Research ArticleBIOCHEMISTRY

One-pot synthesis of amino acid precursors with insoluble organic matter in planetesimals with aqueous activity

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Science Advances  17 Mar 2017:
Vol. 3, no. 3, e1602093
DOI: 10.1126/sciadv.1602093
  • Fig. 1 UPLC/QToF-MS chromatograms.

    Representative UPLC/QToF-MS chromatograms for the 6 M HCl acid-hydrolyzed (total) reaction product solution from the hydrothermal experiment with ammonia, formaldehyde, and glycolaldehyde heated at 150°C for 72 hours, the control blank sample, and the amino acid standard solution. Chromatograms show derivatized positive ionization m/z values of (A) 395.0913, 409.1069, 367.0964, 381.112, and 337.0858, (B) 351.1015 (C3 amino acids), and (C) 365.1171 (C4 amino acids), respectively. Each subplot is scaled against the highest peak within the section, and thus, the peak sizes are proportional between the samples. The peak numbers correspond to the amino acids listed in Table 1. arb. units, arbitrary units.

  • Fig. 2 Amino acid yields (concentrations in micromolar) in the reaction products after acid hydrolysis.

    The yields without acid hydrolysis are also shown for the 150°C product. To demonstrate reproducibility and errors, the results of duplicate hydrothermal experiments for 150°C are shown, and duplicate analytical runs of the same sample are also shown for 200°C.

  • Fig. 3 Amino acid abundances relative to glycine (acid-hydrolyzed) on a molar basis.

    Experimental products are compared with those extracted from (A) CM, CI, and CR carbonaceous chondrites and (B) CO3 and CV3 carbonaceous chondrites and type 3 ordinary chondrites (OC). β-ABA and α-AIB were only analyzed for the 150°C sample with the UPLC/QToF-MS method. For the 150°C product, the average of three experiments with 1σ error is shown. The Murchison meteorite data are the average of seven analyses (2932, 3739) with maximum and minimum values. The Orgueil meteorite data are the average of four analyses (3032, 38) with maximum and minimum values. CR1 data are the average of two analyses of GRO 95577 (30, 33) with maximum and minimum values. CR2 data are the average of eight analyses for four meteorites [Renazzo (31); EET 92042 (30, 33); GRA 95229 (33, 52); LAP 02342 (41)] with maximum and minimum values. CR3 data are from the QUE 99177 meteorite (30). CO3 data are the average of five meteorites [MIL 05013, DOM 08006, and ALHA77307 (CO3.0) (24); Colony (CO3.0) and Ornans (CO3.4) (25)] with maximum and minimum values. CV3 data are the average of six analyses for five meteorites [Allende (31); Allende, ALH 84028, LAP 02206, LAR 06317, and GRA 06101 (24)] with maximum and minimum values. Type 3 ordinary chondrite (OC3) data are the average of two meteorites [Bishunpur (LL3.15) and Chainpur (LL3.4) (25)] with maximum and minimum values.

  • Table 1 Amino acid abundance.

    Summary of the average amino acid abundance (micromolar) of the blank-corrected 6 M HCl acid-hydrolyzed reaction product solution from the hydrothermal experiment containing ammonia, formaldehyde, and glycolaldehyde heated at each temperature for 72 hours and analyzed by HPLC and UPLC-FD/QToF-MS. Quantification of the amino acids included background-level corrections using a control sample treated under the same experimental conditions without the presence of ammonia. The associated errors are SDs. The amino acid solutions were derivatized by ο-phthaldialdehyde (OPA)/N-acetyl-l-cysteine (NAC) derivatization (15 min for UPLC/QToF-MS and in-line for HPLC) and identified by comparison to the retention time of the amino acid standard run on the same day. The abundance (micromolar) of each amino acid was acquired by the peak area integration of the corresponding representative mass/charge ratio (m/z). 2nd, second run of the hydrothermal experiments; 3rd, third run of the hydrothermal experiments; free, amino acid analyses conducted without acid hydrolysis. Enantiomers could not be separated under the present chromatographic conditions for β-AIB and α-ABA. Asp, aspartic acid; Glu, glutamic acid; Ser, serine; Thr, threonine; Gly, glycine; Ala, alanine; Iva, isovaline; Val, valine; n.d., not detected.

    Peak no.Amino acidConcentration in micromolar
    HPLCUPLC/QToF-MS
    90°C150°C150°C 2nd150°C free150°C 2nd (free)200°C250°C150°C 3rd
    1d-Aspn.d.n.d.n.d.n.d.n.d.n.d.n.d.<3.4
    2l-Asp2.6 ± 0.3
    3l-Glu582433n.d.n.d.8–1412.39 ± 3.4
    4d-Glu11.8 ± 0.6
    5d-Sern.d.n.d.n.d.n.d.n.d.n.d.n.d.2.5 ± 0.3
    6l-Ser<0.1
    7d-Thrn.d.n.d.n.d.n.d.n.d.n.d.n.d.<0.1
    8l-Thr<0.1
    9Gly2493312783122272–30853.0344.1 ± 11
    10β-Ala199171187403038–42n.d.218.9 ± 6.3
    11d-Ala495479534247182687–759n.d.635.8 ± 13
    12l-Ala444.8 ± 11.6
    13γ-ABA163148n.d.2132–143133.353.4 ± 9.9
    14d,l-β-AIB1969n.d.n.d.n.d.n.d.<0.1
    15d-β-ABA13.1 ± 0.3
    16l-β-ABA13.4 ± 0
    17α-AIB3.9 ± 0.1
    18d,l-α-ABA7810053n.d.n.d.140–191n.d.38.2 ± 3.2
    19d-Iva<0.1
    20l-Iva<0.1
    21l-Valn.d.n.d.n.d.n.d.n.d.35–64n.d.<10.9
    22d-Val<1.0
    Total1115114111423192351313–15211991792

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/3/e1602093/DC1

    fig. S1. Experimental and analytical scheme.

    fig. S2. Mobile phase gradient for the amino acid analyses.

    fig. S3. HPLC chromatograms of amino acids in the standard solution and the reaction products from the hydrothermal experiments.

    fig. S4. The 0- to 40-min region of the UPLC-FD chromatograms for the 6 M HCl acid-hydrolyzed reaction product solution from the hydrothermal experiment containing ammonia, formaldehyde, and glycolaldehyde heated at 150°C for 72 hours, the control blank sample, and the amino acid standard solution, measured at NASA JSC.

    fig. S5. Mass spectra of the OPA/NAC-derivatized amino acids with an m/z of 337.0858 (corresponds to glycine), 351.1015 (alanine), 365.1171 (C4 amino acids; for example, AIB), 367.0964 (serine), 379.1328 (C5 amino acids; for example, valine), 381.112 (threonine), 393.1484 (C6 amino acids; for example, leucine), 395.0913 (aspartic acid), and 409.1069 (glutamic acid).

    table S1. Wako Amino Acids Mixture Standard Solution (0.1 M HCl).

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. Experimental and analytical scheme.
    • fig. S2. Mobile phase gradient for the amino acid analyses.
    • fig. S3. HPLC chromatograms of amino acids in the standard solution and the reaction products from the hydrothermal experiments.
    • fig. S4. The 0- to 40-min region of the UPLC-FD chromatograms for the 6 M HCl acid-hydrolyzed reaction product solution from the hydrothermal experiment containing ammonia, formaldehyde, and glycolaldehyde heated at 150°C for 72 hours, the control blank sample, and the amino acid standard solution, measured at NASA JSC.
    • fig. S5. Mass spectra of the OPA/NAC-derivatized amino acids with an m/z of 337.0858 (corresponds to glycine), 351.1015 (alanine), 365.1171 (C4 amino acids; for example, AIB), 367.0964 (serine), 379.1328 (C5 amino acids; for example, valine), 381.112 (threonine), 393.1484 (C6 amino acids; for example, leucine), 395.0913 (aspartic acid), and 409.1069 (glutamic acid).
    • table S1. Wako Amino Acids Mixture Standard Solution (0.1 M HCl).

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