## 3 Results and Discussion
### Size Characterization in Aqueous Solutions  
The self-assembly properties of pEFSS8-26 and pEFSS8-46 homopolymers in aqueous solutions were investigated by means of dynamic light scattering (DLS) at room temperature. The homopolymer exhibited a bimodal intensity size distribution at room temperature in aqueous solution (5 g/L), with one narrow peak characterized by a hydrodynamic diameter of 6-7 nm and a second, wider one indicating larger diameters (centered at 300 nm) (Figure 1). The smaller diameter peak accounted for 99.9% of particle volume, thus resulting in a unimodal volume distribution. The population at higher diameters may be attributed to the self-assembly of a small portion of polymeric chains into larger multichain aggregates. This kind of bimodal intensity distribution and unimodal volume distribution is a common feature of the self-folding and assembly of amphiphilic random polymers containing fluorous elements [27; 28]. The dominant population in volume distribution was slightly smaller in size than that previously found for random copolymers of pentafluostyrene and oligo(ethylene glycol) methacrylate (10-15 nm) [32] and it was similar or smaller in size than those measured for self-folded chains formed by other POEGMA-based amphiphilic random copolymers [27; 41; 42]. Thus, the size of pEFSS8-x polymers was compatible with a unimer that, thanks to the amphiphilic nature of the \begin{table}
\begin{tabular}{c c c c c c c c} \hline \hline
**Polymer** & **Atmosphere** & \begin{tabular}{c} **Monomer/** \\ **Initiator****Mole****Ratio** \\ \end{tabular} & **Conversion (\%)** & **x 1** & \begin{tabular}{c} **\(M_{\mathbf{n}}\)****NMR****2** \\ **(g/mol)** \\ \end{tabular} & \
\begin{tabular}{c} **\(M_{\mathbf{n}}\)****GPC****3** \\ **(g/mol)** \\ \end{tabular} &
\begin{tabular}{c} **\(D\)****3** \\ **(\(D\)****3** \\ \end{tabular} \\ \hline pEFSS8-26 & N2 & 24 & 99 & 26 & 14,410 & 10,800 & 1.26 \\ pEFSS8-46 & Vacuum & 60 & 93 & 46 & 25,490 & 19,800 & 1.25 \\ \hline \hline \end{tabular}  
* Number average degree of polymerization. 2 Molecular weight calculated from 1H nuclear magnetic resonance (1H NMR). 3 Molecular weight and dispersity measured by gel permeation chromatography (GPC).  
\end{table} 
Table 1: Physico-chemical properties of the synthesized pEFSS8-x polymers. polymer, is likely to be in a folded state rather than in a random coiled conformation. An in-depth investigation of the shape and size of the structures formed by pEFS8-x polymers in aqueous solutions is the subject of a forthcoming publication. Both polymers were also studied by DLS at 80 \({}^{\circ}\)C. At this temperature, the analysis showed the formation of large multichain aggregates with \(D_{\rm h}\) above 1 micron. In particular, pEFS8-26 formed structures with a \(D_{\rm h}\) of \(\sim\)3000 nm, whereas pEFS8-46 formed smaller aggregates whose \(D_{\rm h}\) was \(\sim\)1500 nm, with a size distribution significantly narrower than pEFS8-26. Thus, the average degree of polymerization x seemed to have a far larger effect on the self-assembly of the homopolymers at this higher temperature compared to room temperature. The formation of large aggregates is characteristic of an LCST phase transition, which took place between the two temperatures at which the measurements were carried out. pEFS8-46 was also studied in aqueous solutions at other concentrations ranging from 0.5 to 10 g/L to investigate the influence of polymer concentration on its self-assembly (Table 2). The size distributions at 25 \({}^{\circ}\)C did not change significantly with the concentration, with the dominant population in volume distribution remaining at 7 nm (Table 2). This indicates that concentration has little influence on the self-assembly of the polymer chains at this temperature.