Peptide-amphiphile nanofibers: a versatile scaffold for the preparation of self-assembling materials - PubMed (original) (raw)
Peptide-amphiphile nanofibers: a versatile scaffold for the preparation of self-assembling materials
Jeffrey D Hartgerink et al. Proc Natl Acad Sci U S A. 2002.
Abstract
Twelve derivatives of peptide-amphiphile molecules, designed to self-assemble into nanofibers, are described. The scope of amino acid selection and alkyl tail modification in the peptide-amphiphile molecules are investigated, yielding nanofibers varying in morphology, surface chemistry, and potential bioactivity. The results demonstrate the chemically versatile nature of this supramolecular system and its high potential for manufacturing nanomaterials. In addition, three different modes of self-assembly resulting in nanofibers are described, including pH control, divalent ion induction, and concentration.
Figures
Figure 1
Chemical structure of PA 4.
Figure 2
Time sequence of pH-controlled PA self-assembly and disassembly. (Upper) From left to right molecule 6dissolved in water at a concentration of 0.5% by weight at pH 8 is exposed to HCl vapor. As the acid diffused into the solution a gel phase is formed, which self-supports upon inversion (Far Left). (Lower) The same gel is treated with NH4OH vapor, which increases the pH and disassembles the gel, returning it to a fully dissolved solution.
Figure 3
Light microscopy image of a gel formed from PA 4 between crossed polarizers. Birefringence indicates orientation of the material at the level of tens of microns.
Figure 4
TEM image of fibers formed from molecules 3 (a) and 5 (b). Samples were negatively stained with phosphotungstic acid.
Figure 5
Schematic illustrating the self-assembly and covalent capture of the PAs based on pH and oxidation state. Molecules self-assemble upon acidification and dissassemble at neutral and basic pH when fully reduced. Molecules that are oxidized will not self-assemble at acidic pH, likely because of the distorted conformation required by intramolecular disulfide bonds. Supramolecular fibers that are oxidized (polymerized) lose their sensitivity to pH and are thus stable across a much broader range of pH, including physiological.
Figure 6
TEM image of fibers formed from molecules 6 (a) and 7 (b). Samples were negatively stained with phosphotungstic acid. PA 6 displays a strong tendency to form parallel arrays of fibers whereas PA 7 does not.
Figure 7
TEM images of fibers formed from molecules 9 (a),11 (b), and 12 (c). Samples were negatively stained with phosphotungstic acid. Although fibers with a diameter between 5 and 8 nm are formed in all cases, the length and stiffness of the fibers formed vary considerably.
Figure 8
TEM images of molecule 3 (a) self-assembled by drying directly onto a TEM grid without adjusted pH and molecule4 (b) self-assembled by mixing with CaCl2. Molecule 3 is negatively stained with phosphotungstic acid whereas molecule 4 is positively stained with uranyl acetate. In both cases the same fibrous morophology is observed as is seen by pH-induced self-assembly.
Similar articles
- Peptide nanofibers with dynamic instability through nonequilibrium biocatalytic assembly.
Debnath S, Roy S, Ulijn RV. Debnath S, et al. J Am Chem Soc. 2013 Nov 13;135(45):16789-92. doi: 10.1021/ja4086353. Epub 2013 Oct 31. J Am Chem Soc. 2013. PMID: 24147566 - Self-assembly behavior of peptide amphiphiles (PAs) with different length of hydrophobic alkyl tails.
Xu XD, Jin Y, Liu Y, Zhang XZ, Zhuo RX. Xu XD, et al. Colloids Surf B Biointerfaces. 2010 Nov 1;81(1):329-35. doi: 10.1016/j.colsurfb.2010.07.027. Epub 2010 Jul 16. Colloids Surf B Biointerfaces. 2010. PMID: 20678903 - Electrostatic effects on nanofiber formation of self-assembling peptide amphiphiles.
Toksoz S, Mammadov R, Tekinay AB, Guler MO. Toksoz S, et al. J Colloid Interface Sci. 2011 Apr 1;356(1):131-7. doi: 10.1016/j.jcis.2010.12.076. Epub 2011 Jan 1. J Colloid Interface Sci. 2011. PMID: 21269637 - Peptide synthesis and self-assembly.
Maude S, Tai LR, Davies RP, Liu B, Harris SA, Kocienski PJ, Aggeli A. Maude S, et al. Top Curr Chem. 2012;310:27-69. doi: 10.1007/128_2011_234. Top Curr Chem. 2012. PMID: 22025061 Review. - Designing peptide based nanomaterials.
Ulijn RV, Smith AM. Ulijn RV, et al. Chem Soc Rev. 2008 Apr;37(4):664-75. doi: 10.1039/b609047h. Epub 2008 Jan 10. Chem Soc Rev. 2008. PMID: 18362975 Review.
Cited by
- A bioactive supramolecular and covalent polymer scaffold for cartilage repair in a sheep model.
Lewis JA, Nemke B, Lu Y, Sather NA, McClendon MT, Mullen M, Yuan SC, Ravuri SK, Bleedorn JA, Philippon MJ, Huard J, Markel MD, Stupp SI. Lewis JA, et al. Proc Natl Acad Sci U S A. 2024 Aug 13;121(33):e2405454121. doi: 10.1073/pnas.2405454121. Epub 2024 Aug 6. Proc Natl Acad Sci U S A. 2024. PMID: 39106310 - Advancing Synthetic Hydrogels through Nature-Inspired Materials Chemistry.
Soliman BG, Nguyen AK, Gooding JJ, Kilian KA. Soliman BG, et al. Adv Mater. 2024 Oct;36(42):e2404235. doi: 10.1002/adma.202404235. Epub 2024 Jul 1. Adv Mater. 2024. PMID: 38896849 Review. - Responsive Supramolecular Polymers for Diagnosis and Treatment.
Martínez-Orts M, Pujals S. Martínez-Orts M, et al. Int J Mol Sci. 2024 Apr 6;25(7):4077. doi: 10.3390/ijms25074077. Int J Mol Sci. 2024. PMID: 38612886 Free PMC article. Review. - A Self-Assembled 3D Model Demonstrates How Stiffness Educates Tumor Cell Phenotypes and Therapy Resistance in Pancreatic Cancer.
Liu Y, Okesola BO, Osuna de la Peña D, Li W, Lin ML, Trabulo S, Tatari M, Lawlor RT, Scarpa A, Wang W, Knight M, Loessner D, Heeschen C, Mata A, Pearce OMT. Liu Y, et al. Adv Healthc Mater. 2024 Jul;13(17):e2301941. doi: 10.1002/adhm.202301941. Epub 2024 Mar 22. Adv Healthc Mater. 2024. PMID: 38471128 Free PMC article. - Nanotechnology in sexual medicine.
Podlasek CA. Podlasek CA. J Sex Med. 2024 Jan 30;21(2):81-83. doi: 10.1093/jsxmed/qdad149. J Sex Med. 2024. PMID: 38314625
References
- Clark T D, Kobayashi K, Ghadiri M R. Chem Eur J. 1999;5:782–792.
- Lehn J M. Supramolecular Chemistry: Concepts and Perspectives. Weinheim, Germany: VCH; 1995.
- Hartgerink J D, Clark T D, Ghadiri M R. Chem Eur J. 1998;4:1367–1372.
- Atwood J L, Lehn J M, Davies J E D, MacNicol D D, Vogtle F. Comprehensive Supramolecular Chemistry. New York: Pergamon; 1996.
- Ghadiri M R, Granja J R, Milligan R A, McRee D E, Khazanovich N. Nature (London) 1993;366:324–327. - PubMed
Publication types
MeSH terms
Substances
LinkOut - more resources
Full Text Sources
Other Literature Sources