Molecular Context of Dopa Influences Adhesion of Mussel-Inspired Peptides

Abstract

Improving adhesives for wet surfaces is an ongoing challenge. While the adhesive proteins of marine mussels have inspired many synthetic wet adhesives, the mechanisms of mussel adhesion are still not fully understood. Using surface forces apparatus (SFA) measurements and replica-exchange and umbrella-sampling molecular dynamics simulations, we probed the relationships between the sequence, structure, and adhesion of mussel-inspired peptides. Experimental and computational results reveal that peptides derived from mussel foot protein 3 slow (mfp-3s) containing 3,4-dihydroxy­phenylalanine (Dopa), a post-translationally modified variant of tyrosine commonly found in mussel foot proteins, form adhesive monolayers on mica. In contrast, peptides with tyrosine adsorb as weakly adhesive clusters. We further considered simulations of mfp-3s derivatives on a range of hydrophobic and hydrophilic organic and inorganic surfaces (including silica, self-assembled monolayers, and a lipid bilayer) and demonstrated that the chemical character of the target surface and proximity of cationic and hydrophobic residues to Dopa affect peptide adsorption and adhesion. Collectively, our results suggest that conversion of tyrosine to Dopa in hydrophobic, sparsely charged peptides influences peptide self-association and ultimately dictates their adhesive performance.

Selectively Positioned Catechol Moiety Supports Ultrashort Self-Assembling Peptide Hydrogel Adhesion for Coral Restoration

“…We can speculate that the positive charge provided by lysine is preventing dopa oxidation when inserted in the IIZK peptide . In additon, it was reported that hydrophobic aminoacids can also prevent dopa oxidation, , another possible explanation given the hydrophobic component in the dopa peptides of this study.…”

In Silico Design and Analysis of Plastic-Binding Peptides

“…Instead, PepBD aims to identify potential peptide "hits" that bind strongly to a target material. The hits can be further evaluated using either computational methods, like umbrella sampling 56 or metadynamics, 57 or experimental methods, like surface plasmon resonance 58 or quartz crystal microbalance. 59 We omit these evaluations in the current work, as our aim is to describe the PepBD design algorithm and its outputs.…”

Wetting behavior of polyelectrolyte complex coacervates on solid surfaces

“…11 Emerging technologies of complex coacervates include targeted drug delivery, 12,13 fabrication of hydrogels, 14 and development of wet adhesives. 15 Utilizing complex coacervation relies on understanding the factors that influence the bulk phase behavior and interfacial properties. Knowing the location of the two-phase boundary for a variety of solution conditions is crucial to exploit the phase transition.…”

“…The performance of wet adhesives critically depends on their ability to wet a substrate in complex and challenging environments, such as the human body. 34 Recently, there has been a proliferation of wet adhesive materials inspired by the adhesives created by marine organisms, 15,35 notably the sandcastle worm [36][37][38][39][40] and seawater mussel. 33,[41][42][43][44][45] Both of these creatures secrete glue-like proteins that undergo coacervation (complex coacervation or single-component coacervation), wet the adhering surface, and cure into a strong adhesive.…”

“…11 Emerging technologies of complex coacervates include targeted drug delivery, 12,13 fabrication of hydrogels, 14 and development of wet adhesives. 15…”