CN107121470A - The preparation of molecular engram overoxidised polypyrrole/manganese dioxide/carbon felt composite material - Google Patents
The preparation of molecular engram overoxidised polypyrrole/manganese dioxide/carbon felt composite material Download PDFInfo
- Publication number
- CN107121470A CN107121470A CN201710315124.2A CN201710315124A CN107121470A CN 107121470 A CN107121470 A CN 107121470A CN 201710315124 A CN201710315124 A CN 201710315124A CN 107121470 A CN107121470 A CN 107121470A
- Authority
- CN
- China
- Prior art keywords
- mno
- carbon felt
- manganese dioxide
- molecular engram
- polypyrrole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 238000002484 cyclic voltammetry Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 9
- QIVBCDIJIAJPQS-SECBINFHSA-N D-tryptophane Chemical compound C1=CC=C2C(C[C@@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-SECBINFHSA-N 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
Classifications
-
- 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
Abstract
The present invention relates to a kind of preparation method of molecular engram overoxidised polypyrrole/manganese dioxide/carbon felt composite material, comprise the following steps：Prepare manganese dioxide/carbon felt composite material, prepare molecular engram overoxidised polypyrrole/manganese dioxide/carbon felt composite material.Beneficial effects of the present invention：The preparation cost of molecular engram overoxidised polypyrrole/manganese dioxide/carbon felt composite material is low, and preparation process is simple and environmentally-friendly.
Description
Technical field
The present invention relates to a kind of preparation method of molecular engram overoxidised polypyrrole/manganese dioxide/carbon felt composite material, category
In material and biological research fields.
Background technology
Conducting polymer can be combined molecular imprinting technology with electrochemical techniques, and selection conducting polymer prints as molecule
Mark material.Often there is the less defect of specific surface area in traditional molecular engram conducting polymer, this causes molecular engram site
Largely it is embedded in inside molecularly imprinted polymer, this will substantially reduce the validity in molecular engram site.Nanometer material
Material possesses larger specific surface area, thus nano material be especially suitable for it is relative for changing conventional molecular imprinted material specific surface area
Less present situation.In order to which nano material, molecular imprinting technology and electrochemical techniques are combined, we select carbon felt (CF) and two
Composite (the MnO of manganese oxide nanometer rods2/ CF) as substrate, electrochemistry formated molecular engram peroxide is carried out in this substrate
Change polypyrrole (MIOPPy) film, it is right that the molecular imprinting composite material prepared is applied into electrochemical recognition tryptophan (Trp)
Reflect body.
The content of the invention
The present invention relates to a kind of preparation of use molecular engram polypyrrole/manganese dioxide/carbon felt composite material, including it is following
Step：
A, preparation MnO2/ CF composites：In hydrothermal reaction kettle, by carbon felt (1cm × 1cm) and 5mM KMnO4Mixing,
After reaction 5h under conditions of 160 DEG C, hydrothermal reaction kettle is taken out, is cooled to after room temperature, taking-up is loaded with MnO2CF
(MnO2/ CF), wash, dry, it is standby；
B, preparation MIOPPy/MnO2/ CF composites：By MnO obtained above2/ CF composites soak as working electrode
Enter in the mixed solution (pH=6.7) containing 2mM L-Trp, 0.1M pyrroles and 0.1mM KCl, under the conditions of 0.8V constant potential
Electrochemical polymerization is carried out, polymerization time is 1000s, finally gives the PPy/MnO doped with L-Trp2/ CF composites；Should
Composite is immersed in 0.1M sulfuric acid solutions, applies 0.3V constant potentials 2000s on the composite to slough template point
Son obtains MIPPy/MnO2/CF；In order to avoid PPy oxidation peak for Electrochemical Detection influence, by MIPPy/MnO2/ CF is put
In 0.1M NaOH solution, CV scannings are carried out in 0.45~1.2V potential range, until there are stable CV curves,
Obtained material is designated as MIOPPy/MnO2/CF。
Further, reaction temperature is 160 DEG C in step a, and the reaction time is 5h.
Further, the pH of mixed solution is 6.7 in step b, and polymerization time is 1000s, and the current potential of removing template molecule is
0.3V。
Brief description of the drawings
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is MIOPPy/MnO2/ CF scanning electron microscope (SEM) photograph.
Fig. 2 is MIOPPy/CF scanning electron microscope (SEM) photograph.
Fig. 3 is MIOPPy/MnO2The upper MIOPPy/MnO of/CF2Transmission electron microscope picture.
Fig. 4 L-Trp and D-Trp are in MIOPPy/MnO2DPV figures on/CF.
The DPV figures of Fig. 5 L-Trp and D-Trp on MIOPPy/CF.
Fig. 6 L-Trp and D-Trp are in NIOPPy/MnO2DPV figures on/CF.
Embodiment
Presently in connection with specific embodiment, the present invention will be further described, following examples be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment one：
The step of preparing molecular engram polypyrrole/manganese dioxide/carbon felt composite material is as follows：
(1) MnO is prepared2/ CF composites：In hydrothermal reaction kettle, by carbon felt (1cm × 1cm) and 5mM KMnO4It is mixed
Close, after reaction 5h under conditions of 160 DEG C, take out hydrothermal reaction kettle, be cooled to after room temperature, taking-up is loaded with MnO2CF
(MnO2/ CF), wash, dry, it is standby.
(2) MIOPPy/MnO is prepared2/ CF composites：The MnO that step (1) is obtained2/ CF composites are used as work electricity
In mixed solution (pH=6.7) of the pole immersion containing 2mM L-Trp, 0.1M pyrroles and 0.1mM KCl, in 0.8V constant potential bar
Electrochemical polymerization is carried out under part, polymerization time is 1000s, finally gives the PPy/MnO doped with L-Trp2/ CF composites.
The composite is immersed in 0.1M sulfuric acid solutions, applies 0.3V constant potentials 2000s on the composite to slough mould
Plate molecule obtains MIPPy/MnO2/CF.In order to avoid PPy oxidation peak for Electrochemical Detection influence, by MIPPy/MnO2/
CF is placed in 0.1M NaOH solution, and CV scannings are carried out in 0.45~1.2V potential range, bent until there is stable CV
Line, obtained material is designated as MIOPPy/MnO2/CF。
MIOPPy/MnO2/ CF and MIOPPy/CF electron microscope such as Fig. 1, shown in 2,3, it is found that MIOPPy can pass through electrochemistry
Technology is modified in CF and MnO2On/CF.
Embodiment two：
The preparation process of molecular engram polypyrrole/manganese dioxide/carbon felt composite material is identical with embodiment one.
By MIOPPy/MnO2/ CF composites rest on the 0.1M phosphate that 25mL includes 0.5mM L-Trp and D-Trp
30s in cushioning liquid (pH=4.5), then application -0.2V constant potential 400s is enriched with L-Trp and D- on the composite
Trp, after enrichment terminates, carries out DPV tests in the range of 0.45~1.2V (vs.SCE) electrochemistry, record Trp enantiomers
Electric current, then judges that molecular engram material is imitated for the identification of Trp enantiomers by comparing the difference of Trp enantiomer electric currents
Really.As a result such as Fig. 4, MIOPPy/MnO is as a result found2/ CF is 3.5, this explanation for the identification electric current ratio of Trp enantiomers
MIOPPy/MnO2/ CF has effective recognition effect for Trp enantiomers.
Comparative example one：
Prepare MIOPPy/MnO2/CF、MIOPPy/CF、NIOPPy/MnO2/ CF, compares the identification of its tryptophan enantiomer
Efficiency (as recognizes electric current ratio), as a result as shown in Fig. 3,4,5.NIOPPy/MnO2/ CF has extremely micro- for Trp enantiomers
Selectivity is not present in weak identification electric current ratio, the identification for being primarily due to NIOPPy for Trp enantiomers.MIOPPy modifications are existed
When on CF, DPV shows that the peak current ratio of L-type and D- type amino acid is 2.1；Work as MIOPPy/MnO2When modification is on CF,
DPV shows that the peak current ratio of L-type and D- type amino acid is 3.5.This is mainly due to：The process of synthetic molecules imprinted material
In, due to MnO2MIOPPy modification area can be increased, and trace cavity is with spatial selectivity for Trp enantiomers.
Therefore MIOPPy/pABSA/GCE has more preferable recognition effect for Trp enantiomers.
Beneficial effects of the present invention：The preparation cost of molecular engram overoxidised polypyrrole/manganese dioxide/carbon felt composite material
Low, preparation process is simple and environmentally-friendly.
Claims (3)
1. prepare molecular engram polypyrrole/manganese dioxide/carbon felt composite material, it is characterised in that：Step is as follows：
A, prepare manganese dioxide/carbon felt composite material：In hydrothermal reaction kettle, by carbon felt (1cm × 1cm) and 5mM KMnO4It is mixed
Close, after 4~6h of reaction under conditions of 150~170 DEG C, take out hydrothermal reaction kettle, be cooled to after room temperature, taking-up is loaded with
The carbon felt of manganese dioxide, is washed, and is dried；
B, prepare molecular engram polypyrrole/manganese dioxide/carbon felt composite material：The manganese dioxide/carbon felt that step a is obtained
(MnO2/ CF) composite as working electrode immerse the mixing containing 2mM L-Trps, 0.1M pyrroles and 0.1mM KCl it is molten
In liquid (pH=6~8), electrochemical polymerization is carried out under the conditions of 0.8V constant potential, polymerization time is 800~1200s, is mixed
Miscellaneous polypyrrole/the MnO for having a L-Trp2/ CF composites；The composite is immersed in 0.1M sulfuric acid solutions, compound
Apply 0.2~0.4V constant potentials 2000s on material and obtain molecular engram polypyrrole/MnO to slough template molecule2/CF；By molecule
Trace polypyrrole/MnO2/ CF is placed in 0.1M NaOH solution, and cyclic voltammetric is carried out in 0.45~1.2V potential range and is swept
Retouch, until there is stable cyclic voltammetry curve, obtained material is designated as MIOPPy/MnO2/CF。
2. molecular engram MIOPPy/MnO is prepared according to claim 12/ CF composites：It is characterized in that：In the step a
Reaction temperature is 160 DEG C, and the reaction time is 5h.
3. molecular engram MIOPPy/MnO is prepared according to claim 12/ CF composites：It is characterized in that：In the step b
The pH value of mixed solution is 6.7, and polymerization time is 1000s, and the current potential of removing template molecule is 0.3V.
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|---|---|---|---|
| CN201710315124.2A CN107121470B (en) | 2017-05-08 | 2017-05-08 | The preparation of molecular engram overoxidised polypyrrole/manganese dioxide/carbon felt composite material |
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| CN107121470A true CN107121470A (en) | 2017-09-01 |
| CN107121470B CN107121470B (en) | 2019-05-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108872339A (en) * | 2018-04-20 | 2018-11-23 | 常州大学 | A kind of molecular engram sodium alginate/manganese dioxide modified electrode preparation method for electrochemical recognition cysteine enantiomer |
| CN110596226A (en) * | 2019-11-18 | 2019-12-20 | 西北师范大学 | Construction method of molecularly imprinted Au nanoparticle chiral interface |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108872339A (en) * | 2018-04-20 | 2018-11-23 | 常州大学 | A kind of molecular engram sodium alginate/manganese dioxide modified electrode preparation method for electrochemical recognition cysteine enantiomer |
| CN108872339B (en) * | 2018-04-20 | 2020-05-26 | 常州大学 | Preparation method of molecularly imprinted sodium alginate/manganese dioxide modified electrode for electrochemically identifying cysteine enantiomer |
| CN110596226A (en) * | 2019-11-18 | 2019-12-20 | 西北师范大学 | Construction method of molecularly imprinted Au nanoparticle chiral interface |
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Effective date of registration: 20240104 Address after: 710000 Factory Building 5, South Zone 1, Hongshengxing Aviation Technology Industrial Park, Dunhua Road, Airport New City, Xixian New District, Xi'an City, Shaanxi Province Patentee after: Xi'an Meinan Biotechnology Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |