Reactivity assessment of oligomeric systems associated with crystalline and amorphous cellulose for bioethanol production: a DFT study

Context: The production of bioethanol from renewable raw materials is a decisive factor in the economic development of many countries. However, the complexity of the processes and the numerous experimental variables involved require a deeper understanding of the chemical reactions that take place during bioethanol production to define optimal parameters. Here, we have employed density functional theory–based calculations to investigate the local reactivity of oligomeric systems by considering crystalline and amorphous cellulose models to better understand some details regarding pulp pretreatment processes. Our results evidence a higher chemical susceptibility of amorphous portions of cellulose to chemicals typically employed in acid hydrolysis. Additionally, we observed that glucose monomers coming from cellulose hydrolysis may undergo oxidation, leading to the formation of byproducts such as hydroxymethylfurfural (HMF), acetic acid, formic acid, and levulinic acid. The analysis of local chemical softness indexes indicated that cellulose hydrolysis may be associated with intermediate chemical steps. Finally, we investigated the influence of distinct solvents (dielectric constants) on the local reactivity of the systems, evidencing a relevant role of the solvent dielectric constant for cellulose degradation in glucose. Methods: Initial three-dimensional structures were constructed. Pre-optimizations were performed in a Hartree–Fock (HF) approach employing the PM7 semi-empirical hamiltonian. The structures were then re-optimized via density functional theory (DFT). The local reactivity study of the systems was conducted through the condensed-to-atoms Fukui indexes (CAFI). Systematic changes of the dielectric constants were also considered in geometry optimization and CAFI calculations to estimate the influence of solvents on the reactivity of the systems.