State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, P. R. China.
Faculty of Pharmacy, Université de Montréal, 2900 Edouard-Montpetit, Montréal, Québec H3C 3J7, Canada.
ACS Appl Bio Mater. 2023 Feb 20;6(2):865-873. doi: 10.1021/acsabm.2c01009. Epub 2023 Jan 9.
Synergistic interactions between 3,4-dihydroxyphenylalanine (Dopa, Y*), cationic residues, and the aromatic rings have been recently highlighted as influential factors that enhance the underwater adhesion strength of mussel foot proteins and their derivatives. In this study, we report the first ever evidence of a cation-catechol-benzene ternary synergy between Y*, lysine (Lys, K), and phenylalanine (Phe, F) in adhesive peptides. We synthesized three hexapeptides containing a different combination of Y*, K, and F, , (KY*), (KF), and (KYF), respectively, exploring the relationship between the cohesive performance and molecular architecture of peptides. The peptide with the (KYF) sequence displays the strongest underwater cohesion energy of 10.3 ± 0.3 mJ m from direct nanoscale surface force measurements. Combined with molecular dynamics simulation, we demonstrated that there are more bonding interactions (including cation-π, π-π, and hydrogen bond interactions) in (KYF) compared to the other two peptides. In addition, peptide (KYF) still shows the strongest cohesive energies of 7.6 ± 0.7 and 3.7 ± 0.5 mJ m in acidic and high-ionic strength environments, respectively, although the cohesive energy decreases compared to the value in pure water. Our results further explain the underwater cohesion mechanisms combining multiple interactions and offer insights on designing Dopa containing underwater adhesives.
最近的研究表明，3,4-二羟基苯丙氨酸（Dopa，Y*）、阳离子残基和芳环之间的协同相互作用是增强贻贝足蛋白及其衍生物水下粘附强度的重要因素。在这项研究中，我们首次报道了在黏附肽中存在 Y*、赖氨酸（Lys，K）和苯丙氨酸（Phe，F）之间的阳离子-儿茶酚-苯三元协同作用的证据。我们合成了三个分别包含 Y*、K 和 F 的不同组合的六肽， ，（KY*），（KF）和（KYF），分别探索了肽的凝聚性能和分子结构之间的关系。序列为（KYF）的肽在直接纳米级表面力测量中显示出最强的水下内聚能为 10.3 ± 0.3 mJ m。结合分子动力学模拟，我们证明了（KYF）中存在更多的键合相互作用（包括阳离子-π、π-π 和氢键相互作用），与其他两种肽相比。此外，尽管与纯水中的值相比，在酸性和高离子强度环境中，肽（KYF）的内聚能分别为 7.6 ± 0.7 和 3.7 ± 0.5 mJ m，但仍表现出最强的内聚能。我们的研究结果进一步解释了结合多种相互作用的水下内聚机制，并为设计含 Dopa 的水下粘合剂提供了新的见解。
