Marine mussels use catechol-rich interfacial mussel foot proteins (mfps) as primers that attach to mineral surfaces via hydrogen, metal coordination, electrostatic, ionic, or hydrophobic bonds, creating a secondary surface that promotes bonding to the bulk mfps. Inspired by this biological adhesive primer, it is shown that a ≈1 nm thick catecholic single-molecule priming layer increases the adhesion strength of crosslinked polymethacrylate resin on mineral surfaces by up to an order of magnitude when compared with conventional primers such as noncatecholic silane- and phosphate-based grafts. Molecular dynamics simulations confirm that catechol groups anchor to a variety of mineral surfaces and shed light on the binding mode of each molecule. Here, a ≈50% toughness enhancement is achieved in a stiff load-bearing polymer network, demonstrating the utility of mussel-inspired bonding for processing a wide range of polymeric interfaces, including structural, load-bearing materials.
Bibliographical noteFunding Information:
S.S., D.W.L., J.S.A., and K.C. contributed equally to this work. This work was supported by the Office of Naval ResearchN000141310867 (S.S., J.H.W., B.K.A.), National Institute of HealthR01 DE018468 (D.W.L., J.H.W., J.N.I.), and a generous gift from the Valois Family (J.H.W.). Several experiments made use of the MRL Shared Experimental Facilities supported by the MRSEC Program of the National Science Foundation (NSF) under Award No. DMR 1121053; a member of the NSF-funded Materials Research Facilities Network. Authors wish to thank Osaka Organic Chemical Industry LTD for providing the triethylsilane-protected eugenol acrylate. S.S. was supported by Pusan National University Research Grant, 2017. D.W.L., J.S.A., S.W.J., and E.S., B.S.K. were supported by the National Research Foundation (NRF) 2016R1C1B2014294, the Marine Biotechnology Program D11013214H480000110 and NRF2010-0028684, respectively, funded by the South Korean Government. E.F. was supported by the MRSEC Program of the NSF under Award No. DMR-1121053. M.T.V. acknowledges support of the NSF through Award No. DMR-1410985. K.C. and R.D.L. acknowledge support from FACEPE, CAPES, and CNPq. J.E.S. acknowledges support from the Center for Scientific Computing at the California Nanosystems Institute (NSF Grant CNS-0960316), and the NSF through Award No. MCB-1158577. This work also used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by NSF Grant ACI-1053575 and the computational capabilities of the Texas Advanced Computing Center at the University of Texas at Austin (Grant MCA05S027). Partial computational resources were also provided by LNCC, the Brazilian Scientific Computing Center. Authors thank Alain Dequit from the Institut de Chemie de Clermont-Ferrand for providing the mica coordinates for molecular dynamics analyses and Wei Wei for her assistance in conducting and analyzing the QCM-D experiments. Note: The acknowledgements were corrected on October 12, 2017, after initial publication online to correctly indicate the initials of the equally contributing authors.
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All Science Journal Classification (ASJC) codes
- Materials Science(all)
- Mechanics of Materials
- Mechanical Engineering