Effects of Ca- and Na-lignosulfonate on starch gelatinization and network formation

doi:10.1016/j.carbpol.2004.04.023

Carbohydrate Polymers

Volume 57, Issue 4, 22 September 2004, Pages 369-377

https://doi.org/10.1016/j.carbpol.2004.04.023 Get rights and content

Abstract

The interaction of lignosulfonates with starches was examined by microscopy and viscosity measurements. 8% starch dispersions with Ca- or Na-lignosulfonate, or with only Ca²⁺ or Na⁺, were heated to 97 °C and cooled to 50 °C in a Brabender Viscograph, the gelatinization was followed by light microscopy and image analysis, and the gel network formed after cooling to 4 °C was studied under the transmission electron microscope.

The lignosulfonates (2%) delayed the initial granule swelling in all starches (native maize, waxy maize and waxy barley). The presence of ions enhanced amylose leakage resulting in lower peak viscosity. The viscosity during cooling increased more with Ca-LS than with Na-LS. With a low lignosulfonate concentration the network formed after cooling was homogeneous with fine strands. With Na-lignosulfonate, as well as with Na⁺, the network connectivity deteriorated and spherical aggregates formed. Ca-lignosulfonate induced a network with thick strands, but with Ca²⁺ the strands became thinner.

Introduction

Lignosulfonate is a biopolymer that originates from wood, and is an interesting reaction product of the sulfite pulping process, where lignin reacts with sulfite. The lignosulfonate has a molecular weight of about 5.000–60.000 g/mol and consists of cross-linked phenylpropanoid monomers. It is thought to form a spherical structure with negatively charged sulfonic groups on the surface (Fredheim & Christensen, 2003). Lignosulfonate is water-soluble and has surface-active properties. We have estimated the size of lignosulfonate particles in water to be around 50–60 nm by transmission electron microscopy, micrographs not shown. The size of the particles could make it difficult to penetrate into the granules, so any effect of lignosulfonate on the starch would probably be due to interaction at the surfaces or outside the granules. The great versatility of lignosulfonate makes it suitable for a wide range of products. It is generally used as a dispersant or stabilizer (Gargulak & Lebo, 2000). It has also been used for many years in feed. For humans lignosulfonate is defined as a dietary fibre since it is not degraded in the intestine. The surface-active properties in combination with being a dietary fibre could make it useful as a functional ingredient in foodstuffs. It would then be important to know how it interacts with other components in the food.

Starch is one of the most abundant carbohydrates and used in foodstuffs as a thickener and binder. During heating in water the granules swell, the viscosity increases and amylose leaks out into the solution (Doublier et al., 1987, Langton and Hermansson, 1989, Richardson et al., 2003, Steeneken, 1989). The starch gelatinization can easily be altered by other components such as surface-active agents. For example, the interaction with emulsifiers may delay the gelatinization substantially (Deffenbaugh, 1997, Richardson et al., 2003). The effects of lignosulfonate on starch gelatinization have not been examined.

In the sulfite process, sodium or calcium hydrogen sulfite is used, which gives Na-lignosulfonate or Ca-lignosulfonate. Ion exchange gives lignosulfonates with slightly different properties. Since ions have a low molecular weight, and are loosely bound to lignosulfonate, they are considered to easily diffuse into the amorphous parts of the starch granule along with water (French, 1984). Studies with polarized light on wheat starch granules have shown that the gelatinization can begin both at the centre and on the periphery of the granules, depending on the kind and concentration of added ions (Gough & Pybus, 1973). They also reported that sodium chloride had a slight decreasing effect on the gelatinization temperature, while calcium chloride could both decrease and increase the gelatinization temperature, depending on concentration. The changes in starch granule swelling due to salt addition have been reported by many, e.g. Jane (1993), who measured the enthalpy changes with DSC. On the other hand, in pure amylose gels with added NaCl, CaCl₂ or AlCl₃, Hermansson, Kidman, and Svegmark (1995) did not observe any major changes in structure except a slightly higher degree of aggregation.

The ions can also affect the viscoelasticity of the cooled gel. Muhrbeck and Eliasson (1987) have shown that the dynamic viscosity and complex modulus of potato starch gels dropped at higher ionic strength, and that divalent cations had a larger effect than monovalent ions. This effect was not seen in cassava starch. Since the two starches differ in phosphate content, they suggested that the ions may block the interactions between phosphate groups on the granule surfaces and hinder cross-linking between the granules.

The objective of this work was to determine the effects of lignosulfonates on starch gelatinization and network formation, and whether these effects could be attributed to the lignosulfonate molecule itself or to the ions that are naturally present. The effects on the different starch components, amylose and amylopectin, were also studied by using starches varying in amylose content.

Section snippets

Materials

C☆Gel 03401 native maize starch (23% amylose, fat 0.1%, protein 0.3%, moisture 12%) and C☆Gel 04201 waxy maize starch (1–2% amylose, fat 0.1%, protein 0.3%, moisture 13%) from Cerestar Benelux BV, Sas van Gent, Netherlands.

Waxy barley starch (6% amylose) from Lyckeby Stärkelsen, Kristianstad, Sweden.

Ca-lignosulfonate (DP751, 3.6% Ca²⁺, 1.1% Na⁺, 6.0% S₀, 2–3% reduced sugars) and Na-lignosulfonate (DP752, 0.4% Ca²⁺, 6.1% Na⁺, 5.3% S₀, 2–3% reduced sugars) from LignoTech, Vargön, Sweden.

NaCl and

Maize starch gelatinization with lignosulfonates

The Brabender viscosity of a native maize starch solution was measured during heating with low (0.001%) and high (2%) concentrations of Ca-LS (calcium lignosulfonate) or Na-LS (sodium lignosulfonate). The Brabender viscographs for these four pastes are shown in Fig. 1. The viscosity of the low-LS samples followed the general trend for maize starch shown by e.g. Yoshimoto, Takenouchi, and Takeda (2002). It increased rapidly at about 80 °C, reached a peak of 580 B.U. at about 90 °C and decreased to

Conclusions

In this study it was shown that lignosulfonates had effects on starch gelatinization and gel formation. Some of the effects, such as a delayed granule swelling, a more gradual granule breakdown, a lower peak viscosity and greater inhomogeneity of the gel, were due to the lignosulfonate molecule itself. Other effects, such as an earlier amylose leakage during heating and a poor network formation after cooling, could be assigned to the presence of Ca²⁺ and Na⁺ ions in the lignosulfonate. With the

Acknowledgements

This work was part of a project financed by Vinnova (the Swedish Agency for Innovation Systems) and the collaboration partners Borregaard LignoTech, Chips Scandinavian Company AB, Lyckeby Stärkelsen and PPM Potato Processing Machinery AB. We are very grateful for all their help. Ingredients were also provided by Cerestar.

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Effects of Ca- and Na-lignosulfonate on starch gelatinization and network formation

Abstract

Introduction

Section snippets

Materials

Maize starch gelatinization with lignosulfonates

Conclusions

Acknowledgements

Carbohydrate Polymers

Carbohydrate Polymers

Food Hydrocolloids

Carbohydrate Polymers

Carbohydrate Polymers

Carbohydrate/emulsifier interactions

Polyelectrolyte complexes: interactions between lignosulfonate and chitosan

Biomacromolecules

Commercial use of lignin-based materials