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Ultrasensitive Mercury Ion Detection Using DNA-functionalized Molybdenum Disulfide Nanosheet/Gold Nanoparticle Hybrid Field-Effect Transistor Device guihua zhou, Jingbo Chang, Haihui Pu, Keying Shi, Shun Mao, Xiaoyu Sui, Ren Ren, Shumao Cui, and Junhong Chen ACS Sens., Just Accepted Manuscript • DOI: 10.1021/acssensors.5b00241 • Publication Date (Web): 18 Jan 2016 Downloaded from http://pubs.acs.org on January 21, 2016
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Ultrasensitive Mercury Ion Detection Using DNA-functionalized Molybdenum Disulfide Nanosheet/Gold Nanoparticle Hybrid Field-Effect Transistor Device Guihua Zhou, Jingbo Chang, Haihui Pu, Keying Shi, Shun Mao, Xiaoyu Sui, Ren Ren, Shumao Cui* and Junhong Chen* Department of Mechanical Engineering, University of Wisconsin-Milwaukee, 3200 North Cramer Street, Milwaukee, Wisconsin 53211, United States *Corresponding email:
[email protected],
[email protected] Abstract
Mercury, one of the most harmful pollutants in water, has a significant negative impact on human health. The molybdenum disulfide (MoS2) nanosheet, due to its unique electronic properties, is a promising candidate for high-performance sensing materials. Here, we report a DNA-functionalized MoS2 nanosheet/gold nanoparticle hybrid field-effect transistor (FET) sensor for the ultrasensitive detection of Hg2+ in an aqueous environment. Specific DNA was used in the hybrid structure as the capture probe for the label-free detection. By monitoring the electrical characteristics of the FET device, the performance of the sensor was investigated. Our sensor shows a rapid response (1-2 s) to Hg2+ and an ultralow detection limit of 0.1 nM, which is much lower than the maximum contaminant level (MCL) for Hg2+ in drinking water (9.9 nM) recommended by the U.S. Environmental Protection Agency (EPA). In addition, the sensor shows a high selectivity to Hg2+ compared with other interfering metal ions, e.g., As5+, Cd2+, Pb2+, etc. This rapid and ultrasensitive method for Hg2+ detection can be potentially developed into either stand-alone handheld sensors or 1
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integrated into existing water equipment for continuously monitoring the water quality. Keywords: field-effect transistor, DNA, molybdenum disulfide, gold nanoparticle, Hg2+ detection
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It is widely known that mercury is highly toxic, whose accumulation in the human body can cause fatal illnesses, such as cyanosis syndrome, nephrotic syndrome, minamata disease and pulmonary edema.1 Mercury can also damage the nervous system and gastrointestinal function and even result in the kidney or respiratory failure.2 However, mercury is still being extensively used in both domestic and industrial applications, threatening the water safety in many different ways. Therefore, it is very important to develop platforms towards the detection of mercury ions in drinking water to mitigate such health risks. So far, techniques to detect mercury ions involve the atomic absorption spectrometry,3 the cold vapor generation,4 the inductively coupled plasma mass spectrometry,5 the colorimetric analysis,6-8 the electrochemical characterization,9-12 the fluorescence spectroscopy,13 and the ion selective electrodes.14
Nanomaterials-based field-effect transistor (FET) sensors (e.g., nanoparticles15,
nanowires16, nanotubes17 and nanosheets18) are now becoming an attractive approach for the detection of metal ion species due to their various excellent features, including the convenient fabrication, low-cost, real-time response, ultrahigh sensitivity, user-friendly analytical platform for in-line analysis, and label-free detection through the interaction between the analyte and the semiconductor. Moreover, their performances are comparable to or even better than those of the above mentioned techniques. In principle, a FET sensor works by transducing and monitoring the absorbates-induced perturbations into the conductance change in the channel materials, typically in terms of the source-drain current. The channel material with high surface to volume ratio is favored generally since it implies higher adsorption site density available, while it has been reported that semiconducting materials outperform the metallic ones in sensing. 19. Consequently, two 3
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dimensional (2D) semiconducting materials are promising candidates for sensing applications. As a model of 2D nanomaterials, graphene has been comprehensively studied due to its unique electronic properties.20 Nevertheless, its application in transistor devices is limited as the lack of a finite band gap leads to a high off-state current.21 Although band gap could be introduced by cutting graphene into narrow ribbons22 or reducing graphene oxide (GO)23, it is only sizable when the ribbon is narrow enough or GO is highly oxidized before reduction. In addition, cutting graphene into nanoribbons is hardly in a precisely controllable manner24 and reduced GO is highly amorphous with low carrier mobility25. Recently, the 2D-layered transition-metal dichalcogenides (TMDs) are attracting various research interests due to their layer dependent electronic properties. For example, the single-layer MoS2 nanosheet, unlike the semi-metallic graphene, is a semiconductor with a high on/off current ratio of ~108, and a carrier mobility of 200 cm2V-1s-1 at room temperature.26-27 More importantly, the band gap of MoS2 can be tuned from 1.8 eV for monolayer to 1.2 eV for bulk26, 28 by stacking it into multilayer due to the van der Waals interactions between the adjacent layers.27 These unique properties, together with its high flexibility,29 make MoS2 a promising candidate in future FET-based sensing applications. Therefore, it is highly desirable to explore the sensing performance of MoS2/FET-based platform and its underlying mechanism. In this study, we investigated the FET sensors fabricated from the MoS2 thin film decorated with specific DNA-functionalized gold (Au) nanoparticles (NPs) to detect heavy metal ions. In the detection, the heavy metal ions bind to the DNA probes and thus lead to the conductivity change in the MoS2 nanosheet. Our MoS2/DNA-Au NP hybrid sensor shows a remarkable response to Hg2+, with the detection limit down to 0.1 nM. In addition, the FET 4
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sensor responded within 2 s, much faster than standard techniques or electrochemical methods that take 30 s to 3 mins.14, 30-32 The sensor also exhibits good selectivity with much smaller responses to As5+, Ca2+, Cd2+, Cu2+, Fe3+, Mg2+, Na+, Pb2+ and Zn2+ ions. The rapid, sensitive, and selective detection suggests the promising application of the MoS2/DNA-Au NP hybrid structure for real-time detection of Hg2+ ions for the water safety.
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Experimental Methods: Material MoS2 nanosheets were synthesized by a lithium ion exfoliation method at room temperature, primarily due to its capability to control the nanosheet thickness and its potential for low-cost industrial applications29, 33-35 compared with the mechanical exfoliation method36-40. MoS2 powder was intercalated by Li ions and then sonicated in water. Next, MoS2 crystals were immersed in a butyllithium solution for 7 days in a flask filled with argon gas. The LixMoS2 was retrieved by centrifugation and washed with hexane to remove excess lithium and organic residues. Exfoliation was achieved immediately after this by ultrasonicating LixMoS2 in water for 1 h. Later, MoS2 film was prepared by filtering a diluted suspension (0.2 mg mL– 1
) through a mixed cellulose ester membrane with 25 nm pores. The MoS2 film was
delaminated and transferred onto the SiO2 substrate, as shown in Figure S1. All metal ion solutions, including As5+, Ca2+, Cd2+, Cu2+, Hg2+, Fe3+, Mg2+, Na+, Pb2+ and Zn2+, were prepared by adding chloride salts (Sigma-Aldrich) in deionized (DI) water (Cellgro). MoS2 powder (particle size:
