Enantiomeric separation of triacylglycerols containing fatty acids with a ring (cyclofatty acids)

0525471 - MBÚ 2020 RIV NL eng J - Journal Article
Palyzová, Andrea - Řezanka, Tomáš
Enantiomeric separation of triacylglycerols containing fatty acids with a ring (cyclofatty acids).
Journal of Chromatography A. Roč. 1622, JUL 5 (2020), č. článku 461103. ISSN 0021-9673. E-ISSN 1873-3778
R&D Projects: GA MŠMT(CZ) LO1509
Institutional support: RVO:61388971
Keywords : Triacylglycerol * Cyclic fatty acids * Sterculic seeds
OECD category: Microbiology
Impact factor: 4.759, year: 2020
Method of publishing: Limited access
https://www.sciencedirect.com/science/article/pii/S0021967320303241

Triacylglycerols (TAGs) containing cyclofatty acids (cycloFAs) from two oilseeds of Sterculia foetida and Hydnocarpus wightiana were analysed using both reversed-phase (RP18) and chiral phase columns. TAGs were identified using high-resolution electrospray ionization mass spectrometry in the positive ion mode. Fifty-five molecular species of TAGs have been identified in sterculic oil, 27 of which contained at least one cyclopropenyl-FA (e.g., malvalic or sterculic acids). The structures of regioisomers and enantiomers were determined for five major TAGs with cyclopropenyl-FAs.

One hundred thirty-six TAGs were identified in chaulmoogra oil, 71 of which contained at least one cyclopentenyl-FA (e.g., gorlic, chaulmoogric, and hydnocarpic acids, etc.). Furthermore, in three molecular species, regioisomers and enantiomers were identified using HPLC on a chiral phase column. Eight molecular species of TAGs were prepared through organic synthesis to facilitate the identification of enantiomers. Retention times of fatty acid-containing triacylglycerols with one ring and one double bond are very similar to triacylglycerols with a dienoic fatty acid, but elution times are shorter. For example, dimalvaloylpalmitate elutes earlier than dilinoleylpalmitate.

The order of elution of TAGs on the chiral column differs. In TAGs with 2 degrees of unsaturation (ring and double bond, e.g. PStP-StPP-PPSt), the order of elution is symmetric-asymmetric-asymmetric TAGs. TAGs with 4 degrees of unsaturation (one ring and three double bonds or two rings and two double bonds) present a different pattern. When TAGs contain two rings and two double bonds, the order of elution TAGs is asymmetric-symmetric-asymmetric (StStP-StPSt-PStSt), when TAGs contain a ring and 3 double bonds, the elution order is symmetric-asymmetric-asymmetric TAGs (OStO-StOO-OOSt). In species with a higher degree of unsaturation (e.g., 5), the elution order of the TAGs is asymmetric-asymmetric-symmetric (e.g. CCO-OCC-COC).
Permanent Link: http://hdl.handle.net/11104/0309601