#METABOLOMICS WORKBENCH atsai_20250207_210246 DATATRACK_ID:5605 STUDY_ID:ST003728 ANALYSIS_ID:AN006115 PROJECT_ID:PR002314 VERSION 1 CREATED_ON February 13, 2025, 5:23 pm #PROJECT PR:PROJECT_TITLE Comprehensive Nucleoside Analysis of Archaeal RNA Modification Profiles Reveals PR:PROJECT_TITLE a m7G in the Conserved P-loop of 23S rRNA PR:PROJECT_SUMMARY Extremophilic archaea employ diverse chemical RNA modifications, providing a PR:PROJECT_SUMMARY rich source of new enzymes for biotechnologically valuable RNA manipulations. PR:PROJECT_SUMMARY Our understanding of the modified nucleoside profiles in Archaea, as well as the PR:PROJECT_SUMMARY functions and dynamic regulation of specific RNA modifications is far from PR:PROJECT_SUMMARY complete. Here, we established an extensive profile of nucleoside modifications PR:PROJECT_SUMMARY in thermophilic and mesophilic Archaea through highly sensitive LC-MS/MS PR:PROJECT_SUMMARY analysis and rigorous non-coding RNA depletion, identifying - with high PR:PROJECT_SUMMARY confidence - at least four previously unannotated modifications in archaeal PR:PROJECT_SUMMARY mRNAs. Nucleoside quantification analysis conducted on total, large, small, and PR:PROJECT_SUMMARY mRNA-enriched subfractions of the model hyperthermophilic archaeon Thermococcus PR:PROJECT_SUMMARY kodakarensis revealed a series of modifications whose abundance is dynamically PR:PROJECT_SUMMARY responsive to growth temperatures, implying that specific RNA modifications are PR:PROJECT_SUMMARY fitness relevant under specific growth conditions. To predict the RNA-modifying PR:PROJECT_SUMMARY enzymes most likely to generate the new and dynamic RNA modifications, we PR:PROJECT_SUMMARY leveraged a bioinformatics analysis of open-access databases to annotate likely PR:PROJECT_SUMMARY functional domains of archaeal proteins. Putative enzyme activities were PR:PROJECT_SUMMARY confirmed in vitro and in vivo by assessing the presence of the target RNA PR:PROJECT_SUMMARY modification in genetic deletion strains of T. kodakarensis. Our approach led to PR:PROJECT_SUMMARY the discovery of a methyltransferase-encoded gene responsible for m7G PR:PROJECT_SUMMARY modification in the P-loop of 23S rRNA peptidyl transferase center and validates PR:PROJECT_SUMMARY a novel and effective platform for discovering RNA-modifying enzymes through PR:PROJECT_SUMMARY LC-MS/MS analysis that will accelerate efforts of the community towards PR:PROJECT_SUMMARY uncovering the complex and dynamic roles of RNA modifications. PR:INSTITUTE New England Biolabs PR:LAST_NAME Tsai PR:FIRST_NAME Yueh-Lin PR:ADDRESS 44 Dunham Ridge, Beverly, Massachusetts, 01915, USA PR:EMAIL atsai@neb.com PR:PHONE 978-380-6587 #STUDY ST:STUDY_TITLE Identification and quantification of a m7G modification in T. kodakarensis ST:STUDY_TITLE ribosomal RNA ST:STUDY_SUMMARY To investigate the activity of the protein encoded by TK0008, we conducted a ST:STUDY_SUMMARY comprehensive nucleoside analysis comparing the total RNA from the TS559 ST:STUDY_SUMMARY wild-type strain with that of the TK0008-deletion strain. ST:INSTITUTE New England Biolabs ST:LAST_NAME Tsai ST:FIRST_NAME Yueh-Lin ST:ADDRESS 44 Dunham Ridge, Beverly, Massachusetts, 01915, USA ST:EMAIL atsai@neb.com ST:PHONE 978-380-6587 #SUBJECT SU:SUBJECT_TYPE Cultured cells SU:SUBJECT_SPECIES Thermococcus kodakarensis SU:TAXONOMY_ID 311400 #SUBJECT_SAMPLE_FACTORS: SUBJECT(optional)[tab]SAMPLE[tab]FACTORS(NAME:VALUE pairs separated by |)[tab]Raw file names and additional sample data SUBJECT_SAMPLE_FACTORS - TS559_rep1-r001 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=Tk_total_RNAmods_01-r001.d SUBJECT_SAMPLE_FACTORS - TS559_rep1-r002 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=Tk_total_RNAmods_01-r002.d SUBJECT_SAMPLE_FACTORS - TS559_rep1-40x Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=Tk_40x_total_RNAmods_01.d SUBJECT_SAMPLE_FACTORS - TK0008_rep1-r001 Genotype:TK0008 deletion | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=Tk_total_RNAmods_02-r001.d SUBJECT_SAMPLE_FACTORS - TK0008_rep1-r002 Genotype:TK0008 deletion | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=Tk_total_RNAmods_02-r002.d SUBJECT_SAMPLE_FACTORS - TK0008_rep1-40x Genotype:TK0008 deletion | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=Tk_40x_total_RNAmods_02.d SUBJECT_SAMPLE_FACTORS - TS559_rep2-r001 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_Total_01.d SUBJECT_SAMPLE_FACTORS - TS559_rep2-20x Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_Total_20x_01.d SUBJECT_SAMPLE_FACTORS - TK0008_rep2-r001 Genotype:TK0008 deletion | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_Total_02.d SUBJECT_SAMPLE_FACTORS - TK0008_rep2-20x Genotype:TK0008 deletion | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_Total_20x_02.d SUBJECT_SAMPLE_FACTORS - TS559_total_RNA_rep1-r001 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TS559_Expo_TotalRNA_2018-r001.d SUBJECT_SAMPLE_FACTORS - TS559_total_RNA_rep1-r002 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TS559_Expo_TotalRNA_2018-r002.d SUBJECT_SAMPLE_FACTORS - TK0008_total_RNA_rep1-r001 Genotype:TK0008 deletion | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_Expo_TotalRNA_2018-r001.d SUBJECT_SAMPLE_FACTORS - TK0008_total_RNA_rep1-r002 Genotype:TK0008 deletion | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_Expo_TotalRNA_2018-r002.d SUBJECT_SAMPLE_FACTORS - TS559_total_RNA_rep2-r001 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_total_m7G_quant_01-1-r001.d SUBJECT_SAMPLE_FACTORS - TS559_total_RNA_rep2-r002 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_total_m7G_quant_01-1-r002.d SUBJECT_SAMPLE_FACTORS - TK0008_total_RNA_rep2-r001 Genotype:TK0008 deletion | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_total_m7G_quant_02-1-r001.d SUBJECT_SAMPLE_FACTORS - TK0008_total_RNA_rep2-r002 Genotype:TK0008 deletion | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TK0008_total_m7G_quant_02-1-r002.d SUBJECT_SAMPLE_FACTORS - TS559_23S_rep1-r001 Genotype:Wild-type | Sample source:23S_rRNA_Enrichment RAW_FILE_NAME(Raw_File_Names)=TS559_23S-Enriched-r001.d SUBJECT_SAMPLE_FACTORS - TS559_23S_rep1-r002 Genotype:Wild-type | Sample source:23S_rRNA_Enrichment RAW_FILE_NAME(Raw_File_Names)=TS559_23S-Enriched-r002.d SUBJECT_SAMPLE_FACTORS - TK0008_23S_rep1-r001 Genotype:TK0008 deletion | Sample source:23S_rRNA_Enrichment RAW_FILE_NAME(Raw_File_Names)=TK0008_23S-Enriched-r001.d SUBJECT_SAMPLE_FACTORS - TK0008_23S_rep1-r002 Genotype:TK0008 deletion | Sample source:23S_rRNA_Enrichment RAW_FILE_NAME(Raw_File_Names)=TK0008_23S-Enriched-r002.d SUBJECT_SAMPLE_FACTORS - TS559_23S_rep2-r001 Genotype:Wild-type | Sample source:23S_rRNA_Enrichment RAW_FILE_NAME(Raw_File_Names)=TK0008_23S_G_quant_01-r001.d SUBJECT_SAMPLE_FACTORS - TS559_23S_rep2-r002 Genotype:Wild-type | Sample source:23S_rRNA_Enrichment RAW_FILE_NAME(Raw_File_Names)=TK0008_23S_G_quant_01-r002.d SUBJECT_SAMPLE_FACTORS - TK0008_23S_rep2-r001 Genotype:TK0008 deletion | Sample source:23S_rRNA_Enrichment RAW_FILE_NAME(Raw_File_Names)=TK0008_23S_G_quant_02-r001.d SUBJECT_SAMPLE_FACTORS - TK0008_23S_rep2-r002 Genotype:TK0008 deletion | Sample source:23S_rRNA_Enrichment RAW_FILE_NAME(Raw_File_Names)=TK0008_23S_G_quant_02-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_NE_rep1-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_01-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_NE_rep1-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_01-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_0.1uM_rep1-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_02-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_0.1uM_rep1-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_02-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_0.2uM_rep1-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_03-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_0.2uM_rep1-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_03-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_1uM_rep1-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_04-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_1uM_rep1-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_04-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_4uM_rep1-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_05-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_4uM_rep1-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_05-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_NE_rep2-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_01_rep2-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_NE_rep2-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_01_rep2-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_0.1uM_rep2-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_02_rep2-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_0.1uM_rep2-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_02_rep2-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_0.2uM_rep2-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_03_rep2-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_0.2uM_rep2-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_03_rep2-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_1uM_rep2-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_04_rep2-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_1uM_rep2-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_04_rep2-r002.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_4uM_rep2-r001 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_05_rep2-r001.d SUBJECT_SAMPLE_FACTORS - IVT23S_rTK0008_4uM_rep2-r002 Genotype:Synthetic 23S_rRNA | Sample source:In vitro transcription RAW_FILE_NAME(Raw_File_Names)=IVT23S_rTK0008_05_rep2-r002.d SUBJECT_SAMPLE_FACTORS - TS559_Total_RNA_01 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TS559_total_RNA_rep1-1.d SUBJECT_SAMPLE_FACTORS - TS559_Total_RNA_02 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TS559_total_RNA_rep2-1.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Frag_Enrich_01 Genotype:Wild-type | Sample source:23S_Fragment_Enrichment RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Frag_Enrich_rep1.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Frag_Enrich_02 Genotype:Wild-type | Sample source:23S_Fragment_Enrichment RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Frag_Enrich_rep2.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Fragment_01_NoDepl-r001 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Fragment_01-r001-1.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Fragment_01_NoDepl-r002 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Fragment_01-r002-1.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Fragment_02_NoDepl-r001 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Fragment_02-r001-1.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Fragment_02_NoDepl-r002 Genotype:Wild-type | Sample source:Total RNA RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Fragment_02-r002-1.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Fragment_01_Depl-r001 Genotype:Wild-type | Sample source:23S_Fragment_Depletion RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Fragment_03-r001-1.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Fragment_01_Depl-r002 Genotype:Wild-type | Sample source:23S_Fragment_Depletion RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Fragment_03-r002-1.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Fragment_02_Depl-r001 Genotype:Wild-type | Sample source:23S_Fragment_Depletion RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Fragment_04-r001-1.d SUBJECT_SAMPLE_FACTORS - TS559_23S_m7G_Fragment_02_Depl-r002 Genotype:Wild-type | Sample source:23S_Fragment_Depletion RAW_FILE_NAME(Raw_File_Names)=TS559_23S_m7G_Fragment_04-r002-1.d #COLLECTION CO:COLLECTION_SUMMARY The TK0008 open reading frame (ORF) spans positions 7655 to 8755 on the T. CO:COLLECTION_SUMMARY kodakarensis genome. PCR was used to generate an amplicon including the TK0008 CO:COLLECTION_SUMMARY ORF flanked by ~700 bp both up- and down-stream that was cloned into the unique CO:COLLECTION_SUMMARY SwaI site of pTS700 (reference Hileman and Santangelo, PMID: 22701112) 82, CO:COLLECTION_SUMMARY resulting in pCSU-TK0008A. The coding sequence of TK0008 was excised from CO:COLLECTION_SUMMARY pCSU-TK0008A using site-directed QuikChange mutagenesis (Agilent Cat# 200516) to CO:COLLECTION_SUMMARY generate pCSU-TK0008B. All plasmid sequences were confirmed by Sanger CO:COLLECTION_SUMMARY sequencing. pCSU-TK0008B was transformed into T. kodakarensis strain TS559 and CO:COLLECTION_SUMMARY plated onto agmatine-free rich media plates as previously described (reference CO:COLLECTION_SUMMARY PMID: 34752288) 85. Transformants were allowed to grow for 4 days anaerobically CO:COLLECTION_SUMMARY at 85 °C and subsequent colonies were picked into rich liquid media lacking CO:COLLECTION_SUMMARY agmatine and grown overnight. Genomic DNA extracted from 1 mL of cells was used CO:COLLECTION_SUMMARY as a template for PCRs using two sets of primer pairs to determine the site and CO:COLLECTION_SUMMARY directionality of plasmid integration into the genome. One primer from each pair CO:COLLECTION_SUMMARY has homology to the genome with the other having homology to the plasmid to CO:COLLECTION_SUMMARY ensure PCR amplification involves a region flanking TK0008 on the genome. CO:COLLECTION_SUMMARY Colonies confirmed to contain proper integrations at the TK0008 locus were CO:COLLECTION_SUMMARY plated on minimal media containing 1 mM agmatine and 100 µM 6-methyl purine and CO:COLLECTION_SUMMARY grown anaerobically at 85 °C for 2-5 days. Genomic DNA from resultant CO:COLLECTION_SUMMARY colonies was used in diagnostic PCRs to identify strains deleted for TK0008 CO:COLLECTION_SUMMARY preliminarily. The deletion of TK0008 was ultimately confirmed by Sanger CO:COLLECTION_SUMMARY sequencing. In vitro transcribed (IVT) 23S rRNA was prepared using a linearized CO:COLLECTION_SUMMARY plasmid template (pBluescript II KS(-)) and HiScribe T7 High Yield RNA Synthesis CO:COLLECTION_SUMMARY Kit (NEB, Cat #E2040S). The synthesized transcripts were cleaned up using CO:COLLECTION_SUMMARY Monarch Spin RNA Cleanup Kit (NEB, Cat #T2050L). To perform in vitro methylation CO:COLLECTION_SUMMARY reactions, IVT 23S rRNA was heat-denatured at 95 C for 30 seconds and cooled to CO:COLLECTION_SUMMARY 22 C prior to enzyme treatment. Purified recombinant TK0008 (0.1 – 4 uM) was CO:COLLECTION_SUMMARY incubated with 1 uM of IVT 23S rRNA in 1x methyltransferase buffer (25 mM CO:COLLECTION_SUMMARY Tris-HCl pH 7.5, 100 mM NaCl, 1 mM DTT) supplemented with 160 uM of CO:COLLECTION_SUMMARY S-adenosyl-methionine (SAM) (NEB, Cat #B9003S) at 85 C for 30 minutes. The CO:COLLECTION_SUMMARY reactions were cleaned up using Monarch Spin RNA Cleanup Kit (NEB, Cat #T2040L). CO:SAMPLE_TYPE Ribonucleic acid, In Vitro Transcription #TREATMENT TR:TREATMENT_SUMMARY Harvested archaeal cell pellets were resuspended in 10 mL of TRI reagent TR:TREATMENT_SUMMARY (Molecular Research Center, Inc., Cat #TR118). The resuspended cells were TR:TREATMENT_SUMMARY homogenized using a beads beater at 4.0 m/s for 20 seconds x 2 cycles (MP TR:TREATMENT_SUMMARY Biomedicals, FastPrep-24TM). Subsequently, the mixture was centrifuged at 14000 TR:TREATMENT_SUMMARY g for 5 minutes to precipitate any cell debris. Supernatants were collected TR:TREATMENT_SUMMARY post-centrifugation and treated with 50 μL of BAN reagent (Molecular Research TR:TREATMENT_SUMMARY Center, Inc., Cat #BN191) per mL of supernatant for aqueous-organic phase TR:TREATMENT_SUMMARY separation. RNA from the aqueous phase was isolated by isopropanol precipitation TR:TREATMENT_SUMMARY and subjected to DNase I treatment (NEB, Cat #M0303S) to remove genomic DNA TR:TREATMENT_SUMMARY contamination. To further purify the DNase I-treated RNA, an equal volume of TR:TREATMENT_SUMMARY acid phenol-chloroform with isoamyl alcohol (125:24:1, Thermo Fisher Scientific, TR:TREATMENT_SUMMARY Cat #AM9722) was added to the reaction and centrifuged at 21300 g for 2 minutes TR:TREATMENT_SUMMARY to separate the aqueous phase from the organic phase. The aqueous phase TR:TREATMENT_SUMMARY containing RNA was then precipitated with 1.5 volumes of isopropanol and 0.1 TR:TREATMENT_SUMMARY volume of sodium acetate (Sigma Aldrich, Cat #S7899) at –20°C overnight. TR:TREATMENT_SUMMARY Finally, the precipitated RNA pellets were washed with 75% ethanol and dissolved TR:TREATMENT_SUMMARY in nuclease-free water. To enrich m7G-modified rRNA fragment, 50 ug of total RNA TR:TREATMENT_SUMMARY from T. kodakarensis TS559 wild-type strain was mixed with a biotinylated DNA TR:TREATMENT_SUMMARY probe (1 uM) fully complementary to the target sequence in 10 mM Tris buffer (pH TR:TREATMENT_SUMMARY 7.5) and heated to 95 C for 2 minutes followed by a ramp down to 22 C. TR:TREATMENT_SUMMARY Biotinylated DNA probe sequence: TR:TREATMENT_SUMMARY 5’-Biotin-ACCTTCGAGGTGTGCGCCAGCAACTGCCACT-3’. The unhybridized RNAs were TR:TREATMENT_SUMMARY digested with 5 uL of RNase 4 (NEB, Cat #M1284L) in 1x NEB buffer r1.1 at 37 TR:TREATMENT_SUMMARY C for 1 hour. The digestion was stopped by adding 10 L of human placental TR:TREATMENT_SUMMARY RNase inhibitor (NEB, Cat #M0307S) to the reaction mixture and incubated at room TR:TREATMENT_SUMMARY temperature for 10 minutes. Selective enrichment of the probe-hybridized rRNA TR:TREATMENT_SUMMARY region was performed using streptavidin magnetic beads (NEB, Cat #S1421S). TR:TREATMENT_SUMMARY Briefly, 250 uL of streptavidin magnetic beads were washed twice with equal TR:TREATMENT_SUMMARY volume of low-salt buffer (100 mM Tris pH 7.5, 10 mM EDTA, 50 mM NaCl) and TR:TREATMENT_SUMMARY resuspended in 50 uL of high-salt buffer (100 mM Tris pH 7.5, 10 mM EDTA, 250 mM TR:TREATMENT_SUMMARY NaCl). The high-salt buffer was removed, and the beads were incubated with the TR:TREATMENT_SUMMARY reaction mixture for 15 minutes at room temperature with occasional agitation. TR:TREATMENT_SUMMARY The bead-captured DNA-RNA hybrid was washed and eluted by heating to 80 C for 5 TR:TREATMENT_SUMMARY minutes in 30 uL of nuclease-free water. For m7G-modified rRNA fragment TR:TREATMENT_SUMMARY depletion, the same biotinylated DNA probe (1 uM) described above was mixed with TR:TREATMENT_SUMMARY 5 ug of total RNA from TS559 strain in the probe hybridization buffer provided TR:TREATMENT_SUMMARY in NEBNext rRNA Depletion Kit (NEB, Cat #E7850X). The probe-hybridized rRNA TR:TREATMENT_SUMMARY mixture was subjected to rRNA depletion according to the NEBNext rRNA Depletion TR:TREATMENT_SUMMARY Kit protocol. Following the enzymatic treatment, the reactions were cleaned up TR:TREATMENT_SUMMARY using RNA Clean and Concentrator Kit (Zymo Research, Cat #R1017). #SAMPLEPREP SP:SAMPLEPREP_SUMMARY Total or isolated RNAs were digested to nucleosides at 37°C overnight using a SP:SAMPLEPREP_SUMMARY Nucleoside Digestion Mix (NEB, Cat #M0649S). The digested RNAs were subsequently SP:SAMPLEPREP_SUMMARY injected without prior purification on an Agilent 1290 Infinity II UHPLC SP:SAMPLEPREP_SUMMARY equipped with a G7117 diode array detector and an Agilent 6495C SP:SAMPLEPREP_SUMMARY Triple-Quadrupole Mass Spectrometer operating in positive electrospray SP:SAMPLEPREP_SUMMARY ionization (+ESI) mode. #CHROMATOGRAPHY CH:CHROMATOGRAPHY_SUMMARY Solvent A pH is 4.5 CH:CHROMATOGRAPHY_TYPE Reversed phase CH:INSTRUMENT_NAME Agilent 1290 Infinity II CH:COLUMN_NAME Waters XSelect HSS T3 XP (100 × 2.1mm, 2.5um) CH:SOLVENT_A 100% water; 10mM ammonium acetate CH:SOLVENT_B 100% methanol CH:FLOW_GRADIENT 1%-40% Solvent B in 26.5 min CH:FLOW_RATE 0.6 mL/min CH:COLUMN_TEMPERATURE 30 #ANALYSIS AN:ANALYSIS_TYPE MS #MS MS:INSTRUMENT_NAME Agilent 6495 QQQ MS:INSTRUMENT_TYPE Triple quadrupole MS:MS_TYPE ESI MS:ION_MODE POSITIVE MS:MS_COMMENTS Mass spectrometric data were acquired using dynamic multiple reaction monitoring MS:MS_COMMENTS (DMRM) mode. Identification of each nucleoside species was based on the MS:MS_COMMENTS associated retention time and mass transition in the extracted chromatogram. #MS_METABOLITE_DATA MS_METABOLITE_DATA:UNITS Mass Response Ratio MS_METABOLITE_DATA_START Samples TS559_rep1-r001 TS559_rep1-r002 TS559_rep1-40x TK0008_rep1-r001 TK0008_rep1-r002 TK0008_rep1-40x TS559_rep2-r001 TS559_rep2-20x TK0008_rep2-r001 TK0008_rep2-20x Factors Genotype:Wild-type | Sample source:Total RNA Genotype:Wild-type | Sample source:Total RNA Genotype:Wild-type | Sample source:Total RNA Genotype:TK0008 deletion | Sample source:Total RNA Genotype:TK0008 deletion | Sample source:Total RNA Genotype:TK0008 deletion | Sample source:Total RNA Genotype:Wild-type | Sample source:Total RNA Genotype:Wild-type | Sample source:Total RNA Genotype:TK0008 deletion | Sample source:Total RNA Genotype:TK0008 deletion | Sample source:Total RNA N4-acetylcytidine_1 0.04173007 0.040967448 0.039976959 0.039044422 0.067573162 0.060377669 N4-acetylcytidine_2 0.038615789 0.037779635 0.03651396 0.036235049 0.057041041 0.053758882 N4-acetyl-2'-O-methylcytidine_1 0.000457793 0.000399256 0.000399837 0.000397614 0.0002368 0.000241969 0.000151257 0.000264247 N4-acetyl-2'-O-methylcytidine_2 0.000277255 0.000580169 0.000555706 0.000560571 2.56821E-05 7.26955E-05 N6-acetyladenosine_1 1.64291E-05 4.13197E-05 1.9822E-06 3.92048E-06 6.66736E-06 5.25248E-06 N6-acetyladenosine_2 5.47636E-06 7.18604E-06 3.96441E-06 9.80119E-06 4.38066E-06 3.54916E-05 3-(3-amino-3-carboxypropyl)uridine 0.000256674 0.000497636 0.000335233 0.000127755 0.001284482 0.005858175 2'-O-methyladenosine 0.008134222 0.008756187 0.009052725 0.008638771 0.005168027 0.005935408 5-carboxycytidine 0.003739716 0.003374964 0.003740851 0.003519864 3.86271E-06 7.30909E-05 2'-O-methylcytidine 0.043451629 0.042976207 0.044598807 0.04518463 0.039935892 0.038856827 5-carboxymethyluridine_1 0.000256674 0.000311023 0.000134093 0.000255509 0.000537755 0.002552776 5-carboxymethyluridine_2 0.000449179 0.000311023 0.000268186 0.000447141 0.001401975 0.00102231 5-carboxymethylaminomethyluridine_1 0.00038501 0.000746454 0.000134093 0.000319387 0.032550488 0.027296486 5-carboxymethylaminomethyluridine_2 0.000513347 0.000186614 0.000134093 0 0.00076061 0.000341394 5-carboxymethylaminomethyluridine_3 0.000192505 0.000248818 0.000536373 0.000255509 0.011215941 0.021612058 dihydrouridine 0.000962526 0.000124409 0.000536373 0.001085915 0.009189459 0.017594828 5-formylcytidine 5.15823E-05 1.87151E-05 6.7769E-06 1.95548E-05 7.55739E-06 4.17998E-05 N6-formyladenosine_1 1.46036E-05 7.18604E-06 3.96441E-06 3.92048E-06 7.05925E-06 2.89397E-06 N6-formyladenosine_2 3.65091E-06 1.43721E-05 8.32526E-05 7.84095E-06 0.000200453 0.000422307 2'-O-methylguanosine 0.021204326 0.020632869 0.02190187 0.02108349 0.031536829 0.031779101 5-hydroxymethylcytidine 2.57911E-05 6.23838E-06 3.38845E-05 3.25913E-05 3.71124E-05 5.77852E-05 N6-hydroxymethyladenosine_1 9.12727E-06 4.13197E-05 1.38754E-05 3.13638E-05 6.06923E-05 3.72257E-05 N6-hydroxymethyladenosine_2 5.47636E-06 1.25756E-05 1.38754E-05 5.88072E-06 3.37025E-05 2.00787E-05 5-hydroxyuridine 0.000834189 0.000248818 0.00020114 0.000191632 0.0001455 0.000985824 N6-isopentenyladenosine_1 0.002928028 0.003194194 0.00311206 0.003112859 0.003739477 0.0051278 N6-isopentenyladenosine_2 0.003309548 0.003203176 0.00356202 0.003655845 0.003582198 0.006914863 2'-O-methylinosine_1 1.27782E-05 3.95232E-05 4.55907E-05 3.72445E-05 9.18268E-06 3.12829E-06 2'-O-methylinosine_2 1.82545E-05 5.35195E-05 1.56819E-05 8.80511E-06 7.83998E-06 4-demethylwyosine 9.10643E-05 0.000100414 0.000138869 0.000295306 0.000229831 0.000406414 1.44936E-05 4.42693E-06 isowyosine 3.64257E-05 0.000113511 6.44116E-05 8.85918E-05 0.000126642 0.000192566 5.00764E-05 5.37592E-05 N6-(cis-hydroxyisopentenyl)adenosine 1.27782E-05 5.38953E-06 9.91102E-06 7.84095E-06 4.16481E-06 6.86069E-06 1-methyladenosine 0.067883149 0.069149443 0.070982717 0.073259994 0.009721654 0.010240487 1,2'-O-dimethyladenosine 1.27782E-05 3.59302E-06 1.78398E-05 1.96024E-05 1.11631E-06 8.81893E-06 1-methylguanosine 0.004685259 0.004566649 0.003474769 0.002978424 0.009685758 0.009206266 1-methylinosine 0.002787468 0.002818723 0.002949519 0.002987404 0.002257439 0.002275394 1-methylpseudouridine_1 0.003914271 0.0013685 0.005653241 0.004827355 0.004024273 0.005774657 0.00201983 0.004927128 0.001018367 0.005353923 1-methylpseudouridine_2 0.002117556 0.001181886 0.002078445 0.004152028 0.00047786 0.001081337 N2,N2,7-trimethylguanosine 0.001789414 0.001296649 0.002283701 0.001791745 0.002589223 0.004092357 N2,N2-dimethylguanosine 0.007203187 0.006858705 0.007190704 0.00674015 0.017433942 0.019143562 N2,7-dimethylguanosine 0.023831531 0.024269598 0.025494761 0.024854597 0.007354044 0.006834521 2,8-dimethyladenosine 1.82545E-06 1.07791E-05 5.94661E-06 5.88072E-06 7.4652E-07 5.08345E-06 2-methyladenosine 4.92873E-05 6.64708E-05 5.35195E-05 0.000103893 9.92653E-06 1.99083E-05 N2-methylguanosine 0.003419465 0.002916368 0.003272976 0.003273921 0.004416371 0.004283025 N2,2'-O-dimethylguanosine 0.000546386 0.000611215 0.000684126 0.000680113 0.000869057 0.000912969 3-methylcytidine 0.000148299 3.74303E-05 4.74383E-05 2.60731E-05 1.81081E-05 2.01278E-05 3-methylpseudouridine_1 0.001475873 0.003607863 0.003384274 0.000938652 0.004535292 0.003538704 0.002780665 0.007573646 0.000935833 0.007207503 3-methylpseudouridine_2 0.000192505 0.00068425 0.004022796 0.000255509 0.003037153 0.001875962 3-methyluridine 0.003465092 0.003359045 0.003687563 0.00312999 0.007910783 0.009787266 0.003939256 0.010256268 3,2'-O-dimethyluridine 0.000449179 6.22045E-05 0.001206839 0.000319387 0.003508475 0.000343269 N4,N4-dimethylcytidine 0.004358703 0.004485396 0.00426945 0.004243392 0.005027255 0.004859784 N4,N4,2'-O-trimethylcytidine 2.57911E-05 3.11919E-05 3.38845E-05 6.51827E-06 0.00032372 0.000348229 N4-methylcytidine_1 0.025320455 0.024248587 0.025271076 0.025043184 0.02909464 0.027192949 N4-methylcytidine_2 6.44779E-06 9.98141E-05 8.13229E-05 2.60731E-05 2.40617E-05 2.18516E-05 N4,2'-O-dimethylcytidine 1.93434E-05 6.23838E-06 1.35538E-05 6.51827E-06 1.7782E-05 1.23394E-05 5-methylcytidine 0.024424213 0.023868046 0.024349417 0.024560832 0.028128266 0.026587521 5,2'-O-dimethylcytidine 7.73734E-05 3.74303E-05 5.42152E-05 3.91096E-05 4.46266E-05 3.56687E-05 5-methyldihydrouridine 0.000192505 0.000870863 0.001609118 0.001022038 7.66907E-05 0.001190302 5-methyl-2-thiouridine 0.012127823 0.012440906 0.012269527 0.013478122 0.013671064 0.013575267 0.013607687 0.015116634 5-methyluridine 0.003015914 0.002861408 0.003846151 0.00295005 0.0033855 0.003021036 0.009815802 0.003011442 0.005411564 0.00331162 5,2'-O-dimethyluridine 0.000449179 0.000124409 0.000268186 6.38774E-05 0.000448347 0.001291923 N6,N6-dimethyladenosine 0.024565131 0.023505529 0.025903439 0.02531452 0.006794902 0.007696813 N6,N6,2'-O-trimethyladenosine 0 5.38953E-06 1.9822E-06 3.92048E-06 2.5405E-06 2.69682E-06 N6-methyladenosine 0.001538858 0.001584521 0.000761166 0.000678243 0.000784549 0.000704193 N6,2'-O-dimethyladenosine 0.000567716 0.00049943 0.000555017 0.000523384 0.00083617 0.001119812 O6-methylguanine 3.18725E-05 6.54873E-05 8.85918E-05 3.75235E-05 5.00677E-05 0.000438939 N6-methyl-N6-threonylcarbamoyladenosine_1 2.008E-05 5.38953E-06 7.92882E-06 7.84095E-06 7.10053E-06 1.94424E-06 N6-methyl-N6-threonylcarbamoyladenosine_2 1.82545E-06 1.79651E-06 0 1.96024E-06 7.78453E-07 2.41478E-06 7-methylguanosine 0.009698349 0.009045981 0.000438037 0.000464353 0.00249959 0.000109108 8-methyladenosine 0.001478618 0.001541405 0.000699718 0.000588072 0.000798338 0.000795856 5-methoxycarbonylmethyl-2-thiouridine_1 0.004620123 0.000933068 0.000938652 0.005110188 0.012951856 0.007490915 5-methoxycarbonylmethyl-2-thiouridine_2 0.004427618 0.001617318 0.002614817 0.002682849 0.000661092 0.002710495 5-methoxycarbonylmethyluridine_1 0.000128337 0.000186614 0.000469326 0.000383264 0.00020678 0.001278691 5-methoxycarbonylmethyluridine_2 0.000449179 0.000435432 0.00040228 0.001852443 0.001333586 0.001097578 5-methoxycarbonylmethyl-2'-O-methyluridine 0.000256674 6.22045E-05 0.00020114 0.000255509 0.001132372 0.002831358 uridine 5-oxyacetic acid methyl ester_1 0.001347536 0.000559841 0.000603419 0.000255509 0.001660617 0.001714568 uridine 5-oxyacetic acid methyl ester_2 0.002566735 0.002239363 0.002279584 0.000319387 0.002297748 0.000663758 uridine 5-oxyacetic acid methyl ester_3 0.001283368 0.001617318 0.000871606 0.000447141 0.001635388 0.001944828 5-methylaminomethyl-2-thiouridine_1 0.00038501 0.000248818 0.000335233 0.000255509 0.000814612 0.004911714 5-methylaminomethyl-2-thiouridine_2 0.00038501 0.000559841 0.00020114 0.000702651 0.00145339 0.001246108 5-methoxyuridine 0.000320842 0.000124409 0.000536373 0.000319387 0.001118978 0.001346451 2-methylthio-N6-isopentenyladenosine_1 8.57963E-05 9.8808E-05 0.000118932 3.92048E-05 4.52324E-05 4.61705E-05 2-methylthio-N6-isopentenyladenosine_2 3.28582E-05 1.79651E-05 3.76619E-05 4.70457E-05 0.000350928 0.000669615 2-methylthio-N6-methyladenosine 2.19054E-05 3.59302E-06 3.17153E-05 7.84095E-06 7.90676E-07 1.51904E-06 5-carbamoylmethyluridine_1 0.000192505 0.000248818 6.70466E-05 0.000127755 0.00049087 0.000634661 5-carbamoylmethyluridine_2 6.41684E-05 0.000622045 0.00040228 0.000255509 0.00062622 0.000564849 pseudouridine 0.043313655 0.045533715 0.046195106 0.044267007 0.055201024 0.054539234 adenosine 1 1 1 1 1 1 cytidine 1 1 1 1 1 1 guanosine 1 1 1 1 1 1 inosine 6.024E-05 8.62325E-05 0.000141425 4.55907E-05 0.000109773 7.33927E-05 2.96535E-06 3.42698E-06 1.15398E-05 3.65878E-06 uridine 1 1 1 1 1 1 2-thiocytidine 0.003043355 0.00258269 0.003151261 0.003154841 0.005909035 0.005401687 2-thiouridine 0.00038501 0.000311023 0.000335233 6.38774E-05 0.000553075 0.001202801 2-thio-2'-O-methyluridine 0.000513347 0.000746454 0.000469326 0.000255509 0.001298097 4-thiouridine 0.00237423 0.002177158 0.004022796 0.003577132 0.004728912 0.004880689 0.004520402 0.005719155 N6-threonylcarbamoyladenosine_1 0.000124131 6.82674E-05 8.91992E-05 6.27276E-05 0.000113137 0.000214434 N6-threonylcarbamoyladenosine_2 0.000186196 0.000167075 0.000138754 6.86083E-05 0.000197744 0.000266451 2'-O-methyluridine 0.030672485 0.03172431 0.031243714 0.031236027 0.02682181 0.027472608 MS_METABOLITE_DATA_END #METABOLITES METABOLITES_START metabolite_name Mass_Transition N4-acetylcytidine_1 286.1 -> 154.1 N4-acetylcytidine_2 286.1 -> 112.1 N4-acetyl-2'-O-methylcytidine_1 300.1 -> 154.1 N4-acetyl-2'-O-methylcytidine_2 322.1 -> 176.1 N6-acetyladenosine_1 310.1 -> 178.2 N6-acetyladenosine_2 332.1 -> 200.2 3-(3-amino-3-carboxypropyl)uridine 346.1 -> 214.1 2'-O-methyladenosine 282.1 -> 136.1 5-carboxycytidine 288.1 -> 156.1 2'-O-methylcytidine 258.1 -> 112.1 5-carboxymethyluridine_1 303.1 -> 171.1 5-carboxymethyluridine_2 303.1 -> 125.1 5-carboxymethylaminomethyluridine_1 332.1 -> 200.1 5-carboxymethylaminomethyluridine_2 332.1 -> 125.1 5-carboxymethylaminomethyluridine_3 354.1 -> 222.1 dihydrouridine 247.1 -> 115.0 5-formylcytidine 272.1 -> 140.1 N6-formyladenosine_1 296.1 -> 164.1 N6-formyladenosine_2 296.1 -> 136.1 2'-O-methylguanosine 298.1 -> 152.1 5-hydroxymethylcytidine 274.1 -> 142.1 N6-hydroxymethyladenosine_1 298.1 -> 166.1 N6-hydroxymethyladenosine_2 298.1 -> 136.1 5-hydroxyuridine 261.1 -> 129.1 N6-isopentenyladenosine_1 336.1 -> 136.1 N6-isopentenyladenosine_2 336.1 -> 204.2 2'-O-methylinosine_1 283.1 -> 137.1 2'-O-methylinosine_2 305.1 -> 159.1 4-demethylwyosine 344.1 -> 212.1 isowyosine 336.1 -> 204.2 N6-(cis-hydroxyisopentenyl)adenosine 352.1 -> 220.2 1-methyladenosine 282.1 -> 150.1 1,2'-O-dimethyladenosine 296.1 -> 150.1 1-methylguanosine 298.1 -> 166.2 1-methylinosine 283.1 -> 151.1 1-methylpseudouridine_1 259.1 -> 223.1 1-methylpseudouridine_2 259.1 -> 139.1 N2,N2,7-trimethylguanosine 326.1 -> 194.1 N2,N2-dimethylguanosine 312.1 -> 180.2 N2,7-dimethylguanosine 312.1 -> 180.1 2,8-dimethyladenosine 296.1 -> 164.1 2-methyladenosine 282.1 -> 150.2 N2-methylguanosine 298.1 -> 166.2 N2,2'-O-dimethylguanosine 312.1 -> 166.1 3-methylcytidine 258.1 -> 126.1 3-methylpseudouridine_1 259.1 -> 223.1 3-methylpseudouridine_2 259.1 -> 139.1 3-methyluridine 259.1 -> 127.1 3,2'-O-dimethyluridine 273.1 -> 127.1 N4,N4-dimethylcytidine 272.1 -> 140.2 N4,N4,2'-O-trimethylcytidine 286.1 -> 140.2 N4-methylcytidine_1 258.1 -> 126.1 N4-methylcytidine_2 258.1 -> 95.0 N4,2'-O-dimethylcytidine 272.1 -> 126.1 5-methylcytidine 258.1 -> 126.1 5,2'-O-dimethylcytidine 272.1 -> 126.1 5-methyldihydrouridine 261.1 -> 129.1 5-methyl-2-thiouridine 275.1 -> 143.1 5-methyluridine 259.1 -> 127.1 5,2'-O-dimethyluridine 273.1 -> 127.1 N6,N6-dimethyladenosine 296.1 -> 164.2 N6,N6,2'-O-trimethyladenosine 310.1 -> 164.2 N6-methyladenosine 282.1 -> 150.1 N6,2'-O-dimethyladenosine 296.1 -> 150.1 O6-methylguanine 298.1 -> 166.2 N6-methyl-N6-threonylcarbamoyladenosine_1 427.1 -> 295.2 N6-methyl-N6-threonylcarbamoyladenosine_2 427.1 -> 150.1 7-methylguanosine 298.1 -> 166.2 8-methyladenosine 282.1 -> 150.1 5-methoxycarbonylmethyl-2-thiouridine_1 333.1 -> 201.1 5-methoxycarbonylmethyl-2-thiouridine_2 355.1 -> 223.1 5-methoxycarbonylmethyluridine_1 317.1 -> 185.2 5-methoxycarbonylmethyluridine_2 339.1 -> 207.2 5-methoxycarbonylmethyl-2'-O-methyluridine 331.1 -> 185.1 uridine 5-oxyacetic acid methyl ester_1 333.1 -> 201.1 uridine 5-oxyacetic acid methyl ester_2 333.1 -> 141.1 uridine 5-oxyacetic acid methyl ester_3 355.1 -> 223.1 5-methylaminomethyl-2-thiouridine_1 304.1 -> 172.1 5-methylaminomethyl-2-thiouridine_2 304.1 -> 141.0 5-methoxyuridine 275.1 -> 143.1 2-methylthio-N6-isopentenyladenosine_1 382.1 -> 250.2 2-methylthio-N6-isopentenyladenosine_2 382.1 -> 182.1 2-methylthio-N6-methyladenosine 328.1 -> 196.1 5-carbamoylmethyluridine_1 302.1 -> 170.1 5-carbamoylmethyluridine_2 302.1 -> 125.1 pseudouridine 245.1 -> 209.1 adenosine 268.1 -> 136.1 cytidine 244.1 -> 112.1 guanosine 284.1 -> 152.1 inosine 291.1 -> 159.1 uridine 245.1 -> 113.0 2-thiocytidine 260.1 -> 128.1 2-thiouridine 261.1 -> 129.1 2-thio-2'-O-methyluridine 275.1 -> 129.0 4-thiouridine 261.1 -> 129.1 N6-threonylcarbamoyladenosine_1 413.1 -> 136.1 N6-threonylcarbamoyladenosine_2 413.1 -> 281.2 2'-O-methyluridine 259.1 -> 113.0 METABOLITES_END #END