[Key findings and conclusions]: Organocatalytically esterified polysaccharides (OEPs) have generally been synthesized via green catalyst-assisted esterification reactions, with the main objective of grafting short-chain fatty acids (SCFAs), simple organic acids and small hydrophobic moieties onto the backbone of carbohydrate polymers. These SCFA-grafted OEPs, including SFCA-grafted starch, escape digestion and can efficiently deliver SCFAs in the lower gut. SCFA-grafted OEPs can also influence colonic bacteria and derived catabolites in a manner that provides cardiometabolic benefits. OEPs can also be used for the development of food packaging with improved hydrophobicity and thermal stability. Remarkably, their degree of substitution (DS) underlies their improved functionality as dietary compounds and/or food contact materials, with DS values between 0.01 and 0.2 when OEPs are designed for human consumption. It should be noted that the DS of the OEPs is limited by the steric hindrances related to the structure of the native carbohydrate polymers and the grafted functional group, as well as the reaction conditions.

K. V. Ragavan and M. M. Martinez would like to thank the Natural Sciences and Engineering Research Council of Canada (NSERC) [grant number 401499] for financial support. O. Hernandez-Hernandez has received funding from the European Union's Horizon 2020 research and innovation program (grant agreement GLYCO-WAY No 843950). M. M. Martinez would also like to thank the Aarhus University Research Foundation (AUFF Starting Grant) for financial support. T. J. Gutiérrez would like to thank the Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Universidad Nacional de Mar del Plata (UNMdP) and Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT) (grant PICT-2017-1362) for financial support.

[Background]: The esterification of carbohydrate polymers for food applications has been extensively investigated and reviewed. Despite this, the ability of esterified carbohydrate polymers as dietary fiber, as well as bio-based food packaging material makes this research area still of great interest. However, many of the reagents used during esterification lead to moderate to severe environmental pollution.

[Scope and approach]: The objective of this review manuscript was to provide an overview of the reaction mechanisms of organocatalytic esterification of carbohydrate polymers destined for food applications.

Peer reviewed