Abstract
Supramolecular assembly is a powerful method that can be used to generate materials with well-defined structures across multiple length scales. Supramolecular assemblies consisting of biopolymer-synthetic polymer subunits are specifically known to exhibit exceptional structural and functional diversity as well as programmable control of noncovalent interactions through hydrogen bonding in biopolymer subunits. Despite recent progress, there is a need to control and quantitatively understand assembly under nonequilibrium conditions. In this work, we study the nonequilibrium self-assembly of π-conjugated synthetic oligopeptides using a combination of experiments and analytical modeling. By isolating an aqueous peptide solution droplet within an immiscible organic layer, the rate of peptide assembly in the aqueous solution can be controlled by tuning the transport rate of acid that is used to trigger assembly. Using this approach, peptides are guided to assemble under reaction-dominated and diffusion-dominated conditions, with results showing a transition from a diffusion-limited reaction front to spatially homogeneous assembly as the transport rate of acid decreases. Interestingly, our results show that the morphology of self-assembled peptide fibers is controlled by the assembly kinetics such that increasingly homogeneous structures of self-assembled synthetic oligopeptides were generally obtained using slower rates of assembly. We further developed an analytical reaction-diffusion model to describe oligopeptide assembly, and experimental results are compared to the reaction-diffusion model across a range of parameters. Overall, this work highlights the importance of molecular self-assembly under nonequilibrium conditions, specifically showing that oligopeptide assembly is governed by a delicate balance between reaction kinetics and transport processes.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 3977-3984 |
| Number of pages | 8 |
| Journal | ACS Applied Materials and Interfaces |
| Volume | 9 |
| Issue number | 4 |
| DOIs | |
| State | Published - Feb 1 2017 |
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Keywords
- Biohybrid materials
- Diffusion-controlled
- Nonequilibrium assembly
- Optoelectronic materials
- Reaction-controlled
- Supramolecular assembly
- π-conjugated oligopeptides
ASJC Scopus subject areas
- Materials Science(all)
Cite this
Nonequilibrium self-assembly of π-conjugated oligopeptides in solution. / Li, Bo; Li, Songsong; Zhou, Yuecheng; Ardoña, Herdeline Ann M.; Valverde, Lawrence R.; Wilson, William L.; Tovar, John D.; Schroeder, Charles M.
In: ACS Applied Materials and Interfaces, Vol. 9, No. 4, 01.02.2017, p. 3977-3984.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Nonequilibrium self-assembly of π-conjugated oligopeptides in solution
AU - Li, Bo
AU - Li, Songsong
AU - Zhou, Yuecheng
AU - Ardoña, Herdeline Ann M.
AU - Valverde, Lawrence R.
AU - Wilson, William L.
AU - Tovar, John D.
AU - Schroeder, Charles M
PY - 2017/2/1
Y1 - 2017/2/1
N2 - Supramolecular assembly is a powerful method that can be used to generate materials with well-defined structures across multiple length scales. Supramolecular assemblies consisting of biopolymer-synthetic polymer subunits are specifically known to exhibit exceptional structural and functional diversity as well as programmable control of noncovalent interactions through hydrogen bonding in biopolymer subunits. Despite recent progress, there is a need to control and quantitatively understand assembly under nonequilibrium conditions. In this work, we study the nonequilibrium self-assembly of π-conjugated synthetic oligopeptides using a combination of experiments and analytical modeling. By isolating an aqueous peptide solution droplet within an immiscible organic layer, the rate of peptide assembly in the aqueous solution can be controlled by tuning the transport rate of acid that is used to trigger assembly. Using this approach, peptides are guided to assemble under reaction-dominated and diffusion-dominated conditions, with results showing a transition from a diffusion-limited reaction front to spatially homogeneous assembly as the transport rate of acid decreases. Interestingly, our results show that the morphology of self-assembled peptide fibers is controlled by the assembly kinetics such that increasingly homogeneous structures of self-assembled synthetic oligopeptides were generally obtained using slower rates of assembly. We further developed an analytical reaction-diffusion model to describe oligopeptide assembly, and experimental results are compared to the reaction-diffusion model across a range of parameters. Overall, this work highlights the importance of molecular self-assembly under nonequilibrium conditions, specifically showing that oligopeptide assembly is governed by a delicate balance between reaction kinetics and transport processes.
AB - Supramolecular assembly is a powerful method that can be used to generate materials with well-defined structures across multiple length scales. Supramolecular assemblies consisting of biopolymer-synthetic polymer subunits are specifically known to exhibit exceptional structural and functional diversity as well as programmable control of noncovalent interactions through hydrogen bonding in biopolymer subunits. Despite recent progress, there is a need to control and quantitatively understand assembly under nonequilibrium conditions. In this work, we study the nonequilibrium self-assembly of π-conjugated synthetic oligopeptides using a combination of experiments and analytical modeling. By isolating an aqueous peptide solution droplet within an immiscible organic layer, the rate of peptide assembly in the aqueous solution can be controlled by tuning the transport rate of acid that is used to trigger assembly. Using this approach, peptides are guided to assemble under reaction-dominated and diffusion-dominated conditions, with results showing a transition from a diffusion-limited reaction front to spatially homogeneous assembly as the transport rate of acid decreases. Interestingly, our results show that the morphology of self-assembled peptide fibers is controlled by the assembly kinetics such that increasingly homogeneous structures of self-assembled synthetic oligopeptides were generally obtained using slower rates of assembly. We further developed an analytical reaction-diffusion model to describe oligopeptide assembly, and experimental results are compared to the reaction-diffusion model across a range of parameters. Overall, this work highlights the importance of molecular self-assembly under nonequilibrium conditions, specifically showing that oligopeptide assembly is governed by a delicate balance between reaction kinetics and transport processes.
KW - Biohybrid materials
KW - Diffusion-controlled
KW - Nonequilibrium assembly
KW - Optoelectronic materials
KW - Reaction-controlled
KW - Supramolecular assembly
KW - π-conjugated oligopeptides
UR - http://www.scopus.com/inward/record.url?scp=85011697989&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85011697989&partnerID=8YFLogxK
U2 - 10.1021/acsami.6b15068
DO - 10.1021/acsami.6b15068
M3 - Article
VL - 9
SP - 3977
EP - 3984
JO - ACS applied materials & interfaces
JF - ACS applied materials & interfaces
SN - 1944-8244
IS - 4
ER -