TABLE 1.
Assignments of 1H and13C chemical shifts of the resonances of metabolites contained in cinnamon extracts as found in 1H-NMR, 1H,1H-TOCSY, and 1H,13C-HSQC spectra of samples dissolved in D2O and CD3OD. ND (not detected) indicates that the resonances of the metabolites were not found in the 1H-NMR spectrum of the sample. Missing values of chemical shifts are due to overlapped resonances or signals with too low intensity.
| Metabolite | D2O | CD3OD | |||||
|---|---|---|---|---|---|---|---|
| Assignment | 1H chemical shift (ppm) | 13C chemical shift (ppm) | Assignment | 1H chemical shift (ppm) | 13C chemical shift (ppm) | ||
| 1 | Acetate | CH3 | 1,91(s) | 26,13 | CH3 | 1,91–1,94 (s) | 22,18 |
| 2 | Alanine | CHα | 3,77 (m) | ND | |||
| CH3 | 1,47 (d) | ||||||
| 3 | Benzoic acid | CH (3,5) | 7,48 (m) | 132,67 | CH (3;5) | 7,42 (m) | |
| CH (4) | 7,54 (m) | 121,76 | CH (4) | 7,51 (m) | |||
| CH (2,6) | 7,86 (d) | CH (2;6) | 7,98 (d) | 131,92 | |||
| 4 | 2,3-Butanediol | 2 x CH3 | 1,13 (d, J= 5.9 Hz) | 2 x CH3 | 1,13 (d) | ||
| CH (1) | 3,62 (m) | ||||||
| CH (2) | 3,72 (m) | ||||||
| 5 | Capric acid | CH (12) | 0,86 (d) | ND | |||
| CH (6,7,8,9,10,11) | 1,29 (m) | ||||||
| CH (5) | 1,53 (d) | ||||||
| CH (4) | 2,16 (m) | ||||||
| 6 | β-Caryophyllene | ND | CH (5) | 5,33 (m) | 132,28 | ||
| CH2 (3,6,7) | 2,01–1,96 (m) | ||||||
| CH2 (2) | 1,31 (m) | ||||||
| 7 | Choline | 3 x CH3 | 3,21 (s) | 56,17 | 3 x CH3 | 3,20 (s) | 55,25 |
| CH2 (2) | 3,47 (m) | 68,36 | |||||
| 8 | (E)-Cinnamaldehyde | CHO (1) | 9,51 (m) | 200,50 | CHO (1) | 9,65 (d) | 197,67 |
| CH (5,9) | 7,66 (m) | 131,50 | CH (5,9) | 7,67 (m) | 131,31 | ||
| CH (3) | 7,66 (m) | 158,80 | CH (3) | 7,67 (m) | 156,90 | ||
| CH (7) | 7,45 (m) | 131,60 | CH (7) | 7,44 (m) | 131,75 | ||
| CH (6,8) | 7,45 (m) | 134,30 | CH (6,8) | 7,44 (m) | 133,72 | ||
| CH (2) | 6,79 (m) | 130,00 | CH (2) | 6,77 (dd) | 131,08 | ||
| 9 | (Z)-Cinnamaldehyde | ND | CHO (1) | 9,79 (d, J = 7,8 Hz) | |||
| CH (3) | 7,7 (m) | ||||||
| CH (2) | 6,78 (dd) | ||||||
| 10 | Cinnamaldehyde dimethylacetal | ND | CH (3) | 4,92 (d, J = 5,1 Hz) | 106,36 | ||
| CH (2) | 6,14 (dd, J = 16,2–5,2 Hz) | 128,23 | |||||
| CH (1) | 6,71 (d, J = 16,0 Hz) | 136,57 | |||||
| 11 | Cinnamic acid | CH (8) | 6,52 (d) | 126,87 | CH (8) | 6,48 (d, J = 16,0 Hz) | 120,90 |
| CH (7) | 7,39 (d) | 143,57 | CH (7) | ||||
| CH (3,5) | 7,43 (m) | 131,51 | CH (3,4,5) | ||||
| CH (4) | 7,43 (m) | 131,82 | |||||
| CH (2,6) | 7,61 (d) | 130,44 | CH (2,6) | 7,69 (d) | 147,63 | ||
| 12 | Coumarin | ND | CH (3) | 8,02 (d, J = 7,1 Hz) | 132,23 | ||
| CH (6,9) | 7,59 (m) | 136,10 | |||||
| CH (7,8) | 7,47 (m) | 131,22 | |||||
| 13 | Ethanol a | ND | CH2 | 3,61 (q) | 59,65 | ||
| CH3 | 1,16 (t) | 20,02 | |||||
| 14 | Eugenol | ND | CH (3,6) | 6,71 (m) | 115,00 | ||
| CH (5) | 6,62 (m) | 123,67 | |||||
| CH (8) | 5,93 (m) | 141,14 | |||||
| CH2 (9) | 5,03 - 5,00 (ddt) | 117,22 | |||||
| OMe | 3,80 (s) | 58,14 | |||||
| CH2 (7) | 3,28 (m) | 42,78 | |||||
| 15 | Fatty acid (FA) | CH3 (ω0) | 0,85 (t) | CH3 (ω0) | 0,89 (t, J = 6,9 Hz) | 16,52 | |
| CH2 (ω1) | CH2 (ω1) | 1,32 (m) | 25,82 | ||||
| CH2 (ω2) | 1,28 (m) | CH2 (ω2) | 1,28 (m) | 32,34 | |||
| CH2 (3) | 1,53 (m) | CH2 (3) | 1,59 (m) | 27,77 | |||
| CH2 (4) | 2,16 (m) | CH2 (4) | 2,04 (m) | 30,11 | |||
| CH2 (2) | CH2 (2) | 2,26 (t, J = 7,4 Hz) | 36,87 | ||||
| 16 | Formate | CH (1) | 8,45 (s) | CH (1) | 8,44 (s) | ||
| 17 | Fructose (furanose) | CH (4) | 4,11 (m) | 73,50 | ND | ||
| CH (3,5) | 3,81 (m) | 66,60 | |||||
| CH (6.1 b) | 3,67 (m) | 65,00 | |||||
| 18 | GABA (γ-Aminobutyric acid) | CH (2) | 1.89 (m) | ND | |||
| CH (3) | 2.30 (m) | ||||||
| CH (1) | 3.00 (m) | 38.76 | |||||
| 19 | α-Galactose | CH (1) | 5,25 (d) | 94,57 | CH (1) | 5,14 (d, J = 2,4 Hz) | |
| CH (2) | 3,78 (m) | CH (2) | 3,55 (m) | ||||
| CH (3) | 3,85 (m) | 72,06 | CH (3) | 3,63 (m) | |||
| CH (4) | 3,97 (m) | CH (4) | 3,80 (m) | ||||
| CH (5) | 4,07 (m) | 73,35 | |||||
| β-Galactose | CH (1) | 4,58 (d) | 98,88 | ||||
| 20 | α-Glucose | CH (1) | 5,22 (d) | 94,47 | CH (1) | 5,09 (d, J = 3,7 Hz) | 95,35 |
| CH (2) | 3,83 (m) | 73,90 | CH (2) | 3,9 (m) | 75,06 | ||
| CH2 (6) | 3,82–3,76 (m) | 65,00 | CH2 (6) | 3,83–3,77 (m) | 64,20 | ||
| CH (3) | 3,7 (m) | 75,25 | CH (3) | 3,77 (m) | |||
| CH (5) | 3,52 (m) | 73,66 | CH (5) | 3,66 (m) | 76,29 | ||
| CH (4) | 3,40 (m) | 72,04 | CH (4) | 3,34 (m) | 75,00 | ||
| β-Glucose | CH (1) | 4,63 (d) | 98,31 | CH (1) | 4,46 (d, J = 7,8 Hz) | 99,57 | |
| CH2 (6) | 3,71 - 3,89 (m) | 63,21 | CH2 (6) | 4,00–3,83 (dd) | 65,95 | ||
| CH (3), CH (5) | 3,48 (m) | 78,20 | CH (3), CH (5) | 3,45–3,34 | 78 - 75 | ||
| CH (4) | 3,40 (m) | 72,10 | CH (4) | 3,27 | 73,19 | ||
| CH (2) | 3,23 (m) | 76,59 | CH (2) | 3,11 | 76,68 | ||
| 21 | Glycerol | CH2 (1,3) | 3,65 (dd) - 3,56 (dd) | 65,00 | CH2 (1,3) | 3,59 (dd)-3,52 (dd) | 65,79 |
| 22 | 2-Hydroxycinnamaldehyde | ND | CHO (1) | 9,50 (d, J = 7,8 Hz) | |||
| CH (3,5,9) | 7,66 (m) | ||||||
| CH (2) | 6,76 (m) | ||||||
| 23 | Malic acid | CH2 (3) | 2,36 (dd) - 2,67 (d) | 45,40 | ND | ||
| CH (2) | 4,30 (d) | 73,24 | |||||
| 24 | Methanol b | CH3 | 3,34 (s) | 49,90 | CH3 | 3,29 (s) | 50,78 |
| 25 | 2-Methoxycinnamaldehyde | ND | CHO (1) | 9,60 (d, J = 8,0 Hz) | 198,16 | ||
| CH (3) | 7,92 (d, J = 16,0 Hz) | 152,40 | |||||
| CH (2) | 6,82 (m) | 131,60 | |||||
| OMe | 3,83 (s) | 57,83 | |||||
| 26 | Methyl salicylate | ND | CH (7) | 7,62 (dd, J =7,7–1,7 Hz) | 132,11 | ||
| CH (4) | 7,07 (d, J = 8,4 Hz) | 114,41 | |||||
| CH (6) | 7,02 (m) | 117,46 | |||||
| CH (5) | 7,45 (m) | 134,12 | |||||
| OMe | 3,91 (s) | 57,90 | |||||
| 27 | Myo-inositol | CH (5) | 3,27 (t) | 77,13 | ND | ||
| CH (4,6) | 3,51 (d) | 73,98 | |||||
| CH (1,3) | 3,61 (m) | 75,15 | |||||
| CH (2) | 4,05 (t) | 74,93 | |||||
| 28 | Phenylalanine | ND | CH (7,9) | 7,41 (d) | 129,46 | ||
| CH (8) | 7,31 (t, J = 7,7 Hz) | 131,41 | |||||
| CH (6,10) | 7,24 (t, J = 7,2 Hz) | 131,06 | |||||
| CHα | 3,86 (m) | ||||||
| CH2 | 3,13–3,26 (m) | ||||||
| 29 | Quinic acid | CH (7) | 1.86 (m) | 43,47 | ND | ||
| CH (6) | 1.96 (dt) | 40,21 | |||||
| CH (5) | 2.05 (m) | 40,15 | |||||
| CH (4) | 2.05 (m) | 43,47 | |||||
| CH (3) | 3.55 (m) | 77.95 | |||||
| CH (2) | 4.00 (m) | 69.73 | |||||
| CH (1) | 4.13 (dd) | 73,19 | |||||
| 30 | Shikimic acid | CH (2) | 6.43 (m) | 133,83 | CH (2) | 6,74 (m) | 117,50 |
| CH (3) | 4.39 (t) | 68,70 | CH (3) | 4,34 (t) | 68,85 | ||
| CH (5) | 3.98 (m) | 69,52 | CH (5) | 3,96 (m) | 69,80 | ||
| CH (4) | 3.70 (m) | 74.81 | CH (4) | 3,64 (m) | 76,24 | ||
| CH2 (6) | 2,76 (dd) - 2,19 (dd) | 35,23 | CH2 (6) | 2,7 (dd) - 2,18 (dd) | 33,70 | ||
| 31 | Succinate | 2 x CH2 | 2,40 (s) | 36,46 | 2 x CH2 | 2,55 (s) | 31,64 |
| 32 | Sucrose | CH (7) (Glc) | 5,40 (d) | 101,99 | CH (7) (Glc) | 5,38 (d) | 94,99 |
| CH (3) (Fru) | 4,21 (d) | 79,21 | CH (3) (Fru) | 4,16 (d) | 68,85 | ||
| CH (4) (Fru) | 4,04 (t) | 74,60 | CH (4) (Fru) | ||||
| CH (5) (Fru) | 3,96 (m) | 84,18 | CH (5) (Fru) | 3,94 (m) | |||
| CH (9) (Glc) | 3,83 (m) | 74,94 | CH (9) (Glc) | 3,80 (m) | |||
| CH2 (17 + 19) | 3,81 (m) | 63,05–64,90 | CH2 (17 + 19) | ||||
| CH (11) (Glc) | 3,75 (t) | 73,75 | CH (11) (Glc) | 3,68 (t) | |||
| CH2 (13) (Fru) | 3,63 (s) | 65,00 | CH2 (13) (Fru) | ||||
| CH (12) (Glc) | 3,56 (dd) | 73,77 | CH (12) (Glc) | ||||
| CH (10) (Glc) | 3,42 (t) | 72,12 | CH (10) (Glc) | 3,40 (t) | |||
| 33 | Cinnamaldehyde derivative #1 | ND | 9,91 (d) | ||||
| 7,72 (m) | |||||||
| 34 | Cinnamaldehyde derivative #2 | ND | 9,59 (d) | 198,55 | |||
| 7,90 (d, J= 16,0 Hz) | 153,33 | ||||||
| 6,86 (m) | 131,80 | ||||||
| 35 | Cinnamaldehyde derivative #3 | ND | 9,56 (d, J= 7.8 Hz) | ||||
| 7,58 (m) | |||||||
| 6,64 (m) | |||||||
| 36 | Unknown A | ND | 8,03 (m) | ||||
| 7,59 (m) | |||||||
| 7,48 (m) | |||||||
| 6,34 (m) | |||||||
| 37 | Unknown B | ND | 7,54 (m) | ||||
| 7,26 (m) | |||||||
| 6,88 (m) | |||||||
| 38 | Unknown C | ND | 5,35 (s) | 69,51 | |||
| 1,95 (m) | |||||||
| 1,53 (m) | |||||||
| 39 | Unknown D | ND | 5,25 (m) | ||||
| 4,34 (m) | |||||||
| 4,16 (m) | |||||||
| 40 | Unknown E | ND | CH2 | 4,70 (dd, J = 6,4–1,5 Hz) | 67,87 | ||
| 6,67 (m) | |||||||
| 6,32 (m) | |||||||
| 41 | Unknown F | ND | 4,21 (dd, J = 5,7–1,6 Hz) | 65,52 | |||
| 6,60 (m) | |||||||
| 6,31 (m) | |||||||
| 42 | Unknown G | ND | CH2 | 4,16 (m) | 31,50 | ||
| 2,70 (m) | |||||||
| 43 | Unknown H | ND | 4.01 (dd, J = 12,3–1,1 Hz) | ||||
| 3,83 (m) | |||||||
| 3,61 (m) | |||||||
| 44 | Unknown I | ND | CH2 | 3,62 (d) | 66,57 | ||
| 2,67 (m) | |||||||
| 45 | Unknown J | 1,21 (d, J= 6.5 Hz) | ND | ||||
| 3,41 (m) | |||||||
| 3,91 (m) | |||||||
a
Extraction solvent for HE and E extracts.
b
NMR solvent for samples in CD3OD.
Note on nomenclature: The cinnamaldehyde derivatives 2-methoxycinnamaldehyde (IUPAC name (E)-3-(2-methoxyphenyl)prop-2-enal, also called Cassiastearoptene, because it was isolated for the first time from the essential oil of C. cassia) and 2-hydroxycinnamaldehyde (IUPAC name (E)-3-(2-hydroxyphenyl)prop-2-enal) present the substituent (methoxy or hydroxyl group, respectively) in the ortho position.