NMR identification of hexamethylenetetramine and its precursor in Titan tholins: Implications for Titan prebiotic chemistry

He, Chao; Lin, Guangxin; Smith, Mark A.

doi:10.1016/j.icarus.2012.06.007

Cited by 24 publications

(18 citation statements)

References 56 publications

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“…The obtained results are also consistent with those recorded in previous studies on tholins produced on another experimental setup according to the spectrum appearance (He et al, 2012;Somogyi et al, 2005). This comparison emphasizes once again important differences between the soluble and the non-soluble fractions: not on the mass of the molecules as initially thought, but rather in the type of molecules present in each sample.…”

Section: Mass Spectrometry Analysessupporting

confidence: 91%

“…Additional analyses were performed on the soluble fraction of the tholins by mass spectrometry showing a polymeric structure (Bonnet et al, 2013;Gautier et al, 2016;Vuitton et al, 2010). First analyses with ultra-high resolution mass spectrometry also brought to light repetition patterns (CH 2 and HCN) in the tholins' soluble fraction (Anicich et al, 2006;He et al, 2012;Somogyi et al, 2005).…”

Section: Introductionmentioning

confidence: 99%

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Comparison of soluble and insoluble organic matter in analogues of Titan's aerosols

Maillard

Carrasco

Schmitz-Afonso

et al. 2018

Earth and Planetary Science Letters

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Titan, the biggest moon of Saturn, has a thick atmosphere which presents similarities with the one thought to be on Earth at its beginning. The study of Titan's photochemical haze is thus a precious tool in gaining knowledge of the primitive atmosphere of Earth. The chemistry occurring in Titan's atmosphere and the exact processes at act in the formation of the hazes remain largely unknown. The production of analogs samples on Earth has proved to be a useful tool to improve our knowledge of the aerosols formation on Titan. Such solid organic analogs samples, named tholins, were produced with the PAMPRE experiment (French acronym for Aerosols Microgravity Production by Reactive Plasma). PAMPRE tholins were found to be mostly insoluble, with only one-third of the bulk sample that can be dissolved in methanol. This partial solubility limited the previous studies in mass spectrometry, which were done only on the soluble fraction. The goal of the present study is to compare the two fractions of PAMPRE's tholins (insoluble and soluble) using a ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometer (FTICR) equipped with a laser desorption/ionization source. Using modified Van Krevelen diagrams, we compare the global distribution of the molecules within the samples according to their Hydrogen/Carbon ratio and Nitrogen/Carbon ratio. Major differences are observed in the molecular composition of the soluble and the insoluble fraction. The soluble fraction of tholins was previously identified as a set of polymers of average formula (C 2 H 3 N) n . In this work we observe that the insoluble fraction of tholins is comprised of a significantly different set of polymers with an average composition of (C 4 H 3 N 2 ) n .

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Section: Mass Spectrometry Analysessupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Comparison of soluble and insoluble organic matter in analogues of Titan's aerosols

Maillard

Carrasco

Schmitz-Afonso

et al. 2018

Earth and Planetary Science Letters

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“…A compound of interest we were particularly looking for in our sample was HMT (standard 35 13). HMT is a molecule detected in the final products of many astrophysical laboratory 36 experiments, especially the one simulating interstellar ice irradiations (Bernstein et al 1995 Another possibility would be that HMT is actually produced in the case of He et al (2012); 67 but with a mechanism specific to this experiment. Indeed He et al 2012 used an AC plasma, 68…”

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confidence: 99%

Development of HPLC-Orbitrap method for identification of N-bearing molecules in complex organic material relevant to planetary environments

Gautier

Schmitz-Afonso

Touboul

et al. 2016

Icarus

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International audienceAlthough the Cassini Spacecraft and the Huygens lander provided numerous information about Titan atmospheric chemistry and the formation of its aerosols, the exact composition of these aerosols still remains unknown. A fruitful proxy to investigate these aerosols is the use of laboratory experiments that allow producing and studying analogs of Titan aerosol, the so-called tholins. Even when produced in the laboratory, unveiling the exact composition of the aerosol remains problematic due to the high complexity of the material. Numerous advances have been recently made using high-resolution mass spectrometry (HRMS) (0020, 0027 and 0011) that allowed the separation of isobaric compounds and a robust identification of chemical species composing tholins regarding their molecular formulae. Nevertheless isomeric species cannot be resolved by a simple mass measurement. We propose here an analysis of tholins by high performance liquid chromatography (HPLC) coupled to HRMS to unveil this isomeric ambiguity for some of the major tholins compounds. By comparing chromatograms obtained when analyzing tholins and chemical standards, we strictly identified seven molecules in our tholins samples: melamine, cyanoguanidine, 6-methyl-1,3,5-triazine-2,4-diamine, 2,4,6-triaminopyrimidine, 3-amino-1,2,4-triazole, 3,5-Dimethyl-1,2,4-triazole and 2,4-diamino-1,3,5-triazine. Several molecules, including hexamethylenetriamine (HMT) were not present at detectable levels in our sample. The use for the first time of a coupled HPLC-HRMS technique applied to tholins study demonstrated the interest of such a technique compared to single high-resolution mass spectrometry for the study of tholins composition

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“…1 shows that the main ion at m/z 141 is C 6 H 13 N + 4 consistent with protonated HMT. The HMT structure has been confirmed by nuclear magnetic resonance (NMR) analysis (He et al 2012). Secondly, HMT chemical synthesis occurring in Titan's aerosols analogs is different from the one occurring in ice-irradiation experiments designed for simulating ISM or cometary environments.…”

Section: Introductionmentioning

confidence: 92%

Rotationally resolved IR spectroscopy of hexamethylenetetramine (HMT) C₆N₄H₁₂

Pirali

Boudon

Carrasco

et al. 2014

A&A

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Context. Hexamethylenetetramine (HMT) appears to be a potential constituent of several objects in space, including comets or Titan's atmosphere and, as an organic residue of ice irradiation in the laboratory, it may be present in the interstellar medium. Aims. We performed a laboratory study of rotationally resolved intense IR bands of HMT to provide accurate line positions and synthetic spectra to be used for potential astronomical detections. Methods. We used synchrotron-based high-resolution Fourier transform infrared spectroscopy to record the experimental data. A formalism and programs dedicated to the assignment, analysis, and simulation of absorption spectra of tetrahedral molecules were used to exploit the spectra. Results. Infrared spectra of gas phase HMT were recorded and accurate wavenumbers and molecular parameters for four intense bands located in the 1000-1500 cm −1 spectral range suitable for astronomical searches were derived.

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NMR identification of hexamethylenetetramine and its precursor in Titan tholins: Implications for Titan prebiotic chemistry

Cited by 24 publications

References 56 publications

Comparison of soluble and insoluble organic matter in analogues of Titan's aerosols

Comparison of soluble and insoluble organic matter in analogues of Titan's aerosols

Development of HPLC-Orbitrap method for identification of N-bearing molecules in complex organic material relevant to planetary environments

Rotationally resolved IR spectroscopy of hexamethylenetetramine (HMT) C₆N₄H₁₂

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NMR identification of hexamethylenetetramine and its precursor in Titan tholins: Implications for Titan prebiotic chemistry

Cited by 24 publications

References 56 publications

Comparison of soluble and insoluble organic matter in analogues of Titan's aerosols

Comparison of soluble and insoluble organic matter in analogues of Titan's aerosols

Development of HPLC-Orbitrap method for identification of N-bearing molecules in complex organic material relevant to planetary environments

Rotationally resolved IR spectroscopy of hexamethylenetetramine (HMT) C6N4H12

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Rotationally resolved IR spectroscopy of hexamethylenetetramine (HMT) C₆N₄H₁₂