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Dual-stimuli-responsive porous polymer enzyme reactor for tuning enzymolysis efficiency

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Abstract

A strategy for preparing a dual-stimuli-responsive porous polymer membrane enzyme reactor (D-PPMER) is described, consisting of poly (styrene-maleic anhydride-N-isopropylacrylamide-acrylate-3′,3′-dimethyl-6-nitro-spiro[2H-1-benzopyran-2,2′-indoline]-1′-esterspiropyran ester) [P(S-M–N-SP)] and D-amino acid oxidase. Tunable control via “on/off” 365 nm UV light irradiation and temperature variation was used to change the membrane surface configuration and adjust the enzymolysis efficiency of the D-PPMER. A chiral capillary electrophoresis technique was developed for evaluation of the enzymatic efficiency of D-PPMER with a Zn(II)-dipeptide complex as the chiral selector and D,L-serine as the substrate. Interestingly, the enzymatic kinetic reaction rate of D-PPMER under UV irradiation at 36 °C (9.2 × 10−2 mM·min−1) was 3.2-fold greater than that of the free enzyme (2.9 × 10−2 mM·min−1). This was because upon UV irradiation at high temperature, the P(SP) and P(N) moieties altered from a “stretched” to a “curled” state to encapsulate the enzyme in smaller cavities. The confinement effect of the cavities further improved the enzymatic efficiency of the D-PPMER. This protocol highlights the outstanding potential of smart polymers, enables tunable control over the kinetic rates of stimuli-responsive enzyme reactors, and establishes a platform for adjusting enzymolysis efficiency using two different stimuli.

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Funding

This work is supported by the National Natural Science Foundation of China (Nos. 21874138, 21727809, 21635008, and 22074148).

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Author notes

  1. Ji Shen and Juan Qiao contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Beijing National Laboratory for Molecular Sciences, Chinese Academy of Sciences, No. 2 Zhongguancun Beiyijie, Beijing, 100190, People’s Republic of China

    Ji Shen, Juan Qiao, Xinya Zhang & Li Qi

  2. School of Chemical Sciences, University of Chinese Academy of Sciences, No.19A Yuquan Road, Beijing, 100049, People’s Republic of China

    Ji Shen, Juan Qiao & Li Qi

  3. School of Pharmacy, Xinxiang Medical University, No.601 Jinsui Avenue, Xinxiang, 453003, People’s Republic of China

    Xinya Zhang

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  1. Ji Shen
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  2. Juan Qiao
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  3. Xinya Zhang
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  4. Li Qi
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Correspondence to Li Qi.

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Shen, J., Qiao, J., Zhang, X. et al. Dual-stimuli-responsive porous polymer enzyme reactor for tuning enzymolysis efficiency. Microchim Acta 188, 435 (2021). https://doi.org/10.1007/s00604-021-05095-3

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  • DOI: https://doi.org/10.1007/s00604-021-05095-3

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