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Continuous gradient temperature Raman spectroscopy from −100 to 40 °C yields new molecular models of arachidonic acid and 2-Arachidonoyl-1-stearoyl-sn-glycero-3-phosphocholine.
- Source :
- Prostaglandins Leukotrienes & Essential Fatty Acids; Dec2017, Vol. 127, p6-15, 10p
- Publication Year :
- 2017
-
Abstract
- Despite its biochemical importance, a complete Raman analysis of arachidonic acid (AA, 20:4n-6) has never been reported. Gradient temperature Raman spectroscopy (GTRS) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur near and at phase transitions. Herein we utilize the GTRS technique for AA and 1 -18:0, 2 -20:4n-6 phosphatidyl choline (AAPC) from cryogenic to mammalian body temperatures. 20 Mb three-dimensional data arrays with 0.2 °C increments and first/second derivatives allowed complete assignment of solid, liquid and transition state vibrational modes. The AA DSC shows a large exothermic peak at −60 °C indicating crystallization or a similar major structural change. No exothermic peak of this magnitude was observed in six other unsaturated lipids (DHA, n-3DPA, n-6DPA, LA, ALA, OA). Melting in AA occurs over a large range: (−60 to −35 °C): very large frequency offsets and intensity changes correlate with premelting initiating circa −60 °C, followed by melting (−37 °C). Novel, unique 3D structures for both molecules reveal that AA is not symmetric as a free fatty acid, and it changes significantly when in the sn-2 phospholipid position. Further, different CH and CH 2 sites are unequally elastic and nonequivalent. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 09523278
- Volume :
- 127
- Database :
- Supplemental Index
- Journal :
- Prostaglandins Leukotrienes & Essential Fatty Acids
- Publication Type :
- Academic Journal
- Accession number :
- 126252723
- Full Text :
- https://doi.org/10.1016/j.plefa.2017.09.019