Award Abstract # 1847948
CAREER: Photocontrolled Dynamic Covalent Crosslinkers for Light-Responsive Polymer Networks

NSF Org: CHE
Division Of Chemistry
Recipient: NORTHWESTERN UNIVERSITY
Initial Amendment Date: April 3, 2019
Latest Amendment Date: January 24, 2023
Award Number: 1847948
Award Instrument: Continuing Grant
Program Manager: Suk-Wah Tam-Chang
stamchan@nsf.gov
 (703)292-8684
CHE
 Division Of Chemistry
MPS
 Directorate for Mathematical and Physical Sciences
Start Date: May 15, 2019
End Date: April 30, 2025 (Estimated)
Total Intended Award Amount: $700,000.00
Total Awarded Amount to Date: $736,371.00
Funds Obligated to Date: FY 2019 = $723,928.00
FY 2023 = $12,443.00
History of Investigator:
  • Julia Kalow (Principal Investigator)
    jkalow@northwestern.edu
Recipient Sponsored Research Office: Northwestern University
633 CLARK ST
EVANSTON
IL  US  60208-0001
(312)503-7955
Sponsor Congressional District: 09
Primary Place of Performance: Northwestern University
2145 Sheridan Rd
Evanston
IL  US  60208-0834
Primary Place of Performance
Congressional District:
09
Unique Entity Identifier (UEI): EXZVPWZBLUE8
Parent UEI:
NSF Program(s): OFFICE OF MULTIDISCIPLINARY AC,
Macromolec/Supramolec/Nano
Primary Program Source: 01002324DB NSF RESEARCH & RELATED ACTIVIT
01001920DB NSF RESEARCH & RELATED ACTIVIT

01002021DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 1045, CL10
Program Element Code(s): 125300, 688500
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.049

ABSTRACT

Polymers that respond to external cues with changes in their physical properties can serve as sensors, actuators, controlled delivery systems, tissue mimics, and healable materials. Light is one of the most appealing stimuli because it can be delivered remotely with precise control over space, time, intensity, and color. The research group of Professor Julia Kalow at Northwestern University studies how light can be used to control the formation and breakage of reversible chemical bonds in polymers. When these photoswitchable chemical bonds are used to link polymer strands, the resulting polymer networks exhibit reversibly-controlled changes in properties, such as stiffness and adaptability. The novel materials and insights from this research help to create the next generation of high-performance, re-processable polymers. Additionally, the polymer materials may mimic tissue mechanics, acting as user-controlled matrixes to study biological processes like muscle contraction and to build synthetic organs. The broader impacts expand the exposure of students with visual impairment to STEM. The educational program develops assistive technologies for visually impaired students and their teachers. Students with visual impairment are often left out of traditional outreach activities and laboratory experiences. Professor Kalow's team works to fully include these students in STEM as the newly created polymer materials are used to create assistive tactile displays.

With the support of the Macromolecular, Supramolecular, and Nanochemistry program of the Division of Chemistry, the Kalow group prepares new photoswitches and elucidates how control is translated from the molecular to macroscopic level. This fundamental research combines physical organic techniques, synthesis, and mechanical characterization to study three distinct mechanisms for photoswitching dynamic covalent crosslinkers: crosslink stability, crosslink exchange rate, and crosslink topology. The research aims to marry photoswitch conformation and dynamic covalent bonds to achieve dramatic and reversible physical changes in soft materials. The expected outcomes of the research are the development of new photoswitches containing dynamic covalent bonds, improvement in the reversibly photocontrolled gels, elastomers, and vitrimers, and increased fundamental insight into the relationship between molecular reactivity and viscoelasticity.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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Accardo, Joseph V. and McClure, Emily R. and Mosquera, Martín A. and Kalow, Julia A. "Using Visible Light to Tune Boronic AcidEster Equilibria" Journal of the American Chemical Society , v.142 , 2020 https://doi.org/10.1021/jacs.0c08551 Citation Details
Barsoum, David N. and Kirinda, Viraj C. and Kang, Boyeong and Kalow, Julia A. "Remote-Controlled Exchange Rates by Photoswitchable Internal Catalysis of Dynamic Covalent Bonds" Journal of the American Chemical Society , 2022 https://doi.org/10.1021/jacs.2c04658 Citation Details
Kang, Boyeong and Kalow, Julia A. "Internal and External Catalysis in Boronic Ester Networks" ACS Macro Letters , v.11 , 2022 https://doi.org/10.1021/acsmacrolett.2c00056 Citation Details
McAllister, Haley P. and Kalow, Julia A. "Plastics that lose their temper on demand" Science , v.383 , 2024 https://doi.org/10.1126/science.adn3980 Citation Details
McAllister, Haley P. and Kalow, Julia A. "Tandem triumphs in PVC upcycling" Chem Catalysis , v.3 , 2023 https://doi.org/10.1016/j.checat.2023.100578 Citation Details
Zhang, Vivian and Ou, Carrie and Kevlishvili, Ilia and Hemmingsen, Christina M. and Accardo, Joseph V. and Kulik, Heather J. and Kalow, Julia A. "Internal Catalysis in Dynamic Hydrogels with Associative Thioester Cross-Links" ACS Macro Letters , 2024 https://doi.org/10.1021/acsmacrolett.4c00245 Citation Details

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