Elsevier

Talanta

Volume 107, 30 March 2013, Pages 263-269
Talanta

A novel selenium nanoparticles-enhanced chemiluminescence system for determination of dinitrobutylphenol

https://doi.org/10.1016/j.talanta.2012.12.043Get rights and content

Abstract

A novel selenium nanoparticles (Se NPs)-amplified chemiluminescence (CL) reaction, Se NPs–potassium permanganate–dinitrobutylphenol (DNBP), for the determination of DNBP at gram per milliliter level is described. In the present study, it was found that direct reaction of DNBP with potassium permanganate (KMnO4) in the acidic mediums elicited light emission, which was greatly enhanced by selenium nanoparticles. Under optimum conditions, the CL intensity is linearly related to the concentration of DNBP in the range of 1.0×10−7–8.0×10−5 g mL−1 with a detection limit (3σ) of 3.1×10−8 g mL−1. The relative standard deviation for 11 determinations of 2.5×10−5 g mL−1 DNBP is 2.07%. The Se NPs were prepared by the chemical hydrothermal method. It was found that catalytic properties of Se NPs were higher than those of microparticles (MPs). In addition, scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the Se NPs. Appropriate sensitivity, selectivity and precision were among notable features of the proposed method. The method was successfully applied to the determination of DNBP in the water samples of different origins. Moreover, the possible mechanism for the new CL reaction was also discussed.

Highlights

Development of a novel Se NPs-amplified CL reaction for determination of DNBP. ► Enhancement of light emission from KMnO4DNBPHCl CL system by Se NPs. ► Effect of Se NPs is so appreciable in terms of time evolution of CL. ► Se NPs were prepared by the hydrothermal method and display high catalytic properties. ► Appropriate sensitivity, selectivity were notable features of the proposed method.

Introduction

Environmental pollution by toxic alkyl dinitrophenolic compounds can be detrimental to human health and the environment [1]. DNBP is a typical example of this class of toxic compounds [2]. It is usually used as a polymerization inhibitor for the production of styrene in petrochemical industries and also as a pesticide in agriculture industries [3]. Irregular release of DNBP containing wastewater to environment can be detrimental due to its high toxicity and carcinogenicity to mammals, fish and other aquatic organisms [2], [4]. Hence, the determination of DNBP is very important for evaluating the total toxicity of environmental samples. A literature survey reveals several methods for DNBP determination including gas chromatography (GC), liquid chromatography (LC) and high-performance liquid chromatography (HPLC) [2], [3], [4]. On the other hand, CL methods due to their attracting features such as simplicity, simple and inexpensive instrumentation, high sensitivity and rapidity and low background signals, have received keen attention [5], [6]. Hence, CL methods have become important and powerful analytical tools in various fields, such as biotechnology, food analysis, environmental analysis, pharmaceutical analysis and clinical tests [5], [7], [8], [9]. They usually involve the oxidation of a suitable substrate (or analyte) to produce an excited species, which then emits light upon relaxation to ground state. Although many CL reagents have been investigated, only a few number of CL systems have been widely used in analytical chemistry [6], [10], [11], [12], [13]. Among them, KMnO4 in acidic medium has got greater development recently, perhaps, because the reagent is cheap and easily available [7], [14], [15], [16]. In some of CL-based methods, the CL emission generated during oxidation of organic molecules is of relatively low intensity due to low quantum yield [13], [17]. Therefore, enhancement of CL emission for the aim of higher sensitivity is essential for analytical applications. To this aim, in recent years, nanomaterials including metal and semiconductor nanoparticles with unique physical and chemical properties, can participate in CL reactions as reductants, catalysts, luminophors and nano-sized reaction platforms to catalyze redox CL reactions, providing enhanced CL emission [18], [19]. For example, it has been demonstrated that, nanoparticles of metals, such as silver [20], gold [13], [21], [22], [23], platinum [24], as well as semiconductors, such as CdTe [25], [26], CdSe/CdS [27] and TiO2 [17] have been used as signal enhancers. However, to the best of authors' knowledge, Se nanoparticles have not been so far reported as an enhancer in CL systems.

In the present paper, we have proposed for the first time a novel CL method for determination of DNBP. In this context, Se NPs were synthesized by the chemical hydrothermal method and then its effect to the new KMnO4–DNBP CL system was explored. Moreover, it was found that Se NPs could act as a nanocatalyst on the KMnO4–DNBP CL reaction in acidic solution to produce a relatively intense CL emission. Therefore, under the optimized conditions, the novel selenium nanoparticles-enhanced CL system was applied to the determination of DNBP in water samples.

Section snippets

Reagents and materials

All the reagents were of analytical grade, and were used without further purification. The stock standard solution (5.0×10−4 g mL−1) of DNBP (Petrochemical Co. Tabriz, Iran) was prepared by dissolving DNBP in slightly basic water. Double distilled water was used throughout. The test standard solutions were freshly prepared by appropriate dilution of the stock standard solution with water when used. KMnO4 (Merck Co. Germany) stock solution (8.0×10−2 mol L−1) was prepared in a brown bottle and kept

XRD spectrum and SEM image of Se NPs

The formation of Se NPs can easily be confirmed by XRD spectrum (Fig. 1a). It can be observed from Fig. 1a that the peaks in XRD are at 2θ=23°, 28°, 42°, 46° and 52° which corresponded to Se NPs of tridimensional phase. The average crystalline size of the samples was 15 nm according to Debye–Scherrer formula [28].

The SEM images of the synthesized Se NPs and Se MPs are shown in Fig. 1b and c. It shows that the prepared nanoparticles and microparticles are spherical in shape and the size ranges

Conclusions

The Se NPs enhanced-CL method proposed here is simple and showed improved selectivity. Furthermore, it gives sufficient sensitivity without using an expensive CL reagent. The method has been successfully applied to the analysis of DNBP in water samples of different origins and the results were in reasonable agreement with a reference method.

Acknowledgment

The authors thank the Universities of Tabriz and Maragheh, Iran for all the supports provided. This work is funded by the 2011 Yeungnam University Research Grant.

References (40)

  • Q. Zhang et al.

    J. Hazard. Mater.

    (2010)
  • H.-L. Wang et al.

    J. Hazard. Mater.

    (2009)
  • H.-L. Wang et al.

    J. Hazard. Mater.

    (2010)
  • J.L. Adcock et al.

    Anal. Chim. Acta

    (2007)
  • B. Gomez-Taylor Corominas

    Talanta

    (2003)
  • S. Li et al.

    Talanta

    (2008)
  • J. Du et al.

    Talanta

    (2001)
  • J. Du et al.

    Talanta

    (2012)
  • W. Cao et al.

    Spectrochim. Acta, Part A

    (2007)
  • J.W. Costin et al.

    Anal. Chim. Acta

    (2003)
  • N.W. Barnett et al.

    Anal. Chim. Acta

    (2000)
  • J. Wu et al.

    Sens. Actuators B

    (2011)
  • D.L. Giokas et al.

    Trends Anal. Chem.

    (2010)
  • Q. Li et al.

    Trends Anal. Chem.

    (2011)
  • H. Chen et al.

    J. Colloid Interface Sci.

    (2007)
  • E.G. Zisimopoulos et al.

    Talanta

    (2009)
  • Q. Chen et al.

    Talanta

    (2012)
  • B. Liu et al.

    J. Photoch. Photobiol. A—Chem.

    (2011)
  • H. Zhang et al.

    Spectrochim. Acta, Part A

    (2012)
  • Z. Wang et al.

    Talanta

    (2009)
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