Table 1.

Resistance‐related (RR) metabolites, with putative names of identity, detected in six‐row barley genotypes, inoculated with mock or Gibberella zeae.

Exp. mass (M), median	Exp. RT, median	Theor. mass (M)	AME (p.p.m.)	Putative name of identity	Compound group	Molecular formula	RR metabolites	MS/MS fragments	P < 0.05	Fold change	Database
88.01635	2.41	88.01604	3.5	Pyruvic acid	OA	C3H4O3	RRC	87.01, 58.78	0.0116	32.19	A,B,C,D
104.0112	2.53	104.0109	2	Malonic acid	OA	C3H4O4	RRC†	103, 59, 84.99, 74.96	0.007	1.57	A,B,C,D
129.04265	2.42	129.0426	0.39	Pyroglutamic acid	AA	C5H7NO3	RRC	128.14, 110.26, 100.11, 84.25	0.0348	2.33	A,B,C,D
133.03765	2.31	133.0375	1.1	Aspartic acid	AA	C4H7NO4	RRC	115.19, 114.19, 88.19, 89.1	0.0249	1.38	A,C
161.06865	2.42	161.0688	0.92	2‐Aminoadipic acid	AA	C6H11NO4	RRC		0.0440	2.08	A,B,C,D
164.04735	34.43	164.0473	0.31	p‐Coumaric acid	PA	C9H8O3	RRC*	119.05, 163, 145.20, 134.96	0.0076	3.48	A,B,C,D
166.04977	2.35	166.0491	4	3‐Methylxanthine	ALK	C6H6N4O2	RRC	128.93, 75.00, 96.68, 105.08	0.0311	1.33	A,B,C,D
172.14575	40.63	172.1463	3.1	Capric acid	FA	C10H20O2	RRC	171.25, 153.22, 127.26, 148.23	0.0296	1.22	A,B,C,D
174.11165	2.27	174.1116	0.29	l‐Arginine	AA	C6H14N4O2	RRC*	129.05, 155.04 142.93, 154.93	0.0095	2.13	A,B,C,D
186.16165	41.94	186.162	1.8	Undecanoic acid	FA	C11H22O2	RRC	141.19, 167.15, 185.11, 80.17	0.0452	1.31	A,C
192.02715	2.45	192.027	0.78	Citric acid	OA	C6H8O7	RRC†	110.99, 172.99, 84.92, 126.96	0.0002	1.74	A,B,C,D
192.06335	2.34	192.0638	2.3	Quinic acid	PP	C7H12O6	PRs	173.06, 111.11, 127.19, 85.17	0.0394	1.78	A,B,C,D
196.05825	2.32	196.0583	0.24	d‐Gluconate	OA	C6H12O7	RRC†		0.0007	1.58	A,B,C,D
200.17755	43.21	200.1776	0.24	Lauric acid	FA	C12H24O2	RRC*, PRs	181.12, 167.13, 155.09, 135.28	0.0139	1.31	A,B,C,D
216.17235	36.04	216.1725	0.68	Omega‐Hydroxydodecanoic acid	FA	C12H24O3	RRC		0.0497	1.50	A
224.06865	34.53	224.0684	1.1	Sinapate	PA	C11H12O5	RRC	208.13,179.11,164.16	0.0245	1.19	A,C
250.15665	37.82	250.1569	0.99	3β‐Hydroxycinnamolide	ST	C15H22O3	PRs	205.17, 231.09, 184.29, 164.09	0.0387	1.26	A
288.22975	39.28	288.2301	1.2	10,16‐Dihydroxy‐hexadecanoate	FA	C16H32O4	RRC*	243.17, 269.22, 189.19, 259.17, 227.12	0.0021	2.1	A
316.07915	2.49	316.0794	0.78	Quinovic acid	SAP	C13H16O9	RRC†	153.04, 305.64, 165.13, 296.92	0.0007	17.39	A
328.13075	26.02	328.1311	1	Seselinol isovalerate	COU	C19H20O5	RRC	309.19, 291.22, 229.17, 185.09	0.0289	1.74	A
332.07395	2.38	332.0743	1	β‐Glucogallin	Tannin	C13H16O10	RRC†		0.002	4.0	A,C
340.13065	26.02	340.1311	1.3	6‐Prenylnaringenin	FLA	C20H20O5	RRC	289.18, 183.04, 307.20, 321.20	0.0279	1.79	A,C
354.10995	24.68	354.1103	0.98	Licoisoflavone A	ISF	C20H18O6	RRC	235.21, 320.31, 255.26	0.0446	1.65	A,C
358.10645	2.27	358.1052	3.4	5‐Hydroxy‐3,6,7,4′‐tetramethoxyflavone	FLA	C19H18O7	RRC*		0.003	2.37	A
358.14095	26.02	358.1416	1.8	(–)‐Dihydrocubebin	LIG	C20H22O6	RRC		0.0255	1.9	A
418.08895	27.09	418.0899	2.2	Isoscutellarein 7‐xyloside		C20H18O10	RRC	180.92, 237.15, 310.47, 313.03	0.0217	1.43	A
428.16775	23.71	428.1682	1	trans‐p‐Ferulyl alcohol 4‐O‐[6‐(2‐methyl‐3‐hydroxypropionyl)] glucopyranoside	PA	C20H28O10	RRC*		0.0077	2.14	A
432.10485	23.54	432.1056	1.7	Kaempferol 3‐O‐rhamnoside	FLA	C21H20O10	RRC*	153.06, 171.03, 399.24, 385.17	0.0091	3.03	A
432.17785	35.41	432.1784	1.2	Juanislamin	ST	C23H28O8	RRC		0.0424	1.64	A
434.12055	31.01	434.1212	1.4	Naringenin 7‐glucoside	FLA	C21H22O10	RRC	313.19, 253.33, 310.97, 231.08	0.0333	1.62	A
462.11535	24.04	462.1162	1.8	Scoparin	COU	C22H22O11	RRC†	299.13, 300.19, 155.09, 307.07	0.0012	3.6	A,C
484.24265	32.43	484.2434	1.5	Segetalin B		C24H32N6O5	RRC		0.0298	2.34	A
510.28125	38.13	510.2828	3	16‐Diacetoxy‐7α‐hydroxy‐18‐malonyloxy‐ent‐cleroda‐3‐ene	DT	C27H42O9	PRr*	281.26, 227.12, 153.14	0.017	3.44	A
526.26145	31.07	526.262	1	Murranimbine	ALK	C36H34N2O2	RRC*		0.0104	2.93	A
536.18865	16.95	536.1893	1.2	7‐O‐(4‐Methoxycinnamoyl) tecomoside	PP	C26H32O12	RRC	235.31, 299.30, 192.11, 161.01	0.0233	3.46	A
548.15265	2.44	548.1529	4.5	Hemsleyanoside	ISF	C26H28O13	RRC		0.0407	2.57	A
582.20875	28.927	582.2101	2.3	Auriculatin 4′‐O‐glucoside	ISF	C31H34O11	RRC*		0.0193	1.79	A
584.20945	18.45	584.2105	1.7	Sylvestroside III		C27H36O14	RRC	195.05, 282.88, 179.43, 165.20	0.0201	1.57	A
594.15755	23.86	594.1584	1.4	Kaempferol 3‐rhamnoside‐7‐glucoside	FLA	C27H30O15	RRC†		0.0006	5.45	A
608.17255	25.79	608.1741	2.5	Kaempferide 3‐glucoside‐7‐rhamnoside	FLA	C28H32O15	RRC*	299.01, 284.07, 300.49, 269.12	0.004	2.31	A
637.23545	36.90	637.2371	2.5	6′‐O‐α‐d‐Xylopyranosylalangiside	TER	C30H39NO14	RRC*	310.06, 291.99, 507.23, 618.19, 363.2	0.0168	1.66	A
654.17775	25.77	654.1795	2.6	Syringetin 3‐rutinoside	PA	C29H34O17	RRC†		0.0012	2.37	A
710.20435	22.80	710.2058	2	Kaempferol 3‐apiosyl‐(1‐>4)‐rhamnoside‐7‐rhamnoside	FLA	C32H38O18	RRC†	401.08, 311.15, 283.11, 341.12	0.0003	6.48	A
740.21435	21.40	740.2163	2.6	Kaempferol 3‐rhamninoside	FLA	C33H40O19	RRC†		0.0009	8.94	A
740.21465	24.93	740.2163	2.2	Kaempferol 3‐rhamnoside‐7‐glucosyl‐(1‐>2)‐rhamnoside	FLA	C33H40O19	RRC*		0.0152	1.61	A
756.20965	19.57	756.2112	2	Kaempferol 3‐gentiobioside‐7‐rhamnoside	FLA	C33H40O20	RRC†		0.0004	5.15	A
756.20965	22.81	756.2112	2	Kaempferol 3‐sophoroside‐7‐rhamnoside	FLA	C33H40O20	RRC†		0.0003	6.12	A
770.22485	21.72	770.2269	2	Rhamnetin 3‐rhamninoside	FLA	C34H42O20	RRC†		0.0004	7.67	A
784.45935	42.53	784.4609	1.9	Astragaloside III	TT	C41H68O14	RRC		0.0473	3.62	A,C
786.22015	21.41	786.2218	2	Isorhamnetin 3‐rutinoside‐7‐glucoside	FLA	C34H42O21	RRC†		0.0003	9.94	A

Databases used for metabolites identified: A, KNApSAcK; B, METLIN; C, KEGG; D, CAS. MS/MS fragmentation in bold indicates the actual match of the fragment in the database.

AA, amino acid; ALK, alkaloid; AME, accurate mass error (p.p.m.) was calculated using the formula [(Measured accurate mass—Theoretical mass)/(theoretical mass)]; BQ, benzoquinone; COU, coumarin; DT, diterpenoid; FA, fatty acid; FLA, flavonoid; ISF, isoflavonoid; LIG, lignan; OA, organic acid; PA, phenolic acid; PP, phenylpropanoid; PRr, pathogenesis‐related resistant; PRs, pathogenesis‐related susceptible; RRC, resistant‐related constitutive; RT, retention time; SAP, saponine; ST, sesqueterpenoid; TER, terpenoid; TT, triterpenoid.

^* Significant at P≤ 0.01.

^† Significant at P≤ 0.001.