## 2 Results and Discussions
### Volatilomics and Molecular Networking Analysis
\begin{table}
\begin{tabular}{c c c c c c c} \hline GNPS Scan & **t\({}_{\text{k}}\)** & **Metabolite** & **Formula** & **Confidence Level \({}^{*}\)** & **Identification** & **Classey**Fire (SubClass) \\ \hline
86 & 18.92 & ethyl1-8 hexanoate & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
88 & 19.62 & butyl1 butanoate & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
89 & 19.95 & ethyl hexanoate & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
94 & 20.67 & ethyl-4-hexanoate & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
100 & 22.10 & pent-4-en-1-yl butanoate & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 3 & GNPS & Fatty acid esters \\
103 & 22.53 & butan-2-ylyl-methoxybutanoate & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 3 & GNPS, NIST & Fatty acid esters \\
115 & 23.43 & 2-methylbutyl butanoate & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
116 & 23.56 & penta-2-yl polycarbonate & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 3 & GNPS & Carbonic acid desters \\
125 & 25.20 & proppy hexanoate & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
137 & 26.26 & 2-methylphenyl & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 3 & GNPS & Fatty acid esters \\  & 3-methylbut-2-enoate & & & & & \\
139 & 26.77 & 2-methylbutyl-2-enoate & & & & \\  & 3-methylbut-2-en-1-yl & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 2 & GNPS, NIST & Carboxyl acid \\  & 3-methylbut-2-en-1-yl & & & & & derivatives \\
141 & 27.05 & privalate & C\({}_{3}\)H\({}_{2}\)O\({}_{2}\) & 3 & GNPS & Fatty acid esters \\
143 & 27.38 & 4-methylpentyl butanoate & C\({}_{3}\)H\({}_{2}\)O\({}_{2}\) & 3 & GNPS & Fatty acid esters \\
145 & 27.44 & 2-methylpropyl hexanoate & C\({}_{3}\)H\({}_{2}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
157 & 28.81 & ethyl oct-4-enoate & C\({}_{3}\)H\({}_{2}\)O\({}_{2}\) & 3 & NIST & Fatty acid esters \\
158 & 28.88 & butyl hexanoate & C\({}_{3}\)H\({}_{2}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
159 & 29.11 & ethyl octanoate & C\({}_{3}\)H\({}_{2}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
160 & 30.24 & 1,2-dibutoxyethane & C\({}_{3}\)H\({}_{3}\)O\({}_{4}\) & 2 & GNPS, NIST & Faty acid esters \\
161 & 30.56 & ethyl2-phenylethane & C\({}_{3}\)H\({}_{2}\)O\({}_{2}\) & 2 & GNPS, NIST & Benzene and substituted derivatives \\
163 & 30.60 & 2-ethylphenyl ethanoate & C\({}_{3}\)H\({}_{2}\)O\({}_{2}\) & 2 & GNPS, NIST & Phenol esters \\
166 & 30.81 & 3-methylbutyl hexanoate & C\({}_{3}\)H\({}_{2}\)O\({}_{2}\) & 2 & GNPS, NIST & Fatty acid esters \\
57 & 9.27 & 2,2-dimethylpentanoic acid & C\({}_{3}\)H\({}_{1}\)O\({}_{2}\) & 3 & GNPS & Fatty acids and conjugates \\
63 & 11.20 & ethenylbenzene & C\({}_{3}\)H\({}_{3}\) & 3 & GNPS & Syenes \\
109 & 23.00 & 2,7-dimethyl-2,6-catalene & C\({}_{3}\)H\({}_{3}\) & 2 & GNPS, NIST & Branched unsaturated hydrocarbons \\ \hline
33 & 5.41 & unknown & - & 4 & - & unknown \\
43 & 6.27 & unknown & - & 4 & - & unknown \\
51 & 7.80 & unknown & - & 4 & - & unknown \\
65 & 11.30 & unknown & - & 4 & - & unknown \\
75 & 15.34 & unknown & - & 4 & - & unknown \\
79 & 16.16 & unknown & - & 4 & - & unknown \\
80 & 16.33 & unknown & - & 4 & - & unknown \\
90 & 20.07 & unknown & - & 4 & - & unknown \\
92 & 20.38 & unknown & - & 4 & - & unknown \\
95 & 20.80 & unknown & - & 4 & - & unknown \\
114 & 23.30 & unknown & - & 4 & - & unknown \\
122 & 25.16 & unknown & - & 4 & - & unknown \\
126 & 25.30 & unknown & - & 4 & - & unknown \\
133 & 25.53 & unknown & - & 4 & - & unknown \\
147 & 27.76 & unknown & - & 4 & - & unknown \\
151 & 28.25 & unknown & - & 4 & - & unknown \\ \hline \end{tabular} \({}^{*}\) Confidence levels, 1 to a confident 2D structure or reference standard match; 2 to a likely structure or coincidence with the literature spectra; 3 to a possible structure, confirmation with molecular formula; and 4 to an unknown feature or a basic match with libraries. The different compound families were color-coded to facilitate correlation in Molecular network from volatilonic profile of the copoazu in three ripening stages. Alcohols and polychs are represented in blue, monoterenoids in green, esters in light green, dioxanes and dioxolanes in pink, and carbonyl compounds—such as aldehydes, ketones, and acylions—in light orange. Dicarboxylic acids and their derivatives are shown in red, other compounds in gray, and unknowns remain colorless.  
\end{table}