An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide(CO)as both reductant and carbonyl source,which enables facile access to amide...An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide(CO)as both reductant and carbonyl source,which enables facile access to amides with excellent regioselectivity and broad substrate scope.It is found that the counter anions of the Pd catalyst precursors significantly affect the reaction chemoselectivity and amide regioselectivity.Branched amides were mainly obtained with K2PdCl4 as the metal catalyst,and phosphine ligands had no influence on the regioselectivity but affected the catalytic reactivity.However,phosphine ligands had significant effects on aminocarbonylation regioselectivity when Pd(CH3CN)4(OTf)2 was used;monodentate phosphines tended to form branched amides,and bidentate phosphines mainly formed linear amides.Trapping experiments,primary kinetic studies,and control reactions with all possible N-species reduced from nitroarene indicated that the catalytic synthesis of branched and linear amides produced nitrene(further converted to enamide)and aniline,respectively,different from the previous ligand-controlled regioselective synthesis of amides via the aminocarbonylation of olefins with amines.Furthermore,the proposed synthesis route could be applied in the synthesis of gram-scale propanil under mild conditions.展开更多
Formulation of different ecological zone plans according to the corresponding protection targets and the necessity of proper conservation policy is one of the measures to achieve the goal of ecological conservation in...Formulation of different ecological zone plans according to the corresponding protection targets and the necessity of proper conservation policy is one of the measures to achieve the goal of ecological conservation in China.In order to clarify the interrelation among key ecological zone plans,this paper carried out the research on spatial relation of priority areas of biodiversity conservation and three key ecological areas(key ecological function areas,key regions of ecological service function,national nature reserves)and the research on ecological conditions,based on multi-scale ecological spatial theme information,which incorporates elements like ecological quality and type,and by the aid of spatial information analysis and GIS modeling.The results showed a contrastively fine spatial consistency with 68.8%of priority areas of biodiversity conservation overlapping with three key ecological areas.Although the environment in priority areas of biodiversity conservation were in good conditions,protection pressure is also increasing,powerful supervision and protection should not be ignored.The environmental conditions in the overlapping areas,as a whole,were superior to those in the non-overlapping areas.Since two areas have different characteristics,targeted protection measures should be formulated based on this difference,which will be very important for biodiversity conservation in priority areas of biodiversity conservation.展开更多
Based on remote sensing data of the Yangtze River Delta(YRD) in the years of 1991, 2001 and 2008, the paper built an index system of land use potential restraint factors in YRD, according to geological condition, terr...Based on remote sensing data of the Yangtze River Delta(YRD) in the years of 1991, 2001 and 2008, the paper built an index system of land use potential restraint factors in YRD, according to geological condition, terrain condition, water area, natural reserve area and basic farmland, and evaluated construction land potential based on the platform of GIS spatial analysis model. The results showed that:(1) the construction land increased rapidly since 1991 and reached 24,951.21 km2 in 2008, or 21.27% of the total area. Among all the cities in the YRD, Shanghai took the greatest percentage, followed by Jiangsu and Zhejiang. Spatially, areas where government departments are located became the growth center of construction land. Prefecture-level cities were the fastest growth region and the changing trend showed circle layered characteristics and significant increase with Shanghai and Suzhou as the core.(2) The higher the quality of construction land potentials(CLP), the smaller the number of CLP units. High sensitive area accounted for the largest percentage(40.14%) among all types of constraint regions and this was followed by medium sensitive region(31.53%) of the whole region.(3) The comprehensive CLP in the YRD was 24,989.65 km2, or 21.76% of the total YRD. The land use potential showed spatial distribution imbalance. CLP of Zhejiang was obviously larger than that of Jiangsu. CLP was insufficient in regional central city. Moreover, CLP in the YRD formed a circle layered spatial pattern that increasingly expanded centered in prefecture-level cities. Low potential area expanded from north to south. High potential area was mainly located in south YRD. Areas with zero potential in the YRD formed a northwest-southeast "Y-shaped" spatial pattern in north Hangzhou Bay.(4) CLP per capita in YRD was 0.045 ha/person and also unevenly distributed. Some 25.57% of the study units at county level nearly had no construction land and 8.24% of the units had CLP per capita below the national average level. CLP per capita in less than 25% of the county-level units was larger than the YRD average level, which were mainly located in Zhejiang. Therefore, research on the construction potential area in YRD was favorable for analysis of the development status and potential space of this region under the background of rapid urbanization and industrialization.展开更多
The 2 ℃ warming target has been used widely in global and regional climate change research. Previous studies have shown large uncertainties in the time when surface air temperature (SAT) change over China will reac...The 2 ℃ warming target has been used widely in global and regional climate change research. Previous studies have shown large uncertainties in the time when surface air temperature (SAT) change over China will reach 2℃ rela- tive to the pre-industrial era. To understand the uncertainties, we analyzed the projected SAT in the twenty-first century using 40 state-of-the-art climate models under two Repre- sentative Concentration Pathways (RCP4.5 and RCPS.5) from the Coupled Model Intercomparison Project Phase 5. The 2℃ threshold-crossing time (TCT) of SAT averaged across China was around 2033 and 2029 for RCP4.5 and RCP8.5, respectively. Considering a 4-1o- range of inter- model SAT change, the upper and lower bounds of the 2 ℃ TCT could differ by about 25 years or even more. Uncer- tainty in the projected SAT and the warming rate around the TCT are the two main factors responsible for the TCT uncertainty. The former is determined by the climate sensi- tivity represented by the global mean surface temperature response. About 45 % of the intermodel variance of the projected 2 ~C TCT for averaged SAT over China can be explained by climate sensitivity across the models, which is contributed mainly by central and southern China. In a cli- mate more sensitive to CO2 forcing, stronger greenhouse effect, less stratus cloud over the East Asian monsoon region, and less snow cover on the Tibetan Plateau result in increased downward longwave radiation, increased shortwave radia- tion, and decreased shortwave radiation reflected by the surface, respectively, all of which may advance the TCT.展开更多
Selectivity estimation is crucial for query optimizers choosing an optimal spatial execution plan in a spatial database management system.This paper presents an Annular Bucket spatial histogram(AB histogram)that can e...Selectivity estimation is crucial for query optimizers choosing an optimal spatial execution plan in a spatial database management system.This paper presents an Annular Bucket spatial histogram(AB histogram)that can estimate the selectivity in finer spatial selection and spatial join operations even when the spatial query has more operators or more joins.The AB histogram is represented as a set of bucket-range,bucket-count value pairs.The bucket-range often covers an annular region like a sin-gle-cell-sized photo frame.The bucket-count is the number of objects whose Minimum Bounding Rectangles(MBRs)fall between outer rectangle and inner rectangle of the bucket-range.Assuming that all MBRs in each a bucket distribute evenly,for every buck-et,we can obtain serial probabilities that satisfy a certain spatial selection or join conditions from the operations' semantics and the spatial relations between every bucket-range and query ranges.Thus,according to some probability theories,spatial selection or join selectivity can be estimated by the every bucket-count and its probabilities.This paper also shows a way to generate an updated AB histogram from an original AB histogram and those probabilities.Our tests show that the AB histogram not only supports the selectivity estimation of spatial selection or spatial join with "disjoint","intersect","within","contains",and "overlap" operators but also provides an approach to generate a reliable updated histogram whose spatial distribution is close to the distribution of ac-tual query result.展开更多
文摘An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide(CO)as both reductant and carbonyl source,which enables facile access to amides with excellent regioselectivity and broad substrate scope.It is found that the counter anions of the Pd catalyst precursors significantly affect the reaction chemoselectivity and amide regioselectivity.Branched amides were mainly obtained with K2PdCl4 as the metal catalyst,and phosphine ligands had no influence on the regioselectivity but affected the catalytic reactivity.However,phosphine ligands had significant effects on aminocarbonylation regioselectivity when Pd(CH3CN)4(OTf)2 was used;monodentate phosphines tended to form branched amides,and bidentate phosphines mainly formed linear amides.Trapping experiments,primary kinetic studies,and control reactions with all possible N-species reduced from nitroarene indicated that the catalytic synthesis of branched and linear amides produced nitrene(further converted to enamide)and aniline,respectively,different from the previous ligand-controlled regioselective synthesis of amides via the aminocarbonylation of olefins with amines.Furthermore,the proposed synthesis route could be applied in the synthesis of gram-scale propanil under mild conditions.
基金Under the auspices of Public Science and Technology Research Funds of Environment(No.201009021,2011467026,2012467044)National Key Technology R&D Program of China(No.2012BAH32B03)National Natural Science Foundation of China(No.41171318,41001160)
文摘Formulation of different ecological zone plans according to the corresponding protection targets and the necessity of proper conservation policy is one of the measures to achieve the goal of ecological conservation in China.In order to clarify the interrelation among key ecological zone plans,this paper carried out the research on spatial relation of priority areas of biodiversity conservation and three key ecological areas(key ecological function areas,key regions of ecological service function,national nature reserves)and the research on ecological conditions,based on multi-scale ecological spatial theme information,which incorporates elements like ecological quality and type,and by the aid of spatial information analysis and GIS modeling.The results showed a contrastively fine spatial consistency with 68.8%of priority areas of biodiversity conservation overlapping with three key ecological areas.Although the environment in priority areas of biodiversity conservation were in good conditions,protection pressure is also increasing,powerful supervision and protection should not be ignored.The environmental conditions in the overlapping areas,as a whole,were superior to those in the non-overlapping areas.Since two areas have different characteristics,targeted protection measures should be formulated based on this difference,which will be very important for biodiversity conservation in priority areas of biodiversity conservation.
基金National Natural Youth Science Foundation of China,No.41201168
文摘Based on remote sensing data of the Yangtze River Delta(YRD) in the years of 1991, 2001 and 2008, the paper built an index system of land use potential restraint factors in YRD, according to geological condition, terrain condition, water area, natural reserve area and basic farmland, and evaluated construction land potential based on the platform of GIS spatial analysis model. The results showed that:(1) the construction land increased rapidly since 1991 and reached 24,951.21 km2 in 2008, or 21.27% of the total area. Among all the cities in the YRD, Shanghai took the greatest percentage, followed by Jiangsu and Zhejiang. Spatially, areas where government departments are located became the growth center of construction land. Prefecture-level cities were the fastest growth region and the changing trend showed circle layered characteristics and significant increase with Shanghai and Suzhou as the core.(2) The higher the quality of construction land potentials(CLP), the smaller the number of CLP units. High sensitive area accounted for the largest percentage(40.14%) among all types of constraint regions and this was followed by medium sensitive region(31.53%) of the whole region.(3) The comprehensive CLP in the YRD was 24,989.65 km2, or 21.76% of the total YRD. The land use potential showed spatial distribution imbalance. CLP of Zhejiang was obviously larger than that of Jiangsu. CLP was insufficient in regional central city. Moreover, CLP in the YRD formed a circle layered spatial pattern that increasingly expanded centered in prefecture-level cities. Low potential area expanded from north to south. High potential area was mainly located in south YRD. Areas with zero potential in the YRD formed a northwest-southeast "Y-shaped" spatial pattern in north Hangzhou Bay.(4) CLP per capita in YRD was 0.045 ha/person and also unevenly distributed. Some 25.57% of the study units at county level nearly had no construction land and 8.24% of the units had CLP per capita below the national average level. CLP per capita in less than 25% of the county-level units was larger than the YRD average level, which were mainly located in Zhejiang. Therefore, research on the construction potential area in YRD was favorable for analysis of the development status and potential space of this region under the background of rapid urbanization and industrialization.
基金supported jointly by the ‘‘Strategic Priority Research Program–Climate Change: Carbon Budget and Related Issues’’ of the Chinese Academy of Sciences (XDA05110300)the Research Fund for Commonwealth Trades (Meteorology) (GYHY201506012)+1 种基金the National Natural Science Foundation of China (41420104006)the China Postdoctoral Science Foundation (2015M581152)
文摘The 2 ℃ warming target has been used widely in global and regional climate change research. Previous studies have shown large uncertainties in the time when surface air temperature (SAT) change over China will reach 2℃ rela- tive to the pre-industrial era. To understand the uncertainties, we analyzed the projected SAT in the twenty-first century using 40 state-of-the-art climate models under two Repre- sentative Concentration Pathways (RCP4.5 and RCPS.5) from the Coupled Model Intercomparison Project Phase 5. The 2℃ threshold-crossing time (TCT) of SAT averaged across China was around 2033 and 2029 for RCP4.5 and RCP8.5, respectively. Considering a 4-1o- range of inter- model SAT change, the upper and lower bounds of the 2 ℃ TCT could differ by about 25 years or even more. Uncer- tainty in the projected SAT and the warming rate around the TCT are the two main factors responsible for the TCT uncertainty. The former is determined by the climate sensi- tivity represented by the global mean surface temperature response. About 45 % of the intermodel variance of the projected 2 ~C TCT for averaged SAT over China can be explained by climate sensitivity across the models, which is contributed mainly by central and southern China. In a cli- mate more sensitive to CO2 forcing, stronger greenhouse effect, less stratus cloud over the East Asian monsoon region, and less snow cover on the Tibetan Plateau result in increased downward longwave radiation, increased shortwave radia- tion, and decreased shortwave radiation reflected by the surface, respectively, all of which may advance the TCT.
基金Supported by the Innovation Project of IGSNRR (No. O9V90220ZZ)the Research Plan of LREIS (O88RA700KA),CAS
文摘Selectivity estimation is crucial for query optimizers choosing an optimal spatial execution plan in a spatial database management system.This paper presents an Annular Bucket spatial histogram(AB histogram)that can estimate the selectivity in finer spatial selection and spatial join operations even when the spatial query has more operators or more joins.The AB histogram is represented as a set of bucket-range,bucket-count value pairs.The bucket-range often covers an annular region like a sin-gle-cell-sized photo frame.The bucket-count is the number of objects whose Minimum Bounding Rectangles(MBRs)fall between outer rectangle and inner rectangle of the bucket-range.Assuming that all MBRs in each a bucket distribute evenly,for every buck-et,we can obtain serial probabilities that satisfy a certain spatial selection or join conditions from the operations' semantics and the spatial relations between every bucket-range and query ranges.Thus,according to some probability theories,spatial selection or join selectivity can be estimated by the every bucket-count and its probabilities.This paper also shows a way to generate an updated AB histogram from an original AB histogram and those probabilities.Our tests show that the AB histogram not only supports the selectivity estimation of spatial selection or spatial join with "disjoint","intersect","within","contains",and "overlap" operators but also provides an approach to generate a reliable updated histogram whose spatial distribution is close to the distribution of ac-tual query result.