CN105277603B - A kind of high ferro haematoporphyrin material, preparation and application for wrapping up gold nanoparticle - Google Patents
A kind of high ferro haematoporphyrin material, preparation and application for wrapping up gold nanoparticle Download PDFInfo
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- CN105277603B CN105277603B CN201410308786.3A CN201410308786A CN105277603B CN 105277603 B CN105277603 B CN 105277603B CN 201410308786 A CN201410308786 A CN 201410308786A CN 105277603 B CN105277603 B CN 105277603B
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- gold nanoparticle
- pei
- parcel
- haematoporphyrin
- hemin
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Abstract
The invention discloses a kind of new material containing bionic enzyme, this material use PEI synthesizes gold nanoparticle, PEI is a kind of to be rich in imido grpup and amido, the electropositive polymer of good water solubility, it can be coordinated with the gold ion in gold chloride, the gold nanoparticle of uniform particle diameter and stabilization is prepared using the reproducibility of PEI branched-aminos.Further, since containing amino in PEI molecules, amido link easily is formed with Hemin, so as to being connected to Hemin molecules on the PEI containing gold nanoparticle, by centrifuging and isolating and purifying, obtains a kind of high ferro haematoporphyrin biomimetic material for wrapping up gold nanoparticle.This new material not only has the high catalytic performance of bionic enzyme; electrochemical probe detection water pollutant content can be used as; such as hydrogen peroxide; catechol etc.; on the other hand, the cavernous structure due to material in itself, can be to dye molecule; such as methyl orange, rhodamine is adsorbed, and is preserved the ecological environment.
Description
Technical field
The invention belongs to bioassay technique field, and in particular to a kind of biomimetic material, preparation and its application, particularly one
Material, preparation and application of the kind to the detection of hydrogen peroxide high sensitivity.
Background technology
The research and development of nanometer technology provides more wide application space for nano material, focuses mainly on receiving at present
In terms of rice material fixing biological molecules.In numerous nano materials, gold nanoparticle is imitated with its good stability, small size
Should, skin effect, optical effect and the features such as special biological affine effect, become optics, electronics, catalysis, biology
The research of medicine etc. and using hot spot.In terms of electrochemistry, the sensor selectivity prepared using gold nanoparticle is strong, surely
Qualitative good and operating method is easy.Gold nano grain specific surface area is big, and surface free energy is high, and enzyme can obtain strong on its surface
Fixation, easy to leak, aurosol do not have biocompatibility, and good conductivity well, can be transmitted between enzyme and electrode
Electronics, significantly improves the response sensitivity of enzyme electrode.In terms of biological medicine, gold nano grain can be applied to immunochemistry,
DNA is identified and detection, is applied to gene therapy as carrier.Further, since gold nanoparticle has big specific surface area and good
Good biocompatibility, can be combined with small-molecule drug or large biological molecule, therefore Jenner's grain of rice of biological functional
Sub- application field is constantly widened, for example, gold nanoparticle, which is combined the functionalization material prepared with polyethyleneimine, can improve DNA's
Binding ability, so as to promote transfection [Englert, the C. of DNA in vivo；Tauhardt,L.；Hartlieb,M.；Kempe,K.；
Gottschaldt,M.；Schubert,U.S.Biomacromolecules2014,15.1124-1131.].Polyethyleneimine
(Polyethyleneimine, PEI) be it is a kind of be rich in imido grpup and amido, the electropositive polymer of good water solubility, be commonly used for
The preparation of gold colloid or its composite material.Polyamine macromolecule a large amount of amino because intramolecular contains, can be with metallic ion coordination and steady
These fixed metal ions, are widely used in the synthesis and modification of nano-particle.Using PEI in terms of gold nanoparticle is synthesized
The characteristics such as the biocompatibility of advantage and gold nanoparticle, can be by the gold nanoparticle material of PEI functionalization and large biological molecule
With reference to so as to prepare novel bionic material.At present, it is to utilize PEI parcel gold nanoparticle material connections SiRNA, paint mostly
[Song, the W.J. such as enzyme, protein；Du,J.Z.；Sun,T.M.；Zhang,P.Z.；Wang,J.Small2010,6.239-
246.Brondani,D.；de Souza,B.；Souza,B.S.；Neves,A.；Vieira,I.C.Biosensors&
Bioelectronics2013,42.242-247.], and there is not been reported for the combination of PEI parcel gold nano-materials and bionic enzyme.
High ferro haematoporphyrin (Hemin) is the activated centre of horseradish peroxidase, has the good catalytic activity of enzyme, is
A kind of typical bionic enzyme.Hemin has nitrogen, oxygen, nitric oxide, carbon dioxide and peroxide etc. high catalytic
Can, still, due to lacking suitable biomimetic environment, its catalytic activity is significantly less than native enzyme.Gold nano grain specific surface area is big,
Good biocompatibility, and electric conductivity is high, the electron transport rate of hemin can be largely improved, so as to strengthen its catalysis
Performance.Further, since PEI contains a large amount of amino, the PEI materials for wrapping up gold nanoparticle are connected by amido link with Hemin
Afterwards, the material of formation is provided with the absorption property of PEI at the same time, so, this material can have concurrently at the same time Hemin catalytic performance and
The absorption property of PEI.
The content of the invention
Based on above-mentioned background, the object of the present invention is to provide a kind of polyethyleneimine (PEI) parcel gold nanoparticle connection
Biomimetic material, preparation and its application of Hemin.The material has the absorption of the catalytic performance and PEI of Hemin to pollutant at the same time
Performance, thus have more wide application in terms of electrochemistry and water pollutant removal.
Realizing the technical solution of the object of the invention is：A kind of high ferro haematoporphyrin material for wrapping up gold nanoparticle, institute
It is as follows to state material structure：
A kind of preparation method for the high ferro haematoporphyrin material for wrapping up gold nanoparticle, comprises the following steps：
Step 1: prepare the gold nanoparticle material (PEI-AuNPs) of polyethyleneimine parcel；
Step 2: taking above-mentioned PEI-AuNPs materials, 1h is mixed with the Hemin aqueous solutions of 0.1mmol/L, prepares bag
Wrap up in high ferro haematoporphyrin material (PEI-AuNPs-Hemin) mixed solution of gold nanoparticle；
Step 3: by PEI-AuNPs-Hemin mixed solution high speed centrifugations, after, supernatant is removed, with ultrapure washing
Wash.
PEI-AuNPs described in step 1 is prepared by following steps：At room temperature, polyethyleneimine is added to
In the chlorauric acid solution of 1mmol/L, mixed solution is stirred and heated to 80 DEG C, keeps certain time to solution to present shallow ruby red
Color, stops heating and stirring, cools down at room temperature afterwards, wherein, the volume ratio of polyethyleneimine and gold chloride is 1:30~1:
5, preferably 1:10, stir speed (S.S.) is 200~700rpm, preferably 400rpm, and the retention time is 5~30min, preferably 20min.
The ratio between volume of PEI-AuNPs materials and Hemin described in step 2 is 1:1-1:5, preferably 1:3.
Centrifugation rate described in step 3 is 8000~12000rpm, preferably 10000rpm.
Above-mentioned PEI-AuNPs-Hemin nano materials are used to prepare the high sensor of detection hydrogen peroxide.
Inventive principle：Branched PEI be it is a kind of be rich in imido grpup and amido, the electropositive polymer of good water solubility, can and chlorine
Gold ion in auric acid is coordinated and stablizes gold ion, and uniform particle diameter and stabilization is prepared using the reproducibility of PEI branched-aminos
Gold nanoparticle.Because the amino that contains in PEI molecules easily forms amido link with Hemin, thus by Hemin molecules be connected to containing
On the PEI of gold nanoparticle, by centrifuging and isolating and purifying, PEI-AuNPs-Hemin biomimetic materials are obtained.
Beneficial effects of the present invention are：
1st, effective reducing agents and stabilizer of the PEI as gold nanoparticle, the gold nanometer particle grain size being prepared are small
And homogeneity is good.
2nd, PEI contains amino, can form amido link with Hemin, so as to connect on Hemin to PEI-AuNPs, formation it is new
Type biomimetic material stability is good.
3rd, gold nanoparticle specific surface area is big, good biocompatibility, good conductivity, thus electronics can be promoted in Hemin and
Electron transmission between electrode, so as to improve the catalytic efficiency of bionic enzyme.
4th, the novel nano-material prepared contains cavernous structure, can be used to adsorb environmental contaminants, practicality is good.
5th, the biomimetic material of preparation is modified in the biomimetic sensor on electrode, being prepared, because of depositing for gold nanoparticle
A good electron transmission environment is being provided to Hemin, so as to improve the detection sensitivity of sensor.Additionally, due to
The stability of PEI-AuNPs-Hemin materials, when modifying on electrode, its biomimetic environment is not easy to be destroyed, so as to improve sensing
The stability of device.
Brief description of the drawings
Fig. 1 is that (a is Fourier's infrared light for the phenogram of PEI-AuNPs-Hemin materials that in the present invention prepared by embodiment 7
Spectrogram, b are scanning electron microscope (SEM) photograph).
Fig. 2 is the nanometer material modified electrode prepared in the present invention in bare glassy carbon electrode and embodiment 3, embodiment 7 to mistake
The catalytic effect of hydrogen oxide.
Fig. 3 be the embodiment of the present invention 7 prepare PEI-AuNPs-Hemin materials applications when sensor, to hydrogen peroxide
Differential pulse voltammetry figure (a) and the linear relationship chart (b) of concentration and electric current.
Embodiment
The present invention is using PEI parcel gold nanoparticles and connects the PEI-AuNPs-Hemin nano materials of Hemin preparations,
Preparation process is simple, stablizes.And be experimentally confirmed, the biomimetic sensor prepared using this nano material has hydrogen peroxide
Fabulous catalytic effect and higher detection sensitivity.
Embodiment 1：Prepare the gold nanoparticle material (PEI-AuNPs) of polyethyleneimine parcel：At room temperature, by polyethylene
Imines is added in the chlorauric acid solution of 1mmol/L, mixed solution is stirred and heated to 80 DEG C, holding certain time to solution is in
Existing shallow ruby red, stops heating and stirring, cools down at room temperature afterwards.Wherein, the volume ratio of polyethyleneimine and gold chloride
For 1:30, stir speed (S.S.) 200rpm, retention time 5min.
Embodiment 2：Prepare the gold nanoparticle material (PEI-AuNPs) of polyethyleneimine parcel：At room temperature, by polyethylene
Imines is added in the chlorauric acid solution of 1mmol/L, mixed solution is stirred and heated to 80 DEG C, holding certain time to solution is in
Existing shallow ruby red, stops heating and stirring, cools down at room temperature afterwards.Wherein, the volume ratio of polyethyleneimine and gold chloride
For 1:5, stir speed (S.S.) 700rpm, retention time 30min.
Embodiment 3：Prepare the gold nanoparticle material (PEI-AuNPs) of polyethyleneimine parcel：At room temperature, by polyethylene
Imines is added in the chlorauric acid solution of 1mmol/L, mixed solution is stirred and heated to 80 DEG C, holding certain time to solution is in
Existing shallow ruby red, stops heating and stirring, cools down at room temperature afterwards.Wherein, the volume ratio of polyethyleneimine and gold chloride
For 1:10, stir speed (S.S.) 400rpm, retention time 20min.
Embodiment 4：Prepare the polyethyleneimine bionic enzyme material (PEI-AuNPs-Hemin) of parcel gold nanoparticle：Take
PEI-AuNPs colloidal sols prepared by embodiment 3, are mixed 1h with the Hemin aqueous solutions of 0.1mmol/L, prepare parcel gold nano
High ferro haematoporphyrin material (PEI-AuNPs-Hemin) mixed solution of particle, by PEI-AuNPs-Hemin mixed solutions at a high speed from
The heart, after, supernatant is removed, uses milli-Q water.Wherein, the volume ratio of PEI-AuNPs and Hemin solution is 1:1, centrifugation
Speed is 8000rpm.
Embodiment 5：Prepare the polyethyleneimine bionic enzyme material (PEI-AuNPs-Hemin) of parcel gold nanoparticle：Take
PEI-AuNPs colloidal sols prepared by embodiment 3, are mixed 1h with the Hemin aqueous solutions of 0.1mmol/L, prepare parcel gold nano
High ferro haematoporphyrin material (PEI-AuNPs-Hemin) mixed solution of particle, by PEI-AuNPs-Hemin mixed solutions at a high speed from
The heart, after, supernatant is removed, uses milli-Q water.Wherein, the volume ratio of PEI-AuNPs and Hemin solution is 1:5, centrifugation
Speed is 12000rpm.
Embodiment 6：Prepare the polyethyleneimine bionic enzyme material (PEI-AuNPs-Hemin) of parcel gold nanoparticle：Take
PEI-AuNPs colloidal sols prepared by embodiment 3, are mixed 1h with the Hemin aqueous solutions of 0.1mmol/L, prepare parcel gold nano
High ferro haematoporphyrin material (PEI-AuNPs-Hemin) mixed solution of particle, by PEI-AuNPs-Hemin mixed solutions at a high speed from
The heart, after, supernatant is removed, uses milli-Q water.Wherein, the volume ratio of PEI-AuNPs and Hemin solution is 1:3, centrifugation
Speed is 10000rpm.
Embodiment 7：PEI-AuNPs-Hemin materials prepared by Example 6 are dissolved in methanol solution, prepare 0.4mg/mL
PEI-AuNPs-Hemin solution.
Embodiment 8：PEI-AuNPs-Hemin materials prepared by embodiment 7 by Fourier infrared spectrograph (Fig. 1 a) and
Scanning electron microscope (Fig. 1 b) and characterized.The peak at 1649.5cm-1 is the characteristic peak of secondary amide in fig 1 a, illustrates PEI-
AuNPs and Hemin forms being stably connected with for amido link, can be seen that PEI-AuNPs-Hemin contains hole for one kind by Fig. 1 b
The nano material of shape structure.
Application examples 1：Using the glass-carbon electrode of diameter 3mm, electrode is polishing to mirror in 0.05 μm of aluminum oxide suspension
Face, then the ultrasound 2min in second alcohol and water, nitrogen are spare after drying up respectively.1,2,3, No. 4 clean electrode will be handled to distinguish
Carry out different modifying：No. 1 electrode is not modified；PEI-AuNPs nano materials prepared by No. 2 electrode modification embodiments 3；No. 3 electrodes
Modify PEI-AuNPs-Hemin biomimetic materials prepared by embodiment 7；No. 4 electrode modification Hemin (modification amount is 4 μ L).Pass through
Cyclic voltammetry detect different modifying electrode pair hydrogen peroxide catalytic effect, by 1-4 electrodes be respectively placed in containing
In the PBS solution of 0.1mmol/L hydrogen peroxide, using three-electrode system, setting sweep speed is 0.1V/s, scanning current potential from-
0.8~0.3V.By cyclic voltammogram it can be seen that (Fig. 2), No. 1 and No. 2 electrode pair hydrogen peroxide do not have catalytic action, but work as
After electrode modification Hemin, it has hydrogen peroxide obvious catalytic action, contrasts No. 4 electrodes, and No. 3 electrodes are shown more preferably
Catalytic effect, illustrate that catalysis of the gold nanoparticle to Hemin provides a good electronics transfer environment, so as to improve
The catalytic efficiency of sensor.
Application examples 2：Biomimetic sensor to the catalytic efficiency of hydrogen peroxide, the present invention by differential pulse voltammetry (DPV),
Study catalytic performance of this novel sensor to hydrogen peroxide.DPV is a kind of electrochemical means of detection in higher sensitivity, can
The detection substrate in the case where concentration is relatively low.Reference electrode is done using calomel electrode, platinum electrode is done to electrode, modifies embodiment
The work three-electrode system of electrode of the electrode of the 7 PEI-AuNPs-Hemin materials prepared is detected hydrogen peroxide, sets
Current potential is 0.25V, and in the case where 500rpm is stirred, initial sample-adding is 5 μm of ol/L, is obtained by way of gradient concentration dropwise addition
The DPV curves of hydrogen peroxide.Experiment shows, in the range of 1 μm of ol/L-0.25mmol/L of concentration of hydrogen peroxide, itself and catalysis are electric
Intensity of flow is linearly related：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：By being made in traditional potassium permanganate detection method and the present invention
The content of hydrogen peroxide in standby two kinds of means detection serum of sensor.Sensor uses PEI-AuNPs- prepared by embodiment 7
The modification of Hemin materials is in glassy carbon electrode surface, as can be seen from Table 1 for actual sample, the sensor of the invention prepared
It is very nearly the same with potassium permanganate detection, illustrate that PEI-AuNPs-Hemin biomimetic sensors can be advantageously applied to actual sample
The detection of middle hydrogen peroxide.
The Analysis of test results of hydrogen peroxide in 1 actual sample of table
Claims (7)
1. a kind of preparation method for the high ferro haematoporphyrin material for wrapping up gold nanoparticle, it is characterised in that comprise the following steps：
Step 1: the gold nanoparticle material of polyethyleneimine parcel is prepared, wherein, the gold nanoparticle of polyethyleneimine parcel
Material is prepared by following steps：At room temperature, polyethyleneimine is added in the chlorauric acid solution of 1mmol/L, will mixed molten
Liquid is stirred and heated to 80 DEG C, keeps certain time to solution that shallow ruby red is presented, stops heating and stirring afterwards, at room temperature
Cooling, wherein, the volume ratio of polyethyleneimine and gold chloride is 1:30~1:5, stir speed (S.S.) is 200~700rpm, during holding
Between be 5~30min；
Step 2: taking above-mentioned material, 1h is mixed with the Hemin aqueous solutions of 0.1mmol/L, prepares parcel gold nanoparticle
High ferro haematoporphyrin material mixed solution, wherein, the ratio between the gold nanoparticle material of polyethyleneimine parcel and the volume of Hemin are
1：1~1：5；
Step 3: by above-mentioned mixed solution high speed centrifugation, after, supernatant is removed, with milli-Q water, centrifugation rate is
8000~12000rpm.
2. the preparation method of the high ferro haematoporphyrin material of parcel gold nanoparticle according to claim 1, it is characterised in that
The volume ratio of polyethyleneimine and gold chloride is 1 in step 1:10, stir speed (S.S.) 400rpm, retention time 20min.
3. the preparation method of the high ferro haematoporphyrin material of parcel gold nanoparticle according to claim 1, it is characterised in that
The ratio between the gold nanoparticle material of polyethyleneimine parcel described in step 2 and the volume of Hemin are 1:3.
4. the preparation method of the high ferro haematoporphyrin material of parcel gold nanoparticle according to claim 1, it is characterised in that
Centrifugation rate described in step 3 is 10000rpm.
5. the high ferro haematoporphyrin material of parcel gold nanoparticle prepared by the preparation method as described in claim 1-4 is any.
6. the high ferro haematoporphyrin materials application of the parcel gold nanoparticle prepared by any preparation methods of claim 1-4
In the high sensitivity detection to hydrogen peroxide.
7. the high ferro haematoporphyrin material of parcel gold nanoparticle according to claim 6 is applied to as electrode modified material
The high sensitivity of hydrogen peroxide is detected.
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| 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 |
| 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 |
| 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 |
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