Semi⁃interpenetrated Network Hydrogels Prepared by in⁃situ Initiation of Liquid Metal to Construct a Low Fouling Electrochemical Sensing Interface

doi:10.19894/j.issn.1000-0518.220165

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (9): 1464-1474.DOI: 10.19894/j.issn.1000-0518.220165

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Semi⁃interpenetrated Network Hydrogels Prepared by in⁃situ Initiation of Liquid Metal to Construct a Low Fouling Electrochemical Sensing Interface

De LI¹, Nan WANG², Hua-Wei YANG³, Jiao MA¹()

^1.Key Laboratory of Interface Science and Engineering in Advanced Materials Ministry of Education，Taiyuan University of Technology，Taiyuan 030024，China
^2.Key Laboratory for Medical Implantable Devices of Shandong Province，WEGO Holding Company Limited，Weihai 264210，China
^3.State Key Laboratory of Polymer Physics and Chemistry，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China

Received:2022-05-04 Accepted:2022-07-21 Published:2022-09-01 Online:2022-09-08
Contact: Jiao MA
About author:majiao@tyut.edu.cn
Supported by:
the National Natural Science Foundation of China(51903185)

Abstract

Abstract:

Any materials present in complex samples that bind the sensing interface non-specifically will greatly decrease the sensitivity and accuracy of the electrochemical sensor. Traditional antifouling coatings could hinder the electron transfer， resulting in a double-edged strategy. Here， we create a semi-interpenetrated nanocomposite hydrogel， consisting of a liquid metal （LM） conductive core， an antifouling poly（vinyl pyrrolidone）（pNVP） network covalently grafting from it and homogeneously distributed chitosan around the pNVP chain， with excellent antifouling property while maintaining high conductivity. Remarkably， we further propose a polymerization-crosslinking separation strategy， thus facilitating the hydrogel sensing matrix with good processibility， accompanying repeatability and excellent stability. Finally， a label-free electrochemical immunosensor based on the proposed hydrogel-based sensing interface is successfully fabricated， and it possesses excellent repeatability， storage stability， selectivity， a wide linear range from 10 pg/mL~10 μg/mL， and an ultralow detection limit of 6.91 pg/mL for the detection of motilin. Moreover， no change is observed even in the presence of 5% serum. The above results successfully proved the feasibility of using liquid metal nanocomposite hydrogel as electrochemical sensing base， and also provides important reference for the construction of other electrochemical immunosensor.

Key words: Liquid metal, Conductive hydrogel, Antifouling, Electrochemical immunosensor

CLC Number:

O657

De LI, Nan WANG, Hua-Wei YANG, Jiao MA. Semi⁃interpenetrated Network Hydrogels Prepared by in⁃situ Initiation of Liquid Metal to Construct a Low Fouling Electrochemical Sensing Interface[J]. Chinese Journal of Applied Chemistry, 2022, 39(9): 1464-1474.

Figures/Tables 8

Fig.1 （A） Preparation of LM-pNVP/CS semi-interpenetrated network hydrogel；（B） Schematic diagram of electrochemical immunosensor construction

Fig.2 （A） CV curves of APS-pNVP and LM-pNVP；（B） EIS curves of APS-pNVP and LM-pNVP；（C） SEM image of LM- pNVP；（D） FT-IR spectra of composite hydrogels with different compositions

Table 1 The content of different composite gels

样品 Sample	LM浓度 c（LM）/（mol·L^-1）	NVP浓度 c（NVP）/（mol·L^-1）	PEGDMA浓度 c（PEGDMA）/ （mol·L^-1）	CS质量浓度 ρ（CS）/（mg·mL^-1）	APS浓度 c（APS）/（mol·L^-1）
LM?pNVP/CS₁	0.09	1.8	0.12	2	0
LM?pNVP/CS₂	0.12	1.8	0.12	2	0
LM?pNVP/CS₃	0.18	1.8	0.12	2	0
LM?pNVP/CS₄	0.12	1.8	0.09	2	0
LM?pNVP/CS₅	0.12	1.8	0.18	2	0
LM?pNVP	0.12	1.8	0.12	0	0
APS?pNVP	0	1.8	0.12	0	0.12

Fig.3 （A） SEM images of LM-pNVP/CS x semi-interpenetrated network gels with different ratios （x=1， 2， 3， 4， 5）； CV （B） and EIS （C） images of LM-pNVP/CS x semi-interpenetrated network gel with different proportions （x=1， 2， 3）； CV （D） and EIS （E） images of LM-pNVP/CS x semi-interpenetrated network gel with different proportions （x=4， 2， 5）

Fig.4 （A） CV images of electrochemical immunosensor fabrication process；（B） Currents of LM-pNVP/CS2/GCE at different storage times；（C） Electrochemical immunosensor for： Blank solution， motilin （10 ng/mL）， 100 ng/mL of BSA， Lys， Fib and 10 ng/mL motilin mixture（Mix）， BSA （100 ng/mL）， Lys （100 ng/mL）， Fib （100 ng/mL） electrochemical response （The error bar represents the standard deviation of three repeated determinations）

Fig.5 Antifouling properties of naked GCE and LM-pNVP/CS2/GCE in different concentrations of BSA （A）， Fib （B） and goat serum with different volume fraction solutions （C）ΔI = I-I0， I0 and I represent CV signals before and after 30 min of pollutant incubation. The error bar represents the standard deviation of three repeated determinations

Fig.6 （A） SWV response of immunosensor to different concentrations of motilin；（B） corresponding dynamic response range and calibration curve of immunosensor to different concentrations of motilin；（C） Calibration curve of immunosensor in 5% （volume fraction） goat serum solution；（D） Calibration curve of the immunosensor in 10% （volume fraction） goat serum solution （The error bar represents the standard deviation of three repeated determinations）

Table 2 The recovery for motilin analysis in 10% goat serum （n=3）

样品编号 Sample No.	胃动素加标量 Motilin added/（ng·mL^-1）	检测值 Found/（ng·mL^-1）	回收率 Recovery/%	相对标准偏差 RSD/%
1	0.1	0.933 2	93.3	3.8
2	1	0.957	95.7	3.1
3	10	10.69	106.9	4.5
4	100	94.67	94.7	4.3
5	1 000	976.23	97.6	3.6
6	10 000	10 415.12	104.2	3.7

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Semi⁃interpenetrated Network Hydrogels Prepared by in⁃situ Initiation of Liquid Metal to Construct a Low Fouling Electrochemical Sensing Interface

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