Influence of Positional Isomers on the Macroscale and Nanoscale Architectures of Aggregates of Racemic Hydroxyoctadecanoic Acids in Their Molecular Gel, Dispersion, and Solid States

• Published in: Langmuir Vol. 28; no. 11; pp. 4955 - 4964
• Main Authors: Abraham, Shibu, Lan, Yaqi, Lam, Ricky S. H, Grahame, Douglas A. S, Kim, Jennifer Jae Hee, Weiss, Richard G, Rogers, Michael A
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 20.03.2012
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry; Magnetic Resonance Spectroscopy; Spectroscopy, Fourier Transform Infrared; Stearates - chemistry; Stereoisomerism; X-Ray Diffraction; Self assembly; Growth; Hydrogen; Crystals; Fatty acids; X ray diffraction; Dispersion; Isomer; Infrared spectrometry; Solid state; Racemic; Acids; Hydroxyl group; Dimer; Aggregate; Monomer; Structure; Hydrogen bond
• DOI: 10.1021/la204412t
• ISSN: 0743-7463

Inter/intramolecular hydrogen bonding of a series of hydroxystearic acids (HSAs) are investigated. Self-assembly of molecular gels obtained from these fatty acids with isomeric hydroxyl groups is influenced by the position of the secondary hydroxyl group. 2-Hydroxystearic acid (2HSA) does not form a molecular dimer, as indicated by FT-IR, and growth along the secondary axis is inhibited because the secondary hydroxyl group is unable to form intermolecular H-bonds. As well, the XRD long spacing is shorter than the dimer length of hydroxystearic acid. 3-Hydroxystearic acid (3HSA) forms an acyclic dimer, and the hydroxyl groups are unable to hydrogen bond, preventing the crystal structure from growing along the secondary axis. Finally, isomers 6HSA, 8HSA, 10HSA, 12HSA, and 14HSA have similar XRD and FT-IR patterns, suggesting that these molecules all self-assemble in a similar fashion. The monomers form a carboxylic cyclic dimer, and the secondary hydroxyl group promotes growth along the secondary axis.