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Illuminating the intermolecular vs intramolecular excited state energy transfer quenching by Europium(III) ions
摘要： Bright lanthanide based probes relies on sensitised lanthanide luminescence. The outcome of the excited state energy transfer cascade—from sensitizer chromophore to lanthanide(III) ion—should be population of the lanthanide excited state with unity efficiency. This is rarely the case, and is a particular problem for europium(III) due to the low energy of the Eu(II)/Eu(III) redox couple. Thus, photoinduced electron transfer quenching can be an efficient drain for the excited state energy, reducing the brightness of a probe. Here, the effect of intramolecular PeT in a lanthanide based probe is investigated by contrasting intramolecular processes in coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) complexes to intermolecular processes induced through collisional quenching. We find that the excited energy transfer processes involving terbium(III) and europium(III) are slow in the complex when compared to collisional quenching. Further, we show that the quenching event may lead to lanthanide luminescence and suggest that the fate of a PeT quenching event may not be non-radiative loss of the excitation energy.
关键词： Lanthanides,Fluorescence,Luminescence,Excited State Energy Transfer,Solution Structure
更新于2025-09-19 17:15:36
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[Advances in Experimental Medicine and Biology] Glycobiophysics Volume 1104 || Synchrotron-Radiation Vacuum-Ultraviolet Circular-Dichroism Spectroscopy for Characterizing the Structure of Saccharides
摘要： Circular-dichroism (CD) spectroscopy is a powerful tool for analyzing the structures of chiral molecules and biomolecules. The development of CD instruments using synchrotron radiation has greatly expanded the utility of this method by extending the spectra to the vacuum-ultraviolet (VUV) region below 190 nm and thereby yielding information that is unobtainable by conventional CD instruments. This technique is especially advantageous for monitoring the structure of saccharides that contain hydroxy and acetal groups with high-energy transitions in the VUV region. Combining VUVCD spectra with theoretical calculations provides new insight into the contributions of anomeric hydroxy groups and rotational isomers of hydroxymethyl groups to the dynamics, intramolecular hydrogen bonds, and hydration of saccharides in aqueous solution.
关键词： Glycoprotein,Hydration,Circular dichroism,Synchrotron radiation,Time-dependent density functional theory,Molecular dynamics simulation,Saccharide,Intramolecular hydrogen bond,Solution structure,Structural dynamics,Vacuum ultraviolet,Glycosaminoglycan
更新于2025-09-10 09:29:36