近红外光遥控酶催化反应的分子开关纳米平台  

Nanoplatforms with donor-acceptor Stenhouse adduct molecular switch for enzymatic reactions remotely controlled with near-infrared light

作　　者：李可 刘妙登 黄千笑 刘传军 张先正 Ke Li;Miao-Deng Liu;Qian-Xiao Huang;Chuan-Jun Liu;Xian-Zheng Zhang(Key Laboratory of Biomedical Polymers of Ministry of Education&Department of Chemistry,Wuhan University,Wuhan 430072,China)

机构地区：[1]Key Laboratory of Biomedical Polymers of Ministry of Education&Department of Chemistry,Wuhan University,Wuhan 430072,China

出　　处：《Science China Materials》2023年第1期375-384,共10页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(52073219 and 51833007);the National Key Research and Development Program of China(2019YFA0905603)。

摘　　要：酶具有优异的生物催化功能,基于此高效催化性能,体内酶促反应在生物医学领域具有广阔的应用前景.然而,目前的主要局限在于如何在体内实现酶反应的精确控制.本文设计了一种以上转换纳米颗粒为核心,以供体-受体Stenhouse加合物(DASA)分子开关为包覆层的功能化纳米平台,用于近红外光触发的体内酶促反应.在近红外辐射下,上转换纳米颗粒可以发出明亮的绿光使聚合物异构化,进而改变分子开关门控聚合物层的渗透性,使酶与底物接触发生酶促反应.分子开关聚合物的光异构化是可逆过程,调控过程不影响酶的生物活性,因此基于该纳米平台的酶反应器调控具有可逆性,实现了对酶反应的精确时空控制.利用小鼠动物模型进一步证实了近红外光对酶催化反应的时空操控.这种纳米平台不仅拓宽了DASA的应用范围,也为体内药物传递和酶替代治疗提供了新的策略.Enzymes have been widely used in biomedical applications owing to their excellent biocatalysis functions.However,the precise control of enzymatic reactions remains a challenge in vivo.Here,a nanoplatform functionalized with upconversion nanoparticles(UCNPs)as the core and a donoracceptor Stenhouse adduct as a molecular switch(MS)was designed for near-infrared(NIR)-controlled enzymatic reactions.Under NIR irradiation,the UCNPs could emit bright green light to isomerize the MS and then transform the permeability of the MS-gated polymer layer,allowing small molecules to penetrate the polymer layer.Consequently,the contact between the enzyme and substrate could be regulated to control the enzymatic reaction remotely.As the photoisomerism of MS is reversible and the enzyme activity is not changed,the enzyme reactor based on this nanoplatform is also reversible,which can achieve precise temporal and spatial control of the enzyme reaction.Glucose oxidase(GOX),lactate oxidase(LOX),urate oxidase(UOX),and luciferase were used to assess the controllability of the enzymatic reactions.Both the substrates in and out of the nanoplatform were satisfactorily controlled,indicating that the gated nanoplatform equipped with valve-like characteristics could realize remotely controlled enzymatic reactions upon NIR irradiation.

关 键 词：上转换纳米颗粒 酶催化反应 分子开关 近红外光 近红外辐射 聚合物层 药物传递 可逆过程 

分 类 号：TB383[一般工业技术—材料科学与工程]