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

Turksen-Selcuk, Sibel; Rosu, Cornelia; Blake, Alyssa; Soto-Cantu, Erick; Qiu, Jianhong; Wu, Yan; DiTusa, J. F.; Steffens, Amanda; Russo, Paul S.

doi:10.1021/acs.langmuir.9b01931

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

Journal Article · 23 October 2019 · Langmuir

DOI: https://doi.org/10.1021/acs.langmuir.9b01931 · OSTI ID:1676368

Turksen-Selcuk, Sibel ^[1];

^[2]; Blake, Alyssa ^[2]; Soto-Cantu, Erick ^[1]; Qiu, Jianhong ^[1]; Wu, Yan ^[1]; DiTusa, J. F. ^[1]; Steffens, Amanda ^[1];

^[3]

Louisiana State University, Baton Rouge, LA (United States)
Georgia Institute of Technology, Atlanta, GA (United States)
Louisiana State University, Baton Rouge, LA (United States); Georgia Institute of Technology, Atlanta, GA (United States)

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).

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Louisiana State Univ., Baton Rouge, LA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0012432; CHE-0648841; ECCS-1542174

OSTI ID:: 1676368

Alternate ID(s):: OSTI ID: 1632688

Journal Information:: Langmuir, Vol. 35, Issue 44; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 1 work

Citation information provided by
Web of Science

References (44)

Functionalisation of nanoparticles for biomedical applications Thanh, Nguyen T. K.; Green, Luke A. W. Nano Today, Vol. 5, Issue 3 https://doi.org/10.1016/j.nantod.2010.05.003	journal	June 2010
Recent research progress on the preparation and application of magnetic nanospheres Tai, Yulei; Wang, Li; Yan, Guangqing Polymer International, Vol. 60, Issue 7 https://doi.org/10.1002/pi.3078	journal	April 2011
Synthesis of silica/polypeptide hybrid nanomaterials and mesoporous silica by molecular replication of sheet-like polypeptide complexes through biomimetic mineralization Chen, Kuan-Ju; Chen, Hsin-Ling; Tang, Chen-Chi Journal of Colloid and Interface Science, Vol. 542 https://doi.org/10.1016/j.jcis.2019.02.014	journal	April 2019
Mechanisms of Hemagglutinin Targeted Influenza Virus Neutralization Brandenburg, Boerries; Koudstaal, Wouter; Goudsmit, Jaap PLoS ONE, Vol. 8, Issue 12 https://doi.org/10.1371/journal.pone.0080034	journal	December 2013
Solution properties of synthetic polypeptides. XV. Helix-coil transition in poly (?-carbobenzyloxyL-lysine) Matsuoka, Mikio; Norisuye, Takashi; Teramoto, Akio Biopolymers, Vol. 12, Issue 7 https://doi.org/10.1002/bip.1973.360120707	journal	July 1973
Solution properties of synthetic polypeptiedes. XXI. Solvent effect on the helix-coil transition of poly(e-carbobenzoxy L-lysine) Nishioka, Noboru; Maekawa, Akio; Teramoto, Akio Biopolymers, Vol. 17, Issue 3 https://doi.org/10.1002/bip.1978.360170310	journal	March 1978
Dielectric Dispersion of Polypeptide Solutions. II. Helix-Coil Transition of Poly(iε-carbobenzoxy-L-lysine) in m-Cresol Omura, Ikuo; Teramoto, Akio; Fujita, Hiroshi Macromolecules, Vol. 8, Issue 3 https://doi.org/10.1021/ma60045a009	journal	May 1975
Thermodyamics of the helix-coil transition of polypeptides in binary solvent systems Karasz, F. E.; Gajnos, G. E. The Journal of Physical Chemistry, Vol. 77, Issue 9 https://doi.org/10.1021/j100628a012	journal	April 1973
Synthesis and Conformational Transition of Surface-Tethered Polypeptide: Poly( l -lysine) Wang, Yuli; Chang, Ying Chih Macromolecules, Vol. 36, Issue 17 https://doi.org/10.1021/ma034093r	journal	August 2003
Preparation of Unidirectional End-Grafted α-Helical Polypeptides by Solvent Quenching Wang, Yuli; Chang, Ying Chih Journal of the American Chemical Society, Vol. 125, Issue 21 https://doi.org/10.1021/ja034428k	journal	May 2003
Patterning of Polypeptide Thin Films by the Combination of Surface-Initiated Vapor-Deposition Polymerization and Photolithography Wang, Y.; Chang, Y. C. Advanced Materials, Vol. 15, Issue 4 https://doi.org/10.1002/adma.200390069	journal	February 2003
Grafting of Homo- and Block Co-polypeptides on Solid Substrates by an Improved Surface-Initiated Vapor Deposition Polymerization Wang, Yuli; Chang, Ying-Chih Langmuir, Vol. 18, Issue 25 https://doi.org/10.1021/la026343n	journal	November 2002
Synthesis and Conformational Transition of Surface-Tethered Polypeptide: Poly( l -glutamic acid) Wang, Yuli; Chang, Ying Chih Macromolecules, Vol. 36, Issue 17 https://doi.org/10.1021/ma034092z	journal	August 2003
Toward Designing Smart Nanovalves: Modeling of Flow Control through Nanopores via the Helix−Coil Transition of Grafted Polypeptide Chains Adiga, Shashishekar P.; Brenner, Donald W. Macromolecules, Vol. 40, Issue 4 https://doi.org/10.1021/ma0617522	journal	January 2007
Progress in silica polypeptide composite colloidal hybrids: from silica cores to fuzzy shells Rosu, Cornelia; Selcuk, Sibel; Soto-Cantu, Erick Colloid and Polymer Science, Vol. 292, Issue 5 https://doi.org/10.1007/s00396-014-3170-7	journal	March 2014
Hybrid Nanomaterials by Surface Grafting of Synthetic Polypeptides Using N-Carboxyanhydride (NCA) Polymerization Borase, Tushar; Heise, Andreas Advanced Materials, Vol. 28, Issue 27 https://doi.org/10.1002/adma.201504474	journal	January 2016
Synthesis of Well-Defined Polypeptide-Based Materials via the Ring-Opening Polymerization of α-Amino Acid N -Carboxyanhydrides Hadjichristidis, Nikos; Iatrou, Hermis; Pitsikalis, Marinos Chemical Reviews, Vol. 109, Issue 11 https://doi.org/10.1021/cr900049t	journal	November 2009
Stimuli responsive synthetic polypeptides derived from N-carboxyanhydride (NCA) polymerisation Huang, Jin; Heise, Andreas Chemical Society Reviews, Vol. 42, Issue 17 https://doi.org/10.1039/c3cs60063g	journal	January 2013
Synthesis and characterization of Fe3O4@SiO2@poly-l-alanine, peptide brush–magnetic microspheres through NCA chemistry for drug delivery and enrichment of BSA Xu, Zhigang; Feng, Yaoyao; Liu, Xiaoyan Colloids and Surfaces B: Biointerfaces, Vol. 81, Issue 2 https://doi.org/10.1016/j.colsurfb.2010.07.048	journal	December 2010
The Structure of Hair, Muscle, and Related Proteins Pauling, L.; Corey, R. B. Proceedings of the National Academy of Sciences, Vol. 37, Issue 5 https://doi.org/10.1073/pnas.37.5.261	journal	May 1951
Synthesis and characterization of magnetic Fe3O4-silica-poly(γ-benzyl-l-glutamate) composite microspheres Liu, Dong; Li, Yi; Deng, Jianping Reactive and Functional Polymers, Vol. 71, Issue 10 https://doi.org/10.1016/j.reactfunctpolym.2011.07.009	journal	October 2011
Silica−Polypeptide Composite Particles: Controlling Shell Growth Soto-Cantu, Erick; Turksen-Selcuk, Sibel; Qiu, Jianhong Langmuir, Vol. 26, Issue 19 https://doi.org/10.1021/la1023955	journal	September 2010
Organophilic Colloidal Particles with a Synthetic Polypeptide Coating Fong, Brian; Russo, Paul S. Langmuir, Vol. 15, Issue 13 https://doi.org/10.1021/la9815648	journal	June 1999
Colloidal Crystals of Silica−Homopolypeptide Composite Particles Fong, Brian; Turksen, Sibel; Russo, Paul S. Langmuir, Vol. 20, Issue 1 https://doi.org/10.1021/la034762u	journal	November 2003
On the Use of Pattern Fluorescence Photobleaching Recovery with Modulation Detection to Obtain Colloidal Size Distributions Fong, Brian; Stryjewski, Wieslaw; Russo, Paul S. Journal of Colloid and Interface Science, Vol. 239, Issue 2 https://doi.org/10.1006/jcis.2001.7538	journal	July 2001
Synthesis and Rapid Characterization of Amine-Functionalized Silica Soto-Cantu, Erick; Cueto, Rafael; Koch, Jerome Langmuir, Vol. 28, Issue 13 https://doi.org/10.1021/la204981b	journal	March 2012
Preparation and Properties of Silica-Coated Cobalt Nanoparticles ^† Kobayashi, Yoshio; Horie, Mitsuru; Konno, Mikio The Journal of Physical Chemistry B, Vol. 107, Issue 30 https://doi.org/10.1021/jp027759c	journal	July 2003
Poly(colloid)s: “Polymerization” of Poly( l -tyrosine)-silica Composite Particles through the Photoinduced Cross-Linking of Unmodified Proteins Method Rosu, Cornelia; Cueto, Rafael; Russo, Paul S. Langmuir, Vol. 32, Issue 33 https://doi.org/10.1021/acs.langmuir.6b01815	journal	August 2016
The preparation of N-carboxyanhydrides of α-amino acids using bis(trichloromethyl)carbonate Daly, William H.; Poché, Drew Tetrahedron Letters, Vol. 29, Issue 46 https://doi.org/10.1016/S0040-4039(00)82209-1	journal	January 1988
Sculpting the internal architecture of fluorescent silica particles via a template-free approach Rosu, Cornelia; Gorman, Andrew J.; Cueto, Rafael Journal of Colloid and Interface Science, Vol. 467 https://doi.org/10.1016/j.jcis.2016.01.007	journal	April 2016
Enthalpies of helix-coil transitions in polypeptides Karasz, F. E.; Gajnos, G. E. Biopolymers, Vol. 13, Issue 4 https://doi.org/10.1002/bip.1974.360130407	journal	April 1974
Enthalpy changes in the helix-coil transition of poly(?-benzylL-glutamate) Karasz, F. E.; O'Reilly, J. M. Biopolymers, Vol. 5, Issue 1 https://doi.org/10.1002/bip.1967.360050105	journal	January 1967
The Synthesis and Conformation of High Molecular Weight Poly-ε-carbobenzyloxy-L-lysine and Poly-L-lysine·HCl ^1,2 Fasman, G. D.; Idelson, M.; Blout, E. R. Journal of the American Chemical Society, Vol. 83, Issue 3 https://doi.org/10.1021/ja01464a041	journal	February 1961
Polypeptides. IV. The Molecular Weight, Configuration and Association of Poly-γ-benzyl-L-glutamate in Various Solvents Doty, Paul; Bradbury, J. H.; Holtzer, A. M. Journal of the American Chemical Society, Vol. 78, Issue 5 https://doi.org/10.1021/ja01586a021	journal	March 1956
Analysis of Macromolecular Polydispersity in Intensity Correlation Spectroscopy: The Method of Cumulants Koppel, Dennis E. The Journal of Chemical Physics, Vol. 57, Issue 11 https://doi.org/10.1063/1.1678153	journal	December 1972
Polypeptide sidechain secondary structure and the helix-coil transition: A NMR relaxation study Samulski, Edward T.; Chien, Mingchien; Wade, Charles G. Journal of Polymer Science: Polymer Symposia, Vol. 46, Issue 1 https://doi.org/10.1002/polc.5070460125	journal	January 1974
Templated fabrication of pH-responsive poly( l -glutamic acid) based nanogels via surface-grafting and macromolecular crosslinking Yan, Shifeng; Sun, Yuanyuan; Chen, An RSC Advances, Vol. 7, Issue 24 https://doi.org/10.1039/C7RA00631D	journal	January 2017
Improvement of the oxidation stability of cobalt nanoparticles Dobbrow, Celin; Schmidt, Annette M. Beilstein Journal of Nanotechnology, Vol. 3 https://doi.org/10.3762/bjnano.3.9	journal	January 2012
Helical Structures in Proteins Kemp, Josh P.; Chen, Jeff Z. Y. Biomacromolecules, Vol. 2, Issue 2 https://doi.org/10.1021/bm005608e	journal	May 2001
Helix Formation in the Polymer Brush Kastantin, Mark; Tirrell, Matthew Macromolecules, Vol. 44, Issue 12 https://doi.org/10.1021/ma200782e	journal	June 2011
Synthesis of Poly- l -glutamic Acid Grafted Silica Nanoparticles and Their Assembly into Macroporous Structures Kar, Mrityunjoy; Pauline, Minois; Sharma, Kamendra Langmuir, Vol. 27, Issue 19 https://doi.org/10.1021/la202036c	journal	September 2011
Probing Membrane Hydration at the Interface of Self-Assembled Peptide Amphiphiles Using Electron Paramagnetic Resonance Smith, Ian R.; Charlier, Alban H. R.; Pritzlaff, Amanda M. ACS Macro Letters, Vol. 7, Issue 10 https://doi.org/10.1021/acsmacrolett.8b00728	journal	October 2018
Extension Behavior of Helicogenic Polypeptides Buhot, Arnaud; Halperin, Avraham Macromolecules, Vol. 35, Issue 8 https://doi.org/10.1021/ma011631w	journal	March 2002
Structural Changes and Aggregation of Human Influenza Virus Campbell, Jason N.; Epand, Richard M.; Russo, Paul S. Biomacromolecules, Vol. 5, Issue 5 https://doi.org/10.1021/bm049878z	journal	July 2004