Dimensions of Quinoline-Based Foldamers Labeled with Oligo(phenylene vinylene) Probed in Solution by Time-Resolved Fluorescence Anisotropy
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A series of oligoquinolines (Qn with n = 1 – 32) was prepared with an oligo(phenylene vinylene) (OPV) fluorophore covalently attached at one end via a rigid amide bond. The fluorescence decays of the OPV-Qn solutions in chloroform were acquired with a vertically polarized excitation and an emission that was either vertically or horizontally polarized to yield the fluorescence decays IVV(t) and IVH(t), respectively. The IVV(t) and IVH(t) decays were fitted globally assuming a monoexponential anisotropy. The fits were good, indicating that the theoretical tri-exponential anisotropy of these rigid symmetric top macromolecules were well represented by a single exponential over the range of Qn lengths studied. The rotational time retrieved from the global analysis of the IVV(t) and IVH(t) fluorescence decays was found to increase linearly with increasing oligoquinoline chain length in agreement with the notion that these macromolecules were foldamers that adopted a rigid helical conformation in solution. Furthermore, the hydrodynamic volume of the OPV-Qn constructs determined from their rotational times perfectly matched that expected from the known dimensions of the Qn samples obtained from single crystal X-ray diffraction. Unfortunately, the small aspect ratio of the other foldamers prevented the resolution of the separate rotational times that would be expected from symmetric top macromolecules whose geometry could be described as ellipsoids or cylinders. Consequently, reliable values for the D// and D diffusion coefficients representing the tumbling of the foldamers along and perpendicular to the main axis of the symmetric top macromolecule could not be obtained for the OPV-Qn foldamers. Nevertheless, the excellent correlation found between foldamer size and rotational time suggests that time-resolved fluorescence anisotropy is a robust experimental technique to characterize the size and conformation of rigid foldamers in solution.
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Jingqi Wang, Hunter Little, Jean Duhamel, Xuesong Li, Nagula Markandeya, Victor Maurizot, Ivan Huc (2019). Dimensions of Quinoline-Based Foldamers Labeled with Oligo(phenylene vinylene) Probed in Solution by Time-Resolved Fluorescence Anisotropy. UWSpace. http://hdl.handle.net/10012/16679