Environmental and intercellular Pb 2+ ions determination based on encapsulated DNAzyme in nanoscale metal-organic framew

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ORIGINAL PAPER

Environmental and intercellular Pb2+ ions determination based on encapsulated DNAzyme in nanoscale metal-organic frameworks Weihao Wu 1 & Yaofang Fan 1 & Bing Tan 1,2 & Huimin Zhao 1 Received: 20 February 2020 / Accepted: 1 October 2020 # Springer-Verlag GmbH Austria, part of Springer Nature 2020

Abstract With the merits of low cost, simple synthesis procedure, and high affinity for metal ions, deoxyribozyme (DNAzyme) have played important roles in metal ions detection. However, the intracellular applications of DNAzyme are limited because of enzymatic degradation and inefficient cellular uptake. To address these problems, GR-5 as model DNAzyme was encapsulated into zeolitic imidazolate frameworks-8 (ZIF-8) nanoparticles by biomimetic mineralization. The positively charged ZIF-8 with high DNAzyme loading capacity retained their ability to enter cells. Compared with free DNAzyme, the biomimetic mineralization synthesis method has greatly improved the stability of pristine DNAzyme. The as-synthesized DNAzyme@ZIF-8 composite exhibited good stability resisting DNase I, and was used as a sensitive fluorescent nanoprobe for Pb2+ determination and successfully achieved selective and sensitive determination for Pb2+ at λex/λem = 494/522 nm in real samples. The linear range for the determination of Pb2+ is 50 to 500 nM. Moreover, the highly active DNAzyme delivered by ZIF-8 allows noninvasive imaging of Pb2+ measurement in living cells. This strategy will extend the suitability of functional nucleic acids for in vitro and in vivo bioanalysis and bioimaging. Keywords DNAzyme . Metal-organic frameworks . Biomimetic mineralization . Lead detection . Fluorescence

Introduction In 1994, a RNA-cleaving DNA enzyme (DNAzyme) was firstly reported for catalyzing the Pb2+-dependent cleavage of an RNA phosphoester through in vitro selection methods [1]. In the presence of Pb2+, the enzyme strand can cleave the RNA linkage (rA) in the substrate strand. Generally, the DNAzyme is formed by a Weihao Wu and Yaofang Fan contributed equally to this work. Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00604-020-04586-z) contains supplementary material, which is available to authorized users. * Huimin Zhao [email protected] 1

Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China

2

School of Environment, Key Laboratory for Yellow River and Huai River Water Environment and Pollution Control, Ministry of Education, Henan Normal University, Xinxiang 453007, China

substrate strand and an enzyme strand. The substrate strand contains a single rA that serves as a cleavage site while the enzyme strand consists of one catalytic core and two binding arms [2]. Up to now, various DNAzymes have been isolated to catalyze many chemical reactions, including RNA cleavage [3–6], DNA cleavage [7, 8], DNA/RNA ligation [9–11], and DNA phosphorylation