46th Lunar and Planetary Science Conference (2015) 1444.pdf COMPLEX NITROGEN HETEROCYCLES IN AQUEOUS CYANIDE AND FORMALDEHYDE REACTIONS: IMPLICATIONS FOR METEORITIC AND PREBIOTIC CHEMISTRY. M.P. Callahan1 and H.J. Cleaves II2,3,4,5, 1NASA Goddard Space Flight Center, Greenbelt, MD 20771, 2Earth-Life Science Institute, Tokyo Institute of Technology, Tokyo, 152-8550, Japan, 3Institute for Advanced Study, Princeton, NJ 08540, 4Blue Marble Space Institute for Science, Washington, DC 20008, 5Center for Chemical Evolution, Georgia Institute of Technology, Atlanta, GA 30332. Email: [email protected] Introduction: Carbonaceous chondrites contain a plethora of indigenous organic compounds, including those of biological significance. There is strong evidence that purine nucleobases and their structural analogs detected in carbonaceous chondrites were formed from hydrogen cyanide (HCN) chemistry . Additionally, formaldehyde (H2CO) appears to be a major contributor to carbonaceous chondrite organic material based on the detection of numerous polyhydroxylated compounds (e.g., sugars, sugar alcohols, and sugar acids)  and similarities between the insoluble organic matter (IOM) and H2CO polymers . The presence of both HCN and H2CO in carbonaceous chondrites is intriguing because previous studies have suggested that H2CO interferes with HCN oligomerization (the so-called “Miller Paradox”) . Here, we investigated whether the synthesis of nitrogen heterocycles (particularly those found in carbonaceous chondrites) is robust in aqueous reactions containing various concentrations of ammonium cyanide (NH4CN) and H2CO. Notably, Schwartz and coworkers first examined this type of chemistry in the 1980s; however, their experiments were conducted using a very limited range of conditions [5,6]. Thus, we prepared a large set of laboratory reactions (Fig. 1) and analyzed this set without additional sample preparation using a direct analysis in real-time (DART) ion source coupled to a high resolution, accurate mass linear ion trap-orbitrap hybrid mass spectrometer for rapid qualitative analyses of nitrogen heterocycles and other low molecular weight organic compounds. Analytical techniques and samples: Ammonium cyanide (0, 0.001, 0.01, 0.1, 1.0, 2.0, and 5.0 M) and formaldehyde (0, 0.01, 0.05, 0.1, 0.2, 0.5, 1.0, 2.0, and 5.0 M) solutions were prepared, transferred to ampoules, and flame-sealed with minimal headspace under air. Samples were stored in the dark at room temperature for >6 months. The ampoules were opened and the liquid portion (5 µL x 2) was individually spotted on a stainless steel mesh for sample analysis. A Thermo Scientific LTQ Orbitrap XL hybrid mass spectrometer equipped with an IonSense DART ion source was used for analyses (typical mass error <1.0 ppm). Molecular formulae were calculated from observed masses assuming the following possible range of elemental compositions of 14N 0-10, 16O 0-15, 12C 0-30, and 1H 0-60. Molecular formulae corresponding to known nitrogen heterocycles in carbonaceous chondrites were closely monitored in our laboratory samples. Fig 1: Photograph of aqueous reactions containing various concentrations of ammonium cyanide (NH4CN) and formaldehyde (H2CO). At sufficiently high NH4CN concentrations (>0.1 M), the solution is black and a black precipitate forms. The addition of H2CO alters the appearance and pH dramatically. Results and Discussion: DART mass spectrometry: DART mass spectra of solutions containing 2 M NH4CN with various H2CO concentrations are displayed in Fig. 2. The mass spectra are complex although this is not readily apparent due to normalization of the relative abundance scale (and the figure size). Mass peaks at m/z 136.0614 (C5H6N5) and m/z 166.0719 (C6H8N5O) were identified as adenine and 8-hydroxymethyladenine, respectively, based on accurate mass and comparison of its product ion spectra with reference standards. The mass peak at m/z 196.0626 (C7H10N5O2) appears to be dihydroxymethyl-substituted adenine; however, we are conducting further measurements to confirm its exact structure. In addition, we measured mass peaks that would correspond to substituted purines in this concentration series (as well as throughout the entire sample set). Additional compounds were identified based on their elemental composition in conjunction with prior reports of these compounds synthesized in similar 46th Lunar and Planetary Science Conference (2015) chemical reactions . For example, guanidine and its non-covalent dimer (m/z 60.0553 and 119.1036) and urea (m/z 61.0393) were measured in the three samples shown in Fig. 2. Hexamethylenetetramine (HMT, m/z 141.1133), a condensation product of H2CO and NH3, was also measured in multiple samples usually where [H2CO] > [NH4CN]. 1444.pdf did not detect 8-hydroxymethyladenine in carbonaceous chondrites during our previous studies . It is conceivable that 8-hydroxymethyladenine is transformed to adenine during our meteorite work-up (using formic acid) or prolonged periods of aqueous alteration on the meteorite parent body; however further investigations are needed. Fig 2: DART mass spectra of solutions with 2 M NH4CN and different concentrations of H2CO. Mass spectra are normalized to the most intense peak in this set. Blue boxes highlight mass peaks corresponding to assigned nitrogen heterocycles. DART-MS can be used to rapidly screen for nitrogen heterocycles in a large sample set. We generated 3D surface plots using [NH4CN], [H2CO], and mass spectral signal intensity in order to evaluate the production of nitrogen heterocycles under a wide range of conditions. For example, 3D surface plots for adenine and 8-hydroxymethyladenine are shown in Fig. 3. It appears that the synthesis of 8-hydroxymethyladenine is favored over adenine in the presence of H2CO, which is consistent with previous observations by Schwartz and Bakker . Finally, it is worth mentioning that we have highlighted only a few interesting observations from our very large dataset due to space limitations here. Implications for Meteoritic and Prebiotic Chemistry: We conclude that relatively complex nitrogen heterocycles can be synthesized from very simple aqueous reactions, which may have occurred on meteorite parent bodies and early Earth. A significant finding of our work is that H2CO does not entirely inhibit HCN (oligomerization) chemistry, and in fact enhances the yield of nitrogen heterocycles. Furthermore, this combination opens novel reaction pathways which allow for significant diversification of the reaction products (for example, we analyzed these reactions for amino acids which will be published in a separate study). Other low molecular weight compounds such as guanidine and urea are easily synthesized in these reactions and may be important for prebiotic chemistry because they can react with cyanoacetaldehyde to eventually produce uracil and cytosine . Finally, we note that we Fig 3: 3D surface plots for selected nitrogen heterocycles. 8-hydroxymethyladenine can be synthesized under a wider range of concentrations compared to adenine, which suggests a more robust synthesis in aqueous cyanide/formaldehyde reactions. References:  Callahan M. P. et al. (2011) PNAS, 108, 13995-13998.  Cooper G. et al. (2001) Nature, 414, 879-883.  Cody G. D. et al. (2011) PNAS, 108, 1917119176.  Schlesinger G. & Miller S. L. (1973) J. Am. Chem. Soc., 95, 3729-3735.  Schwartz A. W. & Goverde M. (1982) J. Mol. Evol., 18, 351-353.  Schwartz A. W. & Bakker C. G. (1989) Science, 245, 1102-1104.  RuizBermejo M. et al. (2013) Life, 3, 421-448.  Robertson M. P. et al. (1996) J. Mol. Evol., 43, 543-550.
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