Ternary Electrochemiluminescence Nanostructure of Au Nanoclusters

Subscriber access provided by University of Winnipeg Library

Article

Ternary Electrochemiluminescence Nanostructure of Au Nanoclusters as Highly Efficient Signal Label for Ultrasensitive Detection of Cancer Biomarker Ying Zhou, Shihong Chen, Xiliang Luo, Yaqin Chai, and Ruo Yuan Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b02642 • Publication Date (Web): 26 Jul 2018 Downloaded from http://pubs.acs.org on July 28, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Analytical Chemistry

Ternary Electrochemiluminescence Nanostructure of Au Nanoclusters as Highly Efficient Signal Label for Ultrasensitive Detection of Cancer Biomarker Ying Zhou a, Shihong Chen a, Xiliang Luo b, Yaqin Chai a*, and Ruo Yuan a* a

Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest

University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, PR China b

Key Laboratory of Biochemical Analysis, Ministry of Education, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR China

* Corresponding authors at: Tel.: +83 23 68252277, fax: +86 23 68253172. E-mail addresses: [email protected] (R. Yuan), [email protected] (Y. Q. Chai).

1 / 17

ACS Paragon Plus Environment

Analytical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 17

ABSTRACT: Herein, the Au nanoclusters (Au NCs) functionalized ternary nanostructure with significant electrochemiluminescence (ECL) emission was first proposed to fabricate an ultrasensitive immunosensor for carcinoembryonic antigen (CEA) detection, which was established by combining bovine serum albumin (BSA) templated Au NCs as the luminophor, tris(3-aminoethyl)amine (TAEA) as the coreactant and Pd@CuO nanomaterial as the coreaction accelerator via covalent attachment in a nanostructure. Through

the

dual self-catalysis

including

intramolecular coreaction between TAEA and Au NCs, and intramolecular coreaction acceleration from Pd@CuO to TAEA, the Au NCs-TAEA-Pd@CuO achieved excellent ECL performance so that the detection limit of the immunosensor for measuring CEA antigen was down to 16 fg/mL in the absence of any additional signal amplification assay. Moreover, the method for preparing ECL nanostructure-based metal NCs should be devoted to the development of highly efficient ECL signal label, outlining a significant scheme toward biological testing and clinical diagnosis. INTRODUCTION: Electrochemiluminescence

(ECL),

also

known

as

electrogenerated

chemiluminescence, is the process whereby radical cations and anions of luminophore electrogenerated at a working electrode occur electron transfer (ET) reactions that generate excited states for emitting light 1-3. Comparing with traditional research field, ECL has been widely identified to be a powerful analysis tool with many merits, such as simplified operation, well controllability, and low background, and possesses immense potential for sensitive biosensing field. However, the relative low ECL efficiency is the most important restraining factor for its better application, because of the intrinsic complex luminescence mechanism involving mass transport and ET dynamics of abundant radical intermediates electrogenerated on the surface of

2 / 17


Page 3 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


electrode

4, 5

. Numerous electrochemiluminescent systems can remarkably promote

the ECL emission of luminophor through coreactant pathway

6, 7

. Therefore, various

coreactants addition ways are elaborated and applied in the construction of ECL biosensors involving directly adding coreactant in the testing solution 8, modifying coreactant on the surface of electrode 9, or in situ generating coreactant around the electrode 10 and so on. However, the long electron transfers path and great energy loss in the intermolecular ECL reaction restrict the further development of ECL biosensing. In the condition, the self-enhanced ECL label has been designed by integrating luminophore with its coreactant in a molecular structure, which exhibit excellent ECL performance due to shorter electronic transmission distance and less energy loss 11-13. Noble metal nanoclusters, consisting of several to roughly a hundred atoms, are a fascinating ECL nanomaterials, because they show molecule-like properties, including distinctive optical, electrical and chemical properties

14-16

. Unfortunately,

those electrochemical active nanoclusters are stressed on high excess coreactant and extreme excited potentials in ECL process

17-19

. Wang et al reported a self-enhanced

system to promote the ECL emission of Au nanoclusters (Au NCs) based on the covalent

attachment

of

N-diethylethylenediamine

luminophore

Au

NCs

and

its

coreactant

N,

20

. The reported studies demonstrated that self-enhanced

Au NCs system could obtain remarkable ECL signal, however, exploring suitable ECL label-based metal NCs for achieving highly sensitive biosensing was limited by low ECL luminous efficiency of Au NCs. In our previous work, the coreaction accelerator, including some nanoparticle or active micromolecule, was proposed to improve the ECL emission of luminophore through effectively reducing the coreactant to a stronger oxidative or reductive intermediate radical

21-23

. For instance, the ECL

emission of Ag NCs could be significantly amplified by introducing the Fe3O4-CeO2

3 / 17



to react with S2O82- for generating massive SO4•–

Page 4 of 17

24

. Despite the ECL signal of Ag

NCs/S2O82- system can be enhanced, the long electron transfers path and great energy loss in the intermolecular ECL reaction still restrict its ECL luminous efficiency. Therefore, developing a highly efficient ECL label containing luminophore, coreactant and coreaction accelerator in a nanostructure is of significant importance to deal with problem about low sensitive biosensing-based metal NCs. Herein, we combined bovine serum albumin (BSA) stabilized Au NCs as the luminophor, tris(3-aminoethyl)amine (TAEA) as the coreactant and Pd@CuO nanomaterial as the coreaction accelerator to form the Au NCs-TAEA-Pd@CuO ternary nanostructure as highly efficient ECL label for constructing ultrasensitive biosensor. Significantly, the ECL emission of the nanostructure was up to about 40 times as compared to pure Au NCs, owing to the combination of intramolecular coreaction and intramolecular coreaction accelerator. Carcinoembryonic antigen (CEA) as a constitutive protein derive from colon cancer and embryonal tissue, which is used to estimate patients in early diagnosis and decision-making before surgery. By employing CEA as an analysis model, we reported the proof-of-concept of an ultrasensitive and feasible ECL immunosensing platform for CEA monitoring based on highly efficient ECL Au NCs-TAEA-Pd@CuO nanostructure. Through the sandwiched immunoreaction, the ECL immunosensor exhibited a wide linear range from 100 fg/mL to 100 ng/mL, providing a new thought for the construction of ultrasensitive ECL bioanalysis. EXPERIMENTAL SECTION Synthesis of TAEA-Pd@CuO Nanomaterial. The Pd@CuO nanomaterial was prepared by seed-mediated growth method according to the published literature

25-27

with a minor modification as follows: the seed solution was synthesized by mixing

4 / 17


Page 5 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


PVP (21 mg), L-ascorbic acid (12 mg) and KBr (120 mg) in 1.6 mL of deionized water at 80 ºC under intense stirring, following by adding 600 µL of Na2PdCl4 (65 mM) aqueous solution. For 3 h reaction, Pd seed solution was washed with deionized water by centrifugation. Subsequently, 80 µL of Pd seed solution was removed from aqueous solution containing CuCl2·2H2O (8.52 mg) and SDS (144 mg) in under stirring. While 45 mL of mixture solution was adjusted to pH 10 by NaOH (2 M), 1 mL of N2H4·2H2O (2%) and 30 µL of 10 mM Na2PdCl4 was mixed slowly into the solution at 90 ºC for 2 h, generating Pd@CuO nanomaterial. After centrifugation and wash, 25 µL TAEA (98%, HPLC) was dropped in 1 mL of Pd@CuO solution to obtain the TAEA-Pd@CuO nanomaterial via Pd-N covalent bond. Synthesis of Au NCs-TAEA-Pd@CuO by Coupling Reactions. The synthetic procedure of BSA-templated Au nanoclusters (Au NCs) were outlined based on published literature

28, 29

, 1 mL of 10 mM HAuCl4·4H2O aqueous solution and 1 mL

of 50 mg/mL BSA solution were mixed under vigorous stirring for 5 min. After adjusting to pH 10 by NaOH (1 M), the mixture solution was incubated in thermotank at 37 ºC for 12 h. During a reaction time of 12 h, the light yellow solution gradually translated into reddish brown. Meanwhile, the resultant solution emitted a red luminescence under UV irradiation, suggesting the nucleation of Au NCs (Figure S3). After the process of ultrafiltration and centrifugation, the Au NCs solution was kept away from light at 4 ºC for further use. For preparing Au NCs-TAEA-Pd@CuO nanostructure, fresh EDC solution (16 µL, 30 mM) was directly dropped into 3 mL of Au NCs, following by controlling the pH at 6.0 under stirring for 20 min at 37 ºC. And then 100 µL of NaOH (1 M) was added to adjust the pH to 7.2 for quenching the activation reaction. Subsequently, excess TAEA-Pd@CuO was introduced to trigger the coupling reaction, resulting in a

5 / 17



20-fold molar excess of amine to particles. After 4 h reaction, the pH was increased to 8.5 to quench reaction, the Au NCs-TAEA-Pd@CuO was obtained after centrifugation and washing to discard excess reagents. Synthesis of anti-CEA-Au NCs-TAEA-Pd@CuO Bioconjugate. The preparation process of the anti-CEA-Au NCs-TAEA-Pd@CuO was detailedly depicted in the Scheme 1A, 500 µL capture antibody (anti-CEA) was modified on the prepared Au NCs-TAEA-Pd@CuO via the amidation reaction. Under softly stirring for 6 h, anti-CEA-Au NCs-TAEA-Pd@CuO bioconjugate was synthesized by integrating the NH2 groups of TAEA and the COOH groups of anti-CEA. Followed by centrifugation at 9000 rpm to detach excess reagents, the anti-CEA-Au NCs-TAEA-Pd@CuO bioconjugate was obtained and stored for later use. Fabrication of the ECL Immunosensor. Initially, the glassy carbon electrode (GCE) with 4 mm diameter was repeatedly cleaned to realize a mirror-like surface. After that, the treated electrode was modified on a compact Pt nanoparticles (NPs) based on the electrostatic potential deposition method at constant potential -0.2 V for 30 s. Then, 10 µL primary antibody (anti-CEA) was incubated onto the electrode at 4 ºC for 12 h, while the remaining active sites on the electrode were blocked using 10 µL of BSA (1%) solution for 40 min at room temperature. After cleaning with PBS (pH 7.4), CEA antigen with different concentrations could bind abundant antibody at the electrode for 40 min. As a result, the electrode was incubated in the anti-CEA-Au NCs-TAEA-Pd@CuO bioconjugate for sandwich immunereaction between capture antibody, CEA antigen, and primary antibody, and then was thoroughly washed with PBS (pH 7.4) to remove nonspecifically bounded conjugates. The electrochemical performance of the immunosensor was investigated by cyclic voltammetry measurements and was shown in the Figure S1.

6 / 17


Page 6 of 17

Page 7 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Scheme 1. Schematic diagrams showing fabrication of the ECL immunosensor: (A) the construction of Au NCs-TAEA-Pd@CuO nanostructure, possible ECL mechanism of (B) only Au NCs-TAEA and (C) ternary ECL nanostructure with Pd@CuO as the coreaction accelerator.

RESULTS AND DISCUSSION Morphology and Element Characterizations. As shown in Figure 1A, the typical HRTEM images of Pd@CuO nanomaterial exhibited a block shape with a diameter of 30 ± 15 nm. Furthermore, the face-centered cubic Pd (111) lattice facet corresponded to the lattice spacing values of 0.224 nm (JCPDS no. 65-2867), and the fringes with lattice spacing of 0.231 nm and 0.252 nm could be respectively indexed to the monoclinic CuO (200) and (002) lattice facets (JCPDS no. 45-0937). Then the diameter of the Au NCs-TAEA-Pd@CuO (Figure 1B) was not obviously changed compared with that of Pd@CuO, but it could be observed that plentiful dark nanoparticles with an average diameter under 2.0 nm were coated on the core surface of Pd@CuO. To investigate the elemental analysis of Au NCs-TAEA-Pd@CuO nanostructure, according to Figure 1C, characteristic peaks of Cu2p, CuLM2, Au4f, Pd3d, O1s, C1s and N1s regions could be clearly observed in the obtained spectrum of X-ray photoelectron spectroscopy (XPS), and the XPS doublet of Cu2p and Au4f were observed. Besides, the peaks at 568.63 eV and 335.68 eV respectively belonged 7 / 17



to CuLM2 and Pd3d, which verified that Au NCs-TAEA-Pd@CuO was successfully generated.

Figure 1. HRTEM images of (A) Pd@CuO and (B) Au NCs-TAEA-Pd@CuO, the inset of (A) and (B): the amplified HRTEM images of Pd@CuO and Au NCs-TAEA-Pd@CuO, respectively. (C) XPS element analysis of Au NCs-TAEA-Pd@CuO.

ECL Performance of Au NCs-TAEA-Pd@CuO. The ECL and electrochemistry performance of signal labels were investigated by the combination of ECL and cyclic voltammetry. Three proposed signal labels respectively were (a) Au NCs (only luminophore), (b) Au NCs-TAEA (luminophore and coreactant, self-enhanced label), and (c) Au NCs-TAEA-Pd@CuO (luminophore, coreactant and coreaction accelerator, ternary ECL nanostructure). According to Figure 2A, weak ECL was observed from pure Au NCs in PBS (Figure S2), while the same one in PBS containing 2 mM TAEA showed higher ECL peak intensity (1775 a.u., curve a), illustrating that TAEA as a 8 / 17


Page 8 of 17

Page 9 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


coreactant could enhance the ECL emission of Au NCs. Furthermore, Au NCs-TAEA in pH 7.4 PBS obtained 6007 a.u. of ECL peak intensity (curve b), which suggested that the intramolecular ECL reaction of self-enhanced label was endowed with more significant ECL emission. Notably, the ECL intensity of Au NCs-TAEA-Pd@CuO increased to 8634 a.u. (curve c). Meanwhile, the oxidation peak of TAEA shifted positively from -0.454 V to -0.518 V (Figure 2B), indicating that Pd@CuO as the coreaction accelerator improved the oxidation of Au NCs-TAEA to form the more reductive intermediate radical (Au NCs+-TAEA·). In addition, the ECL spectrum of Au NCs had a maximum wavelength at 625 nm (Figure 2C, curve a), which was close to the fluorescence emission spectrum at 628 nm (Figure S3). Due to the intramolecular coreaction between Au NCs and TAEA, the ECL spectrum of Au NCs-TAEA positively shifted to 632 nm (curve b). When the Au NCs-TAEA was immobilized on the surface of the Pd@CuO nanomaterial, a distinguished ECL peak at 642 nm exhibited a slight red shift, which could be attributed to the quantum effect of Pd@CuO (curve c) 30, 31. To further clarify excellent ECL performance of ternary ECL nanostructure, the relationship between ECL response and potential was explored. As displayed in the Figure 2D, a peak of ECL response appeared when the potential was 1.168 V in Au NCs solution (curve a). As comparison, the ECL peak was obtained when the potential was 1.125 V in Au NCs-TAEA solution (curve b) and 1.087 V in Au NCs -TAEA-Pd@CuO solution, respectively. It was remarkable that the maximum ECL intensity and the lowest luminous potential were observed from the ternary ECL nanostructure, which indicated intramolecular ternary system with faster electronic transfer and more effective energy transmission exhibited optimal ECL performance as compared with others ECL systems.

9 / 17



Figure 2. (A) Curves between the ECL intensity and time, (B) cyclic voltammograms, (C) ECL spectra, and (D) curves between the ECL intensity and potential of (a) Au NCs with 2 mM free diffusing TAEA in pH 7.4 PBS, (b) Au NCs-TAEA (Au NCs with TAEA covalently attached) in pH 7.4 PBS, (c) Au NCs-TAEA-Pd@CuO in pH 7.4 PBS.

Possible ECL Emission Mechanism of Au NCs-TAEA-Pd@CuO. Upon anodic scanning in the range of 0 to 1.2 V, ternary ECL reaction occurred between luminophore, coreactant and coreaction accelerator in a nanostructure. Specifically, both Au NCs and TAEA in nanostructure were oxidized to form Au NCs+-TAEA·+. Furthermore, the tertiary amine of TAEA lost a proton to generate Au NCs+-TAEA· intermediate. When Pd@CuO as the coreaction accelerator promoted intramolecular electron transfer and energy transmission, more active radical Au NCs+-TAEA· produced to the excited state Au NCs*-TAEA, which returned to the ground state and

10 / 17


Page 10 of 17

Page 11 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


emitted intense light. The speculated ECL mechanism was analogous to the widely adopted Rubpy-TPrA coreactant pathway, and was listed as follows: 32, 33

ECL Responses of the ECL Immunosensor toward CEA. Using CEA as a model analyte, the proposed immunosensor was utilized for quantitative determination of target CEA in 0.1 M PBS (pH 7.4) by scanning the potential from 0 to 1.2 V at a scanning rate of 300 mV/s. Figure 3A showed the signal intensity of the ECL nanostructure increased with increasing concentration of CEA from 100 fg/mL to 100 ng/mL (curves a-g). As exhibited in Figure 3B, an excellent linear relationship was exhibited between ECL intensity and the logarithm of concentration with the regression equation I = 1457 lgc + 8280 (where I stood for the gained ECL intensity and c stood for the CEA concentration). Furthermore, the limit of detection according as 3Sb/m was calculated to be 16 fg/mL (where Sb is the standard deviation of the blank and m is the slope of the corresponding calibration curve), which was comparable to other CEA detection protocols (Table 1). It could be seen the assay have better sensitivity for CEA measurement, owing to the excellent ECL performance of Au NCs-TAEA-Pd@CuO nanostructure. Table 1. Comparison of Analytical Performance of Different CEA Detection Schemes Detection Method

Linear range

LOD

Ref

Colorimetric biosensor

1 pg/mL-10 µg/mL

0.20 pg/mL

34

Fluorescence biosensor

5 pg/mL-20 ng/mL

6.7 pg/mL

35

Photoelectrochemical biosensor

1 pg/mL-2 ng/mL

0.47 pg/mL

36

Electrochemical immunosensor

1 pg/mL-0.1 µg/mL

0.10 pg/mL

37

ECL immunosensor

20 pg/mL-80 µg/mL

6.8 pg/mL

38

ECL immunosensor

100 fg/mL-100 ng/mL

16 fg/mL

this work

11 / 17



The selectivity of the ECL immunosensor for CEA was monitored by opposing different nontarget substances of α-1-fetoprotein (AFP), cardiac troponin I (cTnI), BSA. As seen from Figure 3C, in comparison with that of the presence of CEA (1 pg/mL), ECL intensities of nontarget substances with 100-fold concentration (100 pg/mL) significantly decreased. Meanwhile, the ECL intensities of the immunosensor with the mixture solution (1 pg/mL CEA containing 100-fold concentration of nontarget substances) exhibited slight change of ECL intensity from pure CEA (1 pg/mL). To investigate the stability of this immunosensor, the ECL signals of the immunosensor with 1 ng/mL and 1 pg/mL of CEA were respectively monitored by continuous CV scanning for 20 cycle scans. As shown in Figure 3D, the ECL intensities simultaneously displayed no obvious change, and the relative standard deviation (RSD) values were 4.10% (1 ng/mL) and 2.73% (1 pg/mL) (n = 20). It indicated that the obtained immunosensor had excellent stability.

Figure 3. (A) ECL profiles of the immunosensor in the presence of different concentrations of CEA (a-g): 100 fg/mL, 1 pg/mL, 10 pg/mL, 100 pg/mL, 1 ng/mL, 10 ng/mL, and 100 ng/mL. (B)

12 / 17


Page 12 of 17

Page 13 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Calibration plots of the immunosensor. (C) Selectivity of the immunosensor of 1 pg/mL CEA against interference proteins: AFP, cTnI, and BSA. (D) Stability of the immunosensor of 1 pg/mL and 1 ng/mL CEA.

Preliminary Analysis of CEA in Samples and Evaluation of Method Accuracy. To estimate the application of the proposed immunosensor, six human serum specimens containing different concentrations CEA (obtained from the Ninth People’s Hospital of Chongqing, China) were detected by the ECL immunosensor, which were further compared with the commercial enzyme-linked immunosorbent assays (ELISA) kit. As presented in Table 2, no significant differences between two methods were obtained in the analysis of six samples, demonstrating that the method had the potential application for the detection of CEA in clinical diagnostics. Table 2. Recovery results of CEA in serum samples got by the developed method and a commercial ELISA method. Sample number

Added concentration/ pg·mL-1

1 2 3 4 5

Mean/pg·mL-1 ± SD and recovery/%

1.0 5.0 10

Our method 1.04 + 4.15 (104.0) 5.13 + 3.72 (103.0) 9.86 +2.92 (98.6)

ELISA 1.03 + 2.64 (103.0) 4.92 + 3.06 (98.4) 10.1 + 3.17 (101.0)

50 100

50.94 + 3.31 (101.9) 103.50 +4.09 (103.5)

49.25 + 2.71 (98.5) 101.6 + 2.33 (101.6)

Relative error of the result/% 0.97 4.67 -2.38 3.45 1.87

CONCLUSION Au NCs-TAEA-Pd@CuO, a ternary ECL nanostructure with highly luminous efficiency, which incorporated the luminophor, the coreactant and the coreaction accelerator into a nanostructure, was probed for the first time. Through the dual intramolecular self-catalysis including intramolecular coreaction and intramolecular coreaction acceleration, Au NCs-TAEA-Pd@CuO nanostructure possessed faster electronic transfer and more effective energy transmission, and was observed remarkable ECL emission. Therefore, the ternary ECL nanostructure based immunosensor showed excellent sensitivity, selectivity and stability for CEA

13 / 17



detection. Moreover, the work revealed the attraction of ternary ECL nanostructure, and leaded to the grand avenue toward the development of ECL nanomaterials with multiple self-catalysis in the application of ultrasensitive biosensing and high-throughput analysis.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at http://pubs.acs.org. Experimental details for reagents and apparatus, electrochemical characterizations of the biosensor, the ECL-time curve of Au NCs, and the fluorescence emission spectrum of Au NCs.

AUTHOR INFORMATION Corresponding Authors *Tel.: +86 23 68252277; fax: +86 23 68253172; e-mail: [email protected]. [email protected]. ORCID Ruo Yuan: 0000-0003-3664-6236 Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation (NNSF) of China (Grants 21775124, 21775122, 21675130 and 51473136) and the

14 / 17


Page 14 of 17

Page 15 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Fundamental Research Funds for the Central Universities (Grant XDJK2018AA003), China. REFERENCES (1) Bard, A. J. Electrogenerated Chemiluminescence; Marcel Dekker: New York, 2004. (2) Hu, L. Z.; Xu, G. B. Chem. Soc. Rev. 2010, 39, 3275-3304. (3) Amelia, M.; Lincheneau, C.; Silvi, S.; Credi, A. Chem. Soc. Rev. 2012, 41, 5728-5743. (4) Miao, W. J.; Choi, J. P.; Bard, A. J. J. Am. Chem. Soc. 2002, 124, 14478-14485. (5) Wang, T. Y.; Wang, D. C.; Padelford, J. W.; Jiang, J.; Wang, G. L. J. Am. Chem. Soc. 2016, 138, 6380-6383. (6) Richter, M. M. Chem. Rev. 2004, 104, 3003-3036. (7) Gao, W. Y., Muzyka, K.; Ma, X. G.; Lou, B. H.; Xu, G. B. Chem. Sci. 2018, 9 3911-3916. (8) Poulpiquet, A.; Diez-Buitrago, B.; Milutinovic, M. D.; Sentic, M.; Arbault, S.; Bouffier, L.; Kuhn, A.; Sojic, N. Anal. Chem. 2016, 88, 6585-6592. (9) Muzyka, K.; Saqib, M.; Liu, Z. Y.; Zhang, W.; Xu, G. B. Biosens. Bioelectron. 2017, 92, 241-258. (10) Wang, H. J.; Yuan, Y. L.; Chai, Y. Q.; Yuan, R. Small 2015, 30, 3703-3709. (11) Carrara, S.; Arcudi, F.; Prato, M.; Cola, L. Angew. Chem. Int. Ed. 2017, 56, 4757-4761. (12) Chen, A. Y.; Zhao, M.; Zhuo, Y.; Chai, Y. Q.; Yuan, R. Anal. Chem. 2017, 89, 9232-9238. (13) Swanick, K. N.; Ladouceur, S.; Zysman-Colman, E.; Ding, Z. F. Angew. Chem. Int. Ed. 2012, 51, 11079-11082. (14) Chen, Y.; Zhou, S. W.; Li, L. L.; Zhu, J. J. Nano Today 2017, 12, 98-115. (15) Hesari, M.; Ding, Z. F. Acc. Chem. Res. 2017, 50, 218-230. (16) Yao, Q. F.; Yuan, X.; Fung, V.; Yu, Y.; Leong, D. T.; Jiang, D.; Xie, J. P. Nat. Commun. 2017, 8, 927. (17) Díez, I.; Pusa, M.; Kulmala, S.; Jiang, H.; Walther, A.; Goldmann, A. S.; Müller, A. H. E.; Ikkala, O.; Ras, R. H. A. Angew. Chem. Int. Ed. 2009, 48, 2122-2125. (18) Fang, Y. M.; Song, J.; Li, J.; Wang, Y. W.; Yang, H. H.; Sun, J. J.; Chen, G. N. Chem. Commun. 2011, 47, 2369-2371. (19) Li, L.; Liu, H.; Shen, Y.; Zhang, J.; Zhu, J. J. Anal. Chem. 2011, 83, 661-665. (20) Wang, T. Y.; Wang, D. C.; Padelford, J. W.; Jiang, J.; Wang, G. L. J. Am. Chem. Soc. 2016, 138, 6380-6383. 15 / 17



(21) Liu, J. L.; Tang, Z. L.; Zhang, J. Q.; Chai, Y. Q.; Zhuo, Y.; Yuan, R. Anal. Chem. 2018, 90, 5298-5305. (22) Yang, X.; Yu, Y. Q.; Peng, L. Z.; Lei, Y. M.; Chai, Y. Q.; Yuan, R.; Zhuo, Y. Anal. Chem. 2018, 90, 3995-4002. (23) Zhou, Y.; Wang, H. J.; Zhuo, Y.; Chai, Y. Q.; Yuan, R. Anal. Chem. 2017, 89, 3732-3738. (24) Zhou, Y.; Chen, M. X.; Zhuo, Y.; Chai, Y. Q.; Xu, W. J.; Yuan, R. Anal. Chem. 2017, 89, 6787-6793. (25) Guo, Y.; Xu, Y. T.; Zhao, B.; Wang, T.; Zhang, K.; Yuen, M. M. F.; Fu, X. Z.; Sun, R., Wong, C. P. J. Mater. Chem. A 2015, 3, 13653-13661. (26) Jin, M.; Zhang, H.; Xie, Z.; Xia, Y. Angew. Chem., Int. Ed. 2011, 50, 7850-7854. (27) Li, G.; Kobayashi, H.; Taylor, J. M.; Ikeda, R.; Kubota, Y.; Kato, K.; Takata, M.; Yamamoto, T.; Toh, S.; Matsumura, S.; Kitagawa, H. Nat. Mater. 2014, 13, 802-806. (28) Dong, L. Y.; Li, M. L.; Zhang, S.; Li, J.; Shen, G. X.; Tu, Y. T.; Zhu, J. T.; Tao, J. Small 2015, 21, 2571-2581. (29) Zhou, Q.; Lin, Y. X.; Xu, M. D.; Gao, Z. Q.; Yang, H. H.; Tang, D. P. Anal. Chem. 2016, 88, 8886-8892. (30) Li, Q. H.; Jin, X.; Yang, Y.; Wang, H. N.; Xu, H. J.; Cheng, Y. Y.; Wei, T.; Qin, Y. C.; Luo, X. B.; Sun, W. F.; Luo, S. L. Adv. Funct. Mater. 2016, 26, 254-266. (31) He, C. B.; Xiao, Y.; Huang, J. C.; Lin, T. T.; Mya, K. Y.; Zhang, X. H. J. Am. Chem. Soc. 2004, 126, 7792-7793. (32) Zu, Y. B.; Bard, A. J. Anal. Chem. 2000, 72, 3223-3232. (33) Yue, X. X.; Zhu, Z. Y.; Zhang, M. N.; Ye, Z. Q. Anal. Chem. 2015, 87, 1839-1845. (34) Peng, J.; Lai, Y. Q.; Chen, Y. Y.; Xu, J.; Sun, L. P.; Weng, J. Small 2017, 13, 1603589. (35) Qiu, Z. L.; Shu, J.; Tang, D. P.; Anal. Chem. 2017, 89, 5152-5160. (36) Zeng, X. X.; Ma, S. S.; Bao, J. C.; Tu, W. W.; Dai, Z. H. Anal. Chem. 2013, 85, 11720-11724. (37) Akanda, Md. R.; Ju, H. X. Anal. Chem. 2016, 88, 9856-9861. (38) Chen, L. C.; Zeng, X. T.; Si, P.; Chen, Y. M.; Chi, Y. W.; Kim, D. H.; Chen, G. N. Anal. Chem. 2014, 86, 4188-4195.

16 / 17


Page 16 of 17

Page 17 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


For TOC only

17 / 17


Ternary Electrochemiluminescence Nanostructure of Au Nanoclusters

Recommend Documents