Gelation of Fmoc-diphenylalanine is a first order phase transition

Dudukovic, Nikola A.; Zukoski, Charles F.

doi:10.1039/c5sm01399b

Gelation of Fmoc-diphenylalanine is a first order phase transition

Journal Article · Mon Aug 17 00:00:00 EDT 2015 · Soft Matter

DOI:https://doi.org/10.1039/c5sm01399b· OSTI ID:1875441

Dudukovic, Nikola A. ^[1]; Zukoski, Charles F. ^[2]

Univ. of Illinois at Urbana-Champaign, IL (United States); University of Illinois
Univ. at Buffalo, NY (United States)

We explore the gel transition of the aromatic dipeptide derivative molecule fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF). The addition of water to a solution of Fmoc-FF in dimethyl sulfoxide (DMSO) results in increased attractions leading to self-assembly of Fmoc-FF molecules into a space-filling fibrous network. We provide evidence that gel formation is associated with a first order phase transition resulting in nucleation and growth of strongly anisotropic crystals with high aspect ratios. The strength of attraction between Fmoc-FF molecules as a function of water concentration is estimated from long-time self-diffusion measurements using 1H NMR diffusion-ordered spectroscopy (DOSY). The resulting phase behavior follows that observed for a wide range of other crystallizing nanoparticles and small molecules – a result consistent with the short-range nature of the intermolecular attractions. Furthermore, we use NMR to measure the rate of increase in the fraction of bound Fmoc-FF molecules after water is suddenly mixed into the system. We observe a lag time in the formation of the new phase indicative of the existence of a free energy barrier to the formation of a crystal nucleus of critical size. Furthermore, the application of classical nucleation theory for a cylindrical nucleus indicates that one-dimensional crystal growth is driven by an imbalance of the surface energies of the ends and sides of the fiber.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: FG02-07ER46471

OSTI ID:: 1875441

Journal Information:: Soft Matter, Journal Name: Soft Matter Journal Issue: 38 Vol. 11; ISSN 1744-683X

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Pulsed-field gradient nuclear magnetic resonance as a tool for studying translational diffusion: Part 1. Basic theory Price, William S. Concepts in Magnetic Resonance, Vol. 9, Issue 5 https://doi.org/10.1002/(SICI)1099-0534(1997)9:5<299::AID-CMR2>3.0.CO;2-U	journal	January 1997
Nanostructured Hydrogels for Three-Dimensional Cell Culture Through Self-Assembly of Fluorenylmethoxycarbonyl–Dipeptides Jayawarna, V.; Ali, M.; Jowitt, T. A. Advanced Materials, Vol. 18, Issue 5 https://doi.org/10.1002/adma.200501522	journal	March 2006
Rigid, Self-Assembled Hydrogel Composed of a Modified Aromatic Dipeptide Mahler, A.; Reches, M.; Rechter, M. Advanced Materials, Vol. 18, Issue 11 https://doi.org/10.1002/adma.200501765	journal	June 2006
Fmoc-Diphenylalanine Self Assembles to a Hydrogel via a Novel Architecture Based on π–π Interlocked β-Sheets Smith, A. M.; Williams, R. J.; Tang, C. Advanced Materials, Vol. 20, Issue 1 https://doi.org/10.1002/adma.200701221	journal	January 2008
Diffusion NMR Spectroscopy in Supramolecular and Combinatorial Chemistry: An Old Parameter?New Insights Cohen, Yoram; Avram, Liat; Frish, Limor Angewandte Chemie International Edition, Vol. 44, Issue 4 https://doi.org/10.1002/anie.200300637	journal	January 2005
Beta-Sheet-Forming, Self-Assembled Peptide Nanomaterials towards Optical, Energy, and Healthcare Applications Kim, Sungjin; Kim, Jae Hong; Lee, Joon Seok Small, Vol. 11, Issue 30 https://doi.org/10.1002/smll.201500169	journal	April 2015
Phase behaviour and structure formation in solutions of poly(2,6-dimethyl-1,4-phenylene ether) Berghmans, S.; Mewis, J.; Berghmans, H. Polymer, Vol. 36, Issue 16 https://doi.org/10.1016/0032-3861(95)97869-H	journal	January 1995
Melting, freezing and colloidal suspensions Löwen, Hartmut Physics Reports, Vol. 237, Issue 5 https://doi.org/10.1016/0370-1573(94)90017-5	journal	February 1994
Molecular Origins of Osmotic Second Virial Coefficients of Proteins Neal, B. L.; Asthagiri, D.; Lenhoff, A. M. Biophysical Journal, Vol. 75, Issue 5 https://doi.org/10.1016/S0006-3495(98)77691-X	journal	November 1998
Protein interactions and crystallization Rosenbaum, D. F.; Zukoski, C. F. Journal of Crystal Growth, Vol. 169, Issue 4 https://doi.org/10.1016/S0022-0248(96)00455-1	journal	December 1996
Correlation of second virial coefficients and solubilities useful in protein crystal growth Guo, B.; Kao, S.; McDonald, H. Journal of Crystal Growth, Vol. 196, Issue 2-4 https://doi.org/10.1016/S0022-0248(98)00842-2	journal	January 1999
Introducing chemical functionality in Fmoc-peptide gels for cell culture Jayawarna, Vineetha; Richardson, Stephen M.; Hirst, Andrew R. Acta Biomaterialia, Vol. 5, Issue 3 https://doi.org/10.1016/j.actbio.2009.01.006	journal	March 2009
Gradient diffusion and protein solubility: use of dynamic light scattering to localize crystallization conditions Mirarefi, Amir Y.; Zukoski, Charles F. Journal of Crystal Growth, Vol. 265, Issue 1-2 https://doi.org/10.1016/j.jcrysgro.2004.01.043	journal	April 2004
Sedimentation in a dilute polydisperse system of interacting spheres. Part 2. Numerical results Batchelor, G. K.; Wen, C. -S. Journal of Fluid Mechanics, Vol. 124, Issue -1 https://doi.org/10.1017/S0022112082002602	journal	November 1982
Calculation of the resistance and mobility functions for two unequal rigid spheres in low-Reynolds-number flow Jeffrey, D. J.; Onishi, Y. Journal of Fluid Mechanics, Vol. 139 https://doi.org/10.1017/S0022112084000355	journal	February 1984
Self-Assembled Fmoc-Peptides as a Platform for the Formation of Nanostructures and Hydrogels Orbach, Ron; Adler-Abramovich, Lihi; Zigerson, Sivan Biomacromolecules, Vol. 10, Issue 9 https://doi.org/10.1021/bm900584m	journal	September 2009
Dense Liquid Precursor for the Nucleation of Ordered Solid Phases from Solution Vekilov, Peter G. Crystal Growth & Design, Vol. 4, Issue 4 https://doi.org/10.1021/cg049977w	journal	July 2004
Functional π-Gelators and Their Applications Babu, Sukumaran Santhosh; Praveen, Vakayil K.; Ajayaghosh, Ayyappanpillai Chemical Reviews, Vol. 114, Issue 4 https://doi.org/10.1021/cr400195e	journal	December 2013
Low Molecular Mass Gelators of Organic Liquids and the Properties of Their Gels Terech, Pierre; Weiss, Richard G. Chemical Reviews, Vol. 97, Issue 8, p. 3133-3160 https://doi.org/10.1021/cr9700282	journal	December 1997
Density, Viscosity, Refractive Index, and Speed of Sound in Aqueous Mixtures of N,N-Dimethylformamide, Dimethyl Sulfoxide, N,N-Dimethylacetamide, Acetonitrile, Ethylene Glycol, Diethylene Glycol, 1,4-Dioxane, Tetrahydrofuran, 2-Methoxyethanol, and 2-Ethoxyethanol at 298.15 K Aminabhavi, Tejraj M.; Gopalakrishna, Bindu Journal of Chemical & Engineering Data, Vol. 40, Issue 4 https://doi.org/10.1021/je00020a026	journal	July 1995
Fast Calculation of Molecular Polar Surface Area as a Sum of Fragment-Based Contributions and Its Application to the Prediction of Drug Transport Properties Ertl, Peter; Rohde, Bernhard; Selzer, Paul Journal of Medicinal Chemistry, Vol. 43, Issue 20 https://doi.org/10.1021/jm000942e	journal	October 2000
Generalized Phase Behavior of Small Molecules and Nanoparticles He, Guangwen; Tan, Reginald B. H.; Kenis, Paul J. A. The Journal of Physical Chemistry B, Vol. 111, Issue 43 https://doi.org/10.1021/jp074632k	journal	October 2007
Nanoparticle Crystal Nucleation: Influence of Solution Conditions Kulkarni, Amit M.; Zukoski, Charles F. Langmuir, Vol. 18, Issue 8 https://doi.org/10.1021/la011282z	journal	March 2002
The Rheological and Structural Properties of Fmoc-Peptide-Based Hydrogels: The Effect of Aromatic Molecular Architecture on Self-Assembly and Physical Characteristics Orbach, Ron; Mironi-Harpaz, Iris; Adler-Abramovich, Lihi Langmuir, Vol. 28, Issue 4 https://doi.org/10.1021/la204426q	journal	December 2011
Mechanical Properties of Self-Assembled Fmoc-Diphenylalanine Molecular Gels Dudukovic, Nikola A.; Zukoski, Charles F. Langmuir, Vol. 30, Issue 15 https://doi.org/10.1021/la500589f	journal	April 2014
Fmoc-Diphenylalanine Self-Assembly Mechanism Induces Apparent p K _a Shifts Tang, Claire; Smith, Andrew M.; Collins, Richard F. Langmuir, Vol. 25, Issue 16 https://doi.org/10.1021/la900653q	journal	August 2009
Designing a Bernal Spiral from Patchy Colloids Morgan, John W. R.; Chakrabarti, Dwaipayan; Dorsaz, Nicolas ACS Nano, Vol. 7, Issue 2 https://doi.org/10.1021/nn304677t	journal	January 2013
Fabrication of novel biomaterials through molecular self-assembly Zhang, Shuguang Nature Biotechnology, Vol. 21, Issue 10 https://doi.org/10.1038/nbt874	journal	September 2003
Fmoc-diphenylalanine hydrogels: understanding the variability in reported mechanical properties Raeburn, Jaclyn; Pont, Guillaume; Chen, Lin Soft Matter, Vol. 8, Issue 4 https://doi.org/10.1039/C1SM06929B	journal	January 2012
Evidence for equilibrium gels of valence-limited particles Dudukovic, Nikola A.; Zukoski, Charles F. Soft Matter, Vol. 10, Issue 39 https://doi.org/10.1039/C4SM01389A	journal	January 2014
The effect of solvent choice on the gelation and final hydrogel properties of Fmoc–diphenylalanine Raeburn, Jaclyn; Mendoza-Cuenca, Cristina; Cattoz, Beatrice N. Soft Matter, Vol. 11, Issue 5 https://doi.org/10.1039/C4SM02256D	journal	January 2015
Peptide-based stimuli-responsive biomaterials Mart, Robert J.; Osborne, Rachel D.; Stevens, Molly M. Soft Matter, Vol. 2, Issue 10 https://doi.org/10.1039/b607706d	journal	January 2006
Designing peptide based nanomaterials Ulijn, Rein V.; Smith, Andrew M. Chemical Society Reviews, Vol. 37, Issue 4 https://doi.org/10.1039/b609047h	journal	January 2008
The role of self-assembling polypeptides in building nanomaterials Liu, Lei; Busuttil, Katerina; Zhang, Shuai Physical Chemistry Chemical Physics, Vol. 13, Issue 39 https://doi.org/10.1039/c1cp21338e	journal	January 2011
Simulations of nucleation and elongation of amyloid fibrils Zhang, Jianing; Muthukumar, M. The Journal of Chemical Physics, Vol. 130, Issue 3 https://doi.org/10.1063/1.3050295	journal	January 2009
Diffusion coefficients and effective viscosity of suspensions of sticky hard spheres with hydrodynamic interactions Cichocki, B.; Felderhof, B. U. The Journal of Chemical Physics, Vol. 93, Issue 6 https://doi.org/10.1063/1.459688	journal	September 1990
Interactions in undersaturated and supersaturated lysozyme solutions: Static and dynamic light scattering results Muschol, Martin; Rosenberger, Franz The Journal of Chemical Physics, Vol. 103, Issue 24 https://doi.org/10.1063/1.469891	journal	December 1995
Classical nucleation theory for the nucleation of the solid phase of spherical particles with a short-ranged attraction Sear, Richard P. The Journal of Chemical Physics, Vol. 111, Issue 5 https://doi.org/10.1063/1.479512	journal	August 1999
Characterizing nanoparticle interactions: Linking models to experiments Ramakrishnan, S.; Zukoski, C. F. The Journal of Chemical Physics, Vol. 113, Issue 3 https://doi.org/10.1063/1.481901	journal	July 2000
Nanoscale dynamics and aging of fibrous peptide-based gels Dudukovic, Nikola A.; Zukoski, Charles F. The Journal of Chemical Physics, Vol. 141, Issue 16 https://doi.org/10.1063/1.4899905	journal	October 2014
Phase Behavior of Small Attractive Colloidal Particles Rosenbaum, D.; Zamora, P. C.; Zukoski, C. F. Physical Review Letters, Vol. 76, Issue 1, p. 150-153 https://doi.org/10.1103/PhysRevLett.76.150	journal	January 1996
Jammed hard-particle packings: From Kepler to Bernal and beyond Torquato, S.; Stillinger, F. H. Reviews of Modern Physics, Vol. 82, Issue 3, p. 2633-2672 https://doi.org/10.1103/RevModPhys.82.2633	journal	September 2010
Brownian Motion of an Ellipsoid Han, Y.; Alsayed, A. M.; Nobili, M. Science, Vol. 314, Issue 5799 https://doi.org/10.1126/science.1130146	journal	October 2006
Role of Intermolecular Forces in Defining Material Properties of Protein Nanofibrils Knowles, T. P.; Fitzpatrick, A. W.; Meehan, S. Science, Vol. 318, Issue 5858 https://doi.org/10.1126/science.1150057	journal	December 2007
Role of metastable states in phase ordering dynamics Evans, R. M. L.; Poon, W. C. K.; Cates, M. E. Europhysics Letters (EPL), Vol. 38, Issue 8 https://doi.org/10.1209/epl/i1997-00289-y	journal	June 1997
Principles of Crystal Nucleation and Growth De Yoreo, J. J. Reviews in Mineralogy and Geochemistry, Vol. 54, Issue 1 https://doi.org/10.2113/0540057	journal	January 2003

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