TY - JOUR
T1 - Rapid Synthesis of Silk-Like Polymers Facilitated by Microwave Irradiation and Click Chemistry
AU - Sarkar, Amrita
AU - Edson, Cody
AU - Tian, Ding
AU - Fink, Tanner D.
AU - Cianciotti, Katherine
AU - Gross, Richard A.
AU - Bae, Chulsung
AU - Zha, R. Helen
N1 - Funding Information:
A.S., T.D.F., and R.H.Z. acknowledge support from the internal startup grant provided by Rensselaer Polytechnic Institute. K.C. acknowledges financial support by the Undergraduate Research Fund at the Rensselaer Polytechnic Institute. The authors thank Dr. D. Zagorevski in the Rensselaer Proteomics Research Core for helpful discussion in mass spectrometry analysis. This research used the Complex Materials Scattering Beamline (11-BM CMS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. This work also made use of the South Carolina SAXS Collaborative, and the authors thank E. Williams for his help in SAXS measurements.
Publisher Copyright:
© 2021 American Chemical Society. All rights reserved.
PY - 2021/1/11
Y1 - 2021/1/11
N2 - Silk is a natural fiber that surpasses most man-made polymers in its combination of strength and toughness. Silk fibroin, the primary protein component of silk, can be synthetically mimicked by a linear copolymer with alternating rigid and soft segments. Strategies for chemical synthesis of such silk-like polymers have persistently resulted in poor sequence control, long reaction times, and low molecular weights. Here, we present a two-stage approach for rapidly synthesizing silk-like polymers with precisely defined rigid blocks. This approach utilizes solid-phase peptide synthesis to create uniform oligoalanine "prepolymers", followed by microwave-assisted step-growth polymerization with bifunctional poly(ethylene glycol). Multiple coupling chemistries and reaction conditions were explored, with microwave-assisted click chemistry yielding polymers with Mw∼14 kg/mol in less than 20 min. These polymers formed antiparallel β-sheets and nanofibers, which is consistent with the structure of natural silk fibroin. Thus, our strategy demonstrates a promising modular approach for synthesizing silk-like polymers.
AB - Silk is a natural fiber that surpasses most man-made polymers in its combination of strength and toughness. Silk fibroin, the primary protein component of silk, can be synthetically mimicked by a linear copolymer with alternating rigid and soft segments. Strategies for chemical synthesis of such silk-like polymers have persistently resulted in poor sequence control, long reaction times, and low molecular weights. Here, we present a two-stage approach for rapidly synthesizing silk-like polymers with precisely defined rigid blocks. This approach utilizes solid-phase peptide synthesis to create uniform oligoalanine "prepolymers", followed by microwave-assisted step-growth polymerization with bifunctional poly(ethylene glycol). Multiple coupling chemistries and reaction conditions were explored, with microwave-assisted click chemistry yielding polymers with Mw∼14 kg/mol in less than 20 min. These polymers formed antiparallel β-sheets and nanofibers, which is consistent with the structure of natural silk fibroin. Thus, our strategy demonstrates a promising modular approach for synthesizing silk-like polymers.
UR - http://www.scopus.com/inward/record.url?scp=85099721500&partnerID=8YFLogxK
U2 - 10.1021/acs.biomac.0c00563
DO - 10.1021/acs.biomac.0c00563
M3 - Article
C2 - 32902261
AN - SCOPUS:85099721500
SN - 1525-7797
VL - 22
SP - 95
EP - 105
JO - Biomacromolecules
JF - Biomacromolecules
IS - 1
ER -