Direct Functionalization of Established 3D-Printed Aza-Michael Liquid Crystal Elastomers with Donor–Acceptor Stenhouse Adducts

Journal Article · Wed Oct 29 00:00:00 UTC 2025 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.5c13996 · OSTI ID:3009208

Paul, Sophie ^[1]; Campos, Jesus Guillen ^[1]; Ford, Michael J.  ^[2]; Nandi, Arnab ^[1]; Hawkes, Elliot ^[1]; de Alaniz, Javier Read  ^[1]

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1. Univ. of California, Santa Barbara, CA (United States)
2. Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Extrusion 3D printing has advanced the manufacturing of complex liquid crystal elastomer (LCE) architectures. In parallel, donor–acceptor Stenhouse adducts (DASAs), a class of white-light-responsive photoswitches, have enabled both photochemical and photothermal LCE actuation. However, DASA–LCEs have yet to be extruded and 3D-printed. Two key challenges exist: DASA’s inherent sensitivity to heat and radicals can lead to degradation during ink preparation and printing, and small changes in the concentration of the added DASA component impact the properties of the extrudable ink, requiring reoptimization of well-established 3D-printing protocols. To overcome these challenges, we present a post-printing functionalization strategy that circumvents these limitations. Residual secondary amines, inherent to inks synthesized via standard aza-Michael addition, serve as active sites for covalent attachment of DASA photoresponsive groups following printing and cross-linking. Our method means that DASAs can be directly grafted onto 3D-printed aza-Michael LCEs without modifying the ink formulation or processing. The resulting DASA–LCEs exhibit wavelength tunability within the visible range and a variety of photothermal and photochemical responses. The post-functionalization can occur within 2 min and enables spatial control of the DASA concentration, producing films with tunable color gradients and locally varied photothermal and photochemical responses under visible light. In conclusion, this approach enables the rapid fabrication of DASA-based light-responsive LCEs using established ink formulations with the potential for the design of complex 3D architectures.

• Research Organization: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
• Sponsoring Organization: National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA)
• Grant/Contract Number: AC52-07NA27344
• OSTI ID: 3009208
• Report Number(s): LLNL--JRNL-2010594
• Journal Information: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 45 Vol. 17; ISSN 1944-8244; ISSN 1944-8252
• Publisher: American Chemical Society (ACS)Copyright Statement
• Country of Publication: United States
• Language: English