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Phase Separation in Xanthan Solutions

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Phase Separation in Xanthan Solutions CELLULOSE CHEMISTRY AND TECHNOLOGY PHASE SEPARATION IN XANTHAN SOLUTIONS SIMONA MORARIU, MARIA BERCEA and CRISTINA-ELIZA BRUNCHI “Petru Poni” Institute of Macromolecular Chemistry, 41A, Grigore Ghica Voda Alley, 700487 Iasi, Romania ✉Corresponding author: Simona Morariu, [email protected] Paper dedicated to Professor Bogdan C. Simionescu on the occasion of his 70th anniversary The effect of ethanol (Et), isopropanol (IP) and NaCl addition on xanthan gum (XG) separation from aqueous solution was investigated by turbidimetry at 25 °C. The turbidity started to increase in the presence of alcohols (above 10% Et and 5% IP), independently of the XG concentration in the initial aqueous solution. In contrast, the NaCl content, which determines an increase of the turbidity, was dependent on the XG quantity according to an established relationship. Upon addition of the alcohols, phase separation into a polymer-poor phase and a polymer‐rich one (with gel-like behaviour) was observed for both XG/water/Et and XG/water/NaCl/IP systems. After one week at rest, the gel-like phase of XG/water/Et system was more structured compared to that of XG/water/NaCl/IP system, in which XG precipitate was observed. NaCl addition reduced the alcohol quantity required to determine the separation of XG due to the enhancement of the polymer–polymer interactions in the presence of salt. The reduced viscosity of XG/water/Et system, higher than those of XG/water/NaCl/IP (at a constant XG/NaCl ratio), has also confirmed that the XG chains present a more compact conformation in the presence of salt. Keywords: xanthan, turbidity, phase separation, salt, alcohol, viscosity INTRODUCTION In the last years, xanthan gum (XG) been developed in order to extend the range of received great attention from both researchers applications of this polysaccharide. The usual and manufacturers due to its non-toxicity, modifications of biochemical parameters and biocompatibility, biodegradability and the morphological changes induced by acceptable cost, which permit its use in various neomycin sulphate can be excluded by its applications. In addition, the high viscosity at administration together with a XG/chitosan low concentrations and the rheological hydrogel complex, resulted from the properties of its solutions make XG applicable interaction of the amino groups of chitosan as a thickener in food,1,2 cosmetics,3,4 with the anionic ones of XG.16 Knowing the pharmaceutical and biomedical products5-7 etc., capacity of XG to improve the viscoelastic as a rheological control agent in aqueous properties of hydrogels and its bioactivity, systems for water-based paints or as a Sehgal et al.17 developed a bioactive tissue- stabilizer for emulsions or suspensions in the engineered scaffold containing xanthan, gellan food industry.8,9 The role of XG as a thickener and chitosan nanoparticles for bone and stabilizing agent in food formulations has regeneration. The eco-friendly hydrogels with been investigated in different combinations superabsorbant properties were prepared by with guar gum,10 rice starch,11 amidated low including different amounts of XG in a methoxyl pectin,12 chitosan,13 gelatin B,14 soy polymer matrix obtained by chemical protein hydrolysate15 etc. crosslinking of cellulose in different Various formulations based on mixtures of allomorphic forms.18 The literature reports XG with neutral or charged polymers have many investigations on the mixtures of XG Cellulose Chem. Technol., 52 (7-8), 569-576 (2018) SIMONA MORARIU et al. with natural (chitosan,19 guar gum,20 formation of two phases: a XG-poor phase and xyloglucan21 etc.) or synthetic (Pluronic a XG-rich one with gel-like properties; 3) for F127,22 poly(ethylene oxide),23 PVA24 etc.) 50%-75% alcohol, a clear separation of the polymers in order to elucidate the nature of the liquid and gel phases was obtained; 4) for an interactions established between the polymer alcohol content higher than 75%, a brittle chains that are responsible for the synergistic precipitate, difficult to separate by properties observed for these systems. centrifugation, is formed.31 XG is an anionic natural polysaccharide The presence of salt in the XG aqueous produced mainly from glucose by solutions decreases the amount of alcohol Xanthomonas campestris bacteria. The required to determine the precipitation of the macromolecules have the main chain with the polymer. The conformational changes and structure of cellulose (β-1,4-linked D-glucose polymer-polymer or polymer-solvent units), to which side chains of trisaccharides interactions from the XG solutions are (two mannose and one glucuronic acid) are influenced by a large number of factors, such attached. Due to its structure, strong polymer- as alcohol structure, pH, temperature, addition polymer interactions are established between of salts and concentration of components in the XG chains or with other polymers in mixture. multicomponent systems. In aqueous solution The study of stability of XG aqueous at 25 °C, the XG backbone is extended, but in solutions in the presence of salt or alcohols partially ordered form (randomly broken represents an important topic for research, as helix), due to the two types of possible well as for practical applications, because interactions between the chains: electrostatic many food formulations or personal care repulsive interactions and attractive products include salt and/or alcohol. In this interactions by hydrogen bonds.25 XG context, the purpose of this paper is to undergoes a transition from the ordered to the investigate the phase separation occurrence in disordered conformation as a function of the XG in water/ethanol and external conditions (temperature, addition of water/NaCl/isopropanol mixtures by salt, pH, solvent quality) and the structural turbidimetry and to analyse the viscometric factors (acetate and pyruvate substituent behaviour in the presence of non-solvent or content).26-28 The nature of ordered and salt. In addition, visual observations will be disordered structures, as well as the conditions made to support the conclusions obtained by in which XG chains adopt one or another of turbidimetry and viscometry concerning the these conformations, are still a matter of phase separation in the studied XG solutions. debate. For applications in the food industry, the EXPERIMENTAL knowledge of the effect of different additives Materials (for example, salt or alcohol) on the A xanthan gum (XG) sample was provided by viscoelastic properties and on the stability of Sigma-Aldrich and it was used as received. The viscometric molecular weight of XG, determined the systems containing XG is very important. previously,27 was 1.165 ×106 g/mol. NaCl, ethanol The decrease of xanthan solubility in water can (Et) and isopropanol (IP) were also purchased from be realized by the addition of salts,27,29,30 water 28,31-33 Sigma-Aldrich and were used without further miscible non-solvents (for example, purification. Homogeneous XG aqueous solutions, methanol, ethanol, isopropanol, acetone) or with concentrations between 0.003 g/dL and 0.4 salt/non-solvent mixtures,34,35 and by g/dL, were prepared by the dissolution of the increasing the solution concentration. polymer in Millipore water (obtained from a Milli- By addition of a non-solvent (ethanol, Q PF apparatus) at room temperature under gentle isopropanol or tert-butanol), the direct stirring. precipitation of XG from its aqueous solution does not occur. The following stages were Viscosity measurements The viscometry measurements were carried out observed as a function of the composition of at 25 °C, using an Ubbelohde viscometer of type I the solvent/non-solvent mixture: 1) up to about with a capillary diameter of 0.63 mm, and by 30% alcohol in the alcohol/water mixture XG sequential dilution. The viscometer was connected does not precipitate; 2) between 30% and 40% to an automatic system Lauda LMV 830 alcohol (as a function of the nature of the Instrument, Germany. Two XG solutions, with the alcohol), the solubility decreases leading to the concentration of about 0.02 g/dL in water/Et and 570 Xanthan water/NaCl/IP mixtures, were prepared. One upon adding up to 30% Et into solutions with solution was diluted with water/Et mixture (11% high XG concentration.36 For the total Et) and the second one was diluted with water/IP precipitation of XG from solutions with mixture (6% IP), keeping the XG/NaCl ratio concentrations higher than 0.3 g/dL, an ethanol constant during the viscometric measurements. The volume to solution volume ratio of 6 was quantity of NaCl was calculated by using the relationship between XG and NaCl, as determined necessary. This ratio was found to be independent of the polymer concentration in from the experimental data reported in the present 34 paper. the initial solution. Turbidimetry investigations Effect of IP addition on the turbidity of The turbidity measurements were performed on XG/NaCl/water mixtures a HACH 2100AN turbidimeter in the range of 400- The effect of salt addition on the solubility 600 nm wavelengths. For turbidimetry of XG in water depends on the valence of the measurements, a small quantity of NaCl solution cations. Thereby, the salts with monovalent (with set concentration) or alcohol (Et or IP) was cations (for example, sodium) do not affect the added into XG aqueous solutions and, after each addition, the turbidity in terms of NTU XG solubility, in contrast to the salts (Nephelometric Turbidity Unit) was determined. containing polyvalent cations, such as calcium, aluminum, quaternary ammonium, which 28,37 RESULTS AND DISCUSSION cause XG precipitation. The use of The behaviour of XG in aqueous solution quaternary ammonium salt in food applications and the effect of different non-solvents on the is not indicated because of its toxicity. phase separation represent subjects still In the present study, a slight increase of the discussed in the literature. The establishment turbidity was evidenced upon addition of NaCl of the conditions for XG phase separation into XG solutions with concentrations between requires good knowledge of the solution 0.01 g/dL and 0.10 g/dL (Fig.
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