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A rapid colorimetric sensor of clenbuterol based on cysteamine modified gold nanoparticles Jingyan Kang, Yujie Zhang, Xing Li, Lijing Miao, and Aiguo Wu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b09079 • Publication Date (Web): 16 Dec 2015 Downloaded from http://pubs.acs.org on December 21, 2015

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ACS Applied Materials & Interfaces

A rapid colorimetric sensor of clenbuterol based on cysteamine modified gold nanoparticles Jingyan Kang,†,‡ Yujie Zhang,‡ Xing Li,*,† Lijing Miao,‡ and Aiguo Wu*,‡ † Faculty of Science, Ningbo University, Ningbo 315211, China ‡ Key Laboratory of Magnetic Materials and Devices, and Division of Functional Materials and Nanodevices, Ningbo Institute of Materials Technology and Engineering, Ningbo 315201, China Supporting Information

ABSTRACT: Demonstrated was a simple visual and rapid colorimetric sensor for detection of clenbuterol (CLB) based on gold nanoparticles (AuNPs) modified with cysteamine (CA) and characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS), UV-vis. The solution color from red to blue grey with increasing clenbuterol concentration resulted from the aggregation of AuNPs. The detection limit of clenbuterol is 50 nM by naked eyes. The selectivity of CA-AuNPs detection system for clenbuterol is excellent compared with other interference in food. This sensor has been successfully applied to detect clenbuterol in real blood sample. KEYWORDS: clenbuterol, colorimetric detection, gold nanoparticle, excellent selectivity, high sensitivity attention due to their high extinction coefficient and strong surface plasma resonance property,16 and this kind of method has been applied on the detection of metal ions (Hg2+,17-18 Pb2+,19 Cu2+,20 Mn2+,21 et. al), proteins,22 organic molecules23 and biological applications.24-25 Up to now, several types of colorimetric methods for clenbuterol detection have been reported based on its reducibility, but most of them have high limit of detection, weak sensitivity and selectivity,26-27 besides, few reports described the detection of clenbuterol based on the aggregative mechanism.28 Herein, we aimed to propose a new facile colormetric detection method for clenbuterol with high sensitivity and excellent selectivity using gold nanoparticles modified by cysteamines. AuNPs was firstly prepared by using sodium citrate reduction method, and citrate-stabilized AuNPs was modified with cysteamine. For the detection, different concentration aqueous solutions of clenbuterol were added into CA-AuNPs solutions, then the mixtures were shaken and stored at room temperature for 15 min, the solution color gradually varied from wine red to blue grey with the increasing concentration of clenbuterol. The possible detection mechanism is shown in Figure S1. Due to the strong Au-S bond, CA can be easily connected to AuNPs and the –NH2 group exposed on the surface of CA-AuNPs. The CA-AuNPs can be well dispersed in the solution for a long time because of the electrostatic repulsion of the negatived charged on the surface of AuNPs, showing a wine red color.21 In the

Clenbuterol is not only a drug used to treat bronchial asthma1-2 but also one kind of adrenal neural stimulants that promote protein synthesis, which can accelerate the transformation and the decomposition of fat.3 For these reasons given above, the clenbuterol is illegally added in the feed for pig and cattle to improve the yield of lean.4-5 However, a large number of experiments have proved that clenbuterol is a medium cumulative drug and residues in animal. If they are eaten, human will suffer from the dizziness, fatigue, arrhythmia and metabolic disorder. So clenbuterol is banned for addition in animal feeds in many countries,6 but illegal abuse of clenbuterol never stopped. Since 1998, clenbuterol poisoning incidents occurred frequently in China, especially in March 2011, Shuanghui Co. clenbuterol events caused great concern of worldwide.7 The current detection methods for clenbuterol mainly include gas chromatography-mass spectrometry (GC-MS),8 liquid chromatography (LC),9 surface molecularly imprinted polymers,10 enzyme-linked immunosorbent (ELISA),11 electro-chemical analysis,12,13 capillary electro14 phoresis, fluorescence biosensor115 and so on. However, these methods need costly instruments or complicated process, making them difficult operation and time-consuming. Therefore, the development of cheap, simple, rapid and visual field-portable analysis method is particularly important for clenbuterol detection. Recently, the detection methods based on the precious metal nanoparticles have attract more and more 1

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presence of clenbuterol, the –NH2 of cysteamine can connect with –OH, –Cl and –NH2 of clenbuterol through hydrogen bonding, the CA-AuNPs aggregated quickly, leading to the color change of the solution from wine red to blue grey, accompanying with the change of surface plasma resonance (SPR) absorption peak and intensity. As shown in Figure S2, CA-AuNPs displayed an intense surface plasma absorption at 525 nm. While in the presence of CLB, two or more dispersive CA-AuNPs are closed by the hydrogen bonding between CLB and CA-AuNPs, and the oscillating electric fields of CAAuNPs can interact to yield new resonances and the surface plasma will be coupled (as SPR frequency is sensitive to the proximity of other nanoparticles), resulting in a new absorbance peak of CA-AuNPs appeared at about 675 nm. The colors of solutions changed from wine red to blue grey, indicating that AuNPs aggregated after adding CLB. Based on the aggregation mechanism above, the CA-AuNPs system is sensitive to clenbuterol. In addition, the selectivity of this detection system is excellent, as other substances which consist in meat or related food such as cysteine, threonine, vitamin C, urea, alanine, phenylalanine, glycerol, glucose, glycine, CaCl2, NaCl, can’t interfere in detection of CLB for the CA-AuNPs. To further verify the reaction mechanism, TEM images and dynamic light scattering (DLS) data were obtained and shown in Figure 1, citrate-stabilized AuNPs was dispersed well in solution (Figure 1a) and the size was about 10 nm (Figure 1e); after AuNPs was modified with cystemine, CA-AuNPs also showed the

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good dispersibility (Figure 1b) and the size was about 13 nm (Figure 1f) which became a little bigger than AuNPs. EDS result indicated that AuNPs has been synthesized (Figure S3a), with the negatived zeta of AuNPs (-42.9 mv) revealing the good stability of AuNPs. The zetapotential of CA-AuNPs (-35.2 mV) was lower compared with the zeta of AuNPs (-42.9 mv) due to the the amino groups of cysteamines can make effect with AuNPs and to decrease the charge of AuNPs.29 However, CAAuNPs rapidly aggregated in the presence of 0.8 µM CLB (Figure 1c) and the size is about 108 nm (Figure 1g) and the EDS result (Figure 3b) indicated that the CLB can located in CA-AuNPs surfaces due to the existence of C, Cl and O of CLB . Since the AuNPs were obtained by using the sodium citrate as the reducing agent, the concentration of citrate could affect the detection capability. Figure S4a showed the relationship between the ratio of A675nm/A525nm and the volume of sodium citrate 1.0 % (wt) while keeping the volume of HAuCl4 solution (1.0 mM, 15 mL). From the graph we known, the ratio of A675nm/A525nm increased with the increasing volume of Na3Ct until 1.8 mL, and then the ratio reduced with the increasing volume of Na3Ct. When the Na3Ct was lack, the stability of AuNPs became bad; the Na3Ct was too much, the charge of AuNPs surfaces was too rich, which could not cause the aggregation of AuNPs. The experiment results showed that the optimum volume of sodium citrate is 1.8 mL, and the best detection effect could be given in this condition.

Figure 1. TEM image of AuNPs (a), CA-AuNPs (b), CA-AuNPs with 0.8 µM CLB (c), DLS of AuNPs (e), CA-AuNPs (f), CA-AuNPs with 0.8 µM CLB (g).

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As reported previously,26 there is strong electrostatic interaction between cysteamine and AuNPs, which can decrease the stability of AuNPs, so the concentration of cysteamines must be appropriate to make sure that the modified AuNPs not only can be used to detect CLB but also are stable in the solution. Figure S4b showed the optimum concentration of cysteamines is 0.25 µM, when the concentration of cysteamines was very low, AuNPs were not modified well by cysteamine and the sensitivity of the assay is poor; oppositely, with too high concentration of cysteamines, CA-AuNPs aggregated themselves in the absence of analytes. Based on these results, AuNPs were modified with cysteamines of 0.25 µM throughout the following experiments. The effect of pH value of CA-AuNPs solution on the detection of CLB was investigated at the range of 3-7. As shown in Figure S4c, the absorbance ratio of A675nm/A525nm increase until pH was 4, and then decreased with the further increase of pH, which indicated that the optimum pH was 4.0 for CLB detection. When pH is lower than 3.0, the dispersed CAAuNPs aggregated easily themselves and when pH is higher than 7.0, CA-AuNPs didn’t aggregate even though CLB was added. As shown in Figure S4d, after reacting with CLB, the absorbance intensity of CAAuNPs at 525 nm kept decreasing until 15 min, indicating that the reaction almost completed under this condition. Therefore, all the experiments were performed for 15 min.

detection limit of CLB was 0.9 µM. For analyzing the color change range, the ratio of the absorbance intensity between A675nm and A525nm was used. A typical plot of the absorbance ratio with CLB concentration was revealed in Figure S5, which indicated that the ratio increased slightly with the low concentration of CLB (≤ 1.0 µM), but the ratio had an obvious increase when the concentration of CLB is higher than 1.0 µM. It proved that CA-AuNPs aggregated when the concentration of CLB is higher than 1.0 µM and this system was not sensitive to CLB at low concentration range. For improving the sensitivity, a possible strategy was adopted to add 1.0 µM CLB to CA-AuNPs solutions with stirring for 30 min before use.30 Under the optimized condition, different concentrations of CLB 100 µL were added into 900 µL solution above, keeping for 15 min, results were showed in Figure 2b, upon increasing concentration of CLB from 50 nM to 1.0 µM, the colors of the solutions changed from wine red to blue grey obviously. It means that the detection limit of CLB is 50 nM by the naked eyes.

Figure 2. (a) The image of the CA-AuNPs with CLB from 0.05 to 0.9 µM; (b) CA-AuNPs with CLB form 0.05 to 1.0 µM (1.0 µM CLB in advance).

The color change of CA-AuNPs solutions induced by CLB was shown in Figure 2a, it could be seen that the addition of 0.9 µM CLB led to a color change from wine red to amaranth. Upon the increasing concentration of CLB, the color of the mixture solution was gradually deepened until the color was grey blue as 1.2 µM of the CLB concentration. But the result showed that the

Figure 3. (a) The image and (b) the UV-Vis absorption ratio A675/A525 of the CA-AuNPs (1.0 µM CLB in advance) in the presence of 0.8µM CLB or different interference (8.0 µM) except the cysteamine is 0.8 µM (A: Alamime, B: Phenylalanine, C: Glycerol, D: Vitamin, E: Threonine, F: Urea, G: Cysteine , H: Glucose, I: Glycine , J: NaCl, K: CaCl2). 3



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The selectivity of the assay was evaluated with other analytes such as alamine, phenylalamine, glycerol, vitamin C, urea, glycine, threonine, glucose, CaCl2 and NaCl at the concentration of 8.0 µM except for the concentration of cysteine of 0.8 µM for the determination of 0.8 µM CLB under the optimal experimental condition. The experimental results clearly showed that only CLB can cause a color change (Figure 3a). Figure 3b gave the UV absorbance ratio of CLB or different interference added into AuNPs above, and a remarkable higher absorption ratio confirmed the excellent selectivity of the proposed assay for CLB.

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showed wine red only for the control, bule grey for all other sultions with CLB (Figure 4a), which exhibited that the existence of other interference have no effect on the detection of CLB. Similarly, Figure 4b showed the UV absorbance ratio of CLB and different interference added into AuNPs above, it indicated that the mixture of CLB and different interference (such as Alamime, Phenylalanine, Glycerol, Vitamin, Threonine, Urea, Cysteamine, Glucose, Glycine, NaCl, CaCl2), could not affect the detection of CLB. Table S1 showed the limit of detection (LOD), specificity and anti-interference of different colorimetric methods for the detection of CLB by naked eyes. Compared with the existing methods, a relatively competitive LOD was achieved in this work. Comparatively speaking, our method is relativity rapid and simple to meet the need of detection of CLB. To test the practicality of the proposed visual approach, the detection of CLB in PBS and blood sample were performed. Different concentrations of CLB was added in PBS and blood samples with standard addition method, and then 100 µL solution above was added into 900 µL of sensor solution under the optimal condition. In PBS solution, the color changed with the increasing concentration of CLB, likewise, in blood solution the differnent concentration of CLB also could cause the color change of the solution (Figure S6). When the concentration of CLB was 0.05 µM in blood, the color changed compared with the control sample. It implied that this sensor has been successfully applied to detect clenbuterol in blood, which may develop a new way for visual clenbuterol probe in real sample. In this work, a new one-step colorimetric sensor has been successfully designed for rapid visual detection of CLB by naked eyes at room temperature, based on CAAuNPs aggregated rapidly and lead to a color change from wine red to blue grey, which offers advantages of simplicity, practicability, high sensitivity, selectivity, high anti-interference (such as Alamime, Phenylalanine, Glycerol, Vitamin, Threonine, Urea, Cysteamine , Glucose, Glycine, NaCl, CaCl2), and economy with the low detection limit (50 nM). Even more importantly, this sensor system can be applied for rapid and visual detection of CLB in the real blood samples. ASSOCIATED CONTENT

Figure 4. (a) The image and (b) the UV-Vis absorption ratio A675/A525 of the CA-AuNPs (1.0 µM CLB in advance) in the presence of the mixture of 0.8 µM CLB and different interference (8.0 µM) except the cysteamine 0.8 µM (A: Alamime, B: Phenylalanine, C: Glycerol, D: Vitamin, E: Threonine, F: Urea, G: Cysteine , H: Glucose, I: Glycine , J: NaCl, K: CaCl2).

Supporting Information Experimental details and characterization data. These materials are available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author

In order to evaluate the anti-interference of the assay, different interference (8.0 µM) except the cysteine concentration of 0.8 µM was mixed with CLB (0.8 µM), and the mixture solution was added in the CA-AuNPs under the optimal condition, the experimental result

* Tel.: +86-574-87600869. E-mail: [email protected]; [email protected] Notes The authors declare no competing financial interest. 4


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ACKNOWLEDGMENTS Authors acknowledge the financial support by the NSFC (21571110, 31128007), the Project for Science and Technology Service of Chinese Academy of Sciences (KFJ-EW-STS-016), the aided program for Science and Technology Innovative Research Team of Ningbo Municipality (2014B82010, and 2015B11002), Hundred Talents Program of Chinese Academy of Sciences (2010-735), and the Program of Zhejiang Provincial Natural Science Foundation of China (R5110230),.the Ningbo Foundation (2014C50037 and 2014A610106), and sponsored K. C. Wong Magna Fund in Ningbo University.

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Graphical Abstract

A rapid colorimetric sensor of clenbuterol based on cysteamine modified gold nanoparticles Jingyan Kang,† Yujie Zhang,‡ Xing Li,*,† Lijing Miao, ‡and Aiguo Wu*,†,‡

Section: Colorimetric Sensor, Clenbuterol Detection Gold Nanoparticles, excellent selectivity and high sensitivity

A visual rapid detection sensor of clenbuterol (CLB) was prepared by using gold nanoparticles (AuNPs) modified with cysteamine, which showed excellent selectivity and high selectivity with low limit of 50 nM by naked eyes in real blood sample.

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Figure 1. TEM image of AuNPs (a), CA-AuNPs (b), CA-AuNPs with 0.8 µM CLB (c), DLS of AuNPs (e), CAAuNPs (f), CA-AuNPs with 0.8 µM CLB (g). 299x176mm (200 x 200 DPI)


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Figure 2. (a) The image of the CA-AuNPs with CLB from 0.05 to 0.9 µM; (b) CA-AuNPs with CLB form 0.05 to 1.0 µM (1.0 µM CLB in advance). 190x164mm (200 x 200 DPI)



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Figure 3. (a) The image and (b) the UV-Vis spectra of the CA-AuNPs (1.0 µM CLB in advance) in the preasence of CLB or different interference (8.0 µM) except the cysteine is 0.8 µM (A: Alamime, B: Phenylalanine, C: Glycerol, D: Vitamin, E: Threonine, F: Urea, G: Cysteine, H: Glucose, I: Glycine , J: NaCl, K: CaCl2). 122x191mm (200 x 200 DPI)


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Figure 4. (a) The image and (b) the UV-Vis spectra of the CA-AuNPs (1.0 µM CLB in advance) in the preasence of the mixture of CLB and different interference (8.0 µM) except the cysteine 0.8 µM (A: Alamime, B: Phenylalanine, C: Glycerol, D: Vitamin, E: Threonine, F: Urea, G: Cysteine, H: Glucose, I: Glycine , J: NaCl, K: CaCl2). 115x191mm (200 x 200 DPI)



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Graphic Abstract 150x106mm (300 x 300 DPI)


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