CN114674900A - Photoelectrochemical microsensor based on small molecular probe and preparation method and application thereof - Google Patents
Photoelectrochemical microsensor based on small molecular probe and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a photoelectrochemical microsensor based on a small molecular probe, which takes cadmium telluride quantum dots as a photoelectric active material and an energy donor, takes an organic small molecular probe as a recognition unit and an energy acceptor, and can perform a specific recognition reaction on a target object to change the light absorption intensity of the probe, thereby changing the light current intensity. The preparation method comprises the following steps: 1) preparing an aqueous solution of cadmium telluride quantum dots; 2) preparing a small molecule probe solution; 3) adding the small molecular probe solution into a cadmium telluride quantum dot aqueous solution to obtain a compound; 4) and modifying the compound on the surface of the steel needle electrode in a self-assembly mode to obtain the composite. The small molecular probe used as the energy receptor has a flexible structure, can be further expanded to other target objects by designing the identification unit, improves the application range of photoelectrochemical detection, and has universality; the detection aim is realized through the chemical recognition reaction between the small molecular probe and the target object, and the specificity of the photoelectrochemical detection is effectively improved.
Description
Technical Field
The invention relates to the technical field of electrochemical analysis, in particular to a photoelectrochemical microsensor based on a small molecular probe and a preparation method and application thereof.
Background
Photoelectrochemical sensing has attracted considerable interest and rapid development by researchers as a emerging and important branch of electrochemical analysis technology. Compared with the traditional electrochemical sensing, the excitation signal (optical signal) and the detection signal (electric signal) in the photoelectrochemical sensing are completely separated, so that the background signal is lower, and higher sensitivity is obtained; and the optical signal replaces the bias voltage to be used as an excitation signal, so that the optical fiber has better biocompatibility. In addition, the photoelectrochemistry sensing inherits the advantages of excellent space-time resolution, simple instrument and operation, easy miniaturization and the like of the electrochemistry sensing, and the unique performance and technical advantages enable the photoelectrochemistry sensing to have good application prospect in the aspect of biological analysis. However, the great challenges of photoelectrochemical sensing still exist in that the non-electroactive substances are difficult to detect (i.e. the universality is insufficient) and the specificity is insufficient in a complex environment, so that the application of photoelectrochemical sensing in related fields is limited. Therefore, developing a photoelectrochemical sensing strategy that is suitable for high universality and specificity in complex environments remains a very desirable but challenging task.
In photoelectrochemical sensing, due to spectral matching between quantum dots (serving as energy donors) and gold nanoparticles (serving as energy acceptors), exciton plasma interaction and exciton energy transfer effects can be generated between the quantum dots and the gold nanoparticles, and the exciton plasma interaction and the exciton energy transfer effects can promote the recombination of electron hole pairs in the quantum dots together, so that a photocurrent signal is sharply reduced. However, the gold nanoparticles have no function of identifying a target object, and an additional identification unit needs to be introduced, so that the complexity and the instability of the photoelectrochemical sensing platform are increased. The organic small molecular probe is a small molecule with flexible structure and adjustable band gap, and can be obtained by coupling with different recognition domains, so that high-specificity recognition and detection can be carried out on different targets, including active oxygen, active sulfur, biological enzyme and other bioactive small molecules. Based on the method, the organic small molecular probe is used as an energy receptor, and a photoelectrochemistry sensing interface regulated and controlled by energy transfer is introduced, so that the problem that the photoelectrochemistry sensing is insufficient in specificity and universality in a complex system is expected to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a small molecule probe-based photoelectrochemical microsensor which has high specificity, wide application range and universality.
The invention also aims to provide a specific preparation method of the photoelectrochemical microsensor based on the small molecule probe.
It is a final object of the present invention to provide a specific application of the above-mentioned small molecule probe-based photoelectrochemical microsensor.
In order to achieve the purpose, the invention is realized by the following technical scheme: a photoelectrochemical microsensor based on a small molecular probe takes cadmium telluride quantum dots as a photoelectric active material and an energy donor, takes an organic small molecular probe as a recognition unit and an energy acceptor, and can perform specific recognition reaction on a target object to change the light absorption intensity of the probe, so that the light current intensity is changed.
The technical principle of the technical scheme is that in the photoelectrochemistry microsensor, an organic small molecular probe is used as an energy receptor, and the energy transfer between the organic small molecular probe and cadmium telluride quantum dots can promote the recombination of electron hole pairs in the quantum dots, so that the photocurrent is quenched; after the analyte reacts with the organic small molecular probe, the light absorption capacity of the organic small molecular probe can be weakened, so that the energy transfer process between the cadmium telluride quantum dot and the organic small molecular probe is inhibited, the hole separation capacity of electrons of the cadmium telluride quantum dot is improved, the photocurrent is increased, and the analyte is detected. The strategy solves the problems of poor adaptability to non-electroactive species and insufficient specificity in a complex environment matrix, and shows the performances of high selectivity, high stability and high reproducibility. More importantly, since the organic small molecule probe has a variable structure, the strategy can be flexibly extended to other targets, including electroactive molecules and non-electroactive molecules, by designing energy receptors of different target recognition units, so that the application of the PEC sensing in different fields is greatly facilitated.
In order to better realize the invention, the chemical structural formula of the organic small molecule probe is as follows:
due to SO2The compound is taken as an electroactive gas signal molecule, and molecules such as CO and CO2 interfere the detection of the molecule, so that the photoelectrochemical detection is difficult to perform by a direct oxidation-reduction method, and the molecule is selected as a concept verification target. When the organic small molecule is (E) -3- (2-carboxyethyl) -2- (2- (6-methoxy-2,3-dihydro-1H-xanthen-4-yl) vinyl) -1, 1-dimethyl-1H-benzol [ E]indol-3-ium), the energy transfer process between the cadmium telluride quantum dot and the small molecule probe further promotes the recombination of electron-hole pairs, resulting in the quenching of photocurrent signals. Object SO2And (E) -3- (2-carboxyethenyl) -2- (2- (6-methoxy-2,3-dihydro-1H-xanthen-4-yl) vinyl) -1, 1-dimethyl-1H-benzol [ E ]]indol-3-ium) to generate specific chemical reaction, the light absorption capacity of the small molecular probe is obviously reduced, and the energy transfer process is inhibited, so that the separation efficiency of electron-hole pairs of the cadmium telluride quantum dots is improved, and finally the photocurrent is increased. Based on the principle, the proposed energy transfer regulation photoelectrochemical sensing strategy based on the small molecule probe as the energy receptor can realize specific recognition and sensitive response to the target.
The invention also provides a preparation method of the photoelectrochemical microsensor based on the small molecular probe, which comprises the following steps:
(1) synthesizing cadmium telluride quantum dots, and dissolving the cadmium telluride quantum dots in water to prepare an aqueous solution;
(2) synthesizing a small molecular probe, and dissolving the small molecular probe in dimethyl sulfoxide to obtain a small molecular probe solution;
(3) adding the small molecular probe solution into a cadmium telluride quantum dot aqueous solution to obtain a compound;
(4) the compound is modified on the surface of the steel needle electrode in a self-assembly mode, and the steel needle electrode modified with the compound is the photoelectrochemical microsensor.
In order to better implement the method of the present invention, further, after the photoelectrochemical microsensor is obtained, a photoelectrochemical test needs to be performed on the photoelectrochemical microsensor, and the test specific process comprises the following steps: the photoelectrochemical microsensors were incubated with different concentrations of sodium sulfite by soaking at 25 ℃ for 8 minutes and then tested on a CHI660E electrochemical workstation using a conventional three electrode system.
In order to better realize the method of the invention, the three-electrode system further comprises a working electrode, a reference electrode and a counter electrode, wherein in the testing process, the working electrode is a photoelectrochemical microsensor to be tested, the reference electrode is a saturated calomel electrode, the counter electrode is a platinum wire electrode, an electrolyte solution is a PBS solution with the concentration of 0.1mol/L and the pH of 7.4, and exciting light is 460nm laser.
In order to better implement the method of the present invention, further, the specific process of synthesizing the cadmium telluride quantum dots in the step (1) is as follows:
(1.1) weighing cadmium nitrate, sodium citrate and mercaptopropionic acid, dissolving in deionized water, and dispersing uniformly by ultrasonic or stirring;
(1.2) adjusting the mixed solution to pH =10.5 with sodium hydroxide solution, transferring into a round bottom flask;
(1.3) respectively adding sodium tellurite and sodium borohydride, and placing the round bottom flask containing the mixture into an oil bath kettle to be stirred and refluxed for 10 hours after the sodium tellurite and the sodium borohydride are dispersed uniformly by ultrasound or stirring;
(1.4) cooling the reaction solution to room temperature after 10h of reaction, adding equivalent isopropanol to directly generate precipitation, standing for 10min, after complete precipitation, centrifugally separating solid through a centrifugal machine, washing the solid with isopropanol, repeating the process for three times, carefully absorbing the upper layer liquid with a liquid-moving gun, collecting the solid to obtain purified cadmium telluride quantum dots, and drying at 40 ℃ in an oven to obtain the cadmium telluride quantum dots.
In order to better implement the method of the present invention, further, the specific process of synthesizing the small molecule probe in step (2) is as follows:
(2.1) dropwise adding phosphorus tribromide into a mixture of dimethylformamide and chloroform under an ice bath condition, stirring and mixing uniformly, dropwise adding cyclohexanone into a mixed solution, and stirring at room temperature for 8 hours; after the reaction was cooled to 0 ℃, the reaction was quenched with saturated sodium bicarbonate solution;
(2.2) extracting the water layer by using dichloromethane, washing the organic layer by using water and saturated saline solution in sequence, and concentrating in vacuum to obtain a product 2-bromo-1-cyclohexene-1-carboxaldehyde;
(2.3) dissolving 2-bromo-1-cyclohexene-1-carboxaldehyde, hydroxy-4-methoxybenzaldehyde and cesium carbonate in a dimethylformamide solution in sequence, stirring at room temperature for 16 hours, stopping the reaction, removing the solvent by a circulating water pump through vacuum filtration, and purifying the crude product through silica gel column chromatography, wherein the volume ratio of ethyl acetate to dichloromethane in the silica gel column chromatography is 9: 1, obtaining a yellow solid intermediate I;
(2.4) adding 1,1, 2-trimethyl-1H-benzo [ e ] indole and iodoacetic acid into toluene in sequence, refluxing and stirring in an oil bath kettle for 12 hours, cooling to room temperature after the reaction is finished, and filtering under reduced pressure to obtain a gray solid intermediate product II;
(2.5) sequentially dissolving the intermediate I, the intermediate II and sodium acetate in acetic anhydride, and stirring for 1h at 70 ℃ in an oil bath kettle;
(2.6) after the reaction is finished, removing the solvent by a circulating water pump through suction filtration under reduced pressure, evaporating the solvent in an oven at 40 ℃, collecting the solid and purifying the solid through silica gel column chromatography, wherein the volume ratio of dichloromethane to methanol in the silica gel column is 20: 1, obtaining a blue solid, namely the micromolecular probe.
The specific synthetic route is as follows:
in order to better implement the method of the present invention, further, the step (3) complex synthesis process is: and adding 0.75 mu mol of the small molecular probe solution into a cadmium telluride quantum dot aqueous solution with the concentration of 0.5mg/mL, and performing ultrasonic treatment at room temperature for 20 min.
In order to better implement the method of the present invention, further, the specific process of modifying the compound on the surface of the steel needle electrode by a self-assembly manner in the step (4) is as follows: the steel needle electrode was immersed in a centrifuge tube containing 10. mu.L of the complex solution and dried in an oven at 60 ℃.
The photoelectrochemical microsensor based on the small molecular probe is used for sensitive detection of sulfur dioxide gas.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention realizes the detection purpose through the chemical recognition reaction between the small molecular probe and the target object, and effectively improves the high specificity of photoelectrochemical detection;
(2) compared with the traditional sulfur dioxide detection method, such as chromatographic analysis, fluorescence imaging and the like, the photoelectrochemical sensing method has the advantages of low background signal, high sensitivity, simple and cheap instrument and equipment, easiness in miniaturization, simplicity in operation, few pretreatment processes on a target and the like;
(3) the invention solves the problems of poor adaptability to non-electroactive species and insufficient specificity in a complex environment matrix, and shows the performances of high selectivity, high stability and high reproducibility, more importantly, as the structure of the organic small molecule probe is variable, the strategy can be flexibly expanded to other targets comprising electroactive molecules and non-electroactive molecules by designing energy receptors of different target recognition units, the application range of photoelectrochemical detection is improved, and the universality is realized, so that the application of PEC sensing in different fields is greatly promoted.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic diagram of the construction of a photoelectrochemical microsensor based on a resonance energy transfer strategy according to the present invention;
FIG. 2 is an XRD pattern of a cadmium telluride quantum dot in accordance with the present invention;
FIG. 3 shows the molecular probe XY-K of the invention1H NMR spectrum;
FIG. 4 is an ultraviolet-visible absorption spectrum of a cadmium telluride quantum dot and a molecular probe in the present invention, and a fluorescence emission spectrum of the cadmium telluride quantum dot under 460nm excitation;
FIG. 5 is a graph showing UV-VIS absorption spectra of probes of the present invention incubated with sodium sulfite at various concentrations;
FIG. 6 is a graph of photocurrent responses of different materials of the present invention;
FIG. 7 is a graph of photocurrent response obtained with the photoelectrochemical microsensor of the present invention incubated with different concentrations of sodium sulfite;
FIG. 8 is a graph of calibration curves obtained for photoelectrochemical microsensors of the present invention incubated with different concentrations of sodium sulfite.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
The present invention will be described in further detail with reference to the following examples for the purpose of making clear the objects, process conditions and advantages of the present invention, but the embodiments of the present invention are not limited thereto, and various substitutions and modifications can be made according to the common technical knowledge and the conventional means in the art without departing from the technical idea of the present invention described above, and the specific examples described herein are only for explaining the present invention and are not intended to limit the present invention.
Example 1:
the embodiment provides a photoelectrochemical microsensor based on a small molecular probe, wherein a cadmium telluride quantum dot is used as a photoelectric active material and an energy donor, an organic small molecular probe is used as a recognition unit and an energy acceptor, and a specific recognition reaction can be performed on a target object to change the light absorption intensity of the probe, so that the light current intensity is changed, and the chemical structural formula of the organic small molecular probe is as follows:
the name of the small molecular probe is (E) -3- (2-carboxyethyl) -2- (2- (6-methoxy-2,3-dihydro-1H-xanthen-4-yl) vinyl) -1, 1-dimethyl-1H-benzol [ E ] indole-3-ium, and for convenience of explanation, the name of the small molecular probe is XY-K and is used for sensitively detecting sulfur dioxide gas.
The specific preparation method comprises the following steps:
(1) synthesizing cadmium telluride quantum dots, and dissolving the cadmium telluride quantum dots in water to prepare an aqueous solution;
(2) synthesizing XY-K, and dissolving the XY-K in dimethyl sulfoxide to obtain an XY-K solution;
(3) adding the XY-K solution into a cadmium telluride quantum dot aqueous solution to obtain a compound;
(4) the compound is modified on the surface of the steel needle electrode in a self-assembly mode, and the steel needle electrode modified with the compound is the photoelectrochemical microsensor.
The photoelectrochemical microsensor is mainly used for sensitive detection of sulfur dioxide gas.
The technical principle is that cadmium telluride quantum dots are used as photoelectric active materials and energy donors, XY-K is used as a recognition unit and an energy acceptor, and the XY-K can be mixed with sulfur dioxide (SO) of a target object2) A specific recognition reaction occurs to change the light absorption intensity. Under the excitation of light, electrons in the cadmium telluride quantum dots transition from a valence band to a conduction band, so that electron-hole pairs are generated. A part of photo-generated electrons in the conduction band react with dissolved oxygen in the solution, and electrons of an external circuit flow into the valence band so as to generate cathode photocurrent; at the same time, a portion of the photo-generated electrons inevitably recombine with holes in the valence band, thereby reducing the photocurrent signal. After XY-K is introduced, the energy transfer process between the cadmium telluride quantum dots and XY-K further promotes the recombination of electron-hole pairs, and leads to the quenching of photocurrent signals. Object SO2After the specific chemical reaction with XY-K, the light absorption capacity of XY-K is obviously reduced, and the energy transfer process is inhibited, so that the separation efficiency of the electron-hole pair of the cadmium telluride quantum dot is improved, and finally the photoelectric current is increased, as shown in figure 1. Based on the principle, the proposed energy transfer modulation photoelectrochemical sensing strategy based on the energy receptor can realize specific recognition and sensitive response to the target.
Example 2:
in this embodiment, on the basis of the above embodiment, the synthesis process of the cadmium telluride quantum dot is further defined as follows:
(1) synthesizing cadmium telluride quantum dots:
i) 59mg of cadmium nitrate, 100mg of sodium citrate and 25. mu.L of mercaptopropionic acid were weighed and dissolved in deionized water, and they were uniformly dispersed by ultrasonic waves or stirring.
ii) the mixed solution was adjusted to pH =10.5 with 1mol/L sodium hydroxide solution and transferred to a round bottom flask.
iii) adding 11.1mg of sodium tellurite and 18.9mg of sodium borohydride respectively, dispersing uniformly by ultrasonic or stirring, and then placing the round-bottom flask containing the mixture into an oil bath kettle to stir and reflux for 10 hours.
iiii) reacting for 10h, cooling the reaction solution to room temperature, adding equivalent isopropanol to directly generate precipitation, standing for 10min, centrifuging and separating solid by a centrifugal machine after complete precipitation, washing the solid by isopropanol, repeating the process for three times, carefully absorbing the upper layer liquid by a liquid-transferring gun, collecting the solid to obtain purified cadmium telluride quantum dots, drying the cadmium telluride quantum dots in an oven at 40 ℃, and preparing 0.5mg/mL aqueous solution for later use.
An XRD (X-ray diffraction) pattern of the cadmium telluride quantum dot is shown in figure 2, and as can be seen from the XRD pattern, sharp diffraction peaks of the cadmium telluride nanocrystals at 2 theta =25.54, 41.75 and 49.17 degrees are respectively assigned to crystal planes (111), (220) and (311), and can be indexed to a cubic zinc blende structure (JCPDS card number 65-1046), so that the prepared quantum dot is proved to be the cadmium telluride quantum dot.
Example 3:
this example further defines the synthetic XY-K synthetic process based on the above examples, and the synthetic route is as follows:
the preparation process comprises the following steps:
i) synthesis of intermediate I: phosphorus tribromide (2.2 mL, 23.4 mmol) was added dropwise to a mixture of dimethylformamide (2 mL, 26 mmol) and chloroform (15 mL) under ice-bath conditions, and the mixture was stirred and mixedAfter the mixture was mixed well, cyclohexanone (1 g, 10.2 mmol) was added dropwise to the mixed solution, and stirred at room temperature for 8 hours. After the reaction was cooled to 0 ℃, the reaction was quenched with saturated sodium bicarbonate solution. Then, the aqueous layer was extracted with dichloromethane, and the organic layer was washed with water and saturated brine in this order, and concentrated in vacuo to give the product 2-bromo-1-cyclohexene-1-carboxaldehyde. 2-bromo-1-cyclohexene-1-carboxaldehyde (408 mg, 2.2 mmol), hydroxy-4-methoxybenzaldehyde (274 mg, 1.8 mmol) and cesium carbonate (1.76 mg, 5.4 mmol) were dissolved in succession in dimethylformamide solution (10 mL), stirred at room temperature for 16h, the reaction was stopped, the solvent was removed by suction filtration under reduced pressure using a circulating water pump, the crude product was purified by silica gel column chromatography (ethyl acetate/dichloromethane = 9: 1,v/v) Purification afforded intermediate I as a yellow solid in 71% yield.
II) Synthesis of intermediate II: 1,1, 2-trimethyl-1H-benzo [ e ] indole (1.25 g,6 mmol) and iodoacetic acid (1.8 g,9 mmol) were added to toluene, and the mixture was stirred in an oil bath under reflux for 12H. After the reaction was completed, it was cooled to room temperature and filtered under reduced pressure to obtain intermediate II as a gray solid with a yield of 67.6%.
iii) Synthesis of Compound XY-K: intermediate I (242 mg, 1.0 mmol), intermediate II (282 mg, 1.0 mmol) and sodium acetate (328 mg, 4.0 mmol) were dissolved in that order in acetic anhydride (10 mL) and stirred in an oil bath at 70 ℃ for 1 h. After the reaction was completed, the solvent was removed by suction filtration under reduced pressure using a circulating water pump, the solvent was evaporated in an oven at 40 ℃, the solid was collected and purified by silica gel column chromatography (dichloromethane/methanol = 20: 1,v/v) Purification gave the blue solid probe XY-K in 32% yield.
Of XY-K1H NMR spectrum as shown in FIG. 3.
1H NMR (400 MHz, CH3OD) δ 8.87 (d, J = 15.1 Hz, 1H), 8.41 - 8.34 (d, 1H), 8.12 (d, J = 8.9 Hz, 1H), 8.07 (d, J = 8.2 Hz, 1H), 7.81 (d, J = 8.9 Hz, 1H), 7.72 (t, J = 7.7 Hz, 1H), 7.59 (t, J = 7.6 Hz, 1H), 7.48 (d, J = 8.6 Hz, 1H), 7.39 (s, 1H), 7.13 (d, J = 2.3 Hz, 1H), 7.04 - 6.93 (m, 1H), 6.70 (d, J= 15.0 Hz, 1H), 4.75 (t, J = 6.9 Hz, 2H), 3.99 (s, 3H), 2.93 (t, J = 6.9 Hz, 2H), 2.79 (q, J = 5.3 Hz, 4H), 2.09 (s, 6H), 2.00 - 1.91 (t2H) of1The H NMR spectrum confirmed that XY-K was successfully synthesized.
Example 4:
on the basis of the above embodiments, the present embodiment further defines a construction process of the photoelectrochemical microsensor, which is specifically as follows:
i) after the probe XY-K is dissolved in dimethyl sulfoxide, an XY-K solution (75 mu M) is added into a cadmium telluride quantum dot aqueous solution (0.5 mg/mL), and ultrasonic treatment is carried out at room temperature for 20min to promote the formation of a compound.
ii) immersing the steel needle electrode into a centrifuge tube filled with 10 mu L of compound solution, drying the centrifuge tube in an oven at 60 ℃, and modifying the compound on the surface of the steel needle electrode by the self-assembly mode, wherein the steel needle electrode modified with the compound is a photoelectrochemical microsensor.
Example 5:
on the basis of the above embodiments, the present embodiment further defines a process of a photoelectrochemical test, specifically as follows:
the photoelectrochemical microsensor was incubated with different concentrations of sodium sulfite by means of a soak at 25 ℃ for 8 minutes. Subsequent experiments were all performed on CHI660E electrochemical workstation using a conventional three-electrode system. The photoelectrochemistry microsensor is a working electrode, and a reference electrode and a counter electrode are respectively a saturated calomel electrode and a platinum wire electrode. The electrolyte solution is PBS solution with the concentration of 0.1mol/L and the pH value of 7.4, and the exciting light is 460nm laser.
Firstly, the energy transfer between the cadmium telluride quantum dot and XY-K is proved through a spectrum experiment. As shown in FIG. 4, under the excitation of 460nm light, the emission band of the cadmium telluride quantum dots is highly matched with the absorption range of the probe, and a precondition is provided for the effective energy transfer. As shown in FIG. 5, the chemical reaction between the target and the probe can reduce the absorption intensity of the probe, and provide a precondition for regulating the energy transfer process between the cadmium telluride quantum dot and the probe.
As shown in FIG. 6, the curves a-e are respectively:
(a) an initial steel needle electrode;
(b) a steel needle electrode;
(c) cadmium telluride quantum dots are independently modified on the steel needle electrode;
(d) modifying a compound of cadmium telluride quantum dots and a probe XY-K on the steel needle electrode;
(e) photocurrent response graph after photoelectrochemical microsensor reaction with 6 μ M sulfite.
Successful construction of photoelectrochemical microsensors was demonstrated by photocurrent response detection of photoelectrochemical microsensors. Firstly, the initial steel needle electrode and the washed steel needle electrode have no photocurrent response, and a larger photocurrent is obtained after the quantum dots are modified, which indicates that the cadmium telluride quantum dots are a better photoelectric active material. The photocurrent signal is reduced after the compound is modified on the steel needle electrode, which shows that the energy transfer effect can quench the photocurrent by promoting the recombination of electron hole pairs, and simultaneously proves the successful construction of the photoelectrochemical microsensor. It has been shown that SO2Is reflected in the equilibrium between bisulphite and sulphite (1: 3M/M), SO sodium sulphite was used as SO in vitro studies2Is representative of (a). After the sensor is incubated with sodium sulfite, the photocurrent is increased, and the fact that the chemical reaction between the sodium sulfite and the probe XY-K reduces the light absorption capacity of the XY-K is proved, so that the energy transfer efficiency is inhibited, and finally the photocurrent is increased. The results prove that the energy transfer regulation photoelectrochemistry sensing strategy using the small molecule probe as the energy acceptor is feasible.
Example 6:
this example is based on the above examples and demonstrates the ability of the constructed photochemical sensor to detect sulfur dioxide gas.
Namely, the photoelectric current signals obtained after the photoelectrochemistry microsensor is incubated with sodium sulfite with different concentrations (the concentration is 0.5, 1,2, 4, 6, 8, 10 and 12 mu M) for 8 min.
The experimental results are shown in fig. 7 and fig. 8, and the cathode photocurrent signals obtained are gradually increased with the increasing concentration of sodium sulfite and are in the range of 0.5 μ M to 8Has good linear relation in the range of 12 mu M, and the linear equation isI = - 35.04 - 4.38 C SO2 (R 2= 0.9973), wherein the limit of detection (LOD) is 89.0 nM. The results prove that the proposed photoelectrochemical microsensor can be used for SO2Sensitive detection of (3).
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. A photoelectrochemical microsensor based on a small molecular probe is characterized in that a cadmium telluride quantum dot is used as a photoelectric active material and an energy donor, an organic small molecular probe is used as a recognition unit and an energy acceptor, and the photoelectrochemical microsensor can perform specific recognition reaction on a target object to change the light absorption intensity of the probe, so that the light current intensity is changed.
2. The photoelectrochemical microsensor based on a small molecule probe according to claim 1, wherein the chemical structural formula of the organic small molecule probe is as follows:
3. the method for preparing the photoelectrochemical microsensor based on the small molecule probe according to the claim 2, characterized by comprising the following steps:
(1) synthesizing cadmium telluride quantum dots, and dissolving the cadmium telluride quantum dots in water to prepare an aqueous solution;
(2) synthesizing a small molecular probe, and dissolving the small molecular probe in dimethyl sulfoxide to obtain a small molecular probe solution;
(3) adding the small molecular probe solution into the cadmium telluride quantum dot aqueous solution to obtain a compound;
(4) the compound is modified on the surface of the steel needle electrode in a self-assembly mode, and the steel needle electrode modified with the compound is the photoelectrochemical microsensor.
4. The method for preparing a photoelectrochemical microsensor based on a small molecule probe according to claim 3, wherein after the photoelectrochemical microsensor is obtained, an electrochemical test is required to be performed, and the specific test process comprises the following steps: the photoelectrochemical microsensors were incubated with different concentrations of sodium sulphite by means of a soak at 25 ℃ for 8 minutes and subsequently tested on a CHI660E electrochemical workstation using a conventional three electrode system.
5. The method for preparing a small-molecule probe-based photoelectrochemical microsensor according to claim 4, wherein the three-electrode system comprises a working electrode, a reference electrode and a counter electrode, wherein during the test, the working electrode is the photoelectrochemical microsensor to be tested, the reference electrode is a saturated calomel electrode, the counter electrode is a platinum wire electrode, an electrolyte solution is a PBS solution with the concentration of 0.1mol/L and the pH of 7.4, and the excitation light is 460nm laser.
6. The preparation method of the photoelectrochemical microsensor based on the small molecule probe is characterized in that the specific process of synthesizing the cadmium telluride quantum dots in the step (1) is as follows:
(1.1) weighing cadmium nitrate, sodium citrate and mercaptopropionic acid, dissolving in deionized water, and dispersing uniformly by ultrasonic or stirring;
(1.2) adjusting the mixed solution to pH =10.5 with sodium hydroxide solution, transferring into a round bottom flask;
(1.3) respectively adding sodium tellurite and sodium borohydride, and placing the round-bottom flask containing the mixture into an oil bath kettle to be stirred and refluxed for 10 hours after the sodium tellurite and the sodium borohydride are dispersed uniformly by ultrasound or stirring;
(1.4) after reacting for 10 hours, cooling the reaction solution to room temperature, adding equivalent isopropanol to directly generate precipitation, standing for 10min, after complete precipitation, centrifugally separating solid through a centrifugal machine, then washing the solid with isopropanol, repeating for three times, carefully absorbing the upper layer liquid with a liquid-transfering gun, collecting the solid to obtain purified cadmium telluride quantum dots, and drying in an oven at 40 ℃ to obtain the cadmium telluride quantum dots.
7. The method for preparing the small molecule probe-based photoelectrochemical microsensor according to any one of claims 3 to 5, wherein the specific process for synthesizing the small molecule probe in the step (2) is as follows:
(2.1) dropwise adding phosphorus tribromide into a mixture of dimethylformamide and chloroform under an ice bath condition, stirring and mixing uniformly, dropwise adding cyclohexanone into a mixed solution, and stirring at room temperature for 8 hours; after the reaction was cooled to 0 ℃, the reaction was quenched with saturated sodium bicarbonate solution;
(2.2) extracting the water layer by using dichloromethane, washing the organic layer by using water and saturated saline solution in sequence, and concentrating in vacuum to obtain a product 2-bromo-1-cyclohexene-1-carboxaldehyde;
(2.3) dissolving 2-bromo-1-cyclohexene-1-carboxaldehyde, hydroxy-4-methoxybenzaldehyde and cesium carbonate in a dimethylformamide solution in sequence, stirring at room temperature for 16 hours, stopping the reaction, removing the solvent by a circulating water pump through vacuum filtration, and purifying the crude product through silica gel column chromatography, wherein the volume ratio of ethyl acetate to dichloromethane in the silica gel column chromatography is 9: 1, obtaining a yellow solid intermediate I;
(2.4) adding 1,1, 2-trimethyl-1H-benzo [ e ] indole and iodoacetic acid into toluene in sequence, refluxing and stirring in an oil bath kettle for 12 hours, cooling to room temperature after the reaction is finished, and filtering under reduced pressure to obtain a gray solid intermediate product II;
(2.5) sequentially dissolving the intermediate I, the intermediate II and sodium acetate in acetic anhydride, and stirring for 1h at 70 ℃ in an oil bath kettle;
(2.6) after the reaction is finished, removing the solvent by a circulating water pump through suction filtration under reduced pressure, evaporating the solvent in an oven at 40 ℃, collecting the solid and purifying the solid through silica gel column chromatography, wherein the volume ratio of dichloromethane to methanol in the silica gel column is 20: 1, obtaining a blue solid, namely the micromolecular probe XY-K.
8. The method for preparing the small molecule probe-based photoelectrochemical microsensor according to any one of claims 3 to 5, wherein the synthesis process of the complex in the step (3) is as follows: 0.75 mu mol of the micromolecular probe solution is added into cadmium telluride quantum dot aqueous solution with the concentration of 0.5mg/mL, and ultrasound treatment is carried out for 20min at room temperature.
9. The method for preparing the photoelectrochemical microsensor based on the small molecule probe according to any one of claims 3 to 5, wherein the specific process of modifying the compound on the surface of the steel needle electrode by the self-assembly in the step (4) is as follows: the steel needle electrode was immersed in a centrifuge tube containing 10. mu.L of the complex solution and dried in an oven at 60 ℃.
10. The small molecule probe-based photoelectrochemical microsensor according to claim 2 or prepared according to any one of claims 3 to 9 for use in sensitive detection of sulphur dioxide gas.
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