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CN109248677B - Germanium dioxide nanoenzyme and pesticide detection application thereof - Google Patents

Germanium dioxide nanoenzyme and pesticide detection application thereof Download PDF

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CN109248677B
CN109248677B CN201811199415.0A CN201811199415A CN109248677B CN 109248677 B CN109248677 B CN 109248677B CN 201811199415 A CN201811199415 A CN 201811199415A CN 109248677 B CN109248677 B CN 109248677B
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韩磊
梁欣
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Qingdao Agricultural University
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Abstract

本发明涉及纳米催化、分析化学领域，具体包括二氧化锗（GeO2）纳米酶及其农药检测应用。GeO2纳米酶在酸性pH下具有过氧化物酶的活性，可催化过氧化氢和有机显色剂发生显色反应。本发明利用制备得到的GeO2纳米酶与乙酰胆碱酯酶偶联实现了有机磷农药的定量分析。该发明可应用于农药残留分析、生物医药、环境监测等领域。The invention relates to the fields of nano-catalysis and analytical chemistry, and specifically includes germanium dioxide (GeO 2 ) nano-enzyme and its pesticide detection application. GeO 2 nanozyme has peroxidase activity at acidic pH, and can catalyze the color reaction between hydrogen peroxide and organic color developer. The present invention utilizes the prepared GeO 2 nanometer enzyme to couple with acetylcholinesterase to realize the quantitative analysis of organophosphorus pesticides. The invention can be applied to the fields of pesticide residue analysis, biomedicine, environmental monitoring and the like.

Description

Germanium dioxide nanoenzyme and pesticide detection application thereof
Technical Field
The invention relates to the field of analytical chemistry, and particularly relates to germanium dioxide nanoenzyme and pesticide detection application thereof.
Background
The nano enzyme is a novel mimic enzyme, and becomes a focus of attention due to strong catalytic activity and potential application in aspects of biosensing, food technology, environmental protection and the like. The nano enzyme overcomes many defects of natural enzyme, such as high price, easy inactivation, strict requirement on storage condition and the like, and has great influence on the fields of biosensing, immunoassay, cancer diagnosis, treatment and the like.
To date, a variety of inorganic nanomaterials (including Co)3O4，CeO2，V2O5，CuO，MnO2CuS, FeS, noble metals, carbon (fullerenes, graphene), metal-organic framework structures and composite nanostructures thereof all exhibit mimetic activity (including mimetic peroxidase, mimetic oxidase, mimetic catalase)Superoxide dismutase-like). However, not all metal oxides have mimic enzyme activity. Germanium dioxide has not been reported to have biomimetic activity.
GeO2Is one of germanium oxides, and has been widely used as an anode material instead of graphite due to its low cost, simple synthesis process, and good environmental stability. At the same time, GeO2Is an important glass forming agent, can effectively adjust the refractive index of glass and the physical and chemical properties of glass materials, and is widely applied to the design of optical fiber core materials and cladding materials. GeO2The nano-structure material has important application prospect in the fields of luminescent devices and the like due to the excellent optical property of the nano-structure material. However, GeO has not been found yet2The nano enzyme has enzyme imitating activity.
Organophosphorus Pesticides (OP) are the most widely used agricultural pesticides and play an important role in increasing agricultural productivity and improving product quality. However, organophosphorus pesticides can cause various diseases such as senile dementia, Parkinson's disease, stroke and the like in human beings. The main reason is that the organophosphorus pesticide can inhibit the activity of acetylcholinesterase (AChE) in human body to a great extent, which leads to excessive accumulation of acetylcholine and further causes related diseases. Meanwhile, due to the high residue characteristic of the organophosphorus pesticide and the serious overuse or nonstandard operation in agricultural production, the high content residue of the pesticide on agricultural products is caused, and the balance of human health and natural ecology is seriously threatened. Therefore, the construction of a high-sensitivity detection platform and the realization of simple, convenient, rapid and high-sensitivity detection of the pesticide have important practical application values. Hitherto, such as High Performance Liquid Chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS), electrochemical analysis, colorimetry, and the like have been applied to the sensing detection of organophosphorus pesticides. However, these methods tend to have lower sensitivity and longer operating times, require special expertise, and rely on expensive large instruments. These factors severely limit the large scale application of the above methods in the field of pesticide residue detection. As described above, GeO having mimic enzyme activity2The nano enzyme has novelty in the field, and no GeO-based nano enzyme is reported at present2And detecting the organophosphorus pesticide by using the nano enzyme.
Disclosure of Invention
The invention aims to provide germanium dioxide nanoenzyme and application thereof in pesticide detection.
In order to achieve the purpose, the invention adopts the technical scheme that:
nano enzyme material and application thereof, and nano enzyme material GeO2The nano enzyme has the activity of imitating peroxidase.
Preferably, the peroxidase-mimetic material GeO2The process for synthesizing the nano enzyme comprises the following steps:
(1) stirring GeO2Dissolving the solid powder in a sodium hydroxide solution, then dissolving a proper amount of Cetyl Trimethyl Ammonium Bromide (CTAB) in a proper amount of distilled water under stirring, and respectively stirring the two solutions at room temperature for 12 hours; (2) pouring CTAB solution into GeO under stirring2Continuously stirring the solution in the alkaline solution at room temperature for 8 hours; (3) the mixture was transferred to an autoclave and kept at 100 ℃ for 56 h, then cooled to room temperature. To obtain germanium dioxide (GeO)2) And (3) nano enzyme.
Further preferably, the peroxidase-mimetic material GeO2The nanoenzymes can be used as peroxidase-mimetic catalysts for applications based on mimetic peroxidase activity.
Still more preferably, the peroxidase-mimetic material GeO2The nano enzyme is used as a catalyst with peroxidase activity under an acidic condition and is used for qualitatively/quantitatively detecting organophosphorus pesticides, and the method comprises the following steps:
(1) incubating phosphate buffer solutions (pH 7.0, 10 mmol/L) containing acetylcholinesterase (400 mU/mL) and varying concentrations of organophosphates (0-50 ng/L) at 37 ℃ for 30 min; (2) taking 10 μ L of the mixed solution to contain a certain amount of thioacetylcholine (0.1 mmol/L) and the GeO2Nano enzyme (100 mug/mL), organic color developing agent (0.5 mmol/L) and H2O2(0.5 mmol/L) acetate buffer (pH 4.0, 100 mmol/L) and incubation continued at 37 ℃ for 30 min; (3) observing the color change of the solution to realize qualitative detection, and detecting the organic substances by using a spectrophotometerThe corresponding light absorption value of the color developing agent oxide is used for realizing quantitative detection.
Still more preferably, said GeO2The nano enzyme can be used for detecting organophosphorus pesticides, and the organophosphorus pesticides can be organophosphorus pesticides such as paraoxon, parathion, dibromophosphorus, diazinon and the like; the organic color developing agent is 2, 2' -dinitro-bis (3-ethylbenzthiazoline-6-sulfonic acid) diamine salt (ABTS), o-phenylenediamine (OPD) or 3, 3', 5, 5' -tetramethyl benzidine (TMB).
The invention has the following effects:
1. the invention synthesizes GeO with peroxidase activity2The nano-enzyme has the optimum pH value of about 4.0, and shows the activity of peroxidase under the condition of acid pH (pH 3.5-5.0).
2. GeO synthesized by the invention2The nano enzyme shows different properties from the reported peroxidase-imitating nano material, namely low stability: the activity decreases sharply at a pH lower or higher than pH 3.5-5.0, and the stability decreases significantly at a pH lower or higher than pH 3.5-5.0.
3. The invention utilizes GeO2Peroxidase activity and low stability of nanoenzyme, GeO2The nano enzyme is applied to qualitative/quantitative analysis of the organophosphorus pesticide, and realizes qualitative/quantitative detection of the organophosphorus pesticide by using a spectrophotometry.
4. The invention provides a material which exerts the activity of the mimic enzyme, and has wide application prospect in the aspects of pesticide residue detection, food safety, environmental monitoring and the like.
Drawings
FIG. 1 shows GeO according to an embodiment of the present invention2Transmission electron microscopy images of nanoenzymes;
FIG. 2 shows GeO according to an embodiment of the present invention2The effect diagram of the activity of the mimic enzyme of the nano enzyme;
FIG. 3 shows GeO according to an embodiment of the present invention2pH optimization effect diagram of the activity of the nano enzyme mimic enzyme;
FIG. 4 shows GeO according to an embodiment of the present invention2pH stability analysis chart of the activity of the nano enzyme mimic enzyme;
FIG. 5 is a diagram of H according to an embodiment of the present invention2O2The standard working curve is quantitatively detected;
FIG. 6 is a schematic diagram of organophosphorus pesticide detection provided by an embodiment of the present invention;
FIG. 7 is a photograph showing the qualitative detection of diazinon as an organophosphorus pesticide provided in the example of the present invention;
FIG. 8 is a standard working curve for quantitative determination of diazinon as an organophosphorus pesticide provided by an embodiment of the present invention;
Detailed Description
In order to more clearly and more deeply illustrate the contents of the present invention, some examples will be further illustrated below, but the present invention is not limited to the illustrated examples. The specific experimental conditions or methods in the following examples, if not noted, were carried out according to conventional conditions or methods in the art.
Example 1
Peroxidase-like material GeO2Preparing nano enzyme:
1.06 g of GeO2The solid powder was added to 10 mL of sodium hydroxide solution, 1.46 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 12 mL of distilled water, and the two solutions were stirred at room temperature for 12 hours, respectively. Then CTAB solution was poured into GeO2In the alkaline solution, the mixture was stirred at room temperature for 8 hours. Finally the mixture was transferred to an autoclave, kept at 100 ℃ for 56 h and then cooled to room temperature. Obtaining the germanium dioxide (GeO) with a triangular structure2) And (3) nano enzyme. FIG. 1 shows GeO observed by a transmission electron microscope2TEM imaging of nanoenzymes.
Example 2
GeO2And (3) verifying the enzyme-imitating activity of the nano enzyme:
experiment system a: the catalytic reaction system comprises H2O2(0.15 mmol/L), GeO obtained in the above example2Nano enzyme (100 mug/mL), organic color reagent TMB (0.5 mmol/L) acetate buffer solution (pH 4.0, 100 mmol/L). After reacting for 30 minutes at room temperature (25 ℃), detecting the light absorption value within 450-800 nm by using an enzyme-linked immunosorbent assay;
two additional comparisons were madeAnd (3) testing: in one of the control experiments b, no GeO was added to the catalytic reaction system2Nano enzyme, reacting for 30 minutes under the same condition with the experimental system, and detecting a light absorption value; another catalytic reaction system for control experiment c was GeO2Standing the nano enzyme (100 mug/mL) in acetate buffer solution (pH 4.0, 100 mmol/L) for 30 minutes under the same condition as the experimental system, and detecting the light absorption value;
as shown in FIG. 2, the experimental system a showed a distinct peak, indicating GeO2The nano enzyme has obvious activity of simulating peroxidase at pH 4.0; control b shows no significant peak around 650 nm, indicating that GeO is absent2The nano enzyme is used as a catalyst and has no obvious reaction; the control test c has no obvious peak near 650 nm, which indicates that the peak of the experimental system a is not GeO2The response peak of the nanoenzyme itself.
Example 3
GeO2pH optimization of the activity of the nano enzyme mimic:
the catalytic reaction system comprises H2O2（0.3 mmol/L）、GeO2The reagent comprises nano enzyme (100 mu g/mL), organic color developing agent TMB (0.5 mmol/L) buffer solutions with different pH values (pH 1.0-2.0, glycine-hydrochloric acid buffer solution; pH 3.0-6.0, acetic acid-sodium acetate buffer solution; pH 6.5-8.0, phosphate buffer solution; pH 9.0-10.0, Tris-hydrochloric acid buffer solution; pH 11.0-12.0, sodium bicarbonate-sodium hydroxide buffer solution). After reacting at room temperature (25 ℃ C.) for 30 minutes, the absorbance at 650 nm was measured using a microplate reader. As shown in FIG. 3, GeO2The nano enzyme shows the activity of peroxidase under acid pH (pH 3.5-5.0), and the optimum pH is about 4.0.
Example 4
GeO2pH stability of the enzyme mimetic activity of the nanoenzyme:
the catalytic reaction system comprises GeO2The nano enzyme (100 mu g/mL) and buffer solutions (pH 1.0-12.0, 10 mmol/L) with different pH values are incubated at room temperature (25 ℃) for 1H, and organic color development agents TMB (0.5 mmol/L), H are added2O2(0.3 mmol/L) and acetate buffer (pH 4.0, 100 mmol/L). Relay (S)Reacting at room temperature (25 deg.C) for 30 min, and detecting light absorption value within 650 nm with enzyme labeling instrument. As shown in FIG. 4, GeO2The enzyme activity of the nano enzyme is most stable when the pH value is 3.0-8.0, and the optimal pH value is about 4.0.
Example 5
H2O2The quantitative detection of (2):
the catalytic reaction system comprises H with different concentrations2O2（0.01−0.3 mmol/L）、GeO2Nano enzyme (100 mug/mL), organic color reagent TMB (0.5 mmol/L) acetate buffer solution (pH 4.0, 100 mmol/L). After reacting for 10 minutes at room temperature (25 ℃), the absorbance value within 300-800 nm is detected by a microplate reader. The blank control is subtracted from the absorbance at 650 nm to plot H2O2Standard operating curve. As shown in fig. 5, the linear range is 0.01-0.15 mmol/L, y =1.97x +0.05 (R)2=0.9955)。
Example 6
Qualitative detection of diazinon:
the thioacetyl choline can be catalyzed by acetylcholinesterase to generate mercaptoacetyl choline, and can be reacted with GeO2Production of Ge by nanoenzyme reaction3+Thereby making GeO2The enzyme-imitating activity of the nano enzyme disappears. The organophosphorus pesticide can inhibit the activity of acetylcholinesterase, so that mercaptoacetylcholine cannot be generated, and GeO cannot be inhibited2The enzyme-imitating activity of the nano enzyme realizes the quantitative detection of the organophosphorus pesticide. FIG. 6 is a schematic diagram of detection of organophosphorus pesticide. The catalytic reaction system is phosphate buffer solution (pH 7, 10 mmol/L) containing acetylcholinesterase (400 mU/mL) and diazinon (0-50 ng/L) with different concentrations. After incubation for 30 minutes at 37 ℃, a certain amount of thioacetylcholine (0.1 mmol/L) and GeO are added into 10 muL of the mixed solution2Nano enzyme (100 mug/mL), organic color development reagent TMB (0.5 mmol/L), H2O2(0.5 mmol/L), acetate buffer (pH 4.0, 100 mmol/L). The incubation was carried out at 37 ℃ for 30 min, and the color change was observed as shown in FIG. 7. The solution color deepens in turn, which shows GeO2The nano enzyme can detect the organophosphorus pesticide.
Example 7
Quantitative detection of diazinon:
the catalytic reaction system is characterized in that after a phosphate buffer solution (pH 7.0, 10 mmol/L) containing acetylcholinesterase (400 mU/mL) and diazinon (0 ‒ 50 ng/L) with different concentrations is incubated for 30 minutes at 37 ℃, a certain amount of thioacetylcholine (0.1 mmol/L) and GeO (0 ‒ ng/L) are added into 10 mU L of the mixed solution2Nano enzyme (100 mug/mL), organic color development reagent TMB (0.5 mmol/L), H2O2(0.5 mmol/L), acetate buffer (pH 4.0, 100 mmol/L). After reacting for 30 minutes, detecting the light absorption value at 650 nm by using an enzyme-labeling instrument and drawing a diazinon standard working curve. As shown in fig. 8, the linear range is 5-30 ng/L, y =0.008x +0.002 (R)2=0.997)。

Claims (5)

1. The application of the quantitative detection of the hydrogen peroxide based on the germanium dioxide nanoenzyme is characterized in that: the germanium dioxide nanoenzyme has the peroxidase-simulated activity, is used as a peroxidase-simulated catalyst and is applied to the quantitative detection of hydrogen peroxide based on the peroxidase-simulated activity, and the application steps of the quantitative detection of the hydrogen peroxide are as follows: the catalytic reaction system is acetate buffer solution with pH of 4, which contains 0.01-0.3 mmol/L of hydrogen peroxide, 100 mug/mL of germanium dioxide nanoenzyme and 0.5 mmol/L of 3, 3', 5, 5' -tetramethylbenzidine; after reacting for 10 minutes at the room temperature of 25 ℃, detecting the light absorption value within 300-800 nm by using a microplate reader.
2. The use of the germanium dioxide nanoenzyme for the quantitative detection of hydrogen peroxide according to claim 1, wherein the germanium dioxide nanoenzyme is synthesized by the steps of:
(1) dissolving germanium dioxide solid powder in sodium hydroxide solution under stirring, dissolving appropriate amount of cetyl trimethyl ammonium bromide in appropriate amount of distilled water under stirring, and stirring the two solutions at room temperature for 12 h respectively; (2) pouring the hexadecyl trimethyl ammonium bromide solution into the germanium dioxide alkaline solution under stirring, and continuously stirring for 8 hours at room temperature; (3) and transferring the mixture into a high-pressure reaction kettle, keeping the temperature at 100 ℃ for 56 hours, and then cooling to room temperature to obtain the germanium dioxide nanoenzyme.
3. The application of the germanium dioxide nanoenzyme-based organophosphorus pesticide detection is characterized in that the germanium dioxide nanoenzyme has peroxidase-imitated activity and is used as a peroxidase-imitated catalyst for the qualitative/quantitative detection application of the organophosphorus pesticide based on the peroxidase-imitated activity, and the qualitative/quantitative detection application of the organophosphorus pesticide comprises the following steps:
(1) incubating a phosphate buffer at pH 7.0 and a concentration of 10 mmol/L comprising 400 mU/mL acetylcholinesterase and from greater than 0 to equal to or less than 50 ng/L diazinon for 30 minutes at 37 ℃; (2) adding 10 μ L of the mixed solution into a mixture containing 0.1 mmol/L of thioacetylcholine, 100 μ g/mL of germanium dioxide nanoenzyme, 0.5 mmol/L of organic color-developing agent and 0.5 mmol/L of H2O2At a pH of 4.0 and a concentration of 100 mmol/L in acetate buffer, and further incubation at 37 ℃ for 30 minutes; (3) and (3) observing the color change of the solution to realize qualitative detection, and detecting the corresponding light absorption value of the organic color developing agent oxide by using a spectrophotometer to realize quantitative detection.
4. The application of the germanium dioxide nanoenzyme-based organophosphorus pesticide in detection is characterized in that the germanium dioxide nanoenzyme is synthesized by the following steps:
(1) dissolving germanium dioxide solid powder in sodium hydroxide solution under stirring, dissolving appropriate amount of cetyl trimethyl ammonium bromide in appropriate amount of distilled water under stirring, and stirring the two solutions at room temperature for 12 h respectively; (2) pouring the hexadecyl trimethyl ammonium bromide solution into the germanium dioxide alkaline solution under stirring, and continuously stirring for 8 hours at room temperature; (3) and transferring the mixture into a high-pressure reaction kettle, keeping the temperature at 100 ℃ for 56 hours, and then cooling to room temperature to obtain the germanium dioxide nanoenzyme.
5. The application of the germanium dioxide nanoenzyme-based organophosphorus pesticide detection method in claim 3 or 4 is characterized in that: the organophosphorus pesticide is paraoxon, parathion, phosphorus dibromide and diazinon, and the organic color developing agent is 3, 3', 5, 5' -tetramethyl benzidine, o-phenylenediamine or 2, 2' -dinitro-bis (3-ethyl benzothiazoline-6-sulfonic acid) diamine salt.
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CN109668882B (en) * 2019-02-01 2019-12-24 中南民族大学 Rapid visual detection method for organophosphorus pesticide
CN113466189B (en) * 2021-05-25 2024-03-08 青岛农业大学 Malathion colorimetric detection method based on double enzyme activity inhibition effect
CN116297419A (en) * 2022-12-02 2023-06-23 成都理工大学 A method for rapid detection of organophosphorus pesticides using a nanozyme-based 3D printing colorimetric device

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