N-Linolenoyl-L-glutamine: 1H-NMR (CD3OD) δ: 5. 33 (m, 6H), 4 N-Linolenoyl-L-glutamine: 1H-NMR (CD3OD) δ: 5.33 (m, 6H), 4.38 (q, 1H, J = 5.0 Hz), 2.80 (t, 4H, J = 6.2 Hz), 2.31 (m, 2H), 2.24 (t, 2H, J = 7.4 Hz), 2.16 (m, 1H), 2.08 (q, 4H, J = 6.4 Hz), 1.95 (m, 1H), 1.62 (quin, 2H, J = 6.8 Hz), 1.34 (m, 8H), 0.90 (t, 3H, J =7.5 Hz). N-Linoleoyl-L-glutamine: 1H-NMR (CD3OD) δ: 5.35 (m, 4H), 4.11 (q, 1H, J = 7.1 Hz), 2.77 (m, 4H), 2.24 (t, 2H, J = 7.4 Hz), 2.07 (q, 4H, J = 6.5 Hz), 1.62 (quin, 2H, J = 7.0 Hz), 1.34 (m, 14H), 0.90 (t, 3H, J = 6.8 Hz). Supplemental Information 1 Chemical shifts of synthesized FACs. Supplemental Information 2 Quantification of FACs in gut content extracts of Spodoptera litura. The amounts of each FAC in gut content extracts of Spodoptera litura were estimated with a calibration curve (see below), which was made by using N-linolenoyl-L-glutamine for the standard. The peak area of selected ion chromatograms of each analyte was used for the quantitation. y538926x, r20.9789 (y, LCMS peak area; x, amount (ng) of analyte; r2, coefficient of determinant.)

Supplemental Information 3 MS parameters. Nebulizer gas flow of 1.5 L/min, drying gas flow of 15 L/min, ESI voltage of 1.8 kV or 1.8 kV, heat block temperature of 200ºC, and DL temperature of 250ºC. Nebulizer gas flow of 1.5 L/min, drying gas flow of 15 L/min, ESI voltage of 1.8 kV, heat block temperature of 200ºC, and DL temperature of 250ºC. Probe voltage of 4.50 kV, detector voltage of 1.73 kV, heat block temperature of 200ºC, CDL temperature of 200ºC, nebulizer gas flow of 1.5 L/min and the analytical mode utilized ESI positive scans. MS1: mass range of m/z 220-1000, repeat 1, ion accumulation time of 50 ms. MS2: mass range of m/z 100-350, repeat 1, precursor isolation range of 3 Da, ion accumulation time of 120 ms, energy of 150%, collision gas of 100%, q  0.169 (30.0 kHz). Probe voltage of 4.50 kV, detector voltage of 1.73 kV, heat block temperature of 200ºC, CDL temperature of 200ºC, nebulizer gas flow of 1.5 L/min and the analytical mode utilized ESI positive scans. MS1: mass range of m/z 220-1000, repeat 1, ion accumulation time of 50 ms. MS2: mass range of m/z 100-350, repeat 1, precursor isolation range of 3 Da, ion accumulation time of 120 ms, energy of 150%, collision gas of 100%, q  0.169 (30.0 kHz). MS3: mass range of m/z 50-350, repeat 1, precursor isolation range of 3 Da, ion accumulation time of 120 ms, energy of 150%, collision gas of 100%, q  0.251 (45.0 kHz). Daidzein, y0.10x, r20.9993 4’,7-Dihydroxyflavone, y0.07x, r20.9999 Genistein, y0.12x, r20.9998 Kaempferol, y0.12x, r20.9994 Apigenin, y0.12x, r20.9985 Formononetin, y0.15x, r20.9998 (y, LCMS peak area ratio of analyte to internal standard; x, amount (pmol) of analyte; r2, coefficient of determinant.) Supplemental Information 4 Calibration curves of flavonoids.

Supplemental Table 1 [13C9]Flavonoid identified by HR-LC-MS in complete-hydrolyzed extracts of soybean leaves. Peak No. Identification tR/min Measured m/z Calculated m/z Elemental [M+H]+ composition 1' [13C9]Daidzein 39.2 264.095 C613C9H10O4 2' [13C9]4',7-Dihydroxyflavone 41.8 3' [13C9]Genistein 45.7 280.091 280.090 C613C9H10O5 4' [13C9]Kaempferol 49.4 296.087 296.085 C613C9H10O6 5' [13C9]Apigenin 50.5 6' [13C9]Formononetin 55.2 278.110 278.111 C713C9H12O4

Supplemental Table 2 [13C9]Flavonoid glycosides identified by HR-LC-MS in intact and heated extracts of soybean leaves. Peak No. Identification tR/min Measured m/z Calculated m/z Elemental [M+H]+ composition 7' [13C9]Daidzin 17.0 426.148 C1213C9H20O9 8' [13C9]Genistin 24.7 442.143 C1213C9H20O10 9' [13C9]Apigetrin 34.0 442.145 10' [13C9]Malonyldaidzin 34.3 512.149 C1513C9H22O12 11' [13C9]Ononin 37.0 440.165 440.164 C1313C9H22O9 12' [13C9]Malonylgenistin 40.4 528.144 C1513C9H22O13 13' [13C9]Malonylapigetrin 46.7 528.137 14' [13C9]Malonylononin 50.5 526.165 526.164 C1613C9H24O12

A: Peak 1 (39. 2 min) B: Daidzein standard 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 m/z 255.065 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 m/z 255.065 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 m/z 137.023 199.075 227.068 MS/MS Precursor: 255.065 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 m/z 137.024 199.076 227.074 MS/MS Precursor: 255.065 Supplemental Fig. 1 (A) The result of CID of peak 1 in complete-hydrolyzed extracts of soybean leaves when [MH] ion at m/z 255.065 was used as the precursor. (B) The result of CID of an authentic peak of daidzein when [MH] ion at m/z 255.065 was used as the precursor.

503 255 200 250 300 350 400 450 500 550 m/z 417 Daidzein 255 200 250 300 350 400 450 500 550 m/z m/z 255 () 10 15 20 25 30 35 40 45 min Supplemental Fig. 2 Qualitative analysis of satellite sets of daidzein by LCMS in positive ion mode. LCMS selected ion chromatogram profiles of m/z 255 ion in intact extracts of soybean leaves. Insert: mass spectra of peaks at tR 17.0 and 34.3 min.

A: Peak 7 (17.0 min) B: Peak 10 (34.3 min) 200 250 300 350 400 450 500 550 m/z 417.118 255.064 200 250 300 350 400 450 500 550 m/z 503.118 255.064 1st generation product ion chromatogram (precursor: 417.118) 1st generation product ion chromatogram (precursor: 503.118) 200 250 300 350 400 450 500 550 m/z 255.064 200 250 300 350 400 450 500 550 m/z 255.064 2nd generation product ion chromatogram (precursor: 255.064) 2nd generation product ion chromatogram (precursor: 255.064) 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 m/z 199.072 137.023 181.062 153.072 227.067 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 m/z 137.024 199.076 181.065 227.068 153.071 Supplemental Fig. 3 (A) The result of CID of peak 7 in heated extracts of soybean leaves when [MH] ion at m/z 417.118 in 1st CID and at m/z 255.064 in 2nd CID were used as the precursor. (B) The result of CID of peak 10 in heated extracts of soybean leaves when [MH] ion at m/z 503.118 in 1st CID and at m/z 255.064 in 2nd CID were used as the precursor.

A 10’ IS 12’ 13’ 14’ m/z 426 () m/z 512 () m/z 442 () m/z 528 () m/z 440 () m/z 526 () m/z 239 () 7’ B 8’ 9’ 11’ IS m/z 426 () m/z 512 () m/z 442 () m/z 528 () m/z 440 () m/z 526 () m/z 239 () 10 15 20 25 30 35 40 45 50 55 min Supplemental Fig. 4 Qualitative analysis of [13C9]flavonoid glycosides by LCMS in positive ion mode. The conversion of [13C9]malonylglucoside into corresponding [13C9]glucoside, following heat treatment. LCMS selected ion chromatogram profiles of [13C9]flavonoid glucosides and malonylglucosides in intact extracts of soybean leaves (A) and heated extracts (B). The chromatograms of m/z 239 was reduced to 0.25 times. The numbers represent (7’) [13C9]daidzin, (8’) [13C9]genistin, (9’) [13C9]apigetrin, (10’) [13C9]malonyldaidzin, (11’) [13C9]ononin, (12’) [13C9]malonylgenistin, (13’) [13C9]malonylapigetrin, and (14’) [13C9]malonylononin.

A 15 TIC () 17 16 m/z 421 () m/z 405 () m/z 407 () 5.0 7.5 10.0 min B 15 16 17 Supplemental Fig. 5 Qualitative analysis of gut content extracts of Spodoptera litura by LCMS in negative ion mode. LCMS selected ion chromatogram profiles of FACs in gut content extracts (A) and their structures (B). The numbers represent (15) volicitin, (16) N-linolenoyl-L-glutamine, and (17) N-linoleoyl-L-glutamine.

(A) m/z 253 () m/z 417 () (B) m/z 253 () m/z 417 () (C) m/z 253 () m/z 417 () (D) m/z 253 () m/z 417 () (E) m/z 253 () m/z 417 () (F) m/z 253 () m/z 417 () Daidzein standard m/z 253 () min 10 20 30 40 Supplemental Fig. 6 Reaction products of -glucosidase activity assay analyzed by LCMS in positive and negative ion mode. The selected ion chromatograms of reaction mixtures incubated for (A) 0 h, (B) 1.5 h, (C) 5 h, and (D) 12 h and without (E) gut content extracts and (F) daidzin incubated for 12 h. The chromatograms of m/z 417 was reduced to 0.1 times. Daidzin was detected as a proton adduct ion at m/z 417 (tR, 17 min). Daidzein was not detected at any incubation time (A)-(D).