Silver nanoparticles decorated and tetraphenylethene probe doped silica nanoparticles: A colorimetric and fluorometric sensor for sensitive and selective detection and intracellular imaging of hydrogen peroxide

doi:10.1016/j.bios.2018.09.023

Biosensors and Bioelectronics

Volume 121, 15 December 2018, Pages 236-242

https://doi.org/10.1016/j.bios.2018.09.023 Get rights and content

Highlights

•
A sensor based on AgNPs decorated and TPE probe doped silica NPs was fabricated.
•
This dual-mode colorimetric and fluorometric sensor was employed for H₂O₂ sensing.
•
The determination of H₂O₂ in human serum was demonstrated.
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The nanosensor was successfully employed for intracellular imaging of H₂O₂.

Abstract

In this work, we report a novel sensor for colorimetric and fluorometric H₂O₂ sensing which is based on silver nanoparticles decorated and tetraphenylethene probe doped silica nanoparticles (Ag@TPE-SiO₂ NPs). A positively charged tetraphenylethene (TPE) probe is doped into silica nanoparticles, and the nanoparticles exhibit strong fluorescence emission due to aggregation-induced emission (AIE) of the TPE probe. Ag nanoparticles (AgNPs) are prepared in situ on the surface of the silica nanoparticles. AgNPs serve as a nanoquencher which can quench the AIE emission of the TPE-SiO₂ NPs efficiently. However, AgNPs can be oxidized to Ag⁺ by H₂O₂, which leads to fluorescence recovery and color fading of the Ag@TPE-SiO₂ NPs. The dual-readout strategy allows sensitive analysis of H₂O₂. The detection limit of the fluorometric and colorimetric assay is 0.28 and 2.1 μM, respectively. And the nanosensor also shows good selectivity. In addition, analysis of H₂O₂ in human serum and intracellular imaging of H₂O₂ are both demonstrated. With the good analytical properties of merit, the proposed nanoprobe has a promising potential for H₂O₂ related bioanalysis and biomedical applications.

Graphical abstract

Introduction

Hydrogen peroxide (H₂O₂) has been widely used in chemical, food and biomedical industries due to its strong oxidizing and reducing properties (Sitnikova et al., 2011, Maji et al., 2014). H₂O₂ is also one of the most important reactive oxygen species (ROS) generated in living organisms (Li et al., 2016, D’Autreaux and Toledano, 2007). Nevertheless, the overabundance of H₂O₂ is associated with serious disorders, such as neurodegenerative disorder, diabetes and cancer (Weinstain et al., 2014, Lippert et al., 2011). In this regard, establishing a sensitive and selective assay to detect H₂O₂ is of significant interest for applications in biology, biomedicine and environmental protection (Nossol and Zarbin, 2009).

Many laboratories have developed various strategies for H₂O₂ analysis such as the fluorescence (Weinstain et al., 2014), chemiluminescence (Yu et al., 2016), electrochemistry (Maji et al., 2014, Li et al., 2016) and colorimetry (Chen et al., 2014b) based methods. Among various sensors for H₂O₂, the colorimetric methods have drawn much attention because of the visible, simple and economical detection without any sophisticated instruments. However, in many cases the colorimetric method cannot be directly applied because of the low detection sensitivity and the strong background color of the assay medium (Kuo et al., 2015). To avoid this problem, fluorescence techniques have been widely used in many fields, for example fluorescence imaging of various analytes in cells, organisms and tissues (Sun et al., 2013). However, methods based on fluorescence quenching (turn off assay) can suffer interference from other quenchers and environmental condition changes (Yuan et al., 2014a). Consequently, it is an urgent need to develop a colorimetric and turn-on fluorometric dual-readout strategy for H₂O₂ analysis.

It is noteworthy that the silver nanoparticles decorated silica nanoparticles (Ag@SiO₂ NPs) show more tailored and enhanced properties in plasmonics (Kang et al., 2013), photocatalysis (Chen et al., 2012) and antibacterial activity (Tian et al., 2014, Song et al., 2013) compared with that of colloidal silver nanoparticles. Herein, we designed new silver nanoparticles decorated and tetraphenylethene probe doped silica nanoparticles (Ag@TPE-SiO₂ NPs) for the colorimetric and fluorometric determination of H₂O₂ (Scheme 1). Tetraphenylethene (TPE) is a typical aggregation-induced emission (AIE) luminogen. Unlike other aggregation-caused quenching (ACQ) luminogens (Ma et al., 2016), TPE probe shows very weak emission in the monomeric state but is highly emissive in the aggregated state (Chen et al., 2014a, Chen et al., 2017, Leung et al., 2013, Zhang et al., 2018). Thus, the TPE probe has a distinct advantage to be used as a doping dye in silica nanoparticles (Faisal et al., 2010), and in fact few reports have used TPE luminogen doped silica nanoparticles for sensing applications. In this paper, a positively charged TPE probe was doped into silica nanoparticles and showed strong fluorescence emission. Silver nanoparticles (AgNPs) were then synthesized in situ on the silica nanoparticles. In this process, large size AgNPs (> 2 nm) were used as a nanoquencher (Li et al., 2015, Cao et al., 2014), and the fluorescence of TPE doped silica nanoparticles (TPE-SiO₂ NPs) was quenched effectively by AgNPs due to the surface plasmon-enhanced energy transfer (SPEET) from the TPE-SiO₂ NPs (donor) to the AgNPs (acceptor) (Ma et al., 2017). AgNPs could be etched by H₂O₂ and converted into Ag⁺. This kind of H₂O₂-induced AgNPs etching resulted in an increase in the fluorescence intensity (Li et al., 2015, Ma et al., 2017). Moreover, the conversion of the AgNPs to Ag⁺ exhibited a clear assay solution color fading, making it possible to detect H₂O₂ by a colorimetric assay (Chen et al., 2014b). Thus, a new colorimetric and turn-on fluorometric method for sensitive and selective detection of H₂O₂ based on the Ag@TPE-SiO₂ NPs was established. And the Ag@TPE-SiO₂ NPs were also used for the detection of H₂O₂ in human serum samples and intracellular imaging of H₂O₂.

Section snippets

Preparation of the polyethyleneimine modified tetraphenylethene doped silica nanoparticles (PEI@TPE-SiO₂ NPs)

Tetraphenylethene (TPE) probe was synthesized according to the literature procedures (Scheme S1, Figs. S1-S4, Supporting Information) (Chen et al., 2014a, Chen et al., 2017, Leung et al., 2013). The PEI@TPE-SiO₂ NPs were prepared based on the Stӧber method (Huang et al., 2017a, Huang et al., 2017b). Briefly, 42.0 mL of ethanol, 4.0 mL of water, 0.5 mL of ammonium hydroxide (25%), 1.5 mL of TEOS and 2.0 mL of TPE probe (4 mM) were mixed and stirred for 24 h at room temperature (25 °C). Then

Synthesis and characterization of the Ag@TPE-SiO₂ NPs

Synthesis of the Ag@TPE-SiO₂ NPs involves three steps: synthesis of the TPE-SiO₂ NPs, introduction of polyethyleneimine (PEI), and incorporation of AgNPs on the silica nanoparticles. Initially, silica nanoparticles were prepared according to the Stӧber method (Huang et al., 2017a, Huang et al., 2017b). The tetraphenylethene (TPE) probe was doped into the silica nanoparticles due to the electrostatic interactions between the positively charged TPE probe and the negatively charged silica matrix (

Conclusions

In summary, a colorimetric and turn-on fluorometric dual-readout sensor is developed for the detection of H₂O₂. A fluorophore-quencher type nanosensor was employed by linking a fluorophore (TPE-SiO₂ NPs) with a quencher (AgNPs). The detriment of quencher (AgNPs) by H₂O₂ led to fluorescence recovery and color fading of the sensor (Ag@TPE-SiO₂ NPs). Thus, the detection of H₂O₂ was achieved through visual and fluorescent readout, which makes the sensing more reliable. The sensor exhibited

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21561162004, 51761145102, 21874128), the Science and Technology Development Project (International Collaboration Program) of Jilin Province (20160414040GH).

References (49)

N.A. Burton et al.
Cell Host Microbe
(2014)
X. Cao et al.
Sens. Actuators B
(2014)
H.J. Forman et al.
Arch. Biochem. Biophys.
(2016)
X. Huang et al.
Anal. Chim. Acta
(2017)
M. Jahanbakhshi et al.
Biosens. Bioelectron.
(2016)
L.S. Walekar et al.
Colloids Surf. A: Physicochem. Eng. Asp.
(2016)
D. Yu et al.
Talanta
(2016)
Y. Zhang et al.
Sens. Actuators B
(2018)
A. Biswas et al.
ACS Omega
(2017)
M.C.Y. Chang et al.
J. Am. Chem. Soc.
(2004)

J. Chen et al.

Chem. Commun.

(2017)

J. Chen et al.

Anal. Chem.

(2014)

K.-H. Chen et al.

J. Phys. Chem. C

(2012)

S. Chen et al.

Anal. Chem.

(2014)

T. Chen et al.

J. Am. Chem. Soc.

(2013)

B. D’Autreaux et al.

Nat. Rev. Mol. Cell Biol.

(2007)

M. Faisal et al.

Chem. Eur. J.

(2010)

N. Fukuda et al.

Langmuir

(2011)

X. Gao et al.

J. Am. Chem. Soc.

(2014)

X. Huang et al.

Microchim Acta

(2017)

H. Kang et al.

ACS Appl. Mater. Interfaces

(2013)

A. Karlsson et al.

J. Leukoc. Boil.

(2000)

S.-Y. Kuo et al.

Anal. Chem.

(2015)

J.-S. Lee et al.

J. Phys. Chem. C

(2017)

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¹: These authors contributed equally to this work.

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Silver nanoparticles decorated and tetraphenylethene probe doped silica nanoparticles: A colorimetric and fluorometric sensor for sensitive and selective detection and intracellular imaging of hydrogen peroxide

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Preparation of the polyethyleneimine modified tetraphenylethene doped silica nanoparticles (PEI@TPE-SiO2 NPs)

Synthesis and characterization of the Ag@TPE-SiO2 NPs

Conclusions

Acknowledgments

Cell Host Microbe

Sens. Actuators B

Arch. Biochem. Biophys.

Anal. Chim. Acta

Biosens. Bioelectron.

Colloids Surf. A: Physicochem. Eng. Asp.

Talanta

Sens. Actuators B

ACS Omega

J. Am. Chem. Soc.

Chem. Commun.

Anal. Chem.

J. Phys. Chem. C

Anal. Chem.

J. Am. Chem. Soc.

Nat. Rev. Mol. Cell Biol.

Chem. Eur. J.

Langmuir

J. Am. Chem. Soc.

Microchim Acta

ACS Appl. Mater. Interfaces

J. Leukoc. Boil.

Anal. Chem.

J. Phys. Chem. C

Preparation of the polyethyleneimine modified tetraphenylethene doped silica nanoparticles (PEI@TPE-SiO₂ NPs)

Synthesis and characterization of the Ag@TPE-SiO₂ NPs