Physicochemical surface properties of Chlorella vulgaris: a multiscale assessment, from electrokinetic and proton uptake descriptors to intermolecular adhesion forces.

Given the growing scientific and industrial interests in green microalgae, a comprehensive understanding of the forces controlling the colloidal stability of these bioparticles and their interactions with surrounding aqueous microenvironment is required. Accordingly, we addressed here the electrostatic and hydrophobic surface properties of Chlorella vulgaris from the population down to the individual cell levels. We first investigated the organisation of the electrical double layer at microalgae surfaces on the basis of electrophoresis measurements. Interpretation of the results beyond zeta-potential framework underlined the need to account for both the hydrodynamic softness of the algae cells and the heterogeneity of their interface formed with the outer electrolyte solution. We further explored the nature of the structural charge carriers at microalgae interfaces through potentiometric proton titrations. Extraction of the electrostatic descriptors of interest from such data was obscured by cell physiology processes and dependence thereof on prevailing measurement conditions, which includes light, temperature and medium salinity. As an alternative, cell electrostatics was successfully evaluated at the cellular level upon mapping the molecular interactions at stake between (positively and negatively) charged atomic force microscopy tips and algal surface via chemical force microscopy. A thorough comparison between charge-dependent tip-to-algae surface adhesion and hydrophobicity level of microalgae surface evidenced that the contribution of electrostatics to the overall interaction pattern is largest, and that the electrostatic/hydrophobic balance can be largely modulated by pH. Overall, the combination of multiscale physicochemical approaches allowed a drawing of some of the key biosurface properties that govern microalgae cell-cell and cell-surface interactions.

Electrostatics of soft (bio)interfaces: Corrections of mean-field Poisson-Boltzmann theory for ion size, dielectric decrement and ion-ion correlations.

HYPOTHESIS: Electrostatics of soft (ion-permeable) (bio)particles (e.g. microorganisms, core/shell colloids) in aqueous electrolytes is commonly formulated by the mean-field Poisson-Boltzmann theory and integration of the charge contributions from electrolyte ions and soft material. However, the effects connected to the size of the electrolyte ions and that of the structural charges carried by the particle, to dielectric decrement and ion-ion correlations on soft interface electrostatics have been so far considered at the margin, despite the limits of the Gouy theory for condensed and/or multivalent electrolytes. EXPERIMENTS: Accordingly, we modify herein the Poisson-Boltzmann theory for core/shell (bio)interfaces to include the aforementioned molecular effects considered separately or concomitantly. The formalism is applicable for poorly to highly charged particles in the thin electric double layer regime and to unsymmetrical multivalent electrolytes. FINDINGS: Computational examples of practical interests are discussed with emphasis on how each considered molecular effect or combination thereof affects the interfacial potential distribution depending on size and valence of cations and anions, size of particle charges, length scale of ionic correlations and shell-to-Debye layer thickness ratio. The origins of here-evidenced pseudo-harmonic potential profile and ion size-dependent screening of core/shell particle charges are detailed. In addition, the existence and magnitude of the Donnan potential when reached in the shell layer are shown to depend on the excluded volumes of the electrolyte ions.