CO_(2) capture is considered as one of the most ideal strategies for solving the environmental issues and against global warming.Recently,experimental evidence has suggested that aluminum double bond(dialumene) specie...CO_(2) capture is considered as one of the most ideal strategies for solving the environmental issues and against global warming.Recently,experimental evidence has suggested that aluminum double bond(dialumene) species can capture CO_(2) and further convert it into value-added products.However,the catalytic application of these species is still in its infancy.Both the dynamics mechanism of CO_(2) fixation and the detailed structures of catalytic intermediates are not well understood.In this work,we investigate the structure dependent resonance Raman(RR) signals for different reaction intermediates.Ab-initio simulations of spontaneous resonance Raman(spRR) and time-domain stimulated resonance Raman(stRR) give spectral signatures correlated to the existence of different intermediates during the CO_(2)-dialumene binding process.The unique Raman vibronic feature s contain rich structural information with high temporal resolution,enabling to monitor the transient catalytic intermediates under reaction conditions.Our work shows that RR can be used to monitor intermediates during the dialumene based CO_(2) capture reaction.The spectral features not only provide insight into the structural information of intermediate species,but also allow a deeper understanding of the dynamical details of this kind of catalytic process.展开更多
Base pair mismatch has been regarded as the main source of DNA point mutations, where minor shortlived tautomers were usually involved. However, the detection and characterization of these unnatural species pose chall...Base pair mismatch has been regarded as the main source of DNA point mutations, where minor shortlived tautomers were usually involved. However, the detection and characterization of these unnatural species pose challenges to existing techniques. Here, by using systematic structural and ultrafast resonance Raman(RR) spectral analysis for the four possible conformers of guanine-cytosine base pairs, the prominent marker Raman bands were identified. We found that the hydrogen bonding vibrational region from 2300 cm^(-1) to 3700 cm^(-1) is ideal for the identification of these short live species. The marker bands provide direct evidence for the existence of the tautomer species, thus offering an effective strategy to detect the short-lived minor species. Ultrafast resonance Raman spectroscopy would be a powerful tool to provide direct evidence of critical dynamical details of complex systems involving protonation or tautomerization.展开更多
基金financial support from the National Natural Science Foundation of China (NSFC,No.21773309)Highlevel Science Foundation of Qingdao Agricultural University (No.663/1114351)+2 种基金the Fundamental Research Funds for the Central Universities (No.19CX05001A)Hubei University of Arts and Science (No.2020kypytd002)Xiangyang Science and Technology Research and Development (No.2020YL09)。
文摘CO_(2) capture is considered as one of the most ideal strategies for solving the environmental issues and against global warming.Recently,experimental evidence has suggested that aluminum double bond(dialumene) species can capture CO_(2) and further convert it into value-added products.However,the catalytic application of these species is still in its infancy.Both the dynamics mechanism of CO_(2) fixation and the detailed structures of catalytic intermediates are not well understood.In this work,we investigate the structure dependent resonance Raman(RR) signals for different reaction intermediates.Ab-initio simulations of spontaneous resonance Raman(spRR) and time-domain stimulated resonance Raman(stRR) give spectral signatures correlated to the existence of different intermediates during the CO_(2)-dialumene binding process.The unique Raman vibronic feature s contain rich structural information with high temporal resolution,enabling to monitor the transient catalytic intermediates under reaction conditions.Our work shows that RR can be used to monitor intermediates during the dialumene based CO_(2) capture reaction.The spectral features not only provide insight into the structural information of intermediate species,but also allow a deeper understanding of the dynamical details of this kind of catalytic process.
基金the financial support from the National Key Research and Development Program of China(No.2019YFA0708703)the National Natural Science Foundation of China(NSFC,No.21773309)+3 种基金the High-level Science Foundation of Qingdao Agricultural University(No.663/1114351)the Hefei National Laboratory for Physical Sciences at the Microscale(No.KF2020004)Xiangyang Science and Technology Research and Development(No.2020YL09)Hubei University of Arts and Science(Nos.HLOM222003,2020kypytd002)。
文摘Base pair mismatch has been regarded as the main source of DNA point mutations, where minor shortlived tautomers were usually involved. However, the detection and characterization of these unnatural species pose challenges to existing techniques. Here, by using systematic structural and ultrafast resonance Raman(RR) spectral analysis for the four possible conformers of guanine-cytosine base pairs, the prominent marker Raman bands were identified. We found that the hydrogen bonding vibrational region from 2300 cm^(-1) to 3700 cm^(-1) is ideal for the identification of these short live species. The marker bands provide direct evidence for the existence of the tautomer species, thus offering an effective strategy to detect the short-lived minor species. Ultrafast resonance Raman spectroscopy would be a powerful tool to provide direct evidence of critical dynamical details of complex systems involving protonation or tautomerization.
