CN110243887A - Construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor - Google Patents
Construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor Download PDFInfo
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Abstract
The invention discloses a kind of construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor, has synthesized the flower-shaped ZnO structure with good optical electro-chemistry signal first, which has big specific surface area, can load more detectable substances；CdS has been loaded on flower-shaped ZnO again, heterojunction structure has been formd, because the matching of energy level further increases optical electro-chemistry signal；In addition CdTe quantum has not only been modified on secondary antibody and alkaline phosphatase is marked, CdTe carries out signal amplification as signal vehicle, utilize the matching energy level of CdTe quantum and ZnO/CdS, it further reduces detection line alkaline phosphatase and generates ascorbic acid supplied for electronic in situ, can be further improved photocurrent response.
Description
Technical field
The present invention relates to the quantitative detection fields of prostate-specific antigen, be in particular based on ZnO/CdS with
The construction method of CdTe quantum dual signal photoelectric sensor.
Background technique
Tumor markers be tumour cell synthesized by gene expression, secrete or body because to tumour generate reaction
And the substance generated extremely, it plays an important role in early diagnosis of tumor.The early detection demand of cancer is to its tumour mark
Show the method for highly selective, highly sensitive, the quick analysis detection of object.Therefore, it is good pernicious to establish simple and quick sensitive and selectivity
Knubble biological marker new detecting method, early detection to malignant tumour and and treatment effectiveness evaluation there is highly important meaning
Justice.
Its working principle of optical electro-chemistry sensed immunological sensor mainly utilizes the specific recognition function of Ag-Ab, institute
The inductive signal of generation is converted into exportable electrochemical signals by signal adapter, the concentration of the signal and target analytes
Certain proportionate relationship is presented, so as to realize the quantitative analysis to target substance.In recent years, optical electro-chemistry immunosensor
By the concern of many researchers because its immune response high specific, shirtsleeve operation, high sensitivity, it is highly selective with
And the advantages that speed is fast is analyzed, it is obtained extensively in clinical medicine, environmental pollution analyte detection, food analysis, biotechnology field
Using.
Summary of the invention
It is an object of the invention to construct a kind of Photoelectrochemistrbiosensor biosensor for prostate-specific antigen detection.
In order to solve the above-mentioned technical problem, the present invention is realized by following measures: one kind based on ZnO/CdS with
The construction method of CdTe quantum dual signal photoelectric sensor, feature the following steps are included:
(1) 0.3 g ZnSO is taken4·7 H2O and 0.75 g PEG 20000 are in 21 ml ultrapure waters and stir 30 min,
Then the NaOH of 4 ml 5mol/L is taken to be added in above-mentioned mixed liquor, adjusts between PH to 11 ~ 12 and be stirred at room temperature 1 h,
Mixed solution is added to again in the reaction kettle of 25 ml, natural cooling at room temperature is heated after 36 h under 120 °C, will be cooled down
Dry 120 h under 60 °C of solution afterwards；
(2) electro-conductive glass is indium tin oxide glass (ITO), electro-conductive glass is cut into 4.0 × 0.5 cm strips, successively with third
Ketone solution, secondary distilled water and dehydrated alcohol are cleaned by ultrasonic 10 min, and ZnO nano piece made from 10 g steps (1) is taken to be dispersed in 5
In the ultrapure water of ml, takes the above-mentioned solution of 20 μ L that dry 1 h on the ITO handled well and under 450 °C is added dropwise, be subsequently cooled to
Room temperature；
(3) electrode made from step (2) is alternately immersed to the Cd (NO of 0.1 mol/L respectively3)2Methanol solution and 0.1 mol/L
Na2Each 1 min, then washs electrode with methanol repeatedly in S methanol/water mixture (1:1, v/v)；
(4) 0.05 g NaBH is taken4In the TeO of 5 ml, 0.01 mol/L2NaHTe solution is prepared in solution, it is then super in 50 ml
Cd (the NO of 1 mmol/L is sequentially added in pure water3)230 are stirred with the mercaptoacetic acid solution of 1.8 mmol/L and under nitrogen protection
Min, adjusts above-mentioned mixed solution PH to 11 with the NaOH of 1 mol/L, be added in mixed solution NaHTe solution obtained and
2 h are heated under 100 °C；
(5) mixture made from the step of taking 2 ml (4) is added to the 1- (3- dimethylamino-propyl)-of 50 μ L, 20 μ g/mL
In the mixed solution of the N- hydroxysuccinimide of 10 mg/mL of 3- ethyl-carbodiimide hydrochloride and 50 μ L and stir 30
Min takes the Ab2 of 20 μ L, 0.5 mg/mL to be add to the above mixed solution with the ALP of 50 μ L, 0.6 mg/mL and reacts 1 h,
Be 4 °C of revolving speeds in temperature by obtained mixture it is to be centrifuged 10 min under 15000 rpm centrifuges, finally disperses mixture
It is in 7.4 phosphate buffers in 200 μ L, the 10 mmol/L pH containing 1 % (w/v) BSA；
(6) modified electrode handled well in step (5) is platinum electrode to electrode, reference electrode is Ag/ as working electrode
AgCl electrode, bias numerical value are 0 V, and for xenon lamp as source stimulating, electrolytic cell is the phosphate-buffered liquid system that pH is 7.4, are surveyed
Constant current I-T curve carries out the detections of photoelectric properties.
Beneficial effects of the present invention:
(1) present invention is low in cost, experimental implementation is simple, easy control of reaction conditions.
(2) for ZnO/CdS as detection platform, CdTe carries out signal amplification as signal vehicle, using CdTe quantum with
The matching energy level of ZnO/CdS, further reduces detection line.
(3) in sensor-based system, alkaline phosphatase is marked on secondary antibody, alkaline phosphatase generates ascorbic acid in situ and supplies
Electronics can be further improved photocurrent response.
Specific embodiment
For a further understanding of the present invention, implemented in conjunction with the embodiments according to technical solution of the present invention, is provided specific
Embodiment:
(1) 0.3 g ZnSO is taken4·7 H2O and 0.75 g PEG 20000 are in 21 ml ultrapure waters and stir 30 min,
Then the NaOH of 4 ml 5mol/L is taken to be added in above-mentioned mixed liquor, adjusts between PH to 11 ~ 12 and be stirred at room temperature 1 h,
Mixed solution is added to again in the reaction kettle of 25 ml, natural cooling at room temperature is heated after 36 h under 120 °C, will be cooled down
Dry 120 h under 60 °C of solution afterwards；
(2) electro-conductive glass is indium tin oxide glass (ITO), electro-conductive glass is cut into 4.0 × 0.5 cm strips, successively with third
Ketone solution, secondary distilled water and dehydrated alcohol are cleaned by ultrasonic 10 min, and ZnO nano piece made from 10 g steps (1) is taken to be dispersed in 5
In the ultrapure water of ml, takes the above-mentioned solution of 20 μ L that dry 1 h on the ITO handled well and under 450 °C is added dropwise, be subsequently cooled to
Room temperature；
(3) electrode made from step (2) is alternately immersed to the Cd (NO of 0.1 mol/L respectively3)2Methanol solution and 0.1 mol/L
Na2Each 1 min, then washs electrode with methanol repeatedly in S methanol/water mixture (1:1, v/v)；
(4) 0.05 g NaBH is taken4In the TeO of 5 ml, 0.01 mol/L2NaHTe solution is prepared in solution, it is then super in 50 ml
Cd (the NO of 1 mmol/L is sequentially added in pure water3)230 are stirred with the mercaptoacetic acid solution of 1.8 mmol/L and under nitrogen protection
Min, adjusts above-mentioned mixed solution PH to 11 with the NaOH of 1 mol/L, be added in mixed solution NaHTe solution obtained and
2 h are heated under 100 °C；
(5) mixture made from the step of taking 2 ml (4) is added to the 1- (3- dimethylamino-propyl)-of 50 μ L, 20 μ g/mL
In the mixed solution of the N- hydroxysuccinimide of 10 mg/mL of 3- ethyl-carbodiimide hydrochloride and 50 μ L and stir 30
Min takes the Ab2 of 20 μ L, 0.5 mg/mL to be add to the above mixed solution with the ALP of 50 μ L, 0.6 mg/mL and reacts 1 h,
Be 4 °C of revolving speeds in temperature by obtained mixture it is to be centrifuged 10 min under 15000 rpm centrifuges, finally disperses mixture
It is in 7.4 phosphate buffers in 200 μ L, the 10 mmol/L pH containing 1 % (w/v) BSA；
(6) modified electrode handled well in step (5) is platinum electrode to electrode, reference electrode is Ag/ as working electrode
AgCl electrode, bias numerical value are 0 V, and for xenon lamp as source stimulating, electrolytic cell is the phosphate solution that pH is 7.4, change forefront
The concentration of gland specific antigen, within the scope of 0.005 ng/mL to 50 ng/mL, the changing value of photocurrent response and pair of concentration
Good linear relationship, and linear equation is presented in numerical value are as follows:I=13.48 2.5867logc, related coefficient 0.997, detection
It is limited to 0.28 pg/mL, therefore, this work realizes high sensitivity, detects prostate-specific antigen to high stability.
Claims (7)
1. the construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor, feature the following steps are included:
(1) ZnO nano piece is synthesized；
(2) ITO/ZnO electrode is constructed；
(3) ITO/ZnO/CdS electrode is constructed；
(4) CdTe quantum is synthesized；
(5) two anti-CdTe quantums-alkaline phosphatase (Ab is synthesized2- CdTe-ALP) compound；
(6) building of dual signal photoelectric sensor (PEC).
2. the construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor according to claim 1, step
(1) the synthesis ZnO nano piece described in, it is characterized in that: taking 0.3 g ZnSO4·7 H2O and 0.75 g PEG 20000 in
In 21 ml ultrapure waters and 30 min are stirred, the NaOH of 4 ml 5mol/L is then taken to be added in above-mentioned mixed liquor, adjustment PH is arrived
Between 11 ~ 12 and 1 h is stirred at room temperature, then mixed solution is added in the reaction kettle of 25 ml, heats 36 under 120 °C
Natural cooling at room temperature after h, by solution after cooling at 60 oC dry 120 h.
3. the construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor according to claim 1, step
(2) the building ITO/ZnO described in cuts electro-conductive glass it is characterized in that: electro-conductive glass is indium tin oxide glass (ITO)
For 4.0 × 0.5 cm strips, successively it is cleaned by ultrasonic 10 min with acetone soln, secondary distilled water and dehydrated alcohol, 10 g is taken to walk
Suddenly ZnO nano piece made from (1) is dispersed in the ultrapure water of 5 ml, and the above-mentioned solution of 20 μ L is taken to be added dropwise on the ITO handled well simultaneously
Dry 1 h, then cools to room temperature under 450 °C.
4. the construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor according to claim 1, step
(3) the building ITO/ZnO/CdS electrode described in, it is characterized in that: electrode made from step (2) is alternately immersed 0.1 respectively
Cd (the NO of mol/L3)2Methanol solution and 0.1 mol/L Na2Each 1 min in S methanol/water mixture (1:1, v/v) is then used
Methanol washs electrode repeatedly.
5. the construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor according to claim 1, step
(4) the synthesis CdTe quantum described in, it is characterized in that: taking 0.05 g NaBH4In the TeO of 5 ml, 0.01 mol/L2Solution
Middle preparation NaHTe solution, then sequentially adds the Cd (NO of 1 mmol/L in 50 ml ultrapure waters3)2With the mercapto of 1.8 mmol/L
Guanidine-acetic acid solution simultaneously stirs 30 min under nitrogen protection, above-mentioned mixed solution PH to 11 is adjusted with the NaOH of 1 mol/L, mixed
It closes and NaHTe solution obtained is added in solution and heats 2 h under 100 °C.
6. the construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor according to claim 1, step
(5) the anti-CdTe quantum of synthesis two-alkaline phosphatase multienzyme complex (ALP-CdTe-Ab2) described in, it is characterized in that: taking 2 ml
The step of (4) made from mixture, be added to 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide of 50 μ L, 20 μ g/mL
In the mixed solution of the N- hydroxysuccinimide of 10 mg/mL of hydrochloride and 50 μ L and 30 min are stirred, take 20 μ L 0.5
The Ab of mg/mL2It is add to the above mixed solution with the ALP of 50 μ L, 0.6 mg/mL and reacts 1 h, obtained mixture is existed
Temperature is that 4 °C of revolving speeds are to be centrifuged 10 min under 15000 rpm centrifuges, and finally mixture is dispersed in containing 1 % (w/v)
200 μ L, the 10 mmol/L pH of BSA is in 7.4 phosphate buffers.
7. the construction method based on ZnO/CdS Yu CdTe quantum dual signal photoelectric sensor according to claim 1, step
(6) building of the dual signal photoelectric sensor (PEC) described in, it is characterized in that: the modified electrode conduct handled well in step (5)
Working electrode is platinum electrode to electrode, and reference electrode is Ag/AgCl electrode, and bias numerical value is 0 V, and xenon lamp is pierced as light source
Swash, electrolytic cell is the phosphate-buffered liquid system that pH is 7.4, measures electric current I-T curve to carry out the detection of photoelectric properties.
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Cited By (4)
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| CN111273014A (en) * | 2020-03-06 | 2020-06-12 | 安徽大学 | Photoelectrochemical immunosensor for detecting prostate specific antigen and preparation method thereof |
| CN114674893A (en) * | 2022-03-18 | 2022-06-28 | 济南大学 | Construction of sensor based on two-dimensional heterojunction and nanoenzyme combination |
| CN115025787A (en) * | 2022-05-24 | 2022-09-09 | 西南科技大学 | Preparation method and application of CdS quantum dot modified ZnO nanoflower heterojunction |
| CN116458872A (en) * | 2023-06-13 | 2023-07-21 | 汶上县人民医院 | Method and system for analyzing respiratory data |
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| CN111273014A (en) * | 2020-03-06 | 2020-06-12 | 安徽大学 | Photoelectrochemical immunosensor for detecting prostate specific antigen and preparation method thereof |
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| CN114674893A (en) * | 2022-03-18 | 2022-06-28 | 济南大学 | Construction of sensor based on two-dimensional heterojunction and nanoenzyme combination |
| CN114674893B (en) * | 2022-03-18 | 2023-08-11 | 济南大学 | Construction of sensor based on two-dimensional heterojunction and nano enzyme combination |
| CN115025787A (en) * | 2022-05-24 | 2022-09-09 | 西南科技大学 | Preparation method and application of CdS quantum dot modified ZnO nanoflower heterojunction |
| CN115025787B (en) * | 2022-05-24 | 2023-10-13 | 西南科技大学 | Preparation method and application of CdS nanoparticle-doped coated ZnO nanoflower powder |
| CN116458872A (en) * | 2023-06-13 | 2023-07-21 | 汶上县人民医院 | Method and system for analyzing respiratory data |
| CN116458872B (en) * | 2023-06-13 | 2023-09-05 | 汶上县人民医院 | Method and system for analyzing respiratory data |
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Application publication date: 20190917 |