The interfacial structure and Young's modulus of peptide films having switchable mechanical properties
Abstract
We report the structure and Young's modulus of switchable films formed by peptide self-assembly at the air–water interface. Peptide surfactant AM1 forms an interfacial film that can be switched, reversibly, from a high- to low-elasticity state, with rapid loss of emulsion and foam stability. Using neutron reflectometry, we find that the AM1 film comprises a thin (approx. 15 Å) layer of ordered peptide in both states, confirming that it is possible to drastically alter the mechanical properties of an interfacial ensemble without significantly altering its concentration or macromolecular organization. We also report the first experimentally determined Young's modulus of a peptide film self-assembled at the air–water interface (E=80 MPa for AM1, switching to E<20 MPa). These findings suggest a fundamental link between E and the macroscopic stability of peptide-containing foam. Finally, we report studies of a designed peptide surfactant, Lac21E, which we find forms a stronger switchable film than AM1 (E=335 MPa switching to E<4 MPa). In contrast to AM1, Lac21E switching is caused by peptide dissociation from the interface (i.e. by self-disassembly). This research confirms that small changes in molecular design can lead to similar macroscopic behaviour via surprisingly different mechanisms.
References
Abbott N.L . 2001New horizons for surfactant science in chemical engineering. AIChE J 47, 2634–2639.doi:10.1002/aic.690471202. Crossref, ISI, Google ScholarAydogan N& Abbott N.L . 2001Comparison of the surface activity and bulk aggregation of ferrocenyl surfactants with cationic and anionic headgroups. Langmuir 17, 5703–5706.doi:10.1021/la010178e. Crossref, ISI, Google ScholarAydogan N, Rosslee C.A& Abbott N.L . 2002Reassessment of the surface activity of ferrocenyldimethylammonium surfactants. Colloids Surf. A Physicochem. Eng. Asp 201, 101–109.doi:10.1016/S0927-7757(01)00823-8. Crossref, ISI, Google ScholarChen N.H, Kuhl T, Tadmor R, Lin Q& Israelachvili J . 2004Large deformations during the coalescence of fluid interfaces. Phys. Rev. Lett 92, 024 501doi:10.1103/PhysRevLett.92.024501. Crossref, ISI, Google ScholarCohen C& Parry D.A.D . 1990α-Helical coiled coils and bundles: how to design an α-helical protein. Proteins 7, 1–15.doi:10.1002/prot.340070102. Crossref, PubMed, ISI, Google ScholarCrick F.H.C . 1952Is α-keratin a coiled coil?Nature 170, 882–883.doi:10.1038/170882b0. Crossref, PubMed, ISI, Google ScholarCrick F.H.C . 1953The packing of α-helices—simple coiled-coils. Acta Crystallogr 6, 689–697.doi:10.1107/S0365110X53001964. Crossref, Google ScholarDagastine R.R, Manica R, Carnie S.L, Chan D.Y.C, Stevens G.W& Grieser F . 2006Dynamic forces between two deformable oil droplets in water. Science 313, 210–213.doi:10.1126/science.1125527. Crossref, PubMed, ISI, Google ScholarDebregeas G, de Gennes P.G& Brochard-Wyart F . 1998The life and death of “bare” viscous bubbles. Science 279, 1704–1707.doi:10.1126/science.279.5357.1704. Crossref, PubMed, ISI, Google ScholarDegrado W.F& Lear J.D . 1985Induction of peptide conformation at apolar/water interfaces. 1. A study with model peptides of defined hydrophobic periodicity. J. Am. Chem. Soc 107, 7684–7689.doi:10.1021/ja00311a076. Crossref, ISI, Google ScholarDexter A.F, Malcolm A.S& Middelberg A.P.J . 2006Reversible active switching of the mechanical properties of a peptide film at a fluid–fluid interface. Nat. Mater 5, 502–506.doi:10.1038/nmat1653. Crossref, PubMed, ISI, Google ScholarFairman R, Chao H.G, Lavoie T.B, Villafranca J.J, Matsueda G.R& Novotny J . 1996Design of heterotetrameric coiled coils: evidence for increased stabilization by Glu(−)–Lys(+) ion pair interactions. Biochemistry 35, 2824–2829.doi:10.1021/bi952784c. Crossref, PubMed, ISI, Google ScholarFragneto G, Thomas R.K, Rennie A.R& Penfold J . 1995Neutron reflection study of bovine beta-casein adsorbed on OTS self-assembled monolayers. Science 267, 657–660.doi:10.1126/science.7839141. Crossref, PubMed, ISI, Google ScholarGallardo B.S, Hwa M.J& Abbott N.L . 1995In-situ and reversible control of the surface-activity of ferrocenyl surfactants in aqueous-solutions. Langmuir 11, 4209–4212.doi:10.1021/la00011a008. Crossref, ISI, Google ScholarGallardo B.S, Metcalfe K.L& Abbott N.L . 1996Ferrocenyl surfactants at the surface of water: principles for active control of interfacial properties. Langmuir 12, 4116–4124.doi:10.1021/la960199m. Crossref, ISI, Google ScholarHenderson M, Perriman A, Robson-Marsden H& White J . 2005Protein–poly(silicic) acid interactions at the air/solution interface. J. Phys. Chem. B 109, 20 878–20 886.doi:10.1021/jp051908k. Crossref, ISI, Google ScholarHolt S.A, Henderson M.J& White J.W . 2002Thermal denaturation of interfacial protein layers. Aust. J. Chem 55, 449–459.doi:10.1071/CH02100. Crossref, ISI, Google ScholarJacrot B& Zaccai G . 1981Determination of molecular weight by neutron scattering. Biopolymers 20, 2413–2426.doi:10.1002/bip.1981.360201110. Crossref, ISI, Google ScholarJones D.B& Middelberg A.P.J Direct determination of the mechanical properties of an interfacially adsorbed protein film. Chem. Eng. Sci 572002a1711–1722.doi:10.1016/S0009-2509(02)00057-X. Crossref, ISI, Google ScholarJones D.B& Middelberg A.P.J Mechanical properties of interfacially adsorbed peptide networks. Langmuir 182002b10 357–10 362.doi:10.1021/la0262203. Crossref, ISI, Google ScholarJones D.B& Middelberg A.P.J Micromechanical testing of interfacial protein networks demonstrates ensemble behaviour characteristic of a nanostructured biomaterial. Langmuir 182002c5585–5591.doi:10.1021/la020090g. Crossref, ISI, Google ScholarJones D.B& Middelberg A.P.J . 2003Interfacial protein networks and their impact on droplet breakup. AIChE J 49, 1533–1541.doi:10.1002/aic.690490617. Crossref, ISI, Google ScholarKohn W.D& Hodges R.S . 1998De novo design of α-helical coiled coils and bundles: models for the development of protein-design principles. Trends Biotechnol 16, 379–389.doi:10.1016/S0167-7799(98)01212-8. Crossref, ISI, Google ScholarLee A.L, Kinnear S.A& Wand A.J . 2000Redistribution and loss of side chain entropy upon formation of a calmodulin–peptide complex. Nat. Struct. Biol 7, 72–77.doi:10.1038/71280. Crossref, PubMed, Google ScholarLeon E, Verma N, Zhang S, Lauffenburger D& Kamm R . 1998Mechanical properties of a self-assembling oligopeptide matrix. J. Biomater. Sci. Polym. Ed 9, 297–312. Crossref, PubMed, ISI, Google ScholarLiu Y, Jessop P.G, Cunningham M, Eckert C.A& Liotta C.L . 2006Switchable surfactants. Science 313, 958–960.doi:10.1126/science.1128142. Crossref, PubMed, ISI, Google ScholarLu J& Thomas R . 1998Neutron reflection from wet interfaces. J. Chem. Soc. Faraday Trans 94, 995–1018.doi:10.1039/a707853f. Crossref, Google ScholarLu J.R, Lee E.M& Thomas R.K . 1996The analysis and interpretation of neutron and X-ray specular reflection. Acta Crystallogr. A 52, 11–41.doi:10.1107/S0108767395011202. Crossref, Google ScholarLu J.R, Perumal S, Powers E.T, Kelly J.W, Webster J.R.P& Penfold J . 2003Adsorption of beta-hairpin peptides on the surface of water: a neutron reflection study. J. Am. Chem. Soc 125, 3751–3757.doi:10.1021/ja0292290. Crossref, PubMed, ISI, Google ScholarLu J.R, Perumal S, Hopkinson I, Webster J.R.P, Penfold J, Hwang W& Zhang S.G . 2004Interfacial nano-structuring of designed peptides regulated by solution pH. J. Am. Chem. Soc 126, 8940–8947.doi:10.1021/ja049477r. Crossref, PubMed, ISI, Google ScholarLu J.R, Su T.J, Thomas R.K, Penfold J& Webster J . 1998Structural conformation of lysozyme layers at the air/water interface studied by neutron reflection. J. Chem. Soc. Faraday Trans 94, 3279–3287.doi:10.1039/a805731a. Crossref, Google ScholarLucassen J . 1981Dynamic properties of free liquid films and foams.& Lucassen-Reynders E.H In Anionic surfactants: physical chemistry of surfactant action. Surfactant science series vol. 11New York, NY:Marcel Dekker, Inc217–265. Google ScholarMalcolm A.S, Dexter A.F& Middelberg A.P.J Foaming properties of a peptide designed to form stimuli–responsive interfacial films. Soft Matter 22006a1057–1066.doi:10.1039/b609960b. Crossref, ISI, Google ScholarMalcolm A.S, Dexter A.F& Middelberg A.P.J Mechanical properties of interfacial films formed by lysozyme self-assembly at the air–water interface. Langmuir 222006b8897–8905.doi:10.1021/la060565u. Crossref, PubMed, ISI, Google ScholarMathur A.M, Drescher B, Scranton A.B& Klier J . 1998Polymeric emulsifiers based on reversible formation of hydrophobic units. Nature 392, 367–370.doi:10.1038/32856. Crossref, ISI, Google ScholarMiddelberg A.P.J, Radke C.J& Blanch H.W . 2000Peptide interfacial adsorption is kinetically limited by the thermodynamic stability of self association. Proc. Natl Acad. Sci. USA 97, 5054–5059.doi:10.1073/pnas.080042597. Crossref, PubMed, ISI, Google ScholarMyers D . 1999Surfaces, interfaces, and colloids: principles and applications. New York, NY:Wiley-VCH. Google ScholarPenfold J& Thomas R . 2002Solvent distribution in non-ionic surfactant monolayers. Phys. Chem. Chem. Phys 4, 2648–2652.doi:10.1039/b108698g. Crossref, ISI, Google ScholarRapaport H . 2006Ordered peptide assemblies at interfaces. Supramol. Chem 18, 445–454.doi:10.1080/10610270600665905. Crossref, ISI, Google ScholarReches M& Gazit E . 2006Controlled patterning of aligned self-assembled peptide nanotubes. Nat. Nanotechnol 1, 195–200.doi:10.1038/nnano.2006.139. Crossref, PubMed, ISI, Google ScholarRosslee C& Abbott N.L . 2000Active control of interfacial properties. Curr. Opin. Colloid Interf. Sci 5, 81–87.doi:10.1016/S1359-0294(00)00035-2. Crossref, ISI, Google ScholarRuben M, Rojo J, Romero-Salguero F.J, Uppadine L.H& Lehn J.M . 2004Grid-type metal ion architectures: functional metallosupramolecular arrays. Angew. Chem. Int. Ed 43, 3644–3662.doi:10.1002/anie.200300636. Crossref, PubMed, ISI, Google ScholarShang T.G, Smith K.A& Hatton T.A . 2003Photoresponsive surfactants exhibiting unusually large, reversible surface tension changes under varying illumination conditions. Langmuir 19, 10 764–10 773.doi:10.1021/la0350958. Crossref, ISI, Google ScholarShin J.Y& Abbott N.L . 1999Using light to control dynamic surface tensions of aqueous solutions of water soluble surfactants. Langmuir 15, 4404–4410.doi:10.1021/la981477f. Crossref, ISI, Google ScholarSjogren H& Ulvenlund S . 2004Effects of pH, ionic strength, calcium, and molecular mass on the arrangement of hydrophobic peptide helices at the air–water interface. J. Phys. Chem. B 108, 20 219–20 227.doi:10.1021/jp047858l. Crossref, ISI, Google ScholarSmith A.E, Moxham K.E& Middelberg A.P.J Wall material properties of yeast cells. Part II. Analysis. Chem. Eng. Sci 552000a2043–2053.doi:10.1016/S0009-2509(99)00501-1. Crossref, ISI, Google ScholarSmith A.E, Zhang Z.B, Thomas C.R, Moxham K.E& Middelberg A.P.J The mechanical properties of Saccharomyces cerevisiae. Proc. Natl Acad. Sci. USA 972000b9871–9874.doi:10.1073/pnas.97.18.9871. Crossref, PubMed, ISI, Google ScholarStrzalka J, Gibney B.R, Satija S& Blasie J.K . 2004Specular neutron reflectivity and the structure of artificial protein maquettes vectorially oriented at interfaces. Phys. Rev. E 70, 061 905doi:10.1103/PhysRevE.70.061905. Crossref, ISI, Google Scholarvan der Rijt J.A.J, van der Werf K.O, Bennink M.L, Dijkstra P.J& Feijen J . 2006Micromechanical testing of individual collagen fibrils. Macromol. Biosci 6, 697–702.doi:10.1002/mabi.200600063. Crossref, PubMed, ISI, Google ScholarZhang S.G . 2003Fabrication of novel biomaterials through molecular self-assembly. Nat. Biotechnol 21, 1171–1178.doi:10.1038/nbt874. Crossref, PubMed, ISI, Google ScholarZhang S . 2006Another brick in the wall. Nat. Nanotechnol 1, 169–170.doi:10.1038/nnano.2006.154. Crossref, PubMed, ISI, Google ScholarZhao X.J& Zhang S.G . 2004Fabrication of molecular materials using peptide construction motifs. Trends Biotechnol 22, 470–476.doi:10.1016/j.tibtech.2004.07.011. Crossref, PubMed, ISI, Google ScholarZhao X& Zhang S . 2006Molecular designer self-assembling peptides. Chem. Soc. Rev 35, 1105–1110.doi:10.1039/b511336a. Crossref, PubMed, ISI, Google Scholar


