TY - JOUR
T1 - Concurrent Folding and Fluorescent Functionalization of Single-Chain Nanoparticles via Heterogeneous Photochemistry
AU - Ma, Tianshu
AU - Mu, Bin
AU - Tian, Wei
N1 - Publisher Copyright:
© 2025 Wiley-VCH GmbH.
PY - 2025/5/19
Y1 - 2025/5/19
N2 - The controlled folding of synthetic polymers, mimicking the complex behaviors of biomacromolecules, offers the potential to create sophisticated nanostructures with diverse functionalities. Of great significance is the integration of functionalization directly with chain folding, especially through the incorporation of artificial elements not found in nature, which allows unprecedented flexibility in materials design. However, this approach faces significant synthetic challenges, owing to the intricate integration of multiple chemical processes within a single chain. Here, a heterogeneous photochemistry strategy is presented to achieve single-chain polymer folding alongside concurrent fluorescent functionalization, inspired by the stepwise folding mechanism of green fluorescent protein. This method involves pre-folding amphiphilic heterograft random copolymers in water, which facilitates heterogeneous aggregation into distinct domains within single-particle nanostructures, including closely aggregated and molecularly dispersed regions. By employing spatial organization-dependent photochemical reactivity of cyanostilbene moieties, two concurrent processes are enabled: intrachain crosslinking via photodimerization in aggregated domains and fluorescent functionalization via photocyclization to form a green fluorophore in dispersed regions. Additionally, the incorporation of fluorescent dyes via intrachain excitation energy transfer allows for the modulation of emission properties, extending from green to red, and even including white light, making them promising candidates for bioimaging and related applications.
AB - The controlled folding of synthetic polymers, mimicking the complex behaviors of biomacromolecules, offers the potential to create sophisticated nanostructures with diverse functionalities. Of great significance is the integration of functionalization directly with chain folding, especially through the incorporation of artificial elements not found in nature, which allows unprecedented flexibility in materials design. However, this approach faces significant synthetic challenges, owing to the intricate integration of multiple chemical processes within a single chain. Here, a heterogeneous photochemistry strategy is presented to achieve single-chain polymer folding alongside concurrent fluorescent functionalization, inspired by the stepwise folding mechanism of green fluorescent protein. This method involves pre-folding amphiphilic heterograft random copolymers in water, which facilitates heterogeneous aggregation into distinct domains within single-particle nanostructures, including closely aggregated and molecularly dispersed regions. By employing spatial organization-dependent photochemical reactivity of cyanostilbene moieties, two concurrent processes are enabled: intrachain crosslinking via photodimerization in aggregated domains and fluorescent functionalization via photocyclization to form a green fluorophore in dispersed regions. Additionally, the incorporation of fluorescent dyes via intrachain excitation energy transfer allows for the modulation of emission properties, extending from green to red, and even including white light, making them promising candidates for bioimaging and related applications.
KW - Cyanostilbene
KW - Fluorescence
KW - Photochemistry
KW - Polymer folding
KW - Single-chain nanoparticle
UR - http://www.scopus.com/inward/record.url?scp=105000373246&partnerID=8YFLogxK
U2 - 10.1002/anie.202500354
DO - 10.1002/anie.202500354
M3 - 文章
AN - SCOPUS:105000373246
SN - 1433-7851
VL - 64
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 21
M1 - e202500354
ER -