In the case of A-pPrOzi-A the hydrophobic core and hydrophilic corona seem to exhibit a more pronounced phase separation, compared to A*-pPrOzi-A* and especially A-pBuOx-A in which B blocks show a greater extent of entanglement with the A blocks, i.e., A blocks interpenetrate the hydrophobic domain to a higher degree; this could be detrimental to the functionality of the former as a solubilizing corona. This interpenetration becomes evident when observing not only the atom densities of A blocks (Figure ), but also e.g. the Rg ratios between B blocks and entire micelles: we clearly see the lowest value for A-pPrOzi-A (Figure ). Also, the B block solvent-accessible surface area (SASA) in contact with A blocks is significantly lower for A-pPrOzi-A in comparison to A*-pPrOzi-A* and A-pBuOx-A at the same level of drug loading (Figure ). It should be noted that pPrOzi is less hydrophobic than pBuOx; the stronger phase separation between pMeOx and pPrOzi is therefore not self-evident but may be explained by reduced miscibility of Ox and Ozi repeat units. The asphericity 𝑄 of all systems is close to zero, within a similar range as found in previous modeling studies for spherical micelles (Table ). 60,70,71 Overall, atom densities of individual micelle constituents demonstrate that, in contrast to e.g. lipid bilayers of liposomes, each structure contains small amounts of water even within the inner hydrophobic core (making up to around ~10 % of atoms, Figure ) and much more so in the outer regions of the hydrophilic shell. These structures are thus not completely desolvated, which conforms to previous hypotheses and results from pyrene fluorescence assays; this suggests water plays an important role in the formation of this form of DDS. Upon closer examination of the H-bonds (HB) that A block oxygens are able to form with water, a lower level for the less hydrophilic A*-pPrOzi-A* is found (Figure ), which is in agreement with the hypothesis of a reduced solvation of this corona. A-pPrOzi-A with the highest maximum LC also shows the largest number of H-bonds both for [10/2] and [10/6] loadings. Performing an analogous analysis on the B blocks reveals, as expected, lower numbers (Figure ). Interestingly, for A-pBuOx-A the amount of H-bonds is much larger in comparison to A-pPrOzi-A and A*-pPrOzi-A*. However, this seems not to be a result from higher water contents within the core (compare Figure ), but rather from the above described lack of clear separation between the core and shell areas. Hence, in these instances, solvent-exposed B blocks in the outer regions of the micelles are present to a greater extent (image in Figure ). Radial distribution functions (RDF) for water oxygens around polymer amide oxygens reveal similar results to these H-bond analyses (Figure and 4D): for A blocks the highest hydration is found for the case of A-pPrOzi-A and the lowest for A*-pPrOzi-A*. Generally speaking, water soluble pOx and pOzi are known to be thermoresponsive, they show a lower critical solution temperature (LCST) type behavior, promoting phase separation upon higher temperatures. In particular, pPrOzi has a LCST at around 11°C. During equilibration, the systems were heated up to 385 K for extended time periods in which micellar structures remained intact.