Discourse markers(DMs) are characterized by multifunctionality in different contexts.This study addressed the use of the Chinese DM,na(那),as a solution to topical divergence,during clinical interactions with right-he...Discourse markers(DMs) are characterized by multifunctionality in different contexts.This study addressed the use of the Chinese DM,na(那),as a solution to topical divergence,during clinical interactions with right-hemisphere-damaged(RHD) patients.Drawing on data collected from clinical interviews between psychotherapists and RHD patients,this study examined the functions of na in response to RHD topical divergence,focusing on the topic and attitudinal aspects.It was found that na was mainly employed by psychotherapists to mark a reproffer of interview topics(i.e.,an attempt to return to earlier topics),and a display of disalignment and disaffiliation with RHD topical divergence.These functions of na reflect the psychotherapists’ attempts to overcome communicative problems arising from RHD topical divergence,so as to ensure the achievement of the communicative goal.Thus,na can be interpreted as a compensatory strategy for dealing with RHD topical divergence on an interpersonal level.These findings not only expand our knowledge about the function spectrum of na,but also offer insights for RHD patients’ interlocutors to enhance conversational communication with RHD patients via the compensatory strategy.展开更多
The development of catalytic asymmetric radical reactions is an attractive but formidable task.The high reactivity of radicals enables the use of readily accessible feedstocks and mild reaction conditions,but it leads...The development of catalytic asymmetric radical reactions is an attractive but formidable task.The high reactivity of radicals enables the use of readily accessible feedstocks and mild reaction conditions,but it leads to substantial difficulty for chiral catalysts to provide sufficient enantiocontrol.Moreover,a racemic background process is often inevitable,further deteriorating enantioselectivity.In this regard,an effective protocol has been established for enantioselective intermolecular[2+2]photocycloadditions to overcome the challenges,which is capitalising on the ground-state preassociations of chiral catalysts with photoactivated substrates.Here,we report the viability of substrate-differentiating synergistic catalysis for this important reaction.In this new platform,energy transfer occurs between DPZ as a photosensitizer and enones or(E)-2-substituted vinylazaarenes for producing triplet-state species,and chiral phosphoric acid interacts with ground-state 2-vinylazaarenes via hydrogen bonding for subsequent enantiofacial cycloaddition.Although all active species are dispersed in the reaction system,valuable enantioenriched mono-and di-azaarene-functionalized cyclobutanes are obtained efficiently and selectively.In addition to constructing all-carbon quaternary stereocentres,flexible modulation of azaaryl groups and other substituents on the cyclobutane ring is also operative.展开更多
Cooperative hydrogen atom transfer and chiral hydrogen‐bonding catalysis as a new platform for the asymmetric synthesis of azaarene derivatives is reported.By using a tetrabutylammonium decatungstate as the photocata...Cooperative hydrogen atom transfer and chiral hydrogen‐bonding catalysis as a new platform for the asymmetric synthesis of azaarene derivatives is reported.By using a tetrabutylammonium decatungstate as the photocatalyst and a chiral phosphoric acid as the hydrogen‐bonding catalyst,transformations of a variety of commercially available hydrocarbons and silanes with diverseα‐branched 2‐vinylazaarenes could efficiently experience a tandem radical conjugate addition and enantioselective protonation process,providing a convenient and fully atom economical approach to access a range of valuable enantioenrichedα‐tertiary azaarenes in high yields with good to excellent enantioselectivities(up to 93%ee).Through the direct use of tert‐butyl methylcarbamate as the feedstock,this method enables a highly practical and concise synthesis of the enantiomerically pure medicinal molecule pheniramine(Avil).展开更多
The meta-instable state(MIS)is the final stage before fault instability during stick-slip movement.Thus,identification of MIS is of great significance for assessing earthquake hazard in fault zones.A rock sample with ...The meta-instable state(MIS)is the final stage before fault instability during stick-slip movement.Thus,identification of MIS is of great significance for assessing earthquake hazard in fault zones.A rock sample with a precut planar fault was loaded on a horizontally biaxial servo-controlled press machine to create stick-slip conditions.Digital images of the sample surface were taken by a high-speed camera at a rate of 1000 frames per second during the stick-slip motion and processed using a 2D digital image correlation method to obtain the displacement field.We define a synergism coefficient that describes the relative dispersion of the accumulative fault slip.The results reveal that:(1)a local pre-slip area spreads very slowly along the fault before the MIS develops.It extends at a higher but still slow speed during meta-instable state I(MIS-I).During the final^1.5%of MIS,in meta-instable state II(MIS-II),the local pre-slip area first extends at a speed of^0.9 m/s,and then expands out of the observed image area at a very high speed.These results indicate that the local pre-slip area transforms from a state of quasi-static extension in MIS-I to quasi-dynamic extension in MIS-II.(2)The synergism coefficient of the fault slip decreases to half of its original value in MIS-I and to a quarter of its original value in MIS-II.This continuous decrease of synergism coefficient indicates that the strengthening of fault slip synergism is a characteristic of MIS.(3)Furthermore,the unstable sliding stage includes three sliding processes:initial-,fast-,and adjusted-sliding.There are two pauses between the three sliding processes.展开更多
Over the past decade many bifunctional amine-thioureas have been developed as active metal-free organocatalysts. Coopera-tive catalysis of these amino-thioureas allows high reaction rates and excellent transfer of ste...Over the past decade many bifunctional amine-thioureas have been developed as active metal-free organocatalysts. Coopera-tive catalysis of these amino-thioureas allows high reaction rates and excellent transfer of stereocbemical information. Despite these impressive advances, the design of new high-performance catalysts for applications in asymmetric catalytic reactions is of ongoing interest in organic chemistry. Herein we describe a cooperative catalyst system consisting of a chiral amine thiourea and an achiral organic acid that promotes the conjugate addition of 4-nonsubstituted pyrazolones to nitroolefins and subsequent dearomative chlorination. The corresponding adducts and the subsequent products were obtained in high to excel lent yields (up to 99%) and high stereoselectivities (up to 99/1 dr, 98% ee) under mild reacton conditions. These transforma tions provide an easy access to enantio-enriched pvrazole derivatives, which could possess Potential oharmaceutical activity.展开更多
基金This study is supported by the following projects:the Chinese Ministry of Education(MOE)Humanities and Social Science Research Funding(18YJC740042)the Research Project of Guangdong Planning Office of Philosophy and Social Science(GD16CWW05)+1 种基金the MOE Key Research Project of Humanities and Social Science(16JJD740006)conducted by the Center for Linguistics and Applied Linguistics(CLAL),Guangdong University of Foreign Studies(GDUFS)supported by both the Department of Education of Guangdong Province and the Center for Linguistics and Applied Linguistics at Guangdong University of Foreign Studies,P.R.China for the frontier research and its theoretical innovations in interpersonal pragmatics(“人际语用学前沿研究与理论创新”项目)(2018WZDXM006).
文摘Discourse markers(DMs) are characterized by multifunctionality in different contexts.This study addressed the use of the Chinese DM,na(那),as a solution to topical divergence,during clinical interactions with right-hemisphere-damaged(RHD) patients.Drawing on data collected from clinical interviews between psychotherapists and RHD patients,this study examined the functions of na in response to RHD topical divergence,focusing on the topic and attitudinal aspects.It was found that na was mainly employed by psychotherapists to mark a reproffer of interview topics(i.e.,an attempt to return to earlier topics),and a display of disalignment and disaffiliation with RHD topical divergence.These functions of na reflect the psychotherapists’ attempts to overcome communicative problems arising from RHD topical divergence,so as to ensure the achievement of the communicative goal.Thus,na can be interpreted as a compensatory strategy for dealing with RHD topical divergence on an interpersonal level.These findings not only expand our knowledge about the function spectrum of na,but also offer insights for RHD patients’ interlocutors to enhance conversational communication with RHD patients via the compensatory strategy.
文摘The development of catalytic asymmetric radical reactions is an attractive but formidable task.The high reactivity of radicals enables the use of readily accessible feedstocks and mild reaction conditions,but it leads to substantial difficulty for chiral catalysts to provide sufficient enantiocontrol.Moreover,a racemic background process is often inevitable,further deteriorating enantioselectivity.In this regard,an effective protocol has been established for enantioselective intermolecular[2+2]photocycloadditions to overcome the challenges,which is capitalising on the ground-state preassociations of chiral catalysts with photoactivated substrates.Here,we report the viability of substrate-differentiating synergistic catalysis for this important reaction.In this new platform,energy transfer occurs between DPZ as a photosensitizer and enones or(E)-2-substituted vinylazaarenes for producing triplet-state species,and chiral phosphoric acid interacts with ground-state 2-vinylazaarenes via hydrogen bonding for subsequent enantiofacial cycloaddition.Although all active species are dispersed in the reaction system,valuable enantioenriched mono-and di-azaarene-functionalized cyclobutanes are obtained efficiently and selectively.In addition to constructing all-carbon quaternary stereocentres,flexible modulation of azaaryl groups and other substituents on the cyclobutane ring is also operative.
文摘Cooperative hydrogen atom transfer and chiral hydrogen‐bonding catalysis as a new platform for the asymmetric synthesis of azaarene derivatives is reported.By using a tetrabutylammonium decatungstate as the photocatalyst and a chiral phosphoric acid as the hydrogen‐bonding catalyst,transformations of a variety of commercially available hydrocarbons and silanes with diverseα‐branched 2‐vinylazaarenes could efficiently experience a tandem radical conjugate addition and enantioselective protonation process,providing a convenient and fully atom economical approach to access a range of valuable enantioenrichedα‐tertiary azaarenes in high yields with good to excellent enantioselectivities(up to 93%ee).Through the direct use of tert‐butyl methylcarbamate as the feedstock,this method enables a highly practical and concise synthesis of the enantiomerically pure medicinal molecule pheniramine(Avil).
基金supported by the National Natural Science Foundation of China(Grant No.41172180)Basic Research Funds from the Institute of Geology,China Earthquake Administration(Grant No.IGCEA1203)
文摘The meta-instable state(MIS)is the final stage before fault instability during stick-slip movement.Thus,identification of MIS is of great significance for assessing earthquake hazard in fault zones.A rock sample with a precut planar fault was loaded on a horizontally biaxial servo-controlled press machine to create stick-slip conditions.Digital images of the sample surface were taken by a high-speed camera at a rate of 1000 frames per second during the stick-slip motion and processed using a 2D digital image correlation method to obtain the displacement field.We define a synergism coefficient that describes the relative dispersion of the accumulative fault slip.The results reveal that:(1)a local pre-slip area spreads very slowly along the fault before the MIS develops.It extends at a higher but still slow speed during meta-instable state I(MIS-I).During the final^1.5%of MIS,in meta-instable state II(MIS-II),the local pre-slip area first extends at a speed of^0.9 m/s,and then expands out of the observed image area at a very high speed.These results indicate that the local pre-slip area transforms from a state of quasi-static extension in MIS-I to quasi-dynamic extension in MIS-II.(2)The synergism coefficient of the fault slip decreases to half of its original value in MIS-I and to a quarter of its original value in MIS-II.This continuous decrease of synergism coefficient indicates that the strengthening of fault slip synergism is a characteristic of MIS.(3)Furthermore,the unstable sliding stage includes three sliding processes:initial-,fast-,and adjusted-sliding.There are two pauses between the three sliding processes.
基金supported by the National Natural Science Foundation of China(21172170 and 21225208)the National Basic Research Program of China(973 Program,2014CB745100)
文摘Over the past decade many bifunctional amine-thioureas have been developed as active metal-free organocatalysts. Coopera-tive catalysis of these amino-thioureas allows high reaction rates and excellent transfer of stereocbemical information. Despite these impressive advances, the design of new high-performance catalysts for applications in asymmetric catalytic reactions is of ongoing interest in organic chemistry. Herein we describe a cooperative catalyst system consisting of a chiral amine thiourea and an achiral organic acid that promotes the conjugate addition of 4-nonsubstituted pyrazolones to nitroolefins and subsequent dearomative chlorination. The corresponding adducts and the subsequent products were obtained in high to excel lent yields (up to 99%) and high stereoselectivities (up to 99/1 dr, 98% ee) under mild reacton conditions. These transforma tions provide an easy access to enantio-enriched pvrazole derivatives, which could possess Potential oharmaceutical activity.