A Novel and Sensitive Chemiluminescence Sensor Based on 2D

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C: Plasmonics; Optical, Magnetic, and Hybrid Materials

A Novel and Sensitive Chemiluminescence Sensor Based on 2DMOFs Nanosheets for One-Step Detection of Glucose in Human Urine Nuanfei Zhu, Lantian Gu, Jin Wang, Xuesong Li, Guo-Xi Liang, Jinhui Zhou, and Zhen Zhang J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.9b00671 • Publication Date (Web): 13 Mar 2019 Downloaded from http://pubs.acs.org on March 14, 2019

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The Journal of Physical Chemistry

A Novel and Sensitive Chemiluminescence Sensor Based on 2D-MOFs Nanosheets for One-Step Detection of Glucose in Human Urine

Nuanfei Zhu1, Lantian Gu1, Jin Wang1,2, Xuesong Li1, Guoxi Liang1, Jinhui Zhou3*, Zhen Zhang1*

1School

of the Environment and Safety Engineering, Jiangsu University,

Zhenjiang 212013, China

2Institute

3Institute

of Life Sciences, Jiangsu University, Zhenjiang 212013, China

of Apicultural Research, Chinese Academy of Agricultural Sciences,

Beijing 100093, PR China

*Corresponding authors: E-mail: [email protected], [email protected]. Tel.: +86-511-88790955, 86-10 62596429;

ACS Paragon Plus Environment

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ABSTRACT The development of a simple and sensitive method for glucose determination is significant in the early diagnosis and treatment of diabetes. However, current analytical approaches have various defects in their applications. Here, an attractive chemiluminescence-based sensor is developed for one-step and rapid detection of glucose in human urine. In this work, a 2D-MOFs nanosheet with peroxidase activity was firstly synthesized, which could catalyze the decomposition of hydrogen peroxide (H2O2) and further oxidize luminol to produce strong chemiluminescence signal. Then, luminol and glucose oxidase (GOD) were successively labeled on the 2D-MOFs nanosheet, obtaining a simple chemiluminescence-functionalized sensor (Co-TCPP(Fe)@luminol@GOD). When the Co-TCPP(Fe)@luminol@GOD was introduced to the detection system containing glucose, substantial H2O2 was released under the catalysis of GOD on the Co-TCPP(Fe). Then, the produced H2O2 was decomposed

by

the

2D-MOFs

nanosheet

and

the

luminol

on

the

Co-TCPP(Fe)@luminol@GOD further oxidized, generating chemiluminescence signal, finally achieving a rapid determination for glucose. Under the optimized condition, fabrication of 2D-MOFs nanosheet as a sensitive glucose sensor exhibited a good performance during the process: (i) good sensitivity (LOD, 10.667 μg/L) with a wide linear range (32-5500 μg/L); (ii) satisfactory accuracy (recoveries, 89-121.2%; CV, 3.5-7.4%); (iii) low cost; (iv) simple operation. And our proposed method here has the potential for screening the glucose in various human urines from hospitals.


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INTRODUCTION The diabetes is a kind of public health problem in the world, characterized by hyperglycemia with the high mortality and morbidity 1. For diabetics, the long-term hyperglycemia easily leads to the chronic damage and dysfunction of their tissues, especially eyes, kidneys, heart, blood vessels and nerves 2. What's worse, the disease can result in other complications of diabetes, like blindness and kidney failure, all of which are due to the excessed concentration of glucose in human blood 3. Previous research have shown that the early diagnosis of diabetics can protect the function of islet P cells and improve the insulin sensitivity, delaying and preventing diabetes-related complications4-5. Therefore, as a common indicator, the rapid and real-time determination of blood glucose is very necessary for the early diagnosis and the diagnosis/adjuvant treatment of diabetes. At present, various available strategies have been applied for detection of glucose from human body fluid or other samples, including colorimetric methods, chemical sensors and so on

6-8.

For example, Wu et al. established a novel and

sensitive electrochemical biosensor based on the co-catalysis effect of glucose oxidase (GOD) and nanoporous gold (NPG) for the glucose detection 9. This biosensor has a very low detection limit of 1.02 μM and the results are in good agreement with those produced by an automatic biochemical analyzer. Besides, Ji et al. reported a smartphone-based cyclic voltammetry (CV) electrochemical devices used to determine glucose in different simples, showing excellent linear and specific responses to the targets

10.

Although these methods have wider liner ranges, high



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sensitivity and low detection of limit, they always suffer from high expenses, cumbersome operation and complex synthesis or modification process. Nanozymes, a kind of nanomaterials with enzyme-mimic activity, have caught great attention over the past decades owing to their great catalytic efficiency, massive active sites and high stability in a wide range of temperatures or pH

11-12.

Currently,

various nanozymes have been used in many fields including biosensor, immunoassay, cancer diagnosis and treatment, neuroprotection

13-15.

For example, Md. N. Karim et

al. developed a rapid and colorimetric method based on a novel 3D matrix of a cotton fabric to detect the glucose from complex biological fluids

16.

In this work, Ag

nanoparticles were embedded within the 3D matrix of a cotton fabric, obtaining a kind of enzyme-mimicking catalytic nanoparticles- Ag@Fabric with the excellent peroxidase-like activity. Furthermore, many nanozymes were also applied in electrochemical sensors for the glucose determination, such as ammoniadoped-prGO/CuO 17, CuONW/CC 8, Cu3P NW/CF 1 and so on. Herein, inspired by these studies, a novel 2D metal-organic frameworks (2D MOFs)- Co-TCPP(Fe) was synthesized and applied in a sensitive chemiluminescence sensor for one-step detection of glucose from human urine samples (shown in Scheme 1). In this work, the GOD and luminol were modified on the Co-TCPP (Fe) to form a simple chemiluminescence-functional sensor, in which the Co-TCPP(Fe) has a high catalysis for the H2O2 produced by the reaction between GOD and glucose, further triggering the chemiluminescence signal of luminol, achieving the quantitative analysis for the glucose.


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MATERIALS AND METHOD Materials

and

Apparatus.

Cobaltous

nitrate

hexahydrate,

pyrazine,

polyvinylpyrrolidone (PVP), luminol, glucose, GOD, NH2-PEG-COOH, ethanol, NaCl, KH2PO4, KCl, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide (EDC), N-hydroxysuccinimide (NHS), NaH2PO4•12H2O, and H2O2 were obtained from the Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China). Horseradish peroxidase (HRP) and 3, 3’, 5, 5’ -tetramethylbenzidine dihydrochloride (TMB) was purchased from Aladdin (USA). N, N-dimethylformamide (DMF), TCPP(Fe) were provided by J&K Scientific. All chemicals and materials were used without further purification. Synthesis of Co-TCPP(Fe). The Co-TCPP (Fe) was synthesized according to the previous literature 18. Preparation of the Co-TCPP(Fe)@luminol. Firstly, 1 mg Co-TCPP(Fe) in 0.1 M PBS (1 mL, pH 7.0) were dispersed by ultrasonic for 20 min. Then, 2 mg EDC/NHS (1:1) was added into the mixed solution, maintaining at 37ºC for 5 h. After that, 2 mg NH2-PEG-COOH was mixed with the above product under vigorous stirring for 12 h at 37ºC. Finally, the obtained product was centrifuged and washed using anhydrous ethanol. Afterwards, the resulting solid was dissolved in 1 mL 0.1 M PBS (pH 7.0). 20 min ultrasound later, the same processing mode was carried out by using 2 mg EDC/NHS (1:1) at 37 ºC for 5 h. Then, 2 mg luminol was added into the above solution and kept reacting 12 h at 37 ºC. After a similar centrifugation and washing step, the Co-TCPP(Fe)@luminol was successfully synthesized and stored at 4 ºC for



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further use. Preparation of Co-TCPP(Fe)@luminol@GOD. First of all, the obtained Co-TCPP(Fe)@luminol was dispersed in 0.1 M PBS (pH 7.0) with ultrasonic waves for

20

min.

Subsequently,

2

mg

EDC/NHS

was

dissolved

into

the

Co-TCPP(Fe)@luminol solution under 37ºC for 5 h. Through the activation, 1 mg GOD was mixed with the above solution. 12 hours later, another centrifugation and washing step were implemented for removing the extra GOD to get the pure Co-TCPP(Fe)@luminol@GOD. RESULTS AND DISCUSSION Synthesis of Co-TCPP(Fe)@luminol and Co-TCPP(Fe)@luminol@GOD. In this

paper,

the

synthesis

of

Co-TCPP(Fe)@luminol

and

Co-TCPP(Fe)@luminol@GOD were the key steps in the preparation of the proposed chemiluminescence sensor. Therefore, several critical factors during the procedure were investigated to achieve the optimal performance, including the concentrations of Co-TCPP(Fe), luminol and GOD, the reaction times of Co-TCPP(Fe)/luminol and Co-TCPP(Fe)@luminol/GOD. As shown in Figure 1, three conditions was optimized for the preparation of Co-TCPP(Fe)@luminol (A. the concentration of Co-TCPP(Fe); B. the concentration of luminol; C. The mixture time of luminol /Co-TCPP(Fe)). Seen from Figure 1A, with the increasing of Co-TCPP(Fe), the chemiluminescence intensity (CL) enhanced initially, following an obvious decrease, achieving the highest peak at 2 mg/L. Therefore, 2 mg/L was selected as the optimum concentration for Co-TCPP(Fe) in


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this reaction. In addition, a similar trend for luminol was observed (Figure 1B), suggesting that the optimized concentration of luminol was 2 mg/L. Besides, according to the results in Figure 1C, 6 h was thought as the most suitable reaction time during the process. The synthesis conditions for Co-TCPP(Fe)@luminol@GOD also were studied. Displayed by Figure 2A, the highest CL value was observed under the reaction time of 8 h, illustrating that was the optimum reactive time. Meanwhile, Figure 2B showed that when GOD was 2 mg/L, the highest CL value was generated, obtaining the best performance for the glucose determination. The

Characterization

of

Co-TCPP(Fe),

Co-TCPP(Fe)@luminol

and

Co-TCPP(Fe)@luminol@GOD. The luminol and GOD were modified on the surface of Co-TCPP(Fe) step by step. And the product and its intermediates were characterized by transmission electron microscope (TEM), Fourier transform infrared spectrometer and UV-visible spectrophotometer. The TEM images of Co-TCPP(Fe) showed an obvious and uniform 2D sheet structure (Figure 3), implying that the material was successfully synthesized. To further test the change of functional groups, the FTIR of Co-TCPP(Fe), Co-TCPP(Fe)@luminol and Co-TCPP(Fe)@luminol@GOD were carried out, and the detailed information was shown in Figure 4A. Seen from the spectrum, a distinct peak (line c) at a wave number of 1600 cm-1 was represented, indicating there were a large number of carboxyl groups in the Co-TCPP(Fe), which was ascribed to the modification of other reagents. After the addition of luminol and GOD, due to that



numerous carboxyl groups on the surface of Co-TCPP(Fe) were consumed, the peaks of Co-TCPP(Fe)@luminol (line b) and Co-TCPP(Fe)@luminol@GOD (line a) at 1600 (cm-1) had a significant reduction. The above characterization showed that the Co-TCPP(Fe)@luminol@GOD had been successfully prepared. Figure 4B indicated that Co-TCPP(Fe)@luminol was produced as expectation, because its three characteristic absorption peaks (line c, at 301, 348, 407 nm) were consistent with these corresponding peaks of the luminol solution (line a, 303, 350 nm) and Co-TCPP(Fe) (line b, 409 nm). After the modification of GOD, except for the characteristic absorption peak of luminol, the other two peaks at 390 nm and 458 nm could be observed in the spectrum of Co-TCPP(Fe)@luminol@GOD, which was similar with the GOD solution (line e, 382, 455 nm), meaning that the Co-TCPP(Fe)@luminol@GOD was obtained. The Peroxidase-like Activity of Co-TCPP(Fe). In order to systematically study the peroxidase-like activity of Co-TCPP(Fe), the 3,3',5,5'-tetramethylbenzidine (TMB) was set as a model substrate in the presence of H2O2, and the absorbance was recorded by an UV-visible spectroscopy. Revealed by Figure 5A, a significant enhancement could be observed in present of Co-TCPP(Fe), which meant the substance had a good performance in peroxidase-like catalysis. Besides, the reaction conditions of the Co-TCPP(Fe) had also been investigated, including the pH (Figure 5B) and temperature (Figure 5C). As shown in Figure 5B, the relative activity of Co-TCPP(Fe) kept increasing with the pH firstly and then decreased, the peak reached at pH=7.0, which was considered as the appropriate pH value in this system.


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Meanwhile, the optimal temperature of Co-TCPP(Fe) was chosen at 37°C. Furthermore, compared with the natural enzyme (HRP as a model), the Co-TCPP(Fe) had greater advantages in tolerance, showing a higher resistance to a strong acid or base and the extreme temperature. The

Optical

Properties

of

Co-TCPP(Fe)@luminol

and

Co-TCPP(Fe)@luminol@GOD. 5 parallel tests were carried out to study the chemiluminescent effect of Co-TCPP(Fe)@luminol with or without H2O2. Seen from Figure

6A,

the

chemiluminescence

enhancement

only

occurred

when

Co-TCPP(Fe)@luminol was mixed with H2O2, proving the luminol had been coupled to the Co-TCPP(Fe). In addition, an obvious increase in chemiluminescence was observed after the glucose solution was added in the Co-TCPP(Fe)@luminol@GOD (Figure

6B).

The

above

evidences

demonstrated

that

the

obtained

Co-TCPP(Fe)@luminol@GOD can be applied in the further detection for glucose as a chemiluminescence sensor. And the selectivity of this chemiluminescence sensor was investigated in a series of experiments and the results showed that the proposed sensor had a high selectivity for glucose (in Figure S1). The Method Validation and Samples Analysis. Under the above optimized conditions, the standard curve for glucose detection was established and shown in Figure 7. The detection range was 32-5500 μg/L with a limit of detection (10.667 μg/L), which was lower than that using other methods (Table S1). In order to evaluate the accuracy and precision of this chemiluminescence sensor, different simples (milk, pure water, tea and energy drink) spiked with a series



concentration of glucose were measured (Table 1). The results showed satisfactory recoveries (89-121.2%) and the good intra-assay coefficient of variation (CV) ranged from 3.5% to 7.4% (under 3 replicates), indicating this proposed sensor could be used as an effective tool for high- throughput analysis of glucose from various samples. This established method was applied to detect the concentration of glucose in human urines that were collected from different population including diabetic patients and health persons, and the results were shown in Table 2. CONCLUSION Herein, based on the catalysis of a novel 2D-MOFs nanosheet, we developed a simple and sensitive chemiluminescence sensor for quick, high-throughput analysis of glucose. After optimized the conditions, this established method displayed a low limit of detection (10.667 μg/L) with a wider detection range (32-5500 μg/L), good accuracy and precision (recoveries, 89-121.2%; CV, 3.5-7.4%), illustrating great potential in the detection of glucose from human blood or urine and other samples. Supporting Information Available The Supporting Information is available free of charge on the ACS Publications website, including the comparisons of different methods and the selectivity of this method. ACKNOWLEDGEMENT The present work was supported by the National Natural Science Foundation of China (Grants 21577051, 21876067) and the Jiangsu Collaborative Innovation Center for Technology and Water Treatment.


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Wu, C.; Sun, H.; Li, Y.; Liu, X.; Du, X.; Wang, X.; Xu, P., Biosensor Based on Glucose

Oxidase-Nanoporous Gold Co-Catalysis for Glucose Detection. Biosens. Bioelectro. 2015, 66, 350-355. 10. Lei, Y.; Tang, L.; Xie, Y.; Xianyu, Y.; Zhang, L.; Wang, P.; Hamada, Y.; Jiang, K.; Zheng, W.; Jiang, X., Gold Nanoclusters-Assisted Delivery of Ngf Sirna for Effective Treatment of Pancreatic Cancer. Nat. Commun. 2017, 8, 15130. 11. Cheng, H., et al., Monitoring of Heparin Activity in Live Rats Using Metal-Organic Framework Nanosheets as Peroxidase Mimics. Anal. Chem. 2017, 89, 11552-11559. 12. Wang, Y., et al., Bioinspired Design of Ultrathin 2d Bimetallic Metal-Organic-Framework Nanosheets Used as Biomimetic Enzymes. Adv. Mater. 2016, 28, 4149-55. 13. Fu, S.; Zhu, C.; Song, J.; Engelhard, M.; Xia, H.; Du, D.; Lin, Y., Pdcupt Nanocrystals with Multibranches for Enzyme-Free Glucose Detection. ACS Appl. Mater. Inter. 2016, 8, 22196-200. 14. Liu, C.; Sheng, Y.; Sun, Y.; Feng, J.; Wang, S.; Zhang, J.; Xu, J.; Jiang, D., A Glucose Oxidase-Coupled Dnazyme Sensor for Glucose Detection in Tears and Saliva. Biosens. Bioelectron. 2015, 70, 455-61. 15. Wang, Q.; Zhang, X.; Huang, L.; Zhang, Z.; Dong, S., One-Pot Synthesis of Fe3o4 Nanoparticle Loaded 3d Porous Graphene Nanocomposites with Enhanced Nanozyme Activity for Glucose Detection. ACS Appl. Mater. Inter. 2017, 9, 7465-7471. 16. Karim, M. N.; Anderson, S. R.; Singh, S.; Ramanathan, R.; Bansal, V., Nanostructured Silver Fabric as a Free-Standing Nanozyme for Colorimetric Detection of Glucose in Urine. Biosens.



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Scheme 1. The principle of the novel chemiluminescence sensor for one-step ultrasensitive glucose detection (A. The preparation of the chemiluminescence sensorCo-TCPP(Fe)@luminol@GOD; B. The process of one-step detection for glucose).



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Tables Table 1. Analysis of glucose-spiked samples using our established method. Background

Added

Found

Recover

CV

(μg/L)

(μg/L)

(μg/L)

(%)

(%)

100

93.00

93.00

3.5

1000

1212

121.2

4.2

3000

2954

98.47

3.7

100

89.00

89.00

5.2

1000

972.0

97.20

4.8

3000

3135

104.5

3.9

100

112.0

112.0

4.6

1000

983.0

98.30

3.7

3000

2893

96.43

5.3

100

107.0

107.0

4.2

1000

982.0

98.20

6.7

3000

2973

99.10

7.4

Sample

Pure water

Milk

Tea

ND

ND

ND

Energy ND drink


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Table 2. The detection of human urine samples using our established method. Found Samples (μg/L) Sample 1

1350

Sample 2

720.0

Sample 3

560.0

Sample 4

1140

Sample 5

3260

Sample 6

3180

Sample 7

4210

Sample 8

3520

Sample 9

2930

Simple 10

4670



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Figure captions Figure 1. The optimization for the synthesis of Co-TCPP(Fe)@luminol (A. The concentration of Co-TCPP(Fe); B. The concentration of luminol; C. The mixture time of luminol and Co-TCPP(Fe)). Figure 2. The optimization for the synthesis of Co-TCPP(Fe)@luminol@GOD (A. The

concentration

of

GOD;

B.

The

mixture

time

between

GOD

and

Co-TCPP(Fe)@luminol@GOD. Figure 3. The TEM images of Co-TCPP(Fe). Figure 4. A. The FTIR spectrum of

(a) Co-TCPP(Fe)@lumino@GOD, (b)

Co-TCPP(Fe)@luminol and (c) Co-TCPP(Fe); B. The UV absorption spectrum of (a) luminol

solution,

(b)

Co-TCPP(Fe),

(c)

Co-TCPP(Fe)@luminol,

(d)

Co-TCPP(Fe)@luminol@GOD and (e) GOD solution. Figure 5. A. The absorbance of TMB-H2O2 substrates with Co-TCPP(Fe) or without; B. The relative activity of Co-TCPP(Fe) and HRP in different pH; C. The relative activity of Co-TCPP(Fe) and HRP at different temperatures. Figure 6. The optical properties of (A) Co-TCPP(Fe)@luminol and (B) Co-TCPP(Fe)@luminol@GOD. Figure 7. The calibration curves of the chemiluminiscence versus glucose concentrations with a LOD of 10.667 μg/L. The error bars represent the standard deviation of three replicates.


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Figure 1. The optimization for the synthesis of Co-TCPP(Fe)@luminol (A. The concentration of Co-TCPP(Fe); B. The concentration of luminol; C. The mixture time of luminol and Co-TCPP(Fe)).



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Figure 2. The optimization for the synthesis of Co-TCPP(Fe)@luminol@GOD (A. The

concentration

of

GOD;

B.

The

mixture

Co-TCPP(Fe)@luminol@GOD.


time

between

GOD

and

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Figure 3. The TEM images of Co-TCPP(Fe).



Figure 4. A. The FTIR spectrum of

Page 20 of 24

(a) Co-TCPP(Fe)@lumino@GOD, (b)

Co-TCPP(Fe)@luminol and (c) Co-TCPP(Fe); B. The UV absorption spectrum of (a) luminol

solution,

(b)

Co-TCPP(Fe),

(c)

Co-TCPP(Fe)@luminol,

Co-TCPP(Fe)@luminol@GOD and (e) GOD solution.


(d)

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Figure 5. A. The absorbance of TMB-H2O2 substrates with Co-TCPP(Fe) or without; B. The relative activity of Co-TCPP(Fe) and HRP in different pH; C. The relative activity of Co-TCPP(Fe) and HRP at different temperatures.



Figure 6. The optical properties of (A) Co-TCPP(Fe)@luminol and (B) Co-TCPP(Fe)@luminol@GOD.


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Figure 7. The calibration curves of the chemiluminiscence versus glucose concentrations with a LOD of 10.667 μg/L. The error bars represent the standard deviation of three replicates.



TOC Graphic


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A Novel and Sensitive Chemiluminescence Sensor Based on 2D

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