Initially, quantitative (Q) H NMR spectroscopy experiments were undertaken in DMSO-d6 1% DCM, in which the DCM was used as an internal standard to identify the presence of either low or high order SSA self-associated aggregates. Here, loworder SSA self-associated aggregates are defined as those directly observable using traditional solution state 1 H NMR spectroscopy (such as the formation of hydrogen bonded anionic dimers), whereas high-order SSA self-associated aggregates are defined as the exact opposite. To determine the presence of low or high-order SSA aggregates, signals corresponding to the anionic or cationic component of the SSA are integrated against those of the internal DCM standard. An apparent 'loss' of signal indicates the presence of larger, NMR silent aggregates, which exhibit solidlike properties and are therefore no longer visible using this experimental technique. As summarised in Table , at concentrations ≤ 112 mM, SSAs 3, 5, 7 and 9 form low order self-associated aggregates in polar organic DMSO-d6 solutions only. This is supported by the results of complimentary 1 H NMR DOSY experiments, here the dH of the SSA anion, was calculated between 0.9-1.7 nm. However, 1:1 enantiomeric mixtures of 3 + 5 and 7 + 9 also confirm the presence of higher order aggregates, providing evidence to support the hypothesis that the interaction of SSA anion enantiomers influences molecular self-association events in DMSO-d6 1 % DCM. We hypothesise that this is driven by the preferential heterogeneous hydrogen bonded complex formation between the SSA anionic components, such as those shown in Figure . Here, the difference in amino acid side chain was also found to influence the relative proportion of the SSA to become incorporated into these higher order SSA aggregates. As the hydrogen bond mediated dimerization constant (Kdim, Table ) calculated for the SSA anion from homogenous DMSO-d6 0.5 % H2O solutions of 3, 5, 7 and 9 was found to be lower for 7 and 9 when compared to 3 and 5, we can discount the strength of hydrogen bonding from influencing the increase in the proportion of SSA to become incorporated into these higher order structures at this concentration. Instead, we hypothesise that this increase in SSA to become incorporated into higher order aggregates is due to a combination of favourable π-π stacking interactions and decreased steric hinderance, afforded by the change in amino acid R-group. H NMR spectroscopy silent. The dH of the SSA species present in DMSO-d6 0.5 % H2O were obtained through H NMR DOSY at a total molecular concentration of 112 mM (298 K). Kdim values are calculated via H NMR spectroscopy dilution study, followed by subsequent fitting of these data to the equal K/dimerization self-associative binding isotherm model using Bindfit v0.5. Electrostatic surface potential energy maximum (Emax) and minimum (Emax) values were calculated using Spartan '20, while consensus LogP values were calculated using the Swiss ADME platform. Further comparative analysis of these Kdim values showed the Kdim calculated for 7 and 9 to be comparative in magnitude to the Kdim calculated for 1. We reason that this similarity in Kdim to be due to the effect that the R-group substitution has on hydrogen bond donor/acceptor spatial positioning and the comparative basicity and acidity of the carboxylate and urea functionalities respectively. It has been shown that electrostatic surface potential values, calculated by low level computational modelling programs such as Spartan, using semi-empirical PM6 molecular modelling methods, can be used to estimate the hydrogen donor/acceptor activity, and thus estimate hydrogen bonding strength. For the SSA anionic component of 1, 3, 5, 7 and 9, Emax and Emin values obtained from electrostatic potential maps were found to correlate with the urea NH and carboxylate residues respectively (Table , ESI Section S24, Table † ). Comparison of these data reveal Emax values to remain comparable across the series of SSAs tested. When comparing the Emin values, 1, 3 and 5 were found to exhibit values similar to each other and lower in magnitude than that of 7 and 9. This difference in Emin indicates the basicity of these carboxylate groups to be enhanced in the former compared to the latter, which corresponds to the increased strength of Kdim observed for 3 and 5 over 7 and 9.