Nanoscale dynamics and aging of fibrous peptide-based gels
Abstract
Solutions of the aromatic dipeptide derivative molecule fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) in dimethyl sulfoxide produce fibrous gels when mixed with water. We study the evolution of density fluctuations of this three-component system using X-ray photon correlation spectroscopy (XPCS) and compare these results to the macroscopic rheology of the gels and optical observations of the microstructure evolution. At the investigated scattering angles, the intensity autocorrelation functions do not follow behavior expected for simple diffusion of individual Fmoc-FF molecules localized within cages of nearest neighbors. Instead, the dynamics are associated with density fluctuations on length scales of ~10–100 nm arising from disaggregation and reformation of fibers, leading to an increasingly uniform network. This process is correlated with the growth of the elastic modulus, which saturates at long times. Autocorrelation functions and relaxation times acquired from XPCS measurements are consistent with relaxation rates of structures at dynamic equilibrium. Furthermore, this study provides further support to the concept of exploring peptide-based gelators as valence-limited patchy particles capable of forming equilibrium gels.
- Authors:
-
- Univ. of Illinois at Urbana-Champaign, IL (United States)
- Univ. at Buffalo, NY (United States)
- Publication Date:
- Research Org.:
- Univ. of Illinois at Urbana-Champaign, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE
- OSTI Identifier:
- 1875822
- Alternate Identifier(s):
- OSTI ID: 1224252
- Grant/Contract Number:
- FG02-07ER46471; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 16; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical compounds; Complex systems theory; Elastic modulus; Reversible process; Colloidal systems; Solvents; Fibrous gels; X ray photon correlation spectroscopy; Peptides; Rheology and fluid dynamics
Citation Formats
Dudukovic, Nikola A., and Zukoski, Charles F. Nanoscale dynamics and aging of fibrous peptide-based gels. United States: N. p., 2014.
Web. doi:10.1063/1.4899905.
Dudukovic, Nikola A., & Zukoski, Charles F. Nanoscale dynamics and aging of fibrous peptide-based gels. United States. https://doi.org/10.1063/1.4899905
Dudukovic, Nikola A., and Zukoski, Charles F. Tue .
"Nanoscale dynamics and aging of fibrous peptide-based gels". United States. https://doi.org/10.1063/1.4899905. https://www.osti.gov/servlets/purl/1875822.
@article{osti_1875822,
title = {Nanoscale dynamics and aging of fibrous peptide-based gels},
author = {Dudukovic, Nikola A. and Zukoski, Charles F.},
abstractNote = {Solutions of the aromatic dipeptide derivative molecule fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) in dimethyl sulfoxide produce fibrous gels when mixed with water. We study the evolution of density fluctuations of this three-component system using X-ray photon correlation spectroscopy (XPCS) and compare these results to the macroscopic rheology of the gels and optical observations of the microstructure evolution. At the investigated scattering angles, the intensity autocorrelation functions do not follow behavior expected for simple diffusion of individual Fmoc-FF molecules localized within cages of nearest neighbors. Instead, the dynamics are associated with density fluctuations on length scales of ~10–100 nm arising from disaggregation and reformation of fibers, leading to an increasingly uniform network. This process is correlated with the growth of the elastic modulus, which saturates at long times. Autocorrelation functions and relaxation times acquired from XPCS measurements are consistent with relaxation rates of structures at dynamic equilibrium. Furthermore, this study provides further support to the concept of exploring peptide-based gelators as valence-limited patchy particles capable of forming equilibrium gels.},
doi = {10.1063/1.4899905},
journal = {Journal of Chemical Physics},
number = 16,
volume = 141,
place = {United States},
year = {Tue Oct 28 00:00:00 EDT 2014},
month = {Tue Oct 28 00:00:00 EDT 2014}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 8 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Fmoc-diphenylalanine hydrogels: understanding the variability in reported mechanical properties
journal, January 2012
- Raeburn, Jaclyn; Pont, Guillaume; Chen, Lin
- Soft Matter, Vol. 8, Issue 4
Peptide-based stimuli-responsive biomaterials
journal, January 2006
- Mart, Robert J.; Osborne, Rachel D.; Stevens, Molly M.
- Soft Matter, Vol. 2, Issue 10
Mechanical Properties of Self-Assembled Fmoc-Diphenylalanine Molecular Gels
journal, April 2014
- Dudukovic, Nikola A.; Zukoski, Charles F.
- Langmuir, Vol. 30, Issue 15
Introducing chemical functionality in Fmoc-peptide gels for cell culture
journal, March 2009
- Jayawarna, Vineetha; Richardson, Stephen M.; Hirst, Andrew R.
- Acta Biomaterialia, Vol. 5, Issue 3
Dynamics of Block Copolymer Micelles Revealed by X-Ray Intensity Fluctuation Spectroscopy
journal, February 1997
- Mochrie, S. G. J.; Mayes, A. M.; Sandy, A. R.
- Physical Review Letters, Vol. 78, Issue 7
Casting Metal Nanowires Within Discrete Self-Assembled Peptide Nanotubes
journal, April 2003
- Reches, M.
- Science, Vol. 300, Issue 5619
Designing peptide based nanomaterials
journal, January 2008
- Ulijn, Rein V.; Smith, Andrew M.
- Chemical Society Reviews, Vol. 37, Issue 4
Relationship between molecular structure, gelation behaviour and gel properties of Fmoc-dipeptides
journal, January 2010
- Adams, Dave J.; Mullen, Leanne M.; Berta, Marco
- Soft Matter, Vol. 6, Issue 9
The Rheological and Structural Properties of Fmoc-Peptide-Based Hydrogels: The Effect of Aromatic Molecular Architecture on Self-Assembly and Physical Characteristics
journal, December 2011
- Orbach, Ron; Mironi-Harpaz, Iris; Adler-Abramovich, Lihi
- Langmuir, Vol. 28, Issue 4
Tuneable mechanical properties in low molecular weight gels
journal, January 2011
- Chen, Lin; Raeburn, Jaclyn; Sutton, Sam
- Soft Matter, Vol. 7, Issue 20
Fabrication of novel biomaterials through molecular self-assembly
journal, September 2003
- Zhang, Shuguang
- Nature Biotechnology, Vol. 21, Issue 10
Relationship between Structural and Stress Relaxation in a Block-Copolymer Melt
journal, June 2006
- Patel, Amish J.; Narayanan, Suresh; Sandy, Alec
- Physical Review Letters, Vol. 96, Issue 25
Gel formation and aging in weakly attractive nanocolloid suspensions at intermediate concentrations
journal, October 2011
- Guo, Hongyu; Ramakrishnan, S.; Harden, James L.
- The Journal of Chemical Physics, Vol. 135, Issue 15
Structure and Transport Anomalies in Soft Colloids
journal, April 2013
- Srivastava, Samanvaya; Archer, Lynden A.; Narayanan, Suresh
- Physical Review Letters, Vol. 110, Issue 14
Nanostructured Hydrogels for Three-Dimensional Cell Culture Through Self-Assembly of Fluorenylmethoxycarbonyl–Dipeptides
journal, March 2006
- Jayawarna, V.; Ali, M.; Jowitt, T. A.
- Advanced Materials, Vol. 18, Issue 5
Universal non-diffusive slow dynamics in aging soft matter
journal, September 2002
- Cipelletti, Luca; Ramos, Laurence; Manley, S.
- Faraday Discussions, Vol. 123
Rigid, Self-Assembled Hydrogel Composed of a Modified Aromatic Dipeptide
journal, June 2006
- Mahler, A.; Reches, M.; Rechter, M.
- Advanced Materials, Vol. 18, Issue 11
Polymer nanocomposites: polymer and particle dynamics
journal, January 2012
- Kim, Daniel; Srivastava, Samanvaya; Narayanan, Suresh
- Soft Matter, Vol. 8, Issue 42
Nanoparticle Motion within Glassy Polymer Melts
journal, February 2009
- Guo, Hongyu; Bourret, Gilles; Corbierre, Muriel K.
- Physical Review Letters, Vol. 102, Issue 7
Self-Assembled Fmoc-Peptides as a Platform for the Formation of Nanostructures and Hydrogels
journal, September 2009
- Orbach, Ron; Adler-Abramovich, Lihi; Zigerson, Sivan
- Biomacromolecules, Vol. 10, Issue 9
Fmoc-Diphenylalanine Self-Assembly Mechanism Induces Apparent p K a Shifts
journal, August 2009
- Tang, Claire; Smith, Andrew M.; Collins, Richard F.
- Langmuir, Vol. 25, Issue 16
Dynamic Signatures of Microphase Separation in a Block Copolymer Melt Determined by X-ray Photon Correlation Spectroscopy and Rheology
journal, February 2010
- Patel, Amish J.; Mochrie, Simon; Narayanan, Suresh
- Macromolecules, Vol. 43, Issue 3
Reversible gels of patchy particles
journal, December 2011
- Sciortino, Francesco; Zaccarelli, Emanuela
- Current Opinion in Solid State and Materials Science, Vol. 15, Issue 6
Use of a gel-forming dipeptide derivative as a carrier for antigen presentation
journal, November 1995
- Vegners, Rolands; Shestakova, Irina; Kalvinsh, Ivars
- Journal of Peptide Science, Vol. 1, Issue 6
Self-sustaining, fluorescent and semi-conducting co-assembled organogel of Fmoc protected phenylalanine with aromatic amines
journal, January 2012
- Bairi, Partha; Roy, Bappaditya; Routh, Parimal
- Soft Matter, Vol. 8, Issue 28
Evolution of dynamics and structure during formation of a cross-linked polymer gel
journal, June 2011
- Czakkel, O.; Madsen, A.
- EPL (Europhysics Letters), Vol. 95, Issue 2
Crowded, Confined, and Frustrated: Dynamics of Molecules Tethered to Nanoparticles
journal, December 2012
- Agarwal, Praveen; Kim, Sung A.; Archer, Lynden A.
- Physical Review Letters, Vol. 109, Issue 25
XPCS: Nanoscale motion and rheology
journal, February 2012
- Leheny, Robert L.
- Current Opinion in Colloid & Interface Science, Vol. 17, Issue 1
Thermal Jamming of a Colloidal Glass
journal, December 2011
- Agarwal, Praveen; Srivastava, Samanvaya; Archer, Lynden A.
- Physical Review Letters, Vol. 107, Issue 26
Anomalous dynamical light scattering in soft glassy gels
journal, November 2001
- Bouchaud, J. -P.; Pitard, E.
- The European Physical Journal E, Vol. 6, Issue 3
Fmoc-Diphenylalanine Self Assembles to a Hydrogel via a Novel Architecture Based on π–π Interlocked β-Sheets
journal, January 2008
- Smith, A. M.; Williams, R. J.; Tang, C.
- Advanced Materials, Vol. 20, Issue 1
Phase Diagram of Patchy Colloids: Towards Empty Liquids
journal, October 2006
- Bianchi, Emanuela; Largo, Julio; Tartaglia, Piero
- Physical Review Letters, Vol. 97, Issue 16
Colloidal gels: equilibrium and non-equilibrium routes
journal, July 2007
- Zaccarelli, Emanuela
- Journal of Physics: Condensed Matter, Vol. 19, Issue 32
Amino acid based smart hydrogel: formation, characterization and fluorescence properties of silver nanoclusters within the hydrogel matrix
journal, January 2011
- Roy, Subhasish; Banerjee, Arindam
- Soft Matter, Vol. 7, Issue 11
Controlled Release from Modified Amino Acid Hydrogels Governed by Molecular Size or Network Dynamics
journal, September 2009
- Sutton, Sam; Campbell, Neil L.; Cooper, Andrew I.
- Langmuir, Vol. 25, Issue 17
Works referencing / citing this record:
Self-assembly pathways and polymorphism in peptide-based nanostructures
journal, January 2018
- Dudukovic, Nikola A.; Hudson, Benjamin C.; Paravastu, Anant K.
- Nanoscale, Vol. 10, Issue 3
Recent applications of synchrotron radiation and neutrons in the study of soft matter
journal, February 2017
- Narayanan, Theyencheri; Wacklin, Hanna; Konovalov, Oleg
- Crystallography Reviews, Vol. 23, Issue 3