CN105277603A - Ferric hemoporphyrin material wrapping gold nanoparticle, preparation method and uses thereof - Google Patents
Ferric hemoporphyrin material wrapping gold nanoparticle, preparation method and uses thereof Download PDFInfo
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- CN105277603A CN105277603A CN201410308786.3A CN201410308786A CN105277603A CN 105277603 A CN105277603 A CN 105277603A CN 201410308786 A CN201410308786 A CN 201410308786A CN 105277603 A CN105277603 A CN 105277603A
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Abstract
The invention discloses a new material containing bionic enzyme. The material is used for preparing gold nanoparticles by using PEI which is an electropositive water-soluble polymer enriched with imino groups and amido groups, and can coordinate with gold ion in the auric chloride acid ; stable gold nanoparticles with uniform sizes are prepared by employing the reduction activity of the branched amino groups of the PEI; furthermore, the amino groups in the PEI are liable to form amide bonds with Hemins so that the Hemin molecules are connected with the PEI containing gold nanoparticles; ferric hemoporphyrin material wrapping gold nanoparticle is obtained through centrifugation and purification. The new materials have good catalytic performance of bionic enzyme, can serve as electrochemical probes to detect contaminant content in water, such as hydrogen peroxide, o-dihydroxybenzene, etc.; the new material can adsorb dye molecules such as methyl orange and rhodamine due to porous structure so that the ecological environment is protected.
Description
Technical field
The invention belongs to bioassay technique field, be specifically related to a kind of biomimetic material, preparation and application thereof, particularly a kind of material to hydrogen peroxide high-sensitivity detection, preparations and applicatio.
Background technology
The research and development of nanometer technology is that nano material provides more wide application space, mainly pays close attention to nano material fixing biological molecules aspect at present.In numerous nano materials, golden nanometer particle, with features such as its good stability, small-size effect, surface effect, optical effect and special biocompatible effects, becomes the investigation and application focus of the aspects such as optics, electronics, catalysis, biological medicine.In galvanochemistry, the sensor selectivity utilizing golden nanometer particle to prepare is strong, good stability and method of operating is easy.Gold nano grain specific surface area is large, and surface free energy is high, and enzyme can obtain strong fixing on its surface, not easy to leak, aurosol has biocompatibility well, and good conductivity, electronics can be transmitted between enzyme and electrode, significantly improve the response sensitivity of enzyme electrode.In biological medicine, gold nano grain can be applied to immunochemistry, DNA identifies and detect, and is applied to gene therapy as carrier.In addition, because golden nanometer particle has large specific surface area and good biocompatibility, can combine with small-molecule drug or biomacromolecule, therefore the golden nanometer particle application of biological functional is constantly widened, such as, golden nanometer particle is combined the binding ability that the functionalization material prepared can improve DNA with polyethyleneimine, thus promotes DNA transfection [Englert, C. in vivo; Tauhardt, L.; Hartlieb, M.; Kempe, K.; Gottschaldt, M.; Schubert, U.S.Biomacromolecules2014,15.1124-1131.].Polyethyleneimine (Polyethyleneimine, PEI) is a kind of electropositivity polymkeric substance being rich in imido grpup and amido, good water solubility, is often used to the preparation of gold colloid or its compound substance.Polyamine macromolecule because of in molecule containing a large amount of amino, these metallic ions can be stablized with metallic ion coordination, be widely used in synthesis and the modification of nano particle.Utilize the advantage of PEI in synthesis golden nanometer particle and the characteristic such as biocompatibility of golden nanometer particle, the golden nanometer particle material of PEI functionalization can be combined with biomacromolecule, thus Novel bionic material can be prepared.At present, be utilize PEI trapping gold nanometer particle material to connect [Song, the W.J. such as SiRNA, laccase, protein mostly; Du, J.Z.; Sun, T.M.; Zhang, P.Z.; Wang, J.Small2010,6.239-246.Brondani, D.; DeSouza, B.; Souza, B.S.; Neves, A.; Vieira, I.C.Biosensors & Bioelectronics2013,42.242-247.], and the combination of PEI trapping gold nano material and bionic enzyme there is not been reported.
Siderosis porphyrin (Hemin) is the activated centre of horseradish peroxidase, has the good catalytic activity of enzyme, is a kind of typical bionic enzyme.Hemin has high catalytic performance to nitrogen, oxygen, nitrogen monoxide, carbon dioxide and superoxide etc., but owing to lacking suitable biomimetic environment, its catalytic activity is significantly less than native enzyme.Gold nano grain specific surface area is large, good biocompatibility, and electric conductivity is high, can improve the electron transport rate of hemin to a great extent, thus strengthen its catalytic performance.In addition, because PEI contains a large amount of amino, after being connected with Hemin by amido link by the PEI material of trapping gold nano particle, the material of formation is provided with the absorption property of PEI simultaneously, so this material can have the catalytic performance of Hemin and the absorption property of PEI concurrently simultaneously.
Summary of the invention
Based on above-mentioned background, the object of this invention is to provide the biomimetic material of a kind of polyethyleneimine (PEI) trapping gold nano particle connection Hemin, preparation and application thereof.This material has the catalytic performance of Hemin and PEI to the absorption property of pollutant simultaneously, thus in galvanochemistry and water pollutant removal, has comparatively wide application.
The technical solution realizing the object of the invention is: a kind of siderosis porphyrin material of trapping gold nano particle, and described material structure is as follows:
A preparation method for the siderosis porphyrin material of trapping gold nano particle, comprises the following steps:
Step one, prepare polyethyleneimine parcel golden nanometer particle material (PEI-AuNPs);
Step 2, get above-mentioned PEI-AuNPs material, stir 1h with the Hemin aqueous solution of 0.1mmol/L, prepare siderosis porphyrin material (PEI-AuNPs-Hemin) mixed solution of trapping gold nano particle;
Step 3, by PEI-AuNPs-Hemin mixed solution high speed centrifugation, after terminating, removing supernatant, use milli-Q water.
PEI-AuNPs described in step one is prepared by following steps: under room temperature, is joined by polyethyleneimine in the chlorauric acid solution of 1mmol/L, mixed solution is stirred and heated to 80 DEG C, certain hour to solution is kept to present shallow ruby red, stop heating afterwards and stir, cooling under room temperature, wherein, the volume ratio of polyethyleneimine and gold chloride is 1:30 ~ 1:5, preferred 1:10, stir speed (S.S.) is 200 ~ 700rpm, preferred 400rpm, retention time is 5 ~ 30min, preferred 20min.
PEI-AuNPs material described in step 2 is 1:1-1:5 with the ratio of the volume of Hemin, preferred 1:3.
Centrifugation rate described in step 3 is 8000 ~ 12000rpm, preferred 10000rpm.
Above-mentioned PEI-AuNPs-Hemin nano material is for the preparation of the high sensor being detected hydrogen oxide.
Inventive principle: branching PEI is a kind of electropositivity polymkeric substance being rich in imido grpup and amido, good water solubility, can stablize gold ion, utilize the reductibility of PEI branched-amino prepare uniform particle diameter and stablize golden nanometer particle with the gold ion coordination in gold chloride.Because the amino contained in PEI molecule is easy and Hemin forms amido link, thus Hemin molecule is connected on the PEI containing golden nanometer particle, by centrifugal and separation and purification, obtains PEI-AuNPs-Hemin biomimetic material.
Beneficial effect of the present invention is:
1, PEI is as the effective reductive agent of golden nanometer particle and stabilizing agent, and the gold nanometer particle grain size prepared is little and homogeneity good.
2, PEI contains amino, can form amido link with Hemin, thus connects on Hemin to PEI-AuNPs, and the Novel bionic stability of material of formation is good.
3, golden nanometer particle specific surface area is large, good biocompatibility, good conductivity, so can promote the electron transmission of electronics between Hemin and electrode, thus improves the catalytic efficiency of bionic enzyme.
4, the novel nano-material of preparation contains cavernous structure, can be used to adsorb environmental contaminants, and practicality is good.
5, the biomimetic material of preparation is modified on electrode, the biomimetic sensor prepared, because of the existence of golden nanometer particle, provide a good electron transmission environment to Hemin, thus improve the detection sensitivity of sensor.In addition due to the stability of PEI-AuNPs-Hemin material, when modifying on electrode, its biomimetic environment is not easily destroyed, thus improves the stability of sensor.
Accompanying drawing explanation
Fig. 1 is the phenogram (a is FTIR spectrum figure, b is scanning electron microscope (SEM) photograph) of the PEI-AuNPs-Hemin material that in the present invention prepared by embodiment 7.
Fig. 2 is that the nanometer material modified electrode of preparation in naked glass-carbon electrode and embodiment 3 in the present invention, embodiment 7 is to the catalytic effect of hydrogen peroxide.
Fig. 3 be the PEI-AuNPs-Hemin materials application prepared of the embodiment of the present invention 7 when sensor, to the linear relationship chart (b) of differential pulse voltammetry figure (a) of hydrogen peroxide and concentration and electric current.
Embodiment
The present invention adopts PEI trapping gold nano particle and connects PEI-AuNPs-Hemin nano material prepared by Hemin, and preparation process is simple, stable.And prove by experiment, the biomimetic sensor utilizing this nano material to prepare has fabulous catalytic effect and higher detection sensitivity to hydrogen peroxide.
Embodiment 1: the golden nanometer particle material (PEI-AuNPs) preparing polyethyleneimine parcel: under room temperature, polyethyleneimine is joined in the chlorauric acid solution of 1mmol/L, mixed solution is stirred and heated to 80 DEG C, certain hour to solution is kept to present shallow ruby red, stop heating afterwards and stir, cooling under room temperature.Wherein, the volume ratio of polyethyleneimine and gold chloride is 1:30, and stir speed (S.S.) is 200rpm, and the retention time is 5min.
Embodiment 2: the golden nanometer particle material (PEI-AuNPs) preparing polyethyleneimine parcel: under room temperature, polyethyleneimine is joined in the chlorauric acid solution of 1mmol/L, mixed solution is stirred and heated to 80 DEG C, certain hour to solution is kept to present shallow ruby red, stop heating afterwards and stir, cooling under room temperature.Wherein, the volume ratio of polyethyleneimine and gold chloride is 1:5, and stir speed (S.S.) is 700rpm, and the retention time is 30min.
Embodiment 3: the golden nanometer particle material (PEI-AuNPs) preparing polyethyleneimine parcel: under room temperature, polyethyleneimine is joined in the chlorauric acid solution of 1mmol/L, mixed solution is stirred and heated to 80 DEG C, certain hour to solution is kept to present shallow ruby red, stop heating afterwards and stir, cooling under room temperature.Wherein, the volume ratio of polyethyleneimine and gold chloride is 1:10, and stir speed (S.S.) is 400rpm, and the retention time is 20min.
Embodiment 4: the polyethyleneimine bionic enzyme material (PEI-AuNPs-Hemin) preparing trapping gold nano particle: PEI-AuNPs colloidal sol prepared by Example 3,1h is stirred with the Hemin aqueous solution of 0.1mmol/L, prepare siderosis porphyrin material (PEI-AuNPs-Hemin) mixed solution of trapping gold nano particle, by PEI-AuNPs-Hemin mixed solution high speed centrifugation, after end, removing supernatant, uses milli-Q water.Wherein, the volume ratio of PEI-AuNPs and Hemin solution is 1:1, and centrifugation rate is 8000rpm.
Embodiment 5: the polyethyleneimine bionic enzyme material (PEI-AuNPs-Hemin) preparing trapping gold nano particle: PEI-AuNPs colloidal sol prepared by Example 3,1h is stirred with the Hemin aqueous solution of 0.1mmol/L, prepare siderosis porphyrin material (PEI-AuNPs-Hemin) mixed solution of trapping gold nano particle, by PEI-AuNPs-Hemin mixed solution high speed centrifugation, after end, removing supernatant, uses milli-Q water.Wherein, the volume ratio of PEI-AuNPs and Hemin solution is 1:5, and centrifugation rate is 12000rpm.
Embodiment 6: the polyethyleneimine bionic enzyme material (PEI-AuNPs-Hemin) preparing trapping gold nano particle: PEI-AuNPs colloidal sol prepared by Example 3,1h is stirred with the Hemin aqueous solution of 0.1mmol/L, prepare siderosis porphyrin material (PEI-AuNPs-Hemin) mixed solution of trapping gold nano particle, by PEI-AuNPs-Hemin mixed solution high speed centrifugation, after end, removing supernatant, uses milli-Q water.Wherein, the volume ratio of PEI-AuNPs and Hemin solution is 1:3, and centrifugation rate is 10000rpm.
Embodiment 7: PEI-AuNPs-Hemin material prepared by Example 6 is dissolved in methanol solution, the PEI-AuNPs-Hemin solution of preparation 0.4mg/mL.
Embodiment 8: (Fig. 1 a) and scanning electron microscope (Fig. 1 b) and characterizing by Fourier infrared spectrograph for the PEI-AuNPs-Hemin material prepared of embodiment 7.The peak at 1649.5cm-1 place is the characteristic peak of secondary amide in fig 1 a, illustrates that PEI-AuNPs and Hemin defines the stable connection of amido link, can find out that PEI-AuNPs-Hemin is a kind of nano material containing cavernous structure by Fig. 1 b.
Application examples 1: the glass-carbon electrode adopting diameter 3mm, polishes electrode to minute surface in the aluminum oxide suspension of 0.05 μm, then ultrasonic 2min in second alcohol and water respectively, and nitrogen dries up rear for subsequent use.1,2,3, No. 4 clean electrode of process is carried out different modifying respectively: No. 1 electrode is not modified; PEI-AuNPs nano material prepared by No. 2 electrode modification embodiments 3; PEI-AuNPs-Hemin biomimetic material prepared by No. 3 electrode modification embodiments 7; No. 4 electrode modification Hemin (modification amount is 4 μ L).The catalytic effect of different modifying electrode pair hydrogen peroxide is detected by cyclic voltammetry, 1-4 electrode is placed in the PBS solution containing 0.1mmol/L hydrogen peroxide respectively, adopt three-electrode system, arranging sweep speed is 0.1V/s, and scanning current potential is from-0.8 ~ 0.3V.Can be found out (Fig. 2) by cyclic voltammogram, No. 1 and No. 2 electrode pair hydrogen peroxide do not have catalytic action, but after electrode modification Hemin, it has obvious catalytic action to hydrogen peroxide, contrast No. 4 electrodes, No. 3 electrodes show better catalytic effect, illustrate that the catalysis of golden nanometer particle to Hemin provides a good electro transfer environment, thus improve the catalytic efficiency of sensor.
Application examples 2: biomimetic sensor is to the catalytic efficiency of hydrogen peroxide, and the present invention, by differential pulse voltammetry (DPV), studies the catalytic performance of this novel sensor to hydrogen peroxide.DPV is the higher a kind of electrochemical means of detection of sensitivity, can when concentration is lower detection substrate.Mercurous chloride electrode is adopted to do contrast electrode, platinum electrode is done electrode, modify the work three-electrode system of electrode of the electrode of PEI-AuNPs-Hemin material prepared by embodiment 7 to detect hydrogen peroxide, arranging current potential is 0.25V, when 500rpm stirs, initial application of sample is 5 μm of ol/L, and the mode dripped by gradient concentration obtains the DPV curve of hydrogen peroxide.Experiment shows, within the scope of concentration of hydrogen peroxide 1 μm of ol/L-0.25mmol/L, it is linearly relevant to catalytic current intensity: during S/N=3, i=0.744+24.5325c, R=0.998, detection sensitivity 0.347mA.mM
-1.cm
-2, detect and be limited to 0.2446nmol/L.
Application examples 3: the detection of hydrogen peroxide in actual sample: the content being detected hydrogen peroxide in serum by the sensor two kinds of means prepared in traditional potassium permanganate detection method and the present invention.The PEI-AuNPs-Hemin material that sensor adopts embodiment 7 to prepare is modified in glassy carbon electrode surface, as can be seen from Table 1 for actual sample, sensor prepared by the present invention and potassium permanganate detect very nearly the same, illustrate that PEI-AuNPs-Hemin biomimetic sensor can be advantageously applied to the detection of hydrogen peroxide in actual sample.
The Analysis of test results of hydrogen peroxide in table 1 actual sample
Claims (10)
1. a siderosis porphyrin material for trapping gold nano particle, it is characterized in that, described material structure is as follows:
2. a preparation method for the siderosis porphyrin material of trapping gold nano particle, is characterized in that, comprise the following steps:
Step one, prepare polyethyleneimine parcel golden nanometer particle material;
Step 2, get above-mentioned material, stir 1h with the Hemin aqueous solution of 0.1mmol/L, prepare the siderosis porphyrin material mixed solution of trapping gold nano particle;
Step 3, by above-mentioned mixed solution high speed centrifugation, after terminating, removing supernatant, use milli-Q water.
3. the preparation method of the siderosis porphyrin material of trapping gold nano particle according to claim 2, it is characterized in that, the golden nanometer particle material of the polyethyleneimine parcel described in step one is prepared by following steps: under room temperature, polyethyleneimine is joined in the chlorauric acid solution of 1mmol/L, mixed solution is stirred and heated to 80, DEG C keep certain hour to solution present shallow ruby red, stop heating afterwards and stir, cool under room temperature, wherein, the volume ratio of polyethyleneimine and gold chloride is 1:30 ~ 1:5, stir speed (S.S.) is 200 ~ 700rpm, retention time is 5 ~ 30min.
4. the preparation method of the siderosis porphyrin material of trapping gold nano particle according to claim 2, is characterized in that, in step one, the volume ratio of polyethyleneimine and gold chloride is 1:10, and stir speed (S.S.) is 400rpm, and the retention time is 20min.
5. the preparation method of the siderosis porphyrin material of trapping gold nano particle according to claim 2, is characterized in that, the golden nanometer particle material of the polyethyleneimine parcel described in step 2 is 1:1 ~ 1:5 with the ratio of the volume of Hemin.
6. the preparation method of the siderosis porphyrin material of trapping gold nano particle according to claim 2, is characterized in that, the golden nanometer particle material of the polyethyleneimine parcel described in step 2 is 1:3 with the ratio of the volume of Hemin.
7. the preparation method of the siderosis porphyrin material of trapping gold nano particle according to claim 2, is characterized in that, the centrifugation rate described in step 3 is 8000 ~ 12000rpm.
8. the preparation method of the siderosis porphyrin material of trapping gold nano particle according to claim 2, is characterized in that, the centrifugation rate described in step 3 is 10000rpm.
9. the siderosis porphyrin materials application of the trapping gold nano particle as described in as arbitrary in claim 1-8 is in the high-sensitivity detection to hydrogen peroxide.
10. the siderosis porphyrin material of trapping gold nano particle according to claim 9 is applied to high-sensitivity detection to hydrogen peroxide as electrode modified material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109613083A (en) * | 2018-12-11 | 2019-04-12 | 河南中医药大学 | Nanogold-highly sensitive detection the H of protoporphyrin copper (II)2O2The building and its application of electrochemical sensor |
| CN109613084A (en) * | 2018-12-11 | 2019-04-12 | 河南中医药大学 | Nanogold-highly sensitive detection the H of protoporphyrin zinc (II)2O2The building and application of electrochemical sensor |
| CN109613082A (en) * | 2018-12-11 | 2019-04-12 | 河南中医药大学 | The highly sensitive detection H of nanogold-cobalt protoporphyrin (II)2O2The building and application of electrochemical sensor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853784A (en) * | 2005-04-19 | 2006-11-01 | 中国科学院化学研究所 | Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst |
| CN101815673A (en) * | 2007-09-03 | 2010-08-25 | Dic株式会社 | Process for producing nanostructure composite covered structure, nanostructure composite covered structure, and reactor using the nanostructure composite covered structure |
| CN103849376A (en) * | 2014-03-20 | 2014-06-11 | 陇南师范高等专科学校 | Method of preparing porphyrin nanogold composite material with core-shell structure |
-
2014
- 2014-07-01 CN CN201410308786.3A patent/CN105277603B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853784A (en) * | 2005-04-19 | 2006-11-01 | 中国科学院化学研究所 | Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst |
| CN101815673A (en) * | 2007-09-03 | 2010-08-25 | Dic株式会社 | Process for producing nanostructure composite covered structure, nanostructure composite covered structure, and reactor using the nanostructure composite covered structure |
| CN103849376A (en) * | 2014-03-20 | 2014-06-11 | 陇南师范高等专科学校 | Method of preparing porphyrin nanogold composite material with core-shell structure |
Non-Patent Citations (4)
| Title |
|---|
| BAOZHEN WANG 等: "《A Facile Preparation of H2O2 Sensors Using Layer-by-Layer Deposited Thin Films Composed of Poly(ethyleneimine) and Carboxymethyl Cellulose as Matrices for Immobilizing Hemin》", 《ELECTROANALYSIS 20》 * |
| JINMING KONG 等: "《A biomimetic enzyme modified electrode for H2O2 highly sensitive detection》", 《ANALYST》 * |
| PEI JING 等: "《A sensitive electrochemical aptasensor based on palladium nanoparticles decorated graphene-molybdenum disulfide flower-like nanocomposites and enzymatic signal amplification》", 《ANALYTICA CHIMICA ACTA》 * |
| WEIWEN HU 等: "《Methyl Orange removal by a novel PEI-AuNPs-hemin nanocomposite》", 《SCIENCEDIRECT》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109613083A (en) * | 2018-12-11 | 2019-04-12 | 河南中医药大学 | Nanogold-highly sensitive detection the H of protoporphyrin copper (II)2O2The building and its application of electrochemical sensor |
| CN109613084A (en) * | 2018-12-11 | 2019-04-12 | 河南中医药大学 | Nanogold-highly sensitive detection the H of protoporphyrin zinc (II)2O2The building and application of electrochemical sensor |
| CN109613082A (en) * | 2018-12-11 | 2019-04-12 | 河南中医药大学 | The highly sensitive detection H of nanogold-cobalt protoporphyrin (II)2O2The building and application of electrochemical sensor |
| CN109613082B (en) * | 2018-12-11 | 2021-04-27 | 河南中医药大学 | High-sensitivity detection H of nano gold-protoporphyrin cobalt (II)2O2Construction and application of electrochemical sensor |
| CN109613084B (en) * | 2018-12-11 | 2021-04-27 | 河南中医药大学 | High-sensitivity detection H of nano gold-protoporphyrin zinc (II)2O2Construction and application of electrochemical sensor |
| CN109613083B (en) * | 2018-12-11 | 2021-05-25 | 河南中医药大学 | High-sensitivity detection H of nano gold-protoporphyrin copper (II)2O2Construction of electrochemical sensor and application thereof |
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