Investigation of the rotamers of 3-furfural by microwave spectroscopy

Gregory, Carolyn; Wijngaarden, Jennifer van

doi:10.1016/j.jms.2020.111374

Cited by 2 publications

(4 citation statements)

References 24 publications

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“…An example is shown in Figure 8a, where the rotational spectra have been obtained with three different polarization powers. These consist of several rotational transitions, also highlighting not well-resolved hyperfine structures due, as already mentioned, to the presence of three 14 N nuclei. Even if not entirely resolved, the hyperfine structures helped us to confirm that the assigned lines belong to creatinine species.…”

Section: The Gas Phasementioning

confidence: 74%

“…The microwave spectroscopic techniques usually employed in the characterization of biomolecular building blocks exploit an adiabatic expansion of the vaporized sample together with a noble carrier gas. Consequently, conformational relaxation can occur through collisions when the interconversion barrier is low enough, [14,15] with non-proteinogenic amino acids offering a significant example. [16] This explains why an exhaustive search of lowenergy minima and an accurate evaluation of their interconversion barriers needs to be carried out to support the experimental work whenever no previous reliable results (as in the present case) are available.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…In the latter respect, rotational spectroscopy plays a central role in determining accurate molecular structures [6][7][8][9] for all low-energy tautomers, isomers, and conformers separated by barriers sufficiently high to avoid interconversion. [10][11][12][13][14][15][16] However, the interpretation of spectroscopic data for large flexible systems is a daunting task because of the concomitant presence of different species and several strongly interconnected parameters. In such a situation, an experiment-theory approach is unavoidable, with the support of QC calculations being fundamental for guiding experiments and interpreting the acquired spectra, provided that accurate state-of-the-art methodologies are employed.…”

Section: Introductionmentioning

confidence: 99%

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Looking for the Elusive Imine Tautomer of Creatinine: Different States of Aggregation Studied by Quantum Chemistry and Molecular Spectroscopy

et al. 2021

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New spectroscopic experiments and state-of-the-art quantumchemical computations of creatinine in different aggregation states unequivocally unveiled a significant tuning of tautomeric equilibrium by the environment: from the exclusive presence of the amine tautomer in the solid state and aqueous solution to a mixture of amine and imine tautomers in the gas phase. Quantum-chemical calculations predict the amine species as the most stable tautomer by about 30 kJ mol À 1 in condensed phases. On the contrary, moving to the isolated forms, both Z and E imine isomers become more stable by about 7 kJ mol À 1 .Since the imine isomers and one amine tautomer are separated by significant energy barriers, all of them should be present in the gas phase. This prediction has indeed been confirmed by high-resolution rotational spectroscopy, which provides the first experimental characterization of the elusive imine tautomer. The interpretation of the complicated hyperfine structure of the rotational spectrum, originated by three 14 N nuclei, makes it possible to use the spectral signatures as a sort of fingerprint for each individual tautomer in the complex sample.

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Section: The Gas Phasementioning

confidence: 74%

Section: Experimental Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Looking for the Elusive Imine Tautomer of Creatinine: Different States of Aggregation Studied by Quantum Chemistry and Molecular Spectroscopy

et al. 2021

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“…In these studies, only the strong Q-branches and the P and R patterns were observed and no rovibrational analysis could be undertaken due to the limited spectral resolution. High-resolution analyses of FF have been performed in the microwave (MW) domain for 2-FF [ 10 ] and 3-FF [ 11 ] by means of jet-cooled Fourier transform microwave (FTMW) spectroscopy. Motiyenko et al [ 10 ] extended their analysis in the millimeter-wave region at room temperature with the assignment and the analysis of the ground state (GS) spectrum for both trans and cis conformers and of the lowest energy torsional state for the most stable trans -2-FF only.…”

Section: Introductionmentioning

confidence: 99%

Rovibrational Spectroscopy of Trans and Cis Conformers of 2-Furfural from High-Resolution Fourier Transform and QCL Infrared Measurements

Asselin

Claus

et al. 2023

Molecules

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The ortho-isomer 2-furfural (2-FF), which is a primary atmospheric pollutant produced from biomass combustion, is also involved in oxidation processes leading to the formation of secondary organic aerosols. Its contribution to radiative forcing remains poorly understood. Thus, monitoring 2-FF directly in the atmosphere or in atmospheric simulation chambers to characterize its reactivity is merited. The present study reports an extensive jet-cooled rovibrational study of trans and cis conformers of 2-FF in the mid-IR region using two complementary setups: a continuous supersonic jet coupled to a high-resolution Fourier transform spectrometer on the IR beamline of the SOLEIL synchrotron (JET-AILES), and a pulsed jet coupled to a mid-IR tunable quantum cascade laser spectrometer (SPIRALES). Firstly, jet-cooled spectra recorded at rotational temperatures ranging between 20 and 50 K were exploited to derive reliable excited-state molecular parameters of trans- and cis-2-FF vibrational bands in the fingerprint region. The parameters were obtained from global fits of 11,376 and 3355 lines distributed over eight and three vibrational states (including the ground state), respectively, with a root mean square of 12 MHz. In a second step, the middle resolution spectrum of 2-FF recorded at 298.15 K and available in the HITRAN database was reconstructed by extrapolating the data derived from our low-temperature high-resolution analyses to determine the cross sections of each vibrational band of both 2-FF conformers in the 700–1800 cm−1 region. Finally, we clearly demonstrated that the contribution of hot bands observed in the room temperature 2-FF spectrum, estimated between 40 and 63% of the fundamental band, must be imperatively introduced in our simulation to correctly reproduce the HITRAN vibrational cross sections of 2-FF with a deviation smaller than 10%.

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Investigation of the rotamers of 3-furfural by microwave spectroscopy

Cited by 2 publications

References 24 publications

Looking for the Elusive Imine Tautomer of Creatinine: Different States of Aggregation Studied by Quantum Chemistry and Molecular Spectroscopy

Looking for the Elusive Imine Tautomer of Creatinine: Different States of Aggregation Studied by Quantum Chemistry and Molecular Spectroscopy

Rovibrational Spectroscopy of Trans and Cis Conformers of 2-Furfural from High-Resolution Fourier Transform and QCL Infrared Measurements

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