CN109248677A - Germanium dioxide nano enzyme and its Pesticides Testing application - Google Patents

Germanium dioxide nano enzyme and its Pesticides Testing application Download PDF

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CN109248677A
CN109248677A CN201811199415.0A CN201811199415A CN109248677A CN 109248677 A CN109248677 A CN 109248677A CN 201811199415 A CN201811199415 A CN 201811199415A CN 109248677 A CN109248677 A CN 109248677A
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CN109248677B (en
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韩磊
梁欣
李峰
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Qingdao Agricultural University
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • C12Q1/00Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/34Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving hydrolase
    • C12Q1/44Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving hydrolase involving esterase
    • C12Q1/46Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving hydrolase involving esterase involving cholinesterase

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Abstract

The present invention relates to nano-catalytics, analytical chemistry field, specifically include germanium dioxide (GeO2) nano enzyme and its Pesticides Testing application.GeO2Nano enzyme has the activity of peroxidase at acidic, can catalyzing hydrogen peroxide and organicvisualization reagent generation chromogenic reaction.The present invention utilizes the GeO being prepared2Nano enzyme and acetylcholinesterase coupling realize the quantitative analysis of organophosphorus pesticide.The invention can be applied to the fields such as pesticide residue analysis, biological medicine, environmental monitoring.

Description

Germanium dioxide nano enzyme and its Pesticides Testing application
Technical field
The present invention relates to analytical chemistry fields, specifically include germanium dioxide nano enzyme and its Pesticides Testing application.
Background technique
Nano enzyme is a kind of novel analogue enztme, due to its powerful catalytic activity and in bio-sensing, food technology, ring Protect etc., which has, potentially to be had also been applied as focus of attention.Nano enzyme overcomes many disadvantages of native enzyme, such as expensive, Easy in inactivation and condition of storage require harshness etc., produce to fields such as bio-sensing, immunoassay, cancer diagnosis and treatments huge It influences.
Up to the present, a variety of inorganic nano materials (including Co3O4, CeO2, V2O5, CuO, MnO2, CuS, FeS, your gold Category, carbon (fullerene, graphene), metallo-organic framework and its composite nanostructure) all to show Mimicry enzyme (including imitative Peroxidase, imitative oxidizing ferment, imitative catalase, imitative superoxide dismutase etc.).However, not all metal oxidation Object all has Mimicry enzyme.Germanium dioxide has not been reported with Mimicry enzyme.
GeO2It is one of chromium oxide, since its is low in cost, synthesis technology is simple, and environmental stability is good, extensive For replacing graphite as anode material.Meanwhile GeO2It is a kind of important glass formers, can effectively adjusts glass The physical and chemical performance of refractive index and glass material is widely used in optical fiber core material and the design of covering material.GeO2Nano junction Structure material is with important application prospects in fields such as luminescent devices with its excellent optical property.But we not yet have found at present GeO2Nano enzyme has Mimicry enzyme.
Organophosphorus pesticide (OP) is most widely used agricultural fungicides, is improving agricultural productive force and is improving product quality Aspect plays an important role.But organophosphorus pesticide will lead to the mankind and generate a variety of diseases, such as senile dementia, Parkinson's disease With apoplexy etc..Its reason is mainly the work that organophosphorus pesticide can largely inhibit acetylcholinesterase in human body (AChE) Property, cause the excessive of acetylcholine to be enriched with and then cause related disease.Simultaneously as the high residue characteristic of organophosphorus pesticide and There are serious excessive use or non-standard operations in agricultural production, cause the high-content of pesticide on agricultural product to remain, serious prestige Coerce the health and balance of nature of the mankind.Therefore, highly sensitive detection platform is constructed, realizes the easy, quick, high of pesticide Sensitive Detection has important practical application value.So far, such as high performance liquid chromatography (HPLC), gas chromatography mass spectrometry (GC-MS), electrification Credit analysis and colorimetric etc. have been applied to the sensing detection of organophosphorus pesticide.But these methods often have lower sensitivity With the longer operating time, special professional is needed, and dependent on expensive large-scale instrument.These factors seriously limit Large-scale application of the above method in Detecting Pesticide field.In conclusion the GeO with Mimicry enzyme2Nano enzyme There is novelty in place field, and have not been reported at present based on GeO2The detection of organic phosphorus pesticide of nano enzyme.
Summary of the invention
The object of the present invention is to provide a kind of germanium dioxide nano enzyme and its applications in terms of Pesticides Testing.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of nano enzyme material and its application, the nano enzyme material GeO2Nano enzyme has imitative peroxidase activity.
Preferably, the imitative peroxidase material GeO2Nano enzyme synthesis process are as follows:
(1) under stiring by GeO2Solid powder is dissolved in sodium hydroxide solution, then by suitable cetyl trimethyl Ammonium bromide (CTAB) is dissolved under stiring in appropriate distilled water, and 12 h are stirred at room temperature in two solution respectively;(2) it is stirring It is lower that CTAB solution is poured into GeO2In alkaline solution, continue to stir 8 h at room temperature;(3) mixture is transferred to reaction under high pressure In kettle, in 100 DEG C of 56 h of holding, then cool to room temperature.Up to germanium dioxide (GeO2) nano enzyme.
It is further preferred, the imitative peroxidase material GeO2Nano enzyme can be used as imitative Catalyzed Synthesis By Peroxidase agent, For the application based on imitative peroxidase activity.
It is still further preferably the imitative peroxidase material GeO2Nano enzyme is in acid condition as with peroxide The catalyst of compound enzymatic activity, for carrying out qualitative/quantitative detection to organophosphorus pesticide, steps are as follows:
(1) will delay comprising the phosphate of organic phosphorus (0 50 ng/L) of acetylcholinesterase (400 mU/mL) and various concentration Fliud flushing (7.0,10 mmol/L of pH) is incubated for 30 minutes at 37 DEG C;(2) take the 10 above-mentioned mixed liquors of μ L in containing a certain amount of GeO described in acetylthiocholine (0.1 mmol/L), claim 132Nano enzyme (100 μ g/mL), organicvisualization reagent (0.5 mmol/L), H2O2In the acetate buffer (4.0,100 mmol/L of pH) of (0.5 mmol/L), continue at 37 DEG C It is incubated for 30 minutes;(3) variation of observation solution colour detects organicvisualization reagent oxygen using spectrophotometer to realize qualitative detection The corresponding light absorption value of compound realizes quantitative detection.
It is still more preferably the GeO2Nano enzyme can be used for detecting organophosphorus pesticide, the organophosphorus pesticide It can be the organophosphorus pesticides such as paraoxon, parathion, 2-dichloroethylk dimethyl phosphate, basudin;The organicvisualization reagent is the 2,2 '-connection bis- (3- of nitrogen- Ethyl benzo thiazole phenanthroline -6- sulfonic acid) diamine salts (ABTS), o-phenylenediamine (OPD) or 3,3 ', 5,5 '-tetramethyl benzidines (TMB).
Effect of the invention is:
1. the present invention has synthesized the GeO with peroxidase activity2Nano enzyme, and optimal pH is 4.0 or so, in acidity (pH 3.5 5.0) shows the activity of peroxidase under the conditions of pH.
2. the GeO that the present invention synthesizes2Nano enzyme shows the property different from imitative peroxidase nano material has been reported Matter --- stability is low: activity drastically reduces at the pH below or above pH 3.5 5.0, is being below or above pH 3.5 5.0 pH stability inferior is substantially reduced.
3. the present invention utilizes GeO2The imitative peroxidase activity of nano enzyme and low stability, by GeO2Nano enzyme is applied to The qualitative quantitative analysis of organophosphorus pesticide is realized and is detected using qualitative/quantitative of the spectrophotometry to organophosphorus pesticide.
4. the present invention provides the materials for playing Mimicry enzyme, in Detecting Pesticide, food safety, environmental monitoring etc. Aspect has broad application prospects.
Detailed description of the invention
Fig. 1 is GeO provided in an embodiment of the present invention2The transmission electron microscope figure of nano enzyme;
Fig. 2 is GeO provided in an embodiment of the present invention2Nano enzyme Mimicry enzyme effect picture;
Fig. 3 is GeO provided in an embodiment of the present invention2The pH effect of optimization figure of nano enzyme Mimicry enzyme;
Fig. 4 is GeO provided in an embodiment of the present invention2The pH stability analysis figure of nano enzyme Mimicry enzyme;
Fig. 5 is H provided in an embodiment of the present invention2O2Quantitative measurement standard working curve;
Fig. 6 is detection of organic phosphorus pesticide schematic diagram provided in an embodiment of the present invention;
Fig. 7 is the qualitative detection photo of organophosphorus pesticide basudin provided in an embodiment of the present invention;
Fig. 8 is the quantitative measurement standard working curve of organophosphorus pesticide basudin provided in an embodiment of the present invention.
Specific embodiment
Illustrate the contents of the present invention deeper into ground to become apparent from, will further enumerate some embodiments, but this hair below It is bright to be not limited to cited embodiment.Specific experiment condition or method are such as not specified in the following example, by this field Normal condition or method carry out.
Embodiment 1
Imitative peroxidase material GeO2The preparation of nano enzyme:
By 1.06 g GeO2Solid powder is added in 10 mL sodium hydroxide solutions, by the cetyl trimethyl bromine of 1.46 g Change ammonium (CTAB) to be dissolved in 12 mL distilled water, 12 h are stirred at room temperature in two solution respectively.Then CTAB solution is poured into GeO2In alkaline solution, 8 h are stirred at room temperature.Finally mixture is transferred in autoclave, in 100 DEG C of 56 h of holding, so After be cooled to room temperature.Up to the germanium dioxide (GeO with triangular structure2) nano enzyme.Fig. 1 is to pass through transmission electron microscope The GeO observed2The TEM of nano enzyme is imaged.
Embodiment 2
GeO2The Mimicry enzyme of nano enzyme is verified:
Experimental system a: catalystic converter system is to include H2O2The GeO that (0.15 mmol/L), above-described embodiment obtain2Nano enzyme (100 μ g/mL), organicvisualization reagent TMB(0.5 mmol/L) acetate buffer (4.0,100 mmol/L of pH).In room After reacting 30 minutes under warm (25 DEG C), the light absorption value in its 450 800 nm is detected using microplate reader;
It separately does two check experiments: GeO is not added in the catalystic converter system of one of control experiment b2Nano enzyme, with it is above-mentioned Light absorption value is detected after reacting 30 minutes under experimental system similarity condition;The catalystic converter system of another control experiment c is GeO2 Nano enzyme (100 μ g/mL) at acetate buffer (4.0,100 mmol/L of pH), with above-mentioned experimental system similarity condition Lower standing detected light absorption value after 30 minutes;
As shown in Fig. 2, experimental system a shows apparent peak, illustrate GeO2Nano enzyme has at pH 4.0 significantly to be imitated The activity of oxide enzyme;Check experiment b near 650 nm without apparent peak, if illustrating without GeO2Nano enzyme makees catalyst for nothing Significant reaction;Check experiment c, without apparent peak, illustrates that the peak of experimental system a is not GeO near 650 nm2Nano enzyme itself Response peak.
Embodiment 3
GeO2The pH of nano enzyme Mimicry enzyme optimizes:
Catalystic converter system is to include H2O2(0.3 mmol/L), GeO2Nano enzyme (100 μ g/mL), organicvisualization reagent TMB Buffer (pH 1.0 2.0, the glycine-HCI buffer of the different pH of (0.5 mmol/L);PH 3.0 6.0, acetic acid-vinegar Sour sodium buffer;PH 6.5 8.0, phosphate buffer;PH 9.0 10.0, Tris hydrochloride buffer;PH 11.0 12.0, Sodium bicarbonate-sodium hydrate buffer solution).After being reacted 30 minutes under room temperature (25 DEG C), detected at its 650 nm using microplate reader Light absorption value.As shown in figure 3, GeO2Nano enzyme shows the activity of peroxidase at acidic (pH 3.5 5.0), and And optimal pH is 4.0 or so.
Embodiment 4
GeO2The pH stability of nano enzyme Mimicry enzyme:
Catalystic converter system is to include GeO2Buffer (the pH 1.0 12.0,10 of nano enzyme (100 μ g/mL), difference pH Mmol/L), after being incubated for 1h under room temperature (25 DEG C), organicvisualization reagent TMB(0.5 mmol/L is added), H2O2(0.3 mmol/L) And acetate buffer (4.0,100 mmol/L of pH).Continuation utilizes microplate reader after reacting 30 min under room temperature (25 DEG C) Detect the light absorption value in its 650 nm.As shown in figure 4, GeO2For nano enzyme at 3.0 8.0 pH, Mimicry enzyme is most stable, and Optimal pH is 4.0 or so.
Embodiment 5
H2O2Quantitative detection:
Catalystic converter system is the H comprising various concentration2O2(0.01 0.3 mmol/L), GeO2Nano enzyme (100 μ g/mL) has Machine color developing agent TMB(0.5 mmol/L) acetate buffer (4.0,100 mmol/L of pH).It is reacted under room temperature (25 DEG C) After ten minutes, the light absorption value in its 300 800 nm is detected using microplate reader.After deducting blank control by 650 nm light absorption values Draw out H2O2Standard working curve.As shown in figure 5, the range of linearity 0.01 0.15 mmol/L, y=1.97x+0.05 (R2= 0.9955)。
Embodiment 6
The qualitative detection of basudin:
Acetylthiocholine can generate mercaptoacetyl choline under acetylcholine ester enzymatic, can be with GeO2Nanometer enzyme reaction generates Ge3+, to make GeO2The Mimicry enzyme of nano enzyme disappears.Organophosphorus pesticide can inhibit the activity of acetylcholinesterase, thus nothing Method generates mercaptoacetyl choline, will not inhibit GeO2The Mimicry enzyme of nano enzyme, to realize the quantitative inspection of organophosphorus pesticide It surveys.Fig. 6 is the detection schematic diagram of organophosphorus pesticide.Catalystic converter system is comprising acetylcholinesterase (400 mU/mL) and not With the phosphate buffer (7,10 mmol/L of pH) of the basudin (0 50 ng/L) of concentration.It is incubated for 30 minutes at 37 DEG C Afterwards, take the above-mentioned mixed liquor of 10 μ L that a certain amount of acetylthiocholine (0.1 mmol/L), GeO is added2Nano enzyme (100 μ g/ ML), organicvisualization reagent TMB(0.5 mmol/L), H2O2(0.5 mmol/L), acetate buffer (4.0,100 mmol/ of pH L).30 min are incubated at 37 DEG C, as shown in fig. 7, observation color change.Solution colour is successively deepened, and illustrates GeO2Nano enzyme It can detecte organophosphorus pesticide.
Embodiment 7
The quantitative detection of basudin:
Catalystic converter system is the basudin (0 50 ng/L) comprising acetylcholinesterase (400 mU/mL) and various concentration After phosphate buffer (7.0,10 mmol/L of pH) is incubated for 30 minutes at 37 DEG C, the above-mentioned mixed liquor of 10 μ L is taken to be added one Quantitative acetylthiocholine (0.1 mmol/L), GeO2Nano enzyme (100 μ g/mL), organicvisualization reagent TMB(0.5 mmol/ L), H2O2(0.5 mmol/L), acetate buffer (4.0,100 mmol/L of pH).After reaction 30 minutes, examined using microplate reader The light absorption value surveyed at its 650 nm simultaneously draws out basudin standard working curve.As shown in figure 8, the range of linearity 5 30 ng/L, y= 0.008x+0.002 (R2=0.997)。

Claims (5)

1. a kind of germanium dioxide (GeO2) nano enzyme, it is characterised in that: the GeO2Nano enzyme has imitative peroxidase activity.
2. germanium dioxide (GeO according to claim 12) nano enzyme, it is characterised in that synthesis step is as follows:
(1) under stiring by GeO2Solid powder is dissolved in sodium hydroxide solution, then by suitable cetyl trimethyl Ammonium bromide (CTAB) is dissolved under stiring in appropriate distilled water, and 12 h are stirred at room temperature in two solution respectively;(2) it is stirring It is lower that CTAB solution is poured into GeO2In alkaline solution, continue to stir 8 h at room temperature;(3) that mixture is transferred to high pressure is anti- It answers in kettle, in 100 DEG C of 56 h of holding, then cools to room temperature to get germanium dioxide (GeO2) nano enzyme.
3. according to claim 1, one kind described in 2 is based on GeO2The application of nano enzyme, it is characterised in that: institute in claim 1,2 State GeO2Nano enzyme can be used as imitative Catalyzed Synthesis By Peroxidase agent, for the application based on imitative peroxidase activity.
4. one kind is based on GeO2The application of the detection of organic phosphorus pesticide of nano enzyme, it is characterised in that organophosphorus pesticide qualitative/quantitative inspection The step of surveying application is as follows:
(1) phosphate-buffered of the basudin (0 50 ng/L) of acetylcholinesterase (400 mU/mL) and various concentration will be included Liquid (7.0,10 mmol/L of pH) is incubated for 30 minutes at 37 DEG C;(2) take the 10 above-mentioned mixed liquors of μ L in containing a certain amount of sulphur For GeO described in acetylcholine (0.1 mmol/L), claim 132Nano enzyme (100 μ g/mL), organicvisualization reagent (0.5 Mmol/L), H2O2In the acetate buffer (4.0,100 mmol/L of pH) of (0.5 mmol/L), continuation is incubated at 37 DEG C 30 minutes;(3) variation of observation solution colour utilizes spectrophotometer detection organicvisualization reagent oxide to realize qualitative detection Corresponding light absorption value realizes quantitative detection.
5. according to claim 4 a kind of based on GeO2The application of the detection of organic phosphorus pesticide of nano enzyme, it is characterised in that: The organophosphorus pesticide can be the organophosphorus pesticides such as paraoxon, parathion, 2-dichloroethylk dimethyl phosphate, basudin, the organic chromogenic Agent is 3,3 ', 5,5 '-tetramethyl benzidines (TMB), o-phenylenediamine (OPD) or 2,2 '-connection bis- (the 3- ethyl benzo thiazole phenanthrolines-of nitrogen- 6- sulfonic acid) diamine salts (ABTS).
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Cited By (2)

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CN109668882A (en) * 2019-02-01 2019-04-23 中南民族大学 A kind of organophosphorus insecticide quick visualization detection method
CN113466189A (en) * 2021-05-25 2021-10-01 青岛农业大学 Malathion colorimetric detection method based on double-enzyme activity inhibition effect

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