Synergistic interaction between κ-carrageenan isolated from Hypnea charoides Lamouroux and galactomannan on its gelation

doi:10.1016/S0963-9969(99)00022-8

Food Research International

Volume 31, Issue 8, October 1998, Pages 543-548

https://doi.org/10.1016/S0963-9969(99)00022-8 Get rights and content

Abstract

The synergistic effects on rheological properties for a series of aqueous solution of κ-carrageenan isolated from Hypnea charoides Lamouroux and galactomannan (locust-bean gum) were investigated. At a concentration of 0.4% of total gums, gelation did not occur at room temperature, but it did at a low temperature (0°C). The maximum dynamic modulus was obtained with a series of the samples composed of K-salt of κ-carrageenan and locust-bean gum in the mixing ratio of 1:1 at low temperature (0°C). The less synergistic effect on the dynamic modulus was obtained in mixture solutions with Na-salt of κ-carrageenan and locust-bean gum. At about 25°C, gel-sol transition was observed in the mixing ratio of κ-carrageenan (K-salt) to locust-bean gum of 3:1 and 4:1. A possible association site between K-salt of κ-carrageenan and locust-bean gum was proposed.

Introduction

A novel and useful property of xanthan in the food industry is not only its curious viscosity and dynamic viscoelasticity (Jeanes, Pittsley, and Senti, 1961Tako, Nagahama, and Nomura, 1977) where a sigmoid curve is observed with increasing temperature but also its reactivity with galactomannan, such as locust-bean gum (Pettitt, 1982Tako, Asato, and Nakamura, 1984), guar gum (Tako and Nakamura, 1985, Tako and Nakamura, 1986a), and tara-bean gum (Tako, 1991a). We have proposed possible binding sites for d-mannose-specific interaction between xanthan and galactomannan (locust-bean gum) involving the side chains of the former and backbone of the latter molecules, as illustrated in Scheme. 1 (Tako, 1991b, Tako, 1992, Tako, 1993). Hydrogen bonding may take place between the hemiacetal oxygen atom of the inner d-mannose side-chain of xanthan and the hydroxyl group at C-2. As the mannan backbone of the locust-bean gum molecule has a rigidity due to an intramolecular hydrogen bonding, O(5)…C(3) ′ (Zugenmaier, 1974) as illustrated in Scheme. 1, the side chains of the xanthan molecule are inserted into the adjacent, unsubstituted segments of the mannan backbone, which is extended into a two-fold, ribbon-like structure, similar to the lock-and-key interaction.

On the other hand, the synergistic interaction between κ-carrageenan and galactomannan (locust-bean gum) in aqueous solution for gelation is well known (Dea, McKinnon, and Rees, 1972Fernandes, Goncalves, and Doublier, 1991Rees, 1972Rochas, Taravel, and Turquois, 1990). Dea, McKinnon, and Rees (1972) proposed a mechanism for the interaction between the double stranded helix of κ-carrageenan and unbranched smooth segments of the d-mannose backbone of locust-bean gum molecule. κ-Carrageenan has alternating disaccharide units of (1–3) linked β-d-galactose-4-sulfate and (1–4) linked 3,6-anhydro-α-d-galactose, and is well known for its gel forming property (Snoeren and Payens, 1976Norton, Goodall, Morris, and Rees, 1983Morris and Chilvers, 1983, Rochas and Rinaudo, 1984).

We have proposed that the κ-carrageenan molecule may form intramolecular cation-bridges between the sulfate group of the d-galactose-4-sulfate residue and the ring oxygen group of an adjacent anhydro-d-galactose residue with large cations, such as K⁺, Rb⁺, and Cs⁺, but not with small cations, Li⁺ or Na⁺, as illustrated in Scheme. 2 (Tako and Nakamura, 1986b). This model could expand to the gelling mechanism of κ-carrageenan molcules in aqueous solution at low temperatures. Intermolecular cation-bridges might also occur after formation of a very large number of intramolecular cations-bridges which may be caused by the decrease of Brownian motion and kinetic energy of the solvent and polymer molecules (Scheme. 2) (Tako and Nakamura, 1986c).

Hypnea charoides Lamouroux which belongs to the red seaweed (Rhodophyceae) group is grown in the northern part of Okinawa Island (Japan). In Okinawa, Hypnea charoides Lamouroux has been used for gelling additives of a health food called “Moi-tofu” for over 200 years (Tohma, 1988). Annual production of Hypena charoides Lamouroux in Okinawa has been reported to be approximately 5 tons (Tohma, 1988). We have previously isolated a κ-carrageenan from Hypena charoides Lamouroux (Qi, Tako, and Toyama, 1997a) and its non-Newtonian behavior and dynamic viscoelasticity were also analyzed with respect to the association characteristics comparison with those of commercial κ-carrageenan (Qi, Tako, and Toyama, 1997b).

In this investigation, we studied the rheological behavior of a mixture system of κ-carrageenan isolated from Hypnea charoides Lamouroux and locust-bean gum in solution, and its rheological properties have been analyzed with respect to its association characteristics in more detail so as to propose a possible model of association-site.

Section snippets

Material

κ-Carrageenan used in the present study was extracted from Hypnea charoides Lamouroux which was collected in March 1995 at Nago City in Okinawa Island (Japan). An air-dried Ibaranori (6 g) was suspended in water and heated at 100°C for 1 h for extraction of κ-carrageenan. The extract was centrifuged at 12 000 g for 20 min and the supernatant was filtered through Celite 545, then KCl (100 mg) was added to the filtrate. The gelatinous precipitate was separated by centrifugation at 12 000 g for 20

Results and discussion

The κ-carrageenan was obtained about 42.1% from the dried seaweed. The κ-carrageenan was composed of d-galactose, 3,6-anhydro-d-galactose, and ester sulfate in a molar ratio of 1.2:0.9:1.2. Molecular mass of the polysaccharide was estimated to be about 230 000, by liquid chromatography. As the intermolecular interaction between κ-carrageenan and galactomannan molecules is closely correlated with the degree of substitution of the mannan chain, the degree of substitution of locust-bean gum was

Conclusions

Though a mixed solution of xanthan and locust-bean gum, and konjac glucomannan gelled at 0.2 and 0.1% total gums at room temperatuire (Tako, Asato, and Nakamura, 1984; Tako and Nakamura, 1986a, Tako, 1991b, Tako, 1992, Tako, 1993), a mixture of κ-carrageenan (K-salt) and locust-bean gum solution did not gel even at 0.4% total gums at room temperature, but gelled at low temperature (0°C). Less interaction was observed in a mixed solution with Na salt of κ-carrageenan. As proposed in our

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κ-carrageenan can synergistically interact with galactomannans, such as locust bean gum and tara gum, to increase the gel strength and water-binding capabilities as well as to modify the gel texture to be more elastic and resilient (Arda, Kara, & Pekcan, 2009; Stading & Hermansson, 1993). The synergism is due to the interactions between double helices of κ-carrageenan and unbranched smooth segments of the d-mannose backbone from galactomannans (Cairns, Miles, & Morris, 1986; Tako & Nakamura, 1986; Tako, Qi, Yoza, & Toyama, 1998). In addition, the synergisms are affected by the blending ratios of the two gums, types of galactomannans and cooling and heating temperatures (Arda et al., 2009; Wu, Ding, & He, 2018).
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Being so it would also influence κ-car-LBG interaction. When LBG is added to the κ-car intermolecular interaction may occur between the ring oxygen atom of the former and OH-2 of the d-mannopyranosyl residue with hydrogen bonding, at which the intramolecular K+-bridge is inserted into the adjacent unsubstituted segments of the backbone of the LBG, as proposed by Tako et al. (1998). At the molecular level, it is known that the formation of a κ-car gel is preceded by a disorder–order transition of polysaccharide conformation, followed by aggregation of helices which gives rise to low crystalline materials, not detected by XRD (Johnson, Busk, & Labuza, 1980).
The development of mixed systems, formed by locust bean gum (LBG), and κ-carrageenan (κ-car) can offer new interesting applications such as the development of edible films with particular properties. κ-car/LBG blend films with different ratios were developed, and their effects on films’ physical properties were assessed. Thermogravimetric analysis (TGA), X-ray diffraction (XRD) patterns, dynamic mechanical analysis (DMA) and Fourier-transform infrared (FTIR) spectroscopy techniques were used to highlight the interactions between the two polysaccharides. The addition of κ-car to LBG improved the barrier properties of the films leading to a decrease of water vapor permeability (WVP). Improved values of elongation-at-break (EB) were registered when the ratio of κ-car/LBG was 80/20 or 40/60 (% w/w). Moreover, the κ-car/LBG blend films enhance the tensile strength (TS) compared to κ-car and LBG films. FTIR results suggested that hydrogen bonds interactions between κ-car and LBG have a great influence in films’ properties e.g. moisture content, WVP. Therefore, different κ-car/LBG ratios can be used to tailor edible films with enhanced barrier and mechanical properties.
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Rheological properties such as flow behaviour, viscosity, viscoelasticity, and thixotropy of solutions of β-glucan purified from barley fibre concentrate and twelve commonly used food gums, alone and in combinations, were characterised using an oscillatory rheometer. Pure gums and gum combinations were evaluated at 0.5% and 0.75% (w/w) total gum concentration in aqueous medium, whereas the β-glucan/gum ratios were kept at 90/10 or 80/20 (w/w). Viscosity synergism was observed for β-glucan solutions in combination with xanthan, iota-carageenan, and carboxymethyl cellulose. However, barley β-glucan blends with lambda-carageenan, Konjac, high- and low-methoxyl pectin, microcrystalline cellulose, alginate, and gum arabic showed marked lowering of the viscosity compared to β-glucan alone. In addition, β-glucan/xanthan gum blends demonstrated improved shear tolerance compared to xanthan dispersions alone, and soft gel transformation. Non-thixotropic behaviour was observed for 0.5 and 0.75% (w/w) β-glucan dispersions and its gum combinations. None of the gum combinations studied demonstrated thixotropy.

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Synergistic interaction between κ-carrageenan isolated from Hypnea charoides Lamouroux and galactomannan on its gelation

Abstract

Introduction

Section snippets

Material

Results and discussion

Conclusions

J. Mol. Biol.

Carbohydr. Polym.

Carbohydr. Polym.

Carbohydr. Res.

Biochim Biophys. Acta

Colloids Surfaces B Biointerfaces

FEBS Lett.

Carbohydr. Res.

A new hydrocolloid polyelectrolyte produced from glucose by bacterial fermentation

J. Appl. Polym. Sci.

A property of bessel function and its application to the theory of two rheometers

J. Appl. Phys.

Equilibrium and dynamic studies of the disorder-order transition of kappa carrageenan

J. Chem. Soc. Faraday Trans.