Influence of Anions and Alkyl Chain Lengths of N-Alkyl-n-(R)-12-Hydroxyoctadecyl Ammonium Salts on Their Hydrogels and Organogels
Abstract

The self-assembly and gelating characteristics of a set of N-alkyl-(R)-12-hydroxyoctadecylammonium salts (n-HOA-X, where n = 0–6, 18 is the length of the alkyl chain on nitrogen, X = Cl, n = 3, and X = Br, NO3, and BF4) are described. Solid–solid phase transitions were observed for powders of n-HOA-Cl, and orthorhombic-type crystal packing arrangements and lattice spacings were calculated from X-ray diffractograms at 22 °C. The diffractogram of 3-HOA-Br indicates the presence of more than one morph at room temperature, and that of 3-HOA-I corresponds to a lamellar packing arrangement. Differences in the molecular packing arrangements of 3-HOA-X are reflected in their gelation abilities. The melting temperatures (Tgel) of the hydrogels of 3-HOA-Br are higher than those of 3-HOA-Cl at the same concentrations, and 3-HOA-I failed to gelate any of the investigated liquids. 3-HOA-NO3 gelated only water and CCl4 and 3-HOA-BF4 formed only hydrogels. Plots of changes in conductivities of the 3-HOA-X salts (where X = Cl, Br, NO3 and BF4) as a function of temperature were used to calculate the critical aggregation concentrations (CGCs). Because the CGCs from the ‘falling drop’ method are nearly the same as those from the conductivity measurements, aggregation, nucleation, and gelation must occur within a very narrow 3-HOA-X concentration range. Tgel values of 2 wt % 3-HOA-Cl hydrogels (prepared by fast cooling of the sol phase) increased upon adding KCl up to 0.1 M. The effects can be attributed principally to the chloride anion rather than its cation partners. The properties of the hydrogels of 3-HOA-X do not follow the Hofmeister ranking rule. The variations in the counterions afford detailed insight into the behavior of 3-HOA-X in their neat solids and assemblies in gels as well as the processes accompanying gel formation in water and organic liquids.
Cited By
This article is cited by 18 publications.
- Richard G. Weiss . The Past, Present, and Future of Molecular Gels. What Is the Status of the Field, and Where Is It Going?. Journal of the American Chemical Society 2014, 136 (21) , 7519-7530. https://doi.org/10.1021/ja503363v
- Peter Kasak, Peter Hrobárik, Josef Osička, Dominika Soláriková, Branislav Horváth, Jan Tkac, Kishor K. Sadasivuni, Mariam A. AlMaadeed, Roman Mikláš. Nicotinamide-based supergelator self-assembling via asymmetric hydrogen bonding NH⋯OC and H⋯Br− pattern for reusable, moldable and self-healable nontoxic fuel gels. Journal of Colloid and Interface Science 2021, 603 , 182-190. https://doi.org/10.1016/j.jcis.2021.06.071
- Hai-Kuan Yang, Chen Zhang, Xiang-Ning He, Pin-You Wang. Effects of alkyl chain lengths on 12-hydroxystearic acid derivatives based supramolecular organogels. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2021, 616 , 126319. https://doi.org/10.1016/j.colsurfa.2021.126319
- Yulong Xiao, Ruilin Zhang, Hongfei Gao, Hongmei Zhao, Xiaohong Cheng. Benzothiadiazole-based bolaamphiphiles: synthesis, self-assembly and white-light emissive properties. Journal of Materials Chemistry C 2019, 7 (5) , 1237-1245. https://doi.org/10.1039/C8TC04890H
- Michael A. Rogers. Crystallization of Fats and Fatty Acids in Edible Oils and Structure Determination. 2017,,, 541-559. https://doi.org/10.1016/B978-0-12-809521-8.00019-2
- Yan Zhang, Richard G. Weiss. How do H-bonding interactions control viscoelasticity and thixotropy of molecular gels? Insights from mono-, di- and tri-hydroxymethylated alkanamide gelators. Journal of Colloid and Interface Science 2017, 486 , 359-371. https://doi.org/10.1016/j.jcis.2016.10.008
- V. Ajay Mallia, Suman Samai, Richard G. Weiss. Cholesterol and Dihydrocholesterol are Simple Steroidal Molecular Gelators: How One Double Bond Controls the Structure and Mechanotropic Properties of Their Gels. ChemistrySelect 2016, 1 (15) , 4965-4972. https://doi.org/10.1002/slct.201601012
- Danielle M. Zurcher, Anne J. McNeil. Tools for Identifying Gelator Scaffolds and Solvents. The Journal of Organic Chemistry 2015, 80 (5) , 2473-2478. https://doi.org/10.1021/jo502915w
- Michael A. Rogers, Richard G. Weiss. Systematic modifications of alkane-based molecular gelators and the consequences to the structures and properties of their gels. New Journal of Chemistry 2015, 39 (2) , 785-799. https://doi.org/10.1039/C4NJ01439A
- Y. Lan, M. G. Corradini, R. G. Weiss, S. R. Raghavan, M. A. Rogers. To gel or not to gel: correlating molecular gelation with solvent parameters. Chemical Society Reviews 2015, 44 (17) , 6035-6058. https://doi.org/10.1039/C5CS00136F
- Laura González-Mendoza, Jorge Escorihuela, Belén Altava, M. Isabel Burguete, Santiago V. Luis. Application of optically active chiral bis(imidazolium) salts as potential receptors of chiral dicarboxylate salts of biological relevance. Organic & Biomolecular Chemistry 2015, 13 (19) , 5450-5459. https://doi.org/10.1039/C5OB00348B
- Samala Murali Mohan Reddy, Ganesh Shanmugam, Natarajan Duraipandy, Manikantan Syamala Kiran, Asit Baran Mandal. An additional fluorenylmethoxycarbonyl (Fmoc) moiety in di-Fmoc-functionalized l -lysine induces pH-controlled ambidextrous gelation with significant advantages. Soft Matter 2015, 11 (41) , 8126-8140. https://doi.org/10.1039/C5SM01767J
- Vicent J. Nebot, Juan J. Ojeda-Flores, Johan Smets, Susana Fernández-Prieto, Beatriu Escuder, Juan F. Miravet. Rational Design of Heat-Set and Specific-Ion-Responsive Supramolecular Hydrogels Based on the Hofmeister Effect. Chemistry - A European Journal 2014, 20 (44) , 14465-14472. https://doi.org/10.1002/chem.201402547
- Francesca D'Anna, Renato Noto. Di- and Tricationic Organic Salts: An Overview of Their Properties and Applications. European Journal of Organic Chemistry 2014, 2014 (20) , 4201-4223. https://doi.org/10.1002/ejoc.201301871
- Tom Coolbaugh, Vijay John, Keith Johnston, Kalliat T. Valsaraj, Alon McCormick, Arijit Bose, Ramanan Krishnamoorti. Fundamental Aspects of the Science and Engineering of Oil Spill Dispersant Systems: An Overview of Recent Research Activities of the Gulf of Mexico Research Initiative-funded CMEDS Project. International Oil Spill Conference Proceedings 2014, 2014 (1) , 721-732. https://doi.org/10.7901/2169-3358-2014.1.721
- V. Ajay Mallia, Richard G. Weiss. Self-assembled fibrillar networks and molecular gels employing 12-hydroxystearic acid and its isomers and derivatives. Journal of Physical Organic Chemistry 2014, 27 (4) , 310-315. https://doi.org/10.1002/poc.3193
- Francesca D'Anna, Carla Rizzo, Paola Vitale, Giuseppe Lazzara, Renato Noto. Dicationic organic salts: gelators for ionic liquids. Soft Matter 2014, 10 (46) , 9281-9292. https://doi.org/10.1039/C4SM01360C
- Runmiao Yang, Shuhua Peng, Wubo Wan, Timothy C. Hughes. Azobenzene based multistimuli responsive supramolecular hydrogels. J. Mater. Chem. C 2014, 2 (43) , 9122-9131. https://doi.org/10.1039/C4TC01649A



