CN-121595674-B - GR/PDDA/PdNPs electrochemical sensing material and preparation method and application thereof

Abstract

The invention relates to the technical field of electrochemical sensing material preparation, in particular to a GR/PDDA/PdNPs electrochemical sensing material, a preparation method and application thereof, wherein PDDA and palladium chloride are sequentially added into graphene oxide suspension, naBH 4 solution is added after uniform stirring, the temperature is raised to 40-60 ℃ for stirring reaction for 5-7 hours, cooling is carried out after completion, and products are centrifugally washed and dried to obtain the GR/PDDA/PdNPs electrochemical sensing material, and the GR/PDDA/PdNPs/GCE electrochemical sensor is prepared by uniformly dripping the electrochemical sensing material onto the surface of a glassy carbon electrode and can be used for detecting the barnidipine content. The invention optimizes the condition for detecting the content of the barnidipine, and the GR/PDDA/PdNPs/GCE electrochemical sensor has the advantages of high detection sensitivity, good reproducibility, strong stability, low manufacturing cost and the like when detecting the content of the barnidipine.

Inventors

• WEI YINGLIANG
• WANG ANTING
• XU XIAOLIN
• LUO YUE
• CHEN KEXIN

Assignees

• 洛阳理工学院

Dates

Publication Date

20260512

Application Date

20260128

Claims (4)

1. The application of the GR/PDDA/PdNPs/GCE electrochemical sensor in detecting the barnidipine content is characterized in that the GR/PDDA/PdNPs/GCE electrochemical sensor is used as a working electrode, a platinum wire electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a linear scanning voltammetry is adopted, an acetic acid-sodium acetate buffer solution with pH value of 6.80-7.20 is used as a supporting electrolyte, the enrichment time is 140-160 s, the barnidipine concentration is in the range of 4.0 multiplied by 10 -7 ～2.0×10 -5 mol/L, the peak current and the concentration are in a linear relation, and the detection limit is 1.3 multiplied by 10 -7 mol/L, and the preparation method of the GR/PDDA/PdNPs/GCE electrochemical sensor comprises the following steps: (1) Ultrasonically dispersing graphene oxide in distilled water to prepare a graphene oxide suspension of 1 mg/mL; (2) Slowly adding a certain amount of PDDA into the graphene oxide suspension obtained in the step (1), stirring for 1-2 h, then adding palladium chloride into the graphene oxide suspension, and continuously stirring for 1-2 h to obtain a mixed solution, wherein the mass fraction of PDDA is 35%, and the volume ratio of the added PDDA to the graphene oxide suspension is 1 (25-50); (3) Dropwise adding NaBH 4 solution into the mixed solution obtained in the step (2), uniformly stirring, heating the mixed system to 40-60 ℃, stirring at the temperature for 5-7 h, and naturally cooling to room temperature after completion; (4) Centrifugally separating the cooled product in the step (3), centrifugally washing the separated solid by using distilled water until the pH value of the washed supernatant fluid is=7.0, and drying the washed solid in a drying box at 60-70 ℃ for 20-24 hours to obtain the GR/PDDA/PdNPs electrochemical sensing material; (5) And ultrasonically dispersing the GR/PDDA/PdNPs electrochemical sensing material in distilled water to obtain GR/PDDA/PdNPs dispersion, transferring 5-7 mu L of GR/PDDA/PdNPs dispersion, uniformly dripping the GR/PDDA/PdNPs dispersion on the surface of the treated glassy carbon electrode, and naturally airing to obtain the GR/PDDA/PdNPs/GCE electrochemical sensor.
2. 2. The application of the GR/PDDA/PdNPs/GCE electrochemical sensor according to claim 1 in the detection of the content of barnidipine, wherein the ratio of the added mass of palladium chloride to the mass of graphene oxide in the step (1) is1 (9-10).
3. 3. The use of the GR/PDDA/PdNPs/GCE electrochemical sensor according to claim 1 for detecting the barnidipine content, wherein the concentration of NaBH 4 solution is 1 mg/mL, and the ratio of the added volume to the volume of the graphene oxide suspension obtained in step (1) is 1 (20-30).
4. 4. The use of the GR/PDDA/PdNPs/GCE electrochemical sensor according to claim 1 for the detection of the barnidipine content, wherein the concentration of the GR/PDDA/PdNPs dispersion in step (5) is1 mg/mL.

Description

GR/PDDA/PdNPs electrochemical sensing material and preparation method and application thereof Technical Field The invention relates to the technical field of electrochemical sensing material preparation, in particular to a GR/PDDA/PdNPs electrochemical sensing material, a preparation method and application thereof. Background Hypertension, one of the major chronic diseases that threatens public health worldwide, has become a central challenge in the prevention and control of cardiovascular disease. In clinical treatment, the selection of the medicine with long-acting antihypertensive, anti-angina and cardiovascular and cerebrovascular protecting effects is important. The barnidipine is used as a second-generation dihydropyridine calcium channel regulator, can realize stable and durable depressurization, can obviously improve myocardial oxygen supply and demand balance and protect vascular endothelial functions, and is an ideal choice for comprehensive treatment of hypertension. Accurate monitoring of the active ingredients of the drugs is a key link for guaranteeing clinical medication safety and efficacy evaluation. The traditional detection method such as the ultra-high performance liquid chromatography-mass spectrometry and ultraviolet spectrophotometry has high sensitivity and specificity, but has the limitations of high instrument cost, complex pretreatment, long detection period and the like, and is difficult to meet the requirement of on-site rapid analysis. In contrast, the electrochemical sensing technology provides a new technical path for drug analysis by virtue of the advantages of simple operation, quick response, low cost and easy miniaturization. The two-dimensional nanomaterial Graphene (GR) has excellent conductivity, mechanical strength and large specific surface area due to the unique sp 2 hybridized honeycomb lattice structure, and becomes an ideal carrier for constructing a high-performance electrochemical sensor. When the graphene is compounded with palladium nano particles (PdNPs), the synergistic effect formed by the palladium nano particles and the palladium nano particles can further optimize the interface electron transmission efficiency, wherein the high catalytic activity and the strong adsorption capacity of the palladium nano particles can effectively enrich target molecules, and the excellent conductivity of graphene can accelerate charge transfer, so that the detection performance of the sensor is improved. At present, high performance liquid chromatography is adopted in the report of the detection of the content of the barnidipine, yang Guang and the like, and the content of the barnidipine hydrochloride and related substances are measured under the detection wavelength of 236 nm, however, the high performance liquid chromatography has the disadvantages of higher cost, more complex operation, strict requirements on the pretreatment of samples and a plurality of inconveniences. Disclosure of Invention Aiming at the problems, the invention provides a GR/PDDA/PdNPs electrochemical sensing material, a preparation method and application thereof, wherein graphene oxide is used as a base material, PDDA (polydiallyl dimethyl ammonium chloride) is used as a reducing agent and a dispersing agent, palladium nano particles are doped at the same time, the GR/PDDA/PdNPs electrochemical sensing material is prepared, the GR/PDDA/PdNPs electrochemical sensing material is uniformly dripped on the surface of a treated glassy carbon electrode to prepare the GR/PDDA/PdNPs/GCE electrochemical sensor, and the GR/PDDA/PdNPs/GCE electrochemical sensor can be applied to the determination of the barnidipine content. The invention optimizes the condition for detecting the content of the barnidipine, and the GR/PDDA/PdNPs/GCE electrochemical sensor has the advantages of high detection sensitivity, good reproducibility, strong stability, low manufacturing cost and the like when detecting the content of the barnidipine. The invention aims at providing a preparation method of GR/PDDA/PdNPs electrochemical sensing material, which specifically comprises the following steps: (1) Ultrasonically dispersing graphene oxide in distilled water to prepare a graphene oxide suspension of 1 mg/mL; (2) Slowly adding a certain amount of PDDA into the graphene oxide suspension obtained in the step (1), stirring for 1-2 h, then adding palladium chloride into the graphene oxide suspension, and continuously stirring for 1-2 h to obtain a mixed solution, wherein the mass fraction of PDDA is 35%, and the volume ratio of the added PDDA to the graphene oxide suspension is 1 (25-50); (3) Dropwise adding NaBH 4 solution into the mixed solution obtained in the step (2), uniformly stirring, heating the mixed system to 40-60 ℃, stirring at the temperature for 5-7 h, and naturally cooling to room temperature after completion; (4) And (3) centrifugally separating the cooled product in the step (3), centrifugally washing the separated