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Surface-Initiated PET-RAFT Enables In Situ Glycopolymer Microarrays for Live-Cell Glycan Profiling and Programmable

Al-Hassan S Mahdy1,2, Jixiong Zhou3, Xiongzhi Ni3

  • 1Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China.

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This study introduces a new method for creating custom glycopolymers on surfaces, enabling precise control over cell adhesion and release. This advance facilitates the development of advanced diagnostics and biomaterials through glycan-protein interaction analysis.

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Area of Science:

  • Polymer Chemistry
  • Biomaterials Science
  • Glycobiology

Background:

  • Existing glycopolymer microarray methods have limitations in surface density and multivalent presentation control.
  • Presynthesized polymers are required for traditional
  • grafting-to
  • approaches, limiting flexibility.

Purpose of the Study:

  • To develop a novel surface-initiated photoinduced electron-transfer RAFT (SI-PET-RAFT) platform for in situ glycopolymer synthesis.
  • To investigate glycan-protein interactions and cell binding preferences using a library of synthesized glycopolymers.
  • To engineer functional biointerfaces for applications in cell adhesion and release.

Main Methods:

  • Utilized surface-initiated photoinduced electron-transfer RAFT (SI-PET-RAFT) for direct glycopolymer growth on substrates.
  • Created a combinatorial library of glycopolymers for high-throughput screening.
  • Mapped cell binding preferences of HepG2, RAW264.7, and HeLa cells.
  • Designed thermoresponsive glycopolymer brushes for controlled cell adhesion and release.

Main Results:

  • Demonstrated in situ growth of well-defined glycopolymers under mild, oxygen-tolerant conditions.
  • Revealed distinct, composition-dependent glycan-recognition signatures in live cells.
  • Showcased multivalent effects driving glycan-protein interactions.
  • Engineered thermoresponsive glycopolymer brushes for selective HepG2 cell adhesion at 37 °C and release at 4 °C.

Conclusions:

  • The SI-PET-RAFT platform offers superior control over glycopolymer synthesis and presentation.
  • High-throughput screening of glycopolymer libraries provides insights into cellular glycan recognition.
  • This integrated workflow enables the rational design of functional biointerfaces for diverse applications.