CN106198694B - A kind of ratio dual signal electrochemical sensor based on bare glassy carbon electrode detection doxorubicin hydrochloride - Google Patents
A kind of ratio dual signal electrochemical sensor based on bare glassy carbon electrode detection doxorubicin hydrochloride Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 17
- MWWSFMDVAYGXBV-RUELKSSGSA-N Doxorubicin hydrochloride Chemical compound Cl.O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 MWWSFMDVAYGXBV-RUELKSSGSA-N 0.000 title abstract description 12
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- 238000004832 voltammetry Methods 0.000 claims 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 34
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- 230000035945 sensitivity Effects 0.000 abstract description 3
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 abstract 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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Abstract
The invention discloses a kind of ratio dual signal electrochemical sensors based on bare glassy carbon electrode detection doxorubicin hydrochloride.Specifically detection method is：1) glass-carbon electrode is immersed in the Phosphate buffered saline containing DOX and methylene blue (MB), by the electrochemical signals intensity of two kinds of substrates than Δ IDOX/ΔIMBIt is associated with DOX concentration, to draw out linear standard curve；2) the SWV signals in the sample containing DOX and MB are surveyed, the content of DOX in serum is determined according to the standard curve of drafting.Ratio dual signal electrochemical sensor based on bare glassy carbon electrode detection DOX prepared by the present invention has easy to operate, high sensitivity, and stability is good, and the dosage of DOX in detection Serum of Cancer Patients is had a very important significance.
Description
Technical field
The present invention relates to a kind of for detecting the electrochemical sensor of antitumor drug, and in particular to one kind is based on naked glass carbon
The ratio dual signal electrochemical sensor of electrode detection antitumor drug doxorubicin hydrochloride, belongs to technical field of biological.
Background technology
Due to aging of population getting worse, ecological environment by destroy, many factors such as unsound life style
Influence, tumor patient number is caused to increase year by year.In recent years, chemotherapy of tumors achieves sizable breakthrough, tumor patient
Life span is extended considerably, and especially has larger breakthrough to the treatment of the malignant tumours such as leukaemia, malignant lymphoma；So
And to effect seriously endangering human life and health, accounting for the treatment of solid tumors of more than 90% malignant tumour and still fail to reach satisfied
Fruit.Doxorubicin hydrochloride (DOX) is one of most widely used anthracyclines antibiotic of current treatment malignant tumour, can to body
Extensive biochemical effect is generated, there is strong cytotoxic effect.The mechanism of action of DOX is mainly that Doxorubicin molecules are embedding
Enter cancer cell DNA and inhibit the synthesis of inhereditary material nucleic acid, there is killing effect to kinds of tumor cells, as breast cancer, lung cancer,
Carcinoma of urinary bladder, thyroid cancer, malignant lymphoma and acute leukemia etc.；But shortcoming is it in the treatment with serious Amplatzer duct occluder
Property, inhibit hemopoietic function of bone marrow and toxic side effect etc..Therefore, applications of the DOX in terms of chemotherapy receives a degree of limitation.
The concentration for measuring DOX in DOX, especially blood sample in body fluid is of great significance for the assessment of drug safety.
The detection common methods of DOX have fluorescent spectrometry, ultra-performance liquid chromatography, liquid-liquid extraction-efficient liquid phase at present
Chromatography and chip capillary cataphoresis fluorescence detection etc., wherein patent of invention " are measured based on magnetic nanometer adsorbent in body fluid
The method of DOX " (patent No. 201310445367.X) is passed through layer assembly magnetism is prepared and received using chemical coprecipitation
Rice adsorbent TSAB-coated Fe3O4/SiO2, the content of DOX in blood plasma and urine sample is detected with this, prepared by this method
Magnetic adsorbent stability it is good, large amount of adsorption is reusable；But complicated for operation, cost is higher.Therefore, how to develop
It is this field urgent problem to be solved for simple, efficient, the quick detection means of DOX.
Invention content
In view of the deficiency of the prior art, an object of the present invention is to provide a kind of based on bare glassy carbon electrode inspection
Survey the ratio dual signal electrochemical sensor of antitumor drug DOX.Utilize DOX and the high spy of methylene blue (MB) electro-chemical activity
Property, the two is directly added into electrolyte, without carrying out any modification to electrode；It is aoxidized between DOX and glass-carbon electrode
, there is significant electric signal in reduction；And MB occurs stable signal as reference；In the case where control MB concentration is constant, with
The increase of DOX additions, electric signal caused by DOX gradually enhances；By electrochemical workstation to the electric signal of DOX and MB into
Row detection realizes ratio duplex transmission number to DOX quickly and highly sensitive detection.
The second object of the present invention is to provide preparation/construction method of above-mentioned electrochemical sensor and its application.
In addition, the present invention also aims to provide a kind of detection method of DOX.
To achieve the above object, the specific present invention uses following technical proposals：
First, the present invention provides a kind of for detecting the construction method of the electrochemical sensor of DOX, includes the following steps：
(1) a certain amount of MB solution and different amounts of DOX solution are added in buffer solution, are uniformly mixed, are configured to one
The mixed solution of the DOX of series concentration gradient and quantitative MB；
(2) it by glass-carbon electrode sanding and polishing, immerses in the mixed solution that step (3) obtains；
(3) using step (2) processed glass-carbon electrode as working electrode, electricity is connected to reference electrode, comparison electrode
Chem workstation, antitumor drug DOX electrochemical sensors can be detected by collectively forming.
In specific preferred technical solution, a concentration of 0.1~1mM of MB solution in step (1), a concentration of the 2 of DOX mother liquors
~200 μM, a series of concentration gradients of DOX are 0.01~4 μM in the mixed solution being configured to.
Preferably, the preparation method of mixed solution is in step (1)：Compound concentration is 0.01-0.05M, pH6.0-7.0's
PBS buffer solutions；A certain amount of MB solution is taken to instill dropwise in PBS buffer solutions under the conditions of being protected from light；Later under the conditions of being protected from light
Different amounts of DOX mother liquors is taken to instill dropwise in above-mentioned solution, ultrasonic disperse is configured to a series of DOX of concentration gradients with quantifying
The mixed solution of MB.
It is furthermore preferred that PBS buffer concentrations are 0.01M, pH 6.5.
In preferred technical solution, in step (2), the processing of glass-carbon electrode sanding and polishing, specially：By glass-carbon electrode successively
With 0.03~0.5 μm of Al2O3Powder is polished into minute surface, is then cleaned with deionized water, then is sequentially placed into deionized water and ethyl alcohol
Middle ultrasonic 1~10min；The glass-carbon electrode handled well is immersed, cyclic voltammetry scanning is carried out in potassium ferricyanide solution so that oxygen
It is 0~80mV to change reduction peak potential difference, and scanning voltage is -0.3~0.6V, sweeps speed as 0~0.05V s-1；After the completion of scanning again
Above-mentioned sanding and polishing step is carried out, is dried up after ultrasonic cleaning with nitrogen.
In preferred technical solution, in step (3), the reference electrode is calomel or Pt or glass-carbon electrode, the comparison
Electrode is calomel or Pt or glass-carbon electrode.
Secondly, the present invention provides the electrochemical sensor for being used to detect DOX that above-mentioned construction method obtains.
In addition, the present invention provides application of the above-mentioned electrochemical sensor in qualitatively or quantitatively detection DOX.
Further, the present invention provides a kind of method for detecting DOX, and step is：
(1) using the processed glass-carbon electrode of sanding and polishing as working electrode, connect with calomel reference electrode, Pt comparison electrodes
It is connected to electrochemical workstation；
(2) by glass-carbon electrode immerse containing same concentrations MB, various concentration DOX PBS mixed solutions in, survey its square wave volt
Pacify (SWV) response, scanning voltage is -0.9~0V, and current potential increment is 0.002V, amplitude 0.025V, frequency 25Hz, and root
According to different DOX concentration DOX and MB electrochemical signals than Δ IDOX/ΔIMBDrawing curve；
(3) a certain amount of MB solution and solution to be measured are added in PBS buffer solution, be uniformly mixed be configured to mix it is molten
Liquid, MB solution and the same step of PBS solution (2)；
(4) with the SWV signals of DOX and MB in glass-carbon electrode determination step (3) mixed solution, according to the standard curve of drafting
Determine the content of DOX.
In preferred technical solution, in step (1), the processing of glass-carbon electrode sanding and polishing, specially：By glass-carbon electrode successively
With 0.03~0.5 μm of Al2O3Powder is polished into minute surface, is then cleaned with deionized water, then is sequentially placed into deionized water and ethyl alcohol
Middle ultrasonic 1~10min；The glass-carbon electrode handled well is immersed, cyclic voltammetry scanning is carried out in potassium ferricyanide solution so that oxygen
It is 0~80mV to change reduction peak potential difference, and scanning voltage is -0.3~0.6V, sweeps speed as 0~0.05Vs-1；After the completion of scanning again
Above-mentioned sanding and polishing step is carried out, is dried up after ultrasonic cleaning with nitrogen.
In specific preferred technical solution, the preparation method of mixed solution is in step (2)：Compound concentration is 0.01-
The PBS buffer solutions of 0.05M, pH 6.0-7.0；A certain amount of MB solution is taken to instill PBS buffer solutions dropwise under the conditions of being protected from light
In；Different amounts of DOX mother liquors is taken to instill dropwise in above-mentioned solution under the conditions of being protected from light later, ultrasonic disperse is configured to a series of
The mixed solution of the DOX of concentration gradient and quantitative MB.
It is furthermore preferred that a concentration of 0.1~1mM of MB solution described in step (2), a concentration of 2~200 μM of DOX mother liquors,
A series of concentration gradients of DOX are 0.01~4 μM in the mixed solution being configured to.
The DOX that the method for detection doxorubicin hydrochloride/DOX of the present invention can be used in detection human plasma, serum or urine
Content can be used for quantifying for DOX in routine test reagent or solution, reaction solution.
The present invention achieves following advantageous effect：
(1) ratio dual signal electrochemical sensor preparation method of the invention is simple, easily manipulates, and reaction condition is mild；
The electrochemical assay of the present invention has many advantages, such as easy to operate, of low cost, high sensitivity and fast response time, especially
It is that the use of ratio dual signal can effectively avoid the error that single signal strength fluctuates and causes measurement, this is one for detection DOX
A ideal selection；
(2) so far, there has been no ratio dual signal electrochemistry DOX sensors, also there has been no based on bare electrode (such as glass carbon
Electrode) on structure ratio dual signal electrochemical sensor domestic and international pertinent literature and patent report；The present invention is for the first time by DOX
It is combined with MB and prepares ratio dual signal electrochemical sensor, realized and DOX is fast and efficiently detected；
(3) electrochemical sensor of the invention is directly detected DOX using bare glassy carbon electrode, without being carried out to electrode
Any modification, can be down to 4nM, high sensitivity to the detection limit of DOX.
Description of the drawings
Fig. 1 is that the ratio dual signal electrochemical sensor of the present invention detects the schematic diagram of DOX
Fig. 2 is the SWV of various concentration gradient DOX and fixed concentration MB
Fig. 3 is for DOX with MB electrochemical signals than Δ IDOX/ΔIMBWith the linear dependence figure of DOX concentration
Specific embodiment
With reference to embodiment, the present invention is further illustrated, it should which explanation, the description below are used for the purpose of
It explains the present invention, its content is not defined.
Instrument and reagent used in experiment are：(1) instrument：(Shanghai Chen Hua instrument has CHI650 electrochemical workstations
Limit company)；Saturated calomel electrode (SCE) is used as reference electrode, platinum electrode is to electrode；(2) reagent：DOX (raw work biologies
Engineering (Shanghai) Co., Ltd.), analysis is pure；MB (Aladdin reagent (Shanghai) Co., Ltd.), analysis are pure.
Other reagents are that analysis is pure, and experimental water is deionized water.
Embodiment 1：
(1) compound concentration be 0.01M, the PBS buffer solutions of pH 6.5.50 μ L, 1mM MB solution are taken under the conditions of being protected from light
It instills in PBS buffer solutions dropwise.Take the PBS that different amounts of 200 μM of DOX instill above-mentioned MB dropwise molten under the conditions of being equally protected from light
In liquid, ultrasonic mixing dispersion is made into concentration gradient as 0.01 μM, 0.05 μM, 0.1 μM, 0.5 μM, 1 μM, 2 μM, 3 μM and 4 μ respectively
M。
(2) by glass-carbon electrode successively with 0.5 μm and 0.03 μm of Al2O3Powder is polished into minute surface, then clear with deionized water
It washes, then is sequentially placed 1~2min of ultrasound in deionized water and ethyl alcohol；The glass-carbon electrode handled well is immersed into potassium ferricyanide solution
Middle progress cyclic voltammetry scanning so that redox peaks potential difference is less than 80mV；Above-mentioned polishing is carried out again after the completion of scanning
Polishing step is dried up after ultrasonic cleaning with nitrogen.Electrode is immersed in above-mentioned mixed solution to the SWV signals for surveying DOX and MB.
Embodiment 2：The measure of actual sample
(1) by human serum 0.01M, the PBS buffer solutions of pH 6.5 dilute ten times.50 μ L, 1mM are taken under the conditions of being protected from light
MB solution is instilled dropwise in human serum solution.A certain amount of DOX is taken to instill the human serum solution of above-mentioned MB under the conditions of being equally protected from light
In, ultrasonic mixing.
(2) the step of the step of measuring the SWV signals of DOX and MB in human serum solution with glass-carbon electrode is with embodiment 1
(2), the content of DOX is determined according to the standard curve of drafting.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Embodiment 3
(1) compound concentration be 0.03M, the PBS buffer solutions of pH 7.0.Take 50 μ L, 0.1mM MB molten under the conditions of being protected from light
Liquid is instilled dropwise in PBS buffer solutions.Different amounts of 100 μM of DOX is taken to instill the PBS of above-mentioned MB dropwise under the conditions of being equally protected from light
In solution, the dispersion of ultrasonic mixing, be made into respectively concentration gradient for 0.01 μM, 0.05 μM, 0.1 μM, 0.5 μM, 1 μM, 2 μM, 3 μM and
4μM。
(2) by glass-carbon electrode successively with 0.5 μm and 0.03 μm of Al2O3Powder is polished into minute surface, then clear with deionized water
It washes, then is sequentially placed the ultrasound 2min in deionized water and ethyl alcohol；The glass-carbon electrode handled well is immersed in potassium ferricyanide solution
Carry out cyclic voltammetry scanning so that redox peaks potential difference is less than 80mV；Above-mentioned polishing throwing is carried out again after the completion of scanning
Light step, is dried up after ultrasonic cleaning with nitrogen.Electrode is immersed in above-mentioned mixed solution to the SWV signals for surveying DOX and MB.
Claims (10)
1. a kind of construction method for the electrochemical sensor for being used to detect DOX, which is characterized in that include the following steps：
(1) a certain amount of MB solution and different amounts of DOX mother liquors are added in buffer solution, are uniformly mixed, are configured to a series of
The mixed solution of the DOX of concentration gradient and quantitative MB；
(2) it by glass-carbon electrode sanding and polishing, immerses in the mixed solution that step (1) obtains；
(3) using step (2) processed glass-carbon electrode as working electrode, electrochemistry is connected to reference electrode, comparison electrode
Work station, antitumor drug DOX electrochemical sensors can be detected by collectively forming.
2. according to the method described in claim 1, it is characterized in that, in step (1) MB solution a concentration of 0.1~1mM, DOX
A series of concentration gradients of DOX are 0.01~4 μM in a concentration of mixed solution 2~200 μM, being configured to of mother liquor.
3. method according to claim 1 or 2, which is characterized in that the preparation method of mixed solution is in step (1)：Match
Make a concentration of 0.01-0.05M, the PBS buffer solutions of pH 6.0-7.0；A certain amount of MB solution is taken to instill dropwise under the conditions of being protected from light
In PBS buffer solutions；Different amounts of DOX mother liquors is taken to instill dropwise in above-mentioned solution under the conditions of being protected from light later, ultrasonic disperse is matched
The mixed solution of the DOX and quantitative MB of a series of concentration gradients is made.
4. according to the method described in claim 1, it is characterized in that, in step (2), glass-carbon electrode sanding and polishing is specially：It will
Glass-carbon electrode is successively with 0.03~0.5 μm of Al2O3Powder is polished into minute surface, is then cleaned with deionized water, then is sequentially placed into
1~10min of ultrasound in ionized water and ethyl alcohol；The glass-carbon electrode handled well is immersed in potassium ferricyanide solution and carries out cyclic voltammetry
Scanning so that redox peaks potential difference is 0~80mV, and scanning voltage is -0.3~0.6V, sweeps speed as 0~0.05V s-1；It sweeps
Above-mentioned sanding and polishing step is carried out again after the completion of retouching, and is dried up after ultrasonic cleaning with nitrogen.
5. according to the method described in claim 1, it is characterized in that, in step (3), the reference electrode is calomel or Pt or glass
Carbon electrode, the comparison electrode are calomel or Pt or glass-carbon electrode.
6. the electrochemical sensor for being used to detect DOX that any one of the claim 1-5 construction methods obtain.
7. application of the electrochemical sensor described in claim 6 in qualitatively or quantitatively detection DOX.
A kind of 8. method for detecting DOX, which is characterized in that step is：
(1) it using the processed glass-carbon electrode of sanding and polishing as working electrode, is connected to calomel reference electrode, Pt comparison electrodes
Electrochemical workstation；
(2) by glass-carbon electrode immerse containing same concentrations MB, various concentration DOX PBS mixed solutions in, survey its square wave volt-ampere
(SWV) respond, scanning voltage be -0.9~0V, current potential increment be 0.002V, amplitude 0.025V, frequency 25Hz, and according to
The electrochemical signals Δ I of the DOX and MB of different DOX concentrationDOX/ΔIMBDrawing curve；
(3) a certain amount of MB solution and solution to be measured are added in PBS buffer solution, are uniformly mixed and are configured to mixed solution, MB
Solution and the same step of PBS solution (2)；
(4) it with the SWV signals of DOX and MB in glass-carbon electrode determination step (3) mixed solution, is determined according to the standard curve of drafting
The content of DOX.
9. according to the method described in claim 8, it is characterized in that, in step (1), the processing of glass-carbon electrode sanding and polishing is specific
For：By glass-carbon electrode successively with 0.03~0.5 μm of Al2O3Powder is polished into minute surface, is then cleaned with deionized water, then successively
It is placed in 1~10min of ultrasound in deionized water and ethyl alcohol；The glass-carbon electrode handled well is immersed in potassium ferricyanide solution and is recycled
Voltammetry scans so that redox peaks potential difference is 0~80mV, and scanning voltage is -0.3~0.6V, sweeps speed as 0~0.05V
s-1；Above-mentioned sanding and polishing step is carried out again after the completion of scanning, is dried up after ultrasonic cleaning with nitrogen.
10. according to the method described in claim 8, it is characterized in that, the preparation method of mixed solution is in step (2)：It prepares
The PBS buffer solutions of a concentration of 0.01-0.05M, pH 6.0-7.0；A certain amount of MB solution is taken to instill dropwise under the conditions of being protected from light
In PBS buffer solutions；Different amounts of DOX mother liquors is taken to instill dropwise in above-mentioned solution under the conditions of being protected from light later, ultrasonic disperse is matched
A series of DOX of concentration gradients is made and quantifies the mixed solution of MB, a concentration of 2~200 μM of the DOX mother liquors；
A concentration of 0.1~1mM of MB solution described in step (2), a series of concentration gradients of DOX in the mixed solution being configured to
It is 0.01~4 μM.
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