CN113113545B - Electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material and preparation method and application thereof - Google Patents
Electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material and a preparation method and application thereof, belonging to the technical field of photoelectric sensing materials. The material takes perylene tetracarboxylic acid as an electron acceptor, takes dopamine as an electron donor, has a Schottky heterostructure, and can realize effective separation of photoelectrons and holes, so that the material has high-efficiency separation of electron-hole pairs and stable photoelectron transmission capability. The sandwich immune reaction is used for constructing the photoelectrochemical biosensor, has high photoelectric conversion efficiency, can provide stable and sensitive PEC signals, and can realize low-background and high-sensitivity target detection without adding a certain concentration of electron donor during PEC test because an electron donor-acceptor group exists simultaneously. The preparation method of the material is simple and easy to operate, and is suitable for expanded production.
Description
Technical Field
The invention belongs to the technical field of photoelectric sensing materials, and particularly relates to an electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material, and a preparation method and application thereof.
Background
Photo Electrochemical (PEC) analysis is a novel Photoelectrochemical analysis method based on an electrochemical technology, in which a substance with photoelectric activity generates photo-generated electrons under the excitation of an external light source to separate and transfer holes to cause the change of photocurrent or photovoltage, and the core of the analysis is photoelectric conversion. The construction of green and economic photo-electrochemical biosensors with high sensitivity and good stability has become a research hotspot in the photoelectric field.
The organic semiconductor is limited in practical application due to low hole-photoelectron separation efficiency and poor conductivity, a single inorganic semiconductor is poor in conductivity, electrons and holes are separated at a heterojunction and are difficult to rapidly transmit, photoelectron-hole recombination is easy to occur, photoelectric efficient separation is limited, the cost is generally high, the environment is polluted, a heterojunction material for synthesizing the organic and inorganic semiconductor is designed, and the photoelectric conversion efficiency of the material can be improved by virtue of a built-in electric field. Therefore, the photoelectric active material with stable structure, high photoelectric conversion efficiency and environmental friendliness can promote the development of a high-sensitivity, high-stability, green and economic sensor.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing an electron donor-type organic semiconductor-gold schottky heterojunction material; the second purpose is to provide an electron donor-type organic semiconductor-gold Schottky heterojunction material; the third purpose is to provide the application of the electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material in a photoinduced electrochemical biosensor; the fourth purpose is to provide a preparation method of the carcinoembryonic antigen photo-induced electrochemical detection kit based on the electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material; the fifth objective is to provide a photo-induced electrochemical detection kit for carcinoembryonic antigen.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of an electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material comprises the following steps:
under the dark condition, firstly, dispersing perylenetetracarboxylic dianhydride in an alkaline solution with the pH of 9-12.5 until the perylenetetracarboxylic dianhydride is completely hydrolyzed, adjusting the pH to 5-6, activating with EDC and NHS, then adding a dopamine hydrochloride solution, uniformly mixing, reacting to obtain an electron donor receptor type organic semiconductor, adding a chloroauric acid solution under stirring, continuously reacting after uniform mixing, centrifugally washing after the reaction is finished, collecting precipitate, and obtaining the electron donor receptor type organic semiconductor-gold Schottky heterojunction material.
Preferably, the mass ratio of the perylenetetracarboxylic dianhydride, the EDC, the NHS, the dopamine hydrochloride and the chloroauric acid is 5.
Preferably, after being mixed uniformly, the mixture is oscillated and reacted at the rotating speed of 30-40r/min for 2 days to obtain the electron donor-acceptor type organic semiconductor.
Preferably, the chloroauric acid solution is added under stirring, and after uniform mixing, the oscillation reaction is continued for 2 to 3 days at the rotating speed of 30 to 40 r/min.
Preferably, the alkaline solution is one of a sodium hydroxide solution or a potassium hydroxide solution.
Preferably, the pH is adjusted to 5-6 by dilute hydrochloric acid with the concentration of 0.1 mol/L.
Preferably, the specific method for activation with EDC and NHS is as follows: adding EDC under stirring at the rotating speed of 150-200r/min, adding NHS after stirring for 10-20min, and continuing stirring for 1.5-2h.
Preferably, the dopamine hydrochloride solution is added at a rate of 0.25-0.5 mL/min; adding chloroauric acid solution at the speed of 8-10 mu L/min under stirring at the rotating speed of 150-200 r/min.
Preferably, the centrifugal washing times are 2-3, and each time, the centrifugal washing is carried out for 10-15min at the rotating speed of 9000-12000 r/min.
2. The electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material prepared by the method.
3. The electron donor acceptor type organic semiconductor-gold Schottky heterojunction material is applied to a photo-induced electrochemical biosensor.
4. The preparation method of the carcinoembryonic antigen photo-induced electrochemical detection kit based on the electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material comprises a photoelectric immune probe and a working electrode; the method comprises the following steps:
(1) Preparation of a photoelectric ImmunoProbe
Dispersing the electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material in water, adding EDC and NHS for activation, then adding carcinoembryonic antibody, incubating and then centrifugally washing to obtain the material;
(2) Preparation of working electrode
And (2) depositing nanogold on a glassy carbon electrode, washing and drying the nanogold, dripping thioglycollic acid, incubating, washing, activating by EDC and NHS, finally adding a carcinoembryonic antibody, incubating, sealing a non-specific binding site by bovine serum albumin, and washing.
Preferably, in the step (1), the electron donor and acceptor type organic semiconductor-gold schottky heterojunction material is dispersed in water, EDC is added under stirring at the rotation speed of 150-200r/min, NHS is added after stirring for 10-20min, stirring is continued for 1.5-2h, then carcinoembryonic antibody is added, incubation is carried out for 8-12h at 4 ℃, and centrifugal washing is carried out for 2-3 times at the rotation speed of 7000-9000r/min, and each time is carried out for 8-15 min.
Preferably, in the step (2), the glassy carbon electrode is immersed in a solution containing HAuCl 4 Na of (2) 2 SO 4 In the solution, electrodepositing nanogold for 5-15s at constant potential of-0.1 to-0.3V, washing and drying, then dripping thioglycollic acid, incubating at room temperature for 50-90min, washing, adding EDC under stirring at the rotating speed of 150-200r/min, adding NHS after stirring for 10-20min, continuing stirring for 1.5-2h, then adding carcinoembryonic antibody, incubating at 4 ℃ for 8-12h, sealing non-specific binding sites with bovine serum albumin, and washing with phosphate buffer solution.
5. The carcinoembryonic antigen photo-induced electrochemical detection kit prepared by the method.
The invention has the beneficial effects that: the invention provides an electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material and a preparation method and application thereof, wherein perylenetetracarboxylic acid is used as an electron acceptor, dopamine is used as an electron donor, the material has a Schottky heterojunction structure, after the material is excited by light, the electron donor generates photogenerated electrons, the electron acceptor generates holes to form photogenerated electron-hole pairs, and the photogenerated electrons and the holes are rapidly separated under the action of a built-in electric field of the Schottky heterojunction. The sandwich immune reaction is used for constructing the photoelectrochemical biosensor, has high electrical conversion efficiency, can provide stable and sensitive PEC signals, and can realize low-background and high-sensitivity target detection without adding a certain concentration of electron donor during PEC test because an electron donor-acceptor group exists simultaneously. The preparation method of the material is simple and easy to operate, and is suitable for expanded production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For a better understanding of the objects, aspects and advantages of the present invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a flow chart of the preparation of PTCs @ Au in the present invention;
FIG. 2 is a TEM image of PTCs @ Au prepared in example 1 at different magnifications;
FIG. 3 is an electron diffraction pattern of the selected region of nanogold in PTCs @ Au prepared in example 1;
FIG. 4 is an EDS plot of PTCs @ Au prepared in example 1;
FIG. 5 is a schematic diagram of the detection principle of carcinoembryonic antigen by a double antibody sandwich immunoassay;
FIG. 6 is a graph showing the results of the test of the effect of DA, PTCA, PTCs and PTCs @ Au on the photoelectricity reaction in example 3 (a, b, c, d are PEC signals of DA, PTCA, PTCs and PTCs @ Au immunoreaction with BSA/Ab/GCE, respectively, and a ', b', c ', d' are PEC signals of DA, PTCA, PTCs and PTCs @ Au immunoreaction with BSA/Ab/Dp Au/GCE, respectively);
FIG. 7 is a diagram showing the results of the analytical performance test of the sensor according to the present invention (A in FIG. 7 is a photocurrent-concentration response diagram, B in FIG. 7 is a calibration curve of the photocurrent versus the logarithm of the CEA concentration);
FIG. 8 is a graph of the sensor stability test results of the present invention;
FIG. 9 is a graph showing the results of the selective testing of the sensor according to the present invention.
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparation of Electron Donor-acceptor type organic semiconductor-gold Schottky heterojunction Material (PTCs @ Au)
As shown in fig. 1, under the condition of keeping out of the sun, firstly dispersing 5mg of perylenetetracarboxylic dianhydride in potassium hydroxide solution (concentration of 0.5 mmol/L) with pH of 10.7, performing ultrasonic treatment until the perylenetetracarboxylic dianhydride is completely hydrolyzed, adjusting the pH to 6 with 0.1mol/L dilute hydrochloric acid, adding 1mL of 2mmol/L EDC solution at a rotation speed of 180r/min, stirring for 15min, adding 87 μ L NHS solution at a concentration of 0.2mol/L, continuing stirring for 2h, then adding 5mL of 2mg/mL dopamine hydrochloride solution at a speed of 0.3mL/min, after mixing, performing oscillatory reaction at a rotation speed of 40r/min for 2 days to obtain an electron donor-acceptor type organic semiconductor, after stirring at a rotation speed of 180r/min, adding 200 μ L chloroauric acid solution at a mass fraction of 0.1% at a speed of 10 μ L/min, continuing oscillatory reaction at a rotation speed of 40r/min for 2 days, after the reaction is completed, performing a rotation speed of 10 μ L/min for 1203-1% mass fraction on the chloroauric acid solution, and finally obtaining the electron donor-acceptor type organic semiconductor, and centrifuging the obtained material, and precipitating the gold donor material, and obtaining the gold donor material.
FIG. 2 shows TEM of PTCs @ Au prepared in example 1 under different times, which shows that the particle size of PTCs @ Au is relatively uniform, and the nanogold is wrapped with a layer of amorphous organic matter with a thickness of about 1 nm.
FIG. 3 is the electron diffraction pattern of the selected region of nanogold in PTCs @ Au prepared in example 1, which indicates that nanogold has body-centered cubic crystal.
FIG. 4 is an EDS chart of PTCs @ Au prepared in example 1, and it is understood that PTCs @ Au contains four elements of C, N, O and Au.
Comparative examples
Preparation of Electron Donor-acceptor-type organic Semiconductors (PTCs)
Under the condition of keeping out of the sun, firstly dispersing 5mg of perylenetetracarboxylic dianhydride in a potassium hydroxide solution (the concentration is 0.5 mmol/L) with the pH value of 10.7 for ultrasonic treatment until the perylenetetracarboxylic dianhydride is completely hydrolyzed, adjusting the pH value to 6 by using dilute hydrochloric acid with the concentration of 0.1mol/L, adding 1mL of EDC solution with the concentration of 2mmol/L under the stirring of the rotation speed of 180r/min, stirring for 15min, adding 87 muL of NHS solution with the concentration of 0.2mol/L, continuing stirring for 2h, then adding 5mL of dopamine hydrochloride solution with the concentration of 2mg/mL at the speed of 0.3mL/min, oscillating and reacting for 4 days after uniformly mixing at the rotation speed of 40r/min, centrifugally washing for 3 times at the rotation speed of 12000r/min after the reaction is finished, taking out the precipitate every 15min, and preparing the electronic donor-receptor type organic semiconductor.
Example 2
Carcinoembryonic antigen (CEA) photo-induced electrochemical detection kit based on electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material
(1) Preparation of a photoelectric ImmunoProbe
PTCs @ Au prepared in example 1 is dispersed in water, 200 mu L of EDC solution with the concentration of 2mmol/L is added under stirring at the rotation speed of 180r/min, 10 mu L of NHS solution with the concentration of 0.2mol/L is added after stirring for 15min, stirring is continued for 2h, then 2mL of cancer embryo antibody (detection antibody, ab 2) with the concentration of 1mg/mL is added, incubation is carried out for 12h at 4 ℃, centrifugal washing is carried out for 3 times at the rotation speed of 8000r/min for 10min each time, so as to prepare the photoelectric immune probe (Ab 2-PTCs @ Au), and the photoelectric immune probe is dispersed in 5mL of phosphate buffer solution with the pH of 7.4 and the concentration of 0.1mol/L for standby;
(2) Preparation of working electrode
Immersing glassy carbon electrode in a solution containing HAuCl 4 Na (b) of 2 SO 4 Solution (HAuCl in solution) 4 In a concentration of 0.5wt.%, na 2 SO 4 0.1 mol/L), electrodepositing nanogold for 10s at a constant potential of-0.2V, washing and drying, then dropwise coating 5 mu L of thioglycolic acid with the concentration of 0.1mmol/L, incubating for 60min at room temperature, washing, adding 200 mu L of EDC solution with the concentration of 2mmol/L under stirring at the rotating speed of 180r/min, adding 10 mu L of NHS solution with the concentration of 0.2mol/L after stirring for 15min, continuing stirring for 2h, then adding 6 mu L of cancer embryo antibody (capture antibody, ab 1) with the concentration of 1mg/mL, incubating for 12h at 4 ℃, sealing non-specific binding sites with 3 mu L of bovine serum albumin with the concentration of 1wt.%, reacting for 2h, and then washing with phosphate buffer solution with the pH of 7.4 and the concentration of 0.1mol/L to prepare the working electrode.
Example 3
Detecting the effect of different substances in a photoelectric reaction
(1) With Dopamine (DA), perylene tetracarboxylic acid (PTCA), the electron donor-type organic Semiconductor (PTCs) prepared in comparative example, and the electron donor-type organic semiconductor-gold schottky heterojunction material (PTCs @ au) prepared in example 1 as the photoelectric materials, 4 different photoelectric immunoprobes were prepared with reference to the method in step (1) of example 2, ab2-DA, ab2-PTCA, ab2-PTCs, and Ab2-PTCs @ au, respectively;
(2) The working electrode prepared in the step (2) of the example 2 is used as the working electrode I (BSA/Ab 1/Dp Au/GCE), and the method in the step (2) of the example 2 is referred to, but the working electrode II (BSA/Ab 1/GCE) is prepared without depositing nano-gold on the glassy carbon electrode;
(3) 4 kinds of photoelectric immune probes are respectively subjected to immunodetection with two working electrodes, and detection is carried out by a double-antibody sandwich immunoassay, the detection principle schematic diagram is shown in figure 5, as can be seen from figure 5, CEA is incubated on the immune electrodes for 30min at 37 ℃, and Ab1 serving as a capture probe captures a target detection object CEA through specific recognition. Then, on the electrode, the photoelectric immune probe Ab2-PTCs @ Au is incubated under the same condition, and the photoelectric active substance is introduced into a sensing interface by a target object through sandwich immune specific recognition. The amount of the target detection species is correlated with the amount of the organic nanocomposite material, and the PEC signal is obtained under illumination. The higher the target concentration, the stronger the signal obtained. During detection, an electrochemical workstation (CHI 440A, shanghai Chenghua instruments Co., ltd., china) is provided with an external visible light source (PEAC 200A) as a detection device, and a three-electrode system comprises: the glassy carbon electrode and the modified glassy carbon electrode are used as working electrodes, the Ag/AgCl electrode is used as a reference electrode, the platinum wire is used as a counter electrode, and the test base solution is 0.1mol/L phosphate buffer solution (pH = 7.4). The working electrode was immersed in 4mL of test base solution with the light source off-on-off set at 10s-20s-10s. The test results are shown in FIG. 6 (a, b, c, d are PEC signal diagrams after the Ab2-DA, ab2-PTCA, ab2-PTCs and Ab2-PTCs @ Au probes are immunoreactive with a BSA/Ab1/GCE sandwich, and a ', b', c ', d' are PEC signal diagrams after the Ab2-DA, ab2-PTCA, ab2-PTCs and Ab2-PTCs @ Au are immunoreactive with the BSA/Ab1/Dp Au/GCE sandwich), the DA generates anode photocurrent without an external electron donor, which indicates that the DA has strong reducibility and can participate in the photoelectric reaction as the electron donor to obtain a PEC response; and the photocurrent signal generated by PTCA is very weak, and the PEC signal generated by PTCs @ Au is higher than that of PTCs, which shows that the nanogold in the compound can effectively separate photo-generated electrons from holes, improve the photoelectric conversion efficiency and realize signal amplification. In addition, the PEC signal of the working electrode decorated by the electrodeposited nano-gold is higher than that of the working electrode without decorated by the nano-gold, which shows that the nano-gold on the working electrode can better accelerate the electron transfer and photoelectric conversion of photoelectric substances, thereby realizing signal amplification.
Example 4
Sensor analysis Performance test
The photoelectric immune probe and the working electrode prepared in example 2 were subjected to an immune test, and an external visible light source (PEAC 200A) was configured as a detection device in an electrochemical workstation (CHI 440A, shanghai chenhua instruments ltd, china) during detection, in a three-electrode system: the glassy carbon electrode and the modified glassy carbon electrode are used as working electrodes, the Ag/AgCl electrode is used as a reference electrode, the platinum wire is used as a counter electrode, and the test base solution is 0.1mol/L phosphate buffer solution (pH = 7.4). The working electrode is immersed in 4mL of detection base solution, the concentration of carcinoembryonic antigen in the detection base solution is changed from 0.01pg/mL to 10 mu g/mL, and the light source is set to be 10s-20s-10s on-off. The detection results are shown in FIG. 7 (A in FIG. 7 is a photocurrent-concentration response graph, B in FIG. 7 is a calibration graph of photocurrent versus logarithm of CEA concentration), PEC signals and logarithm of CEA concentration have good positive correlation, and the linear equation is I = -0.105-0.0027lgc CEA ，R 2 =0.991 (I: photocurrent; c: CEA concentration; R: correlation coefficient), and the limit of detection (LOD) is 0.38pg/mL.
Example 5
Sensor stability assessment
Referring to the method in example 4, the photoelectromagnetic probe and the working electrode prepared in example 2 were subjected to 19 consecutive measurements on 10pg/mL of the target CEA, and the results of the measurements are shown in fig. 8, which indicates that the obtained photocurrent signal had a Relative Standard Deviation (RSD) value of 1.6%, indicating that the PEC sensor has good stability.
Example 6
Sensor selectivity evaluation
Referring to the method of example 4, the photoelectromagnetic probe and the working electrode prepared in example 2 were tested for Prostate Specific Antigen (PSA), alpha-fetoprotein (AFP), bovine Serum Albumin (BSA), carcinoembryonic antigen (CEA), and a Mixture of substances in 4 (mix), all at a concentration of 10pg/mL, respectively, and the results of the tests are shown in fig. 9.
Example 7
CEA was added to 50-fold diluted human serum (0.1 mol/L PBS, pH = 7.4) by a standard addition method, and the detection was performed by using the photo-immune probe prepared in example 2 and the working electrode according to the method of example 4, respectively, and the results are shown in Table 1.
TABLE 1 detection and analysis results of carcinoembryonic antigen in human serum
As can be seen from Table 1, the recovery rate of the added standard is 99.5% -100.3%, the relative standard deviation is 1.6% -3.2%, and the detection effect is good, which indicates that the sensor can be used for detecting carcino-embryonic antigen in biological samples.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of an electron donor-acceptor type organic semiconductor-gold Schottky heterojunction material is characterized by comprising the following steps:
under the dark condition, firstly, perylene tetracarboxylic dianhydride is dispersed in alkaline solution with the pH value of 9-12.5 until the perylene tetracarboxylic dianhydride is completely hydrolyzed, the pH value is adjusted to 5-6, then 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide are used for activation, then dopamine hydrochloride solution is added, after uniform mixing, reaction is carried out until an electron donor receptor type organic semiconductor is obtained, chloroauric acid solution is added under stirring, after uniform mixing, reaction is continued, after the reaction is finished, centrifugation washing is carried out, precipitates are collected, and the electron donor receptor type organic semiconductor-gold Schottky heterojunction material is obtained.
2. The method of claim 1, wherein the mass ratio of perylenetetracarboxylic dianhydride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, dopamine hydrochloride, and chloroauric acid is 5.
3. The method of claim 2, wherein the dopamine hydrochloride solution is added, and after being mixed uniformly, the mixture is shaken at a rotation speed of 30-40r/min for 2 days to react to obtain the electron donor-acceptor type organic semiconductor.
4. The method of claim 3, wherein the chloroauric acid solution is added under stirring, and after uniform mixing, the shaking reaction is continued at a rotation speed of 30-40r/min for 2-3 days.
5. The method of any one of claims 1 to 4, wherein the dopamine hydrochloride solution is added at a rate of 0.25 to 0.5 mL/min; adding chloroauric acid solution at the speed of 8-10 mu L/min under the stirring of the rotating speed of 150-200 r/min.
6. The method according to any one of claims 1 to 4, wherein the number of centrifugal washes is 2 to 3, each centrifugal wash being at a speed of 9000 to 12000r/min for 10 to 15min.
7. An electron donor-type organic semiconductor-gold schottky heterojunction material prepared by the method of any one of claims 1 to 6.
8. Use of the electron donor acceptor type organic semiconductor-gold schottky heterojunction material as defined in claim 7 in a photo-electrochemical biosensor.
9. The method for preparing the carcinoembryonic antigen photo-induced electrochemical detection kit for the electron donor-receptor type organic semiconductor-gold schottky heterojunction material as claimed in claim 7, wherein the kit comprises a photoelectric immunity probe and a working electrode; the method comprises the following steps:
(1) Preparation of a photoelectric ImmunoProbe
Dispersing the electron donor and acceptor type organic semiconductor-gold Schottky heterojunction material in water, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide for activation, then adding a carcinoembryonic antibody, incubating, and then centrifuging and washing to obtain the antibody;
(2) Preparation of working electrode
Depositing nanogold on a glassy carbon electrode, washing and drying the nanogold, dripping thioglycollic acid, incubating, washing, activating by using 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, finally adding a carcinoembryonic antibody, incubating, sealing a non-specific binding site by using bovine serum albumin, and washing.
10. A carcinoembryonic antigen photo-electrochemical detection kit prepared by the method of claim 9.
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| CN105161486A (en) * | 2015-09-28 | 2015-12-16 | 兰州文理学院 | Perylene-3,4,9,10-tetracarboxylic acid dianhydride organic layer optoelectronic coupler and manufacture method |
| CN109939674A (en) * | 2019-04-25 | 2019-06-28 | 重庆工商大学 | A kind of Pd/TiO with Schottky hetero-junctions2Elctro-catalyst and its preparation and application |
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| CN105161486A (en) * | 2015-09-28 | 2015-12-16 | 兰州文理学院 | Perylene-3,4,9,10-tetracarboxylic acid dianhydride organic layer optoelectronic coupler and manufacture method |
| CN109939674A (en) * | 2019-04-25 | 2019-06-28 | 重庆工商大学 | A kind of Pd/TiO with Schottky hetero-junctions2Elctro-catalyst and its preparation and application |
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