CN-122016964-A - Sweat lead ion detection sensor and preparation method and application of electrode thereof

CN122016964ACN 122016964 ACN122016964 ACN 122016964ACN-122016964-A

Abstract

A sweat lead ion detection sensor and a preparation method and application of an electrode thereof relate to the field of sweat detection sensors, wherein the preparation method of the sensor electrode comprises the steps of dispersing Bi-BDC MOFs in an organic solvent to obtain MOF suspension, coating the MOF suspension on a preset area of a paper-based carbon electrode, drying and curing to obtain an electrode intermediate cured with the Bi-BDC MOFs; dispersing a carbon nano tube and a cysteine functionalized ion imprinting polymer in an organic solvent to obtain a polymer suspension, coating the polymer suspension on a Bi-BDC MOF-cured area of an electrode intermediate, drying and curing again to obtain an electrode substrate, and placing the electrode substrate in a pyrrole solution for pyrrole electropolymerization reaction to obtain the sensor electrode after the reaction is completed. The sensor electrode prepared by the invention can realize the sensitive detection of sweat lead ions by the sensor.

Inventors

GUAN YANFANG
HU DAIXIN
WU ZIHAN
ZENG SHUJIE
ZHAO SHANGKUN
JIN TONG
WANG JINGXIN
WU ZAIHUI
LI WUJIE
WAN ZHENSHUAI
LIU LONGTAO
WEI XINXIN
XIA ZHAOYANG

Assignees

河南工业大学

Dates

Publication Date: 20260512
Application Date: 20260129

Claims (10)

1. A method for preparing an electrode of a sweat lead ion detection sensor, which is characterized by comprising the following steps: Swelling the lead ion imprinted polymer containing carboxyl, adding an activating agent and a crosslinking accelerator, stirring, and standing away from light to complete pre-activation treatment to obtain a mixed system, adjusting the pH of the mixed system to 7.0-7.5, adding cysteine, stirring at room temperature for reaction, and washing and drying sequentially after the reaction is completed to obtain the cysteine functionalized ion imprinted polymer for later use; Dispersing Bi-BDC MOF in an organic solvent to obtain MOF suspension, coating the MOF suspension on a preset area of a paper-based carbon electrode, and drying and curing to obtain an electrode intermediate cured with the Bi-BDC MOF; Dispersing a carbon nano tube and a cysteine functionalized ion imprinting polymer in an organic solvent to obtain a polymer suspension, coating the polymer suspension on a Bi-BDC MOF-cured area of an electrode intermediate, and drying and curing again to obtain an electrode substrate; and placing the electrode substrate in pyrrole solution to perform pyrrole electropolymerization reaction, and obtaining the sensor electrode after the reaction is completed.
2. The method for preparing an electrode of a sweat lead ion detection sensor according to claim 1, wherein the activator is EDC, the crosslinking accelerator is NHS, and the organic solvent is ethanol.
3. The method for preparing the sweat lead ion detection sensor electrode according to claim 1, wherein the mass ratio of the carboxyl-containing lead ion imprinted polymer to the cysteine is 100:25-30.
4. The method for preparing the sweat lead ion detection sensor electrode according to claim 1, wherein the swelling process of the lead ion imprinted polymer containing carboxyl is that the lead ion imprinted polymer containing carboxyl is dissolved in MES buffer solution, DMF is added, and stirring is carried out for 1-2h.
5. The method for preparing the electrode of the sweat lead ion detection sensor according to claim 1, wherein the specific method for the pyrrole electropolymerization reaction is that an electrode substrate is used as a working electrode to be connected with an electrochemical workstation, the working electrode is placed in pyrrole solution, and the pyrrole electropolymerization reaction is carried out on the surface of the electrode substrate by adopting a potentiostatic method.
6. The method for preparing the sweat lead ion detection sensor electrode according to claim 1, wherein the preparation method of the lead ion imprinted polymer containing carboxyl is as follows: dissolving a lead source in water, adding a polymer functional monomer, and stirring to react to form a template-monomer complex; dissolving an initiator in deionized water, mixing with a cross-linking agent, and adding the obtained mixture into the template-monomer complex to obtain a mixed material; And (3) carrying out deoxidization treatment on the mixed materials, sealing and carrying out water bath reaction, removing template lead ions after the reaction is finished, alternately washing until washing liquid is neutral, and drying to obtain lead ion imprinted polymer powder.
7. The method for preparing the sweat lead ion detection sensor electrode according to claim 6, wherein the lead source is lead nitrate or lead acetate, the polymer functional monomers are AMPS and MAA, the initiator is APS, and the crosslinking agent is EGDMA.
8. The preparation method of the sweat lead ion detection sensor electrode according to claim 1 is characterized in that the preparation method of the Bi-BDC MOF comprises the steps of dissolving a bismuth source in an amide solvent, adding an organic ligand and a regulator, carrying out hydrothermal reaction on the obtained mixed solution, cooling to room temperature after the reaction is finished, centrifuging to collect a solid product, washing and drying to obtain the Bi-BDC MOF.
9. A sweat lead ion detection sensor having a sweat lead ion detection sensor electrode made by the method of any one of claims 1 to 8.
10. The application of the sweat lead ion detection sensor is characterized in that lead ions of sweat to be detected are detected by an anodic stripping voltammetry.

Description

Sweat lead ion detection sensor and preparation method and application of electrode thereof Technical Field The invention relates to the field of sweat detection sensors, in particular to a sweat lead ion detection sensor and a preparation method and application of an electrode thereof. Background Lead ions are typical heavy metal ions, have the characteristics of strong accumulation and difficult metabolism, can cause irreversible serious damage to a plurality of organs such as nervous system, hematopoietic system, kidneys and the like after entering a human body, and form a great threat to human health, so that the lead ions in the human body are accurately and efficiently detected. At present, the detection method of lead ions in human blood mainly comprises an atomic absorption spectrometry, an inductively coupled plasma mass spectrometry, an ultraviolet-visible spectrophotometry and the like, but the traditional detection methods have a plurality of inherent defects in sweat detection, and are difficult to meet diversified requirements of clinical screening, basic level detection, on-site rapid detection and the like. The method for detecting the lead ions in the blood mostly takes the blood as a sample, belongs to invasive detection, and can not only cause bleeding of wounds, slow healing and even infection during sampling, but also reduce diagnosis and treatment compliance due to interference emotion of partial patients, especially children and elderly patients, caused by pain, meanwhile, the dependent professional equipment has high cost and complex operation, has strict requirements on personnel skills, is difficult to popularize to a base layer and a scene on site, and the sample needs to be subjected to complex pretreatment such as digestion, acidification and the like, so that pollution can be introduced or lead ions can be lost after time and labor are consumed, and the detection accuracy is influenced. In addition, the detection limit of the existing detection equipment is at ppm level, the detection requirement of low-concentration lead ions in sweat can not be met, the concentration of the lead ions in sweat of a healthy human body is generally lower than 10 mug/L, sweat sampling is noninvasive and convenient, the detection equipment is an ideal detection sample, meanwhile, the detection equipment is easily interfered by coexisting ions such as copper ions and calcium ions and organic matters, additional separation steps are needed, and the operation complexity and cost are further increased. Although portable equipment such as test strips and handheld spectrometers can realize on-site rapid detection, the sensitivity is generally lower than that of large laboratory instruments, and the sensitivity is easily interfered by factors such as operation methods, ambient illumination, temperature and humidity, and the like, disposable products such as test strips and the like can also undergo cross reaction, and the error is obvious during low-concentration detection, so that the accuracy is difficult to ensure. Meanwhile, the traditional laboratory detection equipment has high purchase and matching reagent and consumable cost, so that less developed areas and small and medium-sized laboratories are difficult to bear, the single detection time is usually in an hour unit, and the timeliness requirements of quick screening and emergency detection cannot be met. In order to overcome the defects, the ion imprinted polymer has target ion specific recognition capability, and is a research hot spot in the field. However, the detection sensitivity of the existing lead ion sensor based on the ion imprinted polymer still needs to be improved, and lead ions in low-concentration samples such as sweat and the like are difficult to accurately capture, so that the requirements of clinical early screening and basic-level accurate detection cannot be fully met. Disclosure of Invention The invention aims to provide a sweat lead ion detection sensor and a preparation method and application of an electrode thereof, so as to realize the sensitive detection of the sensor on sweat lead ions. The preparation method comprises the steps of swelling a lead ion imprinted polymer containing carboxyl, adding an activating agent and a crosslinking accelerator, stirring, standing away from light to complete pre-activation treatment to obtain a mixed system, adjusting the pH of the mixed system to 7.0-7.5, adding cysteine, stirring at room temperature for reaction, washing and drying sequentially after the reaction is completed to obtain a cysteine functionalized ion imprinted polymer, dispersing Bi-BDC MOF in an organic solvent for standby, obtaining a MOF suspension, coating the MOF suspension on a preset area of a paper-based carbon electrode, drying and curing to obtain an electrode intermediate cured with the Bi-BDC MOF, dispersing a carbon nanotube and the cysteine functionalized ion imprinted polymer in an organic solvent t