Atomistic Characterization of Healthy and Damaged Hair Surfaces: A Molecular Dynamics Study of Fatty Acids on Protein Layer

Abstract Amid the bourgeoning demand for in‐silico designed, environmentally sustainable, and highly effective hair care formulations, a growing interest is evident in the exploration of realistic computational model for the hair surface. In this work, we present an atomistic model for the outermost layer of the hair surface derived through molecular dynamics simulations, which comprises 18‐Methyleicosanoic acid (18‐MEA) fatty acid chains covalently bound onto the keratin‐associated protein 10‐4 (KAP10‐4) at a spacing distance of ~1 nm. Remarkably, this hair surface model facilitates the inclusion of free fatty acids (free 18‐MEA) into the gaps between chemically bound 18‐MEA chains, up to a maximum number that results in a packing density of 0.22 nm 2 per fatty acid molecule, consistent with the optimal spacing identified through free energy analysis. Atomistic insights are provided for the organization of fatty acid chains, structural features, and interaction energies on protein‐inclusive hair surface models with varying amounts of free 18‐MEA (FMEA) depletion, as well as varying degrees of anionic cysteic acid from damaged bound 18‐MEA (BMEA), under both dry and wet conditions. In the presence of FMEA and water, the fatty acid chains in a pristine hair surface prefers to adopt a thermodynamically favored extended chain conformation, forming a thicker protective layer (~3 nm) on the protein surface. Our simulation results reveal that, while the depletion of FMEA can induce a pronounced impact on the thickness, tilt angle, and order parameters of fatty acid chains, the removal of BMEA has a marked effect on water penetration. There is a “sweet spot” spacing between the 18‐MEA whereby damaged hair surface properties can be reinstated by replenishing FMEA. Through the incorporation of the protein layer and free fatty acids, the hair surface models presented in this study enables a realistic representation of the intricate details within the hair epicuticle, facilitating a molecular scale assessment of surface properties during the formulation design process.