1. Yulian Voynikov, Dimitrina Jeleva, Reneta Gevrenova
Hydroxycinnamic acid amide profile of Solanum schimperianum Hochst by UPLC-HRMS
Yulian Voynikov, Dimitrina Jeleva, Reneta Gevrenova

2. Solanum Schimperianum, Hochst
Widely distributed in the tropical Africa, as well as the southern parts of the middle east
No known folkloric usage, known locally as Millyan and Nakhab
Flavonols
Astragalin,
isoquercitin,
3-kaempferol-diglucoside
rutin
Glycoalkaloids
Solanopubamine
α-solamargine and β-solamargine
+ other still non-identified Glycoalkaloids

3. Where we were headed … 80% MeOH extract positive HR-ESI-MS λmax (nm)
220, 315

4. Where we headed … 80% MeOH extract
The appearance of these signals can be explained by cis/trans isomerization of the double bond of HCA residues that is known to be strongly enhanced by light
The total ion current (TIC) chromatograms typically comprised one minor peak closely eluting with another major peak

5. Where we headed …
C16H23O5N2 - C10H9O3 = C6H14O2N2
(the amine moiety)

6. +p fragmentations

7. -p fragmentations

8. COSY

9. HSQC

10. Hydroxycinnamic acid amides (HCAAs)
HCAAs contribute to:
stress such as antioxidant properties,
resistance to cold stress or pathogens,
These compounds seemingly contribute to the formation of a polyphenolic barrier which makes the cell walls more resistant to enzyme attacks
plant growth and organ development
the main phenolic constituent of reproductive organs and seeds
floral induction and reproduction,
control of intracellular polyamine concentrations

11. Hydroxycinnamic acid amides (HCAAs)
Polyamines
Aromatic amines
HCAs

12. Accumulation of HCAAs in different plants and experiments
Reference: Macoy et al. "Biosynthesis, physiology, and functions of hydroxycinnamic acid amides in plants." Plant Biotechnology Reports 9.5 (2015):

13. We decided to search for other HCAAs

14. HCAAs by PRM in +p mode

15. Different isobars of 344.10 [M+H]+

16. Isobars [M+H]+
N-feruloyl-3-methoxytyramine
N-sinapoyl tyramine

17. List of 16 known HCAAs № Name tR (min) Elemental composition [M+H]+
MS2 1
N-coumaroyl cadaverine
5.91
C14H20N2O2
232.13, , , , 86.10 2
N-caffeoyl putrescine
2.11, 3.32
C13H18N2O3
251.14, , , 89.11, 72.08 3
N-feruloyl putrescine
4.30, 5.68
C14H20N2O3
248.13, , , , 89.11, 72.08 4
N-coumaroyl agmatine
4.96, 6.68
C14H20N4O2
260.14, , , , 89.11, 72.08 5
N-feruloyl cadaverine
5.30, 6.99
C15H22N2O3
262.14, , , , , 86.10 6
N-coumaroyl tyramine
10.15, 10.53
C17H17NO3
164.07, , 7
N-caffeoyl agmatine
3.56, 5.29
C14H20N4O3
276.13, , , , 89.11, 72.08 8
N-sinapoyl putrescine
5.03, 6.41
C15H22N2O4
278.14, , , , 89.11, 72.08 9
N-caffeoyl tyramine
9.50, 9.77
C17H17NO4
164.07, , , 10
N-feruloyl agmatine
5.85, 7.68
C15H22N4O3
290.15, , , , 11
N-caffeoyl spermidine
0.78, 1.07, 1.28
C16H25N3O3
291.17, , , , 72.08 12
N-feruloyl tyramine
10.41, 10.81
C18H19NO4
194.08, , , , 13
N-feruloyl spermidine
1.73, 2.74
C17H27N3O3
305.19, , , , 72.08 14
N-sinapoyl agmatine
6.38, 8.27
C16H24N4O4
320.16, , , 15
N-sinapoyl tyramine
10.33, 10.78
C19H21NO5
, , 16
N-feruloyl-3-methoxytyramine
10.63, 11.08
194.08, , ,

18. HCAAs found

19. N-coumaroyl cadaverine

20. HCAAs by PRM in +p mode

21. Schematically ..

23. Thank you for your attention