ReviewCarrageenans: Biological properties, chemical modifications and structural analysis – A review
Introduction
Over the last years, marine microorganisms such as bacteria, microalgae and seaweeds have represented a large source of valuable materials (DeLong, 1997, Rasmussen and Morrissey, 2007). The various unique carbohydrate residues that are found in marine organisms are especially interesting and emphasize the importance of obtaining further knowledge in this area (Michel, Nyval-Collen, Barbeyron, Czjzek, & Helbert, 2006). So far, the three commercially exploited carbohydrate polymers from marine organisms are: (1) alginates, the mannuronic-acid- and guluronic-acid-containing polymers from brown seaweeds; (2) agar, the d-galactose and 3,6-anhydro-l-galactose-containing polymers that are isolated from red seaweeds; and (3) carrageenans (De Ruiter and Rudolph, 1997, Selby and Whistler, 1993).
Carrageenan is a generic name for a family of polysaccharides, obtained by extraction from certain species of red seaweeds (Rhodophyta) (Van De Velde, Knutsen, Usov, Rollema, & Cerezo, 2002). The word carrageenan is derived from the colloquial Irish name for this seaweed, carrageen, which means “little rock”. The aqueous extraction of red seaweeds to obtain these hydrophilic colloids is known in Ireland since 1810 (Stanley, 1987). All seaweeds that produce carrageenan as their main cell-wall material belong to Rhodophyta, but there is almost no information available on the biosynthesis of carrageenans and the genetics of the seaweed plant cell wall (De Ruiter & Rudolph, 1997).
In the food industry, carrageenans are widely utilized due to their excellent physical functional properties, such as thickening, gelling and stabilizing abilities, and have been used to improve the texture of cottage cheese, to control the viscosity and texture of puddings and dairy desserts, and as binders and stabilizers in the meat-processing industry for the manufacture of patties, sausages and low-fat hamburgers.
The food industry accounts for 70–80% of the total world production, estimated at about 45,000 metric tonnes per year, of which about 45% goes to dairy products and 30% to meat and meat derivatives. The total market of carrageenans has been estimated as US $300 million/year (McHugh, 2003).
Carrageenans are also used in various non-food products, such as pharmaceutical, cosmetics, printing and textile formulations (Imeson, 2000). Carrageenans stabilize toothpaste preparations, absorb body fluids when formulated in wound dressings and interact with human carotene to give soft skin and silky hair in hand lotions and shampoos, respectively. They have proved to be useful as tableting excipients due to the good compatibility, high robustness and persistent viscoelasticity of the tablet during compression. These interesting properties indicated that carrageenans are suitable excipients for sustained-release formulations (Bhardwaj, Kanwar, Lal, & Gupta, 2000).
Therefore, considering the extensive applications of carrageenans, the aim of this review article is to present a comprehensive overview of recent and relevant aspects related, principally, to their biological activities, chemical modifications and structural analysis.
Section snippets
Source, structure and physicochemical properties
Carrageenans are obtained from different species of Rhodophyta: Gigartina, Chondrus crispus, Eucheuma and Hypnea (Stanley, 1987). These polysaccharides are traditionally split into six basic forms: Iota (ι)-, Kappa (κ)-, Lambda (λ)-, Mu (μ)-, Nu (ν)- and Theta (θ)- carrageenan. This nomenclature is relevant both for their chemical classification (as discussed below) and to the commercial production, since the different carrageenans subtypes are extracted from distinct weed sources.
κ-Carrageenan
Biological activities
Carrageenans are classically used as agents for the induction of experimental inflammation and inflammatory pain (Morris Christopher, 2003). They have also shown several potential pharmaceutical properties including antitumor, immunomodulatory (Zhou et al., 2004), antihyperlipidemic (Panlasigui, Baello, Dimatangal, & Dumelod, 2003) and anticoagulant activities (Caceres, Carlucci, Damonte, Matsuhiro, & Zuniga, 2000). Some in vitro studies suggest that carrageenans may also have antiviral
Chemical modifications
Several chemical modifications have been proposed to modulate physicochemical properties of carrageenans. Guiseley (1978) proposed the synthesis of κ-carrageenan-containing hydroxyalkyl groups. Aqueous κ-carrageenan gels can display an undesirable large extent of syneresis (the extraction of a liquid from a gel) when subjected to mechanical deformation or aging, a natural process that affects the mechanical, magnetic and rheological properties of the gels. Gels prepared from hydroxyalkyl
Structural analysis of carrageenans
There are not enough suitable analytical techniques to determine the quantity, the polydispersity and the purity of carrageenans in food products and raw materials. Moreover, the relationship of their biological activities with their substitution pattern (position of sulphate group) is still uncertain because of the lack of analytical methods for the determination of the fine structure of carrageenans at the polysaccharide level (Aristotelis, Patrick, William, & Michel, 2007). Thus, proper
Concluding remarks
Carrageenans have been widely used by food industry and may represent, in the future, a valuable and low cost source of new drugs. Current research goals are focused on identifying more potent and specific compounds with antitumor, immunomodulatory, antihyperlipidemic, anticoagulant and antiviral activities. Therapeutic applications of low molecular weight carrageenans have been limited because of their gastrointestinal toxic side effects. In this way, parenteral formulations of carrageenans
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