CN107202822A - The preparation of Nano Silver/carbon nano tube modified electrode aurantiin molecular engram sensor - Google Patents
The preparation of Nano Silver/carbon nano tube modified electrode aurantiin molecular engram sensor Download PDFInfo
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- CN107202822A CN107202822A CN201710379760.1A CN201710379760A CN107202822A CN 107202822 A CN107202822 A CN 107202822A CN 201710379760 A CN201710379760 A CN 201710379760A CN 107202822 A CN107202822 A CN 107202822A
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Abstract
The invention discloses a kind of preparation of Nano Silver/carbon nano tube modified electrode aurantiin molecular engram sensor, first using Nano Silver/carbon nano tube modified glass-carbon electrode, Nano Silver/carbon nano tube modified electrode is made；Then in the reactor, it is separately added into, ethanol：52 ~ 62%, dipentaerythritol triacrylate：8 ~ 15%, itaconic acid：The ethyl imidazol(e) hexafluorophosphate of 5 ~ 10%, 1 acrylic 3：10 ~ 18%, azodiisobutyronitrile：1.0 ~ 3.0%, aurantiin：4.0 ~ 10%, anaerobic atmosphere, 60 ± 2 DEG C of 18 ~ 24h of stirring reaction remove template molecule using methanol and acetic acid mixed solution, produce aurantiin molecularly imprinted polymer；Again by molecularly imprinted polymer drop coating to Nano Silver/carbon nano tube modified electrode, aurantiin molecular engram sensor is obtained.The sensor has high compatibility and selectivity.With sensitivity height, specificity is good, detect quick, can Reusability.
Description
Technical field
The present invention relates to a kind of preparation method of molecular engram sensor and quick detection applied technical field, especially
It is related to a kind of preparation method of Nano Silver/carbon nano tube modified electrode aurantiin molecular engram sensor, for detecting medicine, food
Aurantiin in product, biological sample.
Background technology
Aurantiin（Alias：Naringin, naringin, aurantiin）, its molecular formula is C27H32O14, relative molecular mass is
580.53, white is dissolved under methanol, ethanol, acetone, acetic acid, dilute alkaline soln and hot water, normal temperature to Light yellow crystals powder,
Solubility in water is 0.1%, up to 10% at 75 DEG C.Insoluble in non-polar solvens such as petroleum ether, ether, benzene and chloroforms.Shaddock
Skin glycosides is a kind of Flavanones compound.Due to not being conjugated completely between A rings and B rings, so there is strong purple in 282nm
Outer absworption peak, makes aurantiin show various biological activity and pharmacological action.With anti-inflammatory, antiviral, anticancer, anti-mutation, anti-
Allergy, antiulcer, analgesia, hypotensive activity, can hypercholesterolemia, the formation of reduction thrombus, improvement local microcirculation and nutrition
Supply, cardiovascular and cerebrovascular disease is prevented and treated available for production.Naringin has obvious antiinflammatory action, the naringin pair of 200mg/l concentration
Vesicular stomatitis virus has very strong inhibitory action；Reduce the viscosity of blood, reduce the formation of thrombus, and have analgesia, town
Quiet and stronger increase experimental animal choleresis；There are desensitization and antiallergy, blood circulation promoting spasmolysis, improve local microcirculation and nutrition
The performance of supply, infringement, the toxic side effect of alleviation streptomysin to promotion excretion of drug, releasing streptomysin to the 8th pair of cranial nerve
There is unique curative effect；Naringin is in the basic conditions, oxidation-treated, can obtain dihydrochalcone sweetener, and its sugariness is sucrose
1000 times.Naringin is acted on isovanillin, obtains neohesperidin, neohesperidin is 950 times of dihydrochalcone sugariness, is one
Plant nontoxic, low energy, the sweetener of new generation of high sugariness.
At present, the method for detection aurantiin mainly has high performance liquid chromatography, liquid chromatography-mass spectrography, the chromatographic degree of accuracy
By a definite limitation and instrument is somewhat expensive needs professional to operate, its application also limit.Further, since aurantiin with
It is difficult to separate that other flavonoids molecular structures are very close, is interfered with each other during measure, and accurate detection aurantiin is highly difficult.Therefore,
Find that a kind of selectivity is good, sensitivity is high, the method for the detection aurantiin easy to operate being used for has important use value.
Molecular imprinting technology is one of the current main method of high selectivity material of exploitation with molecular recognition function, it
It is by forming a highly cross-linked rigid macromolecule around template molecule, removing after template molecule in molecular engram polymerization
The recognition site with binding ability is left in the network structure of thing, one kind of high selection recognition performance is shown to template molecule
Technology.This technology imitates precordainment with its structure and specific recognition is increasingly paid close attention to by people, has been used successfully to solid phase
Extraction or micro- SPE, the field such as affinity chromatography or Capillary Electrophoresis and sensor.
The molecular engram sensor prepared according to this technology, applied to Pharmaceutical Analysis, environmental protection and life science
In play a very important role.Functional molecular is modified on electrode in a suitable manner, prepare selectivity good, sensitivity it is high,
There is the reproducible electrochemical sensor of certain service life to turn into the problem that analysis science worker makes great efforts to explore.But it is traditional
Trace film thickness prepared by immunoblot method is difficult to control to, and high-crosslinking-degree causes electron transmission speed and low-response, Monitoring lower-cut
Height, application of the influence molecular imprinting technology in electrochemical sensor.Therefore, a kind of sensitive, quick, easy, specificity is set up
The detection method that high, reproducible economy is used, is determined to the naringin content accurate quantitative analysis in food, medicine, biological sample
It is very necessary.
The content of the invention
The purpose of the present invention is that molecular engram is combined to there is provided a kind of aurantiin molecular engram with electrochemical sensor
The preparation method of electrochemical sensor, mainly using aurantiin as template, glassy carbon electrode surface by oxide/carbon nanometer tube, receive
The modification of rice silver particles, improves the sensitivity of sensor, and aurantiin molecular imprinting electrochemical sensing is prepared using drop coating legal system
Device.
Instrument and reagent
CHI660B electrochemical workstations（Shanghai Chen Hua instrument company）, test and use three-electrode system：Platinum electrode is auxiliary electricity
Pole, Ag/AgCl is reference electrode（SCE）, glass-carbon electrode（GCE）For working electrode；KQ-250E type ultrasonic cleaners（Female peak
Ultrasonic instrument Co., Ltd）.
Oxide/carbon nanometer tube；Pentaerythritol triacrylate (PETA), itaconic acid；1- acrylic -3- ethyl imidazol(e) hexafluoros
Phosphate, azodiisobutyronitrile, absolute ethyl alcohol；Aurantiin；Silver nitrate；Gelatin；Phosphate buffer solution；Agents useful for same is analysis
Pure, experimental water is redistilled water.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of Nano Silver/carbon nano tube modified electrode aurantiin molecular engram sensor, is characterised by, should
Method has following processing step：
（1）It is prepared by Nano Silver/carbon nano tube modified liquid：In the reactor, added by following composition mass percentage concentration, deionization
Water：78 ~ 84%, silver nitrate：2.0 ~ 5.0%, oxide/carbon nanometer tube：3 ~ 8%, ultrasound 20min, is uniformly dispersed, adds matter at room temperature
Amount percentage concentration is 20% hydrazine hydrate：10 ~ 15%, each component content sum is a hundred per cent, and stirring reaction 20min is stood overnight,
Obtain Nano Silver/carbon nano tube modified liquid；
（2）It is prepared by Nano Silver/carbon nano tube modified electrode：Glass-carbon electrode is subjected to surface with 0.2 μm, 0.01 μm of polishing powder successively
Polishing, is then cleaned by ultrasonic with redistilled water respectively, and L nanometers of 15 ~ 18 μ is added dropwise in glassy carbon electrode surface in ethanol washing, drying
Gold-graphene decorating liquid, is placed under infrared lamp, volatilizees after dry solvent, produces Nano Silver/carbon nano tube modified electrode；
（3）The preparation of aurantiin molecularly imprinted polymer：In the reactor, added by following composition mass percentage concentration, ethanol：
52 ~ 62%, dipentaerythritol triacrylate：8 ~ 15%, itaconic acid：5 ~ 10%, 1- acrylic -3- ethyl imidazol(e) hexafluorophosphates：
10 ~ 18%, azodiisobutyronitrile：1.0 ~ 3.0%, aurantiin：4.0 ~ 10%, each component content sum is absolutely, stirring is molten
Solution, leads to the min of inert gas deoxygenation 15, anaerobic atmosphere, 60 ± 2 DEG C of 18 ~ 24h of stirring reaction, by obtained product methanol：Second
Sour volume ratio is 3:1 mixed solution soaks 12 ~ 15h, removes template molecule, dries, produces aurantiin molecularly imprinted polymer；
（4）The preparation method of aurantiin molecular imprinting electrochemical sensor：Appropriate aurantiin molecularly imprinted polymer is taken to disperse
In 1% gelatin solution, 20g/L aurantiin imprinted polymer solution is made；Then by the above-mentioned μ L drops of solution 15 ~ 20
It is added to step（2）Nano Silver/carbon nano tube modified electrode of preparation, is placed under infrared lamp, volatilizees after dry solvent, produces aurantiin
Molecular imprinting electrochemical sensor.
In step（1）Described in silver nitrate and oxide/carbon nanometer tube mass ratio be 1：2 ~ 3 is optimal.
In step（3）Described in dipentaerythritol triacrylate：Itaconic acid：1- acrylic -3- ethyl imidazol(e) hexafluoros
Phosphatic mole is 1：1：1 is optimal.
In step（3）Described in inert gas be neon or argon gas.
In step（3）Described in anaerobic atmosphere be passed through inert gas always for polymerization process.
Advantages of the present invention and effect are：
Engram technology, LBL self-assembly method and drop-coating are combined by the present invention, in Nano Silver/carbon nano tube modified glass-carbon electrode
Surface successfully have developed a kind of aurantiin trace electrochemical sensor with specific selectivity.By being received with Nano Silver/carbon
The response of that of the molecular engram electrode of mitron modification is compared, the sound of aurantiin molecular engram sensor prepared by the present invention
It should greatly improve.The trace sensor shows higher compatibility and selectivity to aurantiin, response current and aurantiin
Concentration is 1.0 × 10-7~2.0×10-4It is in good linear relationship in the range of mol/L, detection is limited to 2.16 × 10-8Mol/L will
Aurantiin molecular imprinting electrochemical sensor prepared by the present invention is used successfully to the inspection of aurantiin in medicine, food, biological sample
In survey, the rate of recovery is between 96.52 ~ 104.12%, therefore aurantiin molecular engram sensor prepared by the present invention can extensive use
In association areas such as chemical industry, biological medicine, food, environmental protection tests.
Embodiment
Embodiment 1
（1）It is prepared by Nano Silver/carbon nano tube modified liquid：In the reactor, it is separately added into, deionized water：8 mL, silver nitrate：
0.3g, oxide/carbon nanometer tube：0.6g, ultrasound 20min, is uniformly dispersed at room temperature, 20% hydrazine hydrate：1.1 mL, stirring reaction
20min, stands overnight, and obtains Nano Silver/carbon nano tube modified liquid；
（2）It is prepared by Nano Silver/carbon nano tube modified electrode：Glass-carbon electrode is subjected to surface with 0.2 μm, 0.01 μm of polishing powder successively
Polishing, is then cleaned by ultrasonic with redistilled water respectively, and 16 μ L nanogold are added dropwise in glassy carbon electrode surface in ethanol washing, drying
Graphene modified liquid, is placed under infrared lamp, volatilizees after dry solvent, produces Nano Silver/carbon nano tube modified electrode；
（3）The preparation of aurantiin molecularly imprinted polymer：In the reactor, it is separately added into, ethanol：72 mL, dipentaerythritol three
Acrylate：12g, itaconic acid：8g, 1- acrylic -3- ethyl imidazol(e) hexafluorophosphates：14g, azodiisobutyronitrile：2.0g, shaddock
Skin glycosides：7g, stirring and dissolving leads to the min of inert gas deoxygenation 15, anaerobic atmosphere, 60 ± 2 DEG C of stirring reaction 20h, by obtained production
Thing methanol：Acetic acid volume ratio is 3:1 mixed solution soaks 13h, removes template molecule, dries, produces aurantiin molecular engram
Polymer；
（4）The preparation method of aurantiin molecular imprinting electrochemical sensor：Appropriate aurantiin molecularly imprinted polymer is taken to disperse
In 1% gelatin solution, 20g/L aurantiin imprinted polymer solution is made；Then the above-mentioned μ L of solution 16 are added dropwise
To step（2）Nano Silver/carbon nano tube modified electrode of preparation, is placed under infrared lamp, after the dry solvent that volatilizees, produces aurantiin point
Sub- trace electrochemical sensor.
Embodiment 2
（1）It is prepared by Nano Silver/carbon nano tube modified liquid：In the reactor, it is separately added into, deionized water：7.8 mL, silver nitrate：
0.2g, oxide/carbon nanometer tube：0.5g, ultrasound 20min, is uniformly dispersed at room temperature, 20% hydrazine hydrate：1.5 mL, stirring reaction
20min, stands overnight, and obtains Nano Silver/carbon nano tube modified liquid；
（2）It is prepared by Nano Silver/carbon nano tube modified electrode：Glass-carbon electrode is subjected to surface with 0.2 μm, 0.01 μm of polishing powder successively
Polishing, is then cleaned by ultrasonic with redistilled water respectively, and 17 μ L nanogold are added dropwise in glassy carbon electrode surface in ethanol washing, drying
Graphene modified liquid, is placed under infrared lamp, volatilizees after dry solvent, produces Nano Silver/carbon nano tube modified electrode；
（3）The preparation of aurantiin molecularly imprinted polymer：In the reactor, it is separately added into, ethanol：6.6mL, dipentaerythritol three
Acrylate：1.5g, itaconic acid：1.0g, 1- acrylic -3- ethyl imidazol(e) hexafluorophosphates：1.0g, azodiisobutyronitrile：
0.3g, aurantiin：1.0g, stirring and dissolving, the logical min of inert gas deoxygenation 15, anaerobic atmosphere, 60 ± 2 DEG C of stirring reaction 18h will
Obtained product methanol：Acetic acid volume ratio is 3:1 mixed solution soaks 12h, removes template molecule, dries, produces aurantiin
Molecularly imprinted polymer；
（4）The preparation method of aurantiin molecular imprinting electrochemical sensor：Appropriate aurantiin molecularly imprinted polymer is taken to disperse
In 1% gelatin solution, 20g/L aurantiin imprinted polymer solution is made；Then the above-mentioned μ L of solution 17 are added dropwise
To step（2）Nano Silver/carbon nano tube modified electrode of preparation, is placed under infrared lamp, after the dry solvent that volatilizees, produces aurantiin point
Sub- trace electrochemical sensor.
Embodiment 3
（1）It is prepared by Nano Silver/carbon nano tube modified liquid：In the reactor, it is separately added into, deionized water：8.4mL, silver nitrate：
0.3g, oxide/carbon nanometer tube：0.3g, ultrasound 20min, is uniformly dispersed at room temperature, 20% hydrazine hydrate：1.0 mL, stirring reaction
20min, stands overnight, and obtains Nano Silver/carbon nano tube modified liquid；
（2）It is prepared by Nano Silver/carbon nano tube modified electrode：Glass-carbon electrode is subjected to surface with 0.2 μm, 0.01 μm of polishing powder successively
Polishing, is then cleaned by ultrasonic with redistilled water respectively, and 15 μ L nanogold are added dropwise in glassy carbon electrode surface in ethanol washing, drying
Graphene modified liquid, is placed under infrared lamp, volatilizees after dry solvent, produces Nano Silver/carbon nano tube modified electrode；
（（3）The preparation of aurantiin molecularly imprinted polymer：In the reactor, it is separately added into, ethanol：7.8mL, dipentaerythritol
Triacrylate：0.8g, itaconic acid：0.8g, 1- acrylic -3- ethyl imidazol(e) hexafluorophosphates：1.8g, azodiisobutyronitrile：
0.1g, aurantiin：0.6g, stirring and dissolving, the logical min of inert gas deoxygenation 15, anaerobic atmosphere, 60 ± 2 DEG C of stirring reaction 24h will
Obtained product methanol：Acetic acid volume ratio is 3:1 mixed solution soaks 14h, removes template molecule, dries, produces aurantiin
Molecularly imprinted polymer；
（4）The preparation method of aurantiin molecular imprinting electrochemical sensor：Appropriate aurantiin molecularly imprinted polymer is taken to disperse
In 1% gelatin solution, 20g/L aurantiin imprinted polymer solution is made；Then the above-mentioned μ L of solution 20 are added dropwise
To step（2）Nano Silver/carbon nano tube modified electrode of preparation, is placed under infrared lamp, after the dry solvent that volatilizees, produces aurantiin point
Sub- trace electrochemical sensor.
Embodiment 4
（1）It is prepared by Nano Silver/carbon nano tube modified liquid：In the reactor, it is separately added into, deionized water：8 .2mL, silver nitrate：
0.2g, oxide/carbon nanometer tube：0.6g, ultrasound 20min, is uniformly dispersed at room temperature, 20% hydrazine hydrate：1.0 mL, stirring reaction
20min, stands overnight, and obtains Nano Silver/carbon nano tube modified liquid；
（2）It is prepared by Nano Silver/carbon nano tube modified electrode：Glass-carbon electrode is subjected to surface with 0.2 μm, 0.01 μm of polishing powder successively
Polishing, is then cleaned by ultrasonic with redistilled water respectively, and 12 μ L nanogold are added dropwise in glassy carbon electrode surface in ethanol washing, drying
Graphene modified liquid, is placed under infrared lamp, volatilizees after dry solvent, produces Nano Silver/carbon nano tube modified electrode；
（3）The preparation of aurantiin molecularly imprinted polymer：In the reactor, it is separately added into, ethanol：7.6mL, dipentaerythritol three
Acrylate：1.0g, itaconic acid：0.7g, 1- acrylic -3- ethyl imidazol(e) hexafluorophosphates：1.7g, azodiisobutyronitrile：
0.2g, aurantiin：0.4g, stirring and dissolving, the logical min of inert gas deoxygenation 15, anaerobic atmosphere, 60 ± 2 DEG C of stirring reaction 19h will
Obtained product methanol：Acetic acid volume ratio is 3:1 mixed solution soaks 15h, removes template molecule, dries, produces aurantiin
Molecularly imprinted polymer；
（4）The preparation method of aurantiin molecular imprinting electrochemical sensor：Appropriate aurantiin molecularly imprinted polymer is taken to disperse
In 1% gelatin solution, 20g/L aurantiin imprinted polymer solution is made；Then the above-mentioned μ L of solution 15 are added dropwise
To step（2）Nano Silver/carbon nano tube modified electrode of preparation, is placed under infrared lamp, after the dry solvent that volatilizees, produces aurantiin point
Sub- trace electrochemical sensor.
Embodiment 5
By the aurantiin molecular imprinting electrochemical sensor prepared by above-described embodiment 1 ~ 4, for the detection of aurantiin, step is such as
Under：
（1）Standard liquid is prepared：The aurantiin standard liquid of one group of various concentrations including blank standard specimen is prepared, bottom liquid is
PH7.2 phosphate buffer solution；
（2）Working curve is drawn：It is reference electrode by Ag/AgCl, platinum electrode is auxiliary electrode, electrode prepared by the present invention is
Working electrode constitutes three-electrode system, CHI660B electrochemical workstations is connected, in K3[Fe(CN)6] in solution, lied prostrate using circulation
Peace method is detected that the response current of blank standard specimen is designated as in -0.20 ~ 1.0V potential rangesI 0 , the shaddock containing various concentrations
The response current of skin glycosides standard liquid isI i , response current reduction difference be△I=I 0 -I i ,△IIt is molten with aurantiin standard
The mass concentration of liquidcBetween it is linear, draw△I ~cWorking curve；
（3）The detection of aurantiin：Step is replaced with testing sample（1）In aurantiin standard liquid, according to step（2）Method
Detected, the difference reduced according to response current△IAnd working curve, obtain the content of aurantiin in testing sample；
The K3[Fe(CN)6] solution concentration be 6.0mmol/L；
The concentration of the phosphate buffer solution of the pH7.2 is in 20m mol/L.
Claims (6)
1. a kind of preparation of Nano Silver/carbon nano tube modified electrode aurantiin molecular engram sensor, is characterised by, this method tool
There is following processing step：
（1）It is prepared by Nano Silver/carbon nano tube modified liquid：In the reactor, added by following composition mass percentage concentration, deionization
Water：78 ~ 84%, silver nitrate：2.0 ~ 5.0%, oxide/carbon nanometer tube：3 ~ 8%, ultrasound 20min, is uniformly dispersed, adds matter at room temperature
Amount percentage concentration is 20% hydrazine hydrate：10 ~ 15%, each component content sum is a hundred per cent, and stirring reaction 20min is stood overnight,
Obtain Nano Silver/carbon nano tube modified liquid；
（2）It is prepared by Nano Silver/carbon nano tube modified electrode：Glass-carbon electrode is subjected to surface with 0.2 μm, 0.01 μm of polishing powder successively
Polishing, is then cleaned by ultrasonic with redistilled water respectively, and L nanometers of 15 ~ 18 μ is added dropwise in glassy carbon electrode surface in ethanol washing, drying
Gold-graphene decorating liquid, is placed under infrared lamp, volatilizees after dry solvent, produces Nano Silver/carbon nano tube modified electrode；
（3）The preparation of aurantiin molecularly imprinted polymer：In the reactor, added by following composition mass percentage concentration, ethanol：
52 ~ 62%, dipentaerythritol triacrylate：8 ~ 15%, itaconic acid：5 ~ 10%, 1- acrylic -3- ethyl imidazol(e) hexafluorophosphates：
10 ~ 18%, azodiisobutyronitrile：1.0 ~ 3.0%, aurantiin：4.0 ~ 10%, each component content sum is absolutely, stirring is molten
Solution, leads to the min of inert gas deoxygenation 15, anaerobic atmosphere, 60 ± 2 DEG C of 18 ~ 24h of stirring reaction, by obtained product methanol：Second
Sour volume ratio is 3:1 mixed solution soaks 12 ~ 15h, removes template molecule, dries, produces aurantiin molecularly imprinted polymer；
（4）The preparation of aurantiin molecular imprinting electrochemical sensor：Appropriate aurantiin molecularly imprinted polymer is taken to be scattered in 1%
Gelatin solution in, be made 20g/L aurantiin imprinted polymer solution；Then the above-mentioned μ L of solution 15 ~ 20 are added drop-wise to
Step（2）Nano Silver/carbon nano tube modified electrode of preparation, is placed under infrared lamp, volatilizees after dry solvent, produces aurantiin molecule
Trace electrochemical sensor.
2. a kind of system of Nano Silver according to claim 1/carbon nano tube modified electrode aurantiin molecular engram sensor
It is standby, it is characterised by, step（1）Described in silver nitrate and oxide/carbon nanometer tube mass ratio be 1：2 ~ 3 is optimal.
3. a kind of system of Nano Silver according to claim 1/carbon nano tube modified electrode aurantiin molecular engram sensor
It is standby, it is characterised by, step（3）Described in dipentaerythritol triacrylate：Itaconic acid：1- acrylic -3- ethyl imidazol(e)s six
Fluorophosphate mole be 1：1：1 is optimal.
4. a kind of system of Nano Silver according to claim 1/carbon nano tube modified electrode aurantiin molecular engram sensor
It is standby, it is characterised by, step（3）Described in inert gas be neon or argon gas.
5. a kind of system of Nano Silver according to claim 1/carbon nano tube modified electrode aurantiin molecular engram sensor
It is standby, it is characterised by, step（3）Described in anaerobic atmosphere be passed through inert gas always for polymerization process.
6. a kind of system of Nano Silver according to claim 1/carbon nano tube modified electrode aurantiin molecular engram sensor
Aurantiin molecular engram sensor prepared by Preparation Method.
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Cited By (6)
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| CN108760849A (en) * | 2018-06-19 | 2018-11-06 | 孙大明 | A kind of preparation method of the molecularly imprinted polymer modified electrode of quick detection Ofloxacin |
| CN109001285A (en) * | 2018-08-29 | 2018-12-14 | 济南大学 | A kind of preparation method of prometryn molecular engram sensor |
| CN109142498A (en) * | 2018-08-29 | 2019-01-04 | 济南大学 | A kind of preparation method of paraquat molecular engram sensor |
| CN109324097A (en) * | 2018-10-11 | 2019-02-12 | 大连大学 | A kind of electrode and its application for melamine measurement |
| CN111551618A (en) * | 2020-04-09 | 2020-08-18 | 济南大学 | Preparation method of sirolimus molecularly imprinted erbium nitride composite paste electrode |
| CN115096976A (en) * | 2022-06-20 | 2022-09-23 | 商丘师范学院 | Silver cluster/nitrogen-doped carbon electrode material and in-situ limited synthesis method and application thereof |
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| CN108760849A (en) * | 2018-06-19 | 2018-11-06 | 孙大明 | A kind of preparation method of the molecularly imprinted polymer modified electrode of quick detection Ofloxacin |
| CN109001285A (en) * | 2018-08-29 | 2018-12-14 | 济南大学 | A kind of preparation method of prometryn molecular engram sensor |
| CN109142498A (en) * | 2018-08-29 | 2019-01-04 | 济南大学 | A kind of preparation method of paraquat molecular engram sensor |
| CN109142498B (en) * | 2018-08-29 | 2020-09-04 | 济南大学 | Preparation method of paraquat molecular imprinting sensor |
| CN109324097A (en) * | 2018-10-11 | 2019-02-12 | 大连大学 | A kind of electrode and its application for melamine measurement |
| CN111551618A (en) * | 2020-04-09 | 2020-08-18 | 济南大学 | Preparation method of sirolimus molecularly imprinted erbium nitride composite paste electrode |
| CN111551618B (en) * | 2020-04-09 | 2022-05-10 | 济南大学 | Preparation method of sirolimus molecularly imprinted erbium nitride composite paste electrode |
| CN115096976A (en) * | 2022-06-20 | 2022-09-23 | 商丘师范学院 | Silver cluster/nitrogen-doped carbon electrode material and in-situ limited synthesis method and application thereof |
| CN115096976B (en) * | 2022-06-20 | 2024-01-26 | 商丘师范学院 | Silver cluster/nitrogen-doped carbon electrode material, in-situ finite field synthesis method and application thereof |
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