We studied the kinetics of the reaction of N-acetyl-l-cysteine (NAC or RSH) with cupric ions at an equimolar ratio of the reactants in aqueous acid solution (pH 1.4–2) using UV/Vis absorption and circular dichroism (CD) spectroscopies. Cu²⁺ showed a strong catalytic effect on the 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) radical (ABTSr) consumption and autoxidation of NAC. Difference spectra revealed the formation of intermediates with absorption maxima at 233 and 302 nm (ε₃₀₂/Cu > 8 × 10³ M⁻¹ cm⁻¹) and two positive Cotton effects centered at 284 and 302 nm. These intermediates accumulate during the first, O₂-independent, phase of the NAC autoxidation. The autocatalytic production of another chiral intermediate, characterized by two positive Cotton effects at 280 and 333 nm and an intense negative one at 305 nm, was observed in the second reaction phase. The intermediates are rapidly oxidized by added ABTSr; otherwise, they are stable for hours in the reaction solution, undergoing a slow pH- and O₂-dependent photosensitive decay. The kinetic and spectral data are consistent with proposed structures of the intermediates as disulfide-bridged dicopper(I) complexes of types cis-/trans-Cu^I₂(RS)₂(RSSR) and Cu^I₂(RSSR)₂. The electronic transitions observed in the UV/Vis and CD spectra are tentatively attributed to Cu(I) → disulfide charge transfer with an interaction of the transition dipole moments (exciton coupling). The catalytic activity of the intermediates as potential O₂ activators via Cu(II) peroxo-complexes is discussed. A mechanism for autocatalytic oxidation of Cu(I)–thiolates promoted by a growing electronically coupled –[Cu^I₂(RSSR)]_n– polymer is suggested. The obtained results are in line with other reported observations regarding copper-catalyzed autoxidation of thiols and provide new insight into these complicated, not yet fully understood systems. The proposed hypotheses point to the importance of the Cu(I)–disulfide interaction, which may have a profound impact on biological systems.

The aim of this work was to separate ethanol in an experimental adsorption–desorption device. We focused on concentrating ethanol by adsorption onto granulated activated carbon in its gaseous phase, which was produced by stripping a matrix with different ethanol concentrations (2, 5, 10, and 15% v/v). For adsorption, three kinds of granulated activated carbon (GAC) were used, marked as GAC1, GAC2, and GAC3. The separation product had a higher ethanol concentration than the initial ethanol concentration before the adsorption–desorption process. The enrichment factor was, in the case of the initial ethanol concentration, 2% v/v at the level of 10. With our new adsorption–desorption device, it is possible to achieve a product with an ethanol concentration of 59.0% v/v with stripping, adsorption, desorption, and condensation. To verify the separation efficiency, a real matrix (fermentation broth) was used. The ethanol concentration in the real matrix was, at the beginning of the separation process, 0.65% v/v; after using our separation device, it was 11.35% v/v. Using a real matrix, the enrichment factor was at the level of 18. The main advantage is the use of our new adsorption–desorption device for the continuous separation of ethanol from fermentation broth. A mathematical model was created, based on which it is possible to calculate the ethanol concentration in the product of the separation process with high accuracy.