Neutral loss of water and ammonia are often significant fragmentation channels upon collisional activation of protonated peptides. Here, we deploy infrared ion spectroscopy to investigate the dehydration reactions of protonated AlaSer, AlaThr, GlySer, GlyThr, PheSer, PheThr, ProSer, ProThr, AsnSer, and AsnThr, focusing on the question of the structure of the resulting [M + H – H 2 O] + fragment ion and the site from which H 2 O is expelled. In all cases, the second residue of the selected peptides contains a hydroxyl moiety, so that H 2 O loss can potentially occur from this side-chain, as an alternative to loss from the C-terminal free acid of the dipeptide. Infrared action spectra of the product ions along with quantum-chemical calculations unambiguously show that dehydration consistently produces fragment ions containing an oxazoline moiety. This contrasts with the common oxazolone structure that would result from dehydration at the C-terminus analogous to the common b/y dissociation forming regular b 2 -type sequence ions. The oxazoline product structure suggests a reaction mechanism involving water loss from the Ser/Thr side-chain with concomitant nucleophilic attack of the amide carbonyl oxygen at its β-carbon, forming an oxazoline ring. However, an extensive quantum-chemical investigation comparing the potential energy surfaces for three entirely different dehydration reaction pathways indicates that it is actually the backbone amide oxygen atom that leaves as the water molecule.

Conventional mechanical Fourier Transform Spectrometers (FTS) can simultaneously measure absorption and dispersion spectra of gas-phase samples. However, they usually need very long measurement times to achieve time-resolved spectra with a good spectral and temporal resolution. Here, we present a mid-infrared dual-comb-based FTS in an asymmetric configuration, providing broadband absorption and dispersion spectra with a spectral resolution of 5 GHz (0.18 nm at a wavelength of 3333 nm), a temporal resolution of 20 μs, a total wavelength coverage over 300 cm−1 and a total measurement time of ~70 s. We used the dual-comb spectrometer to monitor the reaction dynamics of methane and ethane in an electrical plasma discharge. We observed ethane/methane formation as a recombination reaction of hydrocarbon radicals in the discharge in various static and dynamic conditions. The results demonstrate a new analytical approach for measuring fast molecular absorption and dispersion changes and monitoring the fast dynamics of chemical reactions over a broad wavelength range, which can be interesting for chemical kinetic research, particularly for the combustion and plasma analysis community.

Conventional mechanical Fourier Transform Spectrometers (FTS) are able to simultaneously measure absorption and dispersion spectra of gas-phase samples. However, they usually need very long measurement times to achieve time-resolved spectra with a good spectral and temporal resolution. Here, we present a mid-infrared dual-comb-based FTS in an asymmetric configuration, providing broadband absorption and dispersion spectra with a spectral resolution of 5 GHz, a temporal resolution of 20 μs, and a total measurement time of a few minutes. We used the dual-comb spectrometer to monitor the reaction dynamics of methane and ethane in an electrical plasma discharge. We observed ethane/methane formation as a recombination reaction of hydrocarbon radicals in the discharge in various static and dynamic conditions. The results demonstrate a new analytical approach for measuring fast molecular absorption and dispersion changes and monitoring fast dynamics of chemical reactions, which can be interesting for chemical kinetic research and particularly for the combustion and plasma analysis community.

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An asymmetric time-resolved mid-infrared dual-comb spectrometer with 5 GHz spectral resolution is used to monitor the absorption and dispersion dynamics of different species and their rotational distributions within a non-thermal plasma.