In order to investigate the gas-phase mechanisms of the acid catalyzed degradation of ascorbic acid (AA) to furan, we undertook a mass spectrometric (ESI/TQ/MS) and theoretical investigation at the B3LYP/6-31 + G(d,p) level of theory. The gaseous reactant species, the protonated AA, [C6H8O6]H+, were generated by electrospray ionization of a 10−3M H2O/CH3OH (1 : 1) AA solution. In order to structurally characterize the gaseous [C6H8O6]H+ionic reactants, we estimated the proton affinity and the gas-phase basicity of AA by the extended Cooks's kinetic method and by computational methods at the B3LYP/6-31 + G(d,p) level of theory. As expected, computational results identify the carbonyl oxygen atom (O2) of AA as the preferred protonation site. From the experimental proton affinity of 875.0 ± 12 kJ mol−1and protonation entropy ΔSp108.9 ± 2 J mol−1K−1, a gas-phase basicity value of AA of 842.5 ± 12 kJ mol−1at 298 K was obtained, which is in agreement with the value issuing from quantum mechanical computations. Copyright © 2016 John Wiley & Sons, Ltd.

Vitamin C: an experimental and theoretical study on the gas-phase structure and ion energetics of protonated ascorbic acid

Ricci, Andreina
;
2016

Abstract

In order to investigate the gas-phase mechanisms of the acid catalyzed degradation of ascorbic acid (AA) to furan, we undertook a mass spectrometric (ESI/TQ/MS) and theoretical investigation at the B3LYP/6-31 + G(d,p) level of theory. The gaseous reactant species, the protonated AA, [C6H8O6]H+, were generated by electrospray ionization of a 10−3M H2O/CH3OH (1 : 1) AA solution. In order to structurally characterize the gaseous [C6H8O6]H+ionic reactants, we estimated the proton affinity and the gas-phase basicity of AA by the extended Cooks's kinetic method and by computational methods at the B3LYP/6-31 + G(d,p) level of theory. As expected, computational results identify the carbonyl oxygen atom (O2) of AA as the preferred protonation site. From the experimental proton affinity of 875.0 ± 12 kJ mol−1and protonation entropy ΔSp108.9 ± 2 J mol−1K−1, a gas-phase basicity value of AA of 842.5 ± 12 kJ mol−1at 298 K was obtained, which is in agreement with the value issuing from quantum mechanical computations. Copyright © 2016 John Wiley & Sons, Ltd.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11591/404250
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