CN106053571A - Preparation and application of ionic liquid based polymerization liposome-gold nano-particle compound - Google Patents
Preparation and application of ionic liquid based polymerization liposome-gold nano-particle compound Download PDFInfo
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Abstract
The invention discloses an ionic liquid based polymerization liposome-gold nano-particle compound. A method for preparing the ionic liquid based polymerization liposome-gold nano-particle compound includes carrying out reaction by the aid of 2-methylimidazole and bromo-11-carbene to prepare ionic liquid based liposome monomers; carrying out self-assembly on the ionic liquid based liposome monomers in aqueous solution to prepare ionic liquid based liposomes, and preparing ionic liquid based polymerization liposomes from the ionic liquid based liposomes by the aid of thermal initiation processes; further carrying out ion exchange and in-situ reduction to obtain the ionic liquid based polymerization liposome-gold nano-particle compound. The ionic liquid based polymerization liposome-gold nano-particle compound and the method have the advantages that the ionic liquid based polymerization liposome-gold nano-particle compound and horseradish peroxidase are further compounded with each other to prepare HRP (horseradish peroxidase)/Polysome-Au/PVA (polyvinyl alcohol)/GC modified electrodes, accordingly, electrons can be directly transported between active centers of the horseradish peroxidase and the surfaces of the electrodes, oxygen, hydrogen peroxide and sodium nitrite can be electrically electrolyzed by the aid of properties of the ionic liquid based polymerization liposome-gold nano-particle compound, the ionic liquid based polymerization liposome-gold nano-particle compound is wide in detection range, high in sensitivity and low in detection limit, and the like.
Description
Technical field
The invention belongs to enzyme electrochemical field, be specifically related to a kind of ionic liquid base polyester plastid-golden nanometer particle and be combined
The preparation of thing (Polysome-Au) and application.
Background technology
Current mode enzyme electrochemical sensor refers to the electron transmission of enzyme active center and electrode surface, but in the activity of enzyme
The heart is buried inside polypeptide chain, it is difficult to realize electron transmission, it is therefore desirable to the electron transfer that mediator produces enzyme is to electricity
Surface, pole, strengthens electrode response.The development of enzyme electrochemica biological sensor includes the three below stage.
First generation enzyme sensor with oxygen as medium: such sensor is by detection H2O2Concentration change or O2's
Consumption measures the concentration of substrate.But this method also has shortcoming: is on the one hand affected by the concentration of dissolved oxygen and causes
The fluctuation of sensor response；On the other hand sensor is affected the biggest by temperature and pH.Therefore first generation enzyme electrode bio-sensing
Device has some limitations in application.
The second filial generation sensor of mediator based on synthetic: compared with first generation enzyme biologic sensor, second filial generation enzyme
The advantage of biosensor is: promotes the transmission speed of electronics, reduces work potential, improve sensitivity, expands electricity
The detection range of pole.Common electron mediator has: organic dye molecule, Ferrocene and its derivative, polymeric mordant amboceptor, ferrum
Cyanate, organic conductive salt etc..The introducing of these electron mediators enhances enzyme and interelectrode electron transmission.Also bring simultaneously
New problem: the mediator of addition easily produces the activity polluting, reducing enzyme to electrode, therefore can affect the performance of electrode.
The third generation sensor of direct electron transfer: third generation sensor need not introduce electron mediator, mainly enzyme
Active center and electrode surface between direct electron transfer so that the Direct Electrochemistry between minority enzyme and electrode becomes
May.Also eliminating the interference to electrode surface of other materials, this is the advantage that third generation sensor is maximum simultaneously.
The active center of some high molecular enzymes or protein is embedded by polypeptide chain, the adverse effect site or buried of formation
Active center be difficulty with the direct transmission of electronics, protein that only number molecular weight is less or enzyme and have suitably reaction
Site, just it is observed that directly the transmitting of electronics on electrode.Mainly with following several method realize between enzyme and electrode straight
Connect electron transmission: (1) adds accelerator, make between enzyme and accelerator by electrostatic interaction or formation hydrogen bond, the activity of ligase
Center and electrode surface, promote that electronics directly transmits.(2) form electron transfer mediators, shorten electric transmission distance.(3) by enzyme
It is carried on electrode surface.(4) enzyme is combined with conducting polymer.
Summary of the invention
It is an object of the present invention to provide a kind of ionic liquid base polyester plastid-golden nanometer particle complex (Polysome-Au)
Preparation and application, use the method for in-situ polymerization and in-situ reducing to prepare ionic liquid base polyester plastid-gold nano
Particle composite, modifies with horseradish peroxidase (HRP) compound preparation HRP/Polysome-Au/PVA/GC the most further
Electrode, it is achieved the direct electron transmission of the active center of enzyme and electrode surface, and utilize its performance to realize oxygen, hydrogen peroxide
(H2O2), sodium nitrite (NaNO2) electro-catalysis, there is the features such as detection range width, highly sensitive, detection limit is low.
The technical solution used in the present invention is:
Ionic liquid base polyester plastid-golden nanometer particle complex (Polysome-Au), preparation method is, first with
Ionic liquid base liposome monomer (lipid) is prepared in 2-methylimidazole and bromo-11-carbene reaction；Again by ionic liquid base
The self assembly in aqueous of liposome monomer is prepared as ionic liquid base liposome (liposome), utilizes thermal initiation method afterwards
Ionic liquid base liposome is prepared as ionic liquid base polyester plastid (Polysome)；Further exchanged by ion and
In-situ reducing prepares ionic liquid base polyester plastid-golden nanometer particle complex.
Described ionic liquid base polyester plastid-golden nanometer particle complex, preparation method specifically includes following steps:
(1) 2-methylimidazole, triethylamine, bromo-11-carbene are mixed in toluene, reacting by heating, filter afterwards, very
Sky is spin-dried for, recrystallization, obtains yellow-white powder, i.e. ionic liquid base liposome monomer (lipid)；
(2) take ionic liquid base liposome monomer (lipid) to be dissolved in deionized water, ultrasonic obtain clear transparent solutions A,
It is ionic liquid base liposome (liposome) solution；
(3) take ionic liquid base liposome (liposome) solution in two-mouth bottle, add potassium peroxydisulfate (K2S2O8),
Reaction temperature is to react 24h under 100 DEG C of nitrogen protections, obtains clear transparent solutions B and is ionic liquid base polyester plastid
(Polysome)；
(4) take ionic liquid base polyester plastid (Polysome) in sample bottle, drip gold chloride (HAuCl4), in room temperature
Lower vibration 12h, after reaction terminates, centrifugal, centrifugal product dilute is obtained solution A, backward solution A in drip sodium borohydride
(NaBH4) reducing agent reaction 2h, finally obtain ionic liquid base polyester plastid-golden nanometer particle complex.
Described ionic liquid base polyester plastid-golden nanometer particle complex, step 1) in 2-methylimidazole, triethylamine and
The molar ratio of bromo-11-carbene is 6.1:7.3:12.2.
Described ionic liquid base polyester plastid-golden nanometer particle complex, step (1) by 2-methylimidazole, triethylamine,
Bromo-11-carbene is mixed in toluene, after reacting 48h at 90 DEG C, and sucking filtration removing solid, solvent evaporated, with normal hexane repeatedly
Washing, with acetonitrile-ethyl acetate mixed solvent recrystallization after solvent evaporated, obtains yellow-white powder.
Described ionic liquid base polyester plastid-golden nanometer particle complex, the concentration of step (2) clear transparent solutions A
For 1-2mg/mL.
Described ionic liquid base polyester plastid-golden nanometer particle complex, potassium peroxydisulfate (K in step (3)2S2O8) and
The mol ratio of ionic liquid base liposome is 0.6:1.
Described ionic liquid base polyester plastid-golden nanometer particle complex, the gold chloride of reaction dropping in step (4)
HAuCl4Amount be 2mL, 0.02mol/L；The sodium borohydride NaBH that reaction adds4Amount be 4mL, 0.01mol/mL.
A kind of ionic liquid base polyester plastid-golden nanometer particle complex described above is being prepared on enzyme base modified electrode
Application.
Described application, described ionic liquid base polyester plastid-golden nanometer particle complex and horseradish peroxidase
(HRP) enzyme base modified electrode it is built into.
Described application, described enzyme base modified electrode can carry out electro-catalysis to oxygen, hydrogen peroxide and sodium nitrite.
The method have the advantages that
The present invention uses covalent bond effect preparation to have the ionic liquid base polyester matter of good biocompatibility and electric conductivity
Body (Polysome), has boundless application prospect in fields such as biosensor, Chemical Engineering and biological medicines, for
Realizing the nano-complexes such as ionic liquid base polyester plastid provides theoretical foundation in the further industrialization of medicine, chemical field.
This invention address that ionic liquid base polyester plastid-golden nanometer particle complex modified electrode is in electrochemical field
Technique study, and expanded the application of ionic liquid base polyester plastid further.Result shows, utilizes of the present invention
Method, to oxygen, hydrogen peroxide (H2O2), sodium nitrite (NaNO2) have good catalytic effect, embody detection range width,
The features such as highly sensitive, detection limit is low.Ionic liquid base liposome (liposome) and the pattern of complex thereof have been probed into simultaneously
Feature, surface nature and immanent structure.Ionic liquid have steam force down, conductivity height, electrochemical potentials window width, stronger
Many excellent physical and chemical performances such as solvability.Therefore at separating and extracting, catalyze and synthesize and the aspect such as electrochemical research has
Important application.Liposome has the chemical composition similar to cell membrane, has preferable biocompatibility and stability.From
Situ aggregation method is utilized to prepare ionic liquid base polyester plastid on the basis of sub-liquid base liposome (liposome)
(Polysome), recycling ion exchanges and local reduction way obtains ionic liquid base polyester plastid-golden nanometer particle and is combined
Thing (Polysome-Au), further immobilized horseradish peroxidase (HRP) builds enzyme base modified electrode.Therefore can be at this
On the basis of, inquire into the synthesis strategy of such material, property and the application in electrochemical field thereof.
The present invention utilizes 2-methylimidazole and bromo-11-carbene reaction to prepare ionic liquid base liposome monomer
(lipid), reaction equation is as follows:
Ionic liquid base liposome monomer self assembly in aqueous is prepared as ionic liquid base liposome (liposome),
Ionic liquid base liposome is prepared as ionic liquid base polyester plastid (Polysome) by the method utilizing thermal initiation afterwards, enters one
Step ion exchange and in-situ reducing prepare ionic liquid base polyester plastid-golden nanometer particle complex, and utilize himself
Biocompatibility and electric conductivity, build HRP/Polysome-Au/PVA/GC modified electrode with horseradish peroxidase HRP, it is achieved
Electric transmission between active center and the electrode surface of enzyme, utilizes modified electrode to oxygen, hydrogen peroxide (H simultaneously2O2), sub-
Sodium nitrate (NaNO2) there is good catalytic effect, it is achieved thereby that the practical value of modified electrode.
Accompanying drawing explanation
Liposome monomer synthesis schematic diagram in Fig. 1 embodiment 1.
The nucleus magnetic hydrogen spectrum figure of liposome monomer in Fig. 2 embodiment 1.
The infrared absorpting light spectra of liposome monomer in Fig. 3 embodiment 1.
The TEM figure of Polysome-Au in Fig. 4 embodiment 3.
In Fig. 5 embodiment 3 a be HRP/Polysome-Au, b be the uv-visible absorption spectra figure of HRP.
In Fig. 6 embodiment 3 a be HRP/Polysome-Au, b be the infrared absorpting light spectra of HRP.
In Fig. 7 embodiment 5, HRP/Polysome-Au/PVA/GC modified electrode is at N2Saturated phosphate buffer solution PBS
Cyclic voltammogram in (pH 7.0).Sweep speed: 200mV/s.
In Fig. 8 a embodiment 5, (A) HRP/Polysome-Au/PVA/GC modified electrode is at N2Saturated PBS (pH 7.0)
In, sweep speed cyclic voltammetry curve figure of (a → j) from 50mV/s to 500mV/s.
Peak current and the linear relationship chart sweeping speed in Fig. 8 b embodiment 5.
In Fig. 9 embodiment 6, HRP/Polysome-Au/PVA/GC modified electrode is in PBS (pH 7.0), contains: (a)
The cyclic voltammetry curve (sweeping speed: 200mV/s) of 0mL, (b) 5mL, (c) 10mL, (d) 15mL, (e) 20mL oxygen.
In Figure 10 a embodiment 6, HRP/Polysome-Au/PVA/GC modified electrode is at N2In saturated PBS (pH 7.0),
To H2O2Catalytic cycle volt-ampere curve figure (sweeping speed: 200mV/s)；Containing H2O2Concentration respectively: 0.00 μM (a), 327.16
μM (b), 1127.16 μMs (c), 2127.16 μMs (d), 3827.16 μMs (e), 5427.16 μMs (f).
Figure 10 b HRP/Polysome-Au/PVA/GC (a) and HRP/Polysome/PVA/GC (b) catalysis peak current with
H2O2Concentration correction curve chart.
In Figure 11 embodiment 6, HRP/Polysome-Au/PVA/GC modified electrode is at N2In saturated PBS (pH 7.0), right
H2O2The I-t curve of catalysis.
In Figure 12 a embodiment 6, HRP/Polysome-Au/PVA/GC modified electrode is at N2In saturated PBS (pH 5.7),
To NaNO2Catalytic cycle volt-ampere curve figure (sweeping speed: 200mV/s)；Containing NaNO2Concentration respectively: 0.00mM (a),
30.826mM (b), 162.826mM (c), 518.826mM (d), 1418.826mM (e).
Figure 12 b is catalysis peak current and NaNO2Concentration correction curve chart.
Detailed description of the invention
In order to be more fully understood that technical scheme, spy is described in further detail with specific embodiment, but side
Case is not limited to this.
Embodiment 1 (synthesis of ionic liquid base liposome monomer)
Take 50mL toluene in 100mL round-bottomed flask, be added thereto to 2-methylimidazole (6.1mmoL, 0.5000g), so
After add triethylamine (7.3mmoL, 1.017mL) and bromo-11-carbene (12.2mmoL, 2.66mL), 90 DEG C of reaction 48h, it
Rear sucking filtration removes amine salt solid, solvent evaporated, repeatedly washs with normal hexane, molten with acetonitrile-ethyl acetate mixing after solvent evaporated
Agent recrystallization, obtains yellow-white powder.The synthesis of liposome monomer is as shown in Figure 1.
Fig. 2 show the nucleus magnetic hydrogen spectrum figure of liposome monomer, and its nuclear magnetic resonance data is,1HNMR (deuterated methanol): δ=
(7.55 s, 2H), 5.81-5.76 (m, 2H), 4.95-4.89 (dd, 4H), 4.15-4.13 (t, 4H), 2.64 (s, 3H), 2.05-
2.01 (m, 4H), 1.85-1.81 (m, 4H), 1.37-1.31ppm (m, 24H), solvent peak is 4.90 and 3.30ppm.Can by Fig. 2
Knowing, result above is consistent with the structure of liposome monomer.
Fig. 3 is the infrared absorpting light spectra of liposome monomer, from the figure 3, it may be seen that 1191cm-1The C-H being attributed on imidazole ring
In-plane deformation vibration, 1372 and 1456cm-1It is attributed to C-H in-plane bending vibration, 1522cm-1It is attributed to imidazole ring C-N stretch
Vibration absorption peak, 1630cm-1It is attributed to carbon-carbon double bond stretching vibration peak, 3068cm-1It is attributed to C-H stretching vibration on imidazole ring
Absworption peak.Result above is consistent with the structure of liposome monomer.
Embodiment 2 (ionic liquid base liposome and the synthesis of polyester plastid)
Taking ionic liquid base liposome monomer 155.0mg to be dissolved in 100mL deionized water, ultrasonic to obtain clear molten
Liquid, is ionic liquid base liposome (liposome), and concentration is 1.55mg/mL, and liposome solutions is relatively stable, ambient temperatare
Put two weeks without sedimentation phenomenon.
Take liposome solution 25mL (0.1mmoL, 0.0388g) in two-mouth bottle, add 0.0150g (0.06mmoL) mistake
Potassium sulfate (K2S2O8), reaction temperature is to react 24h under 100 DEG C of nitrogen protections, obtains clear transparent solutions and is ionic liquid base
Polyester plastid (Polysome).
Embodiment 3 (synthesis of ionic liquid base polyester plastid-golden nanometer particle complex)
Take the Polysome 4mL of 1.55mg/mL in sample bottle, the gold chloride (HAuCl of dropping 0.02mol/L4) 2mL,
At room temperature vibrate 12h, after reaction terminates, is centrifuged 5min with 10000rpm and removes unnecessary HAuCl4, centrifugal product is added
Water is diluted to 2.0mg/mL, drips the sodium borohydride (NaBH of 0.01mol/mL afterwards4) 4mL reducing agent reaction 2h, finally obtain
The Polysome-Au solution of 1.0mg/mL.Fig. 4 is the TEM figure of Polysome-Au, and Polysome-Au is obvious as shown in Figure 4
Spherical morphology, size is about 200nm, simultaneously it is observed that tiny gold grain is uniformly adhered on Polysome.
The particle diameter of golden nanometer particle is less than 10nm, and this is the result of gold chloride in-situ reducing, and therefore also demonstrating Polysome has preferably
Stability can be as the substrate of nano-complex.Fig. 5 is the uv-visible absorption spectra of HRP/Polysome-Au and HRP
Figure, in curve b, HRP has ultraviolet characteristic absorption peak, the ultraviolet of HRP/Polysome-Au composite at 403nm as shown in Figure 5
Spectrum has absworption peak (curve a), the position phase occurred with the characteristic absorption peak of natural HRP that obvious Soret carries at 408nm
Closely.Illustrate that in enzyme electrode building process, the structure of HRP is not destroyed, and maintains its inherent structure.
Fig. 6 is the infrared absorpting light spectra of HRP/Polysome-Au and HRP, and b curve is it is observed that HRP as shown in Figure 6
At 1652cm-1And 1539cm-1Place is amide I band and the characteristic absorption peak of amide II band respectively, multiple from HRP/Polysome-Au
It is observed that the amide I band (1655cm of immobilized HRP on Polysome-Au in the infrared spectrogram a curve of compound-1) and
Amide II carries (1539cm-1) characteristic absorption peak, the characteristic absorption peak intrinsic with HRP is nearly identical, this demonstrate that immobilized
HRP on modified electrode maintains the secondary structure that it is intrinsic.
Embodiment 4 (preparation of ionic liquid base polyester plastid-golden nanometer particle complex modified electrode)
Take 3 μ L HRP/Polysome-Au complex (1.0mg/mL Polysome-Au and 10mg/mLHRP 2:1 mixes)
Drop coating, to the good electrode surface of pretreatment, covers with beaker and makes moisture slow evaporation under electrode, room temperature, so can be at electrode table
Face forms one layer of HRP/Polysome-Au thin film, and after drying at room temperature, drop coating 3% (polyvinyl alcohol) PVA 5 μ L, i.e. obtains HRP/
Polysome-Au/PVA/GC modified electrode.
Embodiment 5 (chemical property of ionic liquid base polyester plastid-golden nanometer particle complex)
If no special instructions, this experiment is all with 0.1M disodium hydrogen phosphate-sodium dihydrogen phosphate buffer (PBS, pH
7.0) as supporting electrolyte.Cyclic voltammetry experiment uses CHI 760E electrochemical workstation to carry out.All experiments all use
Three-electrode system, with HRP/Polysome-Au/PVA/GC modified electrode as working electrode, platinum electrode is to electrode, Ag/AgCl
(saturated KCl) electrode is reference electrode.All of electro-chemical test is all at room temperature to carry out, and the PBS taking 5.0mL before experiment delays
Dissolved liquid in electrolyzer, high pure nitrogen deoxygenation 30min, experimentation is always maintained at nitrogen atmosphere without specified otherwise.
Fig. 7 is that HRP/Polysome-Au/PVA/GC modified electrode is at N2The saturated cyclic voltammetric in PBS (pH 7.0)
Figure, sweeps speed: 200mV/s.As shown in Figure 7 in electric potential scanning scope 0.2～-0.8V, modified electrode HRP/Polysome-Au/
PVA/GC modified electrode oxidoreduction spike potential is-0.319V respectively ,-0.260V, and the potential difference (△ Ep) of electrode is 76mV.Oxygen
Changing reduction peak is due to oxidation-reduction pair (Fe in HRPIII/FeII) there occurs what Direct electron transfer produced at electrode surface,
Effective reduction peak current of HRP/Polysome-Au/PVA/GC modified electrode is 0.486 μ A, simultaneously HRP/Polysome-Au/
The Middle Eocene of PVA/GC is consistent with the HRP Middle Eocene under the similarity condition of report in document, and HRP/Polysome-Au has well
Biocompatibility and faster electric transmission speed, can be as preferable electrode material.
Fig. 8 a is that HRP/Polysome-Au/PVA/GC modified electrode is at N2In saturated PBS (pH 7.0), sweep speed from
The cyclic voltammetry curve figure of 50mV/s to 500mV/s (a → j)；Fig. 8 b is peak current and the linear relationship chart sweeping speed.Such as Fig. 8 a institute
Showing, with sweeping fast increase, oxidoreduction peak current constantly increases.In-0.8～0.2V potential range, peak current with sweep short-term training
Good linear relationship (such as Fig. 8 b), illustrates that electronics transmittance process between electrode surface and HRP is granule surface contral electrochemistry
Course of reaction.According to Faraday's law Q=nFA Γ *, (Q draws according to the integrated peak areas of reduction peak in cyclic voltammetry curve；n
For electron transfer number；F is Faraday constant 96485；A is the geometric area about 0.07cm of GC electrode2；Γ * is amount of surface coverage
mol·cm-2) it is estimated that electroactive HRP is about 4.28 × 10 in the coverage (Γ *) of electrode surface-11mol·cm-2。
This value is more than horseradish peroxidase in electrode surface monolayer theoretical coverage value (2.0 × 10-11mol·cm-2), it can be said that
Bright immobilized HRP on Polysome-Au there occurs that polyelectron layer shifts.
Embodiment 6 (the electrochemical catalysis performance of ionic liquid base polyester plastid-golden nanometer particle complex)
Fig. 9 is HRP/Polysome-Au/PVA/GC modified electrode catalytic cycle volt in PBS (pH 7.0), to oxygen
Peace curve chart (sweeping speed: 200mV/s)；Volume containing oxygen is respectively: 0ml (a), 5ml (b), 10ml (c), 15ml (d),
20ml (e), HRP/Polysome-Au/PVA/GC modified electrode only has a pair HRPFe as shown in the figureIII/FeIIElectricity to oxidation also
Parent peak.Gradually being passed through oxygen in PBS buffer solution, along with gradually the increasing of amount of the oxygen being passed through, oxidation peak current is gradually
Reduce, and reduction peak current is gradually increased, and illustrates that oxygen is had by HRP/Polysome-Au/PVA/GC modified electrode good simultaneously
Good electrochemical catalysis performance.
Figure 10 a is that HRP/Polysome-Au/PVA/GC modified electrode is at N2In saturated PBS (pH 7.0), to H2O2's
Catalytic cycle volt-ampere curve figure (sweeps speed: 200mV/s)；Containing H2O2Concentration respectively: 0.00 μM (a), 327.16 μMs (b),
1127.16 μMs (c), 2127.16 μMs (d), 3827.16 μMs (e), 5427.16 μMs (f)；Add in PBS buffer solution as seen from the figure
Enter H2O2After, occur in that an obvious reduction peak at about-0.30V, work as H2O2Amount when being gradually increased, reduction peak current is also
Along with being gradually increased, and oxidation peak current is progressively smaller until disappearance.HRP/Polysome-Au/PVA/GC modified electrode is described
To the H added in solution2O2There occurs typical catalytic reduction process.Illustrate modified electrode to be not only able to well and realize HRP's
Direct electron transfer, and monitored the HRP on electrode in real time to H in solution2O2Catalytic reduction process.
Figure 10 b is catalysis peak current and the H of HRP/Polysome-Au/PVA/GC modified electrode2O2Concentration correction curve chart.
Work as H as seen from the figure2O2Concentration 2.00 × 10-8Mol/L～2.13 × 10-3Mol/L and 2.13 × 10-3Mol/L～5.43 ×
10-3Time in the range of mol/L, concentration of substrate value and peak current present good linear relationship, and equation of linear regression is respectively y=
0.0019x+0.48 (R=0.99353) and y=8.97 × 10-4X+2.56 (R=0.99514), minimum detectability is 6.67 ×
10-3μM (S/N=3).According to the slope of curve alignment curve straight line portion, it is appreciated that HRP/Polysome-Au/PVA/GC
The sensitivity of modified electrode is respectively 27.00mA cm-2·M-1With 13.00mA cm-2·M-1.Illustrate, HRP/Polysome-
Au/PVA/GC modified electrode has wider detection range and higher sensitivity.
Figure 11 is that HRP/Polysome-Au/PVA/GC modified electrode is at N2In saturated PBS (pH 7.0), to H2O2Urge
The I-t curve changed.HRP/Polysome-Au/PVA/GC modified electrode is to H as shown in the figure2O2Catalysis I-t curve in, work
It is-0.62V as current potential.Work as H2O2Joining in the PBS buffer solution being stirred continuously, modified electrode response is very fast, but can
To find out the highly sensitive of HRP/Polysome-Au/PVA/GC modified electrode and attenuation process is relatively slow, Polysome-is described
Au has more preferable stability and sensitivity.Steady-state response electric current is along with the H added2O2The increase of concentration and increase, can be fast in 5s
Speed reaches steady-state current.
Figure 12 a is that HRP/Polysome-Au/PVA/GC modified electrode is at N2In saturated PBS (pH 5.7), to NaNO2's
Catalytic cycle volt-ampere curve figure (sweeps speed: 200mV/s)；Containing NaNO2Concentration respectively: 0.00mM (a), 30.826mM (b),
162.826mM (c), 518.826mM (d), 1418.826mM (e)；Understood the NaNO of variable concentrations by Figure 12 a2Solution adds
Time in PBS buffer solution electrolyte, the reduction peak of nitric acid occurs at about-0.8V, and along with NaNO2The continuous increasing of concentration
Adding, reduction peak current constantly increases, and the HRP/Polysome-Au/PVA/GC modified electrode NaNO to adding in solution is described2Send out
Give birth to typical catalytic reduction process.
Figure 12 b is catalysis peak current and NaNO2Concentration correction curve chart.NaNO is understood by Figure 12 b2Concentration is 2.00 × 10-6Becoming good linear relationship with catalysis peak current in the range of mol/L～1.42mol/L, equation of linear regression is y=0.021x
+ 5.85 (R=0.99618), x and y represent NaNO respectively2Concentration (mM) and reduction peak current (μ A), minimum detectability is 6.67
×10-4MM (S/N=3), can be obtained HRP/Polysome-Au/PVA/GC by the partial straight lines slope of calibration trace and modify electricity
The sensitivity of pole is 0.29mA cm-2·M-1。
Claims (10)
1. ionic liquid base polyester plastid-golden nanometer particle complex Polysome-Au, it is characterised in that preparation method is, first
Ionic liquid base liposome monomer lipid is prepared first with 2-methylimidazole and bromo-11-carbene reaction；Pass through ionic liquid again
Body base liposome monomer self assembly in aqueous is prepared as ionic liquid base liposome liposome, utilizes thermal initiation side afterwards
Ionic liquid base liposome is prepared as ionic liquid base polyester plastid Polysome by method；Further exchanged by ion and
In-situ reducing prepares ionic liquid base polyester plastid-golden nanometer particle complex.
2. ionic liquid base polyester plastid-golden nanometer particle complex as claimed in claim 1, it is characterised in that preparation side
Method specifically includes following steps:
(1) 2-methylimidazole, triethylamine, bromo-11-carbene being mixed in toluene, reacting by heating, filter afterwards, vacuum is revolved
Dry, recrystallization, obtain yellow-white powder, i.e. ionic liquid base liposome monomer；
(2) take ionic liquid base liposome monomer to be dissolved in deionized water, ultrasonic obtain clear transparent solutions A, be ionic liquid
Body base liposome solutions；
(3) take ionic liquid base liposome solutions in two-mouth bottle, add potassium peroxydisulfate K2S2O8, it is 100 DEG C of nitrogen in reaction temperature
React 24h under gas shielded, obtain clear transparent solutions B and be ionic liquid base polyester plastid；
(4) take ionic liquid base polyester plastid in sample bottle, drip gold chloride HAuCl4, at room temperature vibrate 12h, reaction knot
Shu Hou, centrifugal, centrifugal product dilute is obtained solution A, backward solution A in drip sodium borohydride NaBH4Reducing agent reacts
2h, finally obtains ionic liquid base polyester plastid-golden nanometer particle complex.
3. ionic liquid base polyester plastid-golden nanometer particle complex as claimed in claim 2, it is characterised in that step 1)
The molar ratio of middle 2-methylimidazole, triethylamine and bromo-11-carbene is 6.1:7.3:12.2.
4. ionic liquid base polyester plastid-golden nanometer particle complex as claimed in claim 2, it is characterised in that step (1)
2-methylimidazole, triethylamine, bromo-11-carbene being mixed in toluene, after reacting 48h at 90 DEG C, sucking filtration removes solid,
Solvent evaporated, repeatedly washs with normal hexane, with acetonitrile-ethyl acetate mixed solvent recrystallization after solvent evaporated, obtains yellow-white
Powder.
5. ionic liquid base polyester plastid-golden nanometer particle complex as claimed in claim 2, it is characterised in that step (2)
The concentration of clear transparent solutions A is 1-2mg/mL.
6. ionic liquid base polyester plastid-golden nanometer particle complex as claimed in claim 2, it is characterised in that step (3)
Middle potassium peroxydisulfate K2S2O8It is 0.6:1 with the mol ratio of ionic liquid base liposome.
7. ionic liquid base polyester plastid-golden nanometer particle complex as claimed in claim 2, it is characterised in that step (4)
The gold chloride HAuCl of middle reaction dropping4Amount be 2mL, 0.02mol/L；The sodium borohydride NaBH that reaction adds4Amount be 4mL,
0.01mol/mL。
8. ionic liquid base polyester plastid-golden nanometer particle complex as claimed in claim 1 is preparing the modification of enzyme base
Application on electrode.
Apply the most as claimed in claim 8, it is characterised in that described ionic liquid base polyester plastid-golden nanometer particle is combined
Thing and horseradish peroxidase HRP are built into enzyme base modified electrode.
Apply the most as claimed in claim 9, it is characterised in that described enzyme base modified electrode can be to oxygen, hydrogen peroxide and Asia
Sodium nitrate carries out electro-catalysis.
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| CN113960139A (en) * | 2021-07-13 | 2022-01-21 | 沈阳师范大学 | Novel modified electrode constructed by liposome-based glucose oxidase, preparation method and direct electrochemical application thereof |
| CN115201300A (en) * | 2022-05-16 | 2022-10-18 | 沈阳师范大学 | Preparation of polymeric ionic liquid-reduced graphene oxide composite material and application of composite material to horseradish peroxidase modified electrode |
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| CN113960139A (en) * | 2021-07-13 | 2022-01-21 | 沈阳师范大学 | Novel modified electrode constructed by liposome-based glucose oxidase, preparation method and direct electrochemical application thereof |
| CN115201300A (en) * | 2022-05-16 | 2022-10-18 | 沈阳师范大学 | Preparation of polymeric ionic liquid-reduced graphene oxide composite material and application of composite material to horseradish peroxidase modified electrode |
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