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Background  To identify and develop the best renewable and low carbon footprint biodiesel substitutes for petroleum diesel, the properties of different biodiesel candidates should be studied and characterized with respect to molecular structures versus biodiesel liquid property relationships. In our previous paper,  1 H low-field nuclear magnetic resonance (LF-NMR) relaxometry was investigated as a tool for studying the liquid-phase molecular packing interactions and morphology of fatty acid methyl esters (FAMEs). The technological potential was demonstrated with oleic acid and methyl oleate standards having similar alkyl chains but different head groups. In the present work, molecular organization versus segmental and translational movements of FAMEs in their pure liquid phase, with different alkyl chain lengths (10–20 carbons) and degrees of unsaturation (0–3 double bonds), were studied with  1 H LF-NMR relaxometry and X-ray,  1 H LF-NMR diffusiometry, and  13 C high-field NMR.    Results  Based on density values and X-ray measurements, it was proposed that FAMEs possess a liquid crystal-like order above their melting point, consisting of random liquid crystal aggregates with void spaces between them, whose morphological properties depend on chain length and degree of unsaturation. FAMEs were also found to exhibit different degrees of rotational and translational motions, which were rationalized by chain organization within the clusters, and the degree and type of molecular interactions and temperature effects. At equivalent fixed temperature differences from melting point, saturated FAME molecules were found to have similar translational motion regardless of chain length, expressed by viscosity, self-diffusion coefficients, and spin-spin ( T  2 )  1 H LF-NMR.  T  2  distributions suggest increased alkyl chain rigidity, and reduced temperature response of the peaks’ relative contribution with increasing unsaturation is a direct result of the alkyl chain’s morphological packing and molecular interactions.    Conclusions  Both the peaks’ assignments for  T  2  distributions of FAMEs and the model for their liquid crystal-like morphology in the liquid phase were confirmed. The study of morphological structures within liquids and their response to temperature changes by  1 H LF-NMR has a high value in the field of biodiesel and other research and applied disciplines in numerous physicochemical- and organizational-based properties, processes, and mechanisms of alkyl chains, molecular interactions, and morphologies.    Electronic supplementary material  The online version of this article (doi:10.1186/s13068-015-0280-5) contains supplementary material, which is available to authorized users.

Liquid-phase characterization of molecular interactions in polyunsaturated and n-fatty acid methyl esters by 1H low-field nuclear magnetic resonance