end faults in the hybrid cascaded HVDC(HC-HVDC)system,the transient voltage drop characteristics under the interaction of the AC/DC hybrid system remain unclear,and the reactive power support provided by the HC-HVDC to the sending-end AC system requires further investigation.To address this problem,the reactive power interaction coupling mechanism between the sending-end AC system and the HC-HVDC is revealed,and the transient voltage mathematical model considering fault severity and duration is established.Under the dynamic change of the AC system voltage,the difference between the reactive power provided only by the reactive power compensation devices and by the combined modular multilevel converters(MMC)and reactive power compensation devices is analyzed.It is concluded that using MMC to provide a proportion of reactive power enhances the reactive power support to the AC system during faults.Then,the transient voltage model considering the reactive power support of MMC is established,and the critical reactive power consumption of line commutated converter(LCC)is quantified.It is concluded that the reactive power consumption of LCC exceeding its critical value deteriorates the transient voltage.A coordinated support strategy for the sending-end AC system based on reactive power support of MMC and reactive power regulation of LCC is proposed.It can effectively address the challenge of weakened reactive power support to the AC system due to voltage drop,thereby preventing the unbalanced reactive power from deteriorating the transient voltage,and realizing active support of the tran-sient voltage.Finally,a simulation model is established on the PSCAD/EMTDC platform,and the simulation results validate the effectiveness of the proposed strategy in supporting the transient voltage,under different fault types,durations,severities,and locations.展开更多
This study investigates the turbulence-induced disturbances and stall precursor triggering mechanism in NACA65-18(10)cascade based on large eddy simulations.The results indicate that the disturbances exist under vario...This study investigates the turbulence-induced disturbances and stall precursor triggering mechanism in NACA65-18(10)cascade based on large eddy simulations.The results indicate that the disturbances exist under various operating conditions along the performance curve.The shear layer is the physical structure responsible for the generation,propagation,and dissipation of disturbances.When operating near stall,the separation on the suction surface intensifies,and strong unsteady backflow occurs at the trailing edge of the passage.Under the influence of inlet disturbances,unsteady behaviors between passages form specific phase differences,leading the entire system to oscillate in a first-order mode.As the flow develops from near-stall to stall,axial momentum decreases further,reducing the main flow’s ability to drive blockages downstream through convection.Consequently,the blockage accumulates during the circumferential propagation process until the stall onset.Based on the above mechanism,this study proposes factors describing the size of the backflow zone,shedding frequency,and convection velocity to characterize blockage dynamics,identifying critical values that represent the stall onset.展开更多
Energy transfers among internal waves in the northern South China Sea are not well characterized,particularly during typhoons,owing to the lack of in situ observations.Based on high-resolution mooring data collected d...Energy transfers among internal waves in the northern South China Sea are not well characterized,particularly during typhoons,owing to the lack of in situ observations.Based on high-resolution mooring data collected during Typhoon Trami(2024),this study reveals the occurrence of robust vertical energy redistribution among diurnal internal tides(D1 ITs)and near-inertial waves(NIWs).Strikingly,the typhoon not only amplified the NIW energy but also triggered an unexpected surge in the D1 IT energy.The observed average net energy transfer rate of 1×10^(-7) W kg^(−1) from typhoon-forced NIWs to D1 ITs occurred at water depths of 120-170 m.Further bispectral analysis indicated that the energy transfer is driven by nonlinear wave—wave interaction.These results reveal the existence of a new energy transfer pathway—from atmospheric forcing to D1 ITs—and redefine the redistribution of the internal wave energy during extreme weather events.展开更多
Tooth morphogenesis is orchestrated by a complex interplay of signaling pathways and transcription factors that control cell proliferation,apoptosis,and differentiation,with the Wnt/β-catenin signaling pathway playin...Tooth morphogenesis is orchestrated by a complex interplay of signaling pathways and transcription factors that control cell proliferation,apoptosis,and differentiation,with the Wnt/β-catenin signaling pathway playing a pivotal role.However,the comprehensive regulatory mechanisms of Wnt/β-catenin signaling remain largely unclear.Smad7,a key antagonist of the TGF-βsuperfamily,is essential for maintaining tissue homeostasis and ensuring proper cellular function.Our previous study has demonstrated that Smad7 knockout in mice leads to impaired proliferative property of tooth germ cells,resulting in small molars.Here,we identified SMAD7 expression in human dental papilla and dental pulp,colocalized with β-CATENIN and cell proliferationrelated proteins.RNA sequencing analysis revealed a significant reduction in Wnt signaling activity in Smad7-deficient mouse tooth germs.Using lentivirus transfection,we established SMAD7-knockdown human dental papilla stem cells,which manifested remarkably blunt proliferation rate,along with diminished Wnt signaling activity.In vivo transplantation investigations further revealed the indispensable role of SMAD7 in dentin formation.Mechanistically,we revealed that β-CATENIN interacts with P-SMAD2/3 and SMAD7 through co-immunoprecipitation and yeast two-hybrid assays.Inhibition of TGF-β pathway or disruption of SMAD7/β-CATENIN transcription factor complex formation potently impacted Wnt/β-catenin activities,indicating both direct and indirect regulatory mechanisms.These findings highlight the critical role of SMAD7 in the proliferation and diffe rentiation of human dental stem cells,which could contribute to dental tissue regeneration and engineering.展开更多
A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7：1-20：1 dr under the catalysis of L-diarylprolinol...A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7：1-20：1 dr under the catalysis of L-diarylprolinol silyl ether. This reaction provides a facile access to highly enantioenriched 4- diphenylphosphinyl chroman-2-ols. It also represents a novel organocatalytic asymmetric phospha- Michael addition of α,β-unsaturated aldehydes with pentavalent P-nucleophiles.展开更多
By using ambient air as the oxidant and malic acid as the promoter,a practical method for the preparation of 2-aminobenzothiazoles through visible-light-initiated cascade reaction of aromatic amines and KSCN in eco-fr...By using ambient air as the oxidant and malic acid as the promoter,a practical method for the preparation of 2-aminobenzothiazoles through visible-light-initiated cascade reaction of aromatic amines and KSCN in eco-friendly bis(methoxypropy)ether under metal-,hazardous additive-,photocatalyst-free conditions was established.展开更多
A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excel...A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excellent yields.展开更多
A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three conti...A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three contiguous quaternary carbon centers in moderate to high yields with excellent diastereoselectivities. In this reaction, the allene moiety was fully fused into the cyclopentene ring.展开更多
We have developed a metal-free radical cascade reaction of N-substituted 2-aryl indoles with readily available sulfonyl hydrazides for the rapid construction of arylsulfonyl-substituted indolo[2,1-a]isoquinolin-6(5H)-...We have developed a metal-free radical cascade reaction of N-substituted 2-aryl indoles with readily available sulfonyl hydrazides for the rapid construction of arylsulfonyl-substituted indolo[2,1-a]isoquinolin-6(5H)-one derivatives.With the TBAI–TBHP catalytic system,a broad series of structurally diverse indolo[2,1-a]isoquinolin-6(5H)-one derivatives were obtained in moderate to excellent yields.The reaction features mild reaction conditions,operationally easiness,scaled-up feasibility,and high functional-group-tolerance.展开更多
基金funds from Natural Science Foundation of Guangxi Province(Nos.2023GXNSFBA026304,2023GXNSFDA026063)the Guangxi Science and Technology Base and Special Talents(No.Guike AD20159047).
文摘A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.
基金funded by the National Natural Science Foundation of China(Nos.22271154,M-0411)the China Postdoctoral Science Foundation(No.2023M731658)+2 种基金the Science Fund for Distinguished Young Scholars of Jiangsu Province(No.BK20240078)the Innovation Support Program of Jiangsu Province(No.BZ2023055)the High-Performance Computing Platform of Peking Uniersity。
文摘Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions.Herein,we investigated the cascade hydrolysis and intramolecular cyclization reactions of three vips with varying lengths within the well-defined nanocavities of cavitands in aqueous solution.Driven by hydrophobic effect,these vips were encapsulated within the dimeric capsules,adopting distinct conformations and orientations due to spatial constraints.Specifically,the shorter vip maintained an extended linear geometry,whereas the longer vips adopted a folded binding mode.Upon initiating the reaction,the terminal residue of the shorter vip displayed lower reactivity,while the longer vips,preorganized within the cavity,underwent efficient cyclization,resulting in significant differences in reaction kinetics.Furthermore,electrostatic potential fields played a critical role in modulating reaction rates,with the positively charged cavitand accelerating the reaction more efficiently compared to its negatively charged counterpart,likely due to stabilization of the anionic transition state.This study provides an effective strategy for designing enzymemimetic nanoreactors through the utilization of well-defined nanospaces.
基金financial support from the National Natural Science Foundation of China(Nos.22125108,22101238,22331004 and 22121001)Yunnan Fundamental Research Project(No.202401CF070024)+2 种基金Natural Science Foundation of Jiangsu Province(No.BK20211059)the Project of Science and Technology of Xuzhou Government(No.KC22080)NFFTBS(No.J1310024)。
文摘The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis.However,examples of asymmetric Meinwald rearrangements are quite scarce,and these reactions have so far been limited to the use of chiral Br?nsted acids as catalysts.Here,we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction,allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities.Thus,this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement,but also constitutes the first example of asymmetric formal monocarbon insertion into C-O bond of ester.Moreover,theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.
基金the Scientific Research Fund of Hunan Provincial Education Department(21B0262 and 22B1094)the Natural Science Foundation of Hunan Province(2022JJ40857)the Hunan Provincial Innovation Foundation For Postgraduate(CX20230757)forfinancial support.
文摘An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite(K_(2)S_(2)O_(5))as a connector is developed for the synthesis of various lactam-substituted alkyl sulfones.Notably,this process does not require a metal catalyst or metal powder reductant,highlighting its environmentally friendly features.The reaction demonstrates outstanding substrate adaptability and a high tolerance towards diverse functional groups.Furthermore,the biologically active molecules and commercially available drugs with a late-stage modification are also highly compatible with this transformation.Mechanistic studies revealed that the reaction proceeds through a single-step process involving intramolecular radical cyclization,"SO_(2)"insertion,and external alkyl incorporation.
基金supported partially by the Kentucky Tobacco Research and Development Center(KTRDC),University of Kentucky.
文摘The evolutionarily conserved mitogen-activated protein kinase(MAPK)cascades relay extracellular signals into cells,triggering a variety of cellular responses.We previously revealed NtMPK4 as a positive regulator of nicotine biosynthesis;however,its upstream regulation remains unclear.Here,we characterized a MAPK cascade,comprising NtMEKK1b,NtMPKK2a,and NtMPK4,that promotes nicotine biosynthesis.This signaling module transduces external cues,including jasmonate and pathogen elicitors such as flg22,into post-translational modifications that enhance transcriptional activity and pathway gene expression.NtMPKK2a physically interacts with and phosphorylates NtMPK4 in vivo,confirming its role as an upstream kinase.RNAi-mediated silencing of NtMPKK2a significantly reduced the expression of nicotine pathway genes and decreased nicotine accumulation,whereas induced-overexpression of NtMPKK2a upregulated nicotine pathway genes and increased nicotine contents in tobacco hairy roots.Overexpression of NtMPKK2a in tobacco cells enhanced the transactivation activity of a NIC2-locus Ethylene Response Factor NtERF221 on Putrescine N-methyltransferase(NtPMT)promotor,further supporting its role in promoting nicotine biosynthesis.Furthermore,we identified NtMEKK1b,a tobacco MEKK that interacts with NtMAPKK2a in yeast cells.Knock-down of NtMEKK1b in transgenic tobacco plants attenuated the expression of nicotine pathway genes and reduced nicotine contents,whereas induced-overexpression of NtMEKK1b upregulated gene expression and nicotine accumulation.Our findings uncover a previously uncharacterized MAPK cascade module,NtMEKK1b-NtMPKK2a-NtMPK4,that regulates nicotine biosynthesis,highlighting the importance of posttranslational regulation in nicotine biosynthesis.
基金Project supported by the National Natural Science Foundation of China(No.22271170)the Taishan Scholars Program from Shandong Province(No.tsqn202408197)the Natural Science Foundation of Shandong Province(No.ZR2024QB154)。
文摘Nickel-catalyzed reductive cross-coupling(RCC)reactions between alkenes and alkyl electrophiles are undoubtedly the attractive approaches to new functionalized heterocycles.However,the alkylation reagents are still rather limited for the arylalkylation of tethered alkenes via RCC reactions.Thus,developing more robust methods to access heterocycles from stable and readily available starting materials under RCC conditions is still highly challenging and desirable.A new nickelcatalyzed reductive arylalkylation of tethered alkenes with cyclosulfonium salts as C(sp^(3))electrophiles to access the sulfurcontaining oxindoles is developed.This tandem ring-opening/cyclization/reductive coupling protocol enables the efficient construction of various oxindoles bearing all-carbon quaternary centers under mild conditions with broad functional group tolerance.Notably,many drug derivatives are readily functionalized using the developed protocol.
文摘One of the main issues in designing optimum tapered cascades for uranium enrichment for annual fuel production in a power reactor is whether to employ large(fat)or small(thin)cascades.What will be the permissible and optimal ranges of the number of machines that can be used in a cascade?For the first time,the permissible and optimal ranges of the number of gas centrifuges that can be utilized in a cascade were investigated using two types of centrifuges,and the performance of small and large tapered cascades was discussed.The particle swarm optimization algorithm(PSO)has been used to optimize tapered cascades.The results show:(1)For the first centrifuge,41 cascades(91≤n≤4897)and for the second centrifuge,49 cascades(18≤n≤3839)with small and large sizes can be used in enrichment facilities,and the best cascade for them has 530(with 23 stages)and 39(with 7 stages)centrifuges,respectively.(2)For both centrifuges,when 600≤n(number of centrifuges=n),the large cascade performance changes are relatively insignificant.(3)For both types of gas centrifuges,the annual los s of separation power in enrichment facilities is approximately 1.25%-4.82%of the total separation work required.
基金financially supported by grants from the National Key Research and Development Program of China (No.2024YFE0102000)the National Natural Science Foundation of China (Nos.81925037,82321004,U22A20371,U24A20782,32170060,22177037,22207039,22307045)+6 种基金the Guangdong Major Project of Basic and Applied Basic Research (No.2023B0303000026)the Guangdong Natural Science Funds for Distinguished Young Scholars (No.2022B1515020028,China)the Guangdong International Science and Technology Cooperation Base (No.2021A0505020015,China)the Guangdong Basic and Applied Basic Research Foundation (Nos.2023B1515040016,2023A1515110388)the Innovative and Research Teams Project of Guangdong Higher Education Institution (No.2021KCXTD001,China)the Guangzhou Science and Technology Project (Nos.202206010020,2024A04J6241,2023A04J0080,China)the Fundamental Research Funds for the Central Universities (Nos.21623105,21624210)。
文摘Mangicol-type sesterterpenoids possess potent anti-inflammatory activity,characterized by a 5-5-6-5tetracyclic carbon skeleton formed by mangicdiene synthase Fg MS.Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization(path a) or C2-C10 cyclization(path b) after the C10carbocation formation,but neither has been experimentally validated.Here,we have identified a second mangicdiene synthase Man D,which is derived from Fusarium sp.JNU-XJ070152-01 and shares high amino acid sequence identity with Fg MS.Through heterologous expression of man D in Aspergillus oryzae NSAR1,we observed production not only of mangicdiene(1) and variecoltetraene(2),previously identified by expression of Fg MS in Escherichia coli,but also two novel sesterterpene skeletons fusadiene(3)and fusatriene(4).The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b,thus experimentally confirming that mangicdiene is built via path b for the first time,consistent with previous density functional theory(DFT) calculation results.
基金National Natural Science Foundation of China (NSFC) (No.22131008)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission,which is constructed by cucurbit[7]uril(CB[7]),cyanostilbene derivative(DAC)and Laponite XLG(LP)via supramolecular cascade assembly.Compared with the free vip molecule DAC,the confinement of macrocycle CB[7]achieve effective near-infrared fluorescence in the aqueous phase from scratch,and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC,which not only result in a substantial enhancement of the fluorescence intensity,but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states.Further,8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt(HPTS)is introduced in the cascade assembly to fabricated photocontrollable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer,which is successfully employed in reversible multiple information encryption.
基金the financial support from the National Natural Science Foundation of China(22408182)the Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(NJYT24024)the Natural Science Foundation of Inner Mongolia Autonomous Region(2023QN02007 and 2025QN02009)。
文摘Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.
基金supported by the National Key Research and Development Program of China(No.2021YFB1507001).
文摘During sending-end faults in the hybrid cascaded HVDC(HC-HVDC)system,the transient voltage drop characteristics under the interaction of the AC/DC hybrid system remain unclear,and the reactive power support provided by the HC-HVDC to the sending-end AC system requires further investigation.To address this problem,the reactive power interaction coupling mechanism between the sending-end AC system and the HC-HVDC is revealed,and the transient voltage mathematical model considering fault severity and duration is established.Under the dynamic change of the AC system voltage,the difference between the reactive power provided only by the reactive power compensation devices and by the combined modular multilevel converters(MMC)and reactive power compensation devices is analyzed.It is concluded that using MMC to provide a proportion of reactive power enhances the reactive power support to the AC system during faults.Then,the transient voltage model considering the reactive power support of MMC is established,and the critical reactive power consumption of line commutated converter(LCC)is quantified.It is concluded that the reactive power consumption of LCC exceeding its critical value deteriorates the transient voltage.A coordinated support strategy for the sending-end AC system based on reactive power support of MMC and reactive power regulation of LCC is proposed.It can effectively address the challenge of weakened reactive power support to the AC system due to voltage drop,thereby preventing the unbalanced reactive power from deteriorating the transient voltage,and realizing active support of the tran-sient voltage.Finally,a simulation model is established on the PSCAD/EMTDC platform,and the simulation results validate the effectiveness of the proposed strategy in supporting the transient voltage,under different fault types,durations,severities,and locations.
基金support of the National Natural Science Foundation of China(Nos.52322603 and U24A20141)the Science Center for Gas Turbine Project of China(No.P2023-B-Ⅱ-001-001)the Fundamental Research Funds for the Central Universities of China and the Beijing Nova Program of China(Nos.20220484074 and 20230484479)。
文摘This study investigates the turbulence-induced disturbances and stall precursor triggering mechanism in NACA65-18(10)cascade based on large eddy simulations.The results indicate that the disturbances exist under various operating conditions along the performance curve.The shear layer is the physical structure responsible for the generation,propagation,and dissipation of disturbances.When operating near stall,the separation on the suction surface intensifies,and strong unsteady backflow occurs at the trailing edge of the passage.Under the influence of inlet disturbances,unsteady behaviors between passages form specific phase differences,leading the entire system to oscillate in a first-order mode.As the flow develops from near-stall to stall,axial momentum decreases further,reducing the main flow’s ability to drive blockages downstream through convection.Consequently,the blockage accumulates during the circumferential propagation process until the stall onset.Based on the above mechanism,this study proposes factors describing the size of the backflow zone,shedding frequency,and convection velocity to characterize blockage dynamics,identifying critical values that represent the stall onset.
基金supported by the National Key R&D Plan Program of China [Grant number 2021YFC3101500]the National Natural Science Foundation of China [Grant number 42305014,42506024]。
文摘Energy transfers among internal waves in the northern South China Sea are not well characterized,particularly during typhoons,owing to the lack of in situ observations.Based on high-resolution mooring data collected during Typhoon Trami(2024),this study reveals the occurrence of robust vertical energy redistribution among diurnal internal tides(D1 ITs)and near-inertial waves(NIWs).Strikingly,the typhoon not only amplified the NIW energy but also triggered an unexpected surge in the D1 IT energy.The observed average net energy transfer rate of 1×10^(-7) W kg^(−1) from typhoon-forced NIWs to D1 ITs occurred at water depths of 120-170 m.Further bispectral analysis indicated that the energy transfer is driven by nonlinear wave—wave interaction.These results reveal the existence of a new energy transfer pathway—from atmospheric forcing to D1 ITs—and redefine the redistribution of the internal wave energy during extreme weather events.
基金supported by the National Key Research and Development Program of China to W.Tian (2022YFA1104400)the National Natural Science Foundation of China to T.Chen (82100959)a grant from the Sichuan Science and Technology Program to Z.Liu (2024YFFK0068)。
文摘Tooth morphogenesis is orchestrated by a complex interplay of signaling pathways and transcription factors that control cell proliferation,apoptosis,and differentiation,with the Wnt/β-catenin signaling pathway playing a pivotal role.However,the comprehensive regulatory mechanisms of Wnt/β-catenin signaling remain largely unclear.Smad7,a key antagonist of the TGF-βsuperfamily,is essential for maintaining tissue homeostasis and ensuring proper cellular function.Our previous study has demonstrated that Smad7 knockout in mice leads to impaired proliferative property of tooth germ cells,resulting in small molars.Here,we identified SMAD7 expression in human dental papilla and dental pulp,colocalized with β-CATENIN and cell proliferationrelated proteins.RNA sequencing analysis revealed a significant reduction in Wnt signaling activity in Smad7-deficient mouse tooth germs.Using lentivirus transfection,we established SMAD7-knockdown human dental papilla stem cells,which manifested remarkably blunt proliferation rate,along with diminished Wnt signaling activity.In vivo transplantation investigations further revealed the indispensable role of SMAD7 in dentin formation.Mechanistically,we revealed that β-CATENIN interacts with P-SMAD2/3 and SMAD7 through co-immunoprecipitation and yeast two-hybrid assays.Inhibition of TGF-β pathway or disruption of SMAD7/β-CATENIN transcription factor complex formation potently impacted Wnt/β-catenin activities,indicating both direct and indirect regulatory mechanisms.These findings highlight the critical role of SMAD7 in the proliferation and diffe rentiation of human dental stem cells,which could contribute to dental tissue regeneration and engineering.
基金Financial support from the National Natural Science Foundation of China(Nos. 21472096, J1103306)
文摘A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7：1-20：1 dr under the catalysis of L-diarylprolinol silyl ether. This reaction provides a facile access to highly enantioenriched 4- diphenylphosphinyl chroman-2-ols. It also represents a novel organocatalytic asymmetric phospha- Michael addition of α,β-unsaturated aldehydes with pentavalent P-nucleophiles.
基金the Hunan Provincial Natural Science Foundation of China(No.2019JJ20008)。
文摘By using ambient air as the oxidant and malic acid as the promoter,a practical method for the preparation of 2-aminobenzothiazoles through visible-light-initiated cascade reaction of aromatic amines and KSCN in eco-friendly bis(methoxypropy)ether under metal-,hazardous additive-,photocatalyst-free conditions was established.
文摘A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excellent yields.
基金supported by the Natural Science Foundation of China(Nos.21871293 and 22071264)。
文摘A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three contiguous quaternary carbon centers in moderate to high yields with excellent diastereoselectivities. In this reaction, the allene moiety was fully fused into the cyclopentene ring.
基金the State Key Basic Research Program of the People’s Republic of China (No. 2018YFC0310900)National Natural Science Foundation of China (Nos. 21871018, 21801005, 21732001)+7 种基金Shenzhen Science and Technology Innovation Committee (Nos. KQTD20190929174023858, JCYJ20180504165454447)Industry and Information Technology Bureau of Shenzhen Municipality (No. 201806151622209330)Guangdong Science and Technology Program (No. 2017B030314002)Shenzhen-Hong Kong Institute of Brain Science-Shenzhen Fundamental Research Institutions (No. 2019SHIBS0004)the National Ten Thousand Talent Program (the Leading Talent Tier) for the financial supportthe Science and Technology Project of Henan Province (No. 202102310328)the Henan Postdoctoral Foundationthe Postdoctoral Innovation Base of Anyang Institute of Technology for financial support
文摘We have developed a metal-free radical cascade reaction of N-substituted 2-aryl indoles with readily available sulfonyl hydrazides for the rapid construction of arylsulfonyl-substituted indolo[2,1-a]isoquinolin-6(5H)-one derivatives.With the TBAI–TBHP catalytic system,a broad series of structurally diverse indolo[2,1-a]isoquinolin-6(5H)-one derivatives were obtained in moderate to excellent yields.The reaction features mild reaction conditions,operationally easiness,scaled-up feasibility,and high functional-group-tolerance.
