AFM-based single-molecule force spectroscopy has been used to study the effect of Hofmeister salts and protein hydrophobicity on the adhesion of recombinant spider silk proteins onto solid substrates. Therefore, a molecular probe consisting of a spider silk protein and an AFM tip has been developed, which (i) is a well-defined, small system that can be simulated by molecular dynamics simulations, (ii) allows access to the whole soluble concentration range for ions, and (iii) provides the distribution of desorption forces rather than just ensemble-averaged mean values. The measured desorption forces follow the Hofmeister series for anions (H2PO4-, Cl-, I-) with a stabilizing energy of more than 15 kBT for 5 M NaH2PO4. Moreover, this effect is influenced by the hydrophobicity of the spider silk protein, indicating that hydrophobic and Hofmeister effects are closely related.
In this paper we probe the influence of surface properties, pH and salt on the adhesion of recombinant spider silk proteins onto solid substrates with single molecule force spectroscopy. A single engineered spider silk protein (monomeric C(16) or dimeric (QAQ)(8)NR3) is covalently bound with one end to an AFM tip, which assures long-time measurements for hours with one and the same protein. The tip with the protein is brought into contact with various substrates at various buffer conditions and then retracted to desorb the protein. We observe a linear dependence of the adhesion force on the concentration of three selected salts (NaCl, NaH(2)PO(4) and NaI) and a Hofmeister series both for anions and cations. As expected, the more hydrophobic C(16) shows a higher adhesion force than (QAQ)(8)NR3, and the adhesion force rises with the hydrophobicity of the substrate. Unexpected is the magnitude of the dependences--we never observe a change of more than 30%, suggesting a surprisingly well-regulated balance between dispersive forces, water-structure-induced forces as well as co-solute-induced forces in biopolymer adhesion.
A method based on atomic force microscopy is used to delineate the properties that determine single-molecule adhesion onto solid substrates in aqueous environment. Hydrophobicity as well as electrical properties of the substrate and the polymer are varied. In addition, the influence of the solvent composition, in particular the effect of ions, on the molecular adhesion at the solid-liquid interface is studied. Surprisingly, the polymer and surface-related properties account for only small changes in adhesion force, while dissolved ions show a much larger effect. These results point towards the energy of solvation as the most important contribution to adhesion for a wide variety of polymers and substrate materials.
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