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Title: Organophilic, Superparamagnetic, and Reversibly Thermoresponsive Silica-Polypeptide Core–Shell Particles

Abstract

Particles with a superparamagnetic cobalt inner core, silica outer core, and covalently bound homopolypeptide shell were investigated under thermal and magnetic stimuli. The homopolypeptide was poly(ε-carbobenzyloxy-l-lysine), PCBL, which is known to exhibit a thermoreversible coil ⇔ helix transition when dissolved as a pure polymer in m-cresol. Tethering to a core particle did not prevent PCBL from undergoing this conformational transition, as confirmed by dynamic light scattering and optical rotation, but the transition was broadened compared to that of the untethered polymer. The Co@SiO2-PCBL hybrid particles retained the superparamagnetic properties of the cobalt inner nougat. Indeed, some response remains even after aging for >5 years. The aged PCBL shell also preserved its responsiveness to temperature, although differences in the shape of the size vs temperature transition curve were determined compared to the freshly made particles. A reversible coil ⇔ helix transition for a particle-bound polypeptide in a pure organic solvent is rare. Further to providing a convenient tool for characterizing coil ⇔ helix transitions for surface-bound polypeptides without interference from pH or the strong ionic forces that dominate behavior in aqueous systems, the Co@SiO2-PCBL/m-cresol system may prove useful in studies of the effect of shell polymer conformation on colloid interactions. Themore » stability of the magnetic core and polypeptide shell suggest a long shelf life for Co@SiO2-PCBL, which can, in principle, be deprotected to yield positively charged Co@SiO2-poly(l-lysine) particles for possible transfection or antimicrobial applications or chained magnetically to produce responsive poly(colloids).« less

Authors:
 [1]; ORCiD logo [2];  [2];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [3]
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  1. Louisiana State University, Baton Rouge, LA (United States)
  2. Georgia Institute of Technology, Atlanta, GA (United States)
  3. Louisiana State University, Baton Rouge, LA (United States); Georgia Institute of Technology, Atlanta, GA (United States)
Publication Date:
Research Org.:
Louisiana State Univ., Baton Rouge, LA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1676368
Alternate Identifier(s):
OSTI ID: 1632688
Grant/Contract Number:  
SC0012432; CHE-0648841; ECCS-1542174
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 35; Journal Issue: 44; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Polymer particles; Peptides and proteins; Cobalt; Particulate matter; Polymers

Citation Formats

Turksen-Selcuk, Sibel, Rosu, Cornelia, Blake, Alyssa, Soto-Cantu, Erick, Qiu, Jianhong, Wu, Yan, DiTusa, J. F., Steffens, Amanda, and Russo, Paul S. Organophilic, Superparamagnetic, and Reversibly Thermoresponsive Silica-Polypeptide Core–Shell Particles. United States: N. p., 2019. Web. doi:10.1021/acs.langmuir.9b01931.
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Turksen-Selcuk, Sibel, Rosu, Cornelia, Blake, Alyssa, Soto-Cantu, Erick, Qiu, Jianhong, Wu, Yan, DiTusa, J. F., Steffens, Amanda, & Russo, Paul S. Organophilic, Superparamagnetic, and Reversibly Thermoresponsive Silica-Polypeptide Core–Shell Particles. United States. https://doi.org/10.1021/acs.langmuir.9b01931
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Turksen-Selcuk, Sibel, Rosu, Cornelia, Blake, Alyssa, Soto-Cantu, Erick, Qiu, Jianhong, Wu, Yan, DiTusa, J. F., Steffens, Amanda, and Russo, Paul S. Wed . "Organophilic, Superparamagnetic, and Reversibly Thermoresponsive Silica-Polypeptide Core–Shell Particles". United States. https://doi.org/10.1021/acs.langmuir.9b01931. https://www.osti.gov/servlets/purl/1676368.
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@article{osti_1676368,
title = {Organophilic, Superparamagnetic, and Reversibly Thermoresponsive Silica-Polypeptide Core–Shell Particles},
author = {Turksen-Selcuk, Sibel and Rosu, Cornelia and Blake, Alyssa and Soto-Cantu, Erick and Qiu, Jianhong and Wu, Yan and DiTusa, J. F. and Steffens, Amanda and Russo, Paul S.},
abstractNote = {Particles with a superparamagnetic cobalt inner core, silica outer core, and covalently bound homopolypeptide shell were investigated under thermal and magnetic stimuli. The homopolypeptide was poly(ε-carbobenzyloxy-l-lysine), PCBL, which is known to exhibit a thermoreversible coil ⇔ helix transition when dissolved as a pure polymer in m-cresol. Tethering to a core particle did not prevent PCBL from undergoing this conformational transition, as confirmed by dynamic light scattering and optical rotation, but the transition was broadened compared to that of the untethered polymer. The Co@SiO2-PCBL hybrid particles retained the superparamagnetic properties of the cobalt inner nougat. Indeed, some response remains even after aging for >5 years. The aged PCBL shell also preserved its responsiveness to temperature, although differences in the shape of the size vs temperature transition curve were determined compared to the freshly made particles. A reversible coil ⇔ helix transition for a particle-bound polypeptide in a pure organic solvent is rare. Further to providing a convenient tool for characterizing coil ⇔ helix transitions for surface-bound polypeptides without interference from pH or the strong ionic forces that dominate behavior in aqueous systems, the Co@SiO2-PCBL/m-cresol system may prove useful in studies of the effect of shell polymer conformation on colloid interactions. The stability of the magnetic core and polypeptide shell suggest a long shelf life for Co@SiO2-PCBL, which can, in principle, be deprotected to yield positively charged Co@SiO2-poly(l-lysine) particles for possible transfection or antimicrobial applications or chained magnetically to produce responsive poly(colloids).},
doi = {10.1021/acs.langmuir.9b01931},
journal = {Langmuir},
number = 44,
volume = 35,
place = {United States},
year = {2019},
month = {10}
}
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https://doi.org/10.1021/acs.langmuir.9b01931
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Figures / Tables:

Scheme 1 Scheme 1: Schematic illustration of the steps involved in the preparation of PCBL-functionalized superparamagnetic silica particles (Co@SiO2-PCBL).
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