The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process,which is the first step of new particle formation(NPF).In the present study,cycloaddition reaction mechanism of sulfur trio...The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process,which is the first step of new particle formation(NPF).In the present study,cycloaddition reaction mechanism of sulfur trioxide(SO_(3))to hydrogen sulfide(H_(2)S)which is a typical air pollutant and toxic gas detrimental to the environment were comprehensively investigate through theoretical calculations and Atmospheric Cluster Dynamic Code simulations.Gas-phase stability and nucleation potential of the product thiosulfuric acid(H_(2)S_(2)O_(3),TSA)were further analyzed to evaluate its atmospheric impact.Without any catalysts,the H_(2)S+SO_(3)reaction is infeasible with a barrier of 24.2 kcal/mol.Atmospheric nucleation precursors formic acid(FA),sulfuric acid(SA),and water(H_(2)O)could effectively lower the reaction barriers as catalysts,even to a barrierless reaction with the efficiency of cis-SA>trans-FA>trans-SA>H_(2)O.Subsequently,the gas-phase stability of TSA was investigated.A hydrolysis reaction barrier of up to 61.4 kcal/mol alone with an endothermic isomerization reaction barrier of 5.1 kcal/mol under the catalytic effect of SA demonstrates the sufficient stability of TSA.Furthermore,topological and kinetic analysis were conducted to determine the nucleation potential of TSA.Atmospheric clusters formed by TSA and atmospheric nucleation precursors(SA,ammonia NH_(3),and dimethylamine DMA)were thermodynamically stable.Moreover,the gradually decreasing evaporation coefficients for TSA-base clusters,particularly for TSA-DMA,suggests that TSA may participate in NPF where the concentration of base molecules are relatively higher.The present new reaction mechanismmay contributes to a better understanding of atmospheric sulfur cycle and NPF.展开更多
氮(N)是植物生长发育需要量最大的矿质营养元素,也是作物产量的限制因子。硝态氮(NO_(3)^(-)-N)是植物吸收利用氮素的主要形态之一。目前,植物中已报道4个基因家族(NPF、NRT2、CLC和SLAC1/SLAH)参与硝态氮的吸收和利用,其中NPF基因家族...氮(N)是植物生长发育需要量最大的矿质营养元素,也是作物产量的限制因子。硝态氮(NO_(3)^(-)-N)是植物吸收利用氮素的主要形态之一。目前,植物中已报道4个基因家族(NPF、NRT2、CLC和SLAC1/SLAH)参与硝态氮的吸收和利用,其中NPF基因家族成员数量众多且功能多样化,近年来获得较多关注和深入研究。模式植物拟南芥和主要粮食作物水稻、玉米和小麦中,分别含有53、93、79和331个NPF基因。拟南芥NPF家族中已有超过一半成员(31/53)的生物学功能被解析,粮食作物水稻中NPF基因功能亦有较多报道。研究表明,NPF基因广泛参与了植物对氮素的吸收及其调控、转运、分配/再分配等过程,一些成员对于改良和提高作物氮素利用率(nitrogen use efficiency,NUE)具有重要作用。因此,从氮素进入植物体及其在植物体内流动的层面出发,发掘具有重要功能的候选NPF基因,对于解析植物利用氮素的分子机制及其遗传改良具有重要意义。本文综述了模式植物拟南芥以及粮食作物中已报道的NPF基因在氮素吸收和利用中的生物学功能。目前粮食作物玉米中仅有4个NPF基因的生物学功能被报道,小麦中尚未有相关报道,未来对玉米和小麦中NPF基因的发掘与功能研究将为改良作物氮素利用效率提供新的基因资源。展开更多
基金supported by the Budget Surplus of Central Financial Science and Technology Plan (No.2021-JY-14)the Project funded by China Postdoctoral Science Foundation (No.2020M680636)+3 种基金the Fundamental Research Funds for Central Public Welfare Scientific Research Institutes of China,Chinese Research Academy of Environmental Sciences (Nos.2022YSKY-21 and 2022YSKY-27)the National Natural Science Foundation of China (No.41375133)the Science Foundation of Chinese Research Academy of Environmental Sciences (No.JY-41375133)Tian He Qingsuo Project-special fund project.
文摘The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process,which is the first step of new particle formation(NPF).In the present study,cycloaddition reaction mechanism of sulfur trioxide(SO_(3))to hydrogen sulfide(H_(2)S)which is a typical air pollutant and toxic gas detrimental to the environment were comprehensively investigate through theoretical calculations and Atmospheric Cluster Dynamic Code simulations.Gas-phase stability and nucleation potential of the product thiosulfuric acid(H_(2)S_(2)O_(3),TSA)were further analyzed to evaluate its atmospheric impact.Without any catalysts,the H_(2)S+SO_(3)reaction is infeasible with a barrier of 24.2 kcal/mol.Atmospheric nucleation precursors formic acid(FA),sulfuric acid(SA),and water(H_(2)O)could effectively lower the reaction barriers as catalysts,even to a barrierless reaction with the efficiency of cis-SA>trans-FA>trans-SA>H_(2)O.Subsequently,the gas-phase stability of TSA was investigated.A hydrolysis reaction barrier of up to 61.4 kcal/mol alone with an endothermic isomerization reaction barrier of 5.1 kcal/mol under the catalytic effect of SA demonstrates the sufficient stability of TSA.Furthermore,topological and kinetic analysis were conducted to determine the nucleation potential of TSA.Atmospheric clusters formed by TSA and atmospheric nucleation precursors(SA,ammonia NH_(3),and dimethylamine DMA)were thermodynamically stable.Moreover,the gradually decreasing evaporation coefficients for TSA-base clusters,particularly for TSA-DMA,suggests that TSA may participate in NPF where the concentration of base molecules are relatively higher.The present new reaction mechanismmay contributes to a better understanding of atmospheric sulfur cycle and NPF.
文摘氮(N)是植物生长发育需要量最大的矿质营养元素,也是作物产量的限制因子。硝态氮(NO_(3)^(-)-N)是植物吸收利用氮素的主要形态之一。目前,植物中已报道4个基因家族(NPF、NRT2、CLC和SLAC1/SLAH)参与硝态氮的吸收和利用,其中NPF基因家族成员数量众多且功能多样化,近年来获得较多关注和深入研究。模式植物拟南芥和主要粮食作物水稻、玉米和小麦中,分别含有53、93、79和331个NPF基因。拟南芥NPF家族中已有超过一半成员(31/53)的生物学功能被解析,粮食作物水稻中NPF基因功能亦有较多报道。研究表明,NPF基因广泛参与了植物对氮素的吸收及其调控、转运、分配/再分配等过程,一些成员对于改良和提高作物氮素利用率(nitrogen use efficiency,NUE)具有重要作用。因此,从氮素进入植物体及其在植物体内流动的层面出发,发掘具有重要功能的候选NPF基因,对于解析植物利用氮素的分子机制及其遗传改良具有重要意义。本文综述了模式植物拟南芥以及粮食作物中已报道的NPF基因在氮素吸收和利用中的生物学功能。目前粮食作物玉米中仅有4个NPF基因的生物学功能被报道,小麦中尚未有相关报道,未来对玉米和小麦中NPF基因的发掘与功能研究将为改良作物氮素利用效率提供新的基因资源。
