High-throughput generation of block copolymer libraries via click chemistry and automated chromatography

Designing block copolymers for specific applications is challenging because of the intricate relationship among molecular structure, self-assembly behavior, and bulk properties, which is compounded by a large design space that traditionally requires time-consuming, iterative synthesis. To overcome these challenges, here we report a library-based strategy leveraging an active ester-based block copolymer and automated chromatography which enables the high-throughput exploration of broad compositional and chemical landscapes without requiring sample-specific optimization. By integrating automated chromatography with robotic synthesis and orthogonal post-polymerization modification chemistry, we efficiently generated a diverse library of 90 well-defined block copolymers from a single as-synthesized “parent” copolymer. This adaptable method enables efficient access to materials with a wide range of compositions, molecular weights, functionalities, and properties. By integrating laboratory au..., , High-Throughput Generation of Block Copolymer Libraries via Click Chemistry and Automated Chromatography

Elizabeth A. Murphy,†,‡,# Katherine G. Roth,‡ Morgan W. Bates,# Megan C. Murphy,†,‡ Jerrick Edmund,†,§ Christopher M. Bates,†,‡,%,# and Craig J. Hawker,†,‡,%,#

†Materials Research Laboratory, ‡Department of Chemistry & Biochemistry, %Materials Department, §Department of Chemical Engineering, and #BioPACIFIC Materials Innovation Platform, University of California, Santa Barbara, California 93106, United States

Macromolecules 2025, 58, 15, 8369–8376

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Data file names are labeled as Sample Name_Characterization Technique and organized into folders corresponding to figure and table numbers in the manuscript.

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Data is acquired from the following analytical characterization techniques. Details of the experimental design and data are highlighted below:

Nuclear Magnetic Resonance Spectroscopy: Solution state nuclear magnetic resonance (NMR) spectra were recorded on a Varian 600 ...,