Revealing substitution priority and pattern of octenylsuccinic groups along the starch chain under a continuous mode

• OS group substitution priority was studied in a continuous mode for the first time. • Backbone-chain branching points were preferentially substituted under controlled OSA. • With limited DS, more branching point substitutions resulted in higher EAI. Octenylsuccinic (OS) groups distribution was considered random under traditional batch mode (BM) process due to excessive available octenyl succinic anhydride (OSA) at early stage, making the functionality optimization of OSA starch under restricted substitution degree (DS) difficult. To reveal the priority rule of substituent position at starch molecular level, a continuous mode (CM, dropwise OSA addition) was applied for OSA starch preparation. Initial OSA substitution was predominately at the branching points of amylopectin backbone, then successive at the branching points of shorter and longer chains with increasing DS. As DS increased over 1.49%, substitution started occurring along the chains and moved towards the non-reducing ends until DS reached 6.65%. At similar DS, more branching point substitutions occurred at CM starch, showing superior emulsifying property over BM starch. OSA substitution priority rule does exist under controlled OSA supply, which would facilitate OSA starch design with specific substitution pattern and favored functionality.