An electronic circular dichroism(ECD)-based chiroptical sensing method has been developed forβ-andγ-chiral primary amines via a C-H activation reaction.With the addition of Pd(OAc)_(2),the flexible remote chiral pri...An electronic circular dichroism(ECD)-based chiroptical sensing method has been developed forβ-andγ-chiral primary amines via a C-H activation reaction.With the addition of Pd(OAc)_(2),the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex,producing an intense ECD response.The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed,together with theoretical verification using timedependent density functional theory(TDDFT).Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity.This work introduces an alternative perspective of C-H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.展开更多
Photocatalytic activation of C-H bonds is versatile but challenging for undergoing oriented conversion processes.Herein,a spatially site-isolated heterojunction(ZS-Vs/ZIS)of ZnIn2S4 with strong Lewis acidity(ZIS)and Z...Photocatalytic activation of C-H bonds is versatile but challenging for undergoing oriented conversion processes.Herein,a spatially site-isolated heterojunction(ZS-Vs/ZIS)of ZnIn2S4 with strong Lewis acidity(ZIS)and ZnS with S-vacancy(ZS-Vs)is constructed for activating α-C‒H bond and forming·O_(2)^(-)to cleave the C-H bond,respectively.ZS-Vs/ZIS displays outstanding performance in visible-light partial photooxidation of bio-based 5-hydroxymethylfurfural(HMF)to 2,5-diformylfuran(DFF)in an unprecedented yield of 95.7%at 25°C.In-situ experiments and calculations reveal that Zn sites of ZIS serve as hole enrichment to adsorb HMF for α-C‒H activation via ligand-to-metal charge transfer.Shallow trap states introduced by S-vacancy in ZS-Vs act as an electron pool to realize directed O_(2) activation into·O_(2)^(-)for breaking pre-activated α-C‒H bond in HMF to exclusively give DFF.Moreover,ZS-Vs/ZIS has good recyclability and universality in the photooxidation of various alcohols to carbonyls(86.4-95.6%yields).The synergistic C-H activation/breaking strategy exhibits high potential in targeted photocatalytic transformations.展开更多
It is important to explore active faults in urban areas and their surroundings for earth- quake disaster mitigation. Satellite remote sensing techniques can play an important role in such active fault exploration. It ...It is important to explore active faults in urban areas and their surroundings for earth- quake disaster mitigation. Satellite remote sensing techniques can play an important role in such active fault exploration. It can not only reveal the pattern of active faults and active tectonics on a macroscop- ic scale, but also monitor the occurrence, development and rules of temporal-spatial evolution of active faults. In this paper, we use the Hangzhou area as an example to introduce methods of extracting de- tailed active fault information when covered by thick unconsolidated Quaternary sediment, using im- age enhancement and image fusion etc. to improve the definition and precision of satellite images and presenting a three-dimensional （3D） image to illustrate tectono-geomorphic features along the relevant faults. We have also collected aeromagnetic anomaly data, shallow seismic exploration data and dating data, and carried out field surveys to validate the characteristics of active faults based on remote sens- ing images. The results revealed about the faults showed a high consistency with traditional geological knowledge, and demonstrate that it is feasible to explore active faults in a weakly active tectonic area by using satellite remote sensing techniques and contribute to large engineering projects and research on neotectonics.展开更多
Hexagonal boron nitride(h-BN)is a highly selective catalyst for oxidative dehydrogenation of light alkanes to produce the corresponding alkenes.Despite intense recent research effort,many aspects of the reaction mecha...Hexagonal boron nitride(h-BN)is a highly selective catalyst for oxidative dehydrogenation of light alkanes to produce the corresponding alkenes.Despite intense recent research effort,many aspects of the reaction mechanism,such as the observed supra-linear reaction order of alkanes,remain unresolved.In this work,we show that the introduction of a low concentration of propane in the feed of ethane oxidative dehydrogenation is able to enhance the C_(2)H_(6) conversion by 47%,indicating a shared reaction intermediate in the activation of ethane and propane.The higher activity of propane makes it the dominant radical generator in the oxidative co-dehydrogenation of ethane and propane(ODEP).This unique feature of the ODEP renders propane an effective probe molecule to deconvolute the two roles of alkanes in the dehydrogenation chemistry,i.e.,radical generator and substrate.Kinetic studies indicate that both the radical generation and the dehydrogenation pathways exhibit a first order kinetics toward the alkane partial pressure,leading to the observed second order kinetics of the overall oxidative dehydrogenation rate.With the steady-state approximation,a radical chain reaction mechanism capable of rationalizing observed reaction behaviors is proposed based on these insights.This work demonstrates the potential of ODEP as a strategy of both activating light alkanes in oxidative dehydrogenation on BN and mechanistic investigations.展开更多
Using the data collected over the Southern Great Plains ARM site from 2006 to 2010, the surface Active Remote Sensing of Cloud （ARSCL） and CloudSat-CALIPSO satellite （CC） retrievals of total cloud and six specifie...Using the data collected over the Southern Great Plains ARM site from 2006 to 2010, the surface Active Remote Sensing of Cloud （ARSCL） and CloudSat-CALIPSO satellite （CC） retrievals of total cloud and six specified cloud types [low, midlow （ML）, high-mid-low （HML）, mid, high-mid （HM） and high] were compared in terms of cloud fraction （CF）, cloud-base height （CBH）, cloud-top height （CTH） and cloud thickness （CT）, on different temporal scales, to identify their respective advantages and limitations. Good agreement between the two methods was exhibited in the total CF. However, large discrepancies were found between the cloud distributions of the two methods at a high （240-m） vertical grid spacing. Compared to the satellites, ARSCL retrievals detected more boundary layer clouds, while they underestimated high clouds. In terms of the six specific cloud types, more low- and mid-level clouds but less HML- and high-level clouds were detected by ARSCL than by CC. In contrast, the ARSCL retrievals of ML- and HM-level clouds agreed more closely with the estimations from the CC product. Lower CBHs tended to be reported by the surface data for low-, ML- and HML-level clouds; however, higher CTHs were often recorded by the satellite product for HML-, HM- and high-level clouds. The mean CTs for low- and ML-level cloud were similar between the two products; however, the mean CTs for HML-, mid-, HM- and high-level clouds from ARSCL were smaller than those from CC.展开更多
Cancer has nowadays become one of the leading causes of death worldwide.Conventional anticancer approaches are associated with different limitations.Therefore,innovative methodologies are being investigated,and severa...Cancer has nowadays become one of the leading causes of death worldwide.Conventional anticancer approaches are associated with different limitations.Therefore,innovative methodologies are being investigated,and several researchers propose the use of remotely activated nanoparticles to trigger cancer cell death.The idea is to conjugate two different components,i.e.,an external physical input and nanoparticles.Both are given in a harmless dose that once combined together act synergistically to therapeutically treat the cell or tissue of interest,thus also limiting the negative outcomes for the surrounding tissues.Tuning both the properties of the nanomaterial and the involved triggering stimulus,it is possible furthermore to achieve not only a therapeutic effect,but also a powerful platform for imaging at the same time,obtaining a nano-theranostic application.In the present review,we highlight the role of nanoparticles as therapeutic or theranostic tools,thus excluding the cases where a molecular drug is activated.We thus present many examples where the highly cytotoxic power only derives from the active interaction between different physical inputs and nanoparticles.We perform a special focus on mechanical waves responding nanoparticles,in which remotely activated nanoparticles directly become therapeutic agents without the need of the administration of chemotherapeutics or sonosensitizing drugs.展开更多
Here,we demonstrate a photochemical strategy to site-specifically deposit Pd atoms on Au nanoparticles.The high-sensitivity low-energy ion scattering spectra combined with the X-ray photoelectron spectra reveal that t...Here,we demonstrate a photochemical strategy to site-specifically deposit Pd atoms on Au nanoparticles.The high-sensitivity low-energy ion scattering spectra combined with the X-ray photoelectron spectra reveal that the surface electronic structure of Pd can be continuously regulated by tailoring the Pd-to-Au molar ratio and the location of Pd atoms in Au Pd nanoparticles.It is revealed that electron-rich Pd atoms are considerably more active than the net Pd atoms in aerobic alcohol oxidation.Remarkably,the catalyst with the most electron-rich Pd sites(binding energy downshift:1.0 e V)exhibits an extremely high turnover frequency(~500000 h-1 vs 12000 h-1 for that with net Pd atoms)for solvent-free selective oxidation of benzyl alcohol,which is,to the best of our knowledge,the highest value ever reported.Kinetic studies reveal that electron-rich Pd atoms can accelerate the oxidation of benzyl alcohol by facilitating C-H cleavage,as indicated by the significant reduction in the activation energy as compared to net Pd atoms.展开更多
The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional g...The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional group tolerance. A dual-core dimeric palladacycle is confirmed by X-ray single crystal crystallography, and probably serves as an active species in the catalytic cycle.展开更多
Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution o...Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.展开更多
The divergent behavior of C-H bond oxidations of aliphatic substrates compared to those of aromatic substrates shown in Gupta’s experiment was mechanistically studied herein by means of density functional theory calc...The divergent behavior of C-H bond oxidations of aliphatic substrates compared to those of aromatic substrates shown in Gupta’s experiment was mechanistically studied herein by means of density functional theory calculations.Our calculations reveal that such difference is caused by different reaction mechanisms between two kinds of substrates(the aliphatic cyclohexane,2,3-dimethylbutane and the aromatic toluene,ethylbenzene and cumene).For the aliphatic substrates,C-H oxidation by the oxidant Fe^(V)(O)(TAML)is a hydrogen atom transfer process;whereas for the aromatic substrates,C-H oxidation is a proton-coupled electron transfer(PCET)process with a proton transfer character on the transition state,that is,a proton-coupled electron transfer process holding a proton transfer-like transition state(PCET(PT)).This difference is caused by the strongπ-πinteractions between the tetra-anionic TAML ring and the phenyl ring of the aromatic substrates,which has a“pull”effect to make the electron transfer from substrates to the Fe=O moiety inefficient.展开更多
Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric syn-thesis of highly valuable chiral products.Herein,a Rh(III)-catalyzed enantioselective allylic C—H alkyl...Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric syn-thesis of highly valuable chiral products.Herein,a Rh(III)-catalyzed enantioselective allylic C—H alkylation of unactivated alkenes withα-diazo carbonyl compounds is described,enabling direct access to chiral products with high efficiency(up to 77%yield,92%ee,and>10∶1 B/L(branched/linear)selectivity).This atom-and step-economical protocol directly converts simple,unactivated substrates into valuable enantioenriched products under mild conditions,providing an efficient catalytic system for asymmetric allylic C—H functionalization.展开更多
Roughness-induced emission from ocean surfaces is one of the main issues that affects the retrieval accuracy of sea surface salinity remote sensing.In previous studies,the correction of roughness effect mainly depende...Roughness-induced emission from ocean surfaces is one of the main issues that affects the retrieval accuracy of sea surface salinity remote sensing.In previous studies,the correction of roughness effect mainly depended on wind speeds retrieved from scatterometers or those provided by other means,which necessitates a high requirement for accuracy and synchronicity of wind-speed measurements.The aim of this study is to develop a novel roughness correction model of ocean emissivity for the salinity retrieval application.The combined active/passive observations of normalized radar cross-sections(NRCSs)and emissivities from ocean surfaces given by the L-band Aquarius/SAC-D mission,and the auxiliary wind directions collocated from the National Centers for Environmental Prediction(NCEP)dataset are used for model development.The model is validated against the observations and the Aquarius standard algorithms of roughness-induced emissivity correction.Comparisons between model computations and measurements indicate that the model has better accuracy in computing wind-induced brightness temperature in the upwind/downwind directions or for the surfaces with smaller NRCSs,which can be better than 0.3 K.However,for crosswind directions and larger NRCSs,the model accuracy is relatively low.A model using HH-polarized NRCSs yields better accuracy than that using VV-polarized ones.For a fair comparison to the Aquarius standard algorithms using wind speeds retrieved from multi-source data,the maximum likelihood estimation is employed to produce results combining our model calculations and those using other sources.Numerical simulations show that combined results basically have higher accuracy than the standard algorithms.展开更多
The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed as...The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization,enabling the efficient synthesis of structurally diverse enantioenriched macrocycles.This robust enantioselective C-H macrocyclization has a broad functional group tolerance,excellent enantioselectivities(up to 98.5:1.5 e.r.)and a mild reaction condition,releasing CO_(2)as the single by-product.More significantly,the resulting unique enantioenriched19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus(ZIKV)activity without obvious cytotoxicity.Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.展开更多
While executing tasks such as ocean pollution monitoring,maritime rescue,geographic mapping,and automatic navigation utilizing remote sensing images,the coastline feature should be determined.Traditional methods are n...While executing tasks such as ocean pollution monitoring,maritime rescue,geographic mapping,and automatic navigation utilizing remote sensing images,the coastline feature should be determined.Traditional methods are not satisfactory to extract coastline in high-resolution panchromatic remote sensing image.Active contour model,also called snakes,have proven useful for interactive specification of image contours,so it is used as an effective coastlines extraction technique.Firstly,coastlines are detected by water segmentation and boundary tracking,which are considered initial contours to be optimized through active contour model.As better energy functions are developed,the power assist of snakes becomes effective.New internal energy has been done to reduce problems caused by convergence to local minima,and new external energy can greatly enlarge the capture region around features of interest.After normalization processing,energies are iterated using greedy algorithm to accelerate convergence rate.The experimental results encompassed examples in images and demonstrated the capabilities and efficiencies of the improvement.展开更多
Catalytic C–H activation-initiated annulation reactions have emerged as a versatile strategy for the efficient construction of diverse ring structural units and complex cyclic molecules in synthetic chemistry.Herein,...Catalytic C–H activation-initiated annulation reactions have emerged as a versatile strategy for the efficient construction of diverse ring structural units and complex cyclic molecules in synthetic chemistry.Herein,we describe a new Rh(Ⅲ)-catalyzed C–H activation-initiated transdiannulation reaction of N,Ndimethyl enaminones with gem-difluorocyclopropenes in the presence of H_(2)O,enabling a facile and oxygen transfer access to ring-fluorinated tricyclicγ-lactones with a 6-5 ring-junction tetrasubstituted stereocenter.This approach features bond-forming/annulation efficiency,good functional group tolerance and complete regioselectivity,which may include a complex process consisting of Rh(Ⅲ)-catalyzed C(sp2)–H activation,cyclic alkene insertion,defluorinated ring-opening of gem-difluorocyclopropane,intramolecular oxygen transfer,intramolecular cyclization and oxidative hydration.展开更多
A highly novel and direct synthesis of benzoxazinones was developed via Cp*Co(Ⅲ)-catalyzed C-H activation and[3+3]annulation between sulfoxonium ylides and dioxazolones.The reaction is conducted under base-free condi...A highly novel and direct synthesis of benzoxazinones was developed via Cp*Co(Ⅲ)-catalyzed C-H activation and[3+3]annulation between sulfoxonium ylides and dioxazolones.The reaction is conducted under base-free conditions and tolerates various functional groups.Starting from diverse readily available sulfoxonium ylides and dioxazolones,a variety of benzoxazinones could be synthesized in one step in 32%-75%yields.展开更多
Semiconductor photocatalysis holds great promise for breaking the inert chemical bonds under mild condition;however,the photoexcitation-induced modulation mechanism has not been well understood at the atomic level.Her...Semiconductor photocatalysis holds great promise for breaking the inert chemical bonds under mild condition;however,the photoexcitation-induced modulation mechanism has not been well understood at the atomic level.Herein,by performing the DFT+U calculations,we quantitatively compare H_(2) activation on rutile TiO_(2)(110)under thermo-versus photo-catalytic condition.It is found that H2 dissociation prefers to occur via the heterolytic cleavage mode in thermocatalysis,but changes to the homolytic cleavage mode and gets evidently promoted in the presence of photoexcited hole(h^(+)).The origin can be ascribed to the generation of highly oxidative lattice O-radical(O_(br)^(·−))with a localized unoccupied O-2p state.More importantly,we identify that this photo-induced promotion effect can be practicable to another kind of important chemical bond,i.e.,C-H bond in light hydrocarbons including alkane,alkene and aromatics;an exception is the C(sp^(1))-H in alkyne(HC≡CH),which encounters inhibition effect from photoexcitation.By quantitative analysis,the origins behind these results are attributed to the interplay between two factors:C-H bond energy(E_(bond))and the acidity.Owing to the relatively high E_(bond) and acidity,it favors the C(sp^(1))-H bond to proceed with the heterolytic cleavage mode in both thermo-and photo-catalysis,and the photoexcited O_(br)^(·−)is adverse to receiving the transferred proton.By contrast,for the other hydrocarbons with moderate/low E_(bond),the O_(br)^(·−)would enable to change their activation mode to a more favored homolytic one and evidently decrease the C-H activation barrier.This work may provide a general picture for understanding the photocatalytic R-H(R=H,C)bond activation over the semiconductor catalyst.展开更多
A high turnover number was achieved in the photocatalytic carbonylation of C - H bonds of cyclohexane catalyzed by Co (acac)2 under ambient conditions (1 atm,25℃) to give mainly cyclohexanecarboxaldehyde.
A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, t...A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n （n = 5=7）. The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized, It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n （n = 3 -7）.展开更多
Volcanic eruption is one of the most serious geological disasters,however,a host of facts have proven that the Changbai Mountains volcano is a modern dormant one and has ever erupted disastrously. With the rapid devel...Volcanic eruption is one of the most serious geological disasters,however,a host of facts have proven that the Changbai Mountains volcano is a modern dormant one and has ever erupted disastrously. With the rapid development of remote sensing technology,space monitoring of volcanic activities has already become possible,particularly in the application of thermal infrared remote sensing. The paper,through the detailed analysis of geothermal anomaly factors such as heat radiation,heat conduction and convection,depicts the monitoring principles by which volcano activities would be monitored efficiently and effectively. Reasons for abrupt geothermal anomaly are mainly analyzed,and transmission mechanism of geothermal anomaly in the volcanic regions is explained. Also,a variety of noises disturbing the transmission of normal geothermal anomaly are presented. Finally,some clues are given based on discussing thermal infrared remote sensing monitoring mechanism toward the volcanic areas.展开更多
基金supported by the CAMS Innovation Fund for Medical Sciences(CIFMS,No.2023-I2M-2-009).
文摘An electronic circular dichroism(ECD)-based chiroptical sensing method has been developed forβ-andγ-chiral primary amines via a C-H activation reaction.With the addition of Pd(OAc)_(2),the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex,producing an intense ECD response.The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed,together with theoretical verification using timedependent density functional theory(TDDFT).Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity.This work introduces an alternative perspective of C-H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
基金supported by the National Natural Science Foundation of China(22478087,22368014)Guizhou Provincial S&T Project(GCC[2023]011,ZK[2022]011)Guizhou Provincial Higher Education Institution Program(Qianjiaoji[2023]082).
文摘Photocatalytic activation of C-H bonds is versatile but challenging for undergoing oriented conversion processes.Herein,a spatially site-isolated heterojunction(ZS-Vs/ZIS)of ZnIn2S4 with strong Lewis acidity(ZIS)and ZnS with S-vacancy(ZS-Vs)is constructed for activating α-C‒H bond and forming·O_(2)^(-)to cleave the C-H bond,respectively.ZS-Vs/ZIS displays outstanding performance in visible-light partial photooxidation of bio-based 5-hydroxymethylfurfural(HMF)to 2,5-diformylfuran(DFF)in an unprecedented yield of 95.7%at 25°C.In-situ experiments and calculations reveal that Zn sites of ZIS serve as hole enrichment to adsorb HMF for α-C‒H activation via ligand-to-metal charge transfer.Shallow trap states introduced by S-vacancy in ZS-Vs act as an electron pool to realize directed O_(2) activation into·O_(2)^(-)for breaking pre-activated α-C‒H bond in HMF to exclusively give DFF.Moreover,ZS-Vs/ZIS has good recyclability and universality in the photooxidation of various alcohols to carbonyls(86.4-95.6%yields).The synergistic C-H activation/breaking strategy exhibits high potential in targeted photocatalytic transformations.
基金supported by the Major Research Project of the Ministry of Land and Resources,China(No.1212011120887)
文摘It is important to explore active faults in urban areas and their surroundings for earth- quake disaster mitigation. Satellite remote sensing techniques can play an important role in such active fault exploration. It can not only reveal the pattern of active faults and active tectonics on a macroscop- ic scale, but also monitor the occurrence, development and rules of temporal-spatial evolution of active faults. In this paper, we use the Hangzhou area as an example to introduce methods of extracting de- tailed active fault information when covered by thick unconsolidated Quaternary sediment, using im- age enhancement and image fusion etc. to improve the definition and precision of satellite images and presenting a three-dimensional （3D） image to illustrate tectono-geomorphic features along the relevant faults. We have also collected aeromagnetic anomaly data, shallow seismic exploration data and dating data, and carried out field surveys to validate the characteristics of active faults based on remote sens- ing images. The results revealed about the faults showed a high consistency with traditional geological knowledge, and demonstrate that it is feasible to explore active faults in a weakly active tectonic area by using satellite remote sensing techniques and contribute to large engineering projects and research on neotectonics.
文摘Hexagonal boron nitride(h-BN)is a highly selective catalyst for oxidative dehydrogenation of light alkanes to produce the corresponding alkenes.Despite intense recent research effort,many aspects of the reaction mechanism,such as the observed supra-linear reaction order of alkanes,remain unresolved.In this work,we show that the introduction of a low concentration of propane in the feed of ethane oxidative dehydrogenation is able to enhance the C_(2)H_(6) conversion by 47%,indicating a shared reaction intermediate in the activation of ethane and propane.The higher activity of propane makes it the dominant radical generator in the oxidative co-dehydrogenation of ethane and propane(ODEP).This unique feature of the ODEP renders propane an effective probe molecule to deconvolute the two roles of alkanes in the dehydrogenation chemistry,i.e.,radical generator and substrate.Kinetic studies indicate that both the radical generation and the dehydrogenation pathways exhibit a first order kinetics toward the alkane partial pressure,leading to the observed second order kinetics of the overall oxidative dehydrogenation rate.With the steady-state approximation,a radical chain reaction mechanism capable of rationalizing observed reaction behaviors is proposed based on these insights.This work demonstrates the potential of ODEP as a strategy of both activating light alkanes in oxidative dehydrogenation on BN and mechanistic investigations.
基金supported by the National Natural Science Foundation of China(Grant Nos.61327810,41275039,41675033,and 91337214)
文摘Using the data collected over the Southern Great Plains ARM site from 2006 to 2010, the surface Active Remote Sensing of Cloud （ARSCL） and CloudSat-CALIPSO satellite （CC） retrievals of total cloud and six specified cloud types [low, midlow （ML）, high-mid-low （HML）, mid, high-mid （HM） and high] were compared in terms of cloud fraction （CF）, cloud-base height （CBH）, cloud-top height （CTH） and cloud thickness （CT）, on different temporal scales, to identify their respective advantages and limitations. Good agreement between the two methods was exhibited in the total CF. However, large discrepancies were found between the cloud distributions of the two methods at a high （240-m） vertical grid spacing. Compared to the satellites, ARSCL retrievals detected more boundary layer clouds, while they underestimated high clouds. In terms of the six specific cloud types, more low- and mid-level clouds but less HML- and high-level clouds were detected by ARSCL than by CC. In contrast, the ARSCL retrievals of ML- and HM-level clouds agreed more closely with the estimations from the CC product. Lower CBHs tended to be reported by the surface data for low-, ML- and HML-level clouds; however, higher CTHs were often recorded by the satellite product for HML-, HM- and high-level clouds. The mean CTs for low- and ML-level cloud were similar between the two products; however, the mean CTs for HML-, mid-, HM- and high-level clouds from ARSCL were smaller than those from CC.
基金the European Research Council(ERC)under the European Union’s Horizon 2020 research and innovation programme(Grant Agreement No 678151-Project Acronym“TROJANANOHORSE”-ERC starting Grant)the Politecnico di Torino and the Moschini Spa Company through a seed funding of Proof-of-Concept Grant No.16417.
文摘Cancer has nowadays become one of the leading causes of death worldwide.Conventional anticancer approaches are associated with different limitations.Therefore,innovative methodologies are being investigated,and several researchers propose the use of remotely activated nanoparticles to trigger cancer cell death.The idea is to conjugate two different components,i.e.,an external physical input and nanoparticles.Both are given in a harmless dose that once combined together act synergistically to therapeutically treat the cell or tissue of interest,thus also limiting the negative outcomes for the surrounding tissues.Tuning both the properties of the nanomaterial and the involved triggering stimulus,it is possible furthermore to achieve not only a therapeutic effect,but also a powerful platform for imaging at the same time,obtaining a nano-theranostic application.In the present review,we highlight the role of nanoparticles as therapeutic or theranostic tools,thus excluding the cases where a molecular drug is activated.We thus present many examples where the highly cytotoxic power only derives from the active interaction between different physical inputs and nanoparticles.We perform a special focus on mechanical waves responding nanoparticles,in which remotely activated nanoparticles directly become therapeutic agents without the need of the administration of chemotherapeutics or sonosensitizing drugs.
文摘Here,we demonstrate a photochemical strategy to site-specifically deposit Pd atoms on Au nanoparticles.The high-sensitivity low-energy ion scattering spectra combined with the X-ray photoelectron spectra reveal that the surface electronic structure of Pd can be continuously regulated by tailoring the Pd-to-Au molar ratio and the location of Pd atoms in Au Pd nanoparticles.It is revealed that electron-rich Pd atoms are considerably more active than the net Pd atoms in aerobic alcohol oxidation.Remarkably,the catalyst with the most electron-rich Pd sites(binding energy downshift:1.0 e V)exhibits an extremely high turnover frequency(~500000 h-1 vs 12000 h-1 for that with net Pd atoms)for solvent-free selective oxidation of benzyl alcohol,which is,to the best of our knowledge,the highest value ever reported.Kinetic studies reveal that electron-rich Pd atoms can accelerate the oxidation of benzyl alcohol by facilitating C-H cleavage,as indicated by the significant reduction in the activation energy as compared to net Pd atoms.
基金the National Natural Science Foundation of China(Nos. 21476074 and 21676088)for financial support
文摘The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional group tolerance. A dual-core dimeric palladacycle is confirmed by X-ray single crystal crystallography, and probably serves as an active species in the catalytic cycle.
文摘Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.
基金supported by the National Natural Science Foundation of China(No.21806018 and No.21873052)the Fundamental Research Funds for the Central Universities(DUT20RC(4)002)+1 种基金Scientific Research Grant of Ningbo University(No.215-432000282)Ningbo Top Talent Project(No.215-432094250)。
文摘The divergent behavior of C-H bond oxidations of aliphatic substrates compared to those of aromatic substrates shown in Gupta’s experiment was mechanistically studied herein by means of density functional theory calculations.Our calculations reveal that such difference is caused by different reaction mechanisms between two kinds of substrates(the aliphatic cyclohexane,2,3-dimethylbutane and the aromatic toluene,ethylbenzene and cumene).For the aliphatic substrates,C-H oxidation by the oxidant Fe^(V)(O)(TAML)is a hydrogen atom transfer process;whereas for the aromatic substrates,C-H oxidation is a proton-coupled electron transfer(PCET)process with a proton transfer character on the transition state,that is,a proton-coupled electron transfer process holding a proton transfer-like transition state(PCET(PT)).This difference is caused by the strongπ-πinteractions between the tetra-anionic TAML ring and the phenyl ring of the aromatic substrates,which has a“pull”effect to make the electron transfer from substrates to the Fe=O moiety inefficient.
文摘Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric syn-thesis of highly valuable chiral products.Herein,a Rh(III)-catalyzed enantioselective allylic C—H alkylation of unactivated alkenes withα-diazo carbonyl compounds is described,enabling direct access to chiral products with high efficiency(up to 77%yield,92%ee,and>10∶1 B/L(branched/linear)selectivity).This atom-and step-economical protocol directly converts simple,unactivated substrates into valuable enantioenriched products under mild conditions,providing an efficient catalytic system for asymmetric allylic C—H functionalization.
基金The National Key R&D Program of China under contract Nos 2018YFA0605403 and 2016YFB0500204the Hainan Provincial Natural Science Foundation of China under contract No.418QN301the National Natural Science Foundation of China under contract No.41801238。
文摘Roughness-induced emission from ocean surfaces is one of the main issues that affects the retrieval accuracy of sea surface salinity remote sensing.In previous studies,the correction of roughness effect mainly depended on wind speeds retrieved from scatterometers or those provided by other means,which necessitates a high requirement for accuracy and synchronicity of wind-speed measurements.The aim of this study is to develop a novel roughness correction model of ocean emissivity for the salinity retrieval application.The combined active/passive observations of normalized radar cross-sections(NRCSs)and emissivities from ocean surfaces given by the L-band Aquarius/SAC-D mission,and the auxiliary wind directions collocated from the National Centers for Environmental Prediction(NCEP)dataset are used for model development.The model is validated against the observations and the Aquarius standard algorithms of roughness-induced emissivity correction.Comparisons between model computations and measurements indicate that the model has better accuracy in computing wind-induced brightness temperature in the upwind/downwind directions or for the surfaces with smaller NRCSs,which can be better than 0.3 K.However,for crosswind directions and larger NRCSs,the model accuracy is relatively low.A model using HH-polarized NRCSs yields better accuracy than that using VV-polarized ones.For a fair comparison to the Aquarius standard algorithms using wind speeds retrieved from multi-source data,the maximum likelihood estimation is employed to produce results combining our model calculations and those using other sources.Numerical simulations show that combined results basically have higher accuracy than the standard algorithms.
基金supported by National Natural Science Foundation of China(No.81973166)Science and Technology Commission of Shanghai Municipality(No.22XD1424600)+4 种基金Natural Science Foundation of Shanghai Municipality(No.22ZR1474100)Taishan Scholar Foundation of Shandong Province(No.tsqn202306322)National Key R&D Program of China(No.2021YFC2300700)Shandong Laboratory Program(No.SYS202205)Shandong Provincial Natural Science Foundation(Nos.ZR2023LSW003 and ZR2023JQ028)。
文摘The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization,enabling the efficient synthesis of structurally diverse enantioenriched macrocycles.This robust enantioselective C-H macrocyclization has a broad functional group tolerance,excellent enantioselectivities(up to 98.5:1.5 e.r.)and a mild reaction condition,releasing CO_(2)as the single by-product.More significantly,the resulting unique enantioenriched19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus(ZIKV)activity without obvious cytotoxicity.Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.
基金Sponsoreds by the National Natural Science Foundation of China (Grant No. 60575016)
文摘While executing tasks such as ocean pollution monitoring,maritime rescue,geographic mapping,and automatic navigation utilizing remote sensing images,the coastline feature should be determined.Traditional methods are not satisfactory to extract coastline in high-resolution panchromatic remote sensing image.Active contour model,also called snakes,have proven useful for interactive specification of image contours,so it is used as an effective coastlines extraction technique.Firstly,coastlines are detected by water segmentation and boundary tracking,which are considered initial contours to be optimized through active contour model.As better energy functions are developed,the power assist of snakes becomes effective.New internal energy has been done to reduce problems caused by convergence to local minima,and new external energy can greatly enlarge the capture region around features of interest.After normalization processing,energies are iterated using greedy algorithm to accelerate convergence rate.The experimental results encompassed examples in images and demonstrated the capabilities and efficiencies of the improvement.
基金financial support from the schoollevel research projects of Yancheng Institute of Technology(No.xjr2020044)the National Natural Science Foundation of China(Nos.22101152,22271123 and 21971090)。
文摘Catalytic C–H activation-initiated annulation reactions have emerged as a versatile strategy for the efficient construction of diverse ring structural units and complex cyclic molecules in synthetic chemistry.Herein,we describe a new Rh(Ⅲ)-catalyzed C–H activation-initiated transdiannulation reaction of N,Ndimethyl enaminones with gem-difluorocyclopropenes in the presence of H_(2)O,enabling a facile and oxygen transfer access to ring-fluorinated tricyclicγ-lactones with a 6-5 ring-junction tetrasubstituted stereocenter.This approach features bond-forming/annulation efficiency,good functional group tolerance and complete regioselectivity,which may include a complex process consisting of Rh(Ⅲ)-catalyzed C(sp2)–H activation,cyclic alkene insertion,defluorinated ring-opening of gem-difluorocyclopropane,intramolecular oxygen transfer,intramolecular cyclization and oxidative hydration.
基金financial support from the Hunan Provincial Innovation Foundation for Postgraduate(No.CX20190267)Natural Science Foundation of Hunan Province(No.2020JJ4171)。
文摘A highly novel and direct synthesis of benzoxazinones was developed via Cp*Co(Ⅲ)-catalyzed C-H activation and[3+3]annulation between sulfoxonium ylides and dioxazolones.The reaction is conducted under base-free conditions and tolerates various functional groups.Starting from diverse readily available sulfoxonium ylides and dioxazolones,a variety of benzoxazinones could be synthesized in one step in 32%-75%yields.
基金supported by National Nature Science Foundation of China(Nos.21873028.91945302)National Ten Thousand Talent Program for Young Top-notch Talents in China,Shanghai Shu-Guang project(No.17SG30)the Fundamental Research Fundsfor the Central Universities.
文摘Semiconductor photocatalysis holds great promise for breaking the inert chemical bonds under mild condition;however,the photoexcitation-induced modulation mechanism has not been well understood at the atomic level.Herein,by performing the DFT+U calculations,we quantitatively compare H_(2) activation on rutile TiO_(2)(110)under thermo-versus photo-catalytic condition.It is found that H2 dissociation prefers to occur via the heterolytic cleavage mode in thermocatalysis,but changes to the homolytic cleavage mode and gets evidently promoted in the presence of photoexcited hole(h^(+)).The origin can be ascribed to the generation of highly oxidative lattice O-radical(O_(br)^(·−))with a localized unoccupied O-2p state.More importantly,we identify that this photo-induced promotion effect can be practicable to another kind of important chemical bond,i.e.,C-H bond in light hydrocarbons including alkane,alkene and aromatics;an exception is the C(sp^(1))-H in alkyne(HC≡CH),which encounters inhibition effect from photoexcitation.By quantitative analysis,the origins behind these results are attributed to the interplay between two factors:C-H bond energy(E_(bond))and the acidity.Owing to the relatively high E_(bond) and acidity,it favors the C(sp^(1))-H bond to proceed with the heterolytic cleavage mode in both thermo-and photo-catalysis,and the photoexcited O_(br)^(·−)is adverse to receiving the transferred proton.By contrast,for the other hydrocarbons with moderate/low E_(bond),the O_(br)^(·−)would enable to change their activation mode to a more favored homolytic one and evidently decrease the C-H activation barrier.This work may provide a general picture for understanding the photocatalytic R-H(R=H,C)bond activation over the semiconductor catalyst.
文摘A high turnover number was achieved in the photocatalytic carbonylation of C - H bonds of cyclohexane catalyzed by Co (acac)2 under ambient conditions (1 atm,25℃) to give mainly cyclohexanecarboxaldehyde.
基金Supported by the National Natural Science Foundation of China(No.20773014 and 20933001)the Research Foundation of Education Bureau of Hebei Province(No.Z2011115)+3 种基金the 111 Project of China(No.B07012)the Natural Science Foundation of Hebei Province(No.B2012105002)the Research Foundation of Tangshan Administration of Science&Technology(121302011a)the Research Foundation of Tangshan normal college(2013A04)for their support of this work
文摘A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n （n = 5=7）. The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized, It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n （n = 3 -7）.
文摘Volcanic eruption is one of the most serious geological disasters,however,a host of facts have proven that the Changbai Mountains volcano is a modern dormant one and has ever erupted disastrously. With the rapid development of remote sensing technology,space monitoring of volcanic activities has already become possible,particularly in the application of thermal infrared remote sensing. The paper,through the detailed analysis of geothermal anomaly factors such as heat radiation,heat conduction and convection,depicts the monitoring principles by which volcano activities would be monitored efficiently and effectively. Reasons for abrupt geothermal anomaly are mainly analyzed,and transmission mechanism of geothermal anomaly in the volcanic regions is explained. Also,a variety of noises disturbing the transmission of normal geothermal anomaly are presented. Finally,some clues are given based on discussing thermal infrared remote sensing monitoring mechanism toward the volcanic areas.
