Resonance enhancement has been increasingly employed in the emergent felntosecond stimu- lated Raman spectroscopy （FSRS） to selectively monitor molecular structure and dynamics with improved spectral and temporal re...Resonance enhancement has been increasingly employed in the emergent felntosecond stimu- lated Raman spectroscopy （FSRS） to selectively monitor molecular structure and dynamics with improved spectral and temporal resolutions and signal-to-noise ratios. Such joint eflforts by the technique- and application-oriented scientists and engineers have laid the foundation for exploiting the tunable FSRS methodology to investigate a great variety of photosensitive systems and elucidate the underlying functional mechanisms on molecular time scales. Dur- ing spectral analysis, peak line shapes remain a major concern with an intricate dependence on resonance conditions. Here, we present a comprehensive study of line shapes by tuning the Rarnan pump wavelength from red to blue side of the ground-state absorption band of the fluorescent dye rhodarnine 6G in solution. Distinct line shape patterns in Stokes and anti-Stokes FSRS as well as from the low to high-frequency modes highlight the competition between multiple third-order and higher-order nonlinear pathways, governed by difl^rent res- onance conditions achieved by Raman pump and probe pulses. In particular, the resonance condition of probe wavelength is revealed to play an important role in generating circular line shape changes through oppositely phased dispersion via hot luminescence （HL） pathways. Meanwhile, on-resonance conditions of the Rarnan pump could promote excited-state vibrational modes which are broadened and red-shifted from the coincident ground-state vibrational modes, posing challenges for spectral analysis. Certain strategies in tuning the Raman pump and probe to characteristic regions across an electronic transition band are discussed to improve the FSRS usability and versatility as a powerful structural dynamics toolset to advance chemical, physical, materials, and biological sciences.展开更多
Characterization of conformation kinetics of proteins at the interfaces is crucial for understanding the biornolecular functions and the mechanisms of interfacial biological action. But it requires to capture the dyna...Characterization of conformation kinetics of proteins at the interfaces is crucial for understanding the biornolecular functions and the mechanisms of interfacial biological action. But it requires to capture the dynamic structures of proteins at the interfaces with suffi- cient structural and temporal resolutions. Here, we demonstrate that a ferntosecond sum frequency generation vibrational spectroscopy （SFG-VS） system developed by our group provides a powerful tool for monitoring the real-tirne peptide transport across the membranes with time resolution of less than one second. By probing the real-time SFG signals in the arnide I and arnide A bands as WALP23 interacts with DMPG lipid bilayer, it is found that WALP23 is initially absorbed at the gel-phase DMPG bilayer with a random coil structure. The absorption of WALP23 on the surface leads to the surface charge reversal and thus changes the orientation of rnembrane-bound water. As the DMPG bilayer changes from gel phase into fluid phase, WALP23 inserts into the fluid-phase bilayer with its N-terminal end moving across the membrane, which causes the membrane dehydration and the transition of WALP23 conformation from random coil to mixed helix/loop structure and then to pure α-helical structure. The established system is ready to be employed in characterizing other interracial fast processes, which will be certainly helpful for providing a clear physical picture of the interracial phenomena.展开更多
基金supported by the U.S.National Science Foundation CAREER grant(CHE-1455353)the Oregon State University(OSU) Research Equipment Reserve Fund(Spring 2014)to C.Fang(USTC9603)the Wei Family Private Foundation in supporting C.Chen(USTC 0903) during his graduate studies at OSU Chemistry
文摘Resonance enhancement has been increasingly employed in the emergent felntosecond stimu- lated Raman spectroscopy （FSRS） to selectively monitor molecular structure and dynamics with improved spectral and temporal resolutions and signal-to-noise ratios. Such joint eflforts by the technique- and application-oriented scientists and engineers have laid the foundation for exploiting the tunable FSRS methodology to investigate a great variety of photosensitive systems and elucidate the underlying functional mechanisms on molecular time scales. Dur- ing spectral analysis, peak line shapes remain a major concern with an intricate dependence on resonance conditions. Here, we present a comprehensive study of line shapes by tuning the Rarnan pump wavelength from red to blue side of the ground-state absorption band of the fluorescent dye rhodarnine 6G in solution. Distinct line shape patterns in Stokes and anti-Stokes FSRS as well as from the low to high-frequency modes highlight the competition between multiple third-order and higher-order nonlinear pathways, governed by difl^rent res- onance conditions achieved by Raman pump and probe pulses. In particular, the resonance condition of probe wavelength is revealed to play an important role in generating circular line shape changes through oppositely phased dispersion via hot luminescence （HL） pathways. Meanwhile, on-resonance conditions of the Rarnan pump could promote excited-state vibrational modes which are broadened and red-shifted from the coincident ground-state vibrational modes, posing challenges for spectral analysis. Certain strategies in tuning the Raman pump and probe to characteristic regions across an electronic transition band are discussed to improve the FSRS usability and versatility as a powerful structural dynamics toolset to advance chemical, physical, materials, and biological sciences.
基金supported by the National Natural Science Foundation of China(No.21473177,No.21633007)the National Key Research and Development Program of China(No.2017YFA0303500 and No.2018YFA0208700)+1 种基金Fundamental Research Funds for the Central Universities(No.WK2340000064)Anhui Initiative in Quantum Information Technologies(No.AHY090000)
文摘Characterization of conformation kinetics of proteins at the interfaces is crucial for understanding the biornolecular functions and the mechanisms of interfacial biological action. But it requires to capture the dynamic structures of proteins at the interfaces with suffi- cient structural and temporal resolutions. Here, we demonstrate that a ferntosecond sum frequency generation vibrational spectroscopy （SFG-VS） system developed by our group provides a powerful tool for monitoring the real-tirne peptide transport across the membranes with time resolution of less than one second. By probing the real-time SFG signals in the arnide I and arnide A bands as WALP23 interacts with DMPG lipid bilayer, it is found that WALP23 is initially absorbed at the gel-phase DMPG bilayer with a random coil structure. The absorption of WALP23 on the surface leads to the surface charge reversal and thus changes the orientation of rnembrane-bound water. As the DMPG bilayer changes from gel phase into fluid phase, WALP23 inserts into the fluid-phase bilayer with its N-terminal end moving across the membrane, which causes the membrane dehydration and the transition of WALP23 conformation from random coil to mixed helix/loop structure and then to pure α-helical structure. The established system is ready to be employed in characterizing other interracial fast processes, which will be certainly helpful for providing a clear physical picture of the interracial phenomena.
