CN110261448B - Preparation method and application of signal inhibition type photoelectrochemical procalcitonin sensor based on zinc-titanium composite material - Google Patents

Preparation method and application of signal inhibition type photoelectrochemical procalcitonin sensor based on zinc-titanium composite material Download PDF

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CN110261448B
CN110261448B CN201910541846.9A CN201910541846A CN110261448B CN 110261448 B CN110261448 B CN 110261448B CN 201910541846 A CN201910541846 A CN 201910541846A CN 110261448 B CN110261448 B CN 110261448B
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范大伟
鲍春竹
刘昕
王欢
王雪莹
吴丹
马洪敏
任祥
胡丽华
孙旭
匡轩
魏琴
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Abstract

The invention relates to a preparation method and application of a signal inhibition type photoelectrochemical procalcitonin sensor based on a zinc-titanium composite material. Synthesizing a zinc titanate/titanium dioxide heterojunction ZTHS polyhedron with a hollow structure by a hydrothermal method. The unique hollow structure enables the ZTCHS to have larger specific surface area and better bearing capacity. Reutilizing terpyridyl ruthenium Ru (bpy)3 2+And bismuth sulfide Bi2S3The co-sensitization of the ZTCHS further enhances the photoelectrochemical properties of the ZTCHS, and the zinc-titanium composite material ZTCHS/Ru (bpy) with obviously improved photoelectric activity is obtained3 2+/Bi2S3. Prepared silicon dioxide/poly dopamine hydrochloride-gold composite material SiO2the/PDA-Au is used as a signal inhibition material to immobilize the procalcitonin detection antibody. Wherein, SiO2The larger steric hindrance of PDA effectively limits the electron transfer, and the Au nanoparticles can absorb visible light, competing with the substrate material for visible light. Based on the aspects, the signal inhibition type photoelectrochemical procalcitonin sensor based on the zinc-titanium composite material is prepared, the ultrasensitive detection of procalcitonin is realized, and the sensor has important significance on the analysis and detection of the procalcitonin.

Description

Preparation method and application of signal inhibition type photoelectrochemical procalcitonin sensor based on zinc-titanium composite material
Technical Field
The invention belongs to the field of photoelectrochemical sensors, and particularly relates to a preparation method and application of a signal inhibition type photoelectrochemical procalcitonin sensor based on a zinc-titanium composite material.
Background
Currently, a Photoelectrochemical (PEC) sensor has become an attractive analytical method and is widely used in the fields of disease diagnosis, food safety detection, environmental protection, and the like. The PEC sensor fixes sensitive biological materials such as active substances of enzyme, antigen, antibody, DNA and the like as recognition elements, and outputs signals expressed by the sensitive biological materials as electric signals under the irradiation of visible light. The specific recognition of the biological material makes PEC sensors with good specificity and sensitivity for the diagnosis of cancer. However, how to construct a stable photoelectric sensing material interface and design an excellent sensing strategy is still an important challenge and is one of the scientific problems to be solved.
In recent years, researchers have constructed ZnO/ZnTiO materials3Nanostructure (Ali A, Li X D, Song J L Q, et al Nature-Mimic ZnO Nanoflower Architecture: Chalcogenide Quantum Dots Coupling with ZnO/ZnTiO)3Nanoheterostructures for Efficient chemical Water splitting, Journal of Physical Chemistry C, 2017, 121(39): 21096-2Hierarchical structure (ZHao G D, Sun M L, Liu X L, et al, contamination of CdS quantum dots sensed ZnO nanorodes/TiO2nanosheets hierarchical structures for enhanced photonic performance, electrochromic Acta, 2019, 304: 334-2Heterostructure (Fan D W, Ren X, Wang H, et al. ultrasensive sandwich-type photoelechemia)l immunosensor based on CdSe sensitized La-TiO2 matrix and signal amplification of polystyrene@Ab2compositions, Biosensors and Bioelectronics, 2017, 87: 593-3Or TiO2PEC performance of (a). According to the invention, a hydrothermal method is adopted to synthesize a zinc titanate/titanium dioxide heterojunction ZTCS polyhedron with a hollow structure so as to adjust the band gap width of the material. Compared with pure zinc titanate or titanium dioxide, the ZTCHS has the advantages of good stability, larger specific surface area and capacity, stronger load capacity and the like, and is beneficial to the load of nano particles. In addition, bismuth sulfide Bi2S3The narrower band gap width is beneficial to the separation of the photo-generated electrons and the holes, and the strength of the photocurrent signal is improved. And, Bi2S3Has a band gap width of about 1.30-1.70 eV (Paul S, Ghosh S, Barma D, et al. maximum of photocatalytic activity of Bi)2S3/TiO2The perfect band gap matching between the material and the ZTCHS effectively accelerates the electron transfer and improves the utilization rate of the material to visible light. In this process, ruthenium terpyridyl Ru (bpy)3 2+Oxidized to ru (iii) complex. The ru (iii) complex reacts with ZTCHS to become excited ru (ii). Subsequently, ru (ii) returns to the ground state with electron transfer and energy transfer, which further improves the photoelectrochemical properties of the material. Thus, the present invention utilizes Ru (bpy)3 2+And Bi2S3Co-sensitizing the ZTCHS to form the zinc-titanium composite material ZTCHS/Ru (bpy) with excellent photoelectrochemical activity3 2+/Bi2S3And then used as a base material for a PEC sensor. In addition, a silicon dioxide/poly hydrochloric acid dopamine-gold composite material SiO is designed2Ab used as procalcitonin detection antibody of PDA-Au2The marker of (1). SiO 22The great steric hindrance of PDA effectively limits the electron transfer, and Au nano particles can absorb visible light and compete with the substrate material for the visible light, so that the photocurrent intensity of the substrate material is reduced, the sensitivity of the PEC sensor is enhanced, and calcitonin can be treatedOriginal ultra-sensitive detection.
Disclosure of Invention
One of the purposes of the invention is to adopt a hydrothermal method to synthesize a hollow-structured ZTCHS polyhedron to adjust the band gap width of the material;
another object of the present invention is to utilize Ru (bpy)3 2+To sensitize ZTCHS and grow narrow bandgap Bi in situ2S3As signal amplification material, ZTCHS/Ru (bpy) is obtained3 2+/Bi2S3A composite material;
the third purpose of the invention is to design SiO2PDA-Au as Ab2The label of (3), reducing the photocurrent intensity of the substrate material, enhancing the sensitivity of the PEC sensor;
the fourth purpose of the invention is to construct a signal inhibition type photoelectrochemical procalcitonin sensor with good selectivity and simple operation by utilizing the specific binding of antigen and antibody, thereby realizing the rapid and sensitive detection of procalcitonin.
The technical scheme of the invention is as follows:
1. a method for preparing a signal inhibition type photoelectrochemical procalcitonin sensor based on a zinc-titanium composite material, wherein the zinc-titanium composite material is terpyridyl ruthenium Ru (bpy)3 2+And bismuth sulfide Bi2S3Co-sensitized zinc titanate/titanium dioxide heterojunction ZTHS composite material ZTHS/Ru (bpy)3 2+/Bi2S3The photoelectrochemical procalcitonin sensor consists of an Indium Tin Oxide (ITO) working electrode, a ZTHS/Ru (bpy)3 2+/Bi2S3Procalcitonin capture antibody Ab1Bovine serum albumin, procalcitonin antigen standard solution and procalcitonin detection antibody marker SiO2/PDA-Au-Ab2Composition is carried out;
the preparation method is characterized by comprising the following preparation steps:
first, ZTCHS/Ru (bpy)3 2+/Bi2S3Preparing;
II, SiO2/PDA-Au-Ab2Preparing;
thirdly, preparing a signal inhibition type photoelectrochemical procalcitonin sensor;
wherein, the first step is to prepare ZTCHS/Ru (bpy)3 2+/Bi2S3The method comprises the following specific steps:
(1) preparation of zeolitic imidazoles framework material 8
Firstly, dissolving 0.3-1.0 g of zinc salt into 15-30 mL of methanol, then adding 10-20 mL of methanol solution containing 1.0-2.0 g of 2-methylimidazole, stirring the solution at room temperature for 20-26 h, centrifuging and washing the obtained product with ethanol and ultrapure water for three times, and finally drying at 80 ℃ for 10-14 h to obtain zeolite imidazole framework material 8 powder;
(2) preparation of ZTCHS
Dissolving 0.05-0.10 g of hexadecyltrimethylamine bromide into 2-10 mL of ethanol solution, stirring for 20-40 min at room temperature, adding 0.05-0.10 g of zeolite imidazole framework material 8, continuing to stir for 20-40 min, adding 100-200 mu L of tetrabutyl titanate into the solution, stirring for 20-40 min, continuing to add 2-4 mL of ultrapure water, stirring the solution for 20-26 h, transferring the solution into a polytetrafluoroethylene reaction kettle, reacting for 20-26 h at 100 ℃, centrifugally washing the obtained product for 3-6 times by using ethanol and ultrapure water respectively, finally drying for 10-14 h under vacuum to obtain ZTCHS powder, dissolving the ZTCHS powder in ultrapure water to obtain a ZTCHS suspension;
(3) cutting an ITO electrode to 2.5 cm multiplied by 0.8 cm, carrying out ultrasonic cleaning for 20-40 min by using acetone, ethanol and ultrapure water in sequence, after drying by using nitrogen, modifying 8-10 mu L of ZTCHS suspension onto the ITO electrode, airing at room temperature, then placing the ITO electrode in a muffle furnace, calcining at 400-500 ℃ for 20-40 min, and finally cooling to room temperature;
(4) modifying the surface of the electrode obtained in the step (3) by 3-4 mu L, wherein the concentration is 0.02-0.04 mol.L-1Ru (bpy)3 2+Drying the solution at room temperature; further modifying the surface of the electrode by 3-4 muL and 0.02-0.04 mol.L-1Bi (NO) of3)3Reacting the nitric acid solution at room temperature for 20-40 min, washing with ultrapure water, and then repairingDecorating 3-4 mu L and 0.1 mol/L Na2The S solution reacts for 20-40 min at room temperature, and is washed by ultrapure water to prepare ZTCHS/Ru (bpy)3 2+/Bi2S3；
The zinc salt is selected from one of the following: zinc chloride, zinc sulfate, zinc nitrate;
wherein, the step two is used for preparing SiO2/PDA-Au-Ab2The method comprises the following specific steps:
（A）SiO2preparation of
Firstly, adding 2-9 mL of tetraethoxysilane into 38-80 mL of mixed solvent, then adding 10-20 mL of 25% ammonia water into the solution, stirring for 3-5 h at 40 ℃, centrifuging to obtain precipitates, washing the precipitates with ultrapure water and ethanol respectively until the pH is neutral, and finally drying for 10-14 h under vacuum to obtain SiO2Powder;
（B）SiO2preparation of PDA
20-40 mg of SiO2And 20-40 mg of dopamine hydrochloride are dissolved in 10-20 mL of 10 mmol.L-1Stirring the solution at room temperature for 10-14 h in a trihydroxymethyl aminomethane buffer solution with the pH of 8.5, centrifuging, washing with ultrapure water and ethanol for 3-4 times respectively, and drying the product in vacuum to obtain SiO2PDA powder;
（C）SiO2preparation of/PDA-Au
Dissolving 0.01-0.02 g of sodium citrate into 20-40 mL of ultrapure water, and then adding 20-40 muL of chloroauric acid and 2-6 mg of SiO2PDA is stirred for 4-6 min at room temperature, then the solution is heated and boiled for 12-20 min, after being cooled to room temperature, the solution is centrifuged and washed with ultrapure water for three times, and finally, the solution is dried under vacuum condition to obtain SiO2/PDA-Au；
（D）SiO2/PDA-Au-Ab2Preparation of
2-6 mg of SiO2The solution of/PDA-Au was dissolved in 1 mL of PBS buffer solution having a pH of 7.4, and then 100 to 200. mu.L of 10. mu.g/mL of the solution was added−1Procalcitonin-detecting antibody Ab2Oscillating and incubating in a constant temperature oscillating incubator at 4 DEG C12 h, centrifugally washing, and dispersing the product in 1 mL of PBS buffer solution containing 1.0 percent of bovine serum albumin by mass and having pH of 7.4 to prepare SiO2/PDA-Au-Ab2Stored in a refrigerator at 4 ℃ for later use;
the mixed solvent is prepared by mixing ultrapure water and ethanol according to the volume ratio of 1: 25;
the third step of preparing the signal inhibition type photoelectrochemical procalcitonin sensor comprises the following specific steps:
(a) the ZTCHS/Ru (bpy) obtained in step one3 2+/Bi2S3Modifying 3-5 muL and 0.1 mol/L thioglycollic acid on the surface of the modified ITO working electrode, airing at room temperature, continuously dropwise adding 3-5 muL 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide/N-hydroxysuccinimide, reacting for 20-40 min, washing with ultrapure water, and naturally airing;
(b) modifying Ab with the surface of the electrode obtained in the step (a) by 4-6 mu L and 1-10 mu g/mL1Reacting the solution for 20-40 min, washing with ultrapure water, and naturally drying;
(c) modifying 4-6 muL bovine serum albumin solution with the mass fraction of 1.0% on the surface of the electrode obtained in the step (b) to seal non-specific active sites on the surface of the electrode, washing with ultrapure water after reacting for 20-40 min, and naturally drying;
(d) continuously dropwise adding 4-6 muL and 0.0001 ng-mL on the surface of the electrode obtained in the step (c)-1 ~ 100 ng·mL-1Reacting the procalcitonin antigen standard solution for 20-40 min, washing with ultrapure water, and naturally drying;
(e) dropwise adding 4-6 mu L, SiO on the surface of the electrode obtained in the step (d)2/PDA-Au-Ab2After reacting for 20-40 min, the solution is washed by ultrapure water and naturally dried to prepare a completely modified ITO electrode, namely a signal inhibition type photoelectrochemical procalcitonin sensor;
the 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide/N-hydroxysuccinimide content is 1 x 10-2mol/L of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and 2X 10-3mol/L of N-hydroxysuccinic acidA succinimide.
2. The application of the prepared signal inhibition type photoelectrochemistry procalcitonin sensor based on the zinc-titanium composite material is characterized by comprising the following application steps:
a. and (3) testing a working curve: taking a saturated calomel electrode as a reference electrode and a platinum wire electrode as an auxiliary electrode, taking the prepared signal inhibition type photoelectrochemical procalcitonin sensor based on the zinc-titanium composite material as a working electrode to form a three-electrode system, and testing in a PBS buffer solution; detecting the analyte by an I-t testing means, setting the voltage to be 0V, the running time to be 100 s, and using an excitation light source as an LED lamp; detecting the photocurrent intensity generated by the procalcitonin antigen standard solutions with different concentrations;
b. drawing a working curve: the photocurrent intensity of standard solutions containing different concentrations of procalcitonin antigen was recordedI i，I iWith procalcitonin antigen standard solution concentrationcIs linearly related to the logarithm of (1), and is drawnI i - logcA working curve;
c. detection of procalcitonin antigen: replacing procalcitonin antigen standard solution with human serum sample to be detected, detecting according to the method in step a, and responding to photocurrent intensityIAnd working curve, obtaining the content of procalcitonin antigen in the sample to be tested;
the PBS buffer solution is 10-15 mL of phosphate buffer solution containing 0.1 mol/L ascorbic acid and having pH of 5.0-8.0.
Advantageous results of the invention
(1) The invention adopts a hydrothermal method to synthesize a hollow-structured ZTCHS polyhedron to adjust the band gap width of the material. Compared with pure zinc titanate or titanium dioxide, the ZTCHS has the advantages of good stability, larger specific surface area and capacity, stronger load capacity and the like, and is beneficial to the load of nano particles.
(2) The invention utilizes Ru (bpy)3 2+To sensitize ZTCHS and grow narrow bandgap Bi in situ2S3As a signal amplification material, the conductivity of the material is improved, and photoelectric activity is obtainedSignificantly enhanced ZTCHS/Ru (bpy)3 2+/Bi2S3A composite material. The composite material has excellent photoelectrochemical activity, effectively promotes electron transfer, reduces the recombination of electron hole pairs, improves the photoelectric conversion efficiency and further enhances the photoelectric activity of the sensor.
(3) The invention designs SiO2PDA-Au as Ab2The signal suppression type sensing strategy is designed, and the linear range of the sensor is further widened. SiO 22The large steric hindrance of the/PDA effectively limits the electron transfer, and the Au nanoparticles can absorb visible light and compete with the substrate material for visible light, thereby reducing the photocurrent intensity of the substrate material and enhancing the sensitivity of the PEC sensor.
(4) The invention constructs a signal inhibition type photoelectrochemical procalcitonin sensor with good selectivity and simple operation by utilizing the specific combination of antigen and antibody. The sensor has a wider detection range and a lower detection limit, and realizes the ultra-sensitive detection of procalcitonin.
Detailed Description
The invention will now be further illustrated by, but not limited to, the following specific embodiments
EXAMPLE 1 preparation of ZTCHS/Ru (bpy)3 2+/Bi2S3The method comprises the following specific steps:
(1) preparation of zeolitic imidazoles framework material 8
Firstly, 0.9 g of zinc salt is dissolved in 30 mL of methanol, 20 mL of methanol solution containing 2.0 g of 2-methylimidazole is added, the solution is stirred for 24 hours at room temperature, the obtained product is centrifugally washed for three times by ethanol and ultrapure water respectively, and finally, the product is dried for 12 hours at 80 ℃ to obtain zeolite imidazole framework material 8 powder;
(2) preparation of ZTCHS
Dissolving 0.1 g of hexadecyltrimethylamine bromide into 8 mL of ethanol solution, stirring for 30 min at room temperature, adding 0.1 g of zeolite imidazole framework material 8, continuing to stir for 30 min, adding 200 mu L of tetrabutyl titanate into the solution, stirring for 30 min, continuing to add 4 mL of ultrapure water, stirring the solution for 24 h, transferring the solution into a polytetrafluoroethylene reaction kettle, reacting for 24 h at 100 ℃, performing centrifugal washing on the obtained product for 3 times by using ethanol and ultrapure water respectively, and finally drying for 12 h under vacuum to obtain ZTCS powder, dissolving the ZTCS powder in the ultrapure water to obtain a ZTCS suspension;
(3) cutting an ITO electrode to a size of 2.5 cm multiplied by 0.8 cm, carrying out ultrasonic cleaning for 30 min by using acetone, ethanol and ultrapure water in sequence, drying the ITO electrode by using nitrogen, modifying 10 mu L of ZTCHS suspension on the ITO electrode, airing the ITO electrode at room temperature, then placing the ITO electrode in a muffle furnace, calcining the ITO electrode at 450 ℃ for 30 min, and finally cooling the ITO electrode to the room temperature;
(4) the surface of the electrode obtained in the step (3) is modified by 4 muL, and the concentration is 0.03 mol.L-1Ru (bpy)3 2+Drying the solution at room temperature; further modifying the surface of the electrode by 4 mu L and 0.03 mol.L-1Bi (NO) of3)3Reacting the nitric acid solution at room temperature for 30 min, washing with ultrapure water, and modifying 4 mu L and 0.1 mol/L Na2S solution is reacted for 30 min at room temperature and is washed by ultrapure water to prepare ZTCHS/Ru (bpy)3 2+/Bi2S3；
The zinc salt is selected from one of the following: zinc chloride, zinc sulfate, zinc nitrate;
example 2 preparation of ZTCHS/Ru (bpy)3 2+/Bi2S3The method comprises the following specific steps:
(1) preparation of zeolitic imidazoles framework material 8
Firstly, 0.4 g of zinc salt is dissolved in 15 mL of methanol, 10 mL of methanol solution containing 1.0 g of 2-methylimidazole is added, the solution is stirred for 24 hours at room temperature, the obtained product is centrifugally washed for three times by ethanol and ultrapure water respectively, and finally, the product is dried for 12 hours at 80 ℃ to obtain zeolite imidazole framework material 8 powder;
(2) preparation of ZTCHS
Dissolving 0.05 g of hexadecyltrimethylamine bromide into 4 mL of ethanol solution, stirring for 30 min at room temperature, adding 0.05 g of zeolite imidazole framework material 8, continuing to stir for 30 min, adding 100 mu L of tetrabutyl titanate into the solution, stirring for 30 min, continuing to add 2 mL of ultrapure water, stirring the solution for 24 h, transferring the solution into a polytetrafluoroethylene reaction kettle, reacting for 24 h at 100 ℃, performing centrifugal washing on the obtained product for 3 times by using ethanol and ultrapure water respectively, and finally drying for 12 h under vacuum to obtain ZTCS powder, dissolving the ZTCS powder into the ultrapure water to obtain a ZTCS suspension;
(3) cutting an ITO electrode to a size of 2.5 cm multiplied by 0.8 cm, carrying out ultrasonic cleaning for 30 min by using acetone, ethanol and ultrapure water in sequence, drying the ITO electrode by using nitrogen, modifying 10 mu L of ZTCHS suspension on the ITO electrode, airing the ITO electrode at room temperature, then placing the ITO electrode in a muffle furnace, calcining the ITO electrode for 30 min at 500 ℃, and finally cooling the ITO electrode to the room temperature;
(4) the surface of the electrode obtained in the step (3) is modified by 4 muL, and the concentration is 0.03 mol.L-1Ru (bpy)3 2+Drying the solution at room temperature; further modifying the surface of the electrode by 4 mu L and 0.03 mol.L-1Bi (NO) of3)3Reacting the nitric acid solution at room temperature for 30 min, washing with ultrapure water, and modifying 4 mu L and 0.1 mol/L Na2S solution is reacted for 30 min at room temperature and is washed by ultrapure water to prepare ZTCHS/Ru (bpy)3 2+/Bi2S3；
The zinc salt is selected from one of the following: zinc chloride, zinc sulfate, zinc nitrate;
example 3 preparation of SiO2/PDA-Au-Ab2The method comprises the following specific steps:
（A）SiO2preparation of
Firstly, adding 7 mL of tetraethoxysilane into 78 mL of mixed solvent, adding 20 mL of 25% ammonia water into the solution, stirring for 4 hours at 40 ℃, centrifuging to obtain precipitates, washing the precipitates with ultrapure water and ethanol respectively until the pH is neutral, and finally drying the precipitates for 12 hours under vacuum to obtain SiO2Powder;
（B）SiO2preparation of PDA
40 mg of SiO2And 40 mg of dopamine hydrochloride dissolved in 20 mL of 10 mmol. multidot.L-1And pH 8.5 in a buffer solution of tris (hydroxymethyl) aminomethaneStirring at room temperature for 12 h, centrifuging, washing with ultrapure water and ethanol for 3 times, respectively, and vacuum drying to obtain SiO2PDA powder;
（C）SiO2preparation of/PDA-Au
Dissolving 0.02 g of sodium citrate into 40 mL of ultrapure water, and then adding 40 mu L of chloroauric acid of 2% and 5 mg of SiO2PDA and stirring at room temperature for 5 min, heating and boiling the solution for 15 min, cooling to room temperature, centrifuging, washing with ultrapure water for three times, and drying under vacuum to obtain SiO2/PDA-Au；
（D）SiO2/PDA-Au-Ab2Preparation of
5 mg of SiO2the/PDA-Au solution was dissolved in 1 mL of PBS buffer solution having a pH of 7.4, followed by addition of 200. mu.L of 10. mu.g/mL−1Procalcitonin-detecting antibody Ab2Oscillating and incubating for 12 h in a constant temperature oscillation incubator at 4 ℃, centrifugally washing, dispersing the product in 1 mL PBS buffer solution containing 1.0 percent of bovine serum albumin by mass and having pH of 7.4 to prepare SiO2/PDA-Au-Ab2Stored in a refrigerator at 4 ℃ for later use;
the mixed solvent is prepared by mixing ultrapure water and ethanol according to the volume ratio of 1: 25;
example 4 preparation of SiO2/PDA-Au-Ab2The method comprises the following specific steps:
（A）SiO2preparation of
Firstly, adding 3 mL of tetraethoxysilane into 39 mL of mixed solvent, then adding 10 mL of 25% ammonia water into the solution, stirring for 4 hours at 40 ℃, centrifuging to obtain precipitates, washing the precipitates with ultrapure water and ethanol respectively until the pH is neutral, and finally drying the precipitates for 12 hours under vacuum to obtain SiO2Powder;
（B）SiO2preparation of PDA
20 mg of SiO2And 20 mg of dopamine hydrochloride dissolved in 10 mL of 10 mmol. multidot.L-1And pH 8.5, stirring the above solution at room temperature for 12 h, centrifuging, washing with ultrapure water and ethanol respectively3 times, drying the product in vacuum to obtain SiO2PDA powder;
（C）SiO2preparation of/PDA-Au
Dissolving 0.01 g of sodium citrate into 20 mL of ultrapure water, and then adding 20 mu L of 2% chloroauric acid and 3 mg of SiO2PDA and stirring at room temperature for 5 min, heating and boiling the solution for 15 min, cooling to room temperature, centrifuging, washing with ultrapure water for three times, and drying under vacuum to obtain SiO2/PDA-Au；
（D）SiO2/PDA-Au-Ab2Preparation of
3 mg of SiO2the/PDA-Au solution was dissolved in 1 mL of a PBS buffer solution having a pH of 7.4, and then 100. mu.L of 10. mu.g/mL was added−1Procalcitonin-detecting antibody Ab2Oscillating and incubating for 12 h in a constant temperature oscillation incubator at 4 ℃, centrifugally washing, dispersing the product in 1 mL PBS buffer solution containing 1.0 percent of bovine serum albumin by mass and having pH of 7.4 to prepare SiO2/PDA-Au-Ab2Stored in a refrigerator at 4 ℃ for later use;
the mixed solvent is prepared by mixing ultrapure water and ethanol according to the volume ratio of 1: 25;
example 5 the specific steps for preparing the signal-suppressed photoelectrochemical procalcitonin sensor are as follows:
(a) in ZTCHS/Ru (bpy)3 2+/Bi2S3Modifying 4 muL and 0.1 mol/L thioglycollic acid on the surface of the modified ITO working electrode, airing at room temperature, continuously dropwise adding 4 muL 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide/N-hydroxysuccinimide, reacting for 30 min, washing with ultrapure water, and naturally airing;
(b) modifying the Ab with 4 muL and 1 mug/mL on the surface of the electrode obtained in the step (a)1Reacting the solution for 30 min, washing with ultrapure water, and naturally drying;
(c) modifying 5 muL bovine serum albumin solution with the mass fraction of 1.0% on the surface of the electrode obtained in the step (b) to seal the nonspecific active sites on the surface of the electrode, washing with ultrapure water after reacting for 30 min, and naturally drying;
(d) continuously dropwise adding 4 muL and 0.0001 ng-mL on the surface of the electrode obtained in the step (c)-1 ~ 100 ng·mL-1Reacting the procalcitonin antigen standard solution for 30 min, washing with ultrapure water, and naturally drying;
(e) dropwise adding 4 mu L, SiO on the surface of the electrode obtained in the step (d)2/PDA-Au-Ab2The solution is washed by ultrapure water after reacting for 30 min and is naturally dried, and an ITO electrode which is completely modified, namely a signal inhibition type photoelectrochemical procalcitonin sensor, is prepared;
the 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide/N-hydroxysuccinimide content is 1 x 10-2mol/L of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and 2X 10-3mol/L of N-hydroxysuccinimide.
Example 6 the specific steps for preparing the signal-suppressed photoelectrochemical procalcitonin sensor are as follows:
(a) in ZTCHS/Ru (bpy)3 2+/Bi2S3Modifying 4 muL and 0.1 mol/L thioglycollic acid on the surface of the modified ITO working electrode, airing at room temperature, continuously dropwise adding 4 muL 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide/N-hydroxysuccinimide, reacting for 30 min, washing with ultrapure water, and naturally airing;
(b) modifying the Ab with 4 muL and 10 mug/mL on the surface of the electrode obtained in the step (a)1Reacting the solution for 30 min, washing with ultrapure water, and naturally drying;
(c) modifying 5 muL bovine serum albumin solution with mass fraction of 1.0% on the surface of the electrode obtained in the step (b) to seal the nonspecific active sites on the surface of the electrode, washing with ultrapure water after reacting for 30 min, and naturally drying;
(d) continuously dropwise adding 4 muL and 0.0001 ng-mL on the surface of the electrode obtained in the step (c)-1 ~ 100 ng·mL-1Reacting the procalcitonin antigen standard solution for 30 min, washing with ultrapure water, and naturally drying;
(e) dropwise adding 4 mu L, SiO on the surface of the electrode obtained in the step (d)2/PDA-Au-Ab2Solution, after 30 min reactionWashing with ultrapure water, and naturally drying to obtain a completely modified ITO electrode, namely a signal inhibition type photoelectrochemical procalcitonin sensor;
the 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide/N-hydroxysuccinimide content is 1 x 10-2mol/L of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and 2X 10-3mol/L of N-hydroxysuccinimide.
The application of the signal inhibition type photoelectrochemical procalcitonin sensor based on the zinc-titanium composite material prepared in the embodiment 7 is characterized by comprising the following application steps:
a. and (3) testing a working curve: taking a saturated calomel electrode as a reference electrode and a platinum wire electrode as an auxiliary electrode, taking the prepared signal inhibition type photoelectrochemical procalcitonin sensor based on the zinc-titanium composite material as a working electrode to form a three-electrode system, and testing in a PBS buffer solution; detecting the analyte by an I-t testing means, setting the voltage to be 0V, the running time to be 100 s, and using an excitation light source as an LED lamp; detecting the photocurrent intensity generated by the procalcitonin antigen standard solutions with different concentrations;
b. drawing a working curve: the photocurrent intensity of standard solutions containing different concentrations of procalcitonin antigen was recordedI i，I iWith procalcitonin antigen standard solution concentrationcIs linearly related to the logarithm of (1), and is drawnI i - logcA working curve;
c. detection of procalcitonin antigen: replacing procalcitonin antigen standard solution with human serum sample to be detected, detecting according to the method in step a, and responding to photocurrent intensityIAnd working curve, obtaining the content of procalcitonin antigen in the sample to be tested;
the PBS buffer solution is 10-15 mL of phosphate buffer solution containing 0.1 mol/L ascorbic acid and having pH of 5.0-8.0.

Claims (2)

1. A preparation method of a signal inhibition type photoelectrochemical procalcitonin sensor based on a zinc-titanium composite material is provided, wherein the zinc-titanium composite material is terpyridylPyridine ruthenium Ru (bpy)3 2+And bismuth sulfide Bi2S3Co-sensitized zinc titanate/titanium dioxide heterojunction ZTHS composite material ZTHS/Ru (bpy)3 2+/Bi2S3The photoelectrochemical procalcitonin sensor consists of an Indium Tin Oxide (ITO) working electrode, a ZTHS/Ru (bpy)3 2+/Bi2S3Procalcitonin capture antibody Ab1Bovine serum albumin, procalcitonin antigen standard solution and procalcitonin detection antibody marker SiO2/PDA-Au-Ab2Composition is carried out;
the preparation method is characterized by comprising the following preparation steps:
first, ZTCHS/Ru (bpy)3 2+/Bi2S3Preparing;
II, SiO2/PDA-Au-Ab2Preparing;
thirdly, preparing a signal inhibition type photoelectrochemical procalcitonin sensor;
wherein, the first step is to prepare ZTCHS/Ru (bpy)3 2+/Bi2S3The method comprises the following specific steps:
(1) preparation of zeolitic imidazoles framework material 8
Firstly, dissolving 0.3-1.0 g of zinc salt into 15-30 mL of methanol, then adding 10-20 mL of methanol solution containing 1.0-2.0 g of 2-methylimidazole, stirring the solution at room temperature for 20-26 h, centrifuging and washing the obtained product with ethanol and ultrapure water for three times, and finally drying at 80 ℃ for 10-14 h to obtain zeolite imidazole framework material 8 powder;
(2) preparation of ZTCHS
Dissolving 0.05-0.10 g of hexadecyltrimethylamine bromide into 2-10 mL of ethanol solution, stirring for 20-40 min at room temperature, adding 0.05-0.10 g of zeolite imidazole framework material 8, continuing to stir for 20-40 min, adding 100-200 mu L of tetrabutyl titanate into the solution, stirring for 20-40 min, continuing to add 2-4 mL of ultrapure water, stirring the solution for 20-26 h, transferring the solution into a polytetrafluoroethylene reaction kettle, reacting for 20-26 h at 100 ℃, centrifugally washing the obtained product for 3-6 times by using ethanol and ultrapure water respectively, finally drying for 10-14 h under vacuum to obtain ZTCHS powder, dissolving the ZTCHS powder in ultrapure water to obtain a ZTCHS suspension;
(3) cutting an ITO electrode to 2.5 cm multiplied by 0.8 cm, carrying out ultrasonic cleaning for 20-40 min by using acetone, ethanol and ultrapure water in sequence, after drying by using nitrogen, modifying 8-10 mu L of ZTCHS suspension onto the ITO electrode, airing at room temperature, then placing the ITO electrode in a muffle furnace, calcining at 400-500 ℃ for 20-40 min, and finally cooling to room temperature;
(4) modifying the surface of the electrode obtained in the step (3) by 3-4 mu L, wherein the concentration is 0.02-0.04 mol.L-1Ru (bpy)3 2+Drying the solution at room temperature; further modifying the surface of the electrode by 3-4 muL and 0.02-0.04 mol.L-1Bi (NO) of3)3Reacting the nitric acid solution at room temperature for 20-40 min, washing with ultrapure water, and then modifying 3-4 muL and 0.1 mol/L Na2The S solution reacts for 20-40 min at room temperature, and is washed by ultrapure water to prepare ZTCHS/Ru (bpy)3 2+/Bi2S3；
The zinc salt is selected from one of the following: zinc chloride, zinc sulfate, zinc nitrate;
wherein, the step two is used for preparing SiO2/PDA-Au-Ab2The method comprises the following specific steps:
（A）SiO2preparation of
Firstly, adding 2-9 mL of tetraethoxysilane into 38-80 mL of mixed solvent, then adding 10-20 mL of 25% ammonia water into the solution, stirring for 3-5 h at 40 ℃, centrifuging to obtain precipitates, washing the precipitates with ultrapure water and ethanol respectively until the pH is neutral, and finally drying for 10-14 h under vacuum to obtain SiO2Powder;
（B）SiO2preparation of PDA
20-40 mg of SiO2And 20-40 mg of dopamine hydrochloride are dissolved in 10-20 mL of 10 mmol.L-1And stirring the solution for 10-14 h at room temperature in a trihydroxymethyl aminomethane buffer solution with the pH of 8.5, centrifuging, washing with ultrapure water and ethanol for 3-4 times respectively, and drying the product in vacuum to obtain SiO2PDA powder;
（C）SiO2preparation of/PDA-Au
Dissolving 0.01-0.02 g of sodium citrate into 20-40 mL of ultrapure water, and then adding 20-40 muL of chloroauric acid and 2-6 mg of SiO2PDA is stirred for 4-6 min at room temperature, then the solution is heated and boiled for 12-20 min, after being cooled to room temperature, the solution is centrifuged and washed with ultrapure water for three times, and finally, the solution is dried under vacuum condition to obtain SiO2/PDA-Au；
（D）SiO2/PDA-Au-Ab2Preparation of
2-6 mg of SiO2The solution of/PDA-Au was dissolved in 1 mL of PBS buffer solution having a pH of 7.4, and then 100 to 200. mu.L of 10. mu.g/mL of the solution was added−1Procalcitonin-detecting antibody Ab2Oscillating and incubating for 12 h in a constant temperature oscillation incubator at 4 ℃, centrifugally washing, dispersing the product in 1 mL PBS buffer solution containing 1.0 percent of bovine serum albumin by mass and having pH of 7.4 to prepare SiO2/PDA-Au-Ab2Stored in a refrigerator at 4 ℃ for later use;
the mixed solvent is prepared by mixing ultrapure water and ethanol according to the volume ratio of 1: 25;
the third step of preparing the signal inhibition type photoelectrochemical procalcitonin sensor comprises the following specific steps:
(a) the ZTCHS/Ru (bpy) obtained in step one3 2+/Bi2S3Modifying 3-5 muL and 0.1 mol/L thioglycollic acid on the surface of the modified ITO working electrode, airing at room temperature, continuously dropwise adding 3-5 muL 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide/N-hydroxysuccinimide, reacting for 20-40 min, washing with ultrapure water, and naturally airing;
(b) modifying Ab with the surface of the electrode obtained in the step (a) by 4-6 mu L and 1-10 mu g/mL1Reacting the solution for 20-40 min, washing with ultrapure water, and naturally drying;
(c) modifying 4-6 muL bovine serum albumin solution with the mass fraction of 1.0% on the surface of the electrode obtained in the step (b) to seal non-specific active sites on the surface of the electrode, washing with ultrapure water after reacting for 20-40 min, and naturally drying;
(d) continuously dropwise adding 4-6 muL and 0.0001 ng-mL on the surface of the electrode obtained in the step (c)-1 ~ 100 ng·mL-1Reacting the procalcitonin antigen standard solution for 20-40 min, washing with ultrapure water, and naturally drying;
(e) dropwise adding 4-6 mu L, SiO on the surface of the electrode obtained in the step (d)2/PDA-Au-Ab2After reacting for 20-40 min, the solution is washed by ultrapure water and naturally dried to prepare a completely modified ITO electrode, namely a signal inhibition type photoelectrochemical procalcitonin sensor;
the 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide/N-hydroxysuccinimide content is 1 x 10-2mol/L of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and 2X 10-3mol/L of N-hydroxysuccinimide.
2. The application of the signal inhibition type photoelectrochemical procalcitonin sensor based on the zinc-titanium composite material prepared by the preparation method of claim 1 is characterized by comprising the following application steps:
a. and (3) testing a working curve: taking a saturated calomel electrode as a reference electrode and a platinum wire electrode as an auxiliary electrode, taking the signal inhibition type photoelectrochemical procalcitonin sensor based on the zinc-titanium composite material prepared by the preparation method of claim 1 as a working electrode to form a three-electrode system, and testing in a PBS buffer solution; detecting the analyte by an I-t testing means, setting the voltage to be 0V, the running time to be 100 s, and using an excitation light source as an LED lamp; detecting the photocurrent intensity generated by the procalcitonin antigen standard solutions with different concentrations;
b. drawing a working curve: the photocurrent intensity of standard solutions containing different concentrations of procalcitonin antigen was recordedI i，I iWith procalcitonin antigen standard solution concentrationcIs linearly related to the logarithm of (1), and is drawnI i - logcA working curve;
c. detection of procalcitonin antigen: substitution of calcitonin with human serum sample to be testedThe antigen standard solution is detected according to the method in the step a, and the detection is carried out according to the intensity of the response light currentIAnd working curve, obtaining the content of procalcitonin antigen in the sample to be tested;
the PBS buffer solution is 10-15 mL of phosphate buffer solution containing 0.1 mol/L ascorbic acid and having pH of 5.0-8.0.
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