CN105259223B - The preparation method of a kind of vomiting mycin sensor based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide structure and application - Google Patents
The preparation method of a kind of vomiting mycin sensor based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide structure and application Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 45
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000010931 gold Substances 0.000 title claims abstract description 40
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 40
- 206010047700 Vomiting Diseases 0.000 title claims abstract description 33
- 230000008673 vomiting Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 30
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 25
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000000427 antigen Substances 0.000 claims description 12
- 102000036639 antigens Human genes 0.000 claims description 12
- 108091007433 antigens Proteins 0.000 claims description 12
- 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 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000008366 buffered solution Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229940098773 bovine serum albumin Drugs 0.000 claims description 5
- HXCHCVDVKSCDHU-LULTVBGHSA-N calicheamicin Chemical compound C1[C@H](OC)[C@@H](NCC)CO[C@H]1O[C@H]1[C@H](O[C@@H]2C\3=C(NC(=O)OC)C(=O)C[C@](C/3=C/CSSSC)(O)C#C\C=C/C#C2)O[C@H](C)[C@@H](NO[C@@H]2O[C@H](C)[C@@H](SC(=O)C=3C(=C(OC)C(O[C@H]4[C@@H]([C@H](OC)[C@@H](O)[C@H](C)O4)O)=C(I)C=3C)OC)[C@@H](O)C2)[C@@H]1O HXCHCVDVKSCDHU-LULTVBGHSA-N 0.000 claims description 5
- 229930195731 calicheamicin Natural products 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000000970 chrono-amperometry Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
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- -1 gold platinum Chlorauric acid Chemical compound 0.000 claims 1
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- 239000000463 material Substances 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 4
- LINOMUASTDIRTM-QGRHZQQGSA-N deoxynivalenol Chemical compound C([C@@]12[C@@]3(C[C@@H](O)[C@H]1O[C@@H]1C=C(C([C@@H](O)[C@@]13CO)=O)C)C)O2 LINOMUASTDIRTM-QGRHZQQGSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- LINOMUASTDIRTM-UHFFFAOYSA-N vomitoxin hydrate Natural products OCC12C(O)C(=O)C(C)=CC1OC1C(O)CC2(C)C11CO1 LINOMUASTDIRTM-UHFFFAOYSA-N 0.000 description 4
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- 231100000678 Mycotoxin Toxicity 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
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- 229910021397 glassy carbon Inorganic materials 0.000 description 2
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- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 206010000234 Abortion spontaneous Diseases 0.000 description 1
- 229930195730 Aflatoxin Natural products 0.000 description 1
- XWIYFDMXXLINPU-UHFFFAOYSA-N Aflatoxin G Chemical compound O=C1OCCC2=C1C(=O)OC1=C2C(OC)=CC2=C1C1C=COC1O2 XWIYFDMXXLINPU-UHFFFAOYSA-N 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
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- HGTYEBNTDPDGIC-UHFFFAOYSA-N [N].[Au] Chemical compound [N].[Au] HGTYEBNTDPDGIC-UHFFFAOYSA-N 0.000 description 1
- 239000005409 aflatoxin Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 229930002954 deoxynivalenol Natural products 0.000 description 1
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Abstract
The present invention relates to the preparation method of a kind of vomiting mycin sensor based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide structure and application, belong to new function material, bio-sensing detection technique field.Based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide, hydrogen peroxide there are good electrochemical catalysis ability and electron transfer capacity, significantly improve the sensitivity of biosensor, the detection vomitting mycin in grain is had great importance.
Description
Technical field
The preparation method of a kind of vomiting mycin sensor based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide structure of the present invention and application.Specifically adopt the flower-shaped gold platinum-flower-shaped ceria-graphene oxide with good electrical chemical catalysis performance, prepare a kind of sensor detecting and vomitting mycin in grain, belong to new function material and bio-sensing detection technique field.
Background technology
Vomitoxin has another name called deoxynivalenol, is a kind of colorless needle crystals, has stronger hot drag.Vomitoxin is the toxic metabolite produced by Fusarium, is distributed in the corn seeds such as Semen Tritici aestivi, Fructus Hordei Vulgaris, Semen Maydis more, and in corn and feedstuff, recall rate is high, is at the most serious mycotoxin of the after stain of aflatoxin.Humans and animals is all had very strong toxicity by vomitoxin, can cause humans and animals vomiting, diarrhoea, skin irritation, refusing to eat, neurological disorders, miscarriage, stillborn fetus etc..
Current biosensor is widely used for the detection of various mycotoxin because biosensor have highly sensitive, selectivity good, simple in construction, easy and simple to handle, be prone to miniaturization, can the series of advantages such as detection analysis continuous, rapid automatized.Wherein, owing to unmarked type sensor is used directly for the identification process of detection antigen-antibody and avoids the interference that label brings, obtains and pay close attention to more widely.
Flower-shaped gold platinum-flower-shaped ceria-graphene oxide is modified glassy carbon electrode surface by the present invention, builds unmarked type sensor.First, flower-shaped gold platinum-flower-shaped ceria-graphene oxide has a good biocompatibility, and can sessile antibody effectively；Second, flower-shaped gold platinum-flower-shaped ceria-graphene oxide has the catalytic Contact area that good electrochemical catalysis is active and bigger, it is possible to increase the sensitivity of sensor；3rd, flower-shaped gold platinum-flower-shaped ceria-graphene oxide has good electron transfer capacity and big specific surface area, it is possible to increases the fixing of antibody further and strengthens electron transmission.The method creates good electrochemical signals in detection process, can be used for vomitting the analysis of mycin.The method has that cost is low, highly sensitive, specificity is good, detect the advantages such as quick, and preparation process is relatively simple, at present effectively detection vomiting mycin provide new way.
Summary of the invention
An object of the present invention is based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide and builds unmarked type biosensor.
The two of the purpose of the present invention are in highly sensitive, the specific detection of vomiting mycin by this unmarked type biosensor application.
Technical scheme is as follows
1.A kind of preparation method of the vomiting mycin sensor built based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide
(1) being polished with the alumina powder foot couple glass-carbon electrode of 1.0,0.3,0.05 μm successively, ultrasonic cleaning in ultra-pure water and ethanol respectively, nitrogen dries up；
(2) drip, at electrode surface, flower-shaped gold platinum-flower-shaped ceria-graphene oxide water solution that 6 μ L concentration are 1 ~ 2mg/mL, dry；
(3) continue the vomiting calicheamicin antibody solution that 6 μ L concentration are 5 ~ 20 μ g/mL is added drop-wise to modified electrode surface, in 4 DEG C of refrigerators, hatch 1h, clean up；
(4) close nonspecific activity site with the bovine serum albumin solution that 3 μ L concentration are 5 ~ 20mg/mL, in 4 DEG C of refrigerators, hatch 1h, clean up；
(5) the vomiting mycin antigen of a series of variable concentrations that 6 μ L concentration are 0.0002 ~ 20ng/mL is used for the specific recognition with antibody, incubated at room temperature 1h, cleans up, store for future use in 4 DEG C of refrigerators.
The preparation of flower-shaped gold platinum-flower-shaped ceria-graphene oxide
(1) preparation of flower-shaped gold platinum
Chlorauric acid solution and 1.5 ~ 6mg potassium chloroplatinate that 25 ~ 100mL ultra-pure water, 0.125 ~ 0.5mL mass fraction are 1% are mixed in there-necked flask, after heated and boiled, rapidly join the sodium citrate aqueous solution that 1.5 ~ 6mL mass fraction is 2%, boil 10min, it is cooled to room temperature, obtains flower-shaped gold platinum solution；
(2) preparation of flower-shaped ceria
0.099g Cerous chloride heptahydrate and 0.5g polyvinylpyrrolidone are dissolved in 7.5 ~ 30mL water, it is subsequently added oxalic acid that 0.25 ~ 1mL concentration is 0.4mmol/L and 0.35 ~ 1.4mL concentration is the ammonia of 5mmol/L, after stirring 30min, add 0.065 ~ 0.26mL hydrogen peroxide, above-mentioned mixing is proceeded in reactor night, 5h is reacted under 150 DEG C of conditions, dry after centrifuge washing, obtain flower-shaped ceria；
(3) preparation of flower-shaped gold platinum-flower-shaped ceria-graphene oxide
Flower-shaped for 0.1g ceria and 0.1mL tri-aminopropyl triethoxysilane are added in 5 ~ 20mL isopropanol, 24h is stirred under room temperature, dry after centrifuge washing, obtain the flower-shaped ceria that three aminopropyl triethoxysilanes are modified, the flower-shaped ceria modify 0.1g tri-aminopropyl triethoxysilane and 20mg graphene oxide join in the water of 25 ~ 100mL, it is subsequently added the flower-shaped gold platinum solution prepared by 15mL, 3h is stirred under room temperature, dry after centrifuge washing, obtain flower-shaped gold platinum-flower-shaped ceria-graphene oxide.
The detection method of vomiting mycin
(1) using electrochemical workstation to test with three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is auxiliary electrode, and prepared sensor is working electrode, tests in the phosphate buffered solution that pH value is 6.8 of 10mL；
(2) selecting chronoamperometry that vomiting mycin antigen is detected, input voltage is set to-0.4V, sampling interval is set to 0.1s, and operation set of time is 400s；
(3) after background current tends towards stability, being the hydrogen peroxide solution of 5mol/L every 50s to injecting 10 μ L concentration in phosphate buffered solution, then record current is over time, drawing curve；
(4) testing sample solution replace vomiting mycin antigen standard solution detect.
The useful achievement of the present invention
(1) present invention adopts flower-shaped gold platinum-flower-shaped ceria-graphene oxide to have good biocompatibility, is chemically bonded to glassy carbon electrode surface by forming gold nitrogen key.
(2) flower-shaped gold platinum-flower-shaped ceria-graphene oxide that the present invention adopts has big specific surface area, it is possible to effectively fixing substantial amounts of antibody.
(3) hydrogen peroxide is had superior electrochemical catalysis performance by flower-shaped gold platinum-flower-shaped ceria-graphene oxide that the present invention adopts, and improves the sensitivity of biosensor.
(4) flower-shaped gold platinum-flower-shaped ceria-graphene oxide that the present invention adopts has the transmission efficiency of good electronics, further increases the sensitivity of biosensor.
(5) the unmarked type biosensor of preparation is used for vomitting the detection of mycin by the present invention, and detection limit is low, range of linearity width, it is possible to achieve simple, quick, sensitive and specific detection.
Detailed description of the invention
Embodiment 1A kind of preparation method of the vomiting mycin sensor built based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide
(1) being polished with the alumina powder foot couple glass-carbon electrode of 1.0,0.3,0.05 μm successively, ultrasonic cleaning in ultra-pure water and ethanol respectively, nitrogen dries up；
(2) drip, at electrode surface, flower-shaped gold platinum-flower-shaped ceria-graphene oxide water solution that 6 μ L concentration are 1mg/mL, dry；
(3) continue the vomiting calicheamicin antibody solution that 6 μ L concentration are 5 μ g/mL is added drop-wise to modified electrode surface, in 4 DEG C of refrigerators, hatch 1h, clean up；
(4) close nonspecific activity site with the bovine serum albumin solution that 3 μ L concentration are 5mg/mL, in 4 DEG C of refrigerators, hatch 1h, clean up；
(5) the vomiting mycin antigen of a series of variable concentrations that 6 μ L concentration are 0.0002 ~ 20ng/mL is used for the specific recognition with antibody, incubated at room temperature 1h, cleans up, store for future use in 4 DEG C of refrigerators.
Embodiment 2A kind of preparation method of the vomiting mycin sensor built based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide
(1) being polished with the alumina powder foot couple glass-carbon electrode of 1.0,0.3,0.05 μm successively, ultrasonic cleaning in ultra-pure water and ethanol respectively, nitrogen dries up；
(2) drip, at electrode surface, flower-shaped gold platinum-flower-shaped ceria-graphene oxide water solution that 6 μ L concentration are 1.5mg/mL, dry；
(3) continue the vomiting calicheamicin antibody solution that 6 μ L concentration are 10 μ g/mL is added drop-wise to modified electrode surface, in 4 DEG C of refrigerators, hatch 1h, clean up；
(4) close nonspecific activity site with the bovine serum albumin solution that 3 μ L concentration are 10mg/mL, in 4 DEG C of refrigerators, hatch 1h, clean up；
(5) the vomiting mycin antigen of a series of variable concentrations that 6 μ L concentration are 0.0002 ~ 20ng/mL is used for the specific recognition with antibody, incubated at room temperature 1h, cleans up, store for future use in 4 DEG C of refrigerators.
Embodiment 3A kind of preparation method of the vomiting mycin sensor built based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide
(1) being polished with the alumina powder foot couple glass-carbon electrode of 1.0,0.3,0.05 μm successively, ultrasonic cleaning in ultra-pure water and ethanol respectively, nitrogen dries up；
(2) drip, at electrode surface, flower-shaped gold platinum-flower-shaped ceria-graphene oxide water solution that 6 μ L concentration are 2mg/mL, dry；
(3) continue the vomiting calicheamicin antibody solution that 6 μ L concentration are 20 μ g/mL is added drop-wise to modified electrode surface, in 4 DEG C of refrigerators, hatch 1h, clean up；
(4) close nonspecific activity site with the bovine serum albumin solution that 3 μ L concentration are 20mg/mL, in 4 DEG C of refrigerators, hatch 1h, clean up；
(5) the vomiting mycin antigen of a series of variable concentrations that 6 μ L concentration are 0.0002 ~ 20ng/mL is used for the specific recognition with antibody, incubated at room temperature 1h, cleans up, store for future use in 4 DEG C of refrigerators.
Embodiment 4The preparation of flower-shaped gold platinum-flower-shaped ceria-graphene oxide
(1) preparation of flower-shaped gold platinum
Chlorauric acid solution and 1.5mg potassium chloroplatinate that 25mL ultra-pure water, 0.125mL mass fraction are 1% are mixed in there-necked flask, after heated and boiled, rapidly join the sodium citrate aqueous solution that 1.5mL mass fraction is 2%, boil 10min, it is cooled to room temperature, obtains flower-shaped gold platinum solution；
(2) preparation of flower-shaped ceria
0.099g Cerous chloride heptahydrate and 0.5g polyvinylpyrrolidone are dissolved in 7.5mL water, it is subsequently added oxalic acid that 0.25mL concentration is 0.4mmol/L and 0.35mL concentration is the ammonia of 5mmol/L, after stirring 30min, add 0.065mL hydrogen peroxide, above-mentioned mixing is proceeded in reactor night, 5h is reacted under 150 DEG C of conditions, dry after centrifuge washing, obtain flower-shaped ceria；
(3) preparation of flower-shaped gold platinum-flower-shaped ceria-graphene oxide
Flower-shaped for 0.1g ceria and 0.1mL tri-aminopropyl triethoxysilane are added in 5mL isopropanol, 24h is stirred under room temperature, dry after centrifuge washing, obtain the flower-shaped ceria that three aminopropyl triethoxysilanes are modified, the flower-shaped ceria modify 0.1g tri-aminopropyl triethoxysilane and 20mg graphene oxide join in the water of 25mL, it is subsequently added the flower-shaped gold platinum solution prepared by 15mL, 3h is stirred under room temperature, dry after centrifuge washing, obtain flower-shaped gold platinum-flower-shaped ceria-graphene oxide.
Embodiment 5The preparation of flower-shaped gold platinum-flower-shaped ceria-graphene oxide
(1) preparation of flower-shaped gold platinum
Chlorauric acid solution and 3mg potassium chloroplatinate that 50mL ultra-pure water, 0.25mL mass fraction are 1% are mixed in there-necked flask, after heated and boiled, rapidly join the sodium citrate aqueous solution that 3mL mass fraction is 2%, boil 10min, it is cooled to room temperature, obtains flower-shaped gold platinum solution；
(2) preparation of flower-shaped ceria
0.099g Cerous chloride heptahydrate and 0.5g polyvinylpyrrolidone are dissolved in 15mL water, it is subsequently added oxalic acid that 0.5mL concentration is 0.4mmol/L and 0.7mL concentration is the ammonia of 5mmol/L, after stirring 30min, add 0.13mL hydrogen peroxide, above-mentioned mixing is proceeded in reactor night, 5h is reacted under 150 DEG C of conditions, dry after centrifuge washing, obtain flower-shaped ceria；
(3) preparation of flower-shaped gold platinum-flower-shaped ceria-graphene oxide
Flower-shaped for 0.1g ceria and 0.1mL tri-aminopropyl triethoxysilane are added in 10mL isopropanol, 24h is stirred under room temperature, dry after centrifuge washing, obtain the flower-shaped ceria that three aminopropyl triethoxysilanes are modified, the flower-shaped ceria modify 0.1g tri-aminopropyl triethoxysilane and 20mg graphene oxide join in the water of 50mL, it is subsequently added the flower-shaped gold platinum solution prepared by 15mL, 3h is stirred under room temperature, dry after centrifuge washing, obtain flower-shaped gold platinum-flower-shaped ceria-graphene oxide.
Embodiment 6The preparation of flower-shaped gold platinum-flower-shaped ceria-graphene oxide
(1) preparation of flower-shaped gold platinum
Chlorauric acid solution and 6mg potassium chloroplatinate that 100mL ultra-pure water, 0.5mL mass fraction are 1% are mixed in there-necked flask, after heated and boiled, rapidly join the sodium citrate aqueous solution that 6mL mass fraction is 2%, boil 10min, it is cooled to room temperature, obtains flower-shaped gold platinum solution；
(2) preparation of flower-shaped ceria
0.099g Cerous chloride heptahydrate and 0.5g polyvinylpyrrolidone are dissolved in 30mL water, it is subsequently added oxalic acid that 1mL concentration is 0.4mmol/L and 1.4mL concentration is the ammonia of 5mmol/L, after stirring 30min, add 0.26mL hydrogen peroxide, above-mentioned mixing is proceeded in reactor night, 5h is reacted under 150 DEG C of conditions, dry after centrifuge washing, obtain flower-shaped ceria；
(3) preparation of flower-shaped gold platinum-flower-shaped ceria-graphene oxide
Flower-shaped for 0.1g ceria and 0.1mL tri-aminopropyl triethoxysilane are added in 20mL isopropanol, 24h is stirred under room temperature, dry after centrifuge washing, obtain the flower-shaped ceria that three aminopropyl triethoxysilanes are modified, the flower-shaped ceria modify 0.1g tri-aminopropyl triethoxysilane and 20mg graphene oxide join in the water of 100mL, it is subsequently added the flower-shaped gold platinum solution prepared by 15mL, 3h is stirred under room temperature, dry after centrifuge washing, obtain flower-shaped gold platinum-flower-shaped ceria-graphene oxide.
Embodiment 7The detection method of vomiting mycin
(1) using electrochemical workstation to test with three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is auxiliary electrode, and prepared sensor is working electrode, tests in the phosphate buffered solution that pH value is 6.8 of 10mL；
(2) selecting chronoamperometry that vomiting mycin antigen is detected, input voltage is set to-0.4V, sampling interval is set to 0.1s, and operation set of time is 400s；
(3) after background current tends towards stability, being the hydrogen peroxide solution of 5mol/L every 50s to injecting 10 μ L concentration in phosphate buffered solution, then record current is over time, drawing curve；
(4) testing sample solution replace vomiting mycin antigen standard solution detect；
(5) the vomiting mycin Detection of antigen range of linearity is 0.0002 ~ 20ng/mL by this biosensor, detection limit 0.1pg/mL.
Claims (2)
1. the preparation method of the vomiting mycin sensor built based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide, it is characterised in that step is as follows:
(1) preparation of flower-shaped gold platinum
Chlorauric acid solution and 1.5 ~ 6mg potassium chloroplatinate that 25 ~ 100mL ultra-pure water, 0.125 ~ 0.5mL mass fraction are 1% are mixed in there-necked flask, after heated and boiled, rapidly join the sodium citrate aqueous solution that 1.5 ~ 6mL mass fraction is 2%, boil 10min, it is cooled to room temperature, obtains flower-shaped gold platinum solution；
(2) preparation of flower-shaped ceria
0.099g Cerous chloride heptahydrate and 0.5g polyvinylpyrrolidone are dissolved in 7.5 ~ 30mL water, it is subsequently added oxalic acid that 0.25 ~ 1mL concentration is 0.4mmol/L and 0.35 ~ 1.4mL concentration is the ammonia of 5mmol/L, after stirring 30min, add 0.065 ~ 0.26mL hydrogen peroxide, above-mentioned mixing is proceeded in reactor night, 5h is reacted under 150 DEG C of conditions, dry after centrifuge washing, obtain flower-shaped ceria；
(3) preparation of flower-shaped gold platinum-flower-shaped ceria-graphene oxide
Flower-shaped for 0.1g ceria and 0.1mL tri-aminopropyl triethoxysilane are added in 5 ~ 20mL isopropanol, 24h is stirred under room temperature, dry after centrifuge washing, obtain the flower-shaped ceria that three aminopropyl triethoxysilanes are modified, the flower-shaped ceria modify 0.1g tri-aminopropyl triethoxysilane and 20mg graphene oxide join in the water of 25 ~ 100mL, it is subsequently added the flower-shaped gold platinum solution prepared by 15mL, 3h is stirred under room temperature, dry after centrifuge washing, obtain flower-shaped gold platinum-flower-shaped ceria-graphene oxide；
(4) preparation of sensor
1) being polished with the alumina powder foot couple glass-carbon electrode of 1.0,0.3,0.05 μm successively, ultrasonic cleaning in ultra-pure water and ethanol respectively, nitrogen dries up；
2) drip, at electrode surface, flower-shaped gold platinum-flower-shaped ceria-graphene oxide water solution that 6 μ L concentration are 1 ~ 2mg/mL, dry；
3) continue the vomiting calicheamicin antibody solution that 6 μ L concentration are 5 ~ 20 μ g/mL is added drop-wise to modified electrode surface, in 4 DEG C of refrigerators, hatch 1h, clean up；
4) close nonspecific activity site with the bovine serum albumin solution that 3 μ L concentration are 5 ~ 20mg/mL, in 4 DEG C of refrigerators, hatch 1h, clean up；
5) the vomiting mycin antigen of a series of variable concentrations that 6 μ L concentration are 0.0002 ~ 20ng/mL is used for the specific recognition with antibody, incubated at room temperature 1h, cleans up, store for future use in 4 DEG C of refrigerators.
2. a kind of vomiting mycin sensor built based on flower-shaped gold platinum-flower-shaped ceria-graphene oxide that prepared by the preparation method as claimed in claim 1 detection method to vomiting mycin, it is characterised in that step is as follows:
(1) using electrochemical workstation to test with three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is auxiliary electrode, and prepared sensor is working electrode, tests in the phosphate buffered solution that pH value is 6.8 of 10mL；
(2) selecting chronoamperometry that vomiting mycin antigen is detected, input voltage is set to-0.4V, sampling interval is set to 0.1s, and operation set of time is 400s；
(3) after background current tends towards stability, being the hydrogen peroxide solution of 5mol/L every 50s to injecting 10 μ L concentration in phosphate buffered solution, then record current is over time, drawing curve；
(4) testing sample solution replace vomiting mycin antigen standard solution detect.
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