From Reduction to Oxidation: pH Controlled Reaction of 1 Hydroxyethyl Radical with Caffeic Acid Analogues.

Aims: The aim is to search for newer and better antioxidants through kinetic spectroscopic studies in combination with product analysis and computation. Background: Antioxidant effect of caffeic acid, its derivative, and analogues have been well reported. The antioxidative efficiencies are related to their molecular structure, and two reaction pathways are well accepted, H-atom transfer (HAT) or single electron transfer. 1-hydroxy ethyl radical (1-HER) being an ethanol-derived free radical might be causing the onset of liver injury detected after alcohol administration. 1-HER has also been reported to react with fatty acids and endogenous antioxidants such as glutathione, ascorbic acid, and alpha-tocopherol Objective: The present study is an attempt to understand the reaction mechanism of 1-HER with caffeic acid, its derivative, and analogues in detail. Method: Pulse radiolysis with kinetic absorption spectroscopy has been employed to follow the reaction pathway and identify the intermediates produced in the reaction. The reaction products have been detected using LCMS/MS. Based on these studies, a consolidated mechanism has been proposed. Cyclic voltammetry measurements and computational calculations have been used in support of the proposed mechanism. Result: In the reaction of 1-hydroxy ethyl radical (1-HER) with caffeic acid and its oligomers, reduction takes place below the pKa1, while oxidation occurs with the deprotonated phenolic moiety. The reduction of caffeic acid generates a carbon-centered radical at the double bond of the side chain with a bimolecular rate constant of 1.5x1010 dm3 mol-1 s-1. Notably, a low concentration of oxygen was able to regenerate a part of the caffeic acid molecules in the reduction process. At pH 10 a phenoxyl radical is formed due to oxidation with a much lower bimolecular rate constant (4.2x108 dm3 mol-1 s-1). In the case of di-hydrocaffeic acid, only phenoxyl radical is formed at pH 10 and, no reaction could be observed below pH 8. Conclusion: Change in reactive pattern from reduction to oxidation with change in pH within the same set of reactants has been evidently established in the present study. The results point towards the importance of  unsaturation in the side chain of caffeic acid oligomers for their reaction with 1-HER at neutral pH. The effect of oxygen concentration on the antioxidative protection offered by this class of molecules might be intriguing for the quest of the effectiveness of antioxidants at low concentrations. Other: It may be inferred that the effect of pH on the reactivity pattern as observed is not 1-HER, but substrate-specific, in the present case, phenolic acids. This study generates further scope for in-depth studies on other polyphenols where unsaturation exists in the side chain.

Seeds of Life in Space (SOLIS)

Context. It is nowadays clear that a rich organic chemistry takes place in protostellar regions. However, the processes responsible for it, that is, the dominant formation routes to interstellar complex organic molecules, are still a source of debate. Two paradigms have been evoked: the formation of these molecules on interstellar dust mantles and their formation in the gas phase from simpler species previously synthesised on the dust mantles. Aims. In the past, observations of protostellar shocks have been used to set constraints on the formation route of formamide (NH2CHO), exploiting its observed spatial distribution and comparison with astrochemical model predictions. In this work, we follow the same strategy to study the case of acetaldehyde (CH3CHO). Methods. To this end, we used the data obtained with the IRAM-NOEMA interferometer in the framework of the Large Program SOLIS to image the B0 and B1 shocks along the L1157 blueshifted outflow in methanol (CH3OH) and acetaldehyde line emission. Results. We imaged six CH3OH and eight CH3CHO lines which cover upper-level energies up to ~30 K. Both species trace the B0 molecular cavity as well as the northern B1 portion, that is, the regions where the youngest shocks (~1000 yr) occurred. The CH3OH and CH3CHO emission peaks towards the B1b clump, where we measured the following column densities and relative abundances: 1.3 × 1016 cm−2 and 6.5 × 10−6 (methanol), and 7 × 1013 cm−2 and 3.5 × 10−8 (acetaldehyde). We carried out a non-LTE (non-Local Thermodinamic Equilibrium) Large Velocity Gradient (LVG) analysis of the observed CH3OH line: the average kinetic temperature and density of the emitting gas are Tkin ~ 90 K and nH2 ~ 4 × 105 cm−3, respectively. The CH3OH and CH3CHO abundance ratio towards B1b is 190, varying by less than a factor three throughout the whole B0–B1 structure. Conclusions. Comparison of astrochemical model predictions with the observed methanol and acetaldehyde spatial distribution does not allow us to distinguish whether acetaldehyde is formed on the grain mantles or in the gas phase, as its gas-phase formation, which is dominated by the reaction of ethyl radical (CH3CH2) with atomic oxygen, is very fast. Observations of acetaldehyde in younger shocks, for example those of ~102 yr old, and/or of the ethyl radical, whose frequencies are not presently available, are necessary to settle the issue.

The 3s versus 3p Rydberg state photodissociation dynamics of the ethyl radical

Photodissociation dynamics of the ethyl radical from the 3s vs. 3p Rydberg states studied by velocity map imaging and ab initio electronic structure calculations.

Site-specific hydrogen-atom elimination in photoexcited ethyl radical

The photochemistry of the ethyl radical following excitation to the 3p Rydberg state is investigated in a joint experimental and theoretical study.

Peter J Derrick and the Grand Scale ‘Magnificent Mass Machine’ mass spectrometer at Warwick

The value of the Grand Scale ‘Magnificent Mass Machine’ mass spectrometer in investigating the reactivity of ions in the gas phase is illustrated by a brief analysis of previously unpublished work on metastable ionised n-pentyl methyl ether, which loses predominantly methanol and an ethyl radical, with very minor contributions for elimination of ethane and water. Expulsion of an ethyl radical is interpreted in terms of isomerisation to ionised 3-pentyl methyl ether, via distonic ions and, possibly, an ion-neutral complex comprising ionised ethylcyclopropane and methanol. This explanation is consistent with the closely similar behaviour of the labelled analogues, C3H7CH2CD2OCH3+. and C3H7CD2CH2OCH3+., and is supported by the greater kinetic energy release associated with loss of ethane from ionised n-propyl methyl ether compared to that starting from directly generated ionised 3-pentyl methyl ether.