## 2 Results and Discussions
### Volatilomics and Molecular Networking Analysis

Table 1: \(Cont.\)The VIP scores (Figure 3b) displayed 47 significant VOCs that allowed differentiation of the three maturation stages with a VIP \(>\) 1. The VOCs were found in high concentrations in the ripe stage, middle concentrations in the overripe stage, and low concentrations in the medium stage. However, the compounds 1,2-dibutoxyethane (160), propyl hexanoate (125), butyl ethanoate (47), \(\beta\)-cis-ocimene (105), 2,2-dimethylpentanoic acid (57), 2-methylbutyl ethanoate (61), and 3-methylbutyl ethanoate (59) were produced in the medium state, reached a maximum concentration in the ripe state, and then decreased in concentration in the overripe state. It is also noticeable that esters and terpen, such as \(\alpha\)-terpineol (155), _trans_-4-methoxythujane (129), and linalool (127), predominated with VIP \(>\) 1.28, followed by 2-methylbutyl butanoate (115), 3-methylbut-2-enoic acid, 2-methylpentyl ester (137), unknown (90), vinyl ethanoate (66), and 2-methylpropyl hexanoate (145) with VIP \(>\) 1.26. These findings suggest that these VOCs, particularly linalool, \(\alpha\)-terpineol, butyl ethanoate, and 3-methylbutyl ethanoate, have potential as biomarkers for copoazu maturation. Although some compounds have been previously identified [13], this study is the first to classify them as maturation stage biomarkers using VIP score analysis. In the ripe stage, several VOCs exhibited the highest concentrations (relative peak area), distinguishing this stage from the others according to PCA. Key compounds included ethyl butanoate (46), butyl ethanoate (47), 3-methylbut-2-enyl ethanoate (71), unknown (77), butyl butanoate (88), ethyl hexanoate (89), unknown (114), 3-methylbut-2-en-1-yl pixulate (141), propyl hexanoate (125), and 2-ethylphenyl ethanoate (163). Although our study focuses on the analysis of total volatile compounds due to the analysis temperature (60 \({}^{\circ}\)C), it is possible to identify semi-volatile compounds that are associated with the fruit aroma. These esters are associated with fruity and sweet flavor profiles [45]. Although terpenoids  
Figure 3: **(a)** PCA score plot for the three maturation stages. **(b)** VIP score plots derived from the PLS-DA analysis, displaying the discriminant features at the three maturation stages, with PLS-DA cross-validation parameters R\({}^{2}\) = 0.95332 and Q\({}^{2}\) = 0.90824, indicating good predictive capability. **(c–f)** Box plots from the ANOVA of the normalized molecular features \(\alpha\)-Terpineol (155), _trans_-4-methoxythujane (129), 1,2-dibutoxyethane (160), and 2-methylbutyl ethanoate (61), respectively. In Figures **(a–f)**, colors represent ripening stages: _red_ for medium, _green_ for overripe, and _blue_ for ripe. In Figure **(b)**, the red-to-blue scale indicates feature intensity across stages. are present at lower concentrations, they are notable differentiators for this maturation stage. Specifically, \(\beta\)_-trans_-ocimene (105) contributes citrus and floral notes, while _trans_-4-methoxythujane (129) imparts green and woody flavors. The overripe stage is dominated by alcohols, which provide a unique aromatic profile. The odor notes among these compounds--2-methyl-3-buten-2-ol (5), 2-methylpropyl alcohol (7), 1-penten-3-ol (11), 3-pentanol (14), 2-methylbutanol (27), 1-pentanol (31), 2,3-butanediol (44), 3-ethoxy-3-methyl-2-butanone (62), pentan-2-yl propyl carbonate (116), and 2-ethyl-1-hexanol (119)--include oily, herbal, fruits, and sweet profiles [45]. Additionally, the terpenoids 3-thujanone (117), terpinen-4-ol (151), and isothujol (152) share notes of spice, woody, and turpentine [45], further contributing to the distinct aroma profile of the overripe state. In the medium stage, the most concentrated VOCs are 3-methylbutyl alcohol (26), hexanal (45), and 2-methyl-1-butanol (27) with flavor notes of fruits and alcoholic nuances. This study highlights the dynamic influence of ripening on the volatile profile and organoleptic properties of copoazu.