Stability of pyruvic acid clusters upon slow electron attachment

Pysanenko, Andriy; Grygoryeva, Kateryna; Kočišek, Jaroslav; P, Ragesh Kumar T; Fedor, Juraj; Ončák, Milan; Fárnı́k, Michal

doi:10.1039/d0cp06464e

Cited by 3 publications

(3 citation statements)

References 49 publications

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“…Pyruvic acid (PA), [CH 3 COCOOH], the simplest form of α-keto acids, has gained considerable interest as a model system in the last few decades because of its variable physical and structural properties in various phases. ,− Previous studies reported the monomeric structure and aggregated structures of PA in liquid, condensed, and gas phases. ,− In an IR/Raman spectroscopy study in 1981, a cyclic intermolecular hydrogen-bonded dimer structure with two CO groups in a trans configuration was observed in the liquid state . Note that shortly before in 1977, a nearly similar structure was characterized in the crystal form at ∼263 K by X-ray diffraction where COs are tilted by 3.5° compared to the trans configuration as reported in the liquid state .…”

Section: Introductionmentioning

confidence: 99%

Structural Characterization of Pyruvic Acid Dimers Formed inside Helium Nanodroplets by Infrared Spectroscopy and Ab Initio Study

Chakraborty,

Henkel,

Schwaab

et al. 2024

J. Phys. Chem. A

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The structural arrangements of α-keto acid complexes hold significant interest across various fields of chemistry such as enzyme modeling, drug design, or polymer blending. Herein, we report mass-selective infrared (IR) spectra of pyruvic acid monomers and dimers in the range 1720−1820 cm −1 recorded in helium nanodroplets at 0.37 K. The monomer features IR bands at 1807.1 and 1734.5 cm −1 , which are assigned to the carboxylic and ketonic C�O stretching vibrations, respectively. Furthermore, the pyruvic acid dimers generated inside the helium nanodroplets are characterized by carboxylic and ketonic C�O stretch vibrations appearing at 1799.2 and 1737.0 cm −1 , respectively. This frequency shift of ±7 cm −1 for both C�O stretching bands from the monomer to the dimer demonstrates that the structural motif of the monomer is maintained upon dimer aggregation in helium nanodroplets. The structural assignments were supported by a comparison of the MP2/aug-cc-pVDZ-predicted harmonic vibrational spectra at the C�O stretching region with the experiments. The global minimum monomer structure with an intramolecular hydrogen bond and its dimer stabilized by both inter-and intramolecular hydrogen bonding interactions reproduce the experimental spectra from the monomer and dimer. This assigned dimer structure lies ca.11 kJ/mol above the corresponding global minimum and is favored in helium nanodroplets due to the long-range realignment of molecules via dipole−dipole interaction, followed by shortrange stabilization upon intermolecular hydrogen bond formation. The barrier for reconfiguration of the precooled monomer conformer leading to the formation of the most stable dimer structure is around 58 kJ/mol, which is infeasible at 0.37 K.

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Section: Introductionmentioning

confidence: 99%

Structural Characterization of Pyruvic Acid Dimers Formed inside Helium Nanodroplets by Infrared Spectroscopy and Ab Initio Study

Chakraborty,

Henkel,

Schwaab

et al. 2024

J. Phys. Chem. A

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“…20 The same research group later investigated the fragmentation pathways of electron attachment to pyruvic acid clusters. 21 Despite the extensive studies, the adiabatic electron affinity (EA) of this important molecule has not been reported. Here, we have measured the kinetics for gas-phase electron attachment to PA and detachment from PA − in a flowing afterglow from 300 to 515 K and derive the EA from that data.…”

Section: ■ Introductionmentioning

confidence: 99%

“…It was recently reported that PA can accept an excess electron to form the thermodynamically stable PA – anion: Zawadzki et al observed PA – from low-energy electron attachment to gas-phase PA, as well as a number of anion fragments . The same research group later investigated the fragmentation pathways of electron attachment to pyruvic acid clusters . Despite the extensive studies, the adiabatic electron affinity (EA) of this important molecule has not been reported.…”

Section: Introductionmentioning

confidence: 99%

Thermal Electron Attachment to Pyruvic Acid, Thermal Detachment from the Parent Anion, and the Electron Affinity of Pyruvic Acid

et al. 2022

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The kinetics of electron attachment to pyruvic acid (CH 3 COCOOH) and thermal detachment from the resulting parent anion were measured from 300−515 K using a flowing afterglow�Langmuir probe apparatus. An adiabatic electron affinity (EA) for pyruvic acid was derived, 0.84 ± 0.02 eV. Electron attachment rate constants to pyruvic acid of 2.1 × 10 −8 and 1.2 × 10 −8 were measured at 300 and 400 K, respectively. Rate constants at higher temperatures are less well-defined due to possible contributions from attachment to zymonic open ketone, an endemic impurity in pyruvic acid. Similarly, unimolecular detachment rates are complicated by secondary proton transfer reaction of the pyruvic acid anion with pyruvic acid to yield an 87 Da anion. The possible contributions from these chemistries are considered, and in all cases the equilibrium constant between attachment and detachment remains well-defined, allowing for determination of the EA.

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Electron scattering processes: fundamentals, challenges, advances, and opportunities

Ptasińska

Varella²,

Khakoo³

et al. 2022

Eur. Phys. J. D

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Much effort has been devoted to describing qualitatively and quantitatively electron scattering processes due to their ever-increasing importance in many industrial and medical applications. We present achievements made in the last years, focusing on some of the advancements and recent progress in the field. Particular reference is made on concrete case studies to probe the level of accord in cross-section data obtained from experiments and theory, as well as on selected instrumentation developments to probe dynamics of dissociative processes induced by electron impact. We stress that the purpose of this colloquium paper is not to be a comprehensive review but rather to provide a snapshot of different research topics in electron scattering by pointing out certain challenges and, therefore, indicating opportunities to facilitate further experimental and theoretical work.

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Stability of pyruvic acid clusters upon slow electron attachment

Abstract: Pyruvic acid represents a key molecule in prebiotic chemistry and it has recently been proposed to be synthesized on interstellar ices. In order to probe the stability of pyruvic acid...

Cited by 3 publications

References 49 publications

Structural Characterization of Pyruvic Acid Dimers Formed inside Helium Nanodroplets by Infrared Spectroscopy and Ab Initio Study

Structural Characterization of Pyruvic Acid Dimers Formed inside Helium Nanodroplets by Infrared Spectroscopy and Ab Initio Study

Thermal Electron Attachment to Pyruvic Acid, Thermal Detachment from the Parent Anion, and the Electron Affinity of Pyruvic Acid

Electron scattering processes: fundamentals, challenges, advances, and opportunities

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