As the benzene 1,3,5-tricarboxamide (BTA) moiety is commonly used as the central assembling unit for the construction of functionalized supramolecular architectures, strategies to tailor the nature and stability of BTA assemblies are needed. The assembly properties of a library of structurally simple BTAs derived from amino dodecyl esters (ester BTAs, 13 members) have been studied, either in the bulk or in cyclohexane solutions, by means of a series of analytical methods (NMR, DSC, POM, FT-IR, UV-Vis, CD, ITC, high-sensitivity DSC, SANS). Two types of hydrogen-bonded species have been identified and characterized: the expected amide-bonded helical rods (or stacks) that are structurally similar to those formed by BTAs with simple alkyl side chains (alkyl BTAs), and ester-bonded dimers in which the BTAs are connected by means of hydrogen bonds linking the amide N–H and the ester CO. MM/MD calculations coupled with simulations of CD spectra allow for the precise determination of the molecular arrangement and of the hydrogen bond pattern of these dimers. Our study points out the crucial influence of the substituent attached on the amino-ester α-carbon on the relative stability of the rod-like versus dimeric assemblies. By varying this substituent, one can precisely tune the nature of the dominant hydrogen-bonded species (stacks or dimers) in the neat compounds and in cyclohexane over a wide range of temperatures and concentrations. In the neat BTAs, stacks are stable up to 213 °C and dimers above 180 °C whilst in cyclohexane stacks form at c* > 3 × 10⁻⁵ M at 20 °C and dimers are stable up to 80 °C at 7 × 10⁻⁶ M. Ester BTAs that assemble into stacks form a liquid-crystalline phase and yield gels or viscous solutions in cyclohexane, demonstrating the importance of controlling the structure of these assemblies. Our systematic study of these structurally similar ester BTAs also allows for a better understanding of how a single atom or moiety can impact the nature and stability of BTA aggregates, which is of importance for the future development of functionalized BTA supramolecular polymers.

Although nanoparticles (NPs) are known to increase foam stability, foam stabilisation is not observed in all surfactant/NP combinations. The present study evaluates the stability of CO₂ foams containing surfactant/NP mixtures with attractive or repulsive electrostatic interactions at the low pH imposed by CO₂ in the presence of a high-salinity brine. Three ionic surfactants and two oxide NPs (SiO₂ and Al₂O₃) were used in combinations of similar or opposite charges. Surface tension, viscosity, ζ-potential and hydrodynamic size experiments allowed the analysis of CO₂ foam stability based on the impact of surfactant–NP interactions on bulk and interfacial properties. All oppositely charged systems improved the foam half-life; however, a higher NP concentration was required to observe a significant effect when more efficient surfactants were present. Both bulk viscosity and rigidity of the interfacial films drastically increased in these systems, reducing foam drainage. The mixture of SiO₂ with a zwitterionic surfactant showed the greatest increase in CO₂ foam stability owing to the synergy of these effects, mediated by attractive interactions. This study showed that the use of NPs should be tailored to the surfactant of choice to achieve an interplay of interfacial and rheological properties able to reduce foam drainage in applications involving CO₂ foam in brine.