Targeted Metabolite Profiling-Based Identification of Antifungal 5-n-Alkylresorcinols Occurring in Different Cereals against Fusarium oxysporum
Abstract
:1. Introduction
2. Results
2.1. Standardization and AR Quantification
2.2. Inhibition of Mycelial Growth on F. oxysporum
2.3. Liquid Chromatography coupled to Electrospray Ionization Mass Spectrometry (LC-ESIMS) Analysis
2.4. Peak Annotation
2.5. Multivariate Analysis
3. Discussion
4. Material and Methods
4.1. Fungal and Plant Material
4.2. Extracts Standardization and Total AR Quantification
4.3. Extraction and Chemical Analyses for Metabolite Profiling
4.3.1. Preparation of AR-Rich Extracts from Different Cereals
4.3.2. High Performance Liquid Chromatography-Electrospray Ionization-Mass Spectrometry (LC-ESI-MS) Analysis
4.3.3. Gas Chromatography-Electron Impact Mass Spectrometry (GC/EIMS) Analysis
4.4. Microscale Amended Medium (MSAM) Assay
4.5. Statistical Analyses
5. Conclusions
Author Contributions
Funding
Conflicts of Interest
Appendix A
Comp. | HRESIMS a | LRESIMS b | EIMS c |
---|---|---|---|
m/z (%), Cluster | m/z (%), Cluster | m/z (%), Fragment | |
1 | 389.3028 (85) [M − H]− | 389 (100) | 268 (100) [(TMSO)2C6H4CH2]+ 534 (10) [M + (TMS)2]+ |
375.3259 (100), [M − CH2-H]− | |||
343.3020 (24), [M − C2H5OH]− | |||
2 | 455.3891 (15) [M − H]− | 455(70), [M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 600 (10) [M + (TMS)2]+ |
296 (60) | |||
574(50) | |||
3 | 347.2976 (100), [M − H]− | 347 (100), [M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 492 (30) [M + (TMS)2]+ |
695.5997 (6), [2M − H]− | 695 (60), [2M − H]− | ||
4 | 373.3130 (100), [M − H]− | 373 (100), [M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 518 (20) [M + (TMS)2]+ |
347.2971 (30), [M − C2H2-H]− | 747 (30), [2M − H]− | ||
747.6278 (5), [2M − H]− | 398 (10) | ||
5 | 375.3289 (100), [M − H]− | 375 (100), [M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 520 (40) [M + (TMS)2]+ |
751.6652 (13), [2M − H]− | 751 (40), [2M − H]− | ||
6 | 401.3413 (40), [M − H]− | 401 (100), [M − H]− 803 (15), [2M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 546 (10) [M + (TMS)2]+ |
375.3279 (100), [M − C2H2-H]− | |||
803.6830 (5), [2M − H]− | |||
7 | 446.3693 (50) [M − H]− | 446 (50), [M − H]− | 268 (80) [(TMSO)2C6H4CH2]+ 591 (30) [M + (TMS)2]+ |
1190 (60) | |||
8 | 403.3596 (100), [M − H]− | 403 (100), [M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 548 (30) [M + (TMS)2]+ |
807.7275 (45), [2M − H]− | 807 (45), [2M − H]− | ||
9 | 415.3187 (80) [M − H]− | 415 (65), [M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 560 (10) [M + (TMS)2]+ |
901 (45) | |||
10 | 431.3903 (100), [M − H]− | 431 (100), [M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 576 (20) [M + (TMS)2]+ |
863.7925 (46), [2M − H]− | 863 (46), [2M − H]− | ||
11 | 479.3919 (100), [M − H]− | 479 (100), [M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 624 (15) [M + (TMS)2]+ |
343.3036 (51), [M − C10H16-H]− | 959 (37), [2M − H]− | ||
12 | 459.4226 (100), [M − H]− | 459 (100), [M − H]− | 268 (100) [(TMSO)2C6H4CH2]+ 604 (20) [M-(TMS)2]+ |
919.8549 (40), [2M − H]− | 919 (40), [2M − H]− |
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Sample Availability: Samples are available from the authors. |
Solvent | Extraction Yield (%w/w) | Total AR Content a (µg OE/g DE) |
---|---|---|
Acetone | 3.9 ± 0.2 B | 706.1 ± 23.2 A |
Methanol | 6.2 ± 0.4 A | 679.6 ± 32.1 AB |
n-Hexane | 4.3 ± 0.3 B | 650.5 ± 21.3 B |
Ethyl acetate | 3.1 ± 0.2 D | 510.7 ± 35.5 C |
iso-Propanol | 3.5 ± 0.1 C | 497.2 ± 28.6 C |
Samples | Code | CO a | EY b | TARC c | MGI d (%) | ||
---|---|---|---|---|---|---|---|
10.0 µg/µL | 1.0 µg/µL | 0.1 µg/µL | |||||
Barley Husk | BH | Co | 0.12 | 24.7 ± 0.5 M | 74.8 ± 1.5 AB | 70.6 ± 1.8 BC | 12.9 ± 1.8 BCD |
Forage Oat Husk | FOH | Cu | 0.693 | 104.8 ± 3.3 IJ | 36.4 ± 11.3 EF | 17.8 ± 1.6 FG | 19.1 ± 5.6 BC |
Rice Husk | RH | Co | 0.509 | 115.8 ± 4.2 I | 33.1 ± 1.7 EFG | 16.2 ± 6.2 FG | 11.7 ± 1.4 CD |
Triticale Husk | TH | Cu | 1.659 | 662.1 ± 20.4 A | 82.5 ± 0.3 AB | 79.4 ± 1.6 AB | 18.8 ± 3.0 BC |
Wheat Husk | WH | Cu | 1.734 | 541.9 ± 24.7 B | 56.6 ± 2.6 CD | 21.3 ± 0.2 DEF | 26.5 ± 1.2 B |
Pearl Barley | PB | Co | 0.666 | 156.3 ± 2.4 GH | 13.5 ± 2.3 HI | 11.5 ± 0.4 G | 7.5 ± 7.7 CD |
Certificate Oat Husk | COH | Co | 0.451 | 81.8 ± 3.7 K | 85.6 ± 0.2 A | 80.7 ± 0.2 A | 80.7 ± 1.4 A |
Certificate Oat Caryopsis | COC | Co | 0.596 | 86.2 ± 3.0 JK | 75.1 ± 2.9 AB | 65.5 ± 0.1 C | 19.2 ± 1.2 BC |
Forage Corn Flour | FCF | Co | 0.724 | 103.9 ± 4.4 IJ | 47.7 ± 2.7 DE | 19.9 ± 0.8 EFG | 9.9 ± 1.1 CD |
Oats Flakes | OF | Co | 0.591 | 85.1 ± 5.2 JK | 36.5 ± 5.7 EF | 23.0 ± 1.2 DEF | 8.2 ± 0.7 CD |
Barley Caryopsis | BC | Co | 0.648 | 117.5 ± 2.0 I | 25.0 ± 3.2 FGH | 18.9 ± 1.0 EFG | 11.6 ± 0.5 CD |
Forage Oat Caryopsis | FOC | Cu | 0.796 | 139.2 ± 2.5 H | 69.9 ± 0.6 BC | 16.5 ± 3.0 FG | 11.7 ± 0.1 CD |
Rice Caryopsis | RC | Co | 0.251 | 56.6 ± 1.4 L | 3.9 ± 0.4 I | 0.0 ± 0.0 H | 0.0 ± 0.0 D |
Sorghum Caryopsis | SC | Co | 0.146 | 26.2 ± 0.7 M | 19.5 ± 0.3 GH | 16.2 ± 0.8 FG | 10.7 ± 6.6 CD |
Soy Seed | SS | Cu | 1.039 | 168.2 ± 2.0 EFG | 77.4 ± 0.7 AB | 25.2 ± 0.2 DEF | 13.7 ± 1.7 BCD |
Triticale Caryopsis | TC | Cu | 0.648 | 185.4 ± 6.9 E | 78.5 ± 3.7 AB | 75.7 ± 4.7 AB | 18.4 ± 2.7 BC |
Wheat Caryopsis | WC | Cu | 0.688 | 177.5 ± 4.6 EF | 76.9 ± 1.3 AB | 63.4 ± 2.1 C | 11.9 ± 3.9 CD |
Wheat flour | WF | Co | 1.314 | 363.0 ± 16.8 C | 77.2 ± 4.3 AB | 30.1 ± 4.0 D | 8.4 ± 0.1 CD |
White Corn Flour | WCF | Co | 1.131 | 162.8 ± 4.6 FG | 52.0 ± 2.1 D | 15.9 ± 0.3 FG | 7.4 ± 5.5 CD |
Yellow Corn | YC | Cu | 1.131 | 215.7 ± 3.2 D | 75.2 ± 0.7 AB | 27.6 ± 1.9 DE | 15.5 ± 0.5 BC |
Yellow Corn Flour | YCF | Co | 1.093 | 157.7 ± 5.6 FGH | 46.0 ± 5.6 DE | 23.1 ± 2.1 DEF | 18.6 ± 6.3 BC |
No | Rt (min) a | [M − H]− (m/z) b | Error (ppm) | Molecular Formula c | Homologue | Name |
---|---|---|---|---|---|---|
1 | 15.4 | 389.3048 | −1.80 | C25H42O3 | C19:1, OH | 5-n-(hydroxynonadecenyl)resorcinol |
2 | 15.6 | 455.3896 | 1.54 | C31H52O2 | C25:2 | 5-n-(pentacosadienyl)-resorcinol |
3 | 15.9 | 347.2956 | 1.73 | C23H40O2 | C17 | 5-n-heptadecylresorcinol |
4 | 16.1 | 373.3113 | 1.88 | C25H42O2 | C19:1 | 5-n-nonadecenylresorcinol |
5 | 16.7 | 375.3269 | 1.60 | C25H44O2 | C19 | 5-n-nonadecanylresorcinol |
6 | 16.9 | 401.3413 | −1.49 | C27H46O2 | C21:1 | 5-n-henicosenylresorcinol |
7 | 17.2 | 445.3693 | 2.69 | C29H50O3 | C23, Oxo | 5-n-(oxotricosanyl)-resorcinol |
8 | 17.4 | 403.3586 | 2.48 | C27H48O2 | C21 | 5-n-henicosylresorcinol |
9 | 17.7 | 415.3201 | −2.65 | C27H44O3 | C21:1, Oxo | 5-n-(oxoheneicosenyl)-resorcinol |
10 | 18.0 | 431.3903 | 3.25 | C29H52O2 | C23 | 5-n-tricosylresorcinol |
11 | 18.3 | 479.3899 | 2.09 | C33H52O2 | C27:4 | 5-n-heptacosatetraenylresorcinol |
12 | 18.8 | 459.4216 | 3.05 | C31H56O2 | C25 | 5-n-pentacosylresorcinol |
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Marentes-Culma, R.; Orduz-Díaz, L.L.; Coy-Barrera, E. Targeted Metabolite Profiling-Based Identification of Antifungal 5-n-Alkylresorcinols Occurring in Different Cereals against Fusarium oxysporum. Molecules 2019, 24, 770. https://doi.org/10.3390/molecules24040770
Marentes-Culma R, Orduz-Díaz LL, Coy-Barrera E. Targeted Metabolite Profiling-Based Identification of Antifungal 5-n-Alkylresorcinols Occurring in Different Cereals against Fusarium oxysporum. Molecules. 2019; 24(4):770. https://doi.org/10.3390/molecules24040770
Chicago/Turabian StyleMarentes-Culma, Ronald, Luisa L. Orduz-Díaz, and Ericsson Coy-Barrera. 2019. "Targeted Metabolite Profiling-Based Identification of Antifungal 5-n-Alkylresorcinols Occurring in Different Cereals against Fusarium oxysporum" Molecules 24, no. 4: 770. https://doi.org/10.3390/molecules24040770