Amphiphile conformation impacts aggregate morphology and solution structure across multiple lengthscales

Although the self-assembly of amphiphiles is well-studied in aqueous solutions, much less understood about fundamental driving forces and structure property relationships non-polar media. In recent work [Journal Physical Chemistry B, 2020, 124, 10822.] authors have studied a series malonomide-based that are relevant to liquid-liquid extraction. That demonstrated aggregation largely driven by local dipole-dipole interactions between molecules. Here, we build upon this observation develop more detailed understanding how balance (controlled conformation) molecular architecture influences morphology aggregates across lengthscales. Using constrained dynamics key degrees freedom, demonstrate conformation N,N-dimethyl,N,N-dioctylhexylethoxy malonamide (DMDOHEMA) N,N-dimethyl,N,N-dibutyltetradecyl (DMDBTDMA) has significant impact self-association - where appropriate conformational sampling essential. To quantify aggregate morphology, several graph theoretic persistent homology based properties determined. The former examines patterns intermolecular within clusters, while latter 3-dimensional spatial distribution. Based these analyses, find aggregates, particularly at higher concentration, depends on dipole alignment alkyl tail sterics. Dipole encourages linear steric result noticeably for DMDOHEMA than DMDBTDMA. This reflected distribution, holes or voids exist extractants distribute solution “swiss cheese” arrangement as opposed filamentous distribution DMBDTDMA. study links amphiphile assemblies, serves basis ongoing multicomponent solutions with polar other solutes, phenomena.