Sulfate groups on cellulose particles such as cellulose nanocrystals (CNCs) provide colloidal stability credit to electrostatic repulsion between the like-charged particles. The introduction of sodium counter cations on the sulfate groups enables drying of the CNC suspensions without irreversible aggregation. Less is known about the effect of other counter cations than sodium on extending the properties of the CNC particles. Here, we introduce the alkali metal counter cations, Li+, Na+, K+, Rb+, and Cs+, on sulfated CNCs without an ion exchange resin, which, so far, has been a common practice. We demonstrate that the facile ion exchange is an efficient method to exchange to any alkali metal cation of sulfate half esters, with exchange rates between 76 and 89%. The ability to form liquid crystalline order in rest was observed by the presence of birefringence patterns and followed the Hofmeister series prediction of a decreasing ability to form anisotropy with an increasing element number. However, we observed the K-CNC rheology and birefringence as a stand-out case within the series of alkali metal modifications, with dynamic moduli and loss tangent indicating a network disruptive effect compared to the other counter cations, whereas observation of the development of birefringence patterns in flow showed the absence of self- or dynamically-assembled liquid crystalline order.
Interactions of biomolecules at interfaces are important for a variety of physiological processes. Among these, interactions of lectins with monosaccharides have been investigated extensively in the past, while polysaccharide-lectin interactions have scarcely been investigated. Here, we explore the adsorption of galactomannans (GM) extracted from Prosopis affinis on cellulose thin films determined by a combination of multi-parameter surface plasmon resonance spectroscopy (MP-SPR) and atomic force microscopy (AFM). The galactomannan adsorbs spontaneously on the cellulose surfaces forming monolayer type coverage (0.60 ± 0.20 mg·m−2). The interaction of a lectin, Concavalin A (ConA), with these GM rendered cellulose surfaces using MP-SPR has been investigated and the dissociation constant KD (2.1 ± 0.8 × 10−8 M) was determined in a range from 3.4 to 27.3 nM. The experiments revealed that the galactose side chains as well as the mannose reducing end of the GM are weakly interacting with the active sites of the lectins, whereas these interactions are potentially amplified by hydrophobic effects between the non-ionic GM and the lectins, thereby leading to an irreversible adsorption.