Commercially available carrageenans show broad variation in their structure, composition, and functionality

Carrageenans are polysaccharides from red algae which are widely used as food additives and in other applications. Their structure is often described by different disaccharide repeating units, although it was already demonstrated that reality is more complex. In many studies, commercial carrageenans were used to establish structure function relationships, but a structural and compositional analysis was rarely conducted. Therefore, the aim of our study was to systematically and comprehensively characterize a broad collection of commercial carrageenans with different specifications from different manufacturers. For a more detailed characterization, an analytical approach based on partial enzymatic hydrolysis in combination with HPLC–MS and HPSEC-RI was developed and applied. Furthermore, rheology was used to gain detailed insights into the functionality of selected samples. Our results demonstrate that significant structural variation can be observed for commercial carrageenans. The samples contained different cations and the carrageenan type specified by the manufacturer did not always represent the structure of the corresponding polysaccharides. This was especially true for λ-carrageenans: Of the six commercial samples analyzed, none contained structural elements from the λ-type. Instead, the corresponding carrageenans contained κ-, ι- and ν-units. The application of the developed enzymatic-chromatographic approach showed that different hybrid carrageenans are present. In addition, the rheological analysis of the commercial carrageenan samples showed clear differences in the gelling properties upon calcium addition which could influence their behavior in different applications. Our results demonstrate that before an investigation of structure–function relationships, commercial carrageenan samples should be analyzed for their structure and composition. We also showed that the enzymatic-chromatographic approach described in this study is well suited for this purpose.