1. 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.)

2. 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 , repeat 1, ion accumulation time of 50 ms. MS2: mass range of m/z , repeat 1, precursor isolation range of 3 Da, ion accumulation time of 120 ms, energy of 150%, collision gas of 100%, q  (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 , repeat 1, ion accumulation time of 50 ms. MS2: mass range of m/z , repeat 1, precursor isolation range of 3 Da, ion accumulation time of 120 ms, energy of 150%, collision gas of 100%, q  (30.0 kHz). MS3: mass range of m/z , repeat 1, precursor isolation range of 3 Da, ion accumulation time of 120 ms, energy of 150%, collision gas of 100%, q  (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.

3. 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
C613C9H10O4 2'
[13C9]4',7-Dihydroxyflavone
41.8 3'
[13C9]Genistein
45.7
C613C9H10O5 4'
[13C9]Kaempferol
49.4
C613C9H10O6 5'
[13C9]Apigenin
50.5 6'
[13C9]Formononetin
55.2
C713C9H12O4

4. 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
C1213C9H20O9 8'
[13C9]Genistin
24.7
C1213C9H20O10 9'
[13C9]Apigetrin
34.0
10'
[13C9]Malonyldaidzin
34.3
C1513C9H22O12
11'
[13C9]Ononin
37.0
C1313C9H22O9
12'
[13C9]Malonylgenistin
40.4
C1513C9H22O13
13'
[13C9]Malonylapigetrin
46.7
14'
[13C9]Malonylononin
50.5
C1613C9H24O12

5. 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
100.0
125.0
150.0
175.0
200.0
225.0
250.0
275.0
m/z
100.0
125.0
150.0
175.0
200.0
225.0
250.0
275.0
m/z
MS/MS
Precursor:
100.0
125.0
150.0
175.0
200.0
225.0
250.0
275.0
m/z
MS/MS
Precursor:
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 was used as the precursor. (B) The result of CID of an authentic peak of daidzein when [MH] ion at m/z was used as the precursor.

6. 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.

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

8. 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.

9. 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.

10. (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).