Fe3O4-AuNPs anchored 2D metal-organic framework nanosheets with DNA regulated switchable peroxidase-like activity.

Two-dimensional (2D) metal-organic framework (MOF) nanosheets emerging as a new member of the 2D family have received significant research interest in recent years. Herein, we have successfully synthesized 2D copper-based MOF nanosheets with bimetallic anchorage using a facile two-step process at room temperature and ambient pressure, denoted as Cu(HBTC)-1/Fe3O4-AuNPs nanosheets. The as-synthesized 2D bimetallic MOF nanosheets displayed enhanced peroxidase-like activity with relatively high catalytic velocity and affinity for substrates compared with previously reported peroxidase mimics. Furthermore, their intrinsic peroxidase-like catalytic activity could be flexibly regulated by single-stranded DNA (ssDNA), exhibiting the enhancement of 3,3',5,5'-tetramethylbenzidine (TMB) oxidation or inhibition of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt (ABTS) oxidation due to the adsorption of ssDNA via π-π stacking. Accordingly, on the basis of their peroxidase-like activity, our prepared 2D bimetallic immobilized MOF nanosheets achieved ultra-sensitive detection of H2O2 with a linear range of 2.86 to 71.43 nM, and comparable detection performance for glucose with a linear range of 12.86 to 257.14 μM. By means of their controllable peroxidase-like activity, a versatile colorimetric sensing platform was developed which realized the detection of sulfadimethoxine (SDM) with a linear range of 3.57 to 357.14 μg L-1 and the limit of detection (LOD) of 1.70 μg L-1. With the multiplexed performance for detecting various targets, our as-synthesized bimetallic MOF nanosheets hold great promise for applications in environmental monitoring, as well as bioassays by virtue of their good biocompatibility.

[1]  Sheng Yang,et al.  Ultraflexible In‐Plane Micro‐Supercapacitors by Direct Printing of Solution‐Processable Electrochemically Exfoliated Graphene , 2016, Advanced materials.

[2]  N. Khlebtsov,et al.  Colorimetric Evaluation of the Viability of the Microalga Dunaliella Salina as a Test Tool for Nanomaterial Toxicity. , 2016, Toxicological sciences : an official journal of the Society of Toxicology.

[3]  Yuming Huang,et al.  Glycine post-synthetic modification of MIL-53(Fe) metal-organic framework with enhanced and stable peroxidase-like activity for sensitive glucose biosensing. , 2017, Talanta.

[4]  B. Mukherjee,et al.  Different shades of cholesterol: Gold nanoparticles supported on MoS2 nanoribbons for enhanced colorimetric sensing of free cholesterol. , 2015, Biosensors & bioelectronics.

[5]  Kai Yang,et al.  In Vivo Long‐Term Biodistribution, Excretion, and Toxicology of PEGylated Transition‐Metal Dichalcogenides MS2 (M = Mo, W, Ti) Nanosheets , 2016, Advanced science.

[6]  Guowu Zhan,et al.  Synthesis and Functionalization of Oriented Metal–Organic‐Framework Nanosheets: Toward a Series of 2D Catalysts , 2016 .

[7]  N. H. Turner,et al.  Determination of peak positions and areas from wide‐scan XPS spectra , 1990 .

[8]  Tianran Lin,et al.  Seeing diabetes: visual detection of glucose based on the intrinsic peroxidase-like activity of MoS2 nanosheets. , 2014, Nanoscale.

[9]  Xinliang Feng,et al.  2D Sandwich‐like Sheets of Iron Oxide Grown on Graphene as High Energy Anode Material for Supercapacitors , 2011, Advanced materials.

[10]  Yang Xu,et al.  Double-Stranded DNA Single-Walled Carbon Nanotube Hybrids for Optical Hydrogen Peroxide and Glucose Sensing , 2007 .

[11]  Shuhong Yu,et al.  Water-stable metal-organic frameworks with intrinsic peroxidase-like catalytic activity as a colorimetric biosensing platform. , 2014, Chemical communications.

[12]  S. Dong,et al.  Nucleic Acid Biosensors: Recent Advances and Perspectives. , 2017, Analytical chemistry.

[13]  Hongtao Yu,et al.  Interface engineering catalytic graphene for smart colorimetric biosensing. , 2012, ACS nano.

[14]  Hua Zhang,et al.  Ultrathin 2D Metal–Organic Framework Nanosheets , 2015, Advanced materials.

[15]  Dawei Feng,et al.  Zirconium-metalloporphyrin PCN-222: mesoporous metal-organic frameworks with ultrahigh stability as biomimetic catalysts. , 2012, Angewandte Chemie.

[16]  Hua Zhang,et al.  Two‐Dimensional Metal–Organic Framework Nanosheets , 2017 .

[17]  Xiaogang Qu,et al.  Graphene Oxide: Intrinsic Peroxidase Catalytic Activity and Its Application to Glucose Detection , 2010, Advanced materials.

[18]  Colin D. Medley,et al.  Molecular engineering of DNA: molecular beacons. , 2009, Angewandte Chemie.

[19]  C. Ban,et al.  A coordination polymer nanobelt (CPNB)-based aptasensor for sulfadimethoxine. , 2012, Biosensors & bioelectronics.

[20]  A. Govindaraj,et al.  Binding of DNA nucleobases and nucleosides with graphene. , 2009, Chemphyschem : a European journal of chemical physics and physical chemistry.

[21]  Jia Song,et al.  Hemin@metal–organic framework with peroxidase-like activity and its application to glucose detection , 2013 .

[22]  Ping Wu,et al.  Electrochemical measurement of the flux of hydrogen peroxide releasing from RAW 264.7 macrophage cells based on enzyme-attapulgite clay nanohybrids. , 2011, Biosensors & bioelectronics.

[23]  Ya Li Liu,et al.  A nanosized metal-organic framework of Fe-MIL-88NH₂ as a novel peroxidase mimic used for colorimetric detection of glucose. , 2013, The Analyst.

[24]  M. Kim,et al.  Highly efficient colorimetric detection of target cancer cells utilizing superior catalytic activity of graphene oxide-magnetic-platinum nanohybrids. , 2014, Nanoscale.

[25]  John M Lachin,et al.  Empagliflozin and Progression of Kidney Disease in Type 2 Diabetes. , 2016, The New England journal of medicine.

[26]  Ying Wang,et al.  Discovering the enzyme mimetic activity of metal-organic framework (MOF) for label-free and colorimetric sensing of biomolecules. , 2016, Biosensors & bioelectronics.

[27]  Xiaoyu Wang,et al.  Nanozymes in bionanotechnology: from sensing to therapeutics and beyond , 2016 .

[28]  Xingguo Chen,et al.  In situ synthesis of self-assembled three-dimensional graphene-magnetic palladium nanohybrids with dual-enzyme activity through one-pot strategy and its application in glucose probe. , 2015, ACS applied materials & interfaces.

[29]  Juewen Liu,et al.  Adsorption of DNA onto gold nanoparticles and graphene oxide: surface science and applications. , 2012, Physical chemistry chemical physics : PCCP.

[30]  Na Wang,et al.  Antibiotic body burden of Chinese school children: a multisite biomonitoring-based study. , 2015, Environmental science & technology.

[31]  Jia Sheng,et al.  Multiplexed Activity of perAuxidase: DNA-Capped AuNPs Act as Adjustable Peroxidase. , 2016, Analytical chemistry.

[32]  R. Yu,et al.  Graphene oxide-peptide conjugate as an intracellular protease sensor for caspase-3 activation imaging in live cells. , 2011, Angewandte Chemie.

[33]  Huimin Zhao,et al.  Three-Dimensional Graphene Supported Bimetallic Nanocomposites with DNA Regulated-Flexibly Switchable Peroxidase-Like Activity. , 2016, ACS applied materials & interfaces.

[34]  Tianran Lin,et al.  Graphite-like carbon nitrides as peroxidase mimetics and their applications to glucose detection. , 2014, Biosensors & bioelectronics.

[35]  Juewen Liu,et al.  Molecular Imprinting on Inorganic Nanozymes for Hundred-fold Enzyme Specificity. , 2017, Journal of the American Chemical Society.

[36]  R. Smalley,et al.  Reversible water-solubilization of single-walled carbon nanotubes by polymer wrapping , 2001 .

[37]  R. T. Yang,et al.  Investigation on Hydrogenation of Metal–Organic Frameworks HKUST-1, MIL-53, and ZIF-8 by Hydrogen Spillover , 2013 .

[38]  Junjie Zhu,et al.  Graphene-like two-dimensional layered nanomaterials: applications in biosensors and nanomedicine. , 2015, Nanoscale.

[39]  Rong Yang,et al.  Pt74Ag26 nanoparticle-decorated ultrathin MoS2 nanosheets as novel peroxidase mimics for highly selective colorimetric detection of H2O2 and glucose. , 2016, Nanoscale.

[40]  Juewen Liu,et al.  Surface modification of nanozymes , 2017, Nano Research.

[41]  Mamata Mohapatra,et al.  Bimetallic nanoparticles for arsenic detection. , 2015, Analytical chemistry.

[42]  K. Schulten,et al.  Molecular biomimetics: nanotechnology through biology , 2003, Nature materials.

[43]  X. Hou,et al.  Colorimetric sensing of bithiols using photocatalytic UiO-66(NH2) as H2O2-free peroxidase mimics. , 2016, Talanta.

[44]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[45]  Juewen Liu,et al.  Accelerating peroxidase mimicking nanozymes using DNA. , 2015, Nanoscale.

[46]  L. Ai,et al.  MIL-53(Fe): a metal-organic framework with intrinsic peroxidase-like catalytic activity for colorimetric biosensing. , 2013, Chemistry.

[47]  Tianran Lin,et al.  Visual detection of blood glucose based on peroxidase-like activity of WS2 nanosheets. , 2014, Biosensors & bioelectronics.

[48]  Xiaogang Qu,et al.  Ionic liquid as an efficient modulator on artificial enzyme system: toward the realization of high-temperature catalytic reactions. , 2013, Journal of the American Chemical Society.

[49]  Xuping Sun,et al.  Cobalt phosphide nanowires: efficient nanostructures for fluorescence sensing of biomolecules and photocatalytic evolution of dihydrogen from water under visible light. , 2015, Angewandte Chemie.

[50]  Freek Kapteijn,et al.  Metal-organic framework nanosheets in polymer composite materials for gas separation , 2014, Nature materials.

[51]  Yuanjing Cui,et al.  Emerging Multifunctional Metal–Organic Framework Materials , 2016, Advanced materials.

[52]  Xiaogang Qu,et al.  Catalytically active nanomaterials: a promising candidate for artificial enzymes. , 2014, Accounts of chemical research.

[53]  Tom Regier,et al.  Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. , 2011, Nature materials.