Plant Acacia gum exudates are composed by glycosylated hydroxyproline-rich proteins, which have a high proportion of heavily branched neutral and charged sugars in the polysaccharide moiety. These hyperbranched arabinogalactan-proteins (AGP) display a complexity arising from its composition, architecture, and conformation, but also from its polydispersity and capacity to form supramolecular assemblies. Flexibility and hydration partly determined colloidal and interfacial properties of AGPs. In the present article, these parameters were estimated based on measurements of density and sound velocity and the determination of volumetric parameters, e.g., partial specific volume (vs°) and coefficient of partial specific adiabatic compressibility coefficient (βs°). Measurements were done with Acacia senegal, Acacia seyal, and fractions from the former separated according to their hydrophobicity by Hydrophobic Interaction Chromatography, i.e., HIC-F1, HIC-F2, and HIC-F3. Both gums presented close values of vs° and βs°. However, data on fractions suggested a less hydrated and more flexible structure of HIC-F3, in contrast to a less flexible and more hydrated structure of HIC-F2, and especially HIC-F1. The differences between the macromolecular fractions of A. senegal are significantly related to the fraction composition, protein/polysaccharide ratio, and type of amino acids and sugars, with a polysaccharide moiety mainly contributing to the global hydrophilicity and a protein part mainly contributing to the global hydrophobicity. These properties form the basis of hydration ability and flexibility of hyperbranched AGP from Acacia gums.
Adsorption of hyperbranched arabinogalactan-proteins (AGPs) from two plant exudates, A. senegal and A.seyal, was thoroughly studied at the solid–liquid interface using quartz crystal microbalance with dissipation monitoring (QCM-D), surface plasmon resonance (SPR), and atomic force microscopy (AFM). Isotherms of the adsorption reveal that 3.3 fold more AGPs from A. seyal (500 ppm) are needed to cover the gold surface compared to A. senegal (150 ppm). The pH and salt concentration of the environment greatly affected the adsorption behavior of both gums, with the surface density ranging from 0.92 to 3.83 mg m−2 using SPR (i.e., “dry” mass) and from 1.16 to 19.07 mg m−2 using QCM-D (wet mass). Surprisingly, the mass adsorbed was the highest in conditions of strong electrostatic repulsions between the gold substrate and AGPs, i.e., pH 7.0, highlighting the contribution of other interactions involved in the adsorption process. Structural changes of AGPs induced by pH would result in swelling of the polysaccharide blocks and conformational changes of the polypeptide backbone, therefore increasing the protein accessibility and hydrophobic interactions and/or hydrogen bonds with the gold substrate.
The adsorption of Acacia gum from two plant exudates, A. senegal and A. seyal, at the solid-liquid interface on oxide surfaces was studied using a quartz crystal microbalance with dissipation monitoring (QCM-D). The impact of the hydrophobic and electrostatic forces on the adsorption capacity was investigated by different surface, hydrophobicity, and charge properties, and by varying the ionic strength or the pH. The results highlight that hydrophobic forces have higher impacts than electrostatic forces on the Acacia gum adsorption on the oxide surface. The Acacia gum adsorption capacity is higher on hydrophobic surfaces compared to hydrophilic ones and presents a higher stability with negatively charged surfaces. The structural configuration and charge of Acacia gum in the first part of the adsorption process are important parameters. Acacia gum displays an extraordinary ability to adapt to surface properties through rearrangements, conformational changes, and/or dehydration processes in order to reach the steadiest state on the solid surface. Rheological analysis from QCM-D data shows that the A. senegal layers present a viscous behavior on the hydrophilic surface and a viscoelastic behavior on more hydrophobic ones. On the contrary, A. seyal layers show elastic behavior on all surfaces according to the Voigt model or a viscous behavior on the hydrophobic surface when considering the power-law model.