CN107576700B - Nano cupric oxide modified electrode and the method for analyzing Nilvadipine with modified electrode - Google Patents
Nano cupric oxide modified electrode and the method for analyzing Nilvadipine with modified electrode Download PDFInfo
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Abstract
The invention discloses a kind of nano cupric oxide modified electrode methods, including prepare nano cupric oxide, preparation of nano copper oxide suspension and modified glassy carbon electrode.Invention additionally discloses a kind of methods with modified electrode analysis Nilvadipine, comprising steps of preparing Nilvadipine mother liquor；Prepare buffer；Nano cupric oxide modified electrode above-mentioned is provided；Nilvadipine solution is added in buffer, using the nano cupric oxide modified electrode in above-mentioned steps as working electrode, platinum electrode is as auxiliary electrode, and calomel electrode is as corresponding reference electrode, three-electrode system is collectively constituted, detects Nilvadipine content with cyclic voltammetry.The present invention obtains nano cupric oxide modified electrode by the method for nano cupric oxide modified glassy carbon electrode, and analyzes Nilvadipine with modified electrode, and good reproducibility of analysis results, stability are high.
Description
Technical field
The present invention relates to field of nanometer material technology, the especially a kind of method and modified electrode of nano cupric oxide modified electrode
Application in Nilvadipine analysis.
Background technique
Nilvadipine is a kind of a kind of powder of the picture crystallization of yellow, which in ethanol, is not readily dissolved in water.
High performance liquid chromatography, ultraviolet spectrophotometry, voltammetry, nuclear magnetic resonance are divided into for the method that predominantly detects of Nilvadipine at present
Method.These methods reproducibility, stability, in terms of cannot fully meet requirement, it is therefore desirable to a kind of novel analysis
Method carrys out analysis detection Nilvadipine.
Summary of the invention
The present invention provides a kind of favorable reproducibility, the high nano cupric oxide modified electrode method of stability and uses modified electrode
The method for analyzing Nilvadipine.
To achieve the above object, technical scheme is as follows:
A kind of nano cupric oxide modified electrode method, includes the following steps:
S10 prepares nano cupric oxide: PEG being added in acetic acid copper solution, forms solution A；It is added in sodium carbonate liquor
PEG forms B solution after dissolution, then drop evenly solution B in solution A under conditions of ultrasound, then it is ultrasonic appropriate when
Between, black precipitate finally is obtained after magnetic agitation 30 minutes under conditions of 78 DEG C, is centrifuged, it is repeated multiple times to wash
It washs, vacuum drying obtains copper oxide nano material；
Preparation of nano copper oxide suspension: S20 weighs cupric oxide nano powder, is placed in sample cell, then be added dropwise thereto
Distilled water makes the mass ratio 1:200 of cupric oxide nano powder and water, stirs 5-10 minutes, is then added into suspension
It is spare to be finally placed in concussion dispersion 30min in ultrasonic cleaner by 1.00mL1%PVP for sample cell；Before each is used again
Secondary concussion 15-20min, so that nano cupric oxide particle can be uniformly dispersed；
S30, glass-carbon electrode: being first placed on aluminum oxide powder and carry out polishing grinding by modified glassy carbon electrode, then will
Glass-carbon electrode is placed in concussion cleaning 5-10min in the beaker for fill dilute sulfuric acid, then takes out wash with distilled water, is finally placed in room
Temperature is lower to be air-dried；Above-mentioned just 10 microlitres of finely dispersed cupric oxide nano suspension is drawn, using drop-coating drop coating in glass-carbon electrode
Electrode wicking surface, be subsequently placed under infrared light and dry, obtain surface be full of one layer of very thin nano cupric oxide particle modification
Electrode.
A method of Nilvadipine being analyzed with modified electrode, is included the following steps:
S40 prepares Nilvadipine mother liquor；
S50 prepares buffer；
S60 provides nano cupric oxide modified electrode as described above；
Nilvadipine solution is added in buffer by S70, is made using the nano cupric oxide modified electrode in step S60
For working electrode, platinum electrode collectively constitutes three-electrode system as corresponding reference electrode as auxiliary electrode, calomel electrode,
Nilvadipine content is detected with cyclic voltammetry.
Wherein in step S50, buffer is phosphate buffer.
Wherein in step S50, the pH of phosphate buffer is pH=7.80.
Wherein in step S70, nano cupric oxide modified glassy carbon electrode sweep speed is 0.06V/s.
Wherein step S40 specifically comprises the following steps:
Nilvadipine sample treatment: S41 accurately weighs the Nilvadipine tablet of certain mass, is smashed to pieces, be ground into mortar
Then the dehydrated alcohol dissolution filter of certain volume is added in powdery granule, remove insoluble matter, forms transparent clear Buddhist nun and cuts down
Horizon sample solution, it is In Shade, it is pipetted according to concentration needs stand-by；
S42 prepares Nilvadipine mother liquor: weighing Nilvadipine raw medicine, ethyl alcohol dissolution is added, move into volumetric flask and shake up and determine
Hold, is configured to 2.0 × 10-3It is spare to be placed in dark shady place for the mother liquor solution of mol/L.
Wherein step S50 specifically comprises the following steps:
S51 prepares the NaH of (1) 0.4mol/L2PO4: weigh NaH2PO4·2H2O 31.2g adds 500.00ml distillation water-soluble
Solution；
S52 prepares the Na of (2) 0.4mol/L2HPO4: weigh Na2HPO4·12H2O 71.6g adds 500.00ml distillation water-soluble
Solution；
Above-mentioned (1), (2) are mixed to get the phosphate buffer of required pH value according to different ratio column, and pass through pH by S53
Instrument measuring and the cocktail buffer for preparing needs.
The present invention obtains nano cupric oxide modified electrode by the method for nano cupric oxide modified glassy carbon electrode, and with modifying
Electrode analysis Nilvadipine, good reproducibility of analysis results, stability are high.
Detailed description of the invention
Fig. 1 is scanning result schematic diagram of the nano cupric oxide under electron lens in the embodiment of the present invention.
Fig. 2 is CV of the Nilvadipine in bare glassy carbon electrode and nano cupric oxide modified glassy carbon electrode in the embodiment of the present invention
Curve graph.
Fig. 3 is electrochemical response behavior comparison chart of the Nilvadipine in different buffers in the embodiment of the present invention.
Fig. 4 is the relational graph of reduction current and pH in the embodiment of the present invention.
Fig. 5 is the relational graph of reduction current and sweep speed in the embodiment of the present invention.
Fig. 6 is the DPV figure of the Nilvadipine of various concentration under optimum condition in the embodiment of the present invention.
Fig. 7 is the relational graph of reduction current and Nilvadipine concentration in the embodiment of the present invention.
Specific embodiment
With reference to the accompanying drawing and example, the present invention will be further described.
In the present embodiment, nano cupric oxide modified electrode method is outstanding including preparing nano cupric oxide, preparation of nano copper oxide
Three steps of turbid and modified glassy carbon electrode.
The method for preparing nano cupric oxide are as follows: PEG (polyethylene glycol) is added in acetic acid copper solution, forms solution A；In carbon
PEG (polyethylene glycol) is added in acid sodium solution, forms B solution after dissolution.Then solution B is dropped evenly under conditions of ultrasound
Into solution A, then ultrasonic appropriate time, black precipitate finally is obtained after magnetic agitation 30 minutes under conditions of 78 DEG C, it will
It is centrifuged, repeated multiple times washing, and vacuum drying obtains the copper oxide nano material that partial size is 50-70nm or so.Fig. 1 is
The electron lens scanning result of the present embodiment nano cupric oxide finished product.
The preparation of nano cupric oxide suspension: accurately weighing 0.0100g cupric oxide nano powder, be placed in sample cell, then
2.00mL distilled water is added dropwise thereto, slightly stirs 5-10 minutes, 1.00mL1%PVP (polyethylene is then added into suspension
Pyrrolidones), it is spare that sample cell is finally placed in concussion dispersion 30min in ultrasonic cleaner.Before each is used will
15-20min is shaken again, so that nano cupric oxide particle can be uniformly dispersed.
To the method for modifying of glass-carbon electrode: first glass-carbon electrode being placed on aluminum oxide powder and carries out polishing grinding, so
Glass-carbon electrode is placed in concussion cleaning 5-10min in the beaker for fill dilute sulfuric acid afterwards, is then taken out wash with distilled water, most postposition
It air-dries at room temperature.Above-mentioned just 10.00 microlitres of finely dispersed cupric oxide nano suspension is drawn with micro syringe, using drop
Coating drop coating is subsequently placed under infrared light and dries in the electrode wicking surface of glass-carbon electrode, obtains surface and receives full of very thin one layer
The modified electrode of rice copper oxide particle.
In the present embodiment, included the following steps with modified electrode analysis Nilvadipine.
S40 prepares Nilvadipine mother liquor
Including S41, Nilvadipine sample treatment: the Nilvadipine tablet of certain mass is accurately weighed, is smash with mortar
Broken, be ground into powder particle, and the dehydrated alcohol dissolution filter of certain volume is then added, and removes insoluble matter.It is formed transparent
Clear Nilvadipine sample solution, it is In Shade, it is pipetted according to concentration needs stand-by.
S42 prepares Nilvadipine mother liquor: accurately weighing 0.0771g Nilvadipine raw medicine, it is molten that 100.00mL ethyl alcohol is added
Solution moves into volumetric flask and shakes up constant volume, is configured to 2.0 × 10-3It is spare to be placed in dark shady place for the mother liquor solution of mol/L.
S50 prepares buffer, and buffer is phosphate buffer, preparation method in the present embodiment are as follows:
S51 prepares the NaH of (1) 0.4mol/L2PO4: weigh NaH2PO4·2H2O 31.2g adds 500.00ml distillation water-soluble
Solution；
S52 prepares the Na of (2) 0.4mol/L2HPO4: weigh Na2HPO4·12H2O 71.6g adds 500.00ml distillation water-soluble
Solution；
Above-mentioned (1), (2) can be obtained the phosphate buffer of different pH according to different ratio column mixing, and pass through by S53
Accurate pH Instrument measuring and the cocktail buffer for preparing needs.
To select optimized buffer liquid, the present embodiment has also prepared BR buffer, NH3-NH4Cl buffer, Acetic acid-sodium acetate
Buffer.
The preparation of BR buffer: each 50.00mL mixing of the phosphoric acid, boric acid, acetic acid of all 0.04mol/L of concentration is taken, so
Buffer of several groups of pH between 1.81-11.92 is prepared by the way that the NaOH of 0.2mol/L is added afterwards.
The NH of pH=10.003-NH4The preparation of Cl buffer: 5.4gNH is taken4Cl is dissolved in 20mL distilled water, adds 35.00mL
Concentrated ammonia liquor adds water and is diluted to 100mL；
The preparation of the Acetic acid-sodium acetate buffer of pH=6.00: removing 5.4g sodium acetate, adds the vinegar of 10.00mL 2.0mol/L
Acid is allowed to dissolve, and adds water and is diluted to 500mL.
The principle of the present embodiment are as follows: using the glass-carbon electrode for using nano cupric oxide to modify before as working electrode, platinum is electric
Pole collectively constitutes three-electrode system as corresponding reference electrode as auxiliary (to) electrode, 222 type calomel electrodes.With following
Ring voltammetry (CV) qualitative response for finding various drugs under various buffering bottom liquid, then determines optimized buffer liquid and Optimal pH
Value and sweep speed quantitatively do standard curve, reproducibility, minimum detectability and mark-on by DPV again after all determining
Recovering state, so that deducing drug corresponding electrochemical behavior occurs.Experimental data is recorded and saved with electrochemical workstation.
The comparison of bare electrode and modified electrode
Prepare two parts of solution: (1) in small beaker be added 2.0 × 10-3mol/L of 2.00mL Nilvadipine solution, then plus
Enter the phosphate buffer of 5.00mL certain pH；(2) phosphate buffer of 5.00mL certain pH is added in small beaker, adds 2.00mL
Ethanol solution (note: Nilvadipine solution is prepared by ethyl alcohol).Cyclic voltammetry is finally carried out on electrochemical workstation.Figure
A is No. 1 beaker (i.e. measurement Nilvadipine solution) of modified electrode measurement in 2；B is (1) number beaker of bare glassy carbon electrode measurement
(i.e. measurement Nilvadipine solution)；C is (2) number beaker (i.e. measurement phosphate buffer) of modified electrode measurement.As can be seen from Figure 2,
Current potential has an apparent peak between -0.2 to -0.6, and Nilvadipine after nano cupric oxide modified than being not decorated
Bare glassy carbon electrode has apparent response peak, and the glass-carbon electrode after illustrating nano cupric oxide modified takes part in the reduction of Nilvadipine
Process, nano cupric oxide have apparent catalytic action for the reduction of Nilvadipine.And phosphate buffer within this range without
Apparent response.
The selection of buffer
The Nilvadipine solution of same concentrations, same volume is added in different buffer solutions, then uses cyclic voltammetric
Method measures Nanoparticle Modified Electrode in different buffers for the electrochemical behavior of Nilvadipine drug.Buffer has respectively: phosphorus
Acid buffer, BR buffer, sodium tetraborate buffer, NH3-NH4Cl buffer and Na2CO3-NaHCO3Buffer.Such as A in Fig. 3
Response effect is more obvious in phosphoric acid solution known to curve, and peak type is best, so phosphate buffer is optimized buffer liquid.
The determination of Optimal pH
For the selection of pH, do five groups of parallel laboratory tests, configuration concentration is constant, pH is respectively 7.20,7.49,7.80,8.01,
8.34 phosphate buffer, measure nano cupric oxide modified glassy carbon electrode under difference pH phosphate buffer in reduction potential it is big
It is small, Fig. 4 is obtained according to relationship between pH and reduction potential corresponding current size.It can according to the relationship of pH in Fig. 4 and reduction current
Know, the Optimal pH of phosphoric acid bottom liquid is pH=7.80.
The determination of optimum scanning rate
In the phosphate buffer of Optimal pH=7.80, with nano cupric oxide modified glassy carbon electrode, sweep speed point is selected
Not Wei 0.04,0.06,0.08,0.12,0.14V/s, under the different sweep speeds with gradient measure Nilvadipine most
Its electrochemical response size in the case where good pH, can as can be seen from FIG. 5, and electrochemical response peak value is continuous with sweep speed
Increase, forms a maximum value.There is sweep speed corresponding to peak-peak and is equal to 0.06V/s.
The range of linearity and detection limit of Nilvadipine
The experiment under optimum conditions (Optimal pH=7.80, optimum scanning rate=0.06V/s), with repeat DPV
(differential pulse voltammetry) method is respectively as follows: A:1.3 × 10 in figure to concentration-4Mol/L, B:2.6 × 10-4Mol/L, C:3.9 × 10-4Mol/L, D:5.2 × 10-4There is mol/L the Nilvadipine solution of concentration gradient to be measured its reduction current with concentration
Change curve.The linearity curve of concentration and reduction current is produced according to Fig. 6, its concentration is 1.3 × 10 as can be seen from FIG. 7- 4Mol/L~6.5 × 10-4Linear relationship, linear equation y=0.002x+1.222E-06, phase are all had between mol/L range
Closing linear coefficient is 0.9995.According to detection limit formula LOD=3 σ/S, (σ indicates zero standard deviation, and S indicates that calibration curve is oblique
Rate), its detection limit=8.6 × 10-8mol/L can be calculated.
Reproducibility, the stability of Nanoparticle Modified Electrode
The repetition Electrochemical Detection that the Nilvadipine solution of 1.7 × 10-7mol/L has been carried out to 10 times or more, passes through meter
It calculates, the relative standard deviation of peak current maintains 3.6% or so.The reproducibility of the Nanoparticle Modified Electrode is found out by this step
It is relatively good.Equally, Nanoparticle Modified Electrode modification completed is put 10 days at room temperature, then cuts down ground to Buddhist nun for the modified electrode
Flat to carry out Electrochemical Detection, by repeatedly testing repeatedly, peak current size has dropped 3.8%, should by this procedure declaration
Modified electrode has good stability.
The interference experiment of Nanoparticle Modified Electrode
Investigated influence of the auxiliary material to electrochemical response of Nilvadipine, the results showed that 10 times or more of dextrin, talcum powder,
Starch does not generate interference to experimental result.Because being frequently added husky smooth substance in Nilvadipine, repaired by many experiments exclusion
Decorations electrode has response to sartans；Antioxidant substance, organic solvent contained in same medicament etc. interferes journey to it
Degree influences also very little, the results showed that the anti-interference of cupric oxide nano modified electrode is very strong.
The calculating of Nilvadipine assay and recovery of standard addition
Nilvadipine mark-on reclaims amount: the constant Nilvadipine solution of concentration takes three parts of same volume respectively, is added
5mL phosphate buffer simultaneously carries out analysis detection at optimum conditions；Then the Nilvadipine standard that same volume determines amount is added
Carry out analysis detection after solution at optimum conditions again.Calculated value after last every part of Nilvadipine solution mark-on, subtracts
The case where calculated value before mark-on, difference both as a result divided by Nilvadipine standard substance is added are exactly recovery of standard addition.
Specific standards defined formula are as follows:
With the three-electrode system for the electrochemical workstation that nano cupric oxide modified glassy carbon electrode is working electrode, with DPV method
Measurement analysis, the results are shown in Table 1, be 86.9%~95.6% eventually by the recovery of standard addition for learning Nilvadipine is calculated.
The rate of recovery of 1 Nilvadipine of table
Claims (6)
1. a kind of method with modified electrode analysis Nilvadipine, which comprises the steps of:
S10 prepares nano cupric oxide: polyethylene glycol being added in acetic acid copper solution, forms solution A；Add in sodium carbonate liquor
Enter polyethylene glycol, form B solution after dissolution, then drop evenly solution B in solution A under conditions of ultrasound, then ultrasound
Appropriate time finally obtains black precipitate after magnetic agitation 30 minutes under conditions of 78 DEG C, is centrifuged, repeatedly more
Secondary washing, vacuum drying obtain copper oxide nano material；
S20, preparation of nano copper oxide suspension: weighing cupric oxide nano powder, be placed in sample cell, then distillation is added dropwise thereto
Water makes the mass ratio 1:200 of cupric oxide nano powder and water, stirs 5-10 minutes, is then added into suspension
1.00mL1% polyvinylpyrrolidone, finally by sample cell be placed in ultrasonic cleaner concussion dispersion 30 minutes it is spare；Every
It is shaken 15-20 minutes again before secondary use, nano cupric oxide particle is uniformly dispersed；
S30, glass-carbon electrode: being first placed on aluminum oxide powder and carry out polishing grinding by modified glassy carbon electrode, then by glass carbon
Electrode is placed in concussion cleaning 5-10 minutes in the beaker for fill dilute sulfuric acid, then takes out wash with distilled water, is finally placed in room temperature
It is lower to air-dry；Above-mentioned just 10 microlitres of finely dispersed cupric oxide nano suspension is drawn, using drop-coating drop coating in glass-carbon electrode
Electrode wicking surface is subsequently placed under infrared light and dries, and obtains modification electricity of the surface full of one layer of very thin nano cupric oxide particle
Pole；
S40 prepares Nilvadipine mother liquor；
S50 prepares buffer；
S60 provides nano cupric oxide modified electrode made from step S30:
Nilvadipine solution is added in buffer by S70, using the nano cupric oxide modified electrode in step S60 as work
Make electrode, platinum electrode collectively constitutes three-electrode system as corresponding reference electrode as auxiliary electrode, calomel electrode, uses
Cyclic voltammetry detects Nilvadipine content.
2. the method as described in claim 1, which is characterized in that wherein in step S50, buffer is phosphate buffer.
3. method according to claim 2, which is characterized in that wherein in step S50, the pH of phosphate buffer is pH=
7.80。
4. method as claimed in claim 3, which is characterized in that wherein in step S70, nano cupric oxide modified glassy carbon electrode is swept
Retouching rate is 0.06V/s.
5. the method as described in claim 1, which is characterized in that wherein step S40 specifically comprises the following steps:
Nilvadipine sample treatment: S41 accurately weighs the Nilvadipine tablet of certain mass, is smashed to pieces with mortar, grind into powder
Then the dehydrated alcohol dissolution filter of certain volume is added in shape particle, remove insoluble matter, forms transparent clear Nilvadipine
Sample solution, it is In Shade, it is pipetted according to concentration needs stand-by；
S42 prepares Nilvadipine mother liquor: weighing Nilvadipine raw medicine, ethyl alcohol dissolution is added, move into volumetric flask and shake up constant volume, match
It is set to 2.0 × 10-3It is spare to be placed in dark shady place for the mother liquor solution of mol/L.
6. the method as described in claim 1, which is characterized in that wherein step S50 specifically comprises the following steps:
S51 prepares the NaH of (1) 0.4mol/L2PO4: weigh NaH2PO4·2H2O 31.2g adds 500.00ml distilled water to dissolve；
S52 prepares the Na of (2) 0.4mol/L2HPO4: weigh Na2HPO4·12H2O 71.6g adds 500.00ml distilled water to dissolve；
Above-mentioned (1), (2) are mixed to get the phosphate buffer of required pH value according to different ratio column, and pass through pH instrument by S53
Measure and prepare the cocktail buffer of needs.
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| CN102520035A (en) * | 2011-11-04 | 2012-06-27 | 上海大学 | Preparation method for copper oxide-graphene nano-complex modification electrode, and application of modification electrode in glucose detection |
| CN104742549A (en) * | 2015-04-17 | 2015-07-01 | 天津理工大学 | Preparation method for decorating silk-screen printing electrode ethanol sensor by nanometer copper oxide |
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| CN102520035A (en) * | 2011-11-04 | 2012-06-27 | 上海大学 | Preparation method for copper oxide-graphene nano-complex modification electrode, and application of modification electrode in glucose detection |
| CN104742549A (en) * | 2015-04-17 | 2015-07-01 | 天津理工大学 | Preparation method for decorating silk-screen printing electrode ethanol sensor by nanometer copper oxide |
| CN106745180A (en) * | 2017-03-07 | 2017-05-31 | 扬州大学 | A kind of cupric oxide electrode material of porous nanometer structure, preparation method and applications |
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