Interstellar Formation of Biorelevant Pyruvic Acid (CH3COCOOH)

Kleimeier, N. Fabian; Eckhardt, André K.; Schreiner, Peter R.; Kaiser, Ralf I.

doi:10.1016/j.chempr.2020.10.003

Cited by 32 publications

(41 citation statements)

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“…Acetaldehyde and vinyl alcohol were detected in ices containing carbon monoxide and methane (CH 4 ) [14] or carbon dioxide (CO 2 ) and ethylene (C 2 H 4 ), [15] and after UV photolysis and proton irradiation of ices containing acetylene (C 2 H 2 ) and water (H 2 O) [16] . Furthermore, pyruvic acid (CH 3 COCOOH) and 2‐hydroxyacrylic acid (CH 2 =COHCOOH) have been probed in processed acetaldehyde−carbon dioxide ices [17] . Other potential candidates for enols in the ISM include 1,1‐ethenediol (CH 2 =C(OH) 2 ) which could form from hydrogenation of ketene, [18] and 1‐aminoethenol (CH 2 =C(OH)NH 2 ), which could form from ketene and ammonia [19] .…”

Section: Introductionmentioning

confidence: 99%

“…[16] Furthermore, pyruvic acid (CH 3 COCOOH) and 2-hydroxyacrylic acid (CH 2 =COHCOOH) have been probed in processed acetaldehydeÀ carbon dioxide ices. [17] Other potential candidates for enols in the ISM include 1,1-ethenediol (CH 2 =C(OH) 2 ) which could form from hydrogenation of ketene, [18] and 1-aminoethenol (CH 2 =C(OH)NH 2 ), which could form from ketene and ammonia. [19] Their tautomers, acetic acid and acetamide, have both been detected in Sgr B2(N) [20][21] and the precursors for the formation of 1,1-ethenediol and 1-aminoethenol are readily available in this region.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Interstellar Enolization‐Acetaldehyde (CH₃CHO) and Vinyl Alcohol (H₂CCH(OH)) as a Case Study

Kleimeier

Kaiser

2021

ChemPhysChem

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Owing to the unique conditions in cold molecular clouds, enols—the thermodynamically less stable tautomers of aldehydes and ketones—do not undergo tautomerization to their more stable tautomers in the gas phase because they cannot overcome tautomerization barriers at the low temperatures. Laboratory studies of interstellar analog ices have demonstrated the formation of several keto–enol tautomer pairs in astrochemically relevant ice mixtures over the last years. However, so far only one of them, acetaldehyde−vinyl alcohol, has been detected in deep space. Due to their reactivity with electrophiles, enols can play a crucial role in our understanding of the molecular complexity in the interstellar medium and in comets and meteorites. To study the enolization of aldehydes in interstellar ices by interaction with galactic cosmic rays (GCRs), we irradiated acetaldehyde ices with energetic electrons as proxies of secondary electrons generated in the track of GCRs while penetrating interstellar ices. The results indicate that GCRs can induce enolization of acetaldehyde and that intra‐ as well as intermolecular processes are relevant. Therefore, enols should be ubiquitous in the interstellar medium and could be searched for using radio telescopes such as ALMA. Once enols are detected and abundances are established, they can serve as tracers for the non‐equilibrium chemistry in interstellar ices thus eventually constraining fundamental reaction mechanisms deep inside interstellar ices.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Interstellar Enolization‐Acetaldehyde (CH₃CHO) and Vinyl Alcohol (H₂CCH(OH)) as a Case Study

Kleimeier

Kaiser

2021

ChemPhysChem

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“…1−4 Vinyl alcohol [H 2 C=C(OH)H], propenol [CH 3 C(H)=C(OH)H], and 2-hydroxyacrylic acid [CH 2 =C(OH)COOH]the enol of the biologically important pyruvic acid [CH 3 COCOOH] have emerged as tracers of a galactic cosmic ray-mediated nonequilibrium chemistry in interstellar analogue ices exploiting isomer-selective photoionization (PI) coupled with reflectron time-of-flight mass spectrometry (ReTOF-MS) (Figure S1). 8,9 Despite the identification of enols as critical intermediates in hydrocarbon oxidation processes 1−3 and their fundamental role in molecular mass growth processes of complex organic molecules on icy interstellar grains, 8,9 enol transients have only been hypothesized in the decomposition of energetic materials such as of 1,3,5-trinitro-1,3,5-triazinane (RDX; 1; Scheme 1). Behrens and co-workers predicted the existence of both the keto (C 3 H 3 N 3 O; 2a) and enol (C 3 H 2 N 3 OH; 2b) tautomers of oxy-s-triazine (OST) in the thermal decomposition of RDX (1) (Scheme 1).…”

Section: C-(h)=c(oh)h] and Butenol [Ch 3 Ch 2 C(h)=c(oh)h]mentioning

confidence: 99%

“…This approach eventually elucidates which isomer(s) is(are) formed. 8,9,48 The computed structures of most possible cyclic and acyclic isomers of oxy-striazine and 1,3,5-triazine are depicted in Figure 1 S3). Further, ReTOF-MS calibration experiments revealed that the electric field of the extraction plate of the ion optics lowers the ionization energies by 0.03 eV.…”

Section: C-(h)=c(oh)h] and Butenol [Ch 3 Ch 2 C(h)=c(oh)h]mentioning

confidence: 99%

Identification of Elusive Keto and Enol Intermediates in the Photolysis of 1,3,5-Trinitro-1,3,5-Triazinane

Singh

Vuppuluri

Sun

et al. 2021

J. Phys. Chem. Lett.

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Enols have emerged as critical reactive intermediates in combustion processes and in fundamental molecular mass growth processes in the interstellar medium, but the elementary reaction pathways to enols in extreme environments, such as during the decomposition of molecular energetic materials, are still elusive. Here, we report on the original identification of the enol and keto isomers of oxy-s-triazine, as well as its deoxygenated derivative 1,3,5-triazine, formed in the photodecomposition processes of 1,3,5-trinitro-1,3,5-triazinane (RDX)a molecular energetic material. The identification was facilitated by exploiting isomer-selective tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) in conjunction with quantum chemical calculations. The present study reports the first experimental evidence of an enol intermediate in the dissociation domain of a nitramine-based energetic material. Our investigations suggest that the enols like 1,3,5-triazine-2-ol could be the source of hydroxyl radicals, and their inclusion in the theoretical models is important to understand the unprecedented chemistry of explosive materials.

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“…Examples are compounds such as acetic acid already observed in extraterrestrial atmospheres in the gas phase [10]. Recently, Kleimeier et al [11] have designated pyruvic acid to be a detectable species in extraterrestrial sources. They have studied its formation by barrierless recombination of hydroxycarbonyl (HOCO) and acetyl (CH 3 CO) radicals in ices of acetaldehyde (CH 3 CHO) and carbon dioxide (CO 2 ) modeling interstellar conditions driven by cosmic rays.…”

Section: Introductionmentioning

confidence: 99%

Large Amplitude Motions of Pyruvic Acid (CH3-CO-COOH)

Senent

Dalbouha

2021

Molecules

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Torsional and rotational spectroscopic properties of pyruvic acid are determined using highly correlated ab initio methods and combining two different theoretical approaches: Second order perturbation theory and a variational procedure in three-dimensions. Four equilibrium geometries of pyruvic acid, Tc, Tt, Ct, and CC, outcome from a search with CCSD(T)-F12. All of them can be classified in the Cs point group. The variational calculations are performed considering the three internal rotation modes responsible for the non-rigidity as independent coordinates. More than 50 torsional energy levels (including torsional subcomponents) are localized in the 406–986 cm−1 region and represent excitations of the ν24 (skeletal torsion) and the ν23 (methyl torsion) modes. The third independent variable, the OH torsion, interacts strongly with ν23. The A1/E splitting of the ground vibrational state has been evaluated to be 0.024 cm−1 as it was expected given the high of the methyl torsional barrier (338 cm−1). A very good agreement with respect to previous experimental data concerning fundamental frequencies (νCAL − νEXP ~ 1 cm−1), and rotational parameters (B0CAL − B0EXP < 5 MHz), is obtained.

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Interstellar Formation of Biorelevant Pyruvic Acid (CH3COCOOH)

Cited by 32 publications

References 62 publications

Interstellar Enolization‐Acetaldehyde (CH₃CHO) and Vinyl Alcohol (H₂CCH(OH)) as a Case Study

Interstellar Enolization‐Acetaldehyde (CH₃CHO) and Vinyl Alcohol (H₂CCH(OH)) as a Case Study

Identification of Elusive Keto and Enol Intermediates in the Photolysis of 1,3,5-Trinitro-1,3,5-Triazinane

Large Amplitude Motions of Pyruvic Acid (CH3-CO-COOH)

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Interstellar Formation of Biorelevant Pyruvic Acid (CH3COCOOH)

Cited by 32 publications

References 62 publications

Interstellar Enolization‐Acetaldehyde (CH3CHO) and Vinyl Alcohol (H2CCH(OH)) as a Case Study

Interstellar Enolization‐Acetaldehyde (CH3CHO) and Vinyl Alcohol (H2CCH(OH)) as a Case Study

Identification of Elusive Keto and Enol Intermediates in the Photolysis of 1,3,5-Trinitro-1,3,5-Triazinane

Large Amplitude Motions of Pyruvic Acid (CH3-CO-COOH)

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Interstellar Enolization‐Acetaldehyde (CH₃CHO) and Vinyl Alcohol (H₂CCH(OH)) as a Case Study

Interstellar Enolization‐Acetaldehyde (CH₃CHO) and Vinyl Alcohol (H₂CCH(OH)) as a Case Study