### NMR Metabolites Fingerprinting
s) & 2.09 (allycline CH2) & & & C-1 178.8, C-32.4, \\  & C-2 & 2.27 (r, \(J=7.4\) Hz) & 1.59 & 34.7 & (CH2)n 31.6 \\  & C-3 & 1.59 m & 2.27 & 25.8 & C-1 177.8, (CH2)\({}_{\rm n}\) 30.4 \\ \(\omega\)-\(\delta\) Fatty acid (M2) & Bis almilc CH\({}_{2}\) & 2.77 (r, \(J=6.9\) Hz) & 5.33 & 24.7 & Offerlin carbons 131.2, \\ \(\omega\)-\(\delta\) Fatty acid (M3) & Bis almilc CH\({}_{2}\) & 2.87 & 5.33 & 26.3 & Offerlin carbons 131.2, \\  & t+CH\({}_{3}\) & 0.97 & 2.07 (allycline CH2) & 19.5 & 21.6 C-2 \\ \hline  & & \multicolumn{2}{c}{Sugars} & & \\ Rhamoside (M4) & C-6 & 1.23 & 3.77 & 19.5 & (C-4) 69.8, (C-5) 72.8 \\  & C-1 & 5.44 & - & 93.8 & (C-2) 73.8 \\  & C-5 & 3.77 & - & 72.7 & - \\  & C-4 & 3.78 & - & 69.1 & - \\ \(\beta\)-Glucose (M5) & C-1 & 4.48 (d, \(J=7.8\) Hz) & 3.11, 327, 3.32 & 97.9 & - \\  & C-2 & 3.11 & & 76.1 & (C-3) 77.8, (C-1)97.9 \\  & C-3 & 3.35 & & 77.8 & - \\  & C-5 & 3.28 & & 77.7 & (C-6) 62.2 \\  & C-6 & 3.65 & & 62.1 & - \\ \(\alpha\)-Glucose (M6) & C-1 & 5.10 (d, \(J=3.7\) Hz) & 3.35 & 93.7 & (C-4) 72.7, (C-3)74.61 \\  & C-2 & 3.35 & & 73.5 & 74.2 (C-3) \\  & C-3 & 3.84 & & 74.2 & (C-3) \\  & C-4 & 3.77 & & 72.7 & (C-6) 62.5 \\  & C-6 & 3.86 & & 62.5 & - \\ Sucarose (M7) & C-1 & 5.48 (t, \(J=3.6\) Hz) & 3.35, 3.42, 3.69 & 93.3 & (C-3) 74.3, (C-1) 105.0 \\  & C-2 & 3.42 & 3.69 & 72.9 & (C-3) 74.3 \\  & C-3 & 3.69 & 3.35 & 74.2 & (C-2) 72.9 \\  & C-4 & 3.35 & & 72.8 & (C-3) 74.3 \\  & C-2\({}^{\prime}\) & 4.08 & - & 87.9 & (C-1) 105.0 \\  & C-3\({}^{\prime}\) & 4.03 & - & 76.8 & (C-5) 63.1, (C-1) 105.0 \\  & C-4\({}^{\prime}\) & 3.75 & - & 83.6 & (C-6) 63.3 \\  & C-5\({}^{\prime}\) & 3.76 & - & 63.1 & (C-1) 105.0, (C-4) 83.6 \\  & C-6\({}^{\prime}\) & 3.62 & - & 63.9 & (C-1) 105.0 \\  & \multicolumn{2}{c}{Amino acids} & & & \\ Alanine (M8) & C-3 & 1.47 (d, \(J=7.2\)) & 3.64 & 16.9 & 51.5, 174.9 \\  & C-2 & 3.64 & 1.47 & 51.4 & - \\ Aaspartic acid (M9) & C-3a & 2.96 & 2.71, 3.85 & 35.3 & (C-2) 52.6, (C-4) 172.9, \\  & C-3b & 2.71 & - & 35.3 & (C-2) 52.6, (C-4) 172.9 \\  & C-2 & 3.85 & - & 52.6 & (C-4) 172.9, (C-1) 174.9 \\ Glycine (M10) & C-2a & 3.88 & - & 43.6 & (C-2) 172.9, (C-1) 174.9 \\  & C-2b & 4.01 & - & 43.6 & (C-1) 174.7 \\ Tyrosine (M11) & C-3 & 2.98-3.31 & & 40.0 & (C-4) 127.2 \\  & C-2 & 4.14 & 50.6 & & \\  & C-6 C-8 & 6.77 & 7.13 & 116.5 & (C-4) 127.2 \\  & C-5 C-9 & 7.13 & 6.77 & 131.3 & (C-2) 157.6 \\ Typtophan (M12) & C-2 & 3.89 & - & 56.5 & (C-3) 24.9, (C-1) 173.4 \\  & C-8 & 7.05 (t, \(J=7.5\) Hz) & 7.12, 7.37 & 119.8 & (C-7) 1122.2, (C-1) 128.3 \\  & C-9 & 712 (overlap) & 7.69 & 122.5 & (C-6) 138.2, (C-8) 119.0 \\  & C-5 & 7.20 (s) & 124.9 & (C-4) 102.1, (C-6) 138.2 \\  & C-10 & 7.69 (d, \(J=7.9\) Hz) & 7.37 & 118.9 & (C-9) 122.5, (C-6)138.2 \\  & C-7 & 7.37 (d, \(J=8.2\) Hz) & - & 112.2 & - \\ Bufalin and Scillridin & & & & & \\ Bufalin and Scillridin (M13, M14) & & & & & \\ (M13, M14) & C-21 & 7.98 (d, \(J=2.6\) Hz) & 6.25 & 149.9 & \\  & C-22 & 6.27 (d, \(J=3.0\) Hz) & 7.97 & 115.2 & 122.4, 164.3 (C-20, 23) \\  & C-24 & 7.43 (s) & & 150.3 & 122.4, 164.2 (C-20) \\  & C-17 & 2.59 & & 51.7 & 124.2 (C-20) \\  & C-8 & 1.83 & 1.68 & 42.8 & 84.0, 49.0 (C-14, 13) \\ \hline  & & \multicolumn{2}{c}{Sugars} & & \\  & & & & & \\  & & & & & \\  & & & & & \\  & & & & & \\ \(\omega\)-\(\delta\) Fatty acid (M2) & Bis almilc CH\({}_{2}\) & 2.27 (r, \(J=6.9\) Hz) & 5.33 & 24.7 & Offerlin carbons 131.2, \\ \(\omega\)-\(\delta\) Fatty acid (M2) & Bis almilc CH\({}_{2}\) & 2.87 & 5.33 & 26.3 & Offerlin carbons 131.2, \\  & t+CH\({}_{3}\) & 0.97 & 2.07 (allycline CH2) & 19.5 & 21.6 C-2 \\ \hline  & & \multicolumn{2}{c}{Sugars} & & \\ Rhamoside (M4) & C-6 & 1.23 & 3.77 & 19.5 & (C-4) 69.8, (C-5) 72.8 \\  & C-1 & 5.44 & - & 93.8 & (C-2) 73.8 \\  & C-5 & 3.77 & - & 72.7 & - \\  & C-4 & 3.78 & - & 69.1 & - \\ \(\beta\)-Glucose (M5) & C-1 & 4.48 (d, \(J=7.8\) Hz) & 3.11, 327, 3.32 & 97.9 & - \\  & C-2 & 3.11 & & 76.1 & (C-3) 77.8, (C-1)97.9 \\  & C-3 & 3.35