CN110261448A - A kind of preparation method and application of the signal suppressive optical electro-chemistry Procalcitonin sensor based on zinc titanium composite material - Google Patents

A kind of preparation method and application of the signal suppressive optical electro-chemistry Procalcitonin sensor based on zinc titanium composite material Download PDF

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CN110261448A
CN110261448A CN201910541846.9A CN201910541846A CN110261448A CN 110261448 A CN110261448 A CN 110261448A CN 201910541846 A CN201910541846 A CN 201910541846A CN 110261448 A CN110261448 A CN 110261448A
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procalcitonin
sio
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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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University of Jinan
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Abstract

The preparation method and application of the present invention relates to a kind of signal suppressive optical electro-chemistry Procalcitonin sensor based on zinc titanium composite material.Zinc titanate/titanium dioxide heterogeneous knot ZTCHS polyhedron of hollow structure is synthesized by hydro-thermal method.Unique hollow structure makes ZTCHS have biggish specific surface area and preferable bearing capacity.It recycles tris (bipyridine) ruthenium Ru (bpy)3 2+With bismuth sulfide Bi2S3It is sensitized ZTCHS altogether, further enhances the photoelectrochemical behaviour of ZTCHS, obtains the zinc titanium composite material ZTCHS/Ru (bpy) that photoelectric activity significantly improves3 2+/Bi2S3.The silica of preparation/poly- Dopamine hydrochloride-metal/composite material SiO2/ PDA-Au inhibits the immobilized Procalcitonin of material to detect antibody as signal.Wherein, SiO2The biggish steric hindrance of/PDA effectively limits the transfer of electronics, and visible light can be absorbed in Au nanoparticle, competes visible light with base material.Based on above-mentioned several aspects, it is prepared for a kind of signal suppressive optical electro-chemistry Procalcitonin sensor based on zinc titanium composite material, realizes the super sensitivity detection to Procalcitonin, this has great importance to the analysis detection of Procalcitonin.

Description

A kind of signal suppressive optical electro-chemistry Procalcitonin sensing based on zinc titanium composite material The preparation method and application of device
Technical field
The invention belongs to optical electro-chemistry sensor fields, and in particular to a kind of signal suppressive based on zinc titanium composite material The preparation method and application of optical electro-chemistry Procalcitonin sensor.
Background technique
Currently, optical electro-chemistry (PEC) sensor has become a kind of analysis method to attract attention, in medical diagnosis on disease, food The fields such as safety detection, environmental protection are widely applied.PEC sensor is living by sensitive biological materials such as enzyme, antigen, antibody, DNA etc. Property substance be fixed as recognition component, under the irradiation of visible light by sensitive biological materials express signal export as electric signal.It is raw The specific recognition of object material makes PEC sensor have good specificity and sensibility to the diagnosis of cancer.However, how structure Stable electro-optic sensor material interface is built, and designs outstanding sensing strategy, is still an important challenge, and need One of problem in science of solution.
Material is adjusted using zinc titanate/titanium dioxide heterogeneous knot ZTCHS polyhedron of hydro-thermal method synthesis hollow structure Band gap width.Compared with pure zinc titanate or titanium dioxide, ZTCHS is with good stability, biggish specific surface area and capacity, The advantages that stronger load capacity, is conducive to the load of nanoparticle.In addition, bismuth sulfide Bi2S3Relatively narrow band gap width is conducive to The separation of light induced electron and hole improves the intensity of photo-signal.Moreover, Bi2S3The perfect band gap between ZTCHS With the transfer for effectively accelerating electronics, material is improved to the utilization rate of visible light.In the process, tris (bipyridine) ruthenium Ru (bpy)3 2+It is oxidized to Ru (III) complex compound.Ru (III) complex compound is reacted with ZTCHS becomes excitation state Ru (II) *.Then, Ru (II) * returns to ground state and along with electronics transfer and energy transfer, and which further improves the photoelectrochemical behaviours of material.Cause This, the present invention utilizes Ru (bpy)3 2+And Bi2S3It is sensitized ZTCHS to be total to, being formed has the active zinc titanium of excellent optical electro-chemistry compound Material ZTCHS/Ru (bpy)3 2+/Bi2S3, and in this, as the base material of PEC sensor.In addition, design silica/polysalt Sour dopamine-metal/composite material SiO2/ PDA-Au detects antibody A b as Procalcitonin2Marker.SiO2/ PDA's is biggish Steric hindrance effectively limits the transfer of electronics, and visible light can be absorbed in Au nanoparticle, can with base material competition It is light-exposed, to reduce the photo-current intensity of base material, enhance the sensitivity of PEC sensor, realizes the oversoul to Procalcitonin Quick detection.
Summary of the invention
An object of the present invention is that the band gap of material is adjusted using the ZTCHS polyhedron of hydro-thermal method synthesis hollow structure Width.
The second object of the present invention is to utilize Ru (bpy)3 2+To be sensitized ZTCHS, and the Bi of growth in situ narrow band gap2S3Make For signal amplified material, ZTCHS/Ru (bpy) is obtained3 2+/Bi2S3Composite material.
The third object of the present invention is design SiO2/ PDA-Au is as Ab2Marker, reduce the photoelectric current of base material Intensity enhances the sensitivity of PEC sensor.
The fourth object of the present invention is the specific binding using antigen-antibody, and it is good and easy to operate to construct a kind of selectivity Signal suppressive optical electro-chemistry Procalcitonin sensor, realize to quick, the Sensitive Detection of Procalcitonin.
Technical scheme is as follows:
1. a kind of preparation method of the signal suppressive optical electro-chemistry Procalcitonin sensor based on zinc titanium composite material, described Zinc titanium composite material be tris (bipyridine) ruthenium Ru (bpy)3 2+With bismuth sulfide Bi2S3The zinc titanate being sensitized altogether/titanium dioxide heterogeneous knot ZTCHS composite material ZTCHS/Ru (bpy)3 2+/Bi2S3, the optical electro-chemistry Procalcitonin sensor is by tin indium oxide ITO work Make electrode, ZTCHS/Ru (bpy)3 2+/Bi2S3, Procalcitonin capture antibody A b1, bovine serum albumin(BSA), Procalcitonin antigen standard Solution and Procalcitonin detect antibody marker SiO2/PDA-Au-Ab2Composition；
It is characterized in that, the preparation method includes following preparation step:
One, ZTCHS/Ru (bpy)3 2+/Bi2S3Preparation；
Two, SiO2/PDA-Au-Ab2Preparation；
Three, the preparation of signal suppressive optical electro-chemistry Procalcitonin sensor；
Wherein, step 1 preparation ZTCHS/Ru (bpy)3 2+/Bi2S3Specific steps are as follows:
(1) preparation of zeolite imidazole class framework material 8
Firstly, 0.3 ~ 1.0 g zinc salt is dissolved into 15 ~ 30 mL methanol, 10 ~ 20 mL are added containing 2-methylimidazole 20 ~ 26 h are stirred at room temperature in the methanol solution of 1.0 ~ 2.0 g, above-mentioned solution, by products therefrom ethyl alcohol and ultrapure water Three times, finally dry 10 ~ 14 h obtain 8 powder of zeolite imidazole class framework material to each centrifuge washing at 80 DEG C；
(2) preparation of ZTCHS
The cetrimonium bronmide of 0.05 ~ 0.10 g is dissolved into 2 ~ 10 mL ethanol solutions, is stirred at room temperature 20 ~ 40 min add 0.05 ~ 0.10 g zeolite imidazole class framework material 8, continue 20 ~ 40 min of stirring, then by 100 ~ The butyl titanate of 200 μ L is added in above-mentioned solution and stirs 20 ~ 40 min, continuously adds the ultrapure water of 2 ~ 4 mL And solution is stirred into 20 ~ 26 h, then solution is transferred in ptfe autoclave and at 100 DEG C reaction 20 ~ Products therefrom ethyl alcohol and each centrifuge washing of ultrapure water 3 ~ 6 times are finally dried under vacuum 10 ~ 14 h and obtained by 26 h ZTCHS powder, is dissolved in ultrapure water, obtains ZTCHS suspension；
(3) ITO electrode is cut to the cm size of 2.5 cm × 0.8, successively with acetone, ethyl alcohol and ultrapure water ultrasonic cleaning 20 ~ 40 min, by the ZTCHS suspension modification to ITO electrode of 8 ~ 10 μ L, dry, then at room temperature after being dried with nitrogen It places it in and calcines 20 ~ 40 min in Muffle furnace at 400 ~ 500 DEG C, be finally cooled to room temperature；
(4) 3 ~ 4 μ L of electrode face finish that obtains in step (3), concentration are 0.02 ~ 0.04 molL-1Ru (bpy)3 2+Solution dries at room temperature；3 ~ 4 μ L, 0.02 ~ 0.04 molL are further modified in electrode surface-1Bi (NO3)3Nitric acid solution, react 20 ~ 40 min at room temperature, ultrapure water then modifies 3 ~ 4 μ L, 0.1 mol/L Na2S solution, reacts 20 ~ 40 min at room temperature, and ultrapure water is made ZTCHS/Ru (bpy)3 2+/Bi2S3；
The zinc salt is selected from one of following: zinc chloride, zinc sulfate, zinc nitrate；
Wherein, step 2 prepares SiO2/PDA-Au-Ab2Specific steps are as follows:
(A) SiO2Preparation
Firstly, 2 ~ 9 mL ethyl orthosilicates to be added to the in the mixed solvent of 38 ~ 80 mL, then by 10 ~ 20 mL, 25% Ammonium hydroxide be added in above-mentioned solution, 3 ~ 5 h are stirred at 40 DEG C, be centrifugeds to obtain sediment, sediment is respectively with surpassing Pure water and ethanol washing are neutrality to pH, and 10 ~ 14 h are finally dried under vacuum and obtain SiO2Powder；
(B) SiO2The preparation of/PDA
By the SiO of 20 ~ 40 mg210 ~ 20 mL, 10 mmolL are added to the Dopamine hydrochloride of 20 ~ 40 mg-1And In the trishydroxymethylaminomethane buffer solution that pH is 8.5,10 ~ 14 h are stirred at room temperature in above-mentioned solution, be then centrifuged for, It is washed respectively 3 ~ 4 times with ultrapure water and ethyl alcohol, product is dried under vacuum to obtain SiO2/ PDA powder；
(C) SiO2The preparation of/PDA-Au
0.01 ~ 0.02 g sodium citrate is dissolved into 20 ~ 40 mL ultrapure waters, the chlorine gold of 20 ~ 40 μ L, 2% are added The SiO of acid and 2 ~ 6 mg2Simultaneously 4 ~ 6 min are stirred at room temperature in/PDA, then heat above-mentioned solution, boil 12 ~ 20 Min, after being cooled to room temperature, solution centrifugation and with milli-Q water three times, be finally dried to obtain SiO under vacuum conditions2/PDA- Au；
(D) SiO2/PDA-Au-Ab2Preparation
The SiO of 2 ~ 6 mg2/ PDA-Au is dissolved into the PBS buffer solution that 1 mL, pH is 7.4, is then added 100 ~ 200 μL、10 μg·mL−1Procalcitonin detect antibody A b2, 12 h of oscillation hatching, centrifugation are washed in 4 DEG C of constant-temperature shaking incubators It washs, in the PBS buffer solution that product is dispersed in 1 mL, is 1.0% bovine serum albumin(BSA) containing mass fraction and pH is 7.4, is made SiO2/PDA-Au-Ab2, storage is in 4 DEG C of refrigerators with spare；
The mixed solvent is that 1:25 is mixed to prepare by volume for ultrapure water and ethyl alcohol；
Wherein, step 3 prepares the specific steps of signal suppressive optical electro-chemistry Procalcitonin sensor are as follows:
(a) ZTCHS/Ru obtained in step 1 (bpy)3 2+/Bi2S3The ITO working electrode surface of modification modifies 3 ~ 5 μ L, the thioacetic acid of 0.1 mol/L, dries at room temperature, continues the 1- ethyl -3- (3- dimethyl aminopropyl)-of 3 ~ 5 μ L of dropwise addition Carbodiimides/n-hydroxysuccinimide uses ultrapure water, naturally dry after reacting 20 ~ 40 min；
(b) Ab of 4 ~ 6 μ L of electrode face finish, 1 ~ 10 μ g/mL that obtain in step (a)1Solution, reaction 20 ~ Ultrapure water, naturally dry are used after 40 min；
(c) 4 ~ 6 μ L of electrode face finish, the mass fraction obtained in step (b) is molten for 1.0% bovine serum albumin(BSA) Liquid uses ultrapure water, naturally dry after reacting 20 ~ 40 min with nonspecific activity site on enclosed-electrode surface；
(d) electrode surface obtained in step (c) continues 4 ~ 6 μ L of dropwise addition, 0.0001 ngmL-1 ~ 100 ng·mL-1Procalcitonin antigen standard solution uses ultrapure water, naturally dry after reacting 20 ~ 40 min；
(e) 4 ~ 6 μ L, SiO are added dropwise in the electrode surface obtained in step (d)2/PDA-Au-Ab2Solution, reaction 20 ~ 40 Ultrapure water is used after min, the complete ITO electrode of modification, i.e. signal suppressive optical electro-chemistry calcitonin has been made in naturally dry Original sensor；
1- ethyl -3- (the 3- dimethyl aminopropyl)-carbodiimides/n-hydroxysuccinimide contains 1 × 10-2 mol/ 1- ethyl -3- (3- dimethyl aminopropyl)-carbodiimides and 2 × 10 of L-3The n-hydroxysuccinimide of mol/L.
A kind of application of prepared signal suppressive optical electro-chemistry Procalcitonin sensor based on zinc titanium composite material, It is characterised in that it includes following applying step:
A. working curve is tested: using saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, by prepared one Signal suppressive optical electro-chemistry Procalcitonin sensor of the kind based on zinc titanium composite material forms three electrode bodies as working electrode System, is tested in PBS buffer solution；Analyte is detected using I-t means of testing, setting voltage is 0 V, operation 100 s of time, excitation light source are LED light；It is strong to detect the photoelectric current generated to the Procalcitonin antigen standard solution of various concentration Degree；
B. working curve is drawn: the photo-current intensity of the Procalcitonin antigen standard solution containing various concentration is denoted asI i,I iWith Procalcitonin antigen concentration of standard solutioncLogarithm between it is linear, drawI i - logcWorking curve；
C. the detection of Procalcitonin antigen: Procalcitonin antigen standard solution is replaced with human serum sample to be measured, according to step Method in rapid a is detected, according to response photo-current intensityIAnd working curve, obtain Procalcitonin antigen in sample to be tested Content；
The PBS buffer solution is the phosphate containing 0.1 mol/L ascorbic acid that 10 ~ 15 mL, pH are 5.0 ~ 8.0 Buffer solution.
Beneficial achievement of the invention
(1) present invention adjusts the band gap width of material using the ZTCHS polyhedron of hydro-thermal method synthesis hollow structure.With pure metatitanic acid Zinc or titanium dioxide are compared, and ZTCHS is with good stability, biggish specific surface area and capacity, stronger load capacity etc. Advantage is conducive to the load of nanoparticle.
(2) present invention utilizes Ru (bpy)3 2+To be sensitized ZTCHS, and the Bi of growth in situ narrow band gap2S3It is put as signal Big material improves the electric conductivity of material, obtains the ZTCHS/Ru (bpy) that photoelectric activity is remarkably reinforced3 2+/Bi2S3Composite material. The composite material has very excellent optical electro-chemistry activity, effectively facilitates electronics transfer, reduces the compound of electron hole pair, from And incident photon-to-electron conversion efficiency is improved, further enhance the photoelectric activity of sensor.
(3) present invention design SiO2/ PDA-Au is as Ab2Marker, devise a kind of signal suppressive sensing strategy, The range of linearity of sensor is further widened.SiO2The biggish steric hindrance of/PDA effectively limits the transfer of electronics, And visible light can be absorbed in Au nanoparticle, visible light is competed with base material, so that the photoelectric current for reducing base material is strong Degree, enhances the sensitivity of PEC sensor.
(4) present invention is to construct a kind of signal that selectivity is good, easy to operate using the specific binding of antigen-antibody Suppressive optical electro-chemistry Procalcitonin sensor.There is the sensor wider detection range and lower detection to limit, and realize To the super sensitivity detection of Procalcitonin.
Specific embodiment
Now the present invention is further illustrated by specific embodiment, but not limited to this.
Embodiment 1 prepares ZTCHS/Ru (bpy)3 2+/Bi2S3Specific steps are as follows:
(1) preparation of zeolite imidazole class framework material 8
Firstly, 0.9 g zinc salt is dissolved into 30 mL methanol, the methanol solution of 20 mL, 2.0 g containing 2-methylimidazole is added, on It states solution and 24 h is stirred at room temperature, three times by products therefrom ethyl alcohol and each centrifuge washing of ultrapure water, finally done at 80 DEG C Dry 12 h obtains 8 powder of zeolite imidazole class framework material；
(2) preparation of ZTCHS
The cetrimonium bronmide of 0.1 g is dissolved into 8 mL ethanol solutions, and 30 min are stirred at room temperature, add 0.1 g zeolite imidazole class framework material 8 continues to stir 30 min, then the butyl titanate of 200 μ L is added to above-mentioned solution In and stir 30 min, continuously add the ultrapure water of 4 mL and by solution stir 24 h, solution is then transferred to polytetrafluoro 24 h are reacted in ethylene reaction kettle and at 100 DEG C, and products therefrom ethyl alcohol and each centrifuge washing of ultrapure water 3 times finally exist Dry 12 h obtain ZTCHS powder under vacuum, are dissolved in ultrapure water, obtain ZTCHS suspension；
(3) ITO electrode is cut to the cm size of 2.5 cm × 0.8, successively with acetone, ethyl alcohol and ultrapure water ultrasonic cleaning 30 Min, by the ZTCHS suspension modification to ITO electrode of 10 μ L, is dried at room temperature, is then placed after being dried with nitrogen 30 min are calcined at 450 DEG C in Muffle furnace, are finally cooled to room temperature；
(4) 4 μ L of electrode face finish that obtains in step (3), concentration are 0.03 molL-1Ru (bpy)3 2+Solution, It dries at room temperature；4 μ L, 0.03 molL are further modified in electrode surface-1Bi (NO3)3Nitric acid solution, at room temperature instead 30 min are answered, ultrapure water then modifies the Na of 4 μ L, 0.1 mol/L2S solution reacts 30 min, ultrapure water at room temperature It rinses, is made ZTCHS/Ru (bpy)3 2+/Bi2S3；
The zinc salt is selected from one of following: zinc chloride, zinc sulfate, zinc nitrate.
Embodiment 2 prepares ZTCHS/Ru (bpy)3 2+/Bi2S3Specific steps are as follows:
(1) preparation of zeolite imidazole class framework material 8
Firstly, 0.4 g zinc salt is dissolved into 15 mL methanol, the methanol solution of 10 mL, 1.0 g containing 2-methylimidazole is added, on It states solution and 24 h is stirred at room temperature, three times by products therefrom ethyl alcohol and each centrifuge washing of ultrapure water, finally done at 80 DEG C Dry 12 h obtains 8 powder of zeolite imidazole class framework material；
(2) preparation of ZTCHS
The cetrimonium bronmide of 0.05 g is dissolved into 4 mL ethanol solutions, and 30 min are stirred at room temperature, add 0.05 g zeolite imidazole class framework material 8 continues to stir 30 min, then the butyl titanate of 100 μ L is added to above-mentioned solution In and stir 30 min, continuously add the ultrapure water of 2 mL and by solution stir 24 h, solution is then transferred to polytetrafluoro 24 h are reacted in ethylene reaction kettle and at 100 DEG C, and products therefrom ethyl alcohol and each centrifuge washing of ultrapure water 3 times finally exist Dry 12 h obtain ZTCHS powder under vacuum, are dissolved in ultrapure water, obtain ZTCHS suspension；
(3) ITO electrode is cut to the cm size of 2.5 cm × 0.8, successively with acetone, ethyl alcohol and ultrapure water ultrasonic cleaning 30 Min, by the ZTCHS suspension modification to ITO electrode of 10 μ L, is dried at room temperature, is then placed after being dried with nitrogen 30 min are calcined at 500 DEG C in Muffle furnace, are finally cooled to room temperature；
(4) 4 μ L of electrode face finish that obtains in step (3), concentration are 0.03 molL-1Ru (bpy)3 2+Solution, It dries at room temperature；4 μ L, 0.03 molL are further modified in electrode surface-1Bi (NO3)3Nitric acid solution, at room temperature instead 30 min are answered, ultrapure water then modifies the Na of 4 μ L, 0.1 mol/L2S solution reacts 30 min, ultrapure water at room temperature It rinses, is made ZTCHS/Ru (bpy)3 2+/Bi2S3；
The zinc salt is selected from one of following: zinc chloride, zinc sulfate, zinc nitrate.
Embodiment 3 prepares SiO2/PDA-Au-Ab2Specific steps are as follows:
(A) SiO2Preparation
Firstly, 7 mL ethyl orthosilicates to be added to the in the mixed solvent of 78 mL, then the ammonium hydroxide of 20 mL, 25% are added to It states in solution, 4 h is stirred at 40 DEG C, be centrifuged to obtain sediment, sediment uses ultrapure water and ethanol washing to pH respectively For neutrality, 12 h are finally dried under vacuum and obtain SiO2Powder；
(B) SiO2The preparation of/PDA
By the SiO of 40 mg220 mL, 10 mmolL are added to the Dopamine hydrochloride of 40 mg-1And the three hydroxyl first that pH is 8.5 In base aminomethane buffer solution, 12 h are stirred at room temperature in above-mentioned solution, is then centrifuged for, washed respectively with ultrapure water and ethyl alcohol It washs 3 times, product is dried under vacuum to obtain SiO2/ PDA powder；
(C) SiO2The preparation of/PDA-Au
0.02 g sodium citrate is dissolved into 40 mL ultrapure waters, 40 μ L, 2% gold chloride and the SiO of 5 mg are added2/ Simultaneously 5 min are stirred at room temperature in PDA, then heat above-mentioned solution, boil 15 min, and after being cooled to room temperature, solution is centrifuged simultaneously Three times with milli-Q water, it is finally dried to obtain SiO under vacuum conditions2/PDA-Au；
(D) SiO2/PDA-Au-Ab2Preparation
The SiO of 5 mg2/ PDA-Au is dissolved into the PBS buffer solution that 1 mL, pH is 7.4, and 200 μ L, 10 μ g are then added mL−1Procalcitonin detect antibody A b2, 12 h of oscillation hatching in 4 DEG C of constant-temperature shaking incubators, centrifuge washing, product dispersion In 1 mL, be 1.0% bovine serum albumin(BSA) containing mass fraction and PBS buffer solution that pH is 7.4 in, SiO is made2/PDA-Au- Ab2, storage is in 4 DEG C of refrigerators with spare；
The mixed solvent is that 1:25 is mixed to prepare by volume for ultrapure water and ethyl alcohol.
Embodiment 4 prepares SiO2/PDA-Au-Ab2Specific steps are as follows:
(A) SiO2Preparation
Firstly, 3 mL ethyl orthosilicates to be added to the in the mixed solvent of 39 mL, then the ammonium hydroxide of 10 mL, 25% are added to It states in solution, 4 h is stirred at 40 DEG C, be centrifuged to obtain sediment, sediment uses ultrapure water and ethanol washing to pH respectively For neutrality, 12 h are finally dried under vacuum and obtain SiO2Powder；
(B) SiO2The preparation of/PDA
By the SiO of 20 mg210 mL, 10 mmolL are added to the Dopamine hydrochloride of 20 mg-1And the three hydroxyl first that pH is 8.5 In base aminomethane buffer solution, 12 h are stirred at room temperature in above-mentioned solution, is then centrifuged for, washed respectively with ultrapure water and ethyl alcohol It washs 3 times, product is dried under vacuum to obtain SiO2/ PDA powder；
(C) SiO2The preparation of/PDA-Au
0.01 g sodium citrate is dissolved into 20 mL ultrapure waters, 20 μ L, 2% gold chloride and the SiO of 3 mg are added2/ Simultaneously 5 min are stirred at room temperature in PDA, then heat above-mentioned solution, boil 15 min, and after being cooled to room temperature, solution is centrifuged simultaneously Three times with milli-Q water, it is finally dried to obtain SiO under vacuum conditions2/PDA-Au；
(D) SiO2/PDA-Au-Ab2Preparation
The SiO of 3 mg2/ PDA-Au is dissolved into the PBS buffer solution that 1 mL, pH is 7.4, and 100 μ L, 10 μ g are then added mL−1Procalcitonin detect antibody A b2, 12 h of oscillation hatching in 4 DEG C of constant-temperature shaking incubators, centrifuge washing, product dispersion In 1 mL, be 1.0% bovine serum albumin(BSA) containing mass fraction and PBS buffer solution that pH is 7.4 in, SiO is made2/PDA-Au- Ab2, storage is in 4 DEG C of refrigerators with spare；
The mixed solvent is that 1:25 is mixed to prepare by volume for ultrapure water and ethyl alcohol.
Embodiment 5 prepares the specific steps of signal suppressive optical electro-chemistry Procalcitonin sensor are as follows:
(a) at ZTCHS/Ru (bpy)3 2+/Bi2S3The ITO working electrode surface of modification modifies the sulfydryl second of 4 μ L, 0.1 mol/L Acid dries at room temperature, continues 1- ethyl -3- (3- dimethyl aminopropyl)-carbodiimides/N- hydroxysuccinimidyl acyl that 4 μ L are added dropwise Imines uses ultrapure water, naturally dry after reacting 30 min；
(b) Ab of 4 μ L of electrode face finish, 1 μ g/mL that obtain in step (a)1Solution reacts after 30 min with ultrapure Water rinses, naturally dry；
(c) 5 μ L of electrode face finish that obtains in step (b), the bovine serum albumin solution that mass fraction is 1.0%, with Ultrapure water, naturally dry are used after reacting 30 min in nonspecific activity site on enclosed-electrode surface；
(d) electrode surface obtained in step (c) continues that 4 μ L, 0.0001 ngmL are added dropwise-1 ~ 100 ng·mL-1Drop Calcium element Proantigen standard solution uses ultrapure water, naturally dry after reacting 30 min；
(e) 4 μ L, SiO are added dropwise in the electrode surface obtained in step (d)2/PDA-Au-Ab2Solution reacts after 30 min with super The complete ITO electrode of modification, i.e. signal suppressive optical electro-chemistry Procalcitonin sensor has been made in pure water rinsing, naturally dry；
1- ethyl -3- (the 3- dimethyl aminopropyl)-carbodiimides/n-hydroxysuccinimide contains 1 × 10-2 mol/ 1- ethyl -3- (3- dimethyl aminopropyl)-carbodiimides and 2 × 10 of L-3The n-hydroxysuccinimide of mol/L.
Embodiment 6 prepares the specific steps of signal suppressive optical electro-chemistry Procalcitonin sensor are as follows:
(a) at ZTCHS/Ru (bpy)3 2+/Bi2S3The ITO working electrode surface of modification modifies the sulfydryl second of 4 μ L, 0.1 mol/L Acid dries at room temperature, continues 1- ethyl -3- (3- dimethyl aminopropyl)-carbodiimides/N- hydroxysuccinimidyl acyl that 4 μ L are added dropwise Imines uses ultrapure water, naturally dry after reacting 30 min；
(b) Ab of 4 μ L of electrode face finish, 10 μ g/mL that obtain in step (a)1Solution reacts after 30 min with ultrapure Water rinses, naturally dry；
(c) bovine serum albumin solution of 5 μ L of electrode face finish, mass fraction 1.0% that obtain in step (b), with envelope Nonspecific activity site on electrode surface is closed, uses ultrapure water, naturally dry after reacting 30 min；
(d) electrode surface obtained in step (c) continues that 4 μ L, 0.0001 ngmL are added dropwise-1 ~ 100 ng·mL-1Drop Calcium element Proantigen standard solution uses ultrapure water, naturally dry after reacting 30 min；
(e) 4 μ L, SiO are added dropwise in the electrode surface obtained in step (d)2/PDA-Au-Ab2Solution reacts after 30 min with super The complete ITO electrode of modification, i.e. signal suppressive optical electro-chemistry Procalcitonin sensor has been made in pure water rinsing, naturally dry；
1- ethyl -3- (the 3- dimethyl aminopropyl)-carbodiimides/n-hydroxysuccinimide contains 1 × 10-2 mol/ 1- ethyl -3- (3- dimethyl aminopropyl)-carbodiimides and 2 × 10 of L-3The n-hydroxysuccinimide of mol/L.
A kind of signal suppressive optical electro-chemistry Procalcitonin sensing based on zinc titanium composite material prepared by embodiment 7 The application of device, which is characterized in that including following applying step:
A. working curve is tested: using saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, by prepared one Signal suppressive optical electro-chemistry Procalcitonin sensor of the kind based on zinc titanium composite material forms three electrode bodies as working electrode System, is tested in PBS buffer solution；Analyte is detected using I-t means of testing, setting voltage is 0 V, operation 100 s of time, excitation light source are LED light；It is strong to detect the photoelectric current generated to the Procalcitonin antigen standard solution of various concentration Degree；
B. working curve is drawn: the photo-current intensity of the Procalcitonin antigen standard solution containing various concentration is denoted asI i,I iWith Procalcitonin antigen concentration of standard solutioncLogarithm between it is linear, drawI i - logcWorking curve；
C. the detection of Procalcitonin antigen: Procalcitonin antigen standard solution is replaced with human serum sample to be measured, according to step Method in rapid a is detected, according to response photo-current intensityIAnd working curve, obtain Procalcitonin antigen in sample to be tested Content；
The PBS buffer solution is the phosphate containing 0.1 mol/L ascorbic acid that 10 ~ 15 mL, pH are 5.0 ~ 8.0 Buffer solution.

Claims (2)

1. a kind of preparation method of the signal suppressive optical electro-chemistry Procalcitonin sensor based on zinc titanium composite material, described Zinc titanium composite material is tris (bipyridine) ruthenium Ru (bpy)3 2+With bismuth sulfide Bi2S3The zinc titanate being sensitized altogether/titanium dioxide heterogeneous knot ZTCHS composite material ZTCHS/Ru (bpy)3 2+/Bi2S3, the optical electro-chemistry Procalcitonin sensor is by tin indium oxide ITO work Make electrode, ZTCHS/Ru (bpy)3 2+/Bi2S3, Procalcitonin capture antibody A b1, bovine serum albumin(BSA), Procalcitonin antigen standard Solution and Procalcitonin detect antibody marker SiO2/PDA-Au-Ab2Composition；
It is characterized in that, the preparation method includes following preparation step:
ZTCHS/Ru(bpy)3 2+/Bi2S3Preparation；
SiO2/PDA-Au-Ab2Preparation；
Three, the preparation of signal suppressive optical electro-chemistry Procalcitonin sensor；
Wherein, step 1 preparation ZTCHS/Ru (bpy)3 2+/Bi2S3Specific steps are as follows:
(1) preparation of zeolite imidazole class framework material 8
Firstly, 0.3 ~ 1.0 g zinc salt is dissolved into 15 ~ 30 mL methanol, 10 ~ 20 mL are added containing 2-methylimidazole 20 ~ 26 h are stirred at room temperature in the methanol solution of 1.0 ~ 2.0 g, above-mentioned solution, by products therefrom ethyl alcohol and ultrapure water Three times, finally dry 10 ~ 14 h obtain 8 powder of zeolite imidazole class framework material to each centrifuge washing at 80 DEG C；
(2) preparation of ZTCHS
The cetrimonium bronmide of 0.05 ~ 0.10 g is dissolved into 2 ~ 10 mL ethanol solutions, is stirred at room temperature 20 ~ 40 min add 0.05 ~ 0.10 g zeolite imidazole class framework material 8, continue 20 ~ 40 min of stirring, then by 100 ~ The butyl titanate of 200 μ L is added in above-mentioned solution and stirs 20 ~ 40 min, continuously adds the ultrapure water of 2 ~ 4 mL And solution is stirred into 20 ~ 26 h, then solution is transferred in ptfe autoclave and at 100 DEG C reaction 20 ~ Products therefrom ethyl alcohol and each centrifuge washing of ultrapure water 3 ~ 6 times are finally dried under vacuum 10 ~ 14 h and obtained by 26 h ZTCHS powder, is dissolved in ultrapure water, obtains ZTCHS suspension；
(3) ITO electrode is cut to the cm size of 2.5 cm × 0.8, successively with acetone, ethyl alcohol and ultrapure water ultrasonic cleaning 20 ~ 40 min, by the ZTCHS suspension modification to ITO electrode of 8 ~ 10 μ L, dry, then at room temperature after being dried with nitrogen It places it in and calcines 20 ~ 40 min in Muffle furnace at 400 ~ 500 DEG C, be finally cooled to room temperature；
(4) 3 ~ 4 μ L of electrode face finish that obtains in step (3), concentration are 0.02 ~ 0.04 molL-1Ru (bpy)3 2+Solution dries at room temperature；3 ~ 4 μ L, 0.02 ~ 0.04 molL are further modified in electrode surface-1Bi (NO3)3Nitric acid solution, react 20 ~ 40 min at room temperature, ultrapure water then modifies 3 ~ 4 μ L, 0.1 mol/L Na2S solution, reacts 20 ~ 40 min at room temperature, and ultrapure water is made ZTCHS/Ru (bpy)3 2+/Bi2S3；
The zinc salt is selected from one of following: zinc chloride, zinc sulfate, zinc nitrate；
Wherein, step 2 prepares SiO2/PDA-Au-Ab2Specific steps are as follows:
(A) SiO2Preparation
Firstly, 2 ~ 9 mL ethyl orthosilicates to be added to the in the mixed solvent of 38 ~ 80 mL, then by 10 ~ 20 mL, 25% Ammonium hydroxide be added in above-mentioned solution, 3 ~ 5 h are stirred at 40 DEG C, be centrifugeds to obtain sediment, sediment is respectively with surpassing Pure water and ethanol washing are neutrality to pH, and 10 ~ 14 h are finally dried under vacuum and obtain SiO2Powder；
(B) SiO2The preparation of/PDA
By the SiO of 20 ~ 40 mg210 ~ 20 mL, 10 mmolL are added to the Dopamine hydrochloride of 20 ~ 40 mg-1And In the trishydroxymethylaminomethane buffer solution that pH is 8.5,10 ~ 14 h are stirred at room temperature in above-mentioned solution, be then centrifuged for, It is washed respectively 3 ~ 4 times with ultrapure water and ethyl alcohol, product is dried under vacuum to obtain SiO2/ PDA powder；
(C) SiO2The preparation of/PDA-Au
0.01 ~ 0.02 g sodium citrate is dissolved into 20 ~ 40 mL ultrapure waters, the chlorine gold of 20 ~ 40 μ L, 2% are added The SiO of acid and 2 ~ 6 mg2Simultaneously 4 ~ 6 min are stirred at room temperature in/PDA, then heat above-mentioned solution, boil 12 ~ 20 Min, after being cooled to room temperature, solution centrifugation and with milli-Q water three times, be finally dried to obtain SiO under vacuum conditions2/PDA- Au；
(D) SiO2/PDA-Au-Ab2Preparation
The SiO of 2 ~ 6 mg2/ PDA-Au is dissolved into the PBS buffer solution that 1 mL, pH is 7.4, and 100 ~ 200 μ are then added L、10 μg·mL−1Procalcitonin detect antibody A b2, 12 h of oscillation hatching in 4 DEG C of constant-temperature shaking incubators, centrifuge washing, In the PBS buffer solution that product is dispersed in 1 mL, is 1.0% bovine serum albumin(BSA) containing mass fraction and pH is 7.4, SiO is made2/ PDA-Au-Ab2, storage is in 4 DEG C of refrigerators with spare；
The mixed solvent is that 1:25 is mixed to prepare by volume for ultrapure water and ethyl alcohol；
Wherein, step 3 prepares the specific steps of signal suppressive optical electro-chemistry Procalcitonin sensor are as follows:
(a) ZTCHS/Ru obtained in step 1 (bpy)3 2+/Bi2S33 ~ 5 μ L of ITO working electrode surface modification of modification, The thioacetic acid of 0.1 mol/L, dries at room temperature, continues 1- ethyl -3- (3- dimethyl aminopropyl)-carbon of 3 ~ 5 μ L of dropwise addition Change diimine/n-hydroxysuccinimide, uses ultrapure water, naturally dry after reacting 20 ~ 40 min；
(b) Ab of 4 ~ 6 μ L of electrode face finish, 1 ~ 10 μ g/mL that obtain in step (a)1Solution, reaction 20 ~ 40 Ultrapure water, naturally dry are used after min；
(c) 4 ~ 6 μ L of electrode face finish, the mass fraction obtained in step (b) is molten for 1.0% bovine serum albumin(BSA) Liquid uses ultrapure water, naturally dry after reacting 20 ~ 40 min with nonspecific activity site on enclosed-electrode surface；
(d) electrode surface obtained in step (c) continues 4 ~ 6 μ L of dropwise addition, 0.0001 ngmL-1 ~ 100 ng·mL-1 Procalcitonin antigen standard solution uses ultrapure water, naturally dry after reacting 20 ~ 40 min；
(e) 4 ~ 6 μ L, SiO are added dropwise in the electrode surface obtained in step (d)2/PDA-Au-Ab2Solution, reaction 20 ~ 40 Ultrapure water is used after min, the complete ITO electrode of modification, i.e. signal suppressive optical electro-chemistry calcitonin has been made in naturally dry Original sensor；
1- ethyl -3- (the 3- dimethyl aminopropyl)-carbodiimides/n-hydroxysuccinimide contains 1 × 10-2 mol/L 1- ethyl -3- (3- dimethyl aminopropyl)-carbodiimides and 2 × 10-3The n-hydroxysuccinimide of mol/L.
2. a kind of signal suppressive based on zinc titanium composite material prepared by preparation method as described in claim 1 is photoelectrochemical Learn the application of Procalcitonin sensor, which is characterized in that including following applying step:
A. working curve is tested: using saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, will be such as claim 1 A kind of signal suppressive optical electro-chemistry Procalcitonin sensor based on zinc titanium composite material prepared by the preparation method As working electrode, three-electrode system is formed, is tested in PBS buffer solution；Using I-t means of testing to analyte into Row detection, setting voltage are 0 V, and 100 s of runing time, excitation light source is LED light；It detects anti-to the Procalcitonin of various concentration The photo-current intensity that primary standard solution generates；
B. working curve is drawn: the photo-current intensity of the Procalcitonin antigen standard solution containing various concentration is denoted asI i,I iWith Procalcitonin antigen concentration of standard solutioncLogarithm between it is linear, drawI i - logcWorking curve；
C. the detection of Procalcitonin antigen: Procalcitonin antigen standard solution is replaced with human serum sample to be measured, according to step Method in rapid a is detected, according to response photo-current intensityIAnd working curve, obtain Procalcitonin antigen in sample to be tested Content；
The PBS buffer solution is the phosphate containing 0.1 mol/L ascorbic acid that 10 ~ 15 mL, pH are 5.0 ~ 8.0 Buffer solution.
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