CN106198694A - A kind of ratio dual signal electrochemical sensor based on naked glass-carbon electrode detection doxorubicin hydrochloride - Google Patents
A kind of ratio dual signal electrochemical sensor based on naked glass-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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- 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
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 34
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- 206010028980 Neoplasm Diseases 0.000 abstract description 5
- 201000011510 cancer Diseases 0.000 abstract description 4
- 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
- 239000002953 phosphate buffered saline Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound 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 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 description 60
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- 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 sensor based on naked glass-carbon electrode detection doxorubicin hydrochloride.Concrete detection method is: 1) immerse in the Phosphate buffered saline containing DOX and methylene blue (MB) by glass-carbon electrode, by the electrochemical signals strength ratio Δ I of two kinds of substratesDOX/ΔIMBAssociate with DOX concentration, to draw out linear standard curve；2) surveying containing the SWV signal in the sample of DOX and MB, the standard curve according to drawing determines the content of DOX in serum.Ratio dual signal electrochemical sensor based on naked glass-carbon electrode detection DOX prepared by the present invention possesses simple to operate, highly sensitive, and good stability is of great significance for the dosage tool of DOX in detection Serum of Cancer Patients.
Description
Technical field
The present invention relates to a kind of electrochemical sensor for detecting antitumor drug, be specifically related to a kind of 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
Owing to aged tendency of population is day by day serious, the many factors such as destruction, unsound life style are suffered in ecological environment
Impact, cause tumor patient number to increase year by year.In recent years, chemotherapy of tumors achieves sizable breakthrough, tumor patient
Life span is extended considerably, and the especially treatment to the malignant tumor such as leukemia, malignant lymphoma has had bigger breakthrough；So
And healthy to serious harm human life, to account for malignant tumor more than 90% treatment of solid tumors still fails to reach satisfied effect
Really.Doxorubicin hydrochloride (DOX) is one of anthracyclines antibiotic that treatment malignant tumor is most widely used at present, can to body
Produce biochemical effect widely, there is strong cytotoxic effect.It is embedding that the mechanism of action of DOX is mainly Doxorubicin molecules
Enter cancerous cell DNA and suppress the synthesis of hereditary material nucleic acid, kinds of tumor cells is all had killing action, as breast carcinoma, pulmonary carcinoma,
Bladder cancer, thyroid carcinoma, malignant lymphoma and acute leukemia etc.；But shortcoming is that it is in the treatment with serious Amplatzer duct occluder
Property, suppression hemopoietic function of bone marrow and toxic and side effects etc..Therefore, DOX application in terms of chemotherapy receives a certain degree of restriction.
In mensuration body fluid, in DOX, especially blood sample, the concentration of DOX is significant for the assessment of drug safety.
Method conventional for detection DOX at present has fluorescent spectrometry, ultra-performance liquid chromatography, liquid-liquid extraction-efficient liquid phase
Chromatography and chip capillary cataphoresis fluorescence detection etc., wherein patent of invention " measures in body fluid based on magnetic nanometer adsorbent
The method of DOX " (patent No. 201310445367.X) use chemical coprecipitation, and prepare magnetic by layer assembly and receive
Rice adsorbent TSAB-coated Fe3O4/SiO2, detect the content of DOX in blood plasma and urine sample with this, prepared by the method
Magnetic adsorbent good stability, adsorbance is big, reusable；But operation complexity, relatively costly.Therefore, how to develop
For the detection means simple, efficient, quick of DOX, it it is this area problem demanding prompt solution.
Summary of the invention
The deficiency existed for above-mentioned prior art, an object of the present invention is to provide one and examines based on naked glass-carbon electrode
Survey the ratio dual signal electrochemical sensor of antitumor drug DOX.Utilize the spy that DOX is high with methylene blue (MB) electro-chemical activity
Property, the two is directly added in electrolyte, and without electrode is carried out any modification；Aoxidize between DOX and glass-carbon electrode
, there is the significant signal of telecommunication in reduction；And there is stable signal as reference in MB；In the case of control MB concentration is constant, with
The increase of DOX addition, the signal of telecommunication that DOX causes gradually strengthens；By electrochemical workstation, the signal of telecommunication of DOX and MB is entered
Row detection, it is achieved that the quick and highly sensitive detection of ratio duplex transmission number to DOX.
The two of the purpose of the present invention are to provide the preparation/construction method of above-mentioned electrochemical sensor and application thereof.
Additionally, the present invention also aims to provide the detection method of a kind of DOX.
For achieving the above object, the concrete present invention uses following technical proposals:
First, the present invention provides the construction method of a kind of electrochemical sensor for detecting DOX, comprises the following steps:
(1) a certain amount of MB solution and different amounts of DOX solution are joined in buffer, mix homogeneously, it is configured to one
The mixed solution of the DOX of series concentration gradient and quantitative MB；
(2) by glass-carbon electrode sanding and polishing, immerse in the mixed solution that step (3) obtains；
(3) glass-carbon electrode step (2) processed is as working electrode, is connected to electricity with reference electrode, comparison electrode
Chem workstation, collectively forms and can detect antitumor drug DOX electrochemical sensor.
In concrete preferably technical scheme, in step (1), the concentration of MB solution is 0.1～1mM, and the concentration of DOX mother solution is 2
～200 μMs, in the mixed solution being configured to, a series of Concentraton gradient of DOX are 0.01～4 μM.
Preferably, in step (1), the compound method of mixed solution is: compound concentration is 0.01-0.05M, pH6.0-7.0's
PBS buffer solution；Under the conditions of lucifuge, take a certain amount of MB solution dropwise instill in PBS buffer solution；Afterwards under the conditions of lucifuge
Take different amounts of DOX mother solution and dropwise instill in above-mentioned solution, ultrasonic disperse, it is configured to the DOX of a series of Concentraton gradient with quantitative
The mixed solution of MB.
It is furthermore preferred that PBS buffer concentration is 0.01M, pH 6.5.
Preferably in technical scheme, in step (2), glass-carbon electrode sanding and polishing processes, particularly as follows: by glass-carbon electrode successively
Al by 0.03～0.5 μm2O3Powder is polished into minute surface, then cleans with deionized water, then is sequentially placed into deionized water and ethanol
In ultrasonic 1～10min；The glass-carbon electrode handled well is immersed in potassium ferricyanide solution and be circulated voltammetry scanning so that oxygen
Changing reduction peak potential difference is 0～80mV, and scanning voltage is-0.3～0.6V, and sweeping speed is 0～0.05V s-1；After having scanned again
Carry out above-mentioned sanding and polishing step, dry up with nitrogen after ultrasonic cleaning.
Preferably in technical scheme, in step (3), described reference electrode is calomel or Pt or glass-carbon electrode, described contrast
Electrode is calomel or Pt or glass-carbon electrode.
Secondly, the present invention provides the electrochemical sensor for detecting DOX that above-mentioned construction method obtains.
Additionally, the present invention provides the application in qualitative or quantitative detection DOX of the above-mentioned electrochemical sensor.
Further, the present invention provides a kind of method detecting DOX, and step is:
(1) glass-carbon electrode processed by sanding and polishing is as working electrode, with calomel reference electrode, Pt comparison electrode even
Receive electrochemical workstation；
(2) glass-carbon electrode is immersed in the PBS mixed solution containing same concentrations MB, variable concentrations DOX, survey its square wave volt
Peace (SWV) response, scanning voltage is-0.9～0V, and current potential increment is 0.002V, and amplitude is 0.025V, and frequency is 25Hz, and root
According to the electrochemical signals of DOX with MB of different DOX concentration than Δ IDOX/ΔIMBDrawing curve；
(3) joining in PBS by a certain amount of MB solution and solution to be measured, mix homogeneously is configured to mix molten
Liquid, MB solution and the same step of PBS solution (2)；
(4) with the SWV signal of DOX and MB in glass-carbon electrode determination step (3) mixed solution, according to the standard curve drawn
Determine the content of DOX.
Preferably in technical scheme, in step (1), glass-carbon electrode sanding and polishing processes, particularly as follows: by glass-carbon electrode successively
Al by 0.03～0.5 μm2O3Powder is polished into minute surface, then cleans with deionized water, then is sequentially placed into deionized water and ethanol
In ultrasonic 1～10min；The glass-carbon electrode handled well is immersed in potassium ferricyanide solution and be circulated voltammetry scanning so that oxygen
Changing reduction peak potential difference is 0～80mV, and scanning voltage is-0.3～0.6V, and sweeping speed is 0～0.05Vs-1；After having scanned again
Carry out above-mentioned sanding and polishing step, dry up with nitrogen after ultrasonic cleaning.
In concrete preferably technical scheme, in step (2), the compound method of mixed solution is: compound concentration is 0.01-
The PBS buffer solution of 0.05M, pH 6.0-7.0；Under the conditions of lucifuge, take a certain amount of MB solution dropwise instill PBS buffer solution
In；Under the conditions of lucifuge, take different amounts of DOX mother solution afterwards dropwise instill in above-mentioned solution, ultrasonic disperse, it is configured to a series of
The mixed solution of the DOX of Concentraton gradient and quantitative MB.
It is furthermore preferred that the concentration of MB solution is 0.1～1mM described in step (2), the concentration of DOX mother solution is 2～200 μMs,
In the mixed solution being configured to, a series of Concentraton gradient of DOX are 0.01～4 μM.
The method of detection doxorubicin hydrochloride/DOX of the present invention can be used for detecting the DOX in human plasma, serum or urine
Content, it is also possible to DOX's is quantitative in routine test reagent or solution, reactant liquor.
The present invention achieves following beneficial effect:
(1) the ratio dual signal electrochemical sensor preparation method of the present invention is simple, easily manipulates, and reaction condition is gentle；
The electrochemical detection method of the present invention has the plurality of advantages such as simple to operate, with low cost, highly sensitive and fast response time, especially
It is that the use of ratio dual signal can be prevented effectively from single signal strength fluctuation and cause the error of measurement, and this is one for detection DOX
Individual preferable selection；
(2) so far, not yet there is ratio dual signal electrochemistry DOX sensor, the most not yet have based on bare electrode (such as glass carbon
Electrode) go up domestic and international pertinent literature and the report of patent building ratio dual signal electrochemical sensor；The present invention is first by DOX
Be combined with MB and prepare ratio dual signal electrochemical sensor, it is achieved DOX is detected fast and efficiently；
(3) electrochemical sensor of the present invention utilizes naked glass-carbon electrode directly to detect DOX, it is not necessary to carry out electrode
Any modification, to the detection limit of DOX can as little as 4nM, highly sensitive.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the ratio dual signal electrochemical sensor detection DOX of the present invention
Fig. 2 is the SWV of variable concentrations gradient DOX and fixed concentration MB
Fig. 3 is that DOX with MB electrochemical signals is than Δ IDOX/ΔIMBLinear dependence figure with DOX concentration
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, it should explanation, and the description below is only used to
Explain the present invention, its content is not defined.
Instrument and reagent used in experiment is: (1) instrument: (Shanghai occasion China instrument has CHI650 electrochemical workstation
Limit company)；Using saturated calomel electrode (SCE) is reference electrode, and platinum electrode is to electrode；(2) (raw work is biological for reagent: DOX
Engineering (Shanghai) Co., Ltd.), analytical pure；MB (Aladdin reagent (Shanghai) Co., Ltd.), analytical pure.
Other reagent are analytical pure, and experimental water is deionized water.
Embodiment 1:
(1) compound concentration is the PBS buffer solution of 0.01M, pH 6.5.50 μ L, 1mM MB solution is taken under the conditions of lucifuge
Dropwise instill in PBS buffer solution.The PBS that different amounts of 200 μMs of DOX dropwise instill above-mentioned MB is taken molten under the conditions of same lucifuge
In liquid, ultrasonic mixing dispersion, being made into Concentraton gradient respectively is 0.01 μM, 0.05 μM, 0.1 μM, 0.5 μM, 1 μM, 2 μMs, 3 μMs and 4 μ
M。
(2) by glass-carbon electrode successively with 0.5 μm and the Al of 0.03 μm2O3Powder is polished into minute surface, then clear with deionized water
Wash, then be sequentially placed in deionized water and ethanol ultrasonic 1～2min；The glass-carbon electrode handled well is immersed potassium ferricyanide solution
In be circulated voltammetry scanning so that oxidoreduction spike potential difference be less than 80mV；Above-mentioned polishing is again carried out after having scanned
Polishing step, dries up with nitrogen after ultrasonic cleaning.Electrode is immersed the SWV signal surveying DOX and MB in above-mentioned mixed solution.
Embodiment 2: the mensuration of actual sample
(1) the PBS buffer solution of human serum 0.01M, pH 6.5 is diluted ten times.50 μ L, 1mM are taken under the conditions of lucifuge
MB solution dropwise instills in human serum solution.Take a certain amount of DOX under the conditions of same lucifuge and instill the human serum solution of above-mentioned MB
In, ultrasonic mixing.
(2) by the step of the SWV signal of DOX and MB in glass-carbon electrode mensuration human serum solution with the step of embodiment 1
(2) content of DOX, is determined according to the standard curve drawn.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Embodiment 3
(1) compound concentration is the PBS buffer solution of 0.03M, pH 7.0.50 μ L, 0.1mM MB is taken molten under the conditions of lucifuge
Liquid dropwise instills in PBS buffer solution.Take different amounts of 100 μMs of DOX under the conditions of same lucifuge and dropwise instill the PBS of above-mentioned MB
In solution, ultrasonic mixing dispersion, be made into respectively Concentraton gradient be 0.01 μM, 0.05 μM, 0.1 μM, 0.5 μM, 1 μM, 2 μMs, 3 μMs and
4μM。
(2) by glass-carbon electrode successively with 0.5 μm and the Al of 0.03 μm2O3Powder is polished into minute surface, then clear with deionized water
Wash, then be sequentially placed ultrasonic 2min in deionized water and ethanol；The glass-carbon electrode handled well is immersed in potassium ferricyanide solution
It is circulated voltammetry scanning so that oxidoreduction spike potential difference is less than 80mV；Above-mentioned polishing throwing is again carried out after having scanned
Light step, dries up with nitrogen after ultrasonic cleaning.Electrode is immersed the SWV signal surveying DOX and MB in above-mentioned mixed solution.
Claims (10)
1. the construction method being used for detecting the electrochemical sensor of DOX, it is characterised in that comprise the following steps:
(1) a certain amount of MB solution and different amounts of DOX solution are joined in buffer, mix homogeneously, it is configured to a series of
The mixed solution of the DOX of Concentraton gradient and quantitative MB；
(2) by glass-carbon electrode sanding and polishing, immerse in the mixed solution that step (3) obtains；
(3) glass-carbon electrode step (2) processed is as working electrode, is connected to electrochemistry with reference electrode, comparison electrode
Work station, collectively forms and can detect antitumor drug DOX electrochemical sensor.
Method the most according to claim 1, it is characterised in that in step (1), the concentration of MB solution is 0.1～1mM, DOX
The concentration of mother solution is 2～200 μMs, and in the mixed solution being configured to, a series of Concentraton gradient of DOX are 0.01～4 μM.
Method the most according to claim 1 and 2, it is characterised in that in step (1), the compound method of mixed solution is: join
Concentration processed is the PBS buffer solution of 0.01-0.05M, pH 6.0-7.0；Under the conditions of lucifuge, take a certain amount of MB solution dropwise instill
In PBS buffer solution；Under the conditions of lucifuge, take different amounts of DOX mother solution afterwards dropwise instill in above-mentioned solution, ultrasonic disperse, join
Make the mixed solution of the DOX and quantitative MB of a series of Concentraton gradient.
Method the most according to claim 1, it is characterised in that in step (2), glass-carbon electrode sanding and polishing is particularly as follows: incite somebody to action
Glass-carbon electrode is successively with the Al of 0.03～0.5 μm2O3Powder is polished into minute surface, then cleans with deionized water, then is sequentially placed into
In ionized water and ethanol ultrasonic 1～10min；The glass-carbon electrode handled well is immersed in potassium ferricyanide solution and is circulated voltammetry
Scanning so that oxidoreduction spike potential difference is 0～80mV, and scanning voltage is-0.3～0.6V, and sweeping speed is 0～0.05V s-1；Sweep
Again carry out above-mentioned sanding and polishing step after having retouched, dry up with nitrogen after ultrasonic cleaning.
Method the most according to claim 1, it is characterised in that in step (3), described reference electrode is calomel or Pt or glass
Carbon electrode, described comparison electrode is calomel or Pt or glass-carbon electrode.
6. the electrochemical sensor for detecting DOX that construction method described in any one of claim 1-5 obtains.
7. the application in qualitative or quantitative detection DOX of the electrochemical sensor described in claim 6.
8. the method detecting DOX, it is characterised in that step is:
(1) glass-carbon electrode processed by sanding and polishing is as working electrode, is connected to calomel reference electrode, Pt comparison electrode
Electrochemical workstation；
(2) glass-carbon electrode is immersed in the PBS mixed solution containing same concentrations MB, variable concentrations DOX, survey its square wave volt-ampere
(SWV) response, scanning voltage is-0.9～0V, and current potential increment is 0.002V, and amplitude is 0.025V, and frequency is 25Hz, and according to
The electrochemical signals of DOX with MB of different DOX concentration is than Δ IDOX/ΔIMBDrawing curve；
(3) joining in PBS by a certain amount of MB solution and solution to be measured, mix homogeneously is configured to mixed solution, MB
Solution and the same step of PBS solution (2)；
(4) with the SWV signal of DOX and MB in glass-carbon electrode determination step (3) mixed solution, the standard curve according to drawing determines
The content of DOX.
Method the most according to claim 8, it is characterised in that in step (1), glass-carbon electrode sanding and polishing processes concrete
For: by glass-carbon electrode successively with the Al of 0.03～0.5 μm2O3Powder is polished into minute surface, then cleans with deionized water, more successively
It is placed in deionized water and ethanol ultrasonic 1～10min；The glass-carbon electrode handled well is immersed in potassium ferricyanide solution and is circulated
Voltammetry scans so that oxidoreduction spike potential difference is 0～80mV, and scanning voltage is-0.3～0.6V, and sweeping speed is 0～0.05V
s-1；Again carry out above-mentioned sanding and polishing step after having scanned, dry up with nitrogen after ultrasonic cleaning.
Method the most according to claim 8, it is characterised in that in step (2), the compound method of mixed solution is: preparation
Concentration is the PBS buffer solution of 0.01-0.05M, pH 6.0-7.0；Under the conditions of lucifuge, take a certain amount of MB solution dropwise instill
In PBS buffer solution；Under the conditions of lucifuge, take different amounts of DOX mother solution afterwards dropwise instill in above-mentioned solution, ultrasonic disperse, join
Make the mixed solution of the DOX and quantitative MB of a series of Concentraton gradient；
Described in step (2), the concentration of MB solution is 0.1～1mM, and the concentration of DOX mother solution is 2～200 μMs, the mixing being configured to
In solution, a series of Concentraton gradient of DOX are 0.01～4 μM.
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| CN109521071A (en) * | 2018-12-18 | 2019-03-26 | 江西农业大学 | A kind of electrochemical sensing detection method of Ion pairing probenazole |
| CN113252752A (en) * | 2021-05-18 | 2021-08-13 | 青岛大学 | Preparation method of sulfur nanoparticle/MOF/boron nanosheet/ferrocenyl nano hybrid ratio electrochemical sensor |
| CN117288816A (en) * | 2023-08-01 | 2023-12-26 | 广东工业大学 | MXene-DNA-based composite material, sensor, preparation method of sensor and application of sensor in detection of doxorubicin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109521071A (en) * | 2018-12-18 | 2019-03-26 | 江西农业大学 | A kind of electrochemical sensing detection method of Ion pairing probenazole |
| CN109521071B (en) * | 2018-12-18 | 2020-09-11 | 江西农业大学 | Electrochemical sensing detection method for benzimidazole pesticide thiabendazole |
| CN113252752A (en) * | 2021-05-18 | 2021-08-13 | 青岛大学 | Preparation method of sulfur nanoparticle/MOF/boron nanosheet/ferrocenyl nano hybrid ratio electrochemical sensor |
| CN113252752B (en) * | 2021-05-18 | 2023-09-15 | 青岛大学 | Preparation method of sulfur nanoparticle/MOF/boron nanosheet/ferrocenyl nano hybrid ratio electrochemical sensor |
| CN117288816A (en) * | 2023-08-01 | 2023-12-26 | 广东工业大学 | MXene-DNA-based composite material, sensor, preparation method of sensor and application of sensor in detection of doxorubicin |
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