Chemiluminescence behavior of CdTe-hydrogen peroxide enhanced by sodium hypochlorite and sensitized sensing of estrogens
© Ling et al.; licensee Springer. 2014
Received: 22 December 2013
Accepted: 8 April 2014
Published: 1 May 2014
It has been found that sodium hypochlorite enhanced the chemiluminescence (CL) of the CdTe nanocrystal (NC)-hydrogen peroxide system and that estrogens inhibited these CL signals in alkaline solution. CL spectra were used to investigate the mechanism of the CL enhancement. On the basis of the inhibition, a flow-injection CL method has been established for determination of three natural estrogens.
Estrogens are necessary for ovarian differentiation during critical developmental windows in most vertebrates and promote the growth and differentiation of the adult female reproductive system. Natural and synthetic estrogens have been characterized by the largest endocrine disrupting potential, as confirmed by both in vitro and in vivo studies. The relation between estrogens and several human health problems has been previously reported, such as prostate and breast cancer, perturbation of human reproduction, and endocrine disruption on humans and wildlife. Estrone, estradiol, and estriol are three main natural estrogenic hormones existing in the human body. In the past years, they had been used widely as some regulatory factors preventing the aging substance in women and remedies related to women diseases.
Estrogens have been detected with some analytical procedures, including high-performance liquid chromatography[4–9], UV derivative spectrophotometric method, gas chromatography (GC)-mass spectrometry (MS) analytical method, and capillary electrophoresis. Semiconductor nanocrystals have been widely used as fluorescence biological probes, donors or acceptors of fluorescence resonance energy transfer, and in bioimaging. The reduced and oxidized nanocrystals, generated at a certain electrochemical potential, can react through the annihilation process or react with some co-reactants to produce electrochemiluminescence (ECL)[16–20]. The chemiluminescence (CL) of CdTe nanocrystals (NCs) induced by direct chemical oxidation and its size-dependent and surfactant-sensitized effect in aqueous solution were investigated. Since the low luminous efficiency of the direct chemical oxidation, CdTe NCs' chemiluminescence reaction was enhanced by the Tween 20, sulfite, and some metal ions[22–24].
In this work, we found that sodium hypochlorite could enhance the CL of the CdTe NCs-hydrogen peroxide system. The results indicated that the CL emission intensity of CdTe-hydrogen peroxide-sodium hypochlorite system could be inhibited by estrogens. Therefore, the development of a CL system for determination of estrone, estradiol, and estriol was established, and the mechanism was also discussed.
Reagents and solutions
Estrogens were purchased from Sigma (St. Louis, MO, USA) and used without further purification. Stock solutions of estrone, estradiol, and estriol were firstly dissolved using several drops of 0.01 mol/L NaOH solution and the working standard solution was diluted with water. Sodium hypochlorite (NaClO) and H2O2 were purchased from Beijing Chemical Reagents Company, Beijing, China. The stock solution (H2O2) was standardized by titration with a standard solution of KMnO4. All reagents were of analytical grade and the water used was doubly distilled.
All CL measurements were performed on the IFFM-E mode flow-injection chemiluminescence (FI-CL) analysis system (Xi'an Remax Company, Xi'an, China). It has two peristaltic pumps and one injection system synchronized by a microprocessor. All the reactor coils were made of Teflon tubing. The flow cell was a glass tube (i.d. 0.5 mm) connected with a selected high sensitivity, and low-noise photomultiplier tube. Light measurement data (ICL) were transferred to a computer automatically. Data acquisition and treatment were used with REMAX software running under Windows XP. The photoluminescence spectra and UV-visible absorption spectra were performed on a model F-4500 spectrofluorometer (Hitachi, Tokyo, Japan) and a model UV-3010 spectrophotometer (Hitachi, Japan), respectively. The transmission electron microscopy (TEM) images of the nanoparticles were acquired on a JEM-2010 F microscope. The CL spectrum was detected and recorded by a BPCL-2-KIC Ultra-Weak Luminescence Analyzer (Institute of Biophysics, Chinese Academy of Sciences) and combined with a flow injection system.
Results and discussion
Synthesis of GSH-capped CdTe NCs
UV and PL characterizations of CdTe NCs
The sizes of the abovementioned CdTe NCs were around 1.84, 2.34, 2.60, 2.77, 2.88, and 3.01 nm, respectively, corresponding with the PL peaks of 524, 540, 554, 566, 575, and 589 nm (Figure 3).
TEM characterization of CdTe NCs
Effect of CdTe's size
Effect of CdTe NC concentration
Effect of hydrogen peroxide concentration
Effect of sodium hypochlorite concentration
At a lower concentration of NaClO or H2O2, the signal increases gradually, and the maximum CL intensity occurs at a concentration. Over this concentration, poor relative CL intensity was observed. This may be caused by the increasing of solution viscosity and self-decomposition at high concentration[21, 33].
Effect of pH value
Determination of estrogens
Linear ranges, regression equations, correlation coefficients ( R ), and detection limits of estrogens
Linear ranges (mol/L)
Linear regression equation(C × 10-7 mol/L)
Detection limit (mol/L)
1.0 × 10-6 ~ 1.0 × 10-4
I = 4162.13543 - 87.0738C
3.1 × 10-7
1.0 × 10-6 ~ 7.0 × 10-5
I = 3794.98245 - 59.2879C
1.6 × 10-7
3.0 × 10-6 ~ 1.0 × 10-4
I = 3794.20501 - 72.6198C
1.3 × 10-7
Chemiluminescence quenching efficiency in the presence of various biological species
Chemiluminescence quenching efficiency (%)
Possible CL reaction mechanism
A flow-injection CL method has been established for determination on estrone, estradiol, and estriol based on the inhibition of CdTe-hydrogen peroxide CL system enhanced by sodium hypochlorite. The method has the merits of high sensitivity, and wide linear ranges. It is a new principle and alternative method for detection on estrogens and extends the analytical application of CdTe CL system.
The authors are indebted to the National Natural Science Foundation of China (No. 21101053) for financial support and the scientific research project funds support of Hefei Normal University (2014cxy23). This work is also supported by the Anhui Provincial Science Research Projects (KJ2011Z301,KJ2012Z331). Natural Science Foundation of Anhui Province Science Research Projects (1308085 MB23, 1408085 MB30).
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