The ruthenium unit was introduced into the redox-active molecular poly gon to assembly new Ru-Fc metallocycles (Compound 1), in which the redox active (ferrocene) and fluoresecent (ruthenium) signaling subunits are di...The ruthenium unit was introduced into the redox-active molecular poly gon to assembly new Ru-Fc metallocycles (Compound 1), in which the redox active (ferrocene) and fluoresecent (ruthenium) signaling subunits are directly attache d by the putative cation-binding sites. The compound 1 displayed high selectivit y for Ca2+ by electrochemical tests. The measurements of the fluorescence spectr a on titration of 1 with Ca2+, Li+, Na+, K+, Mg2+ or Ba2+ ion indicate the uniqu e ability of 1 to detect Ca2+ ions selectively.展开更多
利用1 H NMR,ESI-MS,UV-Vis,荧光光谱等测试手段研究了基于锌基-有机金属三元大环探针M-1对生物分子谷胱甘肽(GSH)的识别与传感。并且,通过研究识别过程中M-1与组成谷胱甘肽的氨基酸(半胱氨酸、谷氨酸、甘氨酸)的作用关系,确立了M-1对GS...利用1 H NMR,ESI-MS,UV-Vis,荧光光谱等测试手段研究了基于锌基-有机金属三元大环探针M-1对生物分子谷胱甘肽(GSH)的识别与传感。并且,通过研究识别过程中M-1与组成谷胱甘肽的氨基酸(半胱氨酸、谷氨酸、甘氨酸)的作用关系,确立了M-1对GSH的识别机理。结果表明,化合物M-1在H2O/DMF(1∶9,φ)溶液中形成了稳定的[3+3]大环结构;紫外滴定光谱表明,向M-1中加入GSH后303nm处吸收峰强度增加,380nm处吸收峰强度减弱,在330nm处出现了一个等吸收点,紫外滴定和ESI-MS质谱证实了M-1能够1∶1包合GSH,平衡常数(log KGSH)为4.62±0.15。1 H NMR表明谷胱甘肽在M-1中的构型为组成谷胱甘肽的谷氨酸通过羧基与金属中心之间的静电作用深深地进入M-1空穴内部。荧光光谱表明,向M-1中加入GSH时,以330nm的光激发,发射波长从510nm红移至540nm,荧光强度增加1倍;加入半胱氨酸、谷氨酸时,荧光强度分别增加0.4倍和0.2倍;而加入甘氨酸时,荧光没有变化。综合上述结果证明了M-1空穴的限域作用及其底部三元环上的氨基和GSH上的巯基(半胱氨酸)间的氢键作用使M-1的电子构型发生转变,进而引起紫外光谱和荧光光谱发生变化,实现了大环化合物M-1对生物分子谷胱甘肽的可视化、高灵敏度检测,检测限达到3.0×10-6 mol·L^(-1)。展开更多
Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robus...Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.展开更多
Digestate, the product obtained after anaerobic digestion of organic waste for biogas production, is rich in plant nutrients and might be used to fertilize crops. Wheat （Triticum spp. L.） was fertilized with digesta...Digestate, the product obtained after anaerobic digestion of organic waste for biogas production, is rich in plant nutrients and might be used to fertilize crops. Wheat （Triticum spp. L.） was fertilized with digestate, urea, or left unfertilized and cultivated in the greenhouse for 120 d. Emissions of greenhouse gasses （carbon dioxide （CO2）, methane （CH4）, and nitrous oxide （N20）） were monitored and plant growth characteristics were determined at harvest. The digestate was characterized for heavy metals, pathogens, and C and N mineralization potential in an aerobic incubation experiment. No Salmonella spp., Shigella spp., or viable eggs of helminths were detected in the digested pig slurry, but the number of faecal coliforms was as high as 3.6 ~ 104 colony-forming units （CFU） g-1 dry digestate. The concentrations of heavy metals did not surpass the upper limits established by US Environmental Protection Agency （EPA）. After 28 d, 17% of the organic C （436 g kg-1 dry digestate） and 8% of the organic N （6.92 g kg-1 dry digestate） were mineralized. Emissions of CO2 and CH4 were not significantly affected by fertilization in the wheat-cultivated soil, but digestate significantly increased the cumulative N20 emission by 5 times compared to the urea-amended soil and 63 times compared to the uncultivated unfertilized soil. It could be concluded that digestate was nutrient rich and low in heavy metals and pathogens, and did not affect emissions of CH4 and CO2 when applied to a soil cultivated with wheat, but increased emission of N20. Key Words： biodigester, C and N mineralization potential, faecal coliform, heavy metal, pathogen, pig slurry展开更多
文摘The ruthenium unit was introduced into the redox-active molecular poly gon to assembly new Ru-Fc metallocycles (Compound 1), in which the redox active (ferrocene) and fluoresecent (ruthenium) signaling subunits are directly attache d by the putative cation-binding sites. The compound 1 displayed high selectivit y for Ca2+ by electrochemical tests. The measurements of the fluorescence spectr a on titration of 1 with Ca2+, Li+, Na+, K+, Mg2+ or Ba2+ ion indicate the uniqu e ability of 1 to detect Ca2+ ions selectively.
文摘利用1 H NMR,ESI-MS,UV-Vis,荧光光谱等测试手段研究了基于锌基-有机金属三元大环探针M-1对生物分子谷胱甘肽(GSH)的识别与传感。并且,通过研究识别过程中M-1与组成谷胱甘肽的氨基酸(半胱氨酸、谷氨酸、甘氨酸)的作用关系,确立了M-1对GSH的识别机理。结果表明,化合物M-1在H2O/DMF(1∶9,φ)溶液中形成了稳定的[3+3]大环结构;紫外滴定光谱表明,向M-1中加入GSH后303nm处吸收峰强度增加,380nm处吸收峰强度减弱,在330nm处出现了一个等吸收点,紫外滴定和ESI-MS质谱证实了M-1能够1∶1包合GSH,平衡常数(log KGSH)为4.62±0.15。1 H NMR表明谷胱甘肽在M-1中的构型为组成谷胱甘肽的谷氨酸通过羧基与金属中心之间的静电作用深深地进入M-1空穴内部。荧光光谱表明,向M-1中加入GSH时,以330nm的光激发,发射波长从510nm红移至540nm,荧光强度增加1倍;加入半胱氨酸、谷氨酸时,荧光强度分别增加0.4倍和0.2倍;而加入甘氨酸时,荧光没有变化。综合上述结果证明了M-1空穴的限域作用及其底部三元环上的氨基和GSH上的巯基(半胱氨酸)间的氢键作用使M-1的电子构型发生转变,进而引起紫外光谱和荧光光谱发生变化,实现了大环化合物M-1对生物分子谷胱甘肽的可视化、高灵敏度检测,检测限达到3.0×10-6 mol·L^(-1)。
基金supported by the National Key R&D Program of China(2017YFA0700102)the National Natural Science Foundation of China(21573222 and 91545202)+1 种基金the Outstanding Youth Talent Project of Dalian(2017RJ03)the DMTO Project of Dalian Institute of Chemical Physics,CAS(DICP DMTO201702),the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020200),the Youth Innovation Promotion Association,CAS(2015145)~~
文摘Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.
文摘Digestate, the product obtained after anaerobic digestion of organic waste for biogas production, is rich in plant nutrients and might be used to fertilize crops. Wheat （Triticum spp. L.） was fertilized with digestate, urea, or left unfertilized and cultivated in the greenhouse for 120 d. Emissions of greenhouse gasses （carbon dioxide （CO2）, methane （CH4）, and nitrous oxide （N20）） were monitored and plant growth characteristics were determined at harvest. The digestate was characterized for heavy metals, pathogens, and C and N mineralization potential in an aerobic incubation experiment. No Salmonella spp., Shigella spp., or viable eggs of helminths were detected in the digested pig slurry, but the number of faecal coliforms was as high as 3.6 ~ 104 colony-forming units （CFU） g-1 dry digestate. The concentrations of heavy metals did not surpass the upper limits established by US Environmental Protection Agency （EPA）. After 28 d, 17% of the organic C （436 g kg-1 dry digestate） and 8% of the organic N （6.92 g kg-1 dry digestate） were mineralized. Emissions of CO2 and CH4 were not significantly affected by fertilization in the wheat-cultivated soil, but digestate significantly increased the cumulative N20 emission by 5 times compared to the urea-amended soil and 63 times compared to the uncultivated unfertilized soil. It could be concluded that digestate was nutrient rich and low in heavy metals and pathogens, and did not affect emissions of CH4 and CO2 when applied to a soil cultivated with wheat, but increased emission of N20. Key Words： biodigester, C and N mineralization potential, faecal coliform, heavy metal, pathogen, pig slurry
