Citation: Runtan Gao, Yang Zong, Tingting Li, Na Liu, Zongquan Wu. Three-dimensional supramolecular polymer frameworks with precisely tunable and large apertures for enzyme encapsulation[J]. Chinese Chemical Letters, ;2026, 37(1): 111582. doi: 10.1016/j.cclet.2025.111582 shu

Three-dimensional supramolecular polymer frameworks with precisely tunable and large apertures for enzyme encapsulation

Runtan Gao ^a ,
Yang Zong ^a ,
Tingting Li ^a ,
Na Liu ^{b, *,} ,
Zongquan Wu ^{a, *,}

a.
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China
b.
The School of Pharmaceutical Sciences, Jilin University, Changchun 130021, China

liuna606@jlu.edu.cn

zqwu@jlu.edu.cn

Received Date: 10 April 2025
Revised Date: 9 July 2025
Accepted Date: 10 July 2025
Available Online: 11 July 2025

Figures(6)

Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications, e.g., encapsulating enzymes to enhance their stability, activity, and reusability. However, precise control and tune the pore size of such frameworks still remains a significant challenge to date. In this study, we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block. First, a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization. Then 2-ureido-4[1H]-pyrimidinone (Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization. Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units, well-ordered supramolecular polymer frameworks were readily obtained. Notably, the pore size was dependent on the chain length of the polyisocyanide arms. Precisely control the chain length of polyisocyanide arms, supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved. These frameworks, with tunable and large pore apertures, demonstrated exceptional capabilities in encapsulating enzymes of different sizes, such as lipase (TL), horseradish peroxidase (HRP), and glucose oxidase (GOx). The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability. Moreover, the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes, enabling efficient dual-enzyme cascade reactions.
- Supramolecular organic frameworks,
- Living polymerization,
- Supramolecular self-assembly,
- Polyisocyanide,
- Enzyme encapsulation
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