DPPH‐based Antioxidant Screening and Cellulase‐assisted Hydrodistillation of Matourea azurea: Improved Essential Oil Yield and Density Functional Theory Insights Into a Rare Terpene

Essential oils are rich in bioactive molecules like terpenes and phenolic compounds, but have low yields, making process efficiency crucial. Enzyme-assisted hydrodistillation is a sustainable alternative, enhancing oil release by degrading the cell wall. This study applied cellulase enzymolysis before hydrodistillation in Matourea azurea (Linden) Colletta; V.C.Souza (M. azurea) leaves, testing concentrations of 1.0%, 1.5%, and 2.0%, followed by gas chromatography-mass spectrometry (GC─MS) analysis to identify chemical alterations. Antioxidant activity was assessed by 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging, while density functional theory calculations at B3LYP/6-311++G(d,p) level evaluated molecular reactivity. The essential oil yielded 0.60%, with a 24% increase at 1% cellulase. GC-MS confirmed chemical variations while maintaining key compounds (β-copaen-4α-ol, myrtenal, and viridiflorol). The DPPH IC50 was 237.70 µg/mL. Computational studies in gas and CPCM (water) showed that 1,4,7-cycloundecatriene, 1,5,9,9-tetramethyl-Z,Z,Z- is stable, with lower reactivity in aqueous medium, based on the highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap. Condensed Fukui indices suggest antioxidant and oxidant potential, corroborated by total and projected density of states analysis, indicating nucleophilic and electrophilic reactive sites. These findings highlight enzyme-assisted hydrodistillation as an effective strategy to improve essential oil extraction and bioactivity while maintaining sustainable processing.