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Article Cite This: ACS Omega 2018, 3, 1386−1394
Gold Nanorod-Based Chrono-Colorimetric Sensor Arrays: A Promising Platform for Chemical Discrimination Applications Nafiseh Fahimi-Kashani† and M. Reza Hormozi-Nezhad*,†,‡ †
Department of Chemistry and ‡Institute of Nanoscience and Nanotechnology, Sharif University of Technology, Tehran 11155-9516, Iran S Supporting Information *
ABSTRACT: Most array-based sensing platforms, to date, utilize static response patterns for discrimination of a wide variety of analytes, but only a few studies have focused on the important task of quantitatively resolving structural isomers, which are nowadays important because of their broad usage in medicines and industries. A possible way of accomplishing this feat is to combine kinetic (rather than static) sensor response profiles with the chemical tongue strategy to allow the development of arraybased sensors for isomeric discrimination. Here, by adding the time dimension, a simple and novel gold nanorod (AuNR)-based chrono-colorimetric sensor array is proposed for chemical discrimination applications. Because of their similar structure but different redox potentials, dihydroxybenzene (DHB) structural isomers have been chosen, as models, to evaluate the applicability of the proposed array. The principle of the array relies on various growth rates of silver shells on AuNRs at different silver ion/ AuNR concentration ratios owing to the different kinetic behaviors of DHBs, which can be used as fingerprints to identify DHBs with the help of multivariate analysis methods. The combinatorial colorimetric response of AuNRs upon DHB addition has been analyzed by linear discriminant analysis and hierarchical cluster analysis. Finally, identification of individual DHBs or their mixtures in real samples confirms the potential application of the proposed array.
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INTRODUCTION Catechol (2DHB), resorcinol (3DHB), and hydroquinone (4DHB) are the three isomers of dihydroxybenzene (DHB), which are widely used in cosmetic, pharmaceutical, plastic, rubber, tanning, paint, and dye industries. They are also present in effluents from oil refineries, coal tar, steel, and pulp mill plants.1−3 Because of their low degradability and high toxicity, they have been certified as the second kind of toxic environmental pollutant by the U.S. Environmental Protection Agency (EPA) and the European Union (EU).4 Furthermore, catechol has many important biological significances such as antioxidation and regulation of some enzymatic activities, occurring naturally in many plants such as fruits, teas, vegetables, and traditional Chinese medicines.5 DHB isomers usually coexist and interfere with each other owing to their similar structures and physiochemical properties.6 Therefore, development of reliable, simple, sensitive, rapid, and efficient methods for discrimination and determination of DHB isomers is of great importance to environmental and food safety as well as public health concerns. Several electrochemical,7−9 chromatographic,10,11 chemiluminescence,12,13 capillary electrophoresis,14 phosphorescence,15 fluorescence,16 and spectrophotometric17 methods have been developed thus far for the determination of DHB isomers. Despite the high sensitivity and low cost of the widely explored electrochemical methods, electrode modification is always required because of the electrochemical inactivity of resorcinol © 2018 American Chemical Society
and the broad overlapped peaks of catechol and hydroquinone.18,19 On the other hand, chromatographic methods are time-consuming and costly and rely on sample preparation and complicated instrumentation in spite of their minimal crossinterference. Hence, it is necessary to develop rapid, sensitive, and cost-effective systems for simultaneous detection and discrimination of DHB isomers. Moving from specific individual lock-and-key sensors toward cross-reactive colorimetric sensor arrays enables the recognition and discrimination of groups of target species such as explosives,20−22 toxic gases,23−25 beverages and foods,26,27 biomolecules,28−30 pathogenic bacteria and fungi,31−33 and nanoparticles.34,35 This approach employs semiselective sensing elements to generate composite response patterns which are unique fingerprints of each analyte.36 However, static time responses have been employed in colorimetric sensor arrays so far, which limits their application in discrimination of structural isomers. Considering the limitations involved in the simultaneous determination of DHB isomers owing to their similar structures, array-based approaches based on the kinetic electrochemical behavior of targets are the potential candidate for this purpose. Received: November 12, 2017 Accepted: January 3, 2018 Published: February 1, 2018 1386
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In many other fields, plasmonic gold and silver nanostructures have recently gained immense interest as novel and efficient sensor elements.37−40 This is fueled by fascinating unique photophysical properties of plasmonic nanomaterials which are not accessible with conventional chemically responsive sensing elements. In particular, gold nanorods (AuNRs) are promising plasmonic nanostructures as the next generation of sensing elements in the design of colorimetric arrays. This arises from their intensive longitudinal surface plasmon resonance (LSPR) within the visible or near-IR regions, which is sensitive to their aspect ratio (AR) and the local dielectric constant of the surrounding environment.41−45 Overgrowth of silver nanoshells on the surface of AuNRs leads to a sharp-contrast multicolor change, which has been utilized thus far for colorimetric detection of ascorbic acid (AA),46 biogenic amines,47 perishable products,48 viruses,49 immunoassay,50 and enzyme activity.51 However, the fascinating phenomenon of silver metallization of AuNRs, to date, has not been employed in many array sensors. Accordingly, there are great strides in terms of utilizing AuNRs as simple sensing elements in the fabrication of colorimetric sensor arrays. In this study, contrary to previous reports, by integrating time to colorimetric sensor arrays, we have developed a promising chrono-colorimetric sensor array (CSA) based on the growth of silver shells on AuNRs at different silver ion/ AuNR concentration ratios at different time intervals, which is capable of identifying DHB structural isomers. Catechol and hydroquinone can reduce silver ions (Ag+) to silver atoms (Ag0) with different kinetics at neutral pHs, leading to anisotropic silver nanoshell deposition on the surface of AuNRs. The changes in the surface composition and AR of AuNRs cause a blue shift of the LSPR peak, resulting in a rainbowlike multicolor change from red to orange to yellow to green, providing a colorimetric method for the discrimination of 2DHB and 4DHB. The kinetic behavior of target analytes depends on the silver ion/AuNR concentration ratios. Moreover, in situ formation of spherical silver nanoparticles (AgNPs) in the presence of catechol, resorcinol, and hydroquinone at basic conditions with different growth kinetics and distribution sizes was employed to enhance the discrimination ability of the proposed array. Discerning response patterns, at time intervals of 5 min, can be used as fingerprints to accurately differentiate the DHB isomers by standard statistical methods, hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA).
It was found that the discrimination ability to DHBs was significantly enhanced by the addition of the time dimension to the proposed colorimetric array. Ultimately, the potential application of the proposed chrono-CSA for the determination of catechol, resorcinol, and hydroquinone in skin bleaching cream and tap water was studied.
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RESULTS AND DISCUSSION Principle and Fabrication of the Array. As schematically illustrated in Scheme 1, the array sensing strategy mainly relies on the anisotropic growth of ultrathin silver shells on AuNRs in the presence of catechol and hydroquinone. Figure 1 shows the extinction spectra and transmission electron microscopy (TEM) images of the AuNRs before and after silver overgrowth on AuNRs induced by 40 μM catechol. The as-prepared
Figure 1. (A) Normalized UV−vis absorption spectra of the AuNR solution before and after silver metallization process in the presence of 40 μM catechol. (B) TEM image of the original nanorods showing an AR of 6.5 ± 0.2. (C) TEM image of AuNRs after silver overgrowth induced by 40 μM catechol. 1387
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Figure 2. Chemical structures of DHB isomers and their potential interference.
Figure 3. UV−vis absorption spectra of (A−C) SE1, (D−F) SE2, (G−I) SE3, (J−L) SE4, and (M,N) SE5 at 1, 5, and 10 min in the presence of 2DHB, 3DHB, and 4DHB (at a concentration of 80 μM). (O) Color change patterns of five sensor elements at different times against different DHBs.
AuNRs with a high AR of 6.5 ± 0.2 exhibit an LSPR peak at 970 nm. Target analyte-induced reduction of silver ions (Ag+) to silver atoms (Ag0) results in transverse Ag deposition on AuNRs and thus a decrease of the AR of the Au@Ag core−shell
nanorods. The changes of the surface composition and AR of AuNRs cause a blue shift of the LSPR peak, resulting in a multicolor change of the nanorod solution by increasing the time. In spite of the quite similar structures of DHBs (Figure 1388
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different DHBs at different times and shows different kinetic behaviors of the same DHB with different sensing elements, confirming the cross-reactive property of this chrono-CSA. Discrimination of DHB Isomers. Standard pattern recognition methods were employed to expose the potential of the chronochromic sensor array more explicitly. As shown in Table S1, the absorbance intensity at several wavelengths, Δλ, and Δarea of the response spectra at 1, 5, and 10 min corresponding to each sensing element was chosen for quantitative comparison of the spectral changes of the array. Accordingly, the data matrix (90-dimensional vectors) based on ΔA (i.e., difference between the absorbance after adding analytes and the absorbance of the LSPR peak of AuNRs, as blank), Δλ (i.e., wavelength shift of the LSPR peak of AuNRs after adding analytes), and Δarea (i.e., difference between UV− vis spectrum integral of AuNRs before and after adding analytes) values was generated. HCA, which is a model-free method based on the clustering of the analyte vectors according to their Euclidean distances in their full vector space,59 was performed to analyze the data from the proposed array for different DHBs at concentrations ranging from 10 to 250 μM. As shown in Figure 4, the HCA dendrogram demonstrates that all of the three DHBs are correctly assigned to their respective groups, and different concentrations of each DHB are clustered together accurately without any misclassification (in triplicate trials). The collected response profiles of the array at a concentration range of 10−250 μM for the three DHBs against five sensing elements at 1, 5, and 10 min are shown in Figure
2), the considerable oxidation potential difference (100 mV) between 2DHB and 4DHB on the gold surface causes them to have different kinetic behaviors in inducing Ag overgrowth on AuNRs.54 This further leads to a distinct blue-shift profile of the LSPR peak in time for 2DHB and 4DHB. Furthermore, the blue-shift extent of the LSPR peak highly depends on the number of silver ions reduced by DHBs in the presence of AuNRs. Higher concentration ratios of silver ions to AuNRs are expected to accelerate the silver deposition rate.55,56 In the absence of the target analytes, insignificant spectral changes of AuNRs were observed by the addition of AgNO3 at time intervals of 5 min (Figure S1A−D). In addition, the AuNRs remain unchanged in the presence of resorcinol (3DHB) because the oxidation potential of resorcinol (3DHB) is far away from those of both 2DHB and 4DHB; hence, 3DHB is incapable of reducing silver ions on AuNRs at neutral pHs. Therefore, the DHB-induced formation of AgNPs in the basic medium was employed to improve the discrimination ability of the proposed array. Phenolic groups of DHBs are ionized under basic conditions and converted to phenolate anions which are more reducible, which can facilitate the formation of AgNPs.57 However, silver ions can participate in a reaction known as mirror reaction by the addition of NaOH. Consequently, sodium citrate (5 × 10−3 M) together with NaOH was used as the fifth sensor element. In the presence of citrate, silver ions can exist in the complex form, which thus prevents the precipitation of silver.58 There is no evidence of AgNP formation by the addition of sodium citrate to the silver solution in a basic medium in the absence of DHBs (Figure S1E). Finally, an array of five sensor elements was designed for the discrimination of DHBs. Array Responses to DHBs. Catechol, hydroquinone, and resorcinol with different concentrations (1−800 μM) were added to the five sensor elements, and the UV−vis spectra were recorded at 1, 5, and 10 min (Figure S2). A representative figure of the array response against 80 μM different DHBs at different time intervals indicates that the spectral change profiles of the array are the fingerprints for each DHB, as shown in Figure 3. In the presence of 2DHB and 4DHB, the AuNRs experience a larger blue shift of their LSPR peak (Δλ) with a progressive increase in the silver ion/AuNR concentration ratio at a particular time, whereas no spectral changes occurred in the presence of 3DHB. The LSPR peak shifts to a shorter wavelength with higher intensities in the presence of 2DHB, indicating the formation of a thicker layer of silver nanoshells and hence smaller ARs of AuNRs in comparison with 4DHB. Furthermore, 2DHB and 4DHB show different kinetic behaviors at a particular silver ion/AuNR concentration ratio, which results in various blue shifts of the AuNR LSPR peak at various times. It can be suggested that the distinct chronochromic behaviors, which were observed during silver deposition on the surface of AuNRs at different silver ion/ AuNR concentration ratios, originate from different oxidation potentials and kinetic behaviors of the selected DHB isomers on the Au surface. Moreover, distinctive kinetic behaviors of the AgNP formation and also different properties of the AgNPs in terms of plasmon resonance peak, size distribution, and concentration were observed with the selected DHBs (Figure 3M,N). As demonstrated in Figure 3O, the color change profiles of the array against 80 μM selected DHBs provide a robust fingerprint for each DHB and can be observed directly by the naked eye. As shown in Figure 3, the spectral responses are different for a given sensor element in the presence of
Figure 4. HCA dendrogram with Ward linkages for DHBs. No confusion in classification for DHB isomers was observed. All of the experiments were performed in triplicate. The concentration range of DHBs was 10−800 μM; the concentrations of polyphenols were 5 and 800 μM. 1389
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Figure 5. Response patterns of (A) SE1, (B) SE2, (C) SE3, (D) SE4, and (E) SE5 according to Table S1 against three DHBs at 80 μM at 1, 5, and 10 min.
S3. The fingerprint barplot response patterns for each DHB isomer (80 μM) demonstrate that the response profiles are different for a given sensing element at a particular time in the presence of different DHBs and distinct profiles for a given analyte exposed to different sensing elements at different times, confirming the feasibility of the array for the discrimination of the selected DHBs (Figure 5). To further evaluate the performance of the proposed array to discriminate DHBs, LDA was utilized to quantitatively discriminate DHBs, according to their linear combination of features. Chronochromic response patterns of DHBs against sensing elements at different times were subjected to LDA. As shown in Figure 6, a well-clustered two-dimensional plot with a classification accuracy of 100% was obtained as a result of reduction and transformation of the training matrix (5 sensing elements × 3 various times × 3 DHBs × 7 concentrations × 3 replicates) to canonical scores. Variations (61.6% and 34.5%) in the data for DHBs were obtained, and the DHBs were successfully clustered into three distinct groups and basically have no overlap in the canonical score plot, revealing that the chrono-CSA is capable of discriminating DHBs at wide concentration ranges. Selectivity of the Array. In real indoor sample analysis, DHBs often coexist with other phenolic compounds, such as gallic acid (THBA) and pyrogallol (THB). Accordingly, the selectivity of the proposed array was assessed by changing the above possible interfering species. THBA and THB are known as reducing agents in the synthesis of silver and gold nanoparticles.60,61 Therefore, the response of the sensor in the presence of THBA and THB was recorded to evaluate their capability of reducing silver ions on the AuNR surface. As shown in Figure S4, the array response spectra at 1 and 800 μM polyphenol compounds are totally different from those of the
Figure 6. Two-dimensional canonical score plot for DHBs and other polyphenols, and a control illustrating the ability of the array to discriminate DHB isomers. All of the experiments were performed in triplicate. The concentration range of DHB isomers was 10−800 μM; the concentrations of other polyphenols were 5 and 800 μM.
DHBs. Furthermore, they are clustered in separate groups in the HCA dendrogram (Figure 4) and LDA score plot (Figure 6). It seems that different redox potentials of these polyphenols play a key role in their distinct kinetic behaviors; thereby, they do not consider the interference in the proposed colorimetric array. Color Difference Maps. Color difference maps, as a useful qualitative approach for visualization of the colorimetric sensor array responses, were obtained by subtraction of the absorbance before and after DHB exposure at three visible wavelengths 1390
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because of the fact that mixtures of DHBs are usually present in real samples. To investigate the ability of the proposed array in this dimension, the response of the sensor in the binary and ternary combinations of DHBs was recorded. It was found that binary mixtures of 2DHB, 3DHB, and 4DHB at 40 μM with a molar ratio of 1:1 and also the ternary mixture of them with molar ratios of 1:1:1, 2:1:1, and 1:2:2 have different responses compared with their pure forms (Figure S7). All DHB mixtures were located distinctly in independent clusters in the canonical score plot, and the cross-validation accuracy of identification was found to be 100% (Figure 8A,B). Moreover, the obtained scores of the mixtures were located between the scores of their individual components on the score plot. As shown in Figure 8C, these mixtures as well as pure DHBs were clearly distinguished from each other in the color difference map, demonstrating a 100% correct classification. Detection of DHBs in Real Samples. The performance of our designed sensing array was further evaluated for the discrimination of DHBs in skin bleaching cream and tap water. In this regard, various sensor elements were applied to the cream and tap water spiked with 80 μM DHBs (Figure S8). As shown in Figure 9, each of the DHBs in water samples generates a distinct response and a 100% identification accuracy was obtained for all DHBs. Moreover, the skin bleaching cream sample containing hydroquinone is clustered in the group of 4DHB. These findings reveal the high potential of the sensor array to discriminate DHBs in real-world samples.
(i.e., 700, 800, and 900 nm for SE1−SE4 and 350, 450, and 550 for SE5). Difference patterns presented in Figure 7
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CONCLUSIONS In summary, a novel chrono-CSA is developed for kinetic discrimination of DHB structural isomers at a concentration range of 1−800 μM. Four sensor elements at different AuNRto-silver ion concentration ratios were employed for the discrimination of DHBs. DHB isomers including catechol and hydroquinone, as a reducing agent, are capable of reducing silver ions (Ag+) to silver atoms (Ag0) with different kinetics at neutral pHs, leading to anisotropic growth of silver on the surface of AuNRs. The chronochromic behaviors of AuNRs against DHBs are completely different, which seems to be due to the distinct redox potentials of the target analytes. Furthermore, AgNP formation strategy at a basic medium, as a fifth sensor element, was employed to improve the discrimination capability of the colorimetric sensor array. Moreover, the array could efficiently discriminate among individual DHBs and their mixtures. Finally, the DHBs in real samples were well-distinguished with a 100% discrimination accuracy, which further validates the practical application of this chrono-CSA.
Figure 7. Color difference maps for various concentrations of 2DHB, 3DHB, and 4DHB and pyrogallol and gallic acid as potential interferences.
demonstrate the color change patterns as fingerprints for each DHB at a wide concentration range from 10 to 800 μM. Collected in triplicate trials, the color difference maps show distinctive sensor response patterns that are unique to each DHB, which allows distinguishing them qualitatively even without statistical techniques. As mentioned earlier, the spectral changes observed against THB and THBA are different from those observed for DHBs. DHB Calibration Curves. The correlation between overall array responses was probed as a function of DHB concentration (Figure S5). The calculated calibration curves based on the largest response among the five sensor elements for the determination of each DHB show linear regimes of 10−800, 1− 100, and 1−800 μM for 2DHB, 3DHB, and 4DHB, respectively (Figure S6). The limits of detection (LODs) are summarized in Table 1. On the basis of the results, not only are LODs comparable with a variety of methods reported recently in the literature for the determination of DHBs but they also meet the requirements for the detection of DHBs in applications. Discrimination of DHB Mixtures. Discrimination of DHB mixtures is far more challenging than pure DHBs yet essential
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Table 1. Linear Ranges and LOD for DHBs Based on Calibration Plots Determined Using the Largest Response Among the Five Sensor Elements
linear range (μM) LOD (μM)
2DHB
3DHB
4DHB
10−800 9.2
1−100 0.7
1−800 0.9
EXPERIMENTAL SECTION
Materials. Hydrogen tetrachloroaurate (HAuCl4·3H2O) (99.5%), trisodium citrate, sodium hydroxide (NaOH), hydrochloric acid (HCl 37%), 2DHB, 3DHB, 4DHB, pyrogallol (THB), gallic acid (THBA), sodium borohydride (NaBH4), cetyltrimethylammonium bromide (CTAB), 5-bromosalicylic acid (5-Br-SA), AA, and ethanol were purchased from Merck. Milli-Q grade water, with a resistivity of 18.2 MΩ, was used in all experiments. Instrumentation. Absorbance spectra were recorded using a PerkinElmer (LAMBDA25) spectrophotometer with the use of a 1.0 cm glass cell. Measurements of pH were performed with a Denver Instrument model of 270 pH meter equipped 1391
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Figure 8. (A) Color difference maps and (B,C) two-dimensional score plots, illustrating the discrimination of individual DHBs from their binary and ternary mixtures at DHB concentrations of 40 and 80 μM.
mL of 0.10 M AA were successively added. Finally, 0.06 mL of the seed solution was injected into the solution under gentle stirring. The color of the solution gradually changed within 1 h, and the solution was kept overnight at room temperature. The AuNRs were collected by centrifugation (5000 rpm, 10 min) and redispersion in Milli-Q water twice. Fabrication of Chrono-CSA and Data Acquisition. Totally five sensing elements (SE1−SE5), including silver nitrate (5 × 10−4 M) in the presence of four concentrations of AuNRs (1.25 × 10−11, 6.25 × 10−12, 3.25 × 10−12, and 1.5 × 10−12 M) and silver nitrate (5 × 10−4 M) in the presence of sodium citrate (5 × 10−3 M) and sodium hydroxide (10−3 M), were utilized to fabricate the colorimetric sensor array for discrimination of DHBs. Then, different concentrations of target analytes were added to each sensor in a final volume of 1 mL, and UV−vis spectra were recorded after 1, 5, and 10 min of incubation. All experiments were performed in triplicate. The chemometric analyses were carried out using MATLAB R2014b (version 8.4) and SYSTAT (version 13.0). Real-Sample Analysis. Identification of DHB isomers in tap water and skin bleaching cream (2% 4DHB) samples was explored to investigate the potential applicability of the proposed array. Tap water samples were spiked with 80 μM 2DHB, 3DHB, and 4DHB. The cream sample was prepared as follows:53 100 mg of cream was weighed and dissolved in methanol and diluted to 9 mL with methanol in 10 mL centrifuge tubes. It was then extracted by ultrasonication for 10 min, centrifugation at 4000 rpm for 10 min, and then filtration through a 0.45 μm syringe filter. Stock solution of the cream was obtained by diluting 500 μL of extracted solutions with deionized water to 10 mL. Then, the aforementioned analyses for DHB isomer detection were performed on tap water and cream samples (in triplicate).
Figure 9. Two-dimensional LDA plot after combining the test set (real sample) with the training set data. Tap water samples were spiked with DHBs at concentrations of 60 and 80 μM, and the plot shows the cream clustered in the 4DHB group, which is in agreement with its ingredient.
with a Metrohm glass electrode. TEM images were recorded with a Zeiss EM900 microscope (Germany) at an accelerating voltage of 200 kV. Synthesis of High-AR AuNRs. A stock solution of AuNRs stabilized with CTAB was synthesized using the existing seedmediated growth method with minor modification.52 Briefly, seed solution was prepared by mixing 5.0 mL of 0.1 M CTAB with a 0.05 mL solution of 2.5 × 10−2 M HAuCl4, followed by injection of 0.3 mL of 0.01 M freshly prepared ice-cold NaBH4 under vigorous stirring. The resulted brownish-yellow solution was aged for 2 h at room temperature before use. For growth solution, 0.015 g of 5-Br-SA was added to 50 mL of 0.05 M CTAB under gentle stirring. This was followed by the addition of 1.15 mL of 0.01 M AgNO3. Then, 1 mL of 2.5 × 10−2 M HAuCl4, 0.40 mL of HCl (37 wt % in water, 12.1 M), and 0.30 1392
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsomega.7b01780. Table of responses for quantitative comparison of spectral changes of the array, UV−vis spectra of the sensing elements in the absence of DHBs, UV−vis spectra of sensor elements against different concentrations of DHBs, response pattern barplots, real photographs and UV−vis spectra of the array against other studied polyphenols, calibration plots, and UV−vis spectra related to the mixture and real-sample analysis (PDF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected] (R.H.-N.). ORCID
M. Reza Hormozi-Nezhad: 0000-0002-7472-1850 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS Financial support of the Sharif University of Technology is gratefully acknowledged. REFERENCES
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DOI: 10.1021/acsomega.7b01780 ACS Omega 2018, 3, 1386−1394
