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Molecules 2020, 25, 5572 5 of 26 Figure 4. (a) The originally proposed arrangement of triglyceride molecules in the crystal lattice; (b) the new “tuning fork” structure proposed by Malkin [11] which explains the increase in long spacings measured. (c) The orientation of two molecules in the “tuning fork” shape in a crystal lattice. Images reproduced from Malkin [11]. Figure 5. The tilting of the aliphatic chains in the β’ (a) and β (b) form as proposed by Malkin [11] and Lutton [20], which rationalises the different long d-spacings measured for the polymorphic phases. Images reproduced from Malkin [11]. In terms of short d-spacings, what allows us to distinguish between the various crystal phases is the number of peaks measured. That is, given the higher degree of symmetry when progressing from α → β’ → β phase, an increasing number of short spacing is observed. For example, Lutton [20] reports for both tripalmitin and tristearin only one strong peak at about 4.14 Å for the α phase corresponding to the intramolecular distance between aliphatic chains. In the case of the β’-phase two peaks are observed at 4.18 and 3.78 Å and for the β-phase three peaks arise from the triclinic unit cell at 4.60, 3.85 and 3.70 Å [29]. What is reported above is true for symmetrical and saturated triglycerides. In the case of unsaturated or asymmetrical triglycerides, different conformations arise. Malkin [11] and Hernqvist [23], suggested that in this case the molecules arrange themselves as depicted in Figure 6, thus causing a large increase in the long and short d-spacings [10,11,20,23,30,31]. Figure 6. The different arrangements of asymmetrical or unsaturated triglycerides in the crystal lattice as proposed by Malkin [11] and Hernqvist [23]. Images reproduced from Malkin [11] and Hernqvist [23].PDF Image | Triglycerides as Novel Phase-Change Materials
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