Background: 1H low field nuclear magnetic resonance (LF-NMR) relaxometry has been suggested as a tool to distinguish between different molecular ensembles in complex systems with differential segmental or whole molecular motion and/or different morphologies. In biodiesel applications the molecular structure versus liquid-phase packing morphologies of fatty acid methyl esters (FAMEs) influences physico-chemical characteristics of the fuel, including flow properties, operability during cold weather, blending, and more. Still, their liquid morphological structures have scarcely been studied. It was therefore the objective of this work to explore the potential of this technology for characterizing the molecular organization of FAMEs in the liquid phase. This was accomplished by using a combination of supporting advanced technologies. Results: We show that pure oleic acid (OA) and methyl oleate (MO) standards exhibited both similarities and differences in the 1H LF-NMR relaxation times (T2s) and peak areas, for a range of temperatures. Based on X-ray measurements, both molecules were found to possess a liquid crystal-like order, although a larger fluidity was found for MO, because as the temperature is increased, MO molecules separate both longitudinally and transversely from one another. In addition, both molecules exhibited a preferred direction of diffusion based on the apparent hydrodynamic radius. The close molecular packing arrangement and interactions were found to affect the translational and segmental motions of the molecules, as a result of dimerization of the head group in OA as opposed to weaker polar interactions in MO. Conclusions: A comprehensive model for the liquid crystal-like arrangement of FAMEs in the liquid phase is suggested. The differences in translational and segmental motions of the molecules were rationalized by the differences in the 1H LF-NMR T2 distributions of OA and MO, which was further supported by 13C high field (HF)-NMR spectra and 1H HF-NMR relaxation. The proposed assignment allows for material characterization based on parameters that contribute to properties in applications such as biodiesel fuels.
Bibliographical noteFunding Information:
PB acknowledges support from the Women in Science scholarship of the Israel Ministry of Science and Technology. NM acknowledges support from the Substitutes for Oil Transportation fellowship of the Israel Ministry of Science and Technology. MS acknowledges support from the National Institute of General Medical Sciences of the National Institutes of Health (award U01GM102098). The content is solely the responsibility of the authors and does not necessarily represent the official views of the funding agencies. The authors would like to thank Dr. Dimitri Mogiliansk, Dr. Sharon Hazan, and Dr. Mark Karpasas from the Ilse Katz Institute for Nanoscale Science and Technology at Ben Gurion University for performing the X-ray and dynamic viscosity measurements; and the Phyto-Lipid Biotechnology Lab (PLBL) members at Ben Gurion University of the Negev for their contribution to this work.
© 2015 Berman et al.
- Biodiesel physical properties
- H low field nuclear magnetic resonance relaxometry
- Methyl oleate
- Molecular packing
- Oleic acid
- Segmental motion