Highly sensitive and selective cartap nanosensor based on luminescence resonance energy transfer between NaYF4:Yb,Ho nanocrystals and gold nanoparticles

doi:10.1016/j.talanta.2013.02.069

Talanta

Volume 114, 30 September 2013, Pages 124-130

https://doi.org/10.1016/j.talanta.2013.02.069 Get rights and content

Abstract

Fluorescent detection is an attractive method for the detection of toxic chemicals. However, most chemosensors that are currently utilized in fluorescent detection are based on organic dyes or quantum dots, which suffer from instability, high background noise and interference from organic impurities in solution, which can also be excited by UV radiation. In the present research, we developed a novel NaYF₄:Yb,Ho/Au nanocomposite-based chemosensor with high sensitivity (10 ppb) and selectivity over competing analytes for the detection of the insecticide cartap. This nanosensor is excited with a 970-nm laser instead of UV radiation to give an emission peak at 541 nm. In the presence of cartap, the nanocomposites aggregate, resulting in enhanced luminescence resonance energy transfer between the NaYF₄:Yb,Ho nanocrystals and the gold nanoparticles, which decreases the emission intensity at 541 nm. The relative luminescence intensity at 541 nm has a linear relationship with the concentration of cartap in the solution. Based on this behavior, the developed nanosensor successfully detected cartap in farm produce and water samples with satisfactory results.

Graphical Abstract

A novel NaYF₄:Yb,Ho/Au nanocomposite-based nanosensor was developed. This sensor can be excited with a 970-nm laser and exhibits a high selectivity over competing analytes for the detection of cartap and high sensitivity (10 ppb), far lower than the maximum level (1 ppm) of cartap in farm produce permitted by the environmental protection agencies (EPAs) of the United States and China.

Highlights

► A novel NaYF₄:Yb,Ho/Au hybrid is fabricated by layer-by-layer assembly. ► Cartap results in luminescence resonance energy transfer between the nanosensors. ► The method exhibits good sensitivity, selectivity and accuracy.

Introduction

Environmental pollution by organic toxic chemicals continues to be one of the world's leading challenges to sustainable development. Cartap, which is a nereistoxin derivative, is one of the most widely utilized pesticides in agriculture for crop protection and garden markets [1], [2]. The presence of cartap residues in fruit and vegetable crops as well as in water has been shown to inhibit lysyl oxidase activity and cause significant neuromuscular toxicity, resulting in respiratory failure [3], [4], and it may also induce multisystem organ failure, thereby leading to human death [5]. Concerns about the toxicological impact of cartap have motivated the exploration of a method to detect and monitor cartap residues. Because of the low concentrations of pesticide and the coexistence of matrix interferences, a detection method that is rapid, sensitive and selective for the target molecule in food and environmental matrices is highly desired. A number of technologies, including gas chromatography–mass spectrometry (GC–MS) [6] and liquid chromatography–mass spectrometry (LC–MS) [7], have been utilized to detect cartap. In spite of their enhanced specificity and sensitivity, these GC/LC-MS-based methods have the disadvantages of utilizing expensive equipment, being time-consuming and being complicated.

Fluorescence detection with pesticide-responsive chemosensors offers a promising approach for the simple and rapid tracking of these deleterious compounds [8], [9], [10]. In particular, luminescence resonance energy transfer (LRET) technology is convenient and can be applied routinely at the single molecule detection limit, making it an ideal method to detect trace amount of pesticides [11], [12], [13], [14], [15]. Unfortunately, most of these nanosensors are based on organic fluorophores or quantum dots, which are excited by UV or visible radiation. In the application of these detection techniques, the many impurities that are present in biological, toxicological and environmental samples can also be excited under such conditions, thereby reducing the detection sensitivity.

Identifying a more appropriate luminescent label remains a challenging task and has recently emerged as a focal point in the chemistry and sensing communities. Upconversion (UC) nanophosphors, which are excited in the infrared region instead of the UV and visible region to emit in the visible domain, may be an alternative [16], [17], [18]. Compared to organic fluorophores and quantum dots, UC nanophosphors exhibit long fluorescence lifetimes, low photobleaching, high quantum yields, narrow emission peak, large Stokes shifts, and low toxicity. Furthermore, their low autofluorescence background, high chemical stability, and tunable optical properties, which can be tuned by varying the lanthanide dopants and host matrix, make such nanophosphores suitable fluorescence labels. In particular, the luminescence from biological, toxicological and environmental samples (background) upon excitation with IR radiation is extremely low. All of these favorable properties demonstrate the great potential of UC nanocrystals in the analysis of biological, toxicological and environmental samples.

Here, based on LRET between NaYF₄:Yb,Ho nanocrystals and gold nanoparticles, we demonstrate a novel, highly sensitive and selective nanosensor for the detection of cartap. The nanosensor, a NaYF₄:Yb,Ho/Au nanocomposite, was synthesized through the self-absorption of gold nanoparticles on the surface of thiol-functionalized UC nanocrystals. The nanocomposites were then modified with mercaptopropionic acid (MPA) in which the hydrogen-bonding recognition between MPA and cartap via OH-N and NH₂-O pulls the nanocomposites closer, resulting in LRET taking place between NaYF₄:Yb,Ho nanocrystals (donors) and Au nanoparticles (acceptors) located on the other nanocomposites (Fig. 1). The aggregation status of NaYF₄:Yb,Ho/Au nanocomposites was determined by the decrease in the UC emission intensity, and thus, detection of cartap was achieved by examining the quenching of UC emission of the NaYF₄:Yb,Ho/Au nanocomposites.

Section snippets

Reagents and chemicals

Yttrium oxide (Y₂O₃, 99.99%), ytterbium oxide (Yb₂O₃, 99.99%), holmium oxide (Ho₂O₃, 99.99%), hydrogen tetrachloroaurate trihydrate (HAuCl₄·3H₂O, 99.99%), sodium borohydride (NaBH₄, 99%), 3-mercaptopropyltrimethoxysilane (MPTMS, 95%), and tetraethoxy silane (TEOS, 99%) from Aldrich were used as received. Deionized water with high resistivity (18.2 MΩ·cm) was obtained using a TKA GenPure ultrapure water system. All of the glassware was cleaned with aqua regia (HCl:HNO₃=3:1 vol%), rinsed with

Results and discussion

Fig. 2a illustrates the strategy for the synthesis of UC nanocrystal-Au nanoparticle nanocomposites. The UC nanocrystals we chose to use were NaYF₄:Yb,Ho nanocrystals. As shown in Fig. 2b, the cubic NaYF₄:Yb,Ho nanocrystals have a size of approximately 40 nm. As during the hydrothermal reaction, the carboxyl groups of the oleic acid molecules interacted strongly with the rare-earth ions; the produced NaYF₄:Yb,Ho nanocrystals were protected by a layer of oleic acid with the chains outside of the

Conclusions

The present study has introduced a novel UC nanocrystal/Au nanoparticle nanocomposite-based LRET nanosensor for screening cartap. The as-prepared nanosensor combines the merits of both gold and UC nanocrystals and is formed by chemical bond linkage. The stable UC luminescence and easy functionalization of gold allow the nanocomposites to sense the presence of cartap based on UC luminescence quenching through cartap-induced aggregation. Under the optimal conditions, the sensitivity of the

Acknowledgments

The authors appreciate the financial support of the National Natural Science Foundation of China (Nos. 51102067, 81101087, 81130028 and 31210103913), Science and Technology Research Project of Heilongjiang Education Department (No. 12511325), China Postdoctoral Science Foundation (20110491052, 2012T50321, 2012M510992), Heilongjiang Postdoctoral Foundation (LBH-Z10139, LBH-Z11054), Medical Scientific Research Foundation of Heilongjiang Province Health Department (2011-165) and the Fundamental

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¹: These authors contributed equally to this work.

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Highly sensitive and selective cartap nanosensor based on luminescence resonance energy transfer between NaYF4:Yb,Ho nanocrystals and gold nanoparticles

Abstract

Graphical Abstract

Highlights

Introduction

Section snippets

Reagents and chemicals

Results and discussion

Conclusions

Acknowledgments

Aqua. Toxicol

J. Chromatogr. A

Talanta

J. Alloy Compd

J. Hazard. Mater.

Talanta

J. Colloid Interf. Sci

Environ. Contam. Toxicol

J. Environ. Sci. Health B

Crit. Care Med.

Clin. Toxicol.

J. AOAC Int.

Angew. Chem. Int. Ed.

J. Mater. Chem.

Highly sensitive and selective cartap nanosensor based on luminescence resonance energy transfer between NaYF₄:Yb,Ho nanocrystals and gold nanoparticles