Comparison of Dipolar, H‑Bonding, and Dispersive Interactions on Gelation Efficiency of Positional Isomers of Keto and Hydroxy Substituted Octadecanoic Acids

• Published in: Langmuir Vol. 29; no. 21; pp. 6467 - 6475
• Main Authors: Pal, Amrita, Abraham, Shibu, Rogers, Michael A, Dey, Joykrishna, Weiss, Richard G
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 28.05.2013
• Subjects: Chemistry; Exact sciences and technology; Gels - chemical synthesis; Gels - chemistry; General and physical chemistry; Hydrogen Bonding; Molecular Structure; Solutions; Stearic Acids - chemical synthesis; Stearic Acids - chemistry; Transition Temperature; Molecular packing; Stability; Molar mass; Gelation; Crystals; Dispersion; Isomer; Liquid; Efficiency; Dipole; Stearic acid; Molecular mass; Functional group; Hydrogen bond
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la400664q

A systematic study of the importance of functional group position and type on the gelator efficiencies of structurally simple, low molecular-mass gelators is reported. Thus, the gelation abilities of a series of positional isomers of ketooctadecanoic acid (n-KSA) are compared in a wide range of liquids. The gelation abilities of the n-KSA as a function of n, the keto group position along the chain, are characterized by several structural, thermal, and rheological techniques and are compared with those of the corresponding hydroxyoctadecanoic acid isomers (n-HSA) and the parent molecule, octadecanoic acid (SA). Analyses of the gels according to the strengths of functional group interactions along the alkyl chain in terms of group position and type are made. The conclusions derived from the study indicate that gel stability is enhanced when the functional group is located relatively far from the carboxylic headgroup and when group–group interactions are stronger (i.e., hydrogen-bonding interactions are stronger in the n-HSA than dipole interactions in the n-KSA, which are stronger than the London dispersion interactions in SA). Co-crystals of the keto- and hydroxy-substituted octadecanoic acids are found to be less efficient gelators than even the ketooctadecanoic acids, due to molecular packing and limited group interactions within the gelator networks.