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

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

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

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

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

+p fragmentations

-p fragmentations

COSY

HSQC

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

Hydroxycinnamic acid amides (HCAAs) Polyamines Aromatic amines HCAs

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): 269-278.

We decided to search for other HCAAs

HCAAs by PRM in +p mode

Different isobars of 344.10 [M+H]+

Isobars 344.10 [M+H]+ N-feruloyl-3-methoxytyramine N-sinapoyl tyramine

List of 16 known HCAAs № Name tR (min) Elemental composition [M+H]+ MS2 1 N-coumaroyl cadaverine 5.91 C14H20N2O2 249.15975 232.13, 147.04, 129.10, 103.12, 86.10 2 N-caffeoyl putrescine 2.11, 3.32 C13H18N2O3 251.13901 251.14, 163.04, 115.09, 89.11, 72.08 3 N-feruloyl putrescine 4.30, 5.68 C14H20N2O3 265.15466 248.13, 177.05, 145.03, 115.09, 89.11, 72.08 4 N-coumaroyl agmatine 4.96, 6.68 C14H20N4O2 277.16590 260.14, 147.04, 131.13, 114.10, 89.11, 72.08 5 N-feruloyl cadaverine 5.30, 6.99 C15H22N2O3 279.17031 262.14, 177.05, 149.02, 129.10, 103.12, 86.10 6 N-coumaroyl tyramine 10.15, 10.53 C17H17NO3 284.12811 164.07, 147.04, 121.065 7 N-caffeoyl agmatine 3.56, 5.29 C14H20N4O3 293.16081 276.13, 163.04, 131.13, 114.10, 89.11, 72.08 8 N-sinapoyl putrescine 5.03, 6.41 C15H22N2O4 295.16523 278.14, 207.065, 175.04, 115.09, 89.11, 72.08 9 N-caffeoyl tyramine 9.50, 9.77 C17H17NO4 300.12303 164.07, 163.04, 138.09, 121.065 10 N-feruloyl agmatine 5.85, 7.68 C15H22N4O3 307.17647 290.15, 177.05, 157.11, 131.13, 114.10 11 N-caffeoyl spermidine 0.78, 1.07, 1.28 C16H25N3O3 308.19686 291.17, 237.12, 220.10, 163.04, 72.08 12 N-feruloyl tyramine 10.41, 10.81 C18H19NO4 314.13868 194.08, 177.05, 164.07, 145.03, 121.065 13 N-feruloyl spermidine 1.73, 2.74 C17H27N3O3 322.21251 305.19, 251.14, 234.11, 177.05, 72.08 14 N-sinapoyl agmatine 6.38, 8.27 C16H24N4O4 337.18703 320.16, 207.065, 131.13, 114.10 15 N-sinapoyl tyramine 10.33, 10.78 C19H21NO5 344.14924 207.065, 175.04, 121.065 16 N-feruloyl-3-methoxytyramine 10.63, 11.08 194.08, 177.05, 151.07, 145.03

HCAAs found

N-coumaroyl cadaverine

HCAAs by PRM in +p mode

Schematically ..

Thank you for your attention