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Deoxyribose and Deoxysugar Derivatives from Photoprocessed Astrophysical Ice Analogues and Comparison to Meteorites

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Deoxyribose and Deoxysugar Derivatives from Photoprocessed Astrophysical Ice Analogues and Comparison to Meteorites ARTICLE https://doi.org/10.1038/s41467-018-07693-x OPEN Deoxyribose and deoxysugar derivatives from photoprocessed astrophysical ice analogues and comparison to meteorites Michel Nuevo 1,2, George Cooper3 & Scott A. Sandford 1 Sugars and their derivatives are essential to all terrestrial life. Their presence in meteorites, together with amino acids, nucleobases, amphiphiles, and other compounds of biological 1234567890():,; importance, may have contributed to the inventory of organics that played a role in the emergence of life on Earth. Sugars, including ribose (the sugar of RNA), and other sugar derivatives have been identified in laboratory experiments simulating photoprocessing of ices under astrophysical conditions. In this work, we report the detection of 2-deoxyribose (the sugar of DNA) and several deoxysugar derivatives in residues produced from the ultraviolet irradiation of ice mixtures consisting of H2O and CH3OH. The detection of deoxysugar derivatives adds to the inventory of compounds of biological interest that can form under astrophysical conditions and puts constraints on their abiotic formation pathway. Finally, we report that some of the deoxysugar derivatives found in our residues are also newly identified in carbonaceous meteorites. 1 NASA Ames Research Center, MS 245-6, Moffett Field, CA 94035, USA. 2 BAER Institute, NASA Research Park, MS 18-4, Moffett Field, CA 94035, USA. 3 NASA Ames Research Center, MS 239-4, Moffett Field, CA 94035, USA. Correspondence and requests for materials should be addressed to M.N. (email: [email protected]) NATURE COMMUNICATIONS | (2018) 9:5276 | https://doi.org/10.1038/s41467-018-07693-x | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-018-07693-x ugars (monosaccharides) and their derivatives are ubiqui- contamination. All residues were analyzed with gas chromato- Stous in nature and essential to biological processes in all graphy coupled with mass spectrometry (GC-MS) using three terrestrial life. Sugars themselves play several roles in biol- distinct derivatization methods and temperature programs (see ogy. For example, they are used as structural backbones in RNA Methods). Most compounds were identified via their (+)-butyl/ (ribose) and DNA (deoxyribose), as well as cell walls in plants trifluoroacetyl (but/TFA) derivatives by comparison with com- (cellulose). They also serve as energy sources (glucose) or energy mercial standards prepared in the same manner as the samples, storage (glycogen and starch)1,2. Structurally, sugars are carbo- while some were identified via their tert-butyldimethylsilyl (t- hydrates of general formula CnH2nOn, and the simplest sugars are BDMS) and/or trimethylsilyl (TMS) derivatives (see Methods). defined as aldehydes (aldoses) or ketones (ketoses) containing at GC-MS analysis of residues with the (+)-butanol/TFAA method least two hydroxyl groups3. Sugar derivatives, collectively referred allowed for the enantiomeric separation of most of the sugar to as polyols, include sugar alcohols and sugar acids. In the case of derivatives, thus allowing for an additional assessment of possible aldoses, such sugar alcohols and acids are sugars in which the contamination in the samples. terminal aldehyde group is replaced by a primary alcohol or a carboxylic acid group, respectively. Deoxy variants of sugars, sugar alcohols, and sugar acids, are sugar derivatives that are Results lacking one or more hydroxyl groups with respect to their cor- Identification of deoxyribose and deoxysugar derivatives. All responding parent compounds (e.g., deoxyribose vs. ribose). the residues produced in this work contained a wide variety of The smallest ketose sugar, dihydroxyacetone, as well as several sugars, sugar alcohols, and sugar acids, with a similar distribution sugar acids and sugar alcohols—with up to 6 carbon atoms—have to previous laboratory ice UV irradiation studies27,28. In addition been detected in several carbonaceous chondrites including to these common sugar derivatives, we identified a number of Murchison and Murray, and shown to be extraterrestrial in ori- deoxysugars, deoxysugar alcohols, and deoxysugar acids, i.e., gin4,5. The presence of sugar derivatives in primitive meteorites, compounds in which one or more carbon atoms is not bonded to together with other compounds of biological interest such as a hydroxyl (OH) group relative to the corresponding canonical amino acids6,7, nucleobases8,9, and amphiphiles10,11 is consistent parent sugars, sugar alcohols, and sugar acids, respectively. These fi with a scenario in which a signi cant fraction of the inventory of include the 5-carbon (5C) deoxysugar 2-deoxyribose (C5H10O4) compounds from which biological processes started on the pri- (the structural backbone of DNA), as well as the 3C and 4C mitive Earth may have been delivered via comets, meteorites, and deoxysugar alcohols 1,2-propanediol (C3H8O2), 1,3-propanediol 12,13 interplanetary dust particles (IDPs) . (C3H8O2), 2-methyl-1,3-propanediol (C4H10O2), 1,2,3-butane- Over the last 25 years, laboratory experiments simulating the triol (C4H10O3), and 1,2,4-butanetriol (C4H10O3). The molecular photo-irradiation or particle bombardment of mixtures of structures of all the compounds identified in our residues are astrophysical ice analogs at low temperatures (10‒80 K) have shown in Supplementary Fig. 1. This is the first definitive iden- shown that organic compounds can form under astrophysical, tification of a deoxysugar in laboratory ice photolysis residues. non-biological conditions. In particular, the ultraviolet (UV) Only one other deoxysugar derivative, namely, 1,3-propanediol irradiation of ice mixtures consisting of H2O, CH3OH, CO, CO2, (deoxysugar alcohol, also present in our residues) was unam- CH4, and/or NH3 leads to the formation of compounds of biguously detected in one other laboratory residue in a previous astrobiological interest such as amino acids14–16, nucleobases17,18, study, together with tentative identifications of 2-methylglycerol functionalized polycyclic aromatic hydrocarbons (PAHs)19,20, (deoxysugar alcohol) and 2-methylglyceric acid (deoxysugar acid) amphiphiles21, as well as urea, hydantoin, and small aldehydes22– (not detected in our residues)28. 24. A variety of organic compounds have also been shown to form The GC-MS chromatograms and mass spectra supporting the at 5 K when ice mixtures containing CH3OH were UV irradiated identification of 2-deoxyribose and several deoxysugar alcohols in 25,26 or bombarded with energetic electrons . Finally, a large variety our residues, produced from the UV irradiation of H2O:CH3OH 13 of sugar alcohols, sugars (including ribose, the sugar of (2:1) and H2O: CH3OH (2:1) ice mixtures, are shown in Fig. 1 RNA), and sugar acids with up to 5 carbon atoms have been (deoxyribose), Fig. 2 (4C deoxysugar alcohols), and Supplemen- identified in residues produced from the UV irradiation of ice tary Fig. 2 (3C deoxysugar alcohols). The peaks eluting at 27,28 mixtures containing H2O and CH3OH at low temperatures . retention times around 57.0 and 57.3 min in Fig. 1a are tentatively In contrast, only 1,3-propanediol (3C deoxysugar alcohol) was assigned to the D and L enantiomers of 2-deoxyxylose, unambiguously identified in a laboratory residue28, while several respectively. This tentative identification is based on the mass deoxysugar acids have been found in meteorites4,5. The previous spectra of these peaks (Supplementary Fig. 3), which are very non-detection of deoxysugar derivatives in laboratory residues led similar to that of 2-deoxyribose (Fig. 1b), and because 2- to the conclusion that in such photo-irradiation experiments, deoxyxylose is the only possible diastereomer of 2-deoxyribose. sugar derivatives were formed via a formose-type reaction Although its identification is not formally confirmed yet for lack pathway28. of a standard, the mass spectra of diastereomers of polyols are The present study is based on the analysis of 5 independent usually identical with the derivatization methods used in the residues produced from the UV irradiation of H2O:CH3OH and present work. 13 H2O: CH3OH ice mixtures in relative proportions of 2:1 at 12 K. Typical residues were produced from H2O:CH3OH (2:1) and 13 The results obtained for these 5 residues are consistent with 12 H2O: CH3OH (2:1) ice mixtures in which totals of 1.23 mmol of 13 other residues produced from H2O:CH3OH ice mixtures in H2O and 0.61 mmol of CH3OH/ CH3OH were co-deposited at relative proportions 2:1 and 5:1 that were originally analyzed for rates of about 1.7 µmol min−1, while being simultaneously the presence of other sugar derivatives. The 2:1 ratio between irradiated for 17–19 h with photon doses of 0.35–0.39 photons −1 H2O and CH3OH ices corresponds to the upper limit of the molecule . The deoxysugar derivatives, as well as ribose for 29,30 fi 12 13 [H2O]/[CH3OH] ratio observed in cold interstellar clouds .In comparison, identi ed in all regular (i.e., mostly C) and C- two of the 5 experiments prepared for the present study, labeled residues are summarized in Table 1. Note that the methanol was isotopically labeled with 13C in order to verify that abundances given for 1,2-propanediol and 1,3-propanediol are the compounds detected in the residues were not due to lower limits, because these compounds are very volatile and a 2 NATURE COMMUNICATIONS | (2018) 9:5276 | https://doi.org/10.1038/s41467-018-07693-x | www.nature.com/naturecommunications NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-018-07693-x ARTICLE 120 ab81 100 195 Peak @ 61.22 min 2-Deoxyribose (12C Sample) 2-Deoxyxylose? 80 2000 L 60 D L 40 D 309 20 212 239 Relative intensity Relative 0 50 75 100 125 150 175 200 225 250 275 300 325 350 1500 12 C Sample 120 86 But/TFA 100 Peak @ 61.16 min 13 SIM 195 Da 80 ( C Sample) 1000 60 200 Intensity D L 40 314 L D 20 217 243 13 intensity Relative 0 C Sample 50 75 100 125 150 175 200 225 250 275 300 325 350 500 But/TFA 120 SIM 200 Da 81 100 2-Deoxyribose standard HO 80 195 O 0 60 OH 40 OH 55 56 57 58 59 60 61 62 20 212 239 309 Relative intensity Relative 0 Retention time (min) 50 75 100 125 150 175 200 225 250 275 300 325 350 m/z (Da) Fig.
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