CN105036069A - Gold/poly(o-aminophenol), gold/poly(p-phenylenediamine) and gold/poly(o-phenylenediamine) nanoparticles as well as preparation method and application thereof - Google Patents
Gold/poly(o-aminophenol), gold/poly(p-phenylenediamine) and gold/poly(o-phenylenediamine) nanoparticles as well as preparation method and application thereof Download PDFInfo
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- CN105036069A CN105036069A CN201510346403.6A CN201510346403A CN105036069A CN 105036069 A CN105036069 A CN 105036069A CN 201510346403 A CN201510346403 A CN 201510346403A CN 105036069 A CN105036069 A CN 105036069A
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Abstract
The invention discloses gold/poly(o-aminophenol), gold/poly(p-phenylenediamine) and gold/poly(o-phenylenediamine) nanoparticles as well as a preparation method and an application thereof. O-aminophenol, p-phenylenediamine and o-phenylenediamine are oxidized and polymerized by use of chloroauric acid respectively, to prepare a novel conductive composite nanomaterial having electrochemical activity; the preparation method of the composite nanomaterial is mild and easily controllable in preparation conditions, and simple and fast in preparation process; the gold/poly(zero-aminophenol), gold/poly(p-phenylenediamine) and gold/poly(o-phenylenediamine) composite nanoparticles possess single and differentiable electrochemical signals respectively, are high in electrical conductivity and large in specific surface area, and contain functional groups such as an amino group and an imino group; the composite nanoparticles can be taken as a good electrochemical sensing material and have wide application prospect in the field of electrochemical detection and analysis.
Description
Technical field
The present invention relates to gold/poly-o-aminophenol, gold/poly-p-phenylenediamine (PPD) and gold/poly-o-phenylenediamine model electrochemical reactive nanoparticles and preparation method thereof, described composite nano materials has electro-chemical activity, single, differentiable electrochemical signals can be produced, good conductivity, with functional groups such as amino, imino groups, can be used for the analytic target in Electrochemical Detection water body, urine, serum, air.The invention belongs to bioelectrochemistry field, it may be used for electrochemical analysis and detection.
Background technology
Electroactive substance plays a part indispensable at Electrochemical Detection analysis field, and it can produce redox chemistry signal, is converted into the signal of telecommunication that can measure by electrochemical apparatus, thus realizes electrochemical ingredient analysis.The electroactive substance meeting requirement of experiment of current discovery have ferrocene and and derivative, thionine, toluidine blue, methylene blue, the organic dyestuff class such as Prussian blue, Cu
2+, Zn
2+, Pb
2+, Cd
2+deng metal ion class.These electroactive substances have single signal peak, but molecular weight is little, be difficult to be further purified, normally form composite particles with material with carbon element, noble metal granule or magnetic material and be used for electrochemical analysis, so just cause that experimentation is loaded down with trivial details, cost increases.In addition, when detecting multiple analytic target at the same time, need the electroactive substance that multiple electrochemical signals can be distinguished, but the signal of telecommunication that Ferrocene and its derivative produces and the Prussian blue signal of telecommunication cannot be distinguished from each other, the signal of telecommunication of thionine, toluidine blue and methylene blue also cannot be distinguished from each other, therefore can not realize three kinds and above to analysis thing while detect.Although Cu
2+, Zn
2+, Pb
2+, Cd
2+can produce the signal of telecommunication that is single, that can be distinguished from each other Deng metal ion, but metal ion has bio-toxicity, and a constructed determination method poor reproducibility, therefore constrain its application in bioelectrochemistry.To sum up, finding the novel electroactive substance that has is realize the key that electrochemistry detects multiple analytes simultaneously.
Polyaniline derivative has the advantages such as good biocompatibility, easily modified, good electric conductivity and electro-chemical activity, is considered to good material in bioelectrochemistry field.The type of the functional group of anil monomer and the Different Effects of the position electro-chemical activity of its polymer.Utilize this feature can prepare the polyaniline derivative with different electro-chemical activity, thus realize electrochemistry and detect multiple analytes simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is to provide one gold chloride oxidation polymerization o-aminophenol, p-phenylenediamine (PPD) and o-phenylenediamine respectively, prepare the method for gold/poly-o-aminophenol, gold/poly-p-phenylenediamine (PPD) and gold/poly-o-phenylenediamine model electrochemical reactive nanoparticles, prepared nano composite material can produce single, discrete electrochemical signals, and has good electric conductivity; Have the gentle easily control of preparation condition, preparation process simple and fast, the composite nanometer particle pattern of acquisition is homogeneous, the feature of good dispersion.
For reaching above-mentioned purpose, a kind of gold of the present invention/poly-o-aminophenol nano particle, described nano particle comprises gold and poly-o-aminophenol.
Prepare a method for described gold/poly-o-aminophenol nano particle, comprise the following steps:
Hydrochloric acid is joined in the mixed solution of water and ethanol, in above-mentioned solution, add a certain amount of o-aminophenol, after stirring certain hour, add gold chloride fast, after reaction certain hour, use deionized water eccentric cleaning.
Wherein said concentration of hydrochloric acid is 10mM-1M, and the volume ratio of water and ethanol is 0.1:1-2:1, and the ratio of the amount of substance of o-aminophenol and gold chloride is 0.1:1-10:1; Mixing time is 0.5-2h, and the reaction time is 2-10h, and stirring and reaction temperature are 0-50 DEG C.
A kind of gold/poly-p-phenylenediamine (PPD) nano particle, described nano particle comprises gold and poly-p-phenylenediamine (PPD).
Prepare a method for described gold/poly-p-phenylenediamine (PPD) nano particle, comprise the following steps:
Citric acid is joined in the mixed solution of water and ethanol, in above-mentioned solution, add a certain amount of p-phenylenediamine (PPD), after stirring certain hour, add gold chloride fast, after reaction certain hour, use deionized water eccentric cleaning.
The concentration of wherein said natrium citricum is 10mM-1M, and the volume ratio of water and ethanol is 0.1:1-2:1, and the ratio of the amount of substance of p-phenylenediamine (PPD) and gold chloride is 0.1:1-10:1; Mixing time is 0.5-2h, and the reaction time is 2-10h, and stirring and reaction temperature are 0-50 DEG C.
A kind of gold/poly-o-phenylenediamine nano particle, described nano particle comprises gold and poly-o-phenylenediamine.
Prepare a method for described gold/poly-o-phenylenediamine nano particle, comprise the following steps:
Hydrochloric acid is added to the water, in above-mentioned solution, adds a certain amount of o-phenylenediamine, after stirring certain hour, add gold chloride fast, after reaction certain hour, use deionized water eccentric cleaning.
Wherein said concentration of hydrochloric acid is 10mM-1M, and the ratio of the amount of substance of o-phenylenediamine and gold chloride is 0.1:1-10:1; Mixing time is 5-60min, and the reaction time is 2-10h, and stirring and reaction temperature are 10-100 DEG C.
An application for gold/poly-o-aminophenol, gold/poly-p-phenylenediamine (PPD) and gold/poly-o-phenylenediamine nano particle, is used for building electrochemical immunosensor by described gold/poly-o-phenylenediamine, described gold/poly-p-phenylenediamine (PPD) and described gold/poly-o-phenylenediamine nano composite material.
The invention difference from existing technology is that the present invention achieves following technique effect:
The inventive method is simple, and prepares gold/poly-o-aminophenol, the gold/gather p-phenylenediamine (PPD) and gold/poly-o-phenylenediamine of nano-scale, has the electrochemical signals of distinguishable polymer.Therefore this gold/poly-o-phenylenediamine, gold/poly-p-phenylenediamine (PPD) and gold/poly-o-phenylenediamine nano composite material can be used for building electrochemical immunosensor, detect while realizing Diagnostic Value of Several Serum Tumor Markers.
Below in conjunction with accompanying drawing, the invention will be further described.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of (A) gold/poly-o-aminophenol nano particle prepared by one embodiment of the invention, (B) the transmission electron microscope picture of gold/poly-p-phenylenediamine (PPD) nano particle, the transmission electron microscope picture of (C) gold/poly-o-phenylenediamine nano particle;
Fig. 2 embodiment of the present invention 1 prepare the square wave voltammogram of (a) poly-o-aminophenol (PoAP), poly-p-phenylenediamine (PPD) (PpPD) and poly-o-phenylenediamine (PoPD), the square wave voltammogram of (b) gold/poly-o-aminophenol (Au-PoAP), gold/gather p-phenylenediamine (PPD) (Au-PpPD) and gold-o-phenylenediamine (Au-PoPD) nano particle;
Fig. 3 embodiment of the present invention 2 prepare the square wave voltammogram of gold/poly-o-aminophenol (Au-PoAP), gold/poly-p-phenylenediamine (PPD) (Au-PpPD) and gold-o-phenylenediamine (Au-PoPD) nano particle;
Fig. 4 embodiment of the present invention 3 prepare the square wave voltammogram of gold/poly-o-aminophenol (Au-PoAP), gold/poly-p-phenylenediamine (PPD) (Au-PpPD) and gold-o-phenylenediamine (Au-PoPD) nano particle.
Detailed description of the invention
Below in conjunction with embodiment, to above-mentioned being described in more detail with other technical characteristic and advantage of the present invention.
Embodiment 1:
The preparation of 1, gold/poly-o-aminophenol composite nanometer particle
The hydrochloric acid of 1mL0.1M joins in the ultra-pure water of 3mL and the ethanolic solution of 0.5mL, then adds 5mg o-aminophenol, stirs 1h at 20 DEG C.Then add 970 μ L2% gold chlorides fast, reaction 4h, product is centrifugal, and ultra-pure water cleans.
The preparation of 2, gold/poly-p-phenylenediamine (PPD) composite nanometer particle
The citric acid of 2mL0.5M joins in the ethanolic solution of 3mL ultra-pure water and 3mL, then adds 5mg p-phenylenediamine (PPD), stirs 1h at 30 DEG C.Then add 970 μ L2% gold chlorides fast, reaction 4h, product is centrifugal, and ultra-pure water cleans.
The preparation of 3, gold/poly-o-phenylenediamine composite nanometer particle
1mL1M hydrochloric acid adds in 5mL ultra-pure water, then adds 5mg o-phenylenediamine, therefore constrains its application on a sensor.Lower stirring 10min.Then add 970 μ L2% gold chlorides fast, reaction 4h, product is centrifugal, and ultra-pure water cleans.
Embodiment 2:
The preparation of 1, gold/poly-o-aminophenol composite nanometer particle
The hydrochloric acid of 3mL1M joins in the ultra-pure water of 6mL and the ethanolic solution of 9mL, then adds 2mg o-aminophenol, stirs 45min at 20 DEG C.Then add 6.45mL3% gold chloride fast, reaction 4h, product is centrifugal, and ultra-pure water cleans.
The preparation of 2, gold/poly-p-phenylenediamine (PPD) composite nanometer particle
The citric acid of 6mL1M joins in the ethanolic solution of 1mL ultra-pure water and 1mL, then adds 5mg p-phenylenediamine (PPD), stirs 1h at 20 DEG C.Then add 6.45mL3% gold chloride fast, reaction 4h, product is centrifugal, and ultra-pure water cleans.
The preparation of 3, gold/poly-o-phenylenediamine composite nanometer particle
2mL1M hydrochloric acid adds in 8mL ultra-pure water, then adds 5mg o-phenylenediamine, stirs 10min at 40 DEG C.Then add 6.45mL3% gold chloride fast, reaction 4h, product is centrifugal, and ultra-pure water cleans.
Embodiment 3:
The preparation of 1, gold/poly-o-aminophenol composite nanometer particle
The hydrochloric acid of 2mL0.5M joins in the ultra-pure water of 2mL and the ethanolic solution of 3mL, then adds 2mg o-aminophenol, stirs 45min at 30 DEG C.Then add 3.87mL10% gold chloride fast, reaction 4h, product is centrifugal, and ultra-pure water cleans.
The preparation of 2, gold/poly-p-phenylenediamine (PPD) composite nanometer particle
The citric acid of 1mL0.5M joins in the ethanolic solution of 1.5mL ultra-pure water and 1.5mL, then adds 2mg p-phenylenediamine (PPD), stirs 1h at 30 DEG C.Then add 3.87mL10% gold chloride fast, reaction 4h, product is centrifugal, and ultra-pure water cleans.
The preparation of 3, gold/poly-o-phenylenediamine composite nanometer particle
1mL0.5M hydrochloric acid adds in 2mL ultra-pure water, then adds 2mg o-phenylenediamine, stirs 10min at 30 DEG C.Then add 3.87mL10% gold chloride fast, reaction 4h, product is centrifugal, and ultra-pure water cleans.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (10)
1. gold/poly-o-aminophenol nano particle, is characterized in that: described nano particle comprises gold and poly-o-aminophenol.
2. prepare a method for gold/poly-o-aminophenol nano particle as claimed in claim 1, it is characterized in that comprising the following steps:
Hydrochloric acid is joined in the mixed solution of water and ethanol, in above-mentioned solution, add a certain amount of o-aminophenol, after stirring certain hour, add gold chloride fast, after reaction certain hour, use deionized water eccentric cleaning.
3. the preparation method of gold/poly-o-aminophenol nano particle as claimed in claim 2, it is characterized in that: described concentration of hydrochloric acid is 10mM-1M, the volume ratio of water and ethanol is 0.1:1-2:1, and the ratio of the amount of substance of o-aminophenol and gold chloride is 0.1:1-10:1; Mixing time is 0.5-2h, and the reaction time is 2-10h, and stirring and reaction temperature are 0-50 DEG C.
4. gold/poly-p-phenylenediamine (PPD) nano particle, is characterized in that: described nano particle comprises gold and poly-p-phenylenediamine (PPD).
5. prepare a method for gold/poly-p-phenylenediamine (PPD) nano particle as claimed in claim 4, its feature is being to comprise the following steps:
Citric acid is joined in the mixed solution of water and ethanol, in above-mentioned solution, add a certain amount of p-phenylenediamine (PPD), after stirring certain hour, add gold chloride fast, after reaction certain hour, use deionized water eccentric cleaning.
6. the preparation method of gold/poly-p-phenylenediamine (PPD) nano particle as claimed in claim 5, it is characterized in that: the concentration of described natrium citricum is 10mM-1M, the volume ratio of water and ethanol is 0.1:1-2:1, and the ratio of the amount of substance of p-phenylenediamine (PPD) and gold chloride is 0.1:1-10:1; Mixing time is 0.5-2h, and the reaction time is 2-10h, and stirring and reaction temperature are 0-50 DEG C.
7. gold/poly-o-phenylenediamine nano particle, is characterized in that: described nano particle comprises gold and poly-o-phenylenediamine.
8. prepare a method for gold/poly-o-phenylenediamine nano particle as claimed in claim 7, it is characterized in that comprising the following steps:
Hydrochloric acid is added to the water, in above-mentioned solution, adds a certain amount of o-phenylenediamine, after stirring certain hour, add gold chloride fast, after reaction certain hour, use deionized water eccentric cleaning.
9. the preparation method of gold/poly-o-phenylenediamine nano particle as claimed in claim 8, it is characterized in that: described concentration of hydrochloric acid is 10mM-1M, the ratio of the amount of substance of o-phenylenediamine and gold chloride is 0.1:1-10:1; Mixing time is 5-60min, and the reaction time is 2-10h, and stirring and reaction temperature are 10-100 DEG C.
10. an application for gold/poly-o-aminophenol, gold/poly-p-phenylenediamine (PPD) and gold/poly-o-phenylenediamine nano particle, is characterized in that: described gold/poly-o-phenylenediamine, described gold/poly-p-phenylenediamine (PPD) and described gold/poly-o-phenylenediamine nano composite material are used for building electrochemical immunosensor.
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| CN201510346403.6A CN105036069A (en) | 2015-06-19 | 2015-06-19 | Gold/poly(o-aminophenol), gold/poly(p-phenylenediamine) and gold/poly(o-phenylenediamine) nanoparticles as well as preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111602672A (en) * | 2020-06-01 | 2020-09-01 | 南方科技大学 | Antibacterial nano material and preparation method and application thereof |
| CN113797979A (en) * | 2021-09-15 | 2021-12-17 | 中国科学院长春应用化学研究所 | Modified nano particle, preparation method and application thereof |
| WO2024020615A1 (en) * | 2022-07-27 | 2024-02-01 | Universität Graz | Storage-stable composition comprising 4-aminophenol and to the use thereof in the determination of cannabinoids |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629930A (en) * | 2009-06-19 | 2010-01-20 | 东南大学 | Boron-doped diamond electrode modified with gold-nanofiber composite preparation method |
| CN102746667A (en) * | 2012-07-12 | 2012-10-24 | 新疆大学 | Polyaniline/nanogold composite material synthesized by solid-phase method |
| CN102891326A (en) * | 2012-10-23 | 2013-01-23 | 南京交通职业技术学院 | Nitrogen-doped hollow carbon ball loaded palladium-based catalyst and preparation method thereof, and alcohol fuel cell applying same |
-
2015
- 2015-06-19 CN CN201510346403.6A patent/CN105036069A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629930A (en) * | 2009-06-19 | 2010-01-20 | 东南大学 | Boron-doped diamond electrode modified with gold-nanofiber composite preparation method |
| CN102746667A (en) * | 2012-07-12 | 2012-10-24 | 新疆大学 | Polyaniline/nanogold composite material synthesized by solid-phase method |
| CN102891326A (en) * | 2012-10-23 | 2013-01-23 | 南京交通职业技术学院 | Nitrogen-doped hollow carbon ball loaded palladium-based catalyst and preparation method thereof, and alcohol fuel cell applying same |
Non-Patent Citations (1)
| Title |
|---|
| LIYUAN WANG, NA LIU, ZHANFANG MA: "Novel gold-decorated polyaniline derivatives as redox-active species for simultaneous detection of three biomarkers of lung cancer", 《JOURNAL OF MATERIALS CHEMISTRY B》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111602672A (en) * | 2020-06-01 | 2020-09-01 | 南方科技大学 | Antibacterial nano material and preparation method and application thereof |
| CN113797979A (en) * | 2021-09-15 | 2021-12-17 | 中国科学院长春应用化学研究所 | Modified nano particle, preparation method and application thereof |
| CN113797979B (en) * | 2021-09-15 | 2022-12-20 | 中国科学院长春应用化学研究所 | Modified nano particle, preparation method and application thereof |
| WO2024020615A1 (en) * | 2022-07-27 | 2024-02-01 | Universität Graz | Storage-stable composition comprising 4-aminophenol and to the use thereof in the determination of cannabinoids |
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