{
"METABOLOMICS WORKBENCH":{"STUDY_ID":"ST001489","ANALYSIS_ID":"AN002467","VERSION":"1","CREATED_ON":"September 22, 2020, 10:04 am"},

"PROJECT":{"PROJECT_TITLE":"Metabolomics by UHPLC-HRMS reveals the impact of heat stress on pathogen-elicited immunity in maize","PROJECT_SUMMARY":"Studies investigating crop resistance to biotic and abiotic stress have largely focused on plant responses to singular forms of stress and individual biochemical pathways that only partially represent stress responses. Thus, combined biotic and abiotic stress treatments and the global assessment of their elicited metabolic expression remains largely unexplored. In this study, we employed targeted and untargeted metabolomics to investigate the metabolic responses of maize (Zea mays) to both individual and combinatorial stress treatments using heat (abiotic) and Cochliobolus heterostrophus infection (biotic) experiments. Ultra-high-performance liquid chromatography-high-resolution mass spectrometry revealed significant metabolic responses to C. heterostrophus infection and heat stress, and comparative analyses between these individual forms of stress demonstrated differential elicitation between the two global metabolomes. In combinatorial experiments, treatment with heat stress prior to fungal inoculation negatively impacted maize disease resistance against C. heterostrophus, and distinct metabolome separation between combinatorial stressed plants and the non-heat stressed infected controls was observed. Targeted analysis revealed inducible primary and secondary metabolite responses to biotic/abiotic stress, and combinatorial experiments indicated that deficiency in the hydroxycinnamic acid, p-coumaric acid, may lead to the heat-induced susceptibility of maize to C. heterostrophus. Collectively, these findings demonstrate that abiotic stress can predispose crops to more severe disease symptoms, underlining the increasing need to investigate defense chemistry in plants under combinatorial stress.","INSTITUTE":"Agricultural Research Service, United States Department of Agriculture","LAST_NAME":"Christensen","FIRST_NAME":"Shawn","ADDRESS":"1600 SW 23rd Drive Gainesville, FL 32608, Gainesville, Florida, 32607, USA","EMAIL":"shawn.christensen@usda.gov","PHONE":"3523745739"},

"STUDY":{"STUDY_TITLE":"Metabolomics by UHPLC-HRMS reveals the impact of heat stress on pathogen-elicited immunity in maize","STUDY_SUMMARY":"Studies investigating crop resistance to biotic and abiotic stress have largely focused on plant responses to singular forms of stress and individual biochemical pathways that only partially represent stress responses. Thus, combined biotic and abiotic stress treatments and the global assessment of their elicited metabolic expression remains largely unexplored. In this study, we employed targeted and untargeted metabolomics to investigate the metabolic responses of maize (Zea mays) to both individual and combinatorial stress treatments using heat (abiotic) and Cochliobolus heterostrophus infection (biotic) experiments. Ultra-high-performance liquid chromatography-high-resolution mass spectrometry revealed significant metabolic responses to C. heterostrophus infection and heat stress, and comparative analyses between these individual forms of stress demonstrated differential elicitation between the two global metabolomes. In combinatorial experiments, treatment with heat stress prior to fungal inoculation negatively impacted maize disease resistance against C. heterostrophus, and distinct metabolome separation between combinatorial stressed plants and the non-heat stressed infected controls was observed. Targeted analysis revealed inducible primary and secondary metabolite responses to biotic/abiotic stress, and combinatorial experiments indicated that deficiency in the hydroxycinnamic acid, p-coumaric acid, may lead to the heat-induced susceptibility of maize to C. heterostrophus. Collectively, these findings demonstrate that abiotic stress can predispose crops to more severe disease symptoms, underlining the increasing need to investigate defense chemistry in plants under combinatorial stress.","INSTITUTE":"Agricultural Research Service, United States Department of Agriculture","DEPARTMENT":"Center of Medical, Agricultural, and Veterinary Entomology","LABORATORY":"Chemistry Research Unit","LAST_NAME":"Christensen","FIRST_NAME":"Shawn","ADDRESS":"1600 SW 23rd Drive Gainesville, FL 32608","EMAIL":"shawn.christensen@usda.gov","PHONE":"3523745739"},

"SUBJECT":{"SUBJECT_TYPE":"Plant","SUBJECT_SPECIES":"Zea mays","TAXONOMY_ID":"4577"},
"SUBJECT_SAMPLE_FACTORS":[
{
"Subject ID":"-",
"Sample ID":"1_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"01_SLB_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"2_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"02_SLB_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"3_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"03_SLB_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"4_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"04_SLB_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"5_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"05_SLB_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"6_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"06_SLB_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"7_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"07_Tween_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"8_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"08_Tween_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"9_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"09_Tween_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"10_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"10_Tween_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"11_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"11_Tween_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"12_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 28°C under watered conditions","RAW_FILE_NAME":"12_Tween_28_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"25_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 28°C","RAW_FILE_NAME":"25_SLB_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"26_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 28°C","RAW_FILE_NAME":"26_SLB_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"27_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 28°C","RAW_FILE_NAME":"27_SLB_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"28_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 28°C","RAW_FILE_NAME":"28_SLB_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"29_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 28°C","RAW_FILE_NAME":"29_SLB_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"30_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 28°C","RAW_FILE_NAME":"30_SLB_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"31_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 38°C under watered conditions,  then returned to 28°C","RAW_FILE_NAME":"31_Tween_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"32_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 38°C under watered conditions,  then returned to 28°C","RAW_FILE_NAME":"32_Tween_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"33_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 38°C under watered conditions,  then returned to 28°C","RAW_FILE_NAME":"33_Tween_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"34_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"38 returned to 28"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 38°C under watered conditions,  then returned to 28°C","RAW_FILE_NAME":"34_Tween_38_3d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"49_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 38°C","RAW_FILE_NAME":"49_SLB_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"50_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 38°C","RAW_FILE_NAME":"50_SLB_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"51_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 38°C","RAW_FILE_NAME":"51_SLB_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"52_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 38°C","RAW_FILE_NAME":"52_SLB_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"53_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 38°C","RAW_FILE_NAME":"53_SLB_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"54_",
"Factors":{"Sample Type":"SLB inoculation","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"3d post SLB (C. heterostrophus) inoculation on 3rd leaf, 14d old plant grown at 38°C under watered conditions, then returned to 38°C","RAW_FILE_NAME":"54_SLB_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"55_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 38°C under watered conditions,  then returned to 38°C","RAW_FILE_NAME":"55_Tween_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"56_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 38°C under watered conditions,  then returned to 38°C","RAW_FILE_NAME":"56_Tween_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"57_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 38°C under watered conditions,  then returned to 38°C","RAW_FILE_NAME":"57_Tween_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"58_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 38°C under watered conditions,  then returned to 38°C","RAW_FILE_NAME":"58_Tween_38_6d_H2O"}
},
{
"Subject ID":"-",
"Sample ID":"59_",
"Factors":{"Sample Type":"Control","Age":"14 day","Growth Temperature":"38 returned to 38"},
"Additional sample data":{"Description":"Tween 20 control treated 3rd leaf, 14d old plant grown at 38°C under watered conditions,  then returned to 38°C","RAW_FILE_NAME":"59_Tween_38_6d_H2O"}
}
],
"COLLECTION":{"COLLECTION_SUMMARY":"Samples were collected and flash frozen in liquid N2","SAMPLE_TYPE":"Plant"},

"TREATMENT":{"TREATMENT_SUMMARY":"For inoculations, single isolates of Cochliobolus heterostrophus were cultured on V8 agar for 3-4 weeks as described by (Christensen et al., 2018). Spot inoculations were performed on 14-d-old plants in which four 10 μl droplets of either C. heterostrophus suspension (1x106 spores mL-1) or control solution (sterile 0.1% Tween 20) were applied in a staggered fashion (Fig. 2a and Fig. 4a) onto the middle portion of the third leaf about 10cm from the distal tip. Following inoculation, both heat-stressed and non-heat-stressed plants were placed in a plastic humidity chamber and placed in the 28°C Percival. At 24 hours post-inoculation, infected and non-infected controls were removed from the humidity chambers and maintained at 28°C for the remainder of the experiment. At 72 hours post-inoculation, leaves (n=6) were photographed and immediately harvested into liquid N2. Lesions were digitally measured using ImageJ software (ImageJ 1.36b; Wayne Rasband, NIH, Bethesda, MD, USA)."},

"SAMPLEPREP":{"SAMPLEPREP_SUMMARY":"LCMS grade reagents (Thermo Fisher Scientific) were used throughout the extraction. Frozen 1.5-mL fast prep tubes with Zirmil® beads (1.1mm; SEPR Ceramic Beads and Powders, Mountainside, NJ, USA) containing 50 mg of ground and frozen tissue were carefully thawed to 4°C then transferred to ice. An internal standard mix of 12 μL containing caffeine, D6-Abscisic acid, D5-Jasmonic acid, D5-Cinnamic acid, D5-Indole-3-acetic acid, 13C-alpha linolenic acid, and nicotine at 8.33 μg/mL was added to each sample along with 750 μL of 10 mM of ammonium acetate and 750 μL of methanol (MeOH). Samples were mixed by vortex then homogenized at 6000 RPM for 30 seconds in a FastPrep® FP 120 tissue homogenizer (Qbiogene) and then sonicated in an ambient water bath for 15 min. Samples were centrifuged for 10 minutes at 20,000 RCF at ambient temperature, then 1 mL of supernatant was transferred to individual 4 mL glass vials. The supernatant was dried under a nitrogen stream at 30°C, reconstituted in 200 μL of 0.1% formic acid in water, and vortexed for 30 seconds. Vial contents were transferred to a 1.5-mL snap-cap tube, placed on ice for 10 minutes, then centrifuged at 20,000 RCF for 10 minutes at ambient temperature. 150 μL of supernatant was transferred to glass LC vials for UHPLC-HRMS analysis."},

"CHROMATOGRAPHY":{"CHROMATOGRAPHY_TYPE":"Reversed phase","INSTRUMENT_NAME":"Thermo Vanquish","COLUMN_NAME":"ACE Excel 2 C18-PFP (100 x 2.1mm, 2um)"},

"ANALYSIS":{"ANALYSIS_TYPE":"MS"},

"MS":{"INSTRUMENT_NAME":"Thermo Q Exactive Orbitrap","INSTRUMENT_TYPE":"Orbitrap","MS_TYPE":"ESI","ION_MODE":"NEGATIVE","MS_COMMENTS":"The raw acquisition data were processed using a similar workflow described in previous work (Chamberlain et al., 2019a, b), which we detail here. Raw data files were converted from .raw to .mzxml format using RawConverter (He et al., 2015). MZmine 2 was used for processing the raw data including detecting masses, building chromatograms, grouping isotopic peaks, removing duplicate peaks, and aligning features (Pluskal et al., 2010). Identification was assigned to features by m/z (≤5 ppm) and retention time (0.2 min) (level 1 – identified compounds according to Metabolomics Standards Initiative standards (Sumner et al., 2007)) matching tousing our method-specific metabolite library produced from pure standards previously analyzed using this the above-mentioned chromatographic gradient. Processed data were exported from MZmine as a feature list containing the signal intensity for each feature in each sample. A small value (half the minimum value in the dataset) was used to replace zeros (no detection). The data were filtered to remove sample features with  10% signal contribution from their corresponding features in the extraction blanks. From this point, the data were further processed, normalized, and filtered using MetaboAnalyst 4.0 (Chong et al., 2018). For whole-metabolome comparative analyses, the data were normalized to total ion signal and feature intensities were auto-scaled to facilitate statistical comparisons (van den Berg et al., 2006). Statistical significance, defined as p  0.05, was determined using the two-tailed student’s t-test, and values for significance were adjusted for the false discovery rate with the Bonferroni-Holm method (HOLM, 1979)."},

"MS_METABOLITE_DATA":{
"Units":"peak intensity",

"Data":[{"Metabolite":"Catechol","1_":"176603.832","2_":"270123.4046","3_":"471865.2675","4_":"362157.0999","5_":"704936.667","6_":"395007.815","7_":"125094.9699","8_":"969175.9919","9_":"632927.4595","10_":"224647.1865","11_":"174560.5441","12_":"734276.3736","25_":"662433.4218","26_":"374088.8393","27_":"289154.8436","28_":"96907.79457","29_":"439849.7913","30_":"315687.8122","31_":"519948.5096","32_":"462429.0279","33_":"464860.2949","34_":"246120.3329","49_":"1437008.298","50_":"355346.6","51_":"545137.0003","52_":"1649.30528","53_":"179964.9176","54_":"99605.70964","55_":"151756.5625","56_":"459808.5568","57_":"109442.9097","58_":"596311.4603","59_":"113758.7951"},{"Metabolite":"Citric acid","1_":"518567107.3","2_":"496978734","3_":"1458279794","4_":"687724620.7","5_":"375680201.3","6_":"881591848.2","7_":"849659070.2","8_":"1063513055","9_":"1558383463","10_":"891833925.9","11_":"918070700","12_":"1305206496","25_":"313373112.6","26_":"512882310.1","27_":"1368930365","28_":"1027908639","29_":"519569498.1","30_":"877271401.7","31_":"1327821126","32_":"803145969.3","33_":"787500375.7","34_":"641239579.8","49_":"365132807.3","50_":"970084301.8","51_":"981341976.1","52_":"185873.9379","53_":"1903978827","54_":"1168260185","55_":"1706593537","56_":"840781639.7","57_":"598763210.6","58_":"227124175.4","59_":"654595975.7"},{"Metabolite":"Cryptochlorogenic acid","1_":"135826.5719","2_":"43277.15678","3_":"484296.3257","4_":"25467.11166","5_":"2611024.035","6_":"605650.3397","7_":"4575462.944","8_":"4179984.231","9_":"2702415.01","10_":"759617.2724","11_":"71235.64353","12_":"692179.1344","25_":"698896.1792","26_":"41898.06966","27_":"5097544.328","28_":"594305.5439","29_":"271890.2975","30_":"42304593.16","31_":"205919711","32_":"21936.25973","33_":"660355.5196","34_":"116029.1421","49_":"2228832.912","50_":"637001.2114","51_":"99574.89227","52_":"497.4088837","53_":"17994227.71","54_":"8041482.477","55_":"19623040.47","56_":"817333.6618","57_":"3791428.736","58_":"137325.1025","59_":"855522.5247"},{"Metabolite":"Mevalonic acid","1_":"606083.3017","2_":"757993.2822","3_":"2726708.659","4_":"938582.5096","5_":"966438.8224","6_":"2843702.08","7_":"2071516.349","8_":"2689738.755","9_":"3762972.941","10_":"1473680.727","11_":"1446876.533","12_":"2350952.632","25_":"1113202.622","26_":"1037348.406","27_":"2869223.256","28_":"2171554.161","29_":"1682130.257","30_":"1657342.551","31_":"5454204.333","32_":"1684655.702","33_":"2594017.998","34_":"2338767.111","49_":"1772007.701","50_":"1812789.47","51_":"1925029.209","52_":"8434.744316","53_":"4881163.247","54_":"2280997.512","55_":"3233592.093","56_":"2259811.919","57_":"1799492.245","58_":"1027053.375","59_":"1782278.669"},{"Metabolite":"Ribose-5-Phosphate","1_":"12723521.15","2_":"12711436.93","3_":"7242452.69","4_":"14666897.45","5_":"12034303.4","6_":"10421408.81","7_":"3482266.522","8_":"3618743.763","9_":"3632940.636","10_":"8578909.733","11_":"17270846.97","12_":"13778661.84","25_":"10473073.46","26_":"9382992.076","27_":"1352116.904","28_":"75265.43262","29_":"7321980.655","30_":"10074911.87","31_":"8044334.157","32_":"9906414.809","33_":"3761975.043","34_":"7719477.295","49_":"9611054.812","50_":"2217118.746","51_":"9811750.772","52_":"45908.14858","53_":"2053123.076","54_":"1469413.707","55_":"3175671.551","56_":"2353099.364","57_":"5774654.156","58_":"7682311.121","59_":"5065569.715"},{"Metabolite":"Salicylic acid","1_":"3068548.58","2_":"3190018.081","3_":"10761842.55","4_":"4831981.198","5_":"5829247.311","6_":"5897326.952","7_":"21517472.31","8_":"17795377.73","9_":"23824189.86","10_":"6494262.011","11_":"3542471.522","12_":"6099924.055","25_":"4261939.068","26_":"3398469.45","27_":"12249572.49","28_":"9316116.458","29_":"5179139.869","30_":"8894124.007","31_":"10847201.34","32_":"8157476.539","33_":"18512609.86","34_":"4819824.644","49_":"6597557.857","50_":"6585791.314","51_":"8669883.126","52_":"1128539.627","53_":"10917402.97","54_":"10126942.22","55_":"14958214.33","56_":"19291141.21","57_":"15715719.03","58_":"3807904.563","59_":"21258797.22"},{"Metabolite":"Shikimic acid","1_":"40899262.23","2_":"33448553.97","3_":"88290894.79","4_":"62638183.55","5_":"49852056.11","6_":"63853240.42","7_":"20511643.57","8_":"57536456.4","9_":"44667334.86","10_":"42269483.82","11_":"43131025.7","12_":"94866752.69","25_":"61703089.78","26_":"38246019.99","27_":"34239395.64","28_":"28780584.61","29_":"47332775.52","30_":"37978457.02","31_":"168768231.4","32_":"19278475.72","33_":"19411273.51","34_":"32944117.66","49_":"107410927.9","50_":"29169587.74","51_":"41661059.88","52_":"2313.130649","53_":"88734209.91","54_":"36808556.79","55_":"53440049.67","56_":"31441027.74","57_":"10916545.76","58_":"54473700.6","59_":"27557196.13"},{"Metabolite":"Valine","1_":"4295135.365","2_":"4154951.486","3_":"16225362.06","4_":"3964097.69","5_":"17710362.31","6_":"7033356.783","7_":"7349628.305","8_":"11286474.96","9_":"11503563.82","10_":"5207066.223","11_":"4230253.972","12_":"16458810.99","25_":"4633852.416","26_":"3439378.586","27_":"15096260.11","28_":"9133744.644","29_":"1717772.011","30_":"7571303.538","31_":"41009809.83","32_":"3301924.896","33_":"7553606.038","34_":"3321536.417","49_":"16428341.97","50_":"11304827.75","51_":"13864643.42","52_":"497.4088837","53_":"13992302.18","54_":"11134399.14","55_":"15577218.8","56_":"7339735.106","57_":"6866768.108","58_":"6470095.87","59_":"7536229.597"},{"Metabolite":"ZealexinA4","1_":"519802.7399","2_":"517495.4505","3_":"666611.7469","4_":"637203.4388","5_":"226360.1108","6_":"806126.695","7_":"166981.8129","8_":"331176.9912","9_":"324834.4659","10_":"499976.4144","11_":"589318.5147","12_":"523103.0448","25_":"403863.6177","26_":"364922.7875","27_":"235017.7881","28_":"219834.6106","29_":"396311.9706","30_":"351692.2062","31_":"205874.6803","32_":"772487.8828","33_":"100437.1942","34_":"652649.4609","49_":"228956.6508","50_":"297741.4903","51_":"229410.3167","52_":"497.4088837","53_":"517998.3117","54_":"262371.6478","55_":"454853.9149","56_":"127519.0998","57_":"339165.8511","58_":"206080.9945","59_":"78481.90429"}],

"Metabolites":[{"Metabolite":"Catechol","quantitated m/z [M-H]-":"109.0289","PubChem":"289"},{"Metabolite":"Citric acid","quantitated m/z [M-H]-":"191.01918","PubChem":"311"},{"Metabolite":"Cryptochlorogenic acid","quantitated m/z [M-H]-":"353.0872","PubChem":"9798666  "},{"Metabolite":"Mevalonic acid","quantitated m/z [M-H]-":"147.0657","PubChem":"439230  "},{"Metabolite":"Ribose-5-Phosphate","quantitated m/z [M-H]-":"229.0113","PubChem":"77982  "},{"Metabolite":"Salicylic acid","quantitated m/z [M-H]-":"137.0239","PubChem":"338  "},{"Metabolite":"Shikimic acid","quantitated m/z [M-H]-":"173.045524","PubChem":"8742"},{"Metabolite":"Valine","quantitated m/z [M-H]-":"116.0711","PubChem":"6287  "},{"Metabolite":"ZealexinA4","quantitated m/z [M-H]-":"247.1334","PubChem":"135398014"}]
}

}