CN113866237B - Flexible photoelectrochemical aptamer sensor and preparation method and application thereof - Google Patents
Flexible photoelectrochemical aptamer sensor and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a flexible photoelectrochemical aptamer sensor, a preparation method and application thereof. The preparation method comprises the following steps: preparing a functionalized three-dimensional carbon fiber composite material; the specific aptamer probe self-assembles the load. The flexible photoelectrochemical aptamer sensor has the advantages of long service life, strong anti-interference capability, wide detection range, low detection limit, high sensitivity, high accuracy, wide application range and the like, can be widely used for detecting target molecules (such as antibiotic molecules) in a solution, has high use value and good application prospect, develops a new path for obtaining a portable flexible sensor, and has the advantages of simple process, convenient and fast operation, low cost, no pollution, high manufacturing efficiency and the like, and is suitable for large-scale preparation and beneficial to industrialized application.
Description
Technical Field
The invention belongs to the technical field of biological sensors, relates to a flexible photoelectrochemical aptamer sensor and a preparation method and application thereof, and in particular relates to a functionalized three-dimensional carbon fiber composite material-based flexible photoelectrochemical aptamer sensor and a preparation method and application thereof.
Background
In recent years, a photoelectrochemical detection technology attracts more and more attention, and the technology is a novel analysis method developed based on photoelectric conversion, wherein light is applied to a photosensitive material to cause electron excitation and charge transfer, electron hole pairs are formed at an interface after photon absorption, oxidation-reduction reaction is carried out on a specific target detection object, so that the charge transfer is influenced, and the obtained electric signal is further analyzed to obtain quantitative analysis on the target detection object. The photoelectrochemistry aptamer sensing technology belongs to one of photoelectrochemistry detection technologies, is a photoelectrochemistry detection technology taking a nucleic acid aptamer as an identification element, has the advantages of higher stability, easiness in synthesis, modification, lower cost, higher selectivity and the like, and is widely focused in the field of micro-molecule detection.
Currently, most photoelectrochemical aptamer sensors rely on the immobilization of a photoelectroactive material on a rigid, non-recyclable substrate surface, such as Indium Tin Oxide (ITO) or fluorine doped SnO 2 Conductive glass (FTO), which is greatlyThe development of photoelectric aptamer sensors to portable and wearable directions is hindered, and the practical application potential is limited. For the reasons, if a flexible photoelectrochemical aptamer sensor with a flexible material as a substrate can be obtained, the sensor can have certain wearable capacity and portability, and the practical application capacity of the sensor can be improved. However, to date, no report has been seen about "flexible photoelectrochemical aptamer sensor based on flexible material". In addition, another key in developing ultrasensitive photoelectric response sensors is to design a photoelectric active material with higher photoelectric conversion efficiency, however, most photoelectric active materials such as titanium dioxide (TiO 2 ) Molybdenum disulfide (MoS) 2 ) Gallium nitride (GaN) and the like have higher photon-generated carrier recombination rate and lower photoelectric conversion efficiency, and directly influence the sensitivity of the photoelectric sensor. Therefore, developing a photoelectric active material with strong visible light absorption capability, low photon-generated carrier recombination rate and high photoelectric conversion efficiency is very important for obtaining a flexible photoelectrochemical aptamer sensor with long service life, strong anti-interference capability, wide detection range, low detection limit, high sensitivity, high accuracy and wide application range.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provide a flexible photoelectrochemical aptamer sensor with high stability, long service life, strong anti-interference capability, wide detection range, low detection limit, high sensitivity, high accuracy and wide application range, and also provide a preparation method of the flexible photoelectrochemical aptamer sensor with simple process, convenient and fast operation, safety, low cost, no pollution and high manufacturing efficiency, and simultaneously provide application of the flexible photoelectrochemical aptamer sensor in detecting antibiotics.
In order to solve the technical problems, the invention adopts the following technical scheme:
the flexible photoelectrochemical aptamer sensor comprises a functionalized three-dimensional carbon fiber composite material, wherein the functionalized three-dimensional carbon fiber composite material takes a three-dimensional carbon fiber composite material as a carrier, a composite film is loaded on the surface of the three-dimensional carbon fiber composite material, the composite film consists of a modified graphite phase carbon nitride nano-sheet composite material, the modified graphite phase carbon nitride nano-sheet composite material comprises a thermal defect graphite phase carbon nitride nano-sheet and alpha-ferric oxide nano-particles, and the alpha-ferric oxide nano-particles are modified on the thermal defect graphite phase carbon nitride nano-sheet; the surface of the composite membrane is self-assembled with a specific aptamer probe for identifying and capturing target molecules.
According to the flexible photoelectrochemical aptamer sensor, the mass ratio of the alpha-ferric oxide nano particles to the thermally defective graphite phase carbon nitride nano sheets in the modified graphite phase carbon nitride nano sheet composite material is 1:8.33-25; the particle size of the alpha-ferric oxide nano particles is 8 nm-10 nm; the three-dimensional carbon fiber composite material is carbon fiber cloth; the length of the carbon fiber cloth is 1cm, the width is 2cm, and the thickness is 1mm.
The invention also provides a preparation method of the flexible photoelectrochemical aptamer sensor, which comprises the following steps of:
s1, coating a modified graphite phase carbon nitride nano sheet composite material suspension on the surface of a three-dimensional carbon fiber composite material, and forming a composite film on the surface of the three-dimensional carbon fiber composite material to obtain a functionalized three-dimensional carbon fiber composite material;
s2, dripping the specific aptamer probe solution onto the composite membrane on the surface of the functionalized three-dimensional carbon fiber composite material obtained in the step S1 for incubation, so that the specific aptamer probe is self-assembled on the surface of the composite membrane, and the flexible photoelectrochemical aptamer sensor is obtained.
In the step S1, the modified graphite phase carbon nitride nano sheet composite material suspension is coated on the surface of the three-dimensional carbon fiber composite material according to the coating dosage of 100 mu L each time, and the three-dimensional carbon fiber composite material is dried and repeated for 3 to 5 times; the modified graphite phase carbon nitride nano sheet composite material suspension is prepared by the following method: ultrasonically dispersing the modified graphite-phase carbon nitride nano-sheet composite material in a perfluorosulfonic acid/ethanol mixed solution to obtain a modified graphite-phase carbon nitride nano-sheet composite material suspension; the mass volume ratio of the modified graphite phase carbon nitride nano-sheet composite material to the perfluorosulfonic acid/ethanol mixed solution in the modified graphite phase carbon nitride nano-sheet composite material suspension is 4 mg-10 mg:1 mL; the volume ratio of the perfluorosulfonic acid to the ethanol in the perfluorosulfonic acid/ethanol mixed solution is 1:1-2.
The preparation method of the modified graphite phase carbon nitride nano-sheet composite material is further improved, and comprises the following steps of:
(1) Mixing the thermally defective graphite-phase carbon nitride nanosheets with an aqueous solution containing ferric salt and polyvinylpyrrolidone, performing ultrasonic dispersion, and stirring to obtain a thermally defective graphite-phase carbon nitride nanosheets suspension;
(2) And (3) carrying out hydrothermal reaction on the thermally defective graphite phase carbon nitride nanosheet suspension obtained in the step (1), centrifuging and drying to obtain the modified graphite phase carbon nitride nanosheet composite material.
In the preparation method, in the step (1), the mass volume ratio of the thermally defective graphite phase carbon nitride nano-sheet to the aqueous solution containing ferric salt and polyvinylpyrrolidone is 2.5 mg-3.0 mg:2.0 mL; the thermal defect graphite phase carbon nitride nano-sheet is prepared by the following preparation method: heating melamine to 640-700 ℃ according to the heating rate of 2-5 ℃/min, performing heat treatment for 2-4 h, and cooling to obtain the graphite-phase carbon nitride nanosheets with thermal defects; the mass ratio of the ferric salt to the polyvinylpyrrolidone in the aqueous solution containing the ferric salt and the polyvinylpyrrolidone is 1-3:2; the ferric salt is ferric nitrate nonahydrate; the ultrasonic dispersion time is 30-60 min; the stirring speed is 500 rpm-600 rpm; the stirring time is 20min;
in the step (2), the hydrothermal reaction is carried out at a temperature of 160-180 ℃; the hydrothermal reaction time is 12-16 h; the rotational speed of the centrifugation is 2500 rpm-3500 rpm; the drying is performed under vacuum; the temperature of the drying was 75 ℃.
In the above preparation method, further improved, in step S2, the specific aptamer probe solution is prepared by the following method: mixing N-hydroxysuccinimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and a solution containing the specific aptamer for activation to obtain a specific aptamer probe solution; the activation is carried out at a temperature of 37 ℃; the activation time is 20-28 h; the incubation is carried out at a temperature of 25-35 ℃; the incubation time is 30-60 min.
The invention also provides an application of the flexible photoelectrochemical aptamer sensor or the flexible photoelectrochemical aptamer sensor prepared by the preparation method in detecting antibiotics.
The above application, further improved, comprising the steps of: dropping an antibiotic solution on the surface of a composite membrane of the flexible photoelectrochemical aptamer sensor for reaction, and utilizing a specific aptamer probe on the surface of the composite membrane to specifically identify and capture the antibiotic; testing a standard antibiotic solution under intermittent illumination by adopting a timing current method, and constructing a detection linear regression equation of the antibiotic concentration and the photocurrent change; detecting the photoelectric value of the to-be-detected antibiotic solution, and calculating the concentration of the antibiotic in the to-be-detected antibiotic solution according to the photoelectric value of the to-be-detected antibiotic solution and by detecting a linear regression equation.
In the application, when the antibiotic in the antibiotic solution is ampicillin, the nucleotide sequence of the specific aptamer probe in the flexible photoelectrochemical aptamer sensor is 5'-COOH-TTA GTT GGG GTT CAG TTG G-3'; the linear regression equation for detecting the change of the concentration and the photocurrent of the ampicillin is as follows:
(I-I 0 )/I 0 ＝0.5844×LogC+2.205 (1)
in the formula (1), I 0 The background peak current is represented, I represents the detection peak current, and the unit is mu A; c is the concentration of ampicillin in the solution to be measured, and the unit is nM; correlation coefficient R of formula (1) 2 = 0.9953, the linear detection range is 0.5pM to 50nM, and the lower detection limit is 0.0125pM;
the reaction time is 0.5 h-1 h; during the test, the bias voltage was set to 0V, and the lamp was turned on and off every 20 s.
Compared with the prior art, the invention has the advantages that:
(1) The invention provides a flexible photoelectrochemical aptamer sensor, which comprises a functionalized three-dimensional carbon fiber composite material, wherein the functionalized three-dimensional carbon fiber composite material takes the three-dimensional carbon fiber composite material as a carrier, a composite film is loaded on the surface of the three-dimensional carbon fiber composite material, the composite film consists of a modified graphite phase carbon nitride nano-sheet composite material, the modified graphite phase carbon nitride nano-sheet composite material comprises a thermal defect graphite phase carbon nitride nano-sheet and alpha-ferric oxide nano-particles, the alpha-ferric oxide nano-particles are modified on the thermal defect graphite phase carbon nitride nano-sheet, and specific aptamer probes for identifying and capturing target molecules are self-assembled on the surface of the composite film. In the invention, the three-dimensional carbon fiber composite material is used as a carrier, and the flexible material is used, so that a composite membrane is loaded on the three-dimensional carbon fiber composite material, and a specific aptamer probe for identifying and capturing target molecules is self-assembled on the surface of the composite membrane, thus the flexible photoelectrochemical aptamer sensor can be formed, and the flexible photoelectrochemical aptamer sensor has very good performance in a bending and flat state. On one hand, the three-dimensional carbon fiber composite material adopted in the invention not only has excellent flexibility and a stronger three-dimensional framework structure, but also has higher strength and better conductivity, the former is favorable for constructing a unique three-dimensional hierarchical structure, and the latter improves the separation efficiency of charge carriers, which is crucial for the flexible photoelectrochemical aptamer sensor based on the nano structure, so that the three-dimensional carbon fiber composite material is taken as a carrier, the area of a reaction site and the rapid reaction kinetics can be increased, the transportation of target molecules under convection is improved, the signal amplification effect is realized, and the beneficial condition is created for improving the photoelectric property of the flexible photoelectrochemical sensor. On the other hand, in the invention, the adopted composite film is composed of a modified graphite phase carbon nitride nano-sheet composite material, and the modified graphite phase carbon nitride nano-sheet composite material is formed by compounding a thermal defect graphite phase carbon nitride nano-sheet and alpha-ferric oxide nano-particles, wherein the thermal defect graphite phase carbon nitride nano-sheet has higher visible light absorption capacity, proper energy band width and good photochemical stability, and meanwhile, the alpha-ferric oxide nano-particles are modified on the thermal defect graphite phase carbon nitride nano-sheet to form an all-solid-state Z-shaped heterojunction, so that the photoelectric activity of the thermal defect graphite phase carbon nitride nano-sheet can be improved, and the electron hole pair with high redox performance can be reserved. Specifically, the alpha-ferric oxide nano particles and the thermally defective graphite phase carbon nitride nano sheet form a heterojunction, so that the recombination rate of photo-generated carriers is reduced; in addition, the all-solid-state Z-shaped heterojunction can change an electron transfer path in the traditional II-shaped heterojunction, so that photo-generated electrons and holes are respectively gathered on a high-potential energy band, the redox capability of electron holes is improved, the strategy converts the defects of a sub-gap structure existing in the thermal defect graphite phase carbon nitride nanosheets into advantages, the material retains higher visible light absorption capability and photoelectric conversion efficiency, and therefore the modified graphite phase carbon nitride nanosheet composite material with strong visible light absorption capability, low photo-generated carrier recombination rate and high photoelectric conversion efficiency is obtained. Therefore, the flexible photoelectrochemical aptamer sensor has the advantages of long service life, strong anti-interference capability, wide detection range, low detection limit, high sensitivity, high accuracy, wide application range and the like, can be widely used for detecting target molecules in a solution, and if the target molecules exist in the solution to be detected, the specific aptamer probe can specifically identify and capture the target molecules, at the moment, photo-generated holes and hydroxyl free radicals gathered on the sensor electrode can generate redox reaction with the target molecules, so that the transfer of photo-generated charges on the electrode is promoted, and photocurrent signals increase along with the increase of the concentration of the target, thereby achieving the purpose of detecting the target.
(2) In the flexible photoelectrochemical aptamer sensor, the mass ratio of the alpha-ferric oxide nano particles to the thermally defective graphite phase carbon nitride nano sheets in the modified graphite phase carbon nitride nano sheet composite material is 1:8.33-25, so that the photoelectroactivity of the composite material is improved, the modified graphite phase carbon nitride nano sheet composite material with excellent photoelectric conversion performance is obtained, and the sensitivity and the accuracy of the flexible photoelectrochemical aptamer sensor are improved.
(3) The invention also provides a preparation method of the flexible photoelectrochemical aptamer sensor, which comprises the steps of coating the modified graphite phase carbon nitride nanosheet composite material suspension on the surface of a three-dimensional carbon fiber composite material, forming a composite film on the surface of the three-dimensional carbon fiber composite material, forming a functional three-dimensional carbon fiber composite material, further dripping a specific aptamer probe solution onto the composite film on the surface of the functional three-dimensional carbon fiber composite material obtained in the step S1 for incubation, and enabling the specific aptamer probe to be self-assembled on the surface of the composite film, thereby preparing the flexible photoelectrochemical aptamer sensor with long service life, strong anti-interference capability, wide detection range, low detection limit, high sensitivity, high accuracy and wide application range. The preparation method provided by the invention only needs conventional tubular furnace, hydrothermal operation, coating annealing and other conventional operations, does not introduce any toxic elements, has the advantages of simple process, convenience and quickness in operation, safety, low cost, no pollution, high preparation efficiency and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(4) The invention also provides application of the flexible photoelectrochemical aptamer sensor in detecting antibiotics, wherein an antibiotic solution is dripped on the surface of a composite membrane of the flexible photoelectrochemical aptamer sensor for reaction, the specific aptamer probe on the surface of the composite membrane is utilized for carrying out specific identification and capture on the antibiotics, and meanwhile, the concentration of the antibiotics in the solution to be detected is calculated according to the photoelectric current value of the solution to be detected and through a detection linear regression equation, so that the concentration of the antibiotics in the solution to be detected can be rapidly and accurately obtained. By taking ampicillin solution as an example, when the flexible photoelectrochemical aptamer sensor is used for detecting ampicillin, ampicillin in water, food and other mediums can be detected, a good detection range and detection limit can be obtained, and the flexible photoelectrochemical aptamer sensor has the advantages of simplicity in operation, low cost, wide application range, high application value and the like, and has very important significance for realizing effective treatment of antibiotic wastewater.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is a graph showing the ultraviolet diffuse reflection spectrum of modified graphite phase carbon nitride nanosheet composite materials with different mass ratios prepared in example 1 of the present invention.
FIG. 2 is a graph showing comparison of photocurrents of modified graphite phase carbon nitride nanoplatelet composites of different mass ratios prepared in example 1 of the present invention.
FIG. 3 shows a functionalized three-dimensional carbon fiber composite material (. Alpha. -Fe) prepared in example 1 of the present invention 2 O 3 /d-C 3 N 4 /CFT).
FIG. 4 shows a functionalized three-dimensional carbon fiber composite material (. Alpha. -Fe) according to example 1 of the present invention 2 O 3 /d-C 3 N 4 CFT) and flexible photoelectrochemical aptamer sensor (aptamer/α -Fe) 2 O 3 /d-C 3 N 4 /CFT).
FIG. 5 is a graph showing the response of the flexible photoelectrochemical aptamer sensor to photocurrent when detecting ampicillin solutions of different concentrations in example 1 of the present invention.
FIG. 6 is a graph showing the linear regression of the changes in ampicillin concentration versus photocurrent for example 1 of the present invention.
FIG. 7 is a graph showing the response of the flexible photoelectrochemical aptamer sensor to photocurrent when detecting different antibiotic solutions in example 3 of the present invention.
Fig. 8 is a photo-current response chart corresponding to the functionalized three-dimensional carbon fiber composite material obtained under different processing conditions in example 4 of the present invention.
FIG. 9 is a schematic diagram of a flexible photoelectrochemical aptamer sensor electrode (aptamer/α -Fe) in example 5 of the invention 2 O 3 /d-C 3 N 4 CFT) photo current signal response plot over 15 days.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
In the following examples, unless otherwise specified, the materials and equipment used were all commercially available, the process used was conventional, the equipment used was conventional, and the data obtained were all averages of three or more replicates.
The light source is taken from a high-brightness xenon lamp parallel light source system instrument, and a 300W xenon lamp (Beijing Porphy) is taken as a visible light source. Electrochemical experiments used the CHI660B electrochemical workstation (Shanghai Chen Hua instruments Co., ltd.).
Example 1
The flexible photoelectrochemical aptamer sensor comprises a functionalized three-dimensional carbon fiber composite material, wherein the functionalized three-dimensional carbon fiber composite material takes the three-dimensional carbon fiber composite material as a carrier, a composite film is loaded on the surface of the three-dimensional carbon fiber composite material, the composite film consists of a modified graphite phase carbon nitride nano-sheet composite material, the modified graphite phase carbon nitride nano-sheet composite material comprises a thermal defect graphite phase carbon nitride nano-sheet and alpha-ferric oxide nano-particles, the alpha-ferric oxide nano-particles are modified on the thermal defect graphite phase carbon nitride nano-sheet, and a specific aptamer probe (which can be selected according to actual needs) for identifying and capturing target molecules is self-assembled on the surface of the composite film.
In the embodiment, the mass ratio of the alpha-ferric oxide nano particles to the thermal defect graphite phase carbon nitride nano sheets in the alpha-ferric oxide nano particle modified thermal defect graphite phase carbon nitride nano sheet composite material is 1:12.5; the average particle diameter of the alpha-ferric oxide nano particles is 8nm; the three-dimensional carbon fiber composite material is carbon fiber cloth, and has the length of 1cm, the width of 2cm and the thickness of 1mm.
In the embodiment, alpha-ferric oxide nano particles are modified on the surface of the thermal defect graphite phase carbon nitride nano sheet by a hydrothermal reaction method.
In this embodiment, the α -iron oxide nanoparticle modified thermally defective graphite phase carbon nitride nanosheet composite material is loaded on the surface of a carbon fiber cloth (also referred to as a three-dimensional carbon fiber cloth) by a repeated coating-baking annealing method.
The preparation method of the photoelectrochemical aptamer sensor of the above embodiment includes the following steps:
(1) Spreading melamine 8.0g in a quartz boat, placing in a tube furnace, heating to 640 ℃ at a speed of 3 ℃/min under the air condition, performing heat treatment for 3 hours, naturally cooling, and grinding to obtain a thermally defective graphite-phase carbon nitride nano-sheet, which is denoted as d-C 3 N 4 。
(2) Weighing 100mg of the thermally defective graphite-phase carbon nitride nano-sheet obtained in the step (1), dissolving in 80mL of a mixed solution containing 80mg of ferric nitrate nonahydrate and 80mg of polyvinylpyrrolidone, performing ultrasonic dispersion for 40min, and stirring for 20min at a rotating speed of 500-600 rpm (which can be adjusted according to practical conditions and can be performed at a rotating speed of 500-600 rpm), thereby obtaining a thermally defective graphite-phase carbon nitride nano-sheet suspension. Pouring a thermal defect graphite phase carbon nitride nano sheet suspension into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a matched steel sleeve, placing the steel sleeve into a baking oven, heating the steel sleeve to 160 ℃ from room temperature, keeping the temperature for 12 hours, cooling the steel sleeve to room temperature, centrifuging the obtained mixed solution at a speed of 3000rpm, and drying the centrifuged product at 75 ℃ to obtain an alpha-ferric oxide nanoparticle modified thermal defect graphite phase carbon nitride nano sheet composite material, namely the modified graphite phase carbon nitride nano sheet composite material, namely alpha-Fe 2 O 3 /d-C 3 N 4 。
(3) 4mg of the alpha-iron oxide nanoparticle modified thermally defective graphite phase carbon nitride nanosheet composite material (alpha-Fe) prepared in the step (2) was subjected to thermal treatment 2 O 3 /d-C 3 N 4 ) Adding into 1mL of mixed solution of perfluorosulfonic acid and ethanol (the volume ratio of perfluorosulfonic acid to ethanol in the mixed solution is 1:1), mixing uniformly, and performing ultrasonic treatment for 40min to obtain alpha-ferric oxide nanoparticle modified alpha-ferric oxide nanoparticleIs prepared from the thermally defective graphite phase carbon nitride nano-sheet composite material suspension.
(4) Uniformly coating 100 mu L of the alpha-ferric oxide nanoparticle modified thermal defect graphite phase carbon nitride nano sheet composite material suspension obtained in the step (3) on the surface of a clean three-dimensional carbon fiber composite material (three-dimensional carbon fiber cloth CFT), placing the three-dimensional carbon fiber composite material in a muffle furnace for baking and annealing, repeating for three times, and forming a composite film consisting of the alpha-ferric oxide nanoparticle modified thermal defect graphite phase carbon nitride nano sheet composite material on the surface of the three-dimensional carbon fiber composite material to obtain alpha-Fe 2 O 3 /d-C 3 N 4 The loaded three-dimensional carbon fiber cloth is the functionalized three-dimensional carbon fiber composite material and is marked as alpha-Fe 2 O 3 /d-C 3 N 4 /CFT。
(5) Absorbing a solution containing 2mol/L of N-hydroxysuccinimide (NHS) and 5mol/L of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), mixing with 20 mu L of a solution containing specific aptamer with the concentration of 2 mu mol/L, and reacting at 37 ℃ to activate the aptamer to obtain an activated specific aptamer probe solution, wherein the specific activation time can be adjusted according to practical conditions and can be 20-28 h; dripping the activated specific aptamer probe solution into the functionalized three-dimensional carbon fiber composite material (alpha-Fe) in the step (4) 2 O 3 /d-C 3 N 4 The surface of the composite membrane of/CFT) is incubated for 40min at 30 ℃ to fix the specific aptamer probe on the surface of the carbon fiber cloth, thus obtaining the flexible photoelectrochemical aptamer sensor, which is named aptamer/alpha-Fe 2 O 3 /d-C 3 N 4 /CFT。
In the embodiment, the alpha-ferric oxide nanoparticle modified thermal defect graphite phase carbon nitride nano sheet composite material (modified graphite phase carbon nitride nano sheet composite material) with different mass ratios is also prepared, wherein the content of ferric nitrate nonahydrate in the mixed solution adopted in the step (2) is 120mg, 100mg, 60mg and 40mg respectively, and the corresponding content of polyvinylpyrrolidone is 120mg, 100mg, 60mg and 40mg respectively, and other conditions are the same, so that the prepared alpha-ferric oxide nanoparticle modified thermal defect graphite phase carbon nitride nano sheetAlpha-iron oxide nanoparticles (alpha-Fe) in composite materials 2 O 3 ) Carbon nitride nanosheets (d-C) phase with thermally defective graphite 3 N 4 ) The mass ratio of (2) is 1:8.33, 1:10, 1:16.67 and 1:25 in sequence.
The modified graphite-phase carbon nitride nano-sheet composite materials with different mass ratios were examined for their visible light absorption capacity, and ultraviolet diffuse reflection tests were performed on the modified graphite-phase carbon nitride nano-sheet composite materials with different mass ratios prepared in the above-described embodiment 1 of the present invention, and the results are shown in fig. 1. FIG. 1 is a graph showing the ultraviolet diffuse reflection spectrum of modified graphite phase carbon nitride nanosheet composite materials with different mass ratios prepared in example 1 of the present invention. As can be seen from fig. 1, in the wavelength range of 200-800nm, when the mass ratio of the α -iron oxide nanoparticles to the thermally defective graphite phase carbon nitride nanosheets is sequentially 1:8.33, 1:10, 1:12.5, 1:16.67, and 1:25, the obtained α -iron oxide nanoparticle-modified thermally defective graphite phase carbon nitride nanosheets composite (modified graphite phase carbon nitride nanosheets composite) exhibits a very strong light absorption signal, and has a very good light absorption capacity, and in particular, when the mass ratio of the α -iron oxide nanoparticles to the thermally defective graphite phase carbon nitride nanosheets is 1:12.5, the obtained α -iron oxide nanoparticle-modified thermally defective graphite phase carbon nitride nanosheets composite (modified graphite phase carbon nitride nanosheets composite) has the strongest light absorption signal, indicating that it has the best visible light absorption capacity.
Photocurrent tests were performed on the modified graphite-phase carbon nitride nano-sheet composites of different mass ratios prepared in example 1 of the present invention, and the results are shown in fig. 2. FIG. 2 is a graph showing comparison of photocurrents of modified graphite phase carbon nitride nanoplatelet composites of different mass ratios prepared in example 1 of the present invention. As can be seen from fig. 2, when the mass ratio of the α -iron oxide nanoparticles to the thermally defective graphite phase carbon nitride nanosheets is sequentially 1:8.33, 1:10, 1:12.5, 1:16.67, and 1:25, the obtained α -iron oxide nanoparticle-modified thermally defective graphite phase carbon nitride nanosheets composite (modified graphite phase carbon nitride nanosheets composite) exhibits a very strong photocurrent signal, and has a very good light absorption capacity, and particularly, when the mass ratio of the α -iron oxide nanoparticles to the thermally defective graphite phase carbon nitride nanosheets is 1:12.5, the obtained α -iron oxide nanoparticle-modified thermally defective graphite phase carbon nitride nanosheets composite (modified graphite phase carbon nitride nanosheets composite) has the highest photocurrent signal, which indicates that the obtained α -iron oxide nanoparticle-modified thermally defective graphite phase carbon nitride nanosheets have the best photoelectric conversion efficiency, and, when the α -iron oxide nanoparticles are too much, the aggregation phenomenon is easily caused, which is unfavorable for improving the light absorption effect of the thermally defective graphite phase carbon nitride nanosheets; and when the alpha-ferric oxide nano particles are too small, a small amount of the alpha-ferric oxide nano particles are insufficient to form heterojunction with the thermal defect graphite phase carbon nitride nano sheet, so that the advantage of the heterojunction is exerted, and the photocurrent signal is relatively weak, so that the improvement of the photoelectric activity is not facilitated.
For the functionalized three-dimensional carbon fiber composite material (α -Fe) prepared in example 1 of the present invention 2 O 3 /d-C 3 N 4 CFT) for scanning electron microscope imaging analysis. The results are shown in FIG. 3. FIG. 3 shows a functionalized three-dimensional carbon fiber composite material (. Alpha. -Fe) prepared in example 1 of the present invention 2 O 3 /d-C 3 N 4 /CFT). As can be seen from fig. 3a, the α -iron oxide nanoparticle modified thermally defective graphite phase carbon nitride nanosheet composite material is well supported on the fiber surface of the three-dimensional carbon fiber cloth to form a composite film, and as can be seen from fig. 3b, the thermally defective graphite phase carbon nitride nanosheet presents a typical lamellar structure, and the surface is modified with α -iron oxide nanoparticles having an average particle diameter of 8nm, which have uniform particle sizes and uniform distribution, which indicates that the modified graphite phase carbon nitride nanosheet composite material formed by compositing the α -iron oxide nanoparticles with the thermally defective graphite phase carbon nitride nanosheet has been successfully supported on the three-dimensional carbon fiber composite material, namely, the functionalized three-dimensional carbon fiber composite material (α -Fe 2 O 3 /d-C 3 N 4 CFT) was successfully prepared.
The application of the flexible photoelectrochemical aptamer sensor in the embodiment in detecting antibiotics is specifically as follows: application of flexible photoelectrochemical aptamer sensor in detecting ampicillin, wherein a specific aptamer probe in the flexible photoelectrochemical aptamer sensor has specific recognition and capture functions on ampicillin, and the method comprises the following steps of
(a) Ampicillin solutions of different concentrations (ampicillin concentrations of 0.0005nM, 0.001nM, 0.005nM, 0.01nM, 0.05nM, 0.1nM, 0.5nM, 1nM, 5nM, 10nM, 50 nM) were added dropwise to the surface of the composite membrane of the flexible photoelectrochemical aptamer sensor prepared in example 1, and incubated at 37℃for 30min to allow the aptamer probe on the surface of the flexible photoelectrochemical aptamer sensor to specifically recognize and capture ampicillin. In this example, the nucleotide sequence of the specific aptamer probe in the flexible photoelectrochemical aptamer sensor was 5'-COOH-TTA GTT GGG GTT CAG TTG G-3', and the other parameters were the same as those of the flexible photoelectrochemical aptamer sensor of example 1.
(b) And (3) testing under intermittent illumination by adopting a chronoamperometry, establishing the relation between ampicillin concentration and photocurrent change, and constructing a detection linear regression equation.
(c) Detecting the ampicillin solution to be detected according to the operations in the steps (a) and (b) to obtain a photoelectric value of the ampicillin solution to be detected, and simultaneously calculating the concentration of the ampicillin in the ampicillin solution to be detected according to the photoelectric value of the ampicillin solution to be detected and through the detection linear regression equation obtained in the step (b).
For the functionalized three-dimensional carbon fiber composite material (α -Fe) prepared in example 1 of the present invention 2 O 3 /d-C 3 N 4 CFT) and flexible photoelectrochemical aptamer sensor (aptamer/α -Fe) 2 O 3 /d-C 3 N 4 CFT is a composition containing KCl and potassium ferricyanide ([ Fe (CN)) 6 ] 3-/4- ) (the concentration of KCl in the aqueous solution is 0.1M, [ Fe (CN)) 6 ] 3-/4- Concentration of mM), the results are shown in fig. 4. FIG. 4 shows a functionalized three-dimensional carbon fiber composite material (. Alpha. -Fe) according to example 1 of the present invention 2 O 3 /d-C 3 N 4 CFT) and flexible photoelectrochemical aptamer sensor (aptamer/α -Fe) 2 O 3 /d-C 3 N 4 /CFT). As can be seen from FIG. 4, with ampicillin specific aptamer probe modified to α -Fe 2 O 3 /d-C 3 N 4 on/CFT, the aptamerr/α-Fe 2 O 3 /d-C 3 N 4 The increased resistance of the CFT indicates that the specific probe was successfully modified to alpha-Fe 2 O 3 /d-C 3 N 4 CFT surface.
FIG. 5 is a graph showing the response of the flexible photoelectrochemical aptamer sensor to photocurrent when detecting ampicillin solutions of different concentrations in example 1 of the present invention. As can be seen from fig. 5, the photocurrent increases with the concentration of ampicillin.
FIG. 6 is a graph showing the linear regression of the changes in ampicillin concentration versus photocurrent for example 1 of the present invention. As can be seen from fig. 6, the linear regression equation for detecting the change in ampicillin concentration and photocurrent is:
(I-I 0 )/I 0 ＝0.5844×LogC+2.205 (1)
in the formula (1), I 0 The background peak current is represented, I represents the detection peak current, and the unit is mu A; c is the concentration of ampicillin in the solution to be measured, and the unit is nM; correlation coefficient R of formula (1) 2 = 0.9953, the linear range of detection is 0.5pM to 50nM, and the lower limit of detection is 0.0125pM.
It can be seen that the functionalized three-dimensional carbon fiber composite material (alpha-Fe 2 O 3 /d-C 3 N 4 The flexible photoelectrochemical aptamer sensor formed by compounding the CFT and a specific probe (the nucleotide sequence is 5'-COOH-TTA GTT GGG GTT CAG TTG G-3') can be used for detecting ampicillin, and the concentration of ampicillin to be detected can be calculated according to a detection linear regression equation.
Example 2
To further verify the results of example 1 from a functionalized three-dimensional carbon fiber composite material (α -Fe 2 O 3 /d-C 3 N 4 The detection effect of the flexible photoelectrochemical aptamer sensor formed by compounding the CFT and a specific probe (the nucleotide sequence is 5'-COOH-TTA GTT GGG GTT CAG TTG G-3') in practical application comprises the following steps: a flexible photoelectrochemical aptamer sensor was used for target detection in an actual sample (measurement method is referred to in example 1), and a recovery rate experiment was performed.
The concentration of the target substance in the sample (containing ampicillin) is shown in table 1, and finally the flexible photoelectrochemical aptamer sensor is used for target detection in an actual sample (measurement method is shown in example 1), and a recovery rate experiment is performed. The measurement results are shown in Table 1.
TABLE 1 results of recovery verification of solutions to be tested
As can be seen from Table 1, the recovery rate of the flexible photoelectrochemical aptamer sensor is basically between 95.70% and 105.87% in a measurable concentration range, and the measurement result is ideal.
As can be seen from Table 1, from the functionalized three-dimensional carbon fiber composite material (α -Fe 2 O 3 /d-C 3 N 4 The flexible photoelectrochemical aptamer sensor formed by compounding the CFT and a specific probe (the nucleotide sequence is 5'-COOH-TTA GTT GGG GTT CAG TTG G-3') can be used for detecting ampicillin in lake water and milk samples, can obtain better detection precision, and can be suitable for different detection systems.
Example 3
And (5) examining the anti-interference capability of the flexible photoelectrochemical aptamer sensor. The test methods such as 0.5nM ampicillin, 500nM ampicillin and tobramycin, 0.5nM ampicillin and 500nM tobramycin, 500nM ampicillin and 500nM ampicillin, 62 nM, and 500nM tobramycin were carried out using the flexible photoelectrochemical aptamer sensor of example 1, respectively.
FIG. 7 is a graph showing the response of the flexible photoelectrochemical aptamer sensor to photocurrent when detecting different antibiotic solutions in example 3 of the present invention. As can be seen from fig. 7, the flexible photoelectrochemical aptamer sensor in example 3 of the present invention has a better photocurrent response to ampicillin and no photocurrent response to other antibiotics, which indicates that the flexible photoelectrochemical aptamer sensor of the present invention has a better anti-interference capability.
Example 4
Reproducibility of a flexible photoelectrochemical aptamer sensor was examined, and 5 parts of the functionalized three-dimensional carbon fiber composite material (. Alpha. -Fe) prepared in example 1 was used, respectively 2 O 3 /d-C 3 N 4 CFT), 5 parts functionalized three-dimensional carbon fiber composite (0.5 nM pentabritin/α -Fe) after dropping and incubation with 0.5nM ampicillin solution 2 O 3 /d-C 3 N 4 CFT) and 5 parts of functionalized three-dimensional carbon fiber composite (10 nM pentanitin/α -Fe) after dropping and incubating with 10nM ampicillin solution 2 O 3 /d-C 3 N 4 CFT) for photocurrent testing. Three tests were performed for each electrode, and the test results are shown in fig. 8.
Fig. 8 is a photo-current response chart corresponding to the functionalized three-dimensional carbon fiber composite material obtained under different processing conditions in example 4 of the present invention. As can be seen from fig. 8, the magnitudes of the photocurrent signals obtained by the different functionalized three-dimensional carbon fiber composites obtained under the different processing conditions in the embodiment 4 of the present invention are substantially the same, which indicates that the flexible photoelectrochemical aptamer sensor of the present invention has good reproducibility.
Example 5
Flexible photoelectric investigationThe service life of the chemical aptamer sensor. The flexible photoelectrochemical aptamer sensing electrode (aptamer/α -Fe) prepared in example 1 2 O 3 /d-C 3 N 4 CFT) was stored in a refrigerator for 15 days, and after dropping and incubating with 0.5nM ampicillin solution at the same time every day, the photocurrent was measured, and the average value was taken three times per test, and the measurement result is shown in fig. 9.
FIG. 9 is a schematic diagram of a flexible photoelectrochemical aptamer sensor electrode (aptamer/α -Fe) in example 5 of the invention 2 O 3 /d-C 3 N 4 CFT) photo current signal response plot over 15 days. As can be seen from fig. 9, the magnitude of the photocurrent signal measured by the same electrode per day is substantially the same within 15 days, and is maintained at about 95% of the initial value, which indicates that the flexible photoelectrochemical aptamer sensor of the invention has a long service life, and can be normally used at least within 15 days.
The detection result shows that the functionalized three-dimensional carbon fiber composite material (alpha-Fe 2 O 3 /d-C 3 N 4 The flexible photoelectrochemical aptamer sensor formed by compounding the CFT) and the specific probe has the advantages of wide detection range, low detection limit, strong anti-interference capability, long service life and the like, can be widely used for detecting target molecules (such as antibiotic molecules) in a solution, and can specifically identify and capture the target molecules if the target molecules exist in the solution to be detected, at the moment, the photo-generated holes and hydroxyl free radicals accumulated on the sensor electrode can undergo redox reaction with the target molecules, so that the transfer of photo-generated charges on the electrode is promoted, and the photocurrent signal increases along with the increase of the concentration of the target, thereby achieving the purpose of detecting the target.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (10)
1. The flexible photoelectrochemical aptamer sensor is characterized by comprising a functionalized three-dimensional carbon fiber composite material, wherein the functionalized three-dimensional carbon fiber composite material takes a three-dimensional carbon fiber composite material as a carrier, a composite film is loaded on the surface of the three-dimensional carbon fiber composite material, the composite film consists of a modified graphite phase carbon nitride nano-sheet composite material, the modified graphite phase carbon nitride nano-sheet composite material comprises a thermal defect graphite phase carbon nitride nano-sheet and alpha-ferric oxide nano-particles, and the alpha-ferric oxide nano-particles are modified on the thermal defect graphite phase carbon nitride nano-sheet; the surface of the composite membrane is self-assembled with a specific aptamer probe for identifying and capturing target molecules.
2. The flexible photoelectrochemical aptamer sensor according to claim 1, wherein the mass ratio of the α -iron oxide nanoparticles to the thermally defective graphite phase carbon nitride nanoplatelets in the modified graphite phase carbon nitride nanoplatelet composite is 1:8.33-25; the particle size of the alpha-ferric oxide nano particles is 8 nm-10 nm; the three-dimensional carbon fiber composite material is carbon fiber cloth; the length of the carbon fiber cloth is 1cm, the width is 2cm, and the thickness is 1mm.
3. A method of manufacturing a flexible photoelectrochemical aptamer sensor according to claim 1 or 2, comprising the steps of:
s1, coating a modified graphite phase carbon nitride nano sheet composite material suspension on the surface of a three-dimensional carbon fiber composite material, and forming a composite film on the surface of the three-dimensional carbon fiber composite material to obtain a functionalized three-dimensional carbon fiber composite material;
s2, dripping the specific aptamer probe solution onto the composite membrane on the surface of the functionalized three-dimensional carbon fiber composite material obtained in the step S1 for incubation, so that the specific aptamer probe is self-assembled on the surface of the composite membrane, and the flexible photoelectrochemical aptamer sensor is obtained.
4. The preparation method according to claim 3, wherein in the step S1, the modified graphite phase carbon nitride nano-sheet composite material suspension is coated on the surface of the three-dimensional carbon fiber composite material according to the coating amount of 100 μl each time, and the three-dimensional carbon fiber composite material is dried and repeated for 3-5 times; the modified graphite phase carbon nitride nano sheet composite material suspension is prepared by the following method: ultrasonically dispersing the modified graphite-phase carbon nitride nano-sheet composite material in a perfluorosulfonic acid/ethanol mixed solution to obtain a modified graphite-phase carbon nitride nano-sheet composite material suspension; the mass volume ratio of the modified graphite phase carbon nitride nano-sheet composite material to the perfluorosulfonic acid/ethanol mixed solution in the modified graphite phase carbon nitride nano-sheet composite material suspension is 4 mg-10 mg:1 mL; the volume ratio of the perfluorosulfonic acid to the ethanol in the perfluorosulfonic acid/ethanol mixed solution is 1:1-2.
5. The method of preparing the modified graphite phase carbon nitride nanosheet composite material of claim 4, comprising the steps of:
(1) Mixing the thermally defective graphite-phase carbon nitride nanosheets with an aqueous solution containing ferric salt and polyvinylpyrrolidone, performing ultrasonic dispersion, and stirring to obtain a thermally defective graphite-phase carbon nitride nanosheets suspension;
(2) And (3) carrying out hydrothermal reaction on the thermally defective graphite phase carbon nitride nanosheet suspension obtained in the step (1), centrifuging and drying to obtain the modified graphite phase carbon nitride nanosheet composite material.
6. The method according to claim 5, wherein in the step (1), the mass-to-volume ratio of the thermally defective graphite-phase carbon nitride nanoplatelets to the aqueous solution containing the ferric salt and polyvinylpyrrolidone is 2.5 mg-3.0 mg:2.0 mL; the thermal defect graphite phase carbon nitride nano-sheet is prepared by the following preparation method: heating melamine to 640-700 ℃ according to the heating rate of 2-5 ℃/min, performing heat treatment for 2-4 h, and cooling to obtain the graphite-phase carbon nitride nanosheets with thermal defects; the mass ratio of the ferric salt to the polyvinylpyrrolidone in the aqueous solution containing the ferric salt and the polyvinylpyrrolidone is 1-3:2; the ferric salt is ferric nitrate nonahydrate; the ultrasonic dispersion time is 30-60 min; the stirring speed is 500 rpm-600 rpm; the stirring time is 20min;
in the step (2), the hydrothermal reaction is carried out at a temperature of 160-180 ℃; the hydrothermal reaction time is 12-16 h; the rotational speed of the centrifugation is 2500 rpm-3500 rpm; the drying is performed under vacuum; the temperature of the drying was 75 ℃.
7. The method according to any one of claims 3 to 6, wherein in step S2, the specific aptamer probe solution is prepared by: mixing N-hydroxysuccinimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and a solution containing the specific aptamer for activation to obtain a specific aptamer probe solution; the activation is carried out at a temperature of 37 ℃; the activation time is 20-28 h; the incubation is carried out at a temperature of 25-35 ℃; the incubation time is 30-60 min.
8. Use of a flexible photoelectrochemical aptamer sensor according to claim 1 or 2 or a flexible photoelectrochemical aptamer sensor prepared by a method of preparation according to any of claims 3 to 7 for the detection of antibiotics.
9. The use according to claim 8, characterized by the steps of: dropping an antibiotic solution on the surface of a composite membrane of the flexible photoelectrochemical aptamer sensor for reaction, and utilizing a specific aptamer probe on the surface of the composite membrane to specifically identify and capture the antibiotic; testing a standard antibiotic solution under intermittent illumination by adopting a timing current method, and constructing a detection linear regression equation of the antibiotic concentration and the photocurrent change; detecting the photoelectric value of the to-be-detected antibiotic solution, and calculating the concentration of the antibiotic in the to-be-detected antibiotic solution according to the photoelectric value of the to-be-detected antibiotic solution and by detecting a linear regression equation.
10. The use according to claim 9, wherein when the antibiotic in the antibiotic solution is ampicillin, the nucleotide sequence of the specific aptamer probe in the flexible photoelectrochemical aptamer sensor is 5'-COOH-TTA GTT GGG GTT CAG TTG G-3'; the linear regression equation for detecting the change of the concentration and the photocurrent of the ampicillin is as follows:
(I-I 0 )/I 0 ＝0.5844×LogC+2.205 (1)
in the formula (1), I 0 The background peak current is represented, I represents the detection peak current, and the unit is mu A; c is the concentration of ampicillin in the solution to be measured, and the unit is nM; correlation coefficient R of formula (1) 2 = 0.9953, the linear detection range is 0.5pM to 50nM, and the lower detection limit is 0.0125pM;
the reaction time is 0.5 h-1 h; during the test, the bias voltage was set to 0V, and the lamp was turned on and off every 20 s.
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