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Stimuli-responsive properties of peptide-based copolymers studied via directional growth of self-assembled patterns on solid substrate.

ABSTRACT: We studied the self-assembly of peptide-based ABA and CBC triblock-copolymers (obtained by bacterial expression) containing random coiled hydrophilic central B blocks flanked with helical A or C blocks. The A and C blocks were of different compositions with respect to the fraction of lysine residues which provided a higher pH sensitivity of the copolymer solutions. The interchain interactions of the copolymers driven by external stimuli (pH and temperature) were explored in the process of macromolecular self-assembling in the thin films of the copolymer solutions deposited on the solid substrate. The interactions involved in the macromolecular association affected the morphology of the developed patterns. The polypeptide of the B block was not involved in the formation of the secondary structures, while the A and C blocks demonstrated helical folding responsible for the intermolecular association. The mechanism of the responsive behavior of the copolymers is based on the reversible assembling of the helices into coiled-coil structures upon the change of pH or temperature. It was found that at low pH values, when electrostatic repulsion was strong and the A/C blocks unfolded, assembling yielded fractal dendrites. Increasing the pH resulted in the recovery of the helical conformation of the A/C blocks and caused a transition from the fractal to compact structures. An elevation of temperature resulted in the disruption of the dendritic structures. The reported here approach to the evaluation of the intermolecular interactions, based on the analysis of the dendritic patterns, provides a rapid and simple method for the characterization of complex processes of self-assembling biomacromolecules.

SUBMITTER: Sheparovych R

PROVIDER: S-EPMC2891947 | biostudies-literature | 2009 Jul

REPOSITORIES: biostudies-literature

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Stimuli-responsive properties of peptide-based copolymers studied via directional growth of self-assembled patterns on solid substrate.

Sheparovych Roman R Roiter Yuri Y Yang Jiyuan J Kopeček Jindřich J Minko Sergiy S

Biomacromolecules 20090617 7

We studied the self-assembly of peptide-based ABA and CBC triblock-copolymers (obtained by bacterial expression) containing random coiled hydrophilic central B blocks flanked with helical A or C blocks. The A and C blocks were of different compositions with respect to the fraction of lysine residues which provided a higher pH sensitivity of the copolymer solutions. The interchain interactions of the copolymers driven by external stimuli (pH and temperature) were explored in the process of macrom ...[more]

PMID: 19534549

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Project description:INTRODUCTION:Intracellular delivery is a key step for many applications in medicine and for investigations into cellular function. This is particularly true for immunotherapy, which often requires controlled delivery of antigen and adjuvants to the cytoplasm of immune cells. Due to the complex responses generated by the stimulation of diverse immune cell populations, it is critical to monitor which cells are targeted during treatment. To address this issue, we have engineered an immunotheranostic polymersome delivery system that fluorescently marks immune cells following intracellular delivery. METHODS:N-(3-bromopropyl)phthalimide end-capped poly(ethylene glycol)-bl-poly(propylene sulfide) (PEG-PPS-PI) was synthesized by anionic ring opening polymerization and linked with PEG-PPS-NH2 via a perylene bisimide (PBI) bridge to form a tetrablock copolymer (PEG-PPS-PBI-PPS-PEG). Block copolymers were assembled into polymersomes by thin film hydration in phosphate buffered saline and characterized by dynamic light scattering, cryogenic electron microscopy and fluorescence spectroscopy. Polymersomes were injected subcutaneously into the backs of mice, and draining lymph nodes were extracted for flow cytometric analysis of cellular uptake and disassembly. RESULTS:Modular self-assembly of tetrablock / diblock copolymers in aqueous solutions induced ?-? stacking of the PBI linker that both red-shifted and quenched the PBI fluorescence. Reactive oxygen species within the endosomes of phagocytic immune cell populations oxidized the PPS blocks, which disassembled the polymersomes for dequenching and shifting of the PBI fluorescence from 640 nm to 550 nm emission. Lymph node resident macrophages and dendritic cells were found to increase in 550 nm emission over the course of 3 days by flow cytometry. CONCLUSIONS:Immunotheranostic polymersomes present a versatile platform to probe the contributions of specific cell populations during the elicitation of controlled immune responses. Flanking PBI with two oxidation-sensitive hydrophobic PPS blocks enhanced ? stacking and introduced a mechanism for disrupting ?-? interactions to shift PBI fluorescence in response to oxidative conditions. Shifts from red (640 nm) to green (550 nm) fluorescence occurred in the presence of physiologically relevant concentrations of reactive oxygen species and could be observed within phagocytic cells both in vitro and in vivo.

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Stimuli-responsive properties of peptide-based copolymers studied via directional growth of self-assembled patterns on solid substrate.

Publications

Stimuli-responsive properties of peptide-based copolymers studied via directional growth of self-assembled patterns on solid substrate.

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