CN110346438A - One kind being based on PbS/Co3O4The preparation method of complex signal attenuated type optical electro-chemistry immunosensor - Google Patents
One kind being based on PbS/Co3O4The preparation method of complex signal attenuated type optical electro-chemistry immunosensor Download PDFInfo
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- procalcitonin
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- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 230000005518 electrochemistry Effects 0.000 title claims abstract description 28
- 230000003287 optical effect Effects 0.000 title claims abstract description 28
- 230000002238 attenuated effect Effects 0.000 title claims abstract description 24
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 108010048233 Procalcitonin Proteins 0.000 claims abstract description 47
- CWCXERYKLSEGEZ-KDKHKZEGSA-N procalcitonin Chemical compound C([C@@H](C(=O)N1CCC[C@H]1C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H]([C@@H](C)CC)C(=O)NCC(=O)N[C@@H](C(C)C)C(=O)NCC(=O)N[C@@H](C)C(=O)N1[C@@H](CCC1)C(=O)NCC(O)=O)[C@@H](C)O)NC(=O)[C@@H](NC(=O)[C@H](CC=1NC=NC=1)NC(=O)[C@H](CC=1C=CC=CC=1)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CC(N)=O)NC(=O)[C@H](CC=1C=CC=CC=1)NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](NC(=O)[C@H](CC=1C=CC(O)=CC=1)NC(=O)[C@@H](NC(=O)CNC(=O)[C@H](CC(C)C)NC(=O)[C@H](CCSC)NC(=O)[C@H]1NC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CO)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(N)=O)NC(=O)CNC(=O)[C@@H](N)CSSC1)[C@@H](C)O)[C@@H](C)O)[C@@H](C)O)C1=CC=CC=C1 CWCXERYKLSEGEZ-KDKHKZEGSA-N 0.000 claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011521 glass Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 97
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000001514 detection method Methods 0.000 claims description 32
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 30
- 239000012498 ultrapure water Substances 0.000 claims description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 206010010254 Concussion Diseases 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005576 amination reaction Methods 0.000 claims description 12
- 230000009514 concussion Effects 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 12
- 239000008055 phosphate buffer solution Substances 0.000 claims description 12
- 239000012086 standard solution Substances 0.000 claims description 9
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012888 bovine serum Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- -1 1- ethyl Chemical group 0.000 claims description 4
- ZFBOVYJITDWWBB-UHFFFAOYSA-N 3-triethoxysilylpropane-1,1,1-triamine Chemical compound CCO[Si](OCC)(OCC)CCC(N)(N)N ZFBOVYJITDWWBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000002211 L-ascorbic acid Substances 0.000 claims description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 4
- 239000012901 Milli-Q water Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000012491 analyte Substances 0.000 claims description 4
- 239000000427 antigen Substances 0.000 claims description 4
- 102000036639 antigens Human genes 0.000 claims description 4
- 108091007433 antigens Proteins 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 150000001718 carbodiimides Chemical class 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 230000002035 prolonged effect Effects 0.000 claims description 4
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012488 sample solution Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 239000010931 gold Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 7
- 208000015181 infectious disease Diseases 0.000 abstract description 5
- 241000894006 Bacteria Species 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000011896 sensitive detection Methods 0.000 abstract description 3
- 206010070834 Sensitisation Diseases 0.000 abstract description 2
- URVGHPZOLQFKJZ-UHFFFAOYSA-N [Bi]=O.[I] Chemical compound [Bi]=O.[I] URVGHPZOLQFKJZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- 230000008313 sensitization Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 abstract 1
- 208000027866 inflammatory disease Diseases 0.000 abstract 1
- 238000012544 monitoring process Methods 0.000 abstract 1
- 239000003550 marker Substances 0.000 description 5
- 201000010099 disease Diseases 0.000 description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 150000008614 2-methylimidazoles Chemical class 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 102000055006 Calcitonin Human genes 0.000 description 2
- 108060001064 Calcitonin Proteins 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 206010040047 Sepsis Diseases 0.000 description 2
- BBBFJLBPOGFECG-VJVYQDLKSA-N calcitonin Chemical compound N([C@H](C(=O)N[C@@H](CC(C)C)C(=O)NCC(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC=1NC=NC=1)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CC=1C=CC(O)=CC=1)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H]([C@@H](C)O)C(=O)NCC(=O)N[C@@H](CO)C(=O)NCC(=O)N[C@@H]([C@@H](C)O)C(=O)N1[C@@H](CCC1)C(N)=O)C(C)C)C(=O)[C@@H]1CSSC[C@H](N)C(=O)N[C@@H](CO)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)O)C(=O)N1 BBBFJLBPOGFECG-VJVYQDLKSA-N 0.000 description 2
- 229960004015 calcitonin Drugs 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 238000003745 diagnosis Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000700 radioactive tracer Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000013399 early diagnosis Methods 0.000 description 1
- 238000004186 food analysis Methods 0.000 description 1
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- 230000006870 function Effects 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000017854 proteolysis Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 210000001685 thyroid gland Anatomy 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Pathology (AREA)
- Peptides Or Proteins (AREA)
Abstract
The present invention relates to one kind to be based on vulcanized lead-cobaltosic oxide compound (PbS/Co3O4) optical electro-chemistry Procalcitonin sensor preparation method and application.The present invention is specifically on tin indium oxide (ITO) electro-conductive glass by black titania nanoparticles (B-TiO2NPs) and iodine oxygen bismuth nanometer sheet (BiOI NSs) and gold nano grain (Au NPs) it is compound be used as base material, the sensitization structure of formation can increase the absorption region of light, promote the separative efficiency of photo-generate electron-hole, while being used for load antibodies.The PbS/Co of preparation3O4Compound and base material competition light source and hole sacrifice agent, construct a kind of optical electro-chemistry immunosensor based on signal attenuated type, realize the Sensitive Detection to Procalcitonin, and this method is of great significance to early diagnosing and monitoring the infection of bacterium inflammatory disease.
Description
Technical field
The invention belongs to nano-functional material, immunoassay and biosensor technique fields, specifically by black titanium dioxide
Nano particle and iodine oxygen bismuth nanometer sheet and gold nano grain (B-TiO2NPs/BiOI NSs/Au NPs) it is used as base material,
PbS/Co3O4As signal antibody marker, the optical electro-chemistry immunosensor of detection Procalcitonin is constructed.
Background technique
Procalcitonin (PCT) is the natural precursor of calcitonin, is generated by parafollicular cells of thyroid gland and proteolysis, is that one kind has
The disease marker for bacterium infection diagnosis of prospect, it is cleverer to diagnosis of sepsis than other known disease marker
It is quick.Procalcitonin is lower than 0.1 ng/mL in the intracorporal content of normal person, but when bacterium infection or pyemia occurs, calcitonin
Former content can increase sharply, and incrementss depend on the degree of infection.Therefore the early diagnosis of Procalcitonin is for bacterium infection
Etc. diseases treatment have important clinical meaning.Currently, having much for the detection method of Procalcitonin, such as enzyme linked immunological
The methods of analytic approach, radiommunoassay, fluorescence or surface plasma body resonant vibration, but the above method has complicated for operation, instrument
The disadvantages such as valuableness, therefore easy to operate, cheap, high sensitivity the detection method of one kind that the present invention develops has important meaning
Justice.The optical electro-chemistry sensor that the present invention constructs is a kind of to determine analysans using the photoelectric conversion property of photoelectric activity substance
The device of concentration is electric signal because it detects signal, and excitation signal is light source, realizes excitation signal and detects point of signal
From, there is lower background signal and higher sensitivity, and its preparation is easy, cost is relatively low, therefore in food analysis, environment
The fields such as detection, water analysis, bioanalysis are widely used.
Light active material is optical electro-chemistry sensor key components.A kind of photoelectric conversion as function admirable is partly led
Body material, titanium dioxide are widely used in the fields such as photocatalysis, fuel cell, its right wide band gap (3.2 eV) makes it can only
It absorbs ultraviolet light and limits its application.Therefore, in this invention, on the basis of titanium dioxide, sodium borohydride is utilized
It is restored to obtain B-TiO2NPs, the Lacking oxygen of generation can increase the utilization rate to visible light.In addition by BiOI NSs and B-
TiO2NPs is compounded to form the transfer that band-gap structure promotes electronics.By forming sensitization knot in electrode surface drop coating Au NPs
Structure increases the electric conductivity of electrode, improves photocurrent response.And with PbS/Co3O4Compound is as signal tracer, using it to light
Competition with hole sacrifice agent absorbs, and improves the sensitivity of optical electro-chemistry sensor.
Summary of the invention
An object of the present invention is to be respectively synthesized B-TiO2NPs, BiOI NSs and Au NPs constitute B-TiO2 NPs/
BiOI NSs/Au NPs MULTILAYER COMPOSITE is sensitized structure, utilizes B-TiO2Band-gap structure between NPs and BiOI NSs and
The good electric conductivity of Au NPs promotes the transfer of light induced electron.
The second object of the present invention is to synthesis PbS/Co3O4Compound, and by it in conjunction with signal antibody, form PbS/
Co3O4-Ab2Bioconjugates.
The object of the invention third is that with B-TiO2It is living as light that NPs/BiOI NSs/Au NPs MULTILAYER COMPOSITE is sensitized structure
Property base material, with PbS/Co3O4Compound constructs interlayer type optical electro-chemistry immunosensor as signal tracer, and uses
In quick, the Sensitive Detection of Procalcitonin.
Technical scheme is as follows:
1. one kind is based on PbS/Co3O4The preparation method of complex signal attenuated type optical electro-chemistry immunosensor, feature exist
In, comprising the following steps:
1) bulk ITO electro-conductive glass is cut into the cm of 2.0 cm × 0.8, successively ultrasound is clear respectively with acetone, ethyl alcohol and ultrapure water
30 min are washed, are dried with nitrogen；
2) 10 μ L, 5-8 mg/mL B-TiO are added dropwise2The evenly dispersed suspension of NPs is to ITO electro-conductive glass conducting surface, at room temperature
It dries, B-TiO is made2NPs electrode；
3) by B-TiO2NPs electrode is respectively in 5-10 mM Bi (NO)3With dip in 10 s in 5-10 mM KI solution, ultrapure water punching
It washes, repeats above-mentioned circulation 20-30 times, B-TiO is made2NPs/BiOI NSs electrode；
4) 8 μ L Au NPs solution are added dropwise to B-TiO2B-TiO is made in NPs/BiOI NSs electrode surface2 NPs/BiOI
NSs/Au NPs electrode；
5) the Procalcitonin capture antibody-solutions of 5 μ L, 8 ~ 12 μ g/mL are added dropwise to modified electrode surface, 4 DEG C of refrigerators dry,
Ultrapure water；
6) it is 1.0% bovine serum albumen solution to modified electrode surface that 3 μ L, mass fraction, which is added dropwise, on enclosed-electrode surface
Nonspecific activity site, 4 DEG C of refrigerators dry, ultrapure water；
7) the Procalcitonin antigen standard solution of 5 μ L, the ng/mL of 0.1 pg/mL ~ 50 is added dropwise to modified electrode surface, 4 DEG C
Refrigerator dries, ultrapure water；
8) 5 μ L, 3.0 ~ 5.0 mg/mL PbS/Co are added dropwise3O4Procalcitonin detects antibody complex solution to electrode surface,
4 DEG C of refrigerators hatch 60 min, and the complete electrode of modification, i.e., a kind of detection Procalcitonin signal attenuated type is made in ultrapure water
Optical electro-chemistry immunosensor.
It is as described in claim 1 a kind of based on PbS/Co3O4Complex signal attenuated type optical electro-chemistry immunosensor
Preparation method, the B-TiO2The preparation of NPs, steps are as follows:
By 25 titania nanoparticles of 4.0-5.0 g P and 1.5-2.0 g NaBH4It mixes and grinds 30 min, argon atmospher
300 DEG C of calcining 50-60 min in the tube furnace enclosed, after being cooled to room temperature, it is clear that products obtained therefrom uses ultrapure water and ethyl alcohol to be centrifuged respectively
It washes 3 times, 35 DEG C in vacuum oven, obtains B-TiO after 12 h2 NPs。
It is as described in claim 1 a kind of based on PbS/Co3O4Complex signal attenuated type optical electro-chemistry immunosensor
Preparation method, the preparation of the BiOI NSs, steps are as follows:
B-TiO will be coated2The ITO electro-conductive glass of NPs is respectively in 5-10 mM Bi (NO)310 are dipped in in 5-10 mM KI solution
S is repeated above-mentioned circulation 20-30 times with ultrapure water, BiOI NSs is made.
It is as described in claim 1 a kind of based on PbS/Co3O4Complex signal attenuated type optical electro-chemistry immunosensor
Preparation method, the preparation of the Au NPs, steps are as follows:
50-55 mL mass fraction is 0.01% HAuCl4Solution boils in 120 DEG C of oil baths, and 2.5-5.0 mL mass fraction is
Above-mentioned solution is added in 1% citric acid three sodium solution, continues to boil 30 min under stirring to solution purpling red, Au NPs is made
Solution.
It is as described in claim 1 a kind of based on PbS/Co3O4Complex signal attenuated type optical electro-chemistry immunosensor
Preparation method, the PbS/Co3O4Procalcitonin detects the preparation of antibody complex solution, and steps are as follows:
1) Co3O4Polyhedral preparation and its amination:
3.0-6.0 g Co(NO3)2·6H2O and 13-16 g 2-methylimidazole is dissolved in respectively in 250 mL methanol, by 2- methyl
Imidazole solution is added to Co (NO3)2In solution, 24 h of aging at room temperature, methanol centrifuge washing 3 times, obtained solid vacuum oven
Middle drying is placed on 350 DEG C of 120 min of calcining in tube furnace, obtains Co3O4Polyhedron, 0.05-0.1 g Co3O4Polyhedron point
It is dispersed in 10 mL ethanol solutions of tri- aminopropyl triethoxysilane Han 0.15 mL, ultrasonic disperse 30 min, flows back at 70 DEG C
24 h, dehydrated alcohol centrifuge washing 3 times, 35 DEG C of 12 h, is made amination Co in a vacuum drying oven3O4Polyhedron；
2) preparation of PbS QDs:
7 ~ 21 μ L thioacetic acid are added to 25 mL, 1 ~ 7 mmol/L Pb (NO3)2After solution, 20 min are bubbled under nitrogen
And adjusting pH value with the sodium hydroxide solution of 1 mol/L is 5 ~ 12, and after being bubbled 20 min, 2 mL 0.01 ~ 0.015 are added
mol/L Na2S solution obtains PbS QDs solution after stirring 4 h under nitrogen atmosphere；
3) PbS/Co3O4Preparation:
5-10 mg amination Co3O4Polyhedron, 0.8 g 1- ethyl -3- (3- dimethyl aminopropyl) carbodiimide and 0.1 g's
N-hydroxysuccinimide is dissolved in 15 mL PbS QDs solution, and above-mentioned mixed liquor is stirred 2 h, milli-Q water 3 at room temperature
It is secondary, then 2 mL ultrapure waters are dispersed by product；
4) PbS/Co3O4The preparation of Procalcitonin detection antibody complex solution:
2 mL, 10 μ g/mL Procalcitonin detects antibody-solutions and 10 μ L, 5 mg/mL 1- ethyl -3- (3- dimethylamino third
Base) carbodiimide and 10 μ L, 1 mg/mL n-hydroxysuccinimide 4 DEG C of concussions 30 min, the PbS/Co of 6 mg3O4It is added
4 DEG C of 6 h of concussion of above-mentioned solution, above-mentioned 4 DEG C of the solution concussions 12 of the bovine serum albumen solution injection that 100 μ L mass fractions are 1%
H is with pH 7.4 phosphate buffer solution eccentric cleaning for 3 times, and is scattered in the phosphate buffer solution that 2 mL pH are 7.4.
One kind of preparation method preparation as described in claim 1 is based on PbS/Co3O4Complex signal attenuated type is photoelectrochemical
Immunosensor is learned, for the detection of Procalcitonin, detecting step is as follows:
(1) it is tested using electrochemical workstation with three-electrode system, the ITO modified electrode as prepared by claim 1 is
Working electrode, saturated calomel electrode are reference electrode, and platinum electrode is auxiliary electrode, contain 0.1 mol/ in 10 mL, pH 7.4
The phosphate buffer solution of L ascorbic acid is tested；
(2) used time m- current method detects analyte, and setting voltage is 0 V, 100 s of runing time, irradiation LED lamp wave
A length of 400 ~ 450 nm；
(3) it after background current tends towards stability, turns on light 10 s of prolonged exposure every 10 s, then records photoelectric current, draw work
Curve；
(4) Procalcitonin standard solution is replaced to detect Procalcitonin sample solution to be measured, the result of detection can pass through
Working curve checks in.
Beneficial achievement of the invention
1. the B-TiO that the present invention synthesizes2NPs/BiOI NSs/Au NPs, B-TiO2The coarse of the surface ITO can be improved in NPs
This is conducive to the growth of BiOI NSs to degree, and then improves the ability of capture light source, while staggered nanometer chip architecture has big
Specific surface area can increase the load capacity of capture antibody, and the good electric conductivity of Au NPs and surface plasmon resonance effect
The electron transport rate that can accelerate electrode surface, significantly improves photoelectric conversion efficiency.
2. synthesizing nano compound material PbS/Co of the present invention3O4As detection antibody marker, signal attenuated type light is constructed
Electrochemical immunosensor.PbS quantum is a kind of semiconductor that band gap is relatively narrow, can be absorbed the visible of 400-1300 nm and
Infrared light, can and B-TiO2NP/BiOI NSs/Au NPs competition absorbs light source and electron donor；Co3O4It is a multi-panel
Body, P-type semiconductor structure have biggish specific surface area, can be used for loading PbS quantum, and have biggish steric hindrance,
The transmitting for hindering electrons and holes sacrifice agent is constituted with PbS quantum and is acted synergistically, so that photocurrent response becomes smaller, constitutes one
The optical electro-chemistry interlayer type immunosensor of kind signal attenuated type.
3. the present invention utilizes nanocomposite PbS/Co3O4Directly in conjunction with marker detection antibody, building is exempted from without enzyme
Epidemic disease sensor avoids because the inactivation of enzyme or leakage cause detection error.PbS/Co is utilized simultaneously3O4Composite material realizes signal
Weaken, greatly improve the detection sensitivity of optical electro-chemistry sensor, there is important scientific meaning and application value.
4. signal attenuated type optical electro-chemistry immunosensor prepared by the present invention, for the detection of Procalcitonin, when response
Between it is short, stability is good, and simple, quick, the highly sensitive and specific detection to Procalcitonin may be implemented.Biography prepared by the present invention
Sensor is the ng/mL of 0.1 pg/mL ~ 200 to the detection range of Procalcitonin, and detection is limited to 0.02 pg/mL.
Specific embodiment
Now the present invention is further illustrated by specific embodiment, but not limited to this.
Embodiment 1 is a kind of to be based on PbS/Co3O4The preparation method of the optical electro-chemistry Procalcitonin sensor of compound, preparation
Steps are as follows:
1) bulk ITO electro-conductive glass is cut into the cm of 2.0 cm × 0.8, successively ultrasound is clear respectively with acetone, ethyl alcohol and ultrapure water
30 min are washed, are dried with nitrogen；
2) 10 μ L, 5 mg/mL B-TiO are added dropwise2The evenly dispersed suspension of NPs dries in the air at room temperature to ITO electro-conductive glass conducting surface
It is dry, B-TiO is made2NPs electrode；
3) by B-TiO2NPs electrode is respectively in 5 mM Bi (NO)3With dip in 10 s in 5 mM KI solution, ultrapure water repeats
B-TiO is made in above-mentioned circulation 20 times2NPs/BiOI NSs electrode；
4) 8 μ L Au NPs solution are added dropwise to B-TiO2B-TiO is made in NPs/BiOI NSs electrode surface2 NPs/BiOI
NSs/Au NPs electrode；
5) the Procalcitonin capture antibody-solutions of 5 μ L, 8 μ g/mL are added dropwise to modified electrode surface, 4 DEG C of refrigerators dry, ultrapure
Water rinses；
6) it is 1.0% bovine serum albumen solution to modified electrode surface that 3 μ L, mass fraction, which is added dropwise, on enclosed-electrode surface
Nonspecific activity site, 4 DEG C of refrigerators dry, ultrapure water；
7) the Procalcitonin antigen standard solution of 5 μ L, the ng/mL of 0.1 pg/mL ~ 50 is added dropwise to modified electrode surface, 4 DEG C
Refrigerator dries, ultrapure water；
8) 5 μ L, 3.0 mg/mL PbS/Co are added dropwise3O4Procalcitonin detects antibody complex solution to electrode surface, 4 DEG C of ice
Case hatches 60 min, and the complete electrode of modification is made in ultrapure water, i.e., a kind of detection Procalcitonin signal attenuated type is photoelectrochemical
Learn immunosensor.
Embodiment 2 is a kind of to be based on PbS/Co3O4The preparation method of the optical electro-chemistry Procalcitonin sensor of compound, preparation
Steps are as follows:
1) bulk ITO electro-conductive glass is cut into the cm of 2.0 cm × 0.8, successively ultrasound is clear respectively with acetone, ethyl alcohol and ultrapure water
30 min are washed, are dried with nitrogen；
2) 10 μ L, 7 mg/mL B-TiO are added dropwise2The evenly dispersed suspension of NPs dries in the air at room temperature to ITO electro-conductive glass conducting surface
It is dry, B-TiO is made2NPs electrode；
3) by B-TiO2NPs electrode is respectively in 8 mM Bi (NO)3With dip in 10 s in 8 mM KI solution, ultrapure water repeats
B-TiO is made in above-mentioned circulation 25 times2NPs/BiOI NSs electrode；
4) 8 μ L Au NPs solution are added dropwise to B-TiO2B-TiO is made in NPs/BiOI NSs electrode surface2 NPs/BiOI
NSs/Au NPs electrode；
5) the Procalcitonin capture antibody-solutions of 5 μ L, 10 μ g/mL are added dropwise to modified electrode surface, 4 DEG C of refrigerators dry, ultrapure
Water rinses；
6) it is 1.0% bovine serum albumen solution to modified electrode surface that 3 μ L, mass fraction, which is added dropwise, on enclosed-electrode surface
Nonspecific activity site, 4 DEG C of refrigerators dry, ultrapure water；
7) the Procalcitonin antigen standard solution of 5 μ L, the ng/mL of 0.1 pg/mL ~ 50 is added dropwise to modified electrode surface, 4 DEG C
Refrigerator dries, ultrapure water；
8) 5 μ L, 5.0 mg/mL PbS/Co are added dropwise3O4Procalcitonin detects antibody complex solution to electrode surface, 4 DEG C of ice
Case hatches 60 min, and the complete electrode of modification is made in ultrapure water, i.e., a kind of detection Procalcitonin signal attenuated type is photoelectrochemical
Learn immunosensor.
3 B-TiO of embodiment2The preparation of NPs, steps are as follows:
By 4.0 g P, 25 titania nanoparticles and 1.5 g NaBH4Mix and grind 30 min, the tubular type of argon atmosphere
300 DEG C of 50 min of calcining in furnace, after being cooled to room temperature, products obtained therefrom uses ultrapure water and ethyl alcohol eccentric cleaning 3 times, vacuum respectively
35 DEG C in drying box, B-TiO is obtained after 12 h2 NPs。
4 B-TiO of embodiment2The preparation of NPs, steps are as follows:
By 5.0 g P, 25 titania nanoparticles and 2.0 g NaBH4Mix and grind 30 min, the tubular type of argon atmosphere
300 DEG C of 60 min of calcining in furnace, after being cooled to room temperature, products obtained therefrom uses ultrapure water and ethyl alcohol eccentric cleaning 3 times, vacuum respectively
35 DEG C in drying box, B-TiO is obtained after 12 h2 NPs。
The preparation of 5 BiOI NSs of embodiment, steps are as follows:
B-TiO will be coated2The ITO electro-conductive glass of NPs is respectively in 5 mM Bi (NO)310 s are dipped in in 5 mM KI solution, with super
Pure water rinsing repeats above-mentioned circulation 20 times, BiOI NSs is made.
The preparation of 6 BiOI NSs of embodiment, steps are as follows:
B-TiO will be coated2The ITO electro-conductive glass of NPs is respectively in 8 mM Bi (NO)310 s are dipped in in 8 mM KI solution, with super
Pure water rinsing repeats above-mentioned circulation 30 times, BiOI NSs is made.
The preparation of 7 Au NPs of embodiment, steps are as follows:
50 mL mass fractions are 0.01% HAuCl4Solution boils in 120 DEG C of oil baths, the lemon that 2.5 mL mass fractions are 1%
Above-mentioned solution is added in sour three sodium solutions, continues to boil 30 min under stirring to solution purpling red, Au NPs solution is made.
The preparation of 8 Au NPs of embodiment, steps are as follows:
55 mL mass fractions are 0.01% HAuCl4Solution boils in 120 DEG C of oil baths, the lemon that 5.0 mL mass fractions are 1%
Above-mentioned solution is added in sour three sodium solutions, continues to boil 30 min under stirring to solution purpling red, Au NPs solution is made.
9 PbS/Co of embodiment3O4Procalcitonin detects the preparation of antibody complex solution, and steps are as follows:
1) Co3O4Polyhedral preparation and its amination:
3.0 g Co(NO3)2·6H2O and 13 g 2-methylimidazoles are dissolved in respectively in 250 mL methanol, and 2-methylimidazole is molten
Liquid is added to Co (NO3)2In solution, 24 h of aging at room temperature methanol centrifuge washing 3 times, is dried in obtained solid vacuum oven
350 DEG C of 120 min of calcining in tube furnace are placed on, Co is obtained3O4Polyhedron, 0.05 g Co3O4Polyhedron is dispersed in containing 0.15
In 10 mL ethanol solutions of tri- aminopropyl triethoxysilane of mL, ultrasonic disperse 30 min, flow back at 70 DEG C 24 h, anhydrous second
Alcohol centrifuge washing 3 times, 35 DEG C of 12 h, is made amination Co in a vacuum drying oven3O4Polyhedron；
2) preparation of PbS QDs:
7 μ L thioacetic acid are added to 25 mL, 1 mmol/L Pb (NO3)2After solution, 20 min are bubbled under nitrogen and with 1
It is 8 that the sodium hydroxide solution of mol/L, which adjusts pH value, and after being bubbled 20 min, the Na of 2 mL, 0.01 mol/L is added2S solution, nitrogen
Atmosphere obtains PbS QDs solution after enclosing 4 h of lower stirring；
3) PbS/Co3O4Preparation:
5 mg amination Co3O4Polyhedron, the N- of 0.8 g 1- ethyl -3- (3- dimethyl aminopropyl) carbodiimide and 0.1 g
HOSu NHS is dissolved in 15 mL PbS QDs solution, and above-mentioned mixed liquor is stirred 2 h, milli-Q water 3 at room temperature
It is secondary, then 2 mL ultrapure waters are dispersed by product；
4) PbS/Co3O4The preparation of Procalcitonin detection antibody complex solution:
1- ethyl -3- (the 3- dimethylamino third of 2 mL, 10 μ g/mL Procalcitonin detection antibody-solutions and 10 μ L, 5 mg/mL
Base) 1 mg/mL of carbodiimide and 10 μ L 4 DEG C of n-hydroxysuccinimide concussions 30 min, the PbS/Co of 6 mg3O4It is added
4 DEG C of 6 h of concussion of above-mentioned solution, above-mentioned 4 DEG C of the solution concussions 12 of the bovine serum albumen solution injection that 100 μ L mass fractions are 1%
H is with pH 7.4 phosphate buffer solution eccentric cleaning for 3 times, and is scattered in the phosphate buffer solution that 2 mL pH are 7.4.
10 PbS/Co of embodiment3O4Procalcitonin detects the preparation of antibody complex solution, and steps are as follows:
1) Co3O4Polyhedral preparation and its amination:
6.0 g Co(NO3)2·6H2O and 16 g 2-methylimidazoles are dissolved in respectively in 250 mL methanol, and 2-methylimidazole is molten
Liquid is added to Co (NO3)2In solution, 24 h of aging at room temperature methanol centrifuge washing 3 times, is dried in obtained solid vacuum oven
350 DEG C of 120 min of calcining in tube furnace are placed on, Co is obtained3O4Polyhedron, 0.1 g Co3O4Polyhedron is dispersed in containing 0.15
In 10 mL ethanol solutions of tri- aminopropyl triethoxysilane of mL, ultrasonic disperse 30 min, flow back at 70 DEG C 24 h, anhydrous second
Alcohol centrifuge washing 3 times, 35 DEG C of 12 h, is made amination Co in a vacuum drying oven3O4Polyhedron；
2) preparation of PbS QDs:
21 μ L thioacetic acid are added to 25 mL, 7 mmol/L Pb (NO3)2After solution, 20 min are bubbled under nitrogen and with 1
It is 11 that the sodium hydroxide solution of mol/L, which adjusts pH value, and after being bubbled 20 min, the Na of 2 mL, 0.015 mol/L is added2S solution,
PbS QDs solution is obtained after stirring 4 h under nitrogen atmosphere；
3) PbS/Co3O4Preparation:
8 mg amination Co3O4Polyhedron, the N- of 0.8 g 1- ethyl -3- (3- dimethyl aminopropyl) carbodiimide and 0.1 g
HOSu NHS is dissolved in 15 mL PbS QDs solution, and above-mentioned mixed liquor is stirred 2 h, milli-Q water 3 at room temperature
It is secondary, then 2 mL ultrapure waters are dispersed by product；
4) PbS/Co3O4The preparation of Procalcitonin detection antibody complex solution:
1- ethyl -3- (the 3- dimethylamino third of 2 mL, 10 μ g/mL Procalcitonin detection antibody-solutions and 10 μ L, 5 mg/mL
Base) 1 mg/mL of carbodiimide and 10 μ L 4 DEG C of n-hydroxysuccinimide concussions 30 min, the PbS/Co of 6 mg3O4It is added
4 DEG C of 6 h of concussion of above-mentioned solution, above-mentioned 4 DEG C of the solution concussions 12 of the bovine serum albumen solution injection that 100 μ L mass fractions are 1%
H is with pH 7.4 phosphate buffer solution eccentric cleaning for 3 times, and is scattered in the phosphate buffer solution that 2 mL pH are 7.4.
One kind prepared by embodiment 11 is based on PbS/Co3O4Complex signal attenuated type optical electro-chemistry immunosensor, is used for
The detection of Procalcitonin, detecting step are as follows:
(1) it is tested using electrochemical workstation with three-electrode system, prepared ITO modified electrode is working electrode, is satisfied
It is reference electrode with calomel electrode, platinum electrode is auxiliary electrode, in 10 mL, pH 7.4 containing 0.1 mol/L ascorbic acid
Phosphate buffer solution is tested；
(2) used time m- current method detects analyte, and setting voltage is 0 V, 100 s of runing time, irradiation LED lamp wave
A length of 400 ~ 450 nm；
(3) it after background current tends towards stability, turns on light 10 s of prolonged exposure every 10 s, then records photoelectric current, draw work
Curve；
(4) Procalcitonin standard solution is replaced to detect Procalcitonin sample solution to be measured, the result of detection can pass through
Working curve checks in.
One kind prepared by embodiment 12 is based on PbS/Co3O4Complex signal attenuated type optical electro-chemistry immunosensor, is used for
The detection of Procalcitonin, detecting step are as follows:
(1) it is tested using electrochemical workstation with three-electrode system, prepared ITO modified electrode is working electrode, is satisfied
It is reference electrode with calomel electrode, platinum electrode is auxiliary electrode, in 10 mL, pH 7.4 containing 0.1 mol/L ascorbic acid
Phosphate buffer solution is tested；
(2) used time m- current method detects analyte, and setting voltage is 0 V, 100 s of runing time, irradiation LED lamp wave
A length of 400 ~ 450 nm；
(3) it after background current tends towards stability, turns on light 10 s of prolonged exposure every 10 s, then records photoelectric current, draw work
Curve；
(4) Procalcitonin standard solution is replaced to detect Procalcitonin sample solution to be measured, the result of detection can pass through
Working curve checks in.
The sensor that 13 Application Example 1 of embodiment and embodiment 2 construct according to embodiment 11 and 12 detection method pair
Procalcitonin standard solution is detected, and the linear detection range for measuring sensor is the ng/mL of 0.1 pg/mL ~ 50, inspection
Survey is limited to 0.02 ng/mL.
Claims (6)
1. one kind is based on PbS/Co3O4The preparation method of complex signal attenuated type optical electro-chemistry immunosensor, feature exist
In, comprising the following steps:
1) bulk ITO electro-conductive glass is cut into the cm of 2.0 cm × 0.8, successively ultrasound is clear respectively with acetone, ethyl alcohol and ultrapure water
30 min are washed, are dried with nitrogen；
2) 10 μ L, 5-8 mg/mL B-TiO are added dropwise2The evenly dispersed suspension of NPs dries in the air at room temperature to ITO electro-conductive glass conducting surface
It is dry, B-TiO is made2NPs electrode；
3) by B-TiO2NPs electrode is respectively in 5-10 mM Bi (NO)3With dip in 10 s in 5-10 mM KI solution, ultrapure water punching
It washes, repeats above-mentioned circulation 20-30 times, B-TiO is made2NPs/BiOI NSs electrode；
4) 8 μ L Au NPs solution are added dropwise to B-TiO2B-TiO is made in NPs/BiOI NSs electrode surface2 NPs/BiOI
NSs/Au NPs electrode；
5) the Procalcitonin capture antibody-solutions of 5 μ L, 8 ~ 12 μ g/mL are added dropwise to modified electrode surface, 4 DEG C of refrigerators dry,
Ultrapure water；
6) it is 1.0% bovine serum albumen solution to modified electrode surface that 3 μ L, mass fraction, which is added dropwise, on enclosed-electrode surface
Nonspecific activity site, 4 DEG C of refrigerators dry, ultrapure water；
7) the Procalcitonin antigen standard solution of 5 μ L, the ng/mL of 0.1 pg/mL ~ 50 is added dropwise to modified electrode surface, 4 DEG C
Refrigerator dries, ultrapure water；
8) 5 μ L, 3.0 ~ 5.0 mg/mL PbS/Co are added dropwise3O4Procalcitonin detects antibody complex solution to electrode surface, and 4
DEG C refrigerator hatches 60 min, and the complete electrode of modification, i.e., a kind of detection Procalcitonin signal attenuated type light is made in ultrapure water
Electrochemical immunosensor.
2. as described in claim 1 a kind of based on PbS/Co3O4The system of complex signal attenuated type optical electro-chemistry immunosensor
Preparation Method, the B-TiO2The preparation of NPs, steps are as follows:
By 25 titania nanoparticles of 4.0-5.0 g P and 1.5-2.0 g NaBH4It mixes and grinds 30 min, argon atmosphere
Tube furnace in 300 DEG C of calcining 50-60 min, after being cooled to room temperature, products obtained therefrom uses ultrapure water and ethyl alcohol eccentric cleaning respectively
3 times, 35 DEG C in vacuum oven, B-TiO is obtained after 12 h2 NPs。
3. as described in claim 1 a kind of based on PbS/Co3O4The system of complex signal attenuated type optical electro-chemistry immunosensor
Preparation Method, the preparation of the BiOI NSs, steps are as follows:
B-TiO will be coated2The ITO electro-conductive glass of NPs is respectively in 5-10 mM Bi (NO)310 are dipped in in 5-10 mM KI solution
S is repeated above-mentioned circulation 20-30 times with ultrapure water, BiOI NSs is made.
4. as described in claim 1 a kind of based on PbS/Co3O4The system of complex signal attenuated type optical electro-chemistry immunosensor
Preparation Method, the preparation of the Au NPs, steps are as follows:
50-55 mL mass fraction is 0.01% HAuCl4Solution boils in 120 DEG C of oil baths, and 2.5-5.0 mL mass fraction is 1%
Citric acid three sodium solution above-mentioned solution is added, it is red to solution purpling to continue to boil 30 min under stirring, and it is molten that Au NPs is made
Liquid.
5. as described in claim 1 a kind of based on PbS/Co3O4The system of complex signal attenuated type optical electro-chemistry immunosensor
Preparation Method, the PbS/Co3O4Procalcitonin detects the preparation of antibody complex solution, and steps are as follows:
1) Co3O4Polyhedral preparation and its amination:
3.0-6.0 g Co(NO3)2·6H2O and 13-16 g 2-methylimidazole is dissolved in respectively in 250 mL methanol, by 2- methyl
Imidazole solution is added to Co (NO3)2In solution, 24 h of aging at room temperature, methanol centrifuge washing 3 times, obtained solid vacuum oven
Middle drying is placed on 350 DEG C of 120 min of calcining in tube furnace, obtains Co3O4Polyhedron, 0.05-0.1 g Co3O4Polyhedron point
It is dispersed in 10 mL ethanol solutions of tri- aminopropyl triethoxysilane Han 0.15 mL, ultrasonic disperse 30 min, flows back at 70 DEG C
24 h, dehydrated alcohol centrifuge washing 3 times, 35 DEG C of 12 h, is made amination Co in a vacuum drying oven3O4Polyhedron；
2) preparation of PbS QDs:
7 ~ 21 μ L thioacetic acid are added to 25 mL, 1 ~ 7 mmol/L Pb (NO3)2After solution, 20 min are bubbled under nitrogen
And adjusting pH value with the sodium hydroxide solution of 1 mol/L is 5 ~ 12, and after being bubbled 20 min, 2 mL 0.01 ~ 0.015 are added
The Na of mol/L2S solution obtains PbS QDs solution after stirring 4 h under nitrogen atmosphere；
3) PbS/Co3O4Preparation:
5-10 mg amination Co3O4Polyhedron, 0.8 g 1- ethyl -3- (3- dimethyl aminopropyl) carbodiimide and 0.1 g's
N-hydroxysuccinimide is dissolved in 15 mL PbS QDs solution, and above-mentioned mixed liquor is stirred 2 h, milli-Q water 3 at room temperature
It is secondary, then 2 mL ultrapure waters are dispersed by product；
4) PbS/Co3O4The preparation of Procalcitonin detection antibody complex solution:
1- ethyl -3- (the 3- dimethylamino third of 2 mL, 10 μ g/mL Procalcitonin detection antibody-solutions and 10 μ L, 5 mg/mL
Base) 1 mg/mL of carbodiimide and 10 μ L 4 DEG C of n-hydroxysuccinimide concussions 30 min, the PbS/Co of 6 mg3O4It is added
4 DEG C of 6 h of concussion of above-mentioned solution, above-mentioned 4 DEG C of the solution concussions 12 of the bovine serum albumen solution injection that 100 μ L mass fractions are 1%
H is with pH 7.4 phosphate buffer solution eccentric cleaning for 3 times, and is scattered in the phosphate buffer solution that 2 mL pH are 7.4.
6. one kind of preparation method preparation as described in claim 1 is based on PbS/Co3O4Complex signal attenuated type optical electro-chemistry
Immunosensor, for the detection of Procalcitonin, detecting step is as follows:
(1) it is tested using electrochemical workstation with three-electrode system, the ITO modified electrode as prepared by claim 1 is
Working electrode, saturated calomel electrode are reference electrode, and platinum electrode is auxiliary electrode, contain 0.1 mol/ in 10 mL, pH 7.4
The phosphate buffer solution of L ascorbic acid is tested；
(2) used time m- current method detects analyte, and setting voltage is 0 V, 100 s of runing time, irradiation LED lamp wave
A length of 400 ~ 450 nm；
(3) it after background current tends towards stability, turns on light 10 s of prolonged exposure every 10 s, then records photoelectric current, draw work
Curve；
(4) Procalcitonin standard solution is replaced to detect Procalcitonin sample solution to be measured, the result of detection can pass through
Working curve checks in.
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