50 MARINE INGREDIENTS
Nature-derived texturiser offers ocean of opportunity
Smita Fulzele – Cargill Beauty
Carrageenans are water-soluble polysaccharides that are extracted from red seaweed. The term carrageenan is derived from an Irish word, “carrageen” meaning a “little rock”. Carrageenans are widely used in the food and personal care industry for properties like gelling, thickening, stabilisation, water-binding and providing wide variety of textures. In personal care, carrageenans are mainly used in oral care applications, with more than 70% of the total volume used (in 2018) being dedicated to oral care. Carrageenans are especially popular in the Asia Pacific region, which uses 45% of the total volume that is used in personal care globally. As the personal care industry is increasingly on the outlook for more natural ingredients, the use of carrageenans has been on the rise, with a projected CAGR of +2.4% for the next 5 years. Carrageenan is an extract from specific
red seaweed species (Rhodophyceae) and can be obtained from various species like, Chondrus crispus, Kappaphycus Striatum, Sarcothalia crispata, Kappaphycus alvarezii, Mazzaella laminaroides, Gigartina skottsbergii. Carrageenans can be found in different geographical locations like Southern Asia, South East Africa, South America and in the North Atlantic each producing specific species of carrageenan. Carrageenans can be produced both from harvested wild or farmed red seaweed. There can be country or region-specific regulations around the type of families/species that can be used to extract carrageenans. Carrageenan, on industrial scale, is obtained
by following steps of extraction, purification and carrageenan recovery by alcohol precipitation or potassium based gelation. The product then undergoes drying and milling to give the refined carrageenan. Semi-refined carrageenan, (Processed Eucheuma Seaweed, P.E.S) differs from refined carrageenan in two main
K+ K+ _ O3 SO
OH H
O O H O H H Figure 1: Carrageenan structure. PERSONAL CARE April 2021 H H OH H O O O H H H H OH H _ O3 SO
respects. Firstly, the only permitted raw material for P.E.S. is Eucheuma Seaweed. Secondly, it is obtained by simple alkaline treatment (no extraction and no filtration). Looking at structural composition,
Carrageenan is a linear polymer of sulphated galactose units (Fig 1). The sulfate content can be between 15 – 40%. The Carrageenan family can be classified into 3 main “ideal” types of molecules Kappa, Iota and lambda. Kappa and Iota respectively have 1 and 2 sulphates groups, with one anhydro-galactose bridge. Lambda has 3 sulphate groups (Fig 2). Carrageenan macromolecules are
heterogeneous, either due to differing molecular structures within the chains or due to differing chains within the seaweed. For example, some carrageenans extracted from South American seaweeds are kappa and iota hybrids, also called kappa 2 or weak kappa carrageenans. Based on the region carrageenan is obtained from, the fractions and their concentration vary.
Kappa and iota carrageenans can give gel
structures thus are known as gelling carrageenan, while lambda is thickening carrageenan. Once carrageenan is solubilised in water,
the gelling mechanism initiates with formation of α-helix zones or spiral-like associations in molecules. Further, single helices arrange with adjacent ones to form double helical structures specially with salt or electrolyte addition. The negative charges (sulfate groups) are all orientated to the external side of the helix. Once the K+ cation is added, all the double helixes will associate to each other (creating a link between the SO3- and the K+). For Kappa carrageenan, the solubilisation
OH H
O O H H O O O H
temperature is 60-70°C. However, a combination of time/temperature/ shear also plays a role. Kappa carrageenan due to its structure results in very brittle gels. Gelation of kappa carrageenan is particularly enhanced by the addition of potassium ion. It induces gel formation at very low concentrations. Because of its small hydro- dynamic size when hydrated, the potassium ion fits into the coil and partially neutralses the sulfate groups. Thus, the double-helices can cluster together and form aggregates that create a strong & brittle gel with a short texture. The gels are thermoreversible and do not exhibit thixotropic behaviour like iota and lambda carrageenan. For Iota carrageenan, the solubilisation
temperature is 50-60°C. Iota has more charges than kappa, thus it is easier to solubilise iota than kappa. The iota molecules also arrange themselves in double helixes. But the structure of all the helixes is more in the shape of a star because it has much more negative charges on
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