Investigating RDF curves separately for the oxygen and sulfur groups at 25 and 75% thionation indicates that the peak for the remaining carbonyl groups within thionated variants is not affected while, simultaneously, the formation of a separate peak around 0.33 nm for thiocarbonyl groups is observed, in line with the peak position for the combined RDF curve at 75%. Recent theoretical investigations and analyses of crystal structures of thiopeptides showed similar distances as we detected in our simulations but also a high dependency of the hydrogen bond strength on the donor-acceptor angles, with remarkably low values down to around 100 °.96 While lone-pair electrons are not directly modelled in classical MDs, measuring hydrogen bonds with conventional cutoff definitions for oxygen-containing moieties (< 0.3 nm, 135 °) showed, as hypothesized, decreased amounts in correlation with the thionation degree. When using much broader cutoff values (< 0.4 nm, 100 °) these differences become less pronounced (Figure ). However, this Previously, the hydrophobic collapse of poly(N-isopropylacrylamide) upon exceeding the LCST was investigated through molecular modeling by tracking the ratio between "hydrophilic" and "hydrophobic water". The former was defined as the amount of waters within the first hydration shell of oxygen and sulfur atoms, respectively, (< 0.4 nm using the above mentioned larger distance, Figure ), the latter represents waters within 0.55 nm of carbon atoms (Figure ).