CN104914147A - Preparation method and application of magnetic nano-NiFe2O4 based electrochemical sensor - Google Patents
Preparation method and application of magnetic nano-NiFe2O4 based electrochemical sensor Download PDFInfo
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Abstract
The invention relates to the technical field of electrochemical analysis, especially to a preparation method and application of a magnetic nano-NiFe2O4 based electrochemical sensor. The magnetic nano-NiFe2O4 based electrochemical sensor electrode is composed of a glassy carbon electrode and an NiFe2O4 dispersion liquid, wherein the electrode structure is formed by coating the glassy carbon electrode surface with a layer of the NiFe2O4 dispersion liquid, and the dosage of the NiFe2O4 dispersion liquid is 2-5microL. The magnetic nano-NiFe2O4 based electrochemical sensor electrode can accurately detect rutin and quercetin simultaneously, reduces the process complexity of rutin and quercetin detection, and lowers the cost, also has good reproducibility, and the disturbing influence of common metal ions and 200 times of glucose, glycine, citric acid, arginine and other impurities on the electrode is low. Also, the electrode can also be applied to simultaneous detection of rutin and quercetin in Fructus Rosae Laevigatae, safflower and sophora japonica, and the detection method is simple and is easy to operate.
Description
Technical field
The present invention relates to electrochemical analysis techniques field, especially a kind of preparation method of the electrochemical sensor based on magnetic Nano NiFe2O4 and application.
Background technology
Flavonoid substances rutin and Quercetin; be present in Chinese medicine widely and have in the plant of health care; they participate in the structure of capillary wall; and perviousness and the fragility of blood vessel can be lowered, have that anti-inflammatory, anti-oxidant, antitumor, platelet aggregation-against, antiallergy, antiviral, anti-melancholy, anti-ambition are loose, step-down and neuroprotection.But deposit improper if some contains the tablet of rutin and soft capsule, perhaps Quercetin appears in the hydrolysate of rutin.As the glycosyl of rutin, Quercetin often and rutin coexist.Often be found jointly to be present in Chinese herbal medicine, such as the fruit of Cherokee rose, safflower, the sophora bud etc.
At present spectroscopic methodology, chromatography, spectrophotometric method, electrochemical process etc. are mainly contained to the analytical approach that Quercetin in plant and rutin detect.Detect while adopting electrochemical process to carry out rutin and Quercetin and have equipment simply, the advantages such as sense cycle is short, processing ease, thus have more wide application prospect.Because traditional Electrochemical Detection adopts conventional glass-carbon electrode, and rutin is close with the oxidizing potential of Quercetin on conventional glass-carbon electrode, the oxidation peak of rutin and Quercetin occurs overlapping, the Simultaneously test of electrochemical method to rutin and Quercetin is made to be difficult to carry out, cause rutin and Quercetin characterization processes complexity, testing cost is comparatively large, further result in containing rutin and the True-false distinguish of Quercetin plant and the accuracy of quartile length lower; And also openly adopt NiFe without any document in the prior art
2o
4dispersion liquid carries out the detection of rutin and Quercetin after carrying out glass-carbon electrode modification.
Summary of the invention
In order to solve the above-mentioned technical matters existed in prior art, the invention provides a kind of based on magnetic Nano NiFe
2o
4electrochemical sensor electrode and its preparation method and application.
Be achieved particular by following technical scheme:
A kind of based on magnetic Nano NiFe
2o
4electrochemical sensor electrode, by glass-carbon electrode and NiFe
2o
4dispersion liquid forms, and wherein, electrode structure is at glassy carbon electrode surface coating layer of Ni Fe
2o
4dispersion liquid, NiFe
2o
4the consumption of dispersion liquid is 2-5 μ L.
The present invention also provides based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode, comprise the following steps:
(1) by FeCl
2solution and NiCl
2solution is (0.9-1.1) according to mol ratio: (2.4-2.6) is uniformly mixed, obtain mixed liquor, add water and glycerine wherein again, and by it through 60-70 DEG C of water bath processing 20-30min, then add mix emulsion fluid wherein, continue stir process 50-65min, add boracic liquid again to stir, at bath temperature is 60-70 DEG C, pass into nitrogen again, and by its reflow treatment 50-65min, filter, washing, dry NiFe
2o
4, then by NiFe
2o
4after mixing with distilled water, adopt ultrasonic disperse process, mixing ratio is the NiFe making to obtain
2o
4the concentration of dispersion liquid is 2-5mg/ml, stand-by;
(2) above-mentioned NiFe is got
2o
4dispersion liquid 2-5 μ L, and it is coated onto the surface of glass-carbon electrode, then dry under being placed on infrared lamp and obtain magnetic Nano NiFe
2o
4modified electrode.
Described adds water and glycerine, and wherein the addition of water is FeCl
2the 1-3 of solution doubly; The addition of glycerine is FeCl
2the 0.3-0.5 of solution doubly.
The addition of described mixed emulsion is 1-3 times of glycerine.
The addition of described boracic liquid is 0.7-1 times of glycerine.
Described mix emulsion fluid is the mixed liquor of lauryl sodium sulfate, n-amyl alcohol, normal heptane, tbp same-size ratio.
Described boracic liquid is the mixed liquor of potassium borohydride, n-amyl alcohol, normal heptane same-size ratio.
The electrochemical sensor electrode that present invention also offers based on magnetic Nano NiFe2O4 is measuring the application in rutin and Quercetin after being prepared into the electrochemical sensor based on magnetic Nano NiFe2O4.
Above-mentioned based on magnetic Nano NiFe
2o
4electrochemical sensor at the application process measuring the application in rutin and Quercetin, comprise the following steps:
(1) by magnetic Nano NiFe
2o
4modified electrode is as working electrode, and saturated calomel electrode makes contrast electrode, and platinum electrode is done electrode, obtains electrochemical sensor;
(2) by step 1) electrochemical sensor that obtains is placed in the phosphate buffer that pH value is 3-6, employing cyclic voltammetry scans, control voltage is 0.1-0.8V, sweep speed is 50mV/s, scanning until the curve of display stable after, be placed in the solution of rutin and Quercetin again, and open circuit enrichment 30-120s is carried out to it, leave standstill 2-5s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, show that this electrochemical sensor is 2.0 × 10 in rutin concentration
-9-1.0 × 10
-5curve within the scope of mol/L and quercetin concentration are 5.0 × 10
-9-5.0 × 10
-4curve within the scope of mol/L, and then measure rutin and Quercetin,
(3) in above-mentioned steps 2) measured after, then by magnetic Nano NiFe
2o
4modified electrode is placed in the phosphate buffered solution that pH is 5.0, and the electrochemical response being scanned up to rutin and Quercetin in-0.2 to 1.2V potential region cyclic voltammetry disappears, i.e. renewable electrode surface adopts NiFe
2o
4after dispersion liquid modified electrode, obtain magnetic Nano NiFe
2o
4modified electrode, and preserve under being placed on room temperature, namely complete magnetic Nano NiFe
2o
4modified electrode is measuring the application in rutin and Quercetin.
What adopt in the present invention is ultrasonic, and its frequency is 20-200kHz.
Above-mentioned employing based on magnetic Nano NiFe
2o
4electrochemical sensor electrode be prepared into based on magnetic Nano NiFe
2o
4electrochemical sensor after at the application process detecting rutin and quercetin content in the fruit of Cherokee rose,
(1) take fruit of Cherokee rose dry product 100g to pulverize, and crossed 20 object sieves, obtain powder, be placed in container accurately taking above-mentioned powder 1g, and in container, adding the ultrasonic extraction process 45min of 20g absolute ethyl alcohol, suction filtration obtains extract, then with absolute ethyl alcohol, extract is settled to 50mL in volumetric flask, shake up, obtain testing sample solution;
(2) step 1 is got) the testing sample solution 0.5ml that obtains, in 100mL volumetric flask, use B-R damping fluid constant volume to be diluted to 50ml, then adopt magnetic Nano NiFe
2o
4modified electrode is as working electrode, saturated calomel electrode makes contrast electrode, platinum electrode is done electrode, obtain electrochemical sensor and carry out open circuit enrichment 30-120s, leave standstill 2-5s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, the detection of rutin and quercetin content in the fruit of Cherokee rose can be completed.
The present invention by the testing result of the rutin in the fruit of Cherokee rose and quercetin content compared with ultraviolet spectrophotometry sign value, its error is less; By 1.0 × 10-6mol/L rutin and Quercetin mixed standard solution METHOD FOR CONTINUOUS DETERMINATION 8 times, the relative standard deviation (RSD) of differential pulse voltammetry oxidation peak peak height is respectively 3.48% and 4.79%, and then can effectively distinguish rutin and Quercetin, and then reach the detection to rutin and Quercetin; And its reappearance is good;
Moreover invention is also through recovery testu process, and the rate of being recycled reaches 97.8% ~ 101.6%, and then visible, the accuracy that this application of electrode detects in rutin and Quercetin is higher.
And the present invention also tests error effect factor, when error is ± 5%, Na
+, K
+, Fe
3+, Cu
2+, A1
3+, Mg
2+, Ca
2+etc. common metal ion, and the glucose of 200 times, glycocoll, citric acid and arginine etc. all do not cause interference to the mensuration of rutin and Quercetin solution, further improve the accuracy detected rutin and quercetin content, reduce detection difficulty.
Prepare magnetic Nano NiFe
2o
4, adopt magnetic Nano NiFe
2o
4ultrasonic disperse, in distilled water, gets NiFe
2o
4dispersant liquid drop is coated onto the surface of processed good glass-carbon electrode, then dries under being placed in infrared lamp and obtain magnetic Nano NiFe
2o
4modified electrode, and form three-electrode system with saturated calomel electrode, platinum electrode, provide the electrochemical method of a kind of Simultaneously test rutin and Quercetin.Through experimental verification, this three-electrode system has higher catalytic activity to rutin and Quercetin, that detects is highly sensitive, the overpotential of oxidation reaction is low, selectivity is good, can realize the Simultaneously test to rutin and Quercetin, is the detecting electrode of a kind of high stability, high sensitivity and high selectivity, and its preparation technology is simple, with low cost.
Embodiment
Below in conjunction with concrete embodiment, further restriction is done to technical scheme of the present invention, but claimed scope is not only confined to done description.
Embodiment 1
A kind of based on magnetic Nano NiFe
2o
4electrochemical sensor electrode, by glass-carbon electrode and NiFe
2o
4dispersion liquid forms, and wherein, electrode structure is at glassy carbon electrode surface coating layer of Ni Fe
2o
4dispersion liquid, NiFe
2o
4the consumption of dispersion liquid is 2 μ L.
Should based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode,
(1) by FeCl
2solution and NiCl
2solution is that 0.9:2.6 is uniformly mixed according to mol ratio, obtain mixed liquor, add water and glycerine wherein again, and by it through 70 DEG C of water bath processing 30min, then add mix emulsion fluid wherein, continue stir process 65min, add boracic liquid again to stir, at bath temperature is 70 DEG C, pass into nitrogen again, and by its reflow treatment 65min, filter, washing, dry NiFe
2o
4, then by NiFe
2o
4after mixing with distilled water, adopt ultrasonic disperse process, mixing ratio is the NiFe making to obtain
2o
4the concentration of dispersion liquid is 5mg/ml, stand-by;
(2) above-mentioned NiFe is got
2o
4dispersion liquid 2 μ L, and it is coated onto the surface of glass-carbon electrode, then dry under being placed on infrared lamp and obtain magnetic Nano NiFe
2o
4modified electrode.
Described adds water and glycerine, and wherein the addition of water is FeCl
21 times of solution; The addition of glycerine is FeCl
20.3 times of solution.
The addition of described mixed emulsion is 1 times of glycerine.
The addition of described boracic liquid is 0.7 times of glycerine.
Described mix emulsion fluid is the mixed liquor of lauryl sodium sulfate, n-amyl alcohol, normal heptane, tbp same-size ratio.
Described boracic liquid is the mixed liquor of potassium borohydride, n-amyl alcohol, normal heptane same-size ratio.
Embodiment 2
A kind of based on magnetic Nano NiFe
2o
4electrochemical sensor electrode, by glass-carbon electrode and NiFe
2o
4dispersion liquid forms, and wherein, electrode structure is at glassy carbon electrode surface coating layer of Ni Fe
2o
4dispersion liquid, NiFe
2o
4the consumption of dispersion liquid is 5 μ L.
Should based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode,
(1) by FeCl
2solution and NiCl
2solution is that 1.1:2.4 is uniformly mixed according to mol ratio, obtain mixed liquor, add water and glycerine wherein again, and by it through 60 DEG C of water bath processing 20min, then add mix emulsion fluid wherein, continue stir process 50min, add boracic liquid again to stir, at bath temperature is 60 DEG C, pass into nitrogen again, and by its reflow treatment 50min, filter, washing, dry NiFe
2o
4, then by NiFe
2o
4after mixing with distilled water, adopt ultrasonic disperse process, mixing ratio is the NiFe making to obtain
2o
4the concentration of dispersion liquid is 2mg/ml, stand-by;
(2) above-mentioned NiFe is got
2o
4dispersion liquid 5 μ L, and it is coated onto the surface of glass-carbon electrode, then dry under being placed on infrared lamp and obtain magnetic Nano NiFe
2o
4modified electrode.
Described adds water and glycerine, and wherein the addition of water is FeCl
23 times of solution; The addition of glycerine is FeCl
20.5 times of solution.
The addition of described mixed emulsion is 3 times of glycerine.
The addition of described boracic liquid is 1 times of glycerine.
Described mix emulsion fluid is the mixed liquor of lauryl sodium sulfate, n-amyl alcohol, normal heptane, tbp same-size ratio.
Described boracic liquid is the mixed liquor of potassium borohydride, n-amyl alcohol, normal heptane same-size ratio.
Embodiment 3
A kind of based on magnetic Nano NiFe
2o
4electrochemical sensor electrode, by glass-carbon electrode and NiFe
2o
4dispersion liquid forms, and wherein, electrode structure is at glassy carbon electrode surface coating layer of Ni Fe
2o
4dispersion liquid, NiFe
2o
4the consumption of dispersion liquid is 3 μ L.
Should based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode,
(1) by FeCl
2solution and NiCl
2solution is that 1:2.5 is uniformly mixed according to mol ratio, obtain mixed liquor, add water and glycerine wherein again, and by it through 65 DEG C of water bath processing 25min, then add mix emulsion fluid wherein, continue stir process 60min, add boracic liquid again to stir, at bath temperature is 65 DEG C, pass into nitrogen again, and by its reflow treatment 60min, filter, washing, dry NiFe
2o
4, then by NiFe
2o
4after mixing with distilled water, adopt ultrasonic disperse process, mixing ratio is the NiFe making to obtain
2o
4the concentration of dispersion liquid is 4mg/ml, stand-by;
(2) above-mentioned NiFe is got
2o
4dispersion liquid 3 μ L, and it is coated onto the surface of glass-carbon electrode, then dry under being placed on infrared lamp and obtain magnetic Nano NiFe
2o
4modified electrode.
Described adds water and glycerine, and wherein the addition of water is FeCl
22 times of solution; The addition of glycerine is FeCl
20.4 times of solution.
The addition of described mixed emulsion is 2 times of glycerine.
The addition of described boracic liquid is 0.8 times of glycerine.
Described mix emulsion fluid is the mixed liquor of lauryl sodium sulfate, n-amyl alcohol, normal heptane, tbp same-size ratio.
Described boracic liquid is the mixed liquor of potassium borohydride, n-amyl alcohol, normal heptane same-size ratio.
Embodiment 4
Embodiment 1 obtained based on magnetic Nano NiFe
2o
4electrochemical sensor electrode be prepared into based on magnetic Nano NiFe
2o
4electrochemical sensor after detecting the application in rutin and quercetin content, concrete application process is: (1) is by magnetic Nano NiFe
2o
4modified electrode is as working electrode, and saturated calomel electrode makes contrast electrode, and platinum electrode is done electrode, obtains electrochemical sensor;
(2) by step 1) electrochemical sensor that obtains is placed in the phosphate buffer that pH value is 3, employing cyclic voltammetry scans, control voltage is 0.1-0.8V, sweep speed is 50mV/s, scanning until the curve of display stable after, be placed in the solution of rutin and Quercetin again, and open circuit enrichment 30s is carried out to it, leave standstill 2s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, show that this electrochemical sensor is 2.0 × 10 in rutin concentration
-9-1.0 × 10
-5curve within the scope of mol/L and quercetin concentration are 5.0 × 10
-9-5.0 × 10
-4curve within the scope of mol/L, and then measure rutin and Quercetin,
(3) in above-mentioned steps 2) measured after, then by magnetic Nano NiFe
2o
4modified electrode is placed in the phosphate buffered solution that pH is 5.0, and the electrochemical response being scanned up to rutin and Quercetin in-0.2 to 1.2V potential region cyclic voltammetry disappears, i.e. renewable electrode surface adopts NiFe
2o
4after dispersion liquid modified electrode, obtain magnetic Nano NiFe
2o
4modified electrode, and preserve under being placed on room temperature, namely complete based on magnetic Nano NiFe
2o
4electrochemical sensor electrode measuring the application in rutin and Quercetin.
Embodiment 5
Embodiment 2 obtained based on magnetic Nano NiFe
2o
4electrochemical sensor electrode be prepared into based on magnetic Nano NiFe
2o
4electrochemical sensor after detecting the application in rutin and quercetin content, concrete application process is: (1) is by magnetic Nano NiFe
2o
4modified electrode is as working electrode, and saturated calomel electrode makes contrast electrode, and platinum electrode is done electrode, obtains electrochemical sensor;
(2) electrochemical sensor that step (1) obtains is placed in the phosphate buffer that pH value is 6, employing cyclic voltammetry scans, control voltage is 0.1-0.8V, sweep speed is 50mV/s, scanning until the curve of display stable after, be placed in the solution of rutin and Quercetin again, and open circuit enrichment 120s is carried out to it, leave standstill 5s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, show that this electrochemical sensor is 2.0 × 10 in rutin concentration
-9-1.0 × 10
-5curve within the scope of mol/L and quercetin concentration are 5.0 × 10
-9-5.0 × 10
-4curve within the scope of mol/L, and then measure rutin and Quercetin,
(3) after above-mentioned steps (2) has measured, then by magnetic Nano NiFe
2o
4modified electrode is placed in the phosphate buffered solution that pH is 5.0, and the electrochemical response being scanned up to rutin and Quercetin in-0.2 to 1.2V potential region cyclic voltammetry disappears, i.e. renewable electrode surface adopts NiFe
2o
4after dispersion liquid modified electrode, obtain magnetic Nano NiFe
2o
4modified electrode, and preserve under being placed on room temperature, namely complete based on magnetic Nano NiFe
2o
4electrochemical sensor electrode measuring the application in rutin and Quercetin.
Embodiment 6
Embodiment 3 obtained based on magnetic Nano NiFe
2o
4electrochemical sensor electrode be prepared into based on magnetic Nano NiFe
2o
4electrochemical sensor after detecting the application in rutin and quercetin content, concrete application process is: (1) is by magnetic Nano NiFe
2o
4modified electrode is as working electrode, and saturated calomel electrode makes contrast electrode, and platinum electrode is done electrode, obtains electrochemical sensor;
(2) electrochemical sensor that step (1) obtains is placed in the phosphate buffer that pH value is 5, employing cyclic voltammetry scans, control voltage is 0.1-0.8V, sweep speed is 50mV/s, scanning until the curve of display stable after, be placed in the solution of rutin and Quercetin again, and open circuit enrichment 90s is carried out to it, leave standstill 3s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, show that this electrochemical sensor is 2.0 × 10 in rutin concentration
-9-1.0 × 10
-5curve within the scope of mol/L and quercetin concentration are 5.0 × 10
-9-5.0 × 10
-4curve within the scope of mol/L, and then measure rutin and Quercetin,
(3) after above-mentioned steps (2) has measured, then by magnetic Nano NiFe
2o
4modified electrode is placed in the phosphate buffered solution that pH is 5.0, and the electrochemical response being scanned up to rutin and Quercetin in-0.2 to 1.2V potential region cyclic voltammetry disappears, i.e. renewable electrode surface adopts NiFe
2o
4after dispersion liquid modified electrode, obtain magnetic Nano NiFe
2o
4modified electrode, and preserve under being placed on room temperature, namely complete based on magnetic Nano NiFe
2o
4electrochemical sensor electrode measuring the application in rutin and Quercetin.
Embodiment 7
Embodiment 1 prepare based on magnetic Nano NiFe
2o
4electrochemical sensor electrode be prepared into based on magnetic Nano NiFe
2o
4electrochemical sensor after at the application process detecting rutin and quercetin content in the fruit of Cherokee rose,
(1) take fruit of Cherokee rose dry product 100g to pulverize, and crossed 20 object sieves, obtain powder, be placed in container accurately taking above-mentioned powder 1g, and in container, adding the ultrasonic extraction process 45min of 20g absolute ethyl alcohol, suction filtration obtains extract, then with absolute ethyl alcohol, extract is settled to 50mL in volumetric flask, shake up, obtain testing sample solution;
(2) get the testing sample solution 0.5ml that step (1) obtains, in 100mL volumetric flask, use B-R damping fluid constant volume to be diluted to 50ml, then adopt magnetic Nano NiFe
2o
4modified electrode is as working electrode, saturated calomel electrode makes contrast electrode, platinum electrode is done electrode, obtain electrochemical sensor and carry out open circuit enrichment 50s, leave standstill 4s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, the detection of rutin and quercetin content in the fruit of Cherokee rose can be completed.
Embodiment 8
Embodiment 2 prepare based on magnetic Nano NiFe
2o
4electrochemical sensor electrode be prepared into based on magnetic Nano NiFe
2o
4electrochemical sensor after at the application process detecting rutin and quercetin content in safflower,
(1) take safflower dry product 100g to pulverize, and crossed 20 object sieves, obtain powder, be placed in container accurately taking above-mentioned powder 1g, and in container, adding the ultrasonic extraction process 45min of 20g absolute ethyl alcohol, suction filtration obtains extract, then with absolute ethyl alcohol, extract is settled to 50mL in volumetric flask, shake up, obtain testing sample solution;
(2) get the testing sample solution 0.5ml that step (1) obtains, in 100mL volumetric flask, use B-R damping fluid constant volume to be diluted to 50ml, then adopt magnetic Nano NiFe
2o
4modified electrode is as working electrode, saturated calomel electrode makes contrast electrode, platinum electrode is done electrode, obtain electrochemical sensor and carry out open circuit enrichment 60s, leave standstill 3s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, the detection of rutin and quercetin content in the fruit of Cherokee rose can be completed.
Embodiment 9
Embodiment 3 prepare based on magnetic Nano NiFe
2o
4electrochemical sensor electrode be prepared into based on magnetic Nano NiFe
2o
4electrochemical sensor after at the application process detecting rutin and quercetin content in the sophora bud,
(1) take sophora bud dry product 100g to pulverize, and crossed 20 object sieves, obtain powder, be placed in container accurately taking above-mentioned powder 1g, and in container, adding the ultrasonic extraction process 45min of 20g absolute ethyl alcohol, suction filtration obtains extract, then with absolute ethyl alcohol, extract is settled to 50mL in volumetric flask, shake up, obtain testing sample solution;
(2) get the testing sample solution 0.5ml that step (1) obtains, in 100mL volumetric flask, use B-R damping fluid constant volume to be diluted to 50ml, then adopt magnetic Nano NiFe
2o
4modified electrode is as working electrode, saturated calomel electrode makes contrast electrode, platinum electrode is done electrode, obtain electrochemical sensor and carry out open circuit enrichment 70s, leave standstill 5s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, the detection of rutin and quercetin content in the fruit of Cherokee rose can be completed.
Claims (10)
1. one kind based on magnetic Nano NiFe
2o
4electrochemical sensor electrode, it is characterized in that, by glass-carbon electrode and NiFe
2o
4dispersion liquid forms, and wherein, electrode structure is at glassy carbon electrode surface coating layer of Ni Fe
2o
4dispersion liquid, NiFe
2o
4the consumption of dispersion liquid is 2-5 μ L.
2. as claimed in claim 1 based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode, it is characterized in that:
(1) by FeCl
2solution and NiCl
2solution is (0.9-1.1) according to mol ratio: (2.4-2.6) is uniformly mixed, obtain mixed liquor, add water and glycerine wherein again, and by it through 60-70 DEG C of water bath processing 20-30min, then add mix emulsion fluid wherein, continue stir process 50-65min, add boracic liquid again to stir, at bath temperature is 60-70 DEG C, pass into nitrogen again, and by its reflow treatment 50-65min, filter, washing, dry NiFe
2o
4, then by NiFe
2o
4after mixing with distilled water, adopt ultrasonic disperse process, mixing ratio is the NiFe making to obtain
2o
4the concentration of dispersion liquid is 2-5mg/ml, stand-by;
(2) above-mentioned NiFe is got
2o
4dispersion liquid 2-5 μ L, and it is coated onto the surface of glass-carbon electrode, then dry under being placed on infrared lamp and obtain magnetic Nano NiFe
2o
4modified electrode.
3. as claimed in claim 2 based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode, it is characterized in that: described adds water and glycerine, wherein the addition of water is FeCl
2the 1-3 of solution doubly; The addition of glycerine is FeCl
2the 0.3-0.5 of solution doubly.
4. as claimed in claim 2 based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode, it is characterized in that: the addition of described mixed emulsion be the 1-3 of glycerine doubly.
5. as claimed in claim 2 based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode, it is characterized in that: the addition of described boracic liquid be the 0.7-1 of glycerine doubly.
6. as described in claim 2 or 4 based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode, it is characterized in that: described mix emulsion fluid is the mixed liquor of lauryl sodium sulfate, n-amyl alcohol, normal heptane, tbp same-size ratio.
7. as described in claim 2 or 5 based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode, it is characterized in that: described boracic liquid is the mixed liquor of potassium borohydride, n-amyl alcohol, normal heptane same-size ratio.
8. as claimed in claim 1 based on magnetic Nano NiFe
2o
4electrochemical sensor electrode and/or as described in any one of claim 2-7 based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode prepare based on magnetic Nano NiFe
2o
4electrochemical sensor electrode measuring the application in rutin and Quercetin.
9. as claimed in claim 8 based on magnetic Nano NiFe
2o
4electrochemical sensor electrode at the application process measuring the application in rutin and Quercetin, it is characterized in that, comprise the following steps:
(1) by magnetic Nano NiFe
2o
4modified electrode is as working electrode, and saturated calomel electrode makes contrast electrode, and platinum electrode is done electrode, obtains electrochemical sensor;
(2) electrochemical sensor that step (1) obtains is placed in the phosphate buffer that pH value is 3-6, employing cyclic voltammetry scans, control voltage is 0.1-0.8V, sweep speed is 50mV/s, scanning until the curve of display stable after, be placed in the solution of rutin and Quercetin again, and open circuit enrichment 30-120s is carried out to it, leave standstill 2-5s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, show that this electrochemical sensor is 2.0 × 10 in rutin concentration
-9-1.0 × 10
-5curve within the scope of mol/L and quercetin concentration are 5.0 × 10
-9-5.0 × 10
-4curve within the scope of mol/L, and then measure rutin and Quercetin,
(3) in above-mentioned steps 2) measured after, then by magnetic Nano NiFe
2o
4modified electrode is placed in the phosphate buffered solution that pH is 5.0, and the electrochemical response being scanned up to rutin and Quercetin in-0.2 to 1.2V potential region cyclic voltammetry disappears, i.e. renewable electrode surface adopts NiFe
2o
4after dispersion liquid modified electrode, obtain magnetic Nano NiFe
2o
4modified electrode, and preserve under being placed on room temperature, namely complete magnetic Nano NiFe
2o
4modified electrode is measuring the application in rutin and Quercetin.
10. as claimed in claim 1 based on magnetic Nano NiFe
2o
4electrochemical sensor electrode and/or as described in any one of claim 2-7 based on magnetic Nano NiFe
2o
4the preparation method of electrochemical sensor electrode prepare based on magnetic Nano NiFe
2o
4electrochemical sensor electrode and/or as in claim 9 based on magnetic Nano NiFe
2o
4electrochemical sensor electrode the application process measuring the application in rutin and Quercetin adopt based on magnetic Nano NiFe
2o
4electrochemical sensor electrode at the application process detecting rutin and quercetin content in the fruit of Cherokee rose, it is characterized in that:
(1) take fruit of Cherokee rose dry product 100g to pulverize, and crossed 20 object sieves, obtain powder, be placed in container accurately taking above-mentioned powder 1g, and in container, adding the ultrasonic extraction process 45min of 20g absolute ethyl alcohol, suction filtration obtains extract, then with absolute ethyl alcohol, extract is settled to 50mL in volumetric flask, shake up, obtain testing sample solution;
(2) get the testing sample solution 0.5ml that step (1) obtains, in 100mL volumetric flask, use B-R damping fluid constant volume to be diluted to 50ml, then adopt magnetic Nano NiFe
2o
4modified electrode is as working electrode, saturated calomel electrode makes contrast electrode, platinum electrode is done electrode, obtain electrochemical sensor and carry out open circuit enrichment 30-120s, leave standstill 2-5s, and differential pulse voltammetry analysis is carried out in the interval that current potential is 0.1-0.8V, differential pulse voltammetry analyst coverage 0.1-0.8V, current potential from 0.1V to 0.8V increases to 0.004V, amplitude: 0.05V, pulse width: 0.2s, sampling width: 0.02s, recurrence interval: 0.5s, the detection of rutin and quercetin content in the fruit of Cherokee rose can be completed.
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