Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Fatty acid [FA; butanoic (C<jats:sub>4</jats:sub>); octanoic (C<jats:sub>8</jats:sub>); tetradecanoic (C<jats:sub>14</jats:sub>); and <jats:italic>cis</jats:italic>‐9,12‐octadecadienoic (C<jats:sub>18:2</jats:sub>) acids] reaction selectivity and the corresponding acyl profiles in differentially accumulating acylglycerol (AG) products (mono‐, di‐, and triacylglycerols; MAG, DAG, TAG, respectively) were evaluated for Celite™‐immobilized potato tuber lipid acyl hydrolase (LAH)‐mediated esterification reactions in isooctane at 35°C and water activity of 0.19. The ordinal pattern of FA selectivities was C<jats:sub>8</jats:sub>>C<jats:sub>14</jats:sub>>C<jats:sub>18:2</jats:sub>>C<jats:sub>4</jats:sub>, and the AG products accumulating were α‐MAG>DAG>β‐MAG>TAG. A dimensionless expression for fatty acid partitioning coefficient (FAPC) was contrived to represent the partitioning patterns of specific FA into specific AG pools on the basis of an equivalent extent of FA reaction. These FAPC values indicated that preferential partitioning of FA was as follows: C<jats:sub>4</jats:sub> was preferentially partitioned into TAG, DAG, and β‐MAG; C<jats:sub>8</jats:sub> was preferentially partitioned into DAG; C<jats:sub>14</jats:sub> was preferentially partitioned into α,β‐MAG; C<jats:sub>18:2</jats:sub> was preferentially partitioned into α,β‐MAG and TAG. These findings infer that the tendency for LAH‐mediated esterifications to accumulate MAG is based, in part, on a constraint in reactivity of α‐MAG of ≥10 acyl carbon groups to serve as acceptors for further esterification events. The general approach taken in this study may assist in identifying the discrete steps in assembling structured glycerides where different biocatalysts exhibit the greatest degree or control of reaction selectivity.</jats:p>