Cardiac troponin I photoelectrochemical sensor: {Mo368} as electrode donor for Bi2S3 and Au co-sensitized FeOOH composite

https://doi.org/10.1016/j.bios.2020.112157Get rights and content

Highlights

  • An unique {Mo368} is designed as the electron donor to capture generated holes.

  • FeOOH with high adsorption capacity is prepared by a simple operation.

  • Co-sensitization of Bi2S3 and Au to FeOOH remarkably enhances the PEC activity.

  • The PEC sensor achieves the ultrasensitive detection of cTnI.

Abstract

A suitable electron donor, which guarantees the stability of the whole system, is considered as the driving force of the PEC sensor. Nowadays, searching appropriate electron donor is still one of the orientations to explorate in the field of sensor. Na48[H496Mo368O1464S48]·ca.1000H2O (abbr. {Mo368}), as a type of polyoxometalate, has perfect morphology, definite size and unique electronic property. Due to the prominent water solubility, {Mo368} usually releases small cations and exists as large anions in the ultrapure water. The interesting property endows {Mo368} with excellent reducibility, which provides great feasibility to become an outstanding electron donor. In addition, FeOOH prepared through a simple operation owns high adsorption capacity, which ensures the fastness of other materials. Subsequently, the narrow band-gap of Bi2S3 and the unique noble metal properties of Au nanoparticles are utilized to co-sensitize FeOOH to improve the light-harvesting capability and photoelectric conversion efficiency. Combined with the specificity recognition of antigen and antibody, a novel photoelectrochemical sensor is constructed with a wide detection range of 1.00 pg mL−1 - 100 ng mL−1 and low detection limit (0.76 pg mL−1), which achieves the sensitive detection of cardiac troponin I in early diagnosis of cardiovascular disease.

Introduction

Photoelectrochemical (PEC) sensor integrating the advantages of photochemical method and electrochemical technology displays superior peculiarities of simple device, reduced background interference, high sensitivity and excellent stability(Li et al., 2019b; Li et al., 2019f; Lv et al., 2018; Zhou et al., 2018). Under the irradiation of visible light, the excited state of photoactive materials is generated, which accelerates the electron transfer, and then facilitates the output of photocurrent signals(Li et al., 2018; Li et al., 2019e; Saha et al., 2018). Meanwhile, electron donor constantly captures photo-generated holes to ensure the stability of PEC sensor(Bao et al., 2019; Chen et al., 2018; Chi et al., 2019; Gao et al., 2019; Li et al., 2019a), which determines that choosing an appropriate electron donor is significant in the design process of PEC sensor.

As a late-model inorganic macromolecules at the nanoscale, polyoxometalate refers to a group of cluster compound which is composed of polymetallic atoms and heteroatoms in a certain structure and bridged by oxygen atoms. On account of the unique electronic properties and structural diversity, polyoxometalate has measureless potential in material(Adhikary et al., 2018; Wang et al., 2019), catalysis(Guo et al., 2018; Li et al., 2019d), supercapacitors(Wang et al., 2018a), and so on. Na48[H496Mo368O1464S48]·ca.1000H2O (abbr. {Mo368}), an important type of polyoxometalate, owns fascinating peculiarities such as perfect morphology, constant composition and definite size. Now, it has attracted the attention of many scholars. For example, Achim Müller et al. have researched the simple preparation method and characters of the hedgehog-shaped {Mo368}(Müller et al., 2004). Later, the group has explored the nanochemistry of {Mo368}(Müller et al., 2010). Subsequently, Somenath Garai et al. have analyzed the distinct electronic and structural properties of {Mo368}, and self-assembled intospherical vesicles encapsulated by surfactant(Garai et al., 2015). {Mo368} is an inorganic macromolecule material that can be easily synthesized, and the most surprising thing is that {Mo368} usually releases small cations and exists as large anions in the ultrapure water because of the prominent water solubility(Garai et al., 2015). Due to the unique electronic property, {Mo368} endows with excellent reducibility, whereby provides a great feasibility to become an outstanding electron donor. Its application in PEC sensor not only enriches the technology in the field of PEC, but also provides a new strategy for the construction of sensor.

If a suitable electron donor is considered as the driving force of the PEC sensor, novel photosensitive materials are the indispensable foundation of the whole sensor system. As a high-profile photosensitive material, iron oxyhydroxide (FeOOH) has boundless prospects in the various fields due to the advantages of low cost, environmental friendliness, excellent photocatalytic activity and so on(Hu et al., 2019; Zhou et al., 2017). For example, Ai et al. have prepared flowerlike α-FeOOH as catalyst to reduce nitro compounds(Ai et al., 2018). Xin et al. have utilized FeOOH nanosheets to enhance the capacitive performance of carbonized wood(Xin et al., 2018). Feng et al. have designed FeOOH/CeO2 heterojunction for the oxygen evolution reaction(Feng et al., 2016). Nonetheless, the wide band-gap of FeOOH impedes electron transfer and further reduces the photoelectric conversion efficiency. Fortunately, abundant active hydroxyl groups are distributed on the surface of FeOOH, which endows FeOOH with high adsorption capacity(Wang et al., 2016). Using the unique property, a novel FeOOH/Bi2S3 heterojunction is synthesized by growing bismuth sulfide (Bi2S3) on the surface of FeOOH in our work.

As one of the most concerned semiconductor nanomaterials, Bi2S3 with narrow band-gap is frequently used to sensitize other materials to adjust the band-gap of the materials(Bao et al., 2019; Cao et al., 2018; Chen et al., 2019; Guo et al., 2019; Wang et al., 2018b). And the absorbance coefficient of Bi2S3 is about 104 cm−1 displaying broad absorption in the visible light spectra(Cui et al., 2018; Li et al., 2019c; Paul et al., 2017). Hence, Bi2S3 is attached on the surface of FeOOH by the ion adsorption reaction between OH and Bi3+, which obviously improves the charge carrier separation and the mass-transfer ability enhancing the photoelectric conversion efficiency. In addition, combining with noble metal nanoparticles (Au, Ag, Pt) is deemed to an effective approach that promotes electron transfer and boosts the performance of nanomaterials because of the surface plasmon resonance (SPR) effect, outstanding optical stability and excellent quantum yield(Jia et al., 2019; Wen et al., 2019). Kaylyn K. Leung et al. have electrodeposited DNA monolayers on Au and evaluated with fluorescence microscopy to further control the preparation of biosensor surface(Leung et al., 2019). Yuan et al. have used the SPR effect of Au nanoparticles (Au NPs) to detect Hg2+(Yuan et al., 2019). Therefore, Au NPs are absorbed tightly on the FeOOH/Bi2S3 heterojunction due to the band of Au–S, which enhances the light-harvesting capability and promotes the ability of electron transfer of materials.

In our work, a novel PEC sensor based on the matrix of FeOOH/Bi2S3/Au is constructed using {Mo368} with unique structure as electron donor for the ultrasensitive detection of cardiac troponin I (cTnI). With the acceleration of aging society, cardiovascular disease has gradually become one of the hot issues in the society. Cardiovascular diseases mainly include hypertension, myocardial infarction, angina pectoris, heart failure and so on, which are critical, acute and severe diseases and lead to an increase in mortality. The concentration of cTnI is significantly different in the serum of normal persons or patients(Sun et al., 2019a; Tan et al., 2017; Welsh et al., 2019). Generally, the content of cTnI in normal human serum is usually below 0.2 ng mL−1. And it implies a direct damage of the myocardium when the concentration of cTnI is higher than 2.0 ng mL−1(Szunerits et al., 2019). Therefore, cTnI is known as one of the biochemical markers of cardiovascular disease(Chapman et al., 2017; Fan et al., 2018a; Lv et al., 2019; Sun et al., 2019b). The ultrasensitive detection of cTnI benefits the early diagnosis of cardiovascular disease.

Section snippets

Materials and reagents

Phosphate buffered saline (PBS, 1/15 mol L−1 of KH2PO4 and 1/15 mol L−1 of Na2HPO4) containing {Mo368} was used as an electrolyte for the PEC measurements. A 100 W LED lamp of white light was used for an irradiation source and the wavelength range of LED lamp was shown in Fig. S1. And other details about materials and apparatus were displayed in the Supporting Information (SI†).

Synthesis of FeOOH on the ITO electrode

The FeOOH was formed by the reaction between prussian blue (PB) and NaOH solution. The PB was prepared according to

Characterization of the applied materials

The SEM, EDS and TEM images were researched to explore the morphology and component of the applied materials. As displayed in Fig. 1A, the obtained FeOOH was composed of abundant nanoparticles. The large specific surface area of FeOOH possessed excellent load capacity. And the EDS image (Fig. 1G) indicated the component of FeOOH consisting of Fe and O elements. In addition, the abundant active OH groups were distributed on the surface of FeOOH, which was further conducive to the absorption of

Conclusion

A novel PEC sensor is proposed to sensitively detect cTnI, while the unique {Mo368} is designed as electron donor. With perfect morphology and interesting electronic characteristics, {Mo368} ensures the stability of the whole electron transfer process. In addition, FeOOH prepared by a simple operation contains abundant active hydroxyl groups. By the adsorption between positive and negative ion, Bi2S3 is utilized to sensitize FeOOH for accelerating the electron transfer. And the SPR effect and

CRediT authorship contribution statement

Chunzhu Bao: Conceptualization, Data curation. Xin Liu: Writing - review & editing, Methodology. Xinrong Shao: Formal analysis. Xiang Ren: Formal analysis. Yong Zhang: Formal analysis. Xu Sun: Formal analysis. Dawei Fan: Writing - review & editing, Methodology, Data curation. Qin Wei: Funding acquisition, Formal analysis. Huangxian Ju: Funding acquisition, Formal analysis.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This research was financially supported by the Innovation team project of colleges and universities in Jinan (No.2019GXRC027), the National Key Scientific Instrument and Equipment Development Project of China (No. 21627809), the National Natural Science Foundation of China (Nos. 21505051, 21575050, 21777056), the Jinan Scientific Research Leader Workshop Project (2018GXRC024).

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