Liisa Hirvonen edited Results.tex  over 8 years ago

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The phosphorescence lifetime of the Ru(bpy)$_2$(mcbpy-O-Su-ester)(PF$_6$)$_2$ compound increases with viscosity; examples of the measured raw decays are shown in Fig~\ref{fig:decays}. The time-resolved anisotropy decays were calculated according to eq~\ref{eq:anisotropy}, and representative examples are shown in Fig~\ref{fig:exampleFits}. The anisotropy decay time (i.e.\ the rotational correlation time) increases with solvent viscosity for each drug, as expected (Fig~\ref{fig:exampleFits}). A double-exponential fit to the anisotropy decay yields excellent fit results for all data sets; the fits results are consistent and largely independent of starting parameters and fitting range, and the residuals are flat without systematic deviations. Representative fits to three different viscosities for each drug are shown in Fig~\ref{fig:exampleFits}.  The longer rotational correlation times corresponding to the drug's rotational diffusion were plotted against the viscosity, see Fig~\ref{fig:results}. For each drug this yields a straight line passing through the origin, as expected from eq~\ref{eq:SED}, whosethe  gradient depends on the molecular volume. Gradients of 43.28$\pm$0.12~ns/cP for BSA, 51.47$\pm$0.12~ns/cP for Eylea, 21.40$\pm$0.11~ns/cP for Lucentis and 98.09$\pm$0.04~ns/cP for Avastin were obtained by straight line fits according to eq~\ref{eq:SED} to the data sets using the least squares method. Using eq~\ref{eq:R_h}, this yields experimental hydrodynamic radii of 3.49$\pm$0.03~nm for BSA, 3.70$\pm$0.03~nm for Eylea, 2.75$\pm$0.04~nm for Lucentis and 4.58$\pm$0.01~nm for Avastin. The theoretical radii of the drugs were also calculated according to eqs~\ref{eq:Erickson}, \ref{eq:Wilkins} and \ref{eq:Dill}. Summary of the calculated and measured hydrodynamic radii is shown in Table~\ref{table:res}.