CN104833716B - Preparation method of estradiol magnetic molecularly imprinted nanoparticle electrochemical sensing membrane - Google Patents
Preparation method of estradiol magnetic molecularly imprinted nanoparticle electrochemical sensing membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of an estradiol magnetic molecularly imprinted nanoparticle electrochemical sensing membrane. According to the preparation method, an estradiol magnetic molecularly imprinted polymer is obtained via preparation of a molecularly imprinted self-assembled solution, polymerization, and template molecule elution. The estradiol magnetic molecularly imprinted nanoparticle electrochemical sensing membrane is high in selectivity, response speed, sensitivity, stability, tolerability, and universality, and is capable of realizing high efficiency, sensitive, real-time detection of estradiol in composite matrix.
Description
Technical field
The invention belongs to technical field of analysis and detection, and in particular to a kind of estradiol magnetic molecule marking nanoparticle electrochemistry
The preparation method of sensing membrane (MMIES).
Background technology
17- β estradiol (E2) as one of incretion interferent, there are some researches show children's sexual precocity, prostate cancer,
The rising of women breast cancer and uterus cancer morbidity is all relevant with the estrogen residual in food.Additionally, it can also influence women
Physiological law, result even in infertile.The other estradiol of trace level can just cause the imbalance of humoral immunity and cellular immunity,
Cause the lesion of immune reproduction, angiocarpy and nervous system.But due to the residual in estrogen production process and illegal addition
Etc. reason, occur the problems such as often result in environmental pollution and food security.In order to ensure consumers in general's healthy, specification
Food products market, it is very necessary and urgent problems to set up a quick estrogen detection method of reliability.
Electrochemical sensor is a kind of important electronic device, because its design is simple, sensitivity is high, cheap, can be real
The advantages of showing human body real-time detection, clinical diagnosis, environmental analysis, food analysis and Product checking needs can be met, increasingly receive
To the concern of people.Molecular imprinting is to prepare the technology with specific selectivity or single-minded selective polymerisation thing.It is most aobvious
Write three big features be：Structure imitates precordainment, specific recognition and broad applicability.Current magnetic molecule marking nano sensing film and
Estradiol correlative study has no report in Electrochemical Detection complex system.
Food, health products due to the complexity of self component, and additive types diversity and non-intellectual the problems such as,
The analysis detection for containing estradiol to it proposes requirement higher.The detection method of existing document report has：HPLC、LC-MS、
GC-MS etc..Although these traditional methods can also realize the measure to estradiol, often due to sample substrate is complicated and need
By cumbersome sample pre-treatments, this leverages the accuracy and agility of target analyte detection.Recently it is based on nano material
With the biology sensor and electrochemical sensor of nanometer technology because being led as popular research the characteristics of having quick, sensitive, stable
Domain.Particularly molecular imprinting electrochemical sensor (MIES) with high sensitivity and selectivity because turning into a kind of electricity of great prospect
Chemobionics sensor, has been widely used in identification and the Sensitive Detection of complex system microscratch amount object.MIES is often
Complicated electrode modification and electrochemical polymerization sensing membrane forming process is needed, is prepared and operating technology requirement is high, be unfavorable for promoting
And application.Although MIPs electropolymerizations sensing membrane can be repeatedly used, polishing electrode regeneration treatment time is long, electrode utilization rate
Low, electrode abrasion cause service life limited.In addition, MIPs structures have a significant effect to electrochemical response, excellent fax is built
Lead and played an important role to improving MIES detection sensitivities with the MIPs of catalysis activity.Therefore design and prepare electroactive structure
MIPs, research has the strong high sensitivity of universality and selectivity MIES by significance.
The content of the invention
It is an object of the invention to provide a kind of magnetic molecule marking nano sensing film for estrogen Electrochemical Detection
Preparation method, the method first construct by combined with electrochemical sensing technology, magnetic absorption technology, the advantage of molecular imprinting nanoparticle three
Magnetic molecule marking nano electrochemical sensing membrane with estradiol as representative, realizes fast to microscratch amount estradiol in complex matrices
Speed detection, this method measure sensitivity is high, strong to object selectivity, simple to operate, with good universality.
The purpose of the present invention can be reached by following measures：
A kind of estradiol magnetic molecule marking nanoparticle electrochemical sensing membrane preparation method, it is characterised in that the method includes
Following steps：
A) preparation of molecular imprinting self assembly solution：In Fe3O4E2- ethanol solutions, stirring are added in@Au-GSH nanoparticles
Reaction, aniline-HCl solution is added after the logical nitrogen deoxygenation of solution, and lucifuge stirs；
B) polymerisation：Initiator ammonium persulfate (APS), lucifuge stirring reaction are added in the solution that step a) is obtained；
C) eluted template molecule：The solution that step b) is obtained, Magnetic Isolation removal supernatant, washing, plus HCl- ethanol
Solution treatment, sloughs template molecule, obtains Fe3O4The magnetic molecularly imprinted nanoparticles of@Au-GSH-PANI (MMIPs)；
D) it is enriched with template molecule：Obtained MMIPs is placed in E2-PBS solution, stirring and adsorbing obtains E2-MMIPs；
E) Electrochemical Detection：Solution containing E2-MMIPs is placed in reaction tank, with magnetic glassy carbon electrode (MGCE) magnetic
Absorption 5min~1h so that electrode surface film forming.
In step a), the Fe per 5mg~20mg3O4@Au-GSH nanoparticles, add 5mL~50mL concentration ranges be
The E2- ethanol solutions of 1mmol/L~20mmol/L, the ethanol for being used is absolute ethyl alcohol, 1~20h of reaction time.Add benzene
The time for leading to nitrogen before amine-HCl solution is 1~50min.
In aniline-HCl solution, the volume range of aniline and HCl is 1：The concentration range of 10~20, HCl is
0.05mol/L~5mol/L.The acidity of solution increases, and electron transfer rate increase, protonation is strengthened, and is conducive to polyaniline
Synthesis, but acidity is excessive, can cause that Magnetic Isolation difficulty is increased, the MMIPs electric conductivities that finally obtain weaken.This experiment
In, the optimum molar concentration ratio of aniline and HCl is 1:2.5.
The reaction temperature of the whole process of step a) is 5~50 DEG C.
In step b), ammonium persulfate is added in the form of ammonium persulfate solution, often the Fe containing 5mg~20mg3O4@Au-
In the pre-assembled solution of molecular imprinting of GSH nanoparticles, add concentration range molten for the ammonium persulfate of 10mmol/L~500mmol/L
Liquid 0.1mL~5mL, polymerization reaction time is 2~20h, and reaction temperature is 0~50 DEG C.Polymerization time influences the effect of the marking, gathers
The conjunction time is too short, and the response of Ip is very weak, and polymerization reaction time is long, and E2 insertions are too deep, and the response of Ip can also reduce.This reality
Optimal polymerization reaction time in testing is 6h.
In step c), the concentration range of HCl- ethanol solutions is 0.05mol/L~2.0mol/L, and mixing time is 5min
~2h, can be processed under 5~50 DEG C of temperature conditionss.
In step d), the addition mass range of MMIPs is 5mg~50mg, and E2-PBS concentration is 0.01~2.0mol/
L, mixing time is 5min~5h.
Fe3O4The preparation of@Au-GSH nanoparticles includes preparing Fe3O4Magnetic nano particle, Fe3O4Surface meets NH2, prepare
Fe3O4@Au nanoparticles, linkage function group sulfydryl step.
Prepare Fe3O4Magnetic nano particle step is specific as follows：
Under nitrogen protection and magnetic agitation, by FeCl3·6H2O and FeCl2·4H2The mixed aqueous solution of O, is heated to
After 20-80 DEG C, NH is added dropwise over3·H2O reacts 20~60min, and Magnetic Isolation removes supernatant, collects reaction precipitate washing, obtains
Obtain Fe3O4Magnetic nano particle.Wherein, FeCl3·6H2O and FeCl2·4H2The mol ratio of O is 3:1~1:1, FeCl3·6H2O exists
The volumetric concentration of mixed aqueous solution is 0.05~0.1mmol/mL, and NH is added per 100-300ml mixed aqueous solutions3·H2The volume of O
Scope is 5mL~20mL.
In Fe3O4Surface meets NH2Step is specific as follows：Take Fe3O4Magnetic nano particle, adds APTES- ethanol solutions, temperature
It is 0~80 DEG C of stirring reaction 1-48h, Magnetic Isolation is gone supernatant, plus ethanol cleaning dissolving, obtains APTES parcels Fe3O4Nanometer
Grain.Wherein, the volume concentration range of APTES- ethanol is 0.1%~5%, per 5-20mgFe3O4The volume that magnetic nano particle is added
Scope is 5mL~20mL.
Prepare Fe3O4@Au nanoparticle steps are specific as follows：Take 1-100mg APTES parcels Fe3O4Nanoparticle, adds 0.1-
10mL volumetric concentrations are the HAuCl4 aqueous solution and 1.4-140mL redistilled waters of 1%-5%, after ultrasonic disperse, continue ultrasound
It is 2mmol/L~20mmol/L NaBH to add concentration range simultaneously4Until solution colour is changed into purple potato color and obtains from yellowish-brown
Fe3O4@Au nanoparticle solution, reaction temperature is 10~100 DEG C.Preparing Fe3O4In@Au nanoparticle steps, NaBH4In the reaction
Make reducing agent, gold ion is reduced into Jenner's grain of rice is wrapped in Fe3O4Surface, the NaBH of preparation4Solution concentration is unsuitable too high,
And rate of addition should slowly simultaneously ultrasonic disperse, reduction reaction can otherwise carried out rapidly, Jenner's grain of rice of generation can not be uniform
Be wrapped in Fe3O4Surface.
In above-mentioned Fe3O4In@Au nanoparticle solution, 0.5mL~30mL 5mmol/L~100mmol/L GSH, stirring are added
Reaction 1-48h, reaction temperature is 5~50 DEG C.Magnetic Isolation removes supernatant, washing, obtains Fe3O4@Au/GSH nanoparticles.Add
GSH can also be other amino acid containing sulfydryl (- SH), such as cysteine.
The preparation method of above-mentioned estradiol magnetic molecule marking nanoparticle electrochemical sensing film, specifically may include following step
Suddenly：
1st, the preparation of magnetic molecule marking nanoparticle electrochemical sensing film
A) Fe is prepared3O4Nanoparticle：Under nitrogen protection, FeCl is heated3·6H2O and FeCl2·4H2The mixing of O is water-soluble
Liquid, NH is added dropwise under conditions of being stirred vigorously3·H2O reacts, and reaction terminates rear Magnetic Isolation and goes supernatant, water washing and precipitating thing to obtain
Fe3O4Magnetic nano particle.
b)Fe3O4Surface meets-NH2：Take Fe3O4Nanoparticle, adds APTES- ethanol solutions, and stirring reaction, Magnetic Isolation is gone
Supernatant, plus ethanol cleaning dissolving, obtain APTES parcels Fe3O4Nanoparticle.
C) Fe is prepared3O4@Au nanoparticles：Take the APTES parcels Fe obtained in step b)3O4Nanoparticle, adds HAuCl4With
Appropriate redistilled water, ultrasonic disperse continues ultrasound and adds NaBH4 simultaneously until solution colour is changed into purple potato from yellowish-brown
Color；
D) linkage function group-sulfydryl：In the solution that step c) is obtained, GSH stirring reactions are added, Magnetic Isolation is gone
Supernatant, washing；Obtain Fe3O4@Au-GSH nanoparticles.
E) molecular imprinting self assembly solution：The Fe that will be obtained3O4E2- ethanol solutions, stirring are added in@Au-GSH nanoparticles
Reaction, aniline-HCl solution is added after the logical nitrogen deoxygenation of solution, and lucifuge stirs；
F) polymerisation：Initiator ammonium persulfate (APS), lucifuge stirring reaction are added in the solution that step e) is obtained；
G) eluted template molecule：The solution that step f) is obtained, Magnetic Isolation removal supernatant, washing, plus HCl- ethanol
Solution treatment, sloughs template molecule, obtains Fe3O4@Au-GSH-PANI magnetic molecule markings nanoparticle (MMIPs)；
H) it is enriched with template molecule：Obtained MMIPs is placed in E2-PBS solution, stirring and adsorbing obtains E2-MMIPs；
I) Electrochemical Detection：Solution containing E2-MMIPs in step h) is placed in reaction tank, magnetic glassy carbon electrode is used
(MGCE) magnetic absorption, carries out electrochemical gaging.
Magnetic control electrochemical sensing film of the present invention is detected by the following method：
Electrochemical detection method and condition：
Cyclic voltammetry (CV) method：Detection potential range is -0.2~0.6V, and sweep speed is 100mVs-1.Test bottom
Liquid is 0.1molL-1KCl and 1mmolL-1K3Fe(CN)6Solution.
Differential pulse method (DPV) method：Detection potential range is -0.2~0.8V, and sweep speed is 50mVs-1, current potential increasing
It is 0.005V to measure, and amplitude is 0.05V, and pulse width is 0.1s, and sampling width is 0.02s, and quiescent time is 2s.Electrode before test
Use Al2O3Powder polishing, ethanol, distilled water ultrasonic cleaning, nitrogen drying.Test bottom liquid is 0.05molL-1PBS(pH
7.0)-0.1mol·L-1KCl solution.
Sample determination：By taking the estradiol in determining milk powder as an example, certain milk powder powder 1g is weighed, dissolved with 20mL EtOH Sonicates
After 1h, 12000rpm centrifugation 5min take supernatant, are vacuum dried.Redissolved with 5mL ethanol after drying, take 0.5mL pH7.0 phosphorus
Phthalate buffer is diluted to 5mL, and MMIPs obtained in the method for embodiment 1 is placed in into stirring and adsorbing 30min in solution.MGCE is being obtained
After the E2-MMIPs solution surface magnetic absorptions 10min for arriving, using the concentration of estradiol in the DPV method determination samples in above-mentioned.
Magnetic molecule marking nanoparticle sensing membrane prepared by this method is used for estradiol electrochemical gaging, and its test limit (LOD) can reach
2.76×10-9mol·L-1(S/N=3), sensitivity is high, and it also has selectivity height, response quickly, stability and tolerance good
Good the features such as, it is capable of achieving efficient, the sensitive and real-time detection of estradiol in complex matrices.
The preparation process of the non-molecular imprinting nanoparticle electrochemical sensing film (MNIES) of magnetic：The non-molecular imprinting nanometer of magnetic
The preparation of grain electrochemical sensing film is exactly to be added without E2- ethanol solutions, and other steps are identical with embodiment.
The sign of MMIPs preparation process
1.UV-VIS
In UV-visible absorption spectrum, the absworption peak of Au NPs connects in 526nm with the 520nm in document report
Closely.And Fe3O4Compared with the absworption peak of Au NPs, there is obvious red shift in the absworption peak of@Au NPs, show Jenner in 560nm
The grain of rice is successfully wrapped in Fe3O4Surface.
2.FTIR
In infrared spectrogram, it can be observed that a series of Fe3O4@Au/GSH characteristic absorption peaks, 543cm-1It is Fe-O peaks,
637cm-1It is C-S peaks, 1084cm-1It is Si-O peaks, 1300cm-1It is C-N peaks, 1670cm-1It is the C=O in second amido link
Peak, the appearance of these characteristic peaks all shows Fe3O4@Au/GSH nanoparticles successfully synthesize.The characteristic peak of polyaniline exists
1593cm-1And 1502cm-1Place, is the C=C peaks on quinone and phenyl ring, and the appearance of the two characteristic peaks shows that polyaniline is smooth
Ground crosslinking is in Fe3O4The surface of@Au NPs.
3.SEM
Fe3O4The morphosis of@Au/GSH and MMIPs can be obtained by SEM.From Fig. 2A, system
Standby Fe3O4@Au/GSH NPs average grain diameters are within 200nm scopes.
4.MMIPs electrochemical Characterizations-each step cycle volt-ampere contrast
By above-mentioned CV methods, the MGCE to MMIPs modifications has carried out cyclic voltammetric sign.Compare Fig. 3 a curves and b curves, send out
The MGCE cyclic voltammetric current-responsives value now modified through MMIPs is raised, and CV area under the curves become big, because Fe3O4@Au nanoparticles
There is excellent electric conductivity with polyaniline, the speed of electro transfer is accelerated.Compare c curves and b curves, find E2-MMIPs
The MGCE cyclic voltammetric current-responsives value of modification declines, and CV area under the curves reduce, it may be possible to because template molecule occupies marking sky
Cave, hinders probe molecule K3[Fe(CN)6] redox reaction, cyclic voltammetric current-responsive value reduction.
The assessment of MMIPs absorption properties
1. Static Adsorption experiment
Fig. 4 A are MMIPs and MNIPs to 0.025 μm of Static Adsorption of ol/L~5mmol/L series estradiol-PBS solutions
Curve.MMIPs and MNIPs are placed in serial estradiol-PBS solution stirring and adsorbing 30min respectively, Ip is determined by above-mentioned DPV methods
Value.In MMIPs adsorption isothermal curves, with being continuously increased for template molecule E2 concentration, Ip values also gradually increase, when concentration is
2mmol·L-1When, absorption reaches balance, and Ip values no longer change, it is believed that now marking hole almost all is occupied by template molecule.
Show that MMIPs markings hole and active binding site have high affinity and special recognition capability to estradiol.And
In MNIPs absorption isotherms, due to not forming marking hole in MNIPs, Ip values are almost without significant change.
2. dynamic adsorption test
Fig. 4 B are MMIPs to 0.1 μm of Dynamic Adsorption curve of ol/L and 1 μm of ol/L estradiol.MMIPs is placed in 0.1 μ
Stirring and adsorbing in the estradiol-PBS solution of two kinds of concentration of mol/L and 1 μm of ol/L, takes when 5,10,20,30,40min
Go out, Ip values are determined by above-mentioned DPV methods.Curve is very fast in starting stage increase ratio, about tends to saturation in 30min.Even if estradiol
Initial concentration it is different, reach saturation state adsorbance essentially identical, it is seen that in film effective marking number of cavities be it is certain,
Further demonstrate the specific hole that estradiol is formd in MMIPs.
3. selective absorption experiment
Selective absorption experiment is the important indicator for investigating molecularly imprinted polymer marking effect and performance quality, is also to pass
Can sensor be applied to the premise of actual sample detection.Design interference is tested for investigating molecular imprinting effect, that is, study
Whether the marking hole of MMIPs has specific selectivity to template molecule, if do not disturbed by other competitive analogs.
Contrast experiment is carried out using oestrone, ethinylestradiol, estriol and estradiol in experiment.Respectively by MMIPs and
After MNIPs is placed in A, B, C, solution D stirring and adsorbing 30min, in 0.05molL-1PBS(pH 7.0)-0.1mol·L-1KCl is molten
DPV scanning analysis are carried out using DPV methods hereinbefore in liquid.Result shows that MNIPs-ES is responded to the oxidation current of A, B, C, D
Value is all very low, and MMIPs-ES is higher and close to the oxidation current response of A, B, C, D.Show in 10 times of concentration chaff interferences
In the presence of under conditions of, MMIPs is basically unchanged to the adsorbance of estradiol, that is, the MMIPs for preparing is to the absorption of estradiol not by female
The interference of ketone, estriol and ethinylestradiol, so that the MMIPs prepared in showing this experiment has the special of stabilization to estradiol
Property adsorption capacity.
A：0.1 μm of estradiol and 1 μm of ol/L oestrone-PBS solution B of ol/L：0.1 μm of estradiol and 1 μm of ol/L of ol/L
Ethinylestradiol-PBS solution C：0.1 μm of estradiol and 1 μm of ol/L estriol-PBS solution D of ol/L：0.1 μm female the two of ol/L
Alcohol-PBS solution.
Sample determination methodology
1. standard curve and test limit
Accurate compound concentration is 0.025 μm of ol L-1~10 μm of ol L-1Estradiol series standard liquid.Will be in optimal reality
After obtained MMIPs is respectively placed in and adsorbs 30min in the estradiol standard liquid of series concentration under the conditions of testing, by side described above
Method carries out DPV measure, and response peak current is with its concentration 2.5 × 10-8~5.0 × 10-7mol·L-1With 5.0 × 10-7~1.0 ×
10-5mol·L-1In the range of be in good linear relationship, equation of linear regression is respectively Ip1=0.08+1.08C (r=
0.902), Ip2=0.58+1.05C (r=0.980).Detection is limited to 2.76nmol/L, S/N=3.
The stability and reappearance of 2.MMIPs
5 parts of MMIPs are prepared with the method for embodiment 1, it is determined in 1 μm of olL-1Ip values after estradiol-PBS solution absorption,
RSD is 3.9%；Same electrode replication Ip value 5 times, RSD is 2.5%.Show MMIPs preparation methods stabilization, reappearance
It is good, and it is excellent to determine repeatability.
It is another MMIPs is preserved 10 days as 4 DEG C of refrigerator after, when its current-responsive is reduced to initial 91%, and oxidation potential
Profile with peak is not changed significantly.
3. actual sample analysis
The MMIPs obtained with the present embodiment 1 determines the estradiol in milk powder, certain milk powder powder 1g is weighed, with 10mL ethanol
After ultrasonic dissolution 1h, 12000rpm centrifugation 5min take supernatant, are vacuum dried.Redissolved with 1mL ethanol after drying, use pH7.0 phosphorus
Phthalate buffer is diluted to 5mL, and obtained MMIPs 10mg are placed in stirring and adsorbing 30min in solution under taking optimal experiment condition.
MGCE after the E2-MMIPs solution surface magnetic absorptions 10min for obtaining, using estradiol in the DPV method determination samples in above-mentioned
Concentration, as a result show that estradiol content in milk powder is 14.71ng/g.Basic, normal, high 3 concentration is added in milk powder respectively
Estradiol standard liquid, carry out average recovery experiment, concrete outcome is shown in Table 1.
The assay of estradiol in the milk powder of table 1
Beneficial effects of the present invention compared with the prior art：
1. the soft modification sensing membrane of the magnetic molecule marking is formed to E2-MMIPs induced by magnetic field by an assembling magnetic pole,
Electrode interface electrochemical response is completed through E2 detect, when taking out the magnetic core in electrode, sensing membrane disappears, and makes cumbersome electrode again
Treatment becomes very simple, with good automatically cleaning effect.
2. the controllable structure sensing membrane in external magnetic field is utilized, and the preparation of MMIES and use condition are gentle, at room temperature can be complete
Into.
3. soft modification sensing membrane of the invention, influences small to electrode surface, makes the sanding and polishing of electrode and cleaning process
It is greatly simplified, extends the service life of electrode.
4. Fe is based on3O4The E2-MMIPs that@Au-GSH@PANI build, with good molecule distinguishability and superior electricity
Chemical property.
5. the MMIPs for building can in batches be prepared and utilized with repetitive cycling, low cost.
6. the preparation of MMIPs of the present invention and the Selective Separation to sample analytes (are washed with the regeneration after enrichment and measure
Stripper plate) electrode is independent of, greatly improve electrode detection efficiency.
7. electrode of the invention is not required to complicated modification, and soft modification film forming and detection can be sequentially completed, simple to operate
And it is quick, personnel are easily mastered general analysis, with good universality.
8. the magnetic molecule marking nano electrochemical sensing membrane that prepared by the present invention has selectivity height, response quickly, sensitive
Degree is high, stability and better tolerance, the features such as universality is strong, be capable of achieving the efficient, sensitive and real-time of estradiol in complex matrices
Detection.
Brief description of the drawings
Fig. 1 is UV-visible absorption spectrum (UV-VIS) and FTIR spectrum figure (FT- in MMIPs preparation process
IR)
In figure, A is Au NPs and Fe3O4The UV-VIS of@Au/GSH
B is Fe3O4The FT-IR of@Au/GSH and MMIPs
Fig. 2 is the electron-microscope scanning figure (SEM) in MMIPs preparation process
In figure, A is Fe3O4@Au/GSH
B is MMIPs
Fig. 3 is each step cycle volt-ampere comparison diagram in MMIPs preparation process
In figure, a is the CV curves of naked-MGCE
B is the CV curves modified after MMIPs
C is the CV curves modified after E2-MMIPs
Fig. 4 is the absorption property evaluation figure of MMIPs
In figure, A is the adsorption isothermal curve figure of MMIPs and MNIPs
B is the dynamic adsorption curve map of MMIPs
C is the selective absorption figure of MMIPs and MNIPs, wherein (1) for 0.1 μm of ol/L estradiol and 1 μm of ol/L oestrone-
PBS solution (2) is 0.1 μm of ol/L estradiol and 1 μm of ol/L ethinylestradiols-PBS solution (3) is 0.1 μm of ol/L estradiol and 1
μm ol/L estriol-PBS solution (4) is 0.1 μm of ol/L estradiol-PBS solution.
Specific embodiment
Medicine and reagent：Estradiol (E2), estriol (E3), ethinyloestradiol (EE), estrone (E1) (Zhejiang celestial being jade pendant pharmacy
Co., Ltd), gold chloride (HAuCl4), glutathione (GSH) (West Asia reagent Co., Ltd), aniline, the ethoxy of 3- aminopropyls three
Base silane (APTES) (Shanghai Aladdin reagent Co., Ltd), experimental water is redistilled water, 0.05molL-1KH2PO4
And 0.05molL-1K2HPO4PBS (the phosphate buffered of solution pH 7.0
solution,PBS)。
Embodiment 1
The preparation of 1.1 magnetic molecules marking nanoparticle electrochemical sensing film (MMIES)
(1) Fe is prepared3O4@Au nanoparticles
Under nitrogen protection and magnetic agitation, 180mL FeCl containing 11.2mmol are added in 250mL flasks3·6H2O and
5.6mmol FeCl2·4H2The aqueous solution of O, after being heated to 50 DEG C, is added dropwise over 12.5mL NH3·H2O reacts 30min, magnetic
Supernatant is removed in separation, is collected reaction precipitate and is washed three times, obtains Fe3O4Magnetic nano particle.
Take 20mgFe3O4Magnetic nano particle, adds 10mL 1% (v/v) APTES- ethanol solutions, and reaction 12h is stirred at room temperature,
Magnetic Isolation goes supernatant, plus ethanol cleaning dissolving, obtains APTES parcels Fe3O4Nanoparticle.
Take obtained 12.5mg APTES parcels Fe3O4Nanoparticle, adds 2.5mL 1%HAuCl4 and 35mL second distillations
Water, after ultrasonic disperse, continues ultrasound and adds 10mL 10mmol/L NaBH simultaneously4Purple potato is changed into from yellowish-brown to solution colour
Color.
(2) linkage function group-sulfydryl
In Fe3O4In@Au nanoparticle solution, 2.2mL 100mmol/L GSH are added, reaction 24h, magnetic point is stirred at room temperature
Leave away supernatant, washing obtains Fe3O4@Au/GSH nanoparticles.
(3) the pre-assembled solution of molecular imprinting
Take 20mg Fe3O4@Au/GSH nanoparticles, it is the E2- ethanol solutions of 10mmol/L to add 22mL concentration, is stirred at room temperature
4h.Logical nitrogen 30min, adds 150 μ L aniline and 2mL 2mol/L HCl, room temperature lucifuge stirring 30min.
(4) polymerisation
In the pre-assembled solution of molecular imprinting, 1.0mL 200mmol/L ammonium persulfate APS are added, at room temperature lucifuge stirring
Reaction 6h.
(5) eluted template molecule
By the solution Magnetic Isolation after polymerisation, supernatant, alcohol is gone to wash, wash, plus 20mL 0.5mol/L HCl- second
Alcoholic solution stirs 20min, sloughs template molecule, obtains Fe3O4@Au/GSH-PANI magnetic molecule markings nanoparticle (MMIPs).
(6) it is enriched with template molecule
Take obtained MMIPs 10mg to be placed in E2-PBS (0.05mol/L pH7.0) solution, stirring and adsorbing 30min is obtained
To E2-MMIPs.
(7) Electrochemical Detection
Solution containing E2-MMIPs is placed in reaction tank, magnetic glassy carbon electrode (MGCE) uses Al2O3Powder is polished, ethanol,
Distilled water is cleaned by ultrasonic, and nitrogen drying, MGCE carries out electrochemical gaging in E2-MMIPs solution surface magnetic absorption 30min.
The preparation of the non-molecular imprinting nanoparticle electrochemical sensing film (MNIES) of 1.2 magnetic
E2- ethanol solutions are added without, other steps are identical with 1.1
Embodiment 2
The preparation of 1.1 magnetic molecules marking nanoparticle electrochemical sensing film (MMIES)
(1) Fe is prepared3O4@Au nanoparticles
Under nitrogen protection and magnetic agitation, 200mL FeCl containing 13.1mmol are added in 250mL flasks3·6H2O and
6.5mmol FeCl2·4H2The aqueous solution of O, after being heated to 50 DEG C, is added dropwise over 12.5mL NH3·H2O reacts 30min, magnetic
Supernatant is removed in separation, is collected reaction precipitate and is washed three times, obtains Fe3O4Magnetic nano particle.Take 25mgFe3O4Magnetic nano particle,
15mL 1% (v/v) APTES- ethanol solutions are added, reaction 15h is stirred at room temperature, Magnetic Isolation goes supernatant, plus ethanol to clean molten
Solution, obtains APTES parcels Fe3O4Nanoparticle.Take obtained 15mg APTES parcels Fe3O4Nanoparticle, adds 4mL 1%
HAuCl4 and 45mL redistilled waters, ultrasonic disperse continues ultrasound and adds 15mL10mmol/L NaBH simultaneously4Until solution face
Color is changed into purple potato color from yellowish-brown.
(2) linkage function group-sulfydryl
In Fe3O4In@Au nanoparticle solution, 3mL 100mmol/L GSH are added, reaction 30h, Magnetic Isolation is stirred at room temperature
Supernatant is removed, is washed, obtain Fe3O4@Au/GSH。
(3) molecular imprinting self assembly solution
Take 20mg Fe3O4@Au-GSH nanoparticles, it is the E2- ethanol solutions of 10mmol/L to add 30mL concentration, is stirred at room temperature
6h.Logical nitrogen 45min, adds 180 μ L aniline and 3mL 2mol/L HCl, room temperature lucifuge stirring 45min.
(4) polymerisation
In molecular imprinting self assembly solution, 2.0mL 200mmol/L ammonium persulfate APS are added, at room temperature lucifuge stirring
Reaction 10h.
(5) eluted template molecule
By the solution Magnetic Isolation after polymerisation, supernatant is removed, washed, plus 30mL 0.5mol/L HCl- ethanol solutions
Treatment 30min, sloughs template molecule, obtains Fe3O4The magnetic molecularly imprinted nanoparticles of@Au/GSH-PANI (MMIPs).
(6) it is enriched with template molecule：
Take obtained MMIPs 20mg to be placed in E2-PBS (0.05mol/L pH7.0) solution, stirring and adsorbing 45min is obtained
To E2-MMIPs.
(7) Electrochemical Detection
Solution containing E2-MMIPs is placed in reaction tank, magnetic glassy carbon electrode (MGCE) uses Al2O3Powder is polished, ethanol,
Distilled water is cleaned by ultrasonic, and nitrogen drying, MGCE carries out electrochemical gaging in solution surface magnetic absorption 45min.
The preparation of the non-molecular imprinting nanoparticle electrochemical sensing film (MNIES) of 1.2 magnetic
E2- ethanol solutions are added without, other steps are identical with 1.1
Embodiment 3
The preparation of 1.1 magnetic molecules marking nanoparticle electrochemical sensing film (MMIES)
(1) Fe is prepared3O4@Au nanoparticles
Under nitrogen protection and magnetic agitation, 150mL FeCl containing 10.2mmol are added in 250mL flasks3·6H2O and
4.9mmol FeCl2·4H2The aqueous solution of O, after being heated to 50 DEG C, is added dropwise over 10mL NH3·H2O reacts 30min, magnetic point
Leave away supernatant, collect reaction precipitate and wash three times, obtain Fe3O4Magnetic nano particle.Take 20mgFe3O4Magnetic nano particle, plus
Enter 8mL 1% (v/v) APTES- ethanol solutions, reaction 10h is stirred at room temperature, Magnetic Isolation removal supernatant, plus ethanol cleaning is molten
Solution, obtains APTES parcels Fe3O4Nanoparticle.Take the Fe of obtained 10.5mg APTES parcels3O4Nanoparticle, adds 2mL 1%
HAuCl4 and 30mL redistilled waters, ultrasonic disperse continues ultrasound and adds 8mL 10mmol/L NaBH simultaneously4Until solution face
Color is changed into purple potato color from yellowish-brown.
(2) linkage function group-sulfydryl
In Fe3O4In@Au nanoparticle solution, 1.8mL 100mmol/L GSH are added, reaction 20h, magnetic point is stirred at room temperature
Leave away supernatant, washing obtains Fe3O4@Au/GSH。
(3) molecular imprinting self assembly solution
Take 10mg Fe3O4@Au/GSH nanoparticles, it is the E2- ethanol solutions of 10mmol/L to add 18mL concentration, is stirred at room temperature
4h.Logical nitrogen 20min, adds 120 μ L aniline and 1.5mL 2mol/L HCl, room temperature lucifuge stirring 20min.
(4) polymerisation
In molecular imprinting self assembly solution, 1.0mL 200mmol/L ammonium persulfate APS are added, at room temperature lucifuge stirring
Reaction 8h.
(5) eluted template molecule
By the solution Magnetic Isolation after polymerisation, supernatant is removed, washed, plus 20mL 0.5mol/L HCl- ethanol solutions
Treatment 20min, sloughs template molecule, obtains Fe3O4The magnetic molecularly imprinted nanoparticles of@Au/GSH-PANI (MMIPs).
(6) it is enriched with template molecule
Take obtained MMIPs 15mg to be placed in E2-PBS (0.05mol/L pH7.0) solution, stirring and adsorbing 20min is obtained
To E2-MMIPs.
(7) Electrochemical Detection
Solution containing E2-MMIPs is placed in reaction tank, magnetic glassy carbon electrode (MGCE) uses Al2O3Powder is polished, ethanol,
Distilled water is cleaned by ultrasonic, and nitrogen drying, MGCE carries out electrochemical gaging in solution surface magnetic absorption 20min.
The preparation of the non-molecular imprinting nanoparticle electrochemical sensing film (MNIES) of 1.2 magnetic
E2- ethanol solutions are added without, other steps are identical with 1.1
Embodiment 4
The preparation of 1.1 magnetic molecules marking nanoparticle electrochemical sensing film (MMIES)
(1) Fe is prepared3O4@Au nanoparticles
Under nitrogen protection and magnetic agitation, 300mL FeCl containing 21mmol are added in 500mL flasks3·6H2O and
11mmol FeCl2·4H2The aqueous solution of O, after being heated to 50 DEG C, is added dropwise over 20mL NH3·H2O reacts 45min, magnetic point
Leave away supernatant, collect reaction precipitate and wash three times, obtain Fe3O4Magnetic nano particle.Take 50mgFe3O4Magnetic nano particle, plus
Enter 18mL 1% (v/v) APTES- ethanol solutions, reaction 24h is stirred at room temperature, Magnetic Isolation goes supernatant, plus ethanol to clean molten
Solution, obtains APTES parcels Fe3O4Nanoparticle.Take obtained 40mgAPTES parcels Fe3O4Nanoparticle, adds 5mL 1.5%
HAuCl4 and 60mL redistilled waters, ultrasonic disperse continues ultrasound and adds 15mL12mmol/L NaBH simultaneously4Until solution face
Color is changed into purple potato color from yellowish-brown.
(2) linkage function group-sulfydryl
In Fe3O4In@Au nanoparticle solution, 3.5mL 80mmol/L GSH are added, reaction 36h, Magnetic Isolation is stirred at room temperature
Supernatant is removed, is washed, obtain Fe3O4@Au/GSH。
(3) molecular imprinting self assembly solution
Take 15mg Fe3O4@Au/GSH nanoparticles, it is 8mmol/L E2- ethanol to add 35mL concentration, and 12h is stirred at room temperature.It is logical
Nitrogen 50min, adds 150 μ L aniline and 2mL 2mol/L HCl, room temperature lucifuge stirring 50min.
(4) polymerisation
In molecular imprinting self assembly solution, 2.0mL 200mmol/L ammonium persulfate APS are added, at room temperature lucifuge stirring
Reaction 12h.
(5) eluted template molecule
By the solution Magnetic Isolation after polymerisation, supernatant is removed, washed, plus at 30mL 1mol/L HCl- ethanol solutions
Reason 30min, sloughs template molecule, obtains Fe3O4The magnetic molecularly imprinted nanoparticles of@Au/GSH-PANI (MMIPs).
(6) it is enriched with template molecule
Take obtained MMIPs 25mg to be placed in the E2-PBS solution of 0.1mol/L, stirring and adsorbing 1h obtains E2-MMIPs.
(7) Electrochemical Detection
Solution containing E2-MMIPs is placed in reaction tank, magnetic glassy carbon electrode (MGCE) uses Al2O3Powder is polished, ethanol,
Distilled water is cleaned by ultrasonic, and nitrogen drying, MGCE carries out electrochemical gaging in solution surface magnetic absorption 45min.
Above-described embodiment electrochemical detection method and condition：
Cyclic voltammetry (CV) method：Detection potential range is -0.2~0.6V, and sweep speed is 100mVs-1.Test bottom
Liquid is 0.1molL-1KCl and 1mmolL-1K3Fe(CN)6Solution.
Differential pulse method (DPV) method：Detection potential range is -0.2~0.8V, and sweep speed is 50mVs-1, current potential increasing
It is 0.005V to measure, and amplitude is 0.05V, and pulse width is 0.1s, and sampling width is 0.02s, and quiescent time is 2s.Electrode before test
Use Al2O3Powder polishing, ethanol, distilled water ultrasonic cleaning, nitrogen drying.Test bottom liquid is 0.05molL-1PBS(pH
7.0)-0.1mol·L-1KCl solution.
Claims (9)
1. a kind of preparation method of estradiol magnetic molecule marking nanoparticle electrochemical sensing film, it is characterised in that the method includes
Following steps：
A) preparation of molecular imprinting self assembly solution：In Fe3O4Addition E2- ethanol solutions in@Au-GSH nanoparticles, stirring reaction,
Aniline-HCl solution is added after the logical nitrogen deoxygenation of solution, lucifuge stirs；
B) polymerisation：Initiator ammonium persulfate, lucifuge stirring reaction are added in the solution that step a) is obtained；
C) eluted template molecule：The solution that step b) is obtained, Magnetic Isolation removal supernatant, washing, plus HCl- ethanol solutions
Treatment, sloughs template molecule, obtains Fe3O4The magnetic molecularly imprinted nanoparticles of@Au-GSH-PANI；
D) it is enriched with template molecule：By obtained Fe3O4The magnetic molecularly imprinted nanoparticles of@Au-GSH-PANI are placed in E2-PBS solution
In, stirring and adsorbing obtains E2-MMIPs；
E) Electrochemical Detection：To be placed in reaction tank containing the solution of E2-MMIPs, with magnetic glassy carbon electrode magnetic absorption 5min~
1h so that electrode surface film forming；
Fe3O4The preparation of@Au-GSH nanoparticles includes preparing Fe3O4Magnetic nano particle, Fe3O4Surface meets NH2, prepare Fe3O4@Au
Nanoparticle, linkage function group sulfydryl step；
Prepare Fe3O4Magnetic nano particle step is specific as follows：
Under nitrogen protection and magnetic agitation, by FeCl3·6H2O and FeCl2·4H2The mixed aqueous solution of O, is heated to 20-80 DEG C
Afterwards, it is added dropwise over NH3·H2O reacts 20~60min, and Magnetic Isolation removes supernatant, collects reaction precipitate washing, obtains Fe3O4
Magnetic nano particle；Wherein, FeCl3·6H2O and FeCl2·4H2The mol ratio of O is 3:1~1:1, FeCl3·6H2O is in mixing water
The volumetric concentration of solution is 0.05~0.1mmol/mL, and NH is added per 100-300ml mixed aqueous solutions3·H2The volume range of O is
5mL~20mL；
In Fe3O4Surface meets NH2Step is specific as follows：Take Fe3O4Magnetic nano particle, add APTES- ethanol solutions, temperature be 0~
80 DEG C of stirring reaction 1-48h, Magnetic Isolation goes supernatant, plus ethanol cleaning dissolving, obtains APTES parcels Fe3O4Nanoparticle；Its
In, the volume concentration range of APTES- ethanol is 0.1%~5%, per 5-20mgFe3O4The volume range that magnetic nano particle is added
It is 5mL~20mL；
Prepare Fe3O4@Au nanoparticle steps are specific as follows：Take 1-100mg APTES parcels Fe3O4Nanoparticle, adds 0.1-10mL
Volumetric concentration is the HAuCl of 1%-5%4The aqueous solution and 1.4-140mL redistilled waters, after ultrasonic disperse, continue ultrasound simultaneously
Addition concentration range is 2mmol/L~20mmol/L NaBH4Until solution colour is changed into purple potato color and obtains Fe from yellowish-brown3O4@
Au nanoparticle solution, reaction temperature is 10~100 DEG C；In above-mentioned Fe3O4In@Au nanoparticle solution, 0.5mL~30mL is added
5mmol/L~100mmol/L GSH, stirring reaction 1-48h, reaction temperature are 5~50 DEG C；Magnetic Isolation removes supernatant, washing,
Obtain Fe3O4@Au-GSH nanoparticles.
2. the preparation method of estradiol magnetic molecule marking nanoparticle electrochemical sensing film according to claim 1, it is special
It is the Fe per 5mg~20mg in step a) to levy3O4@Au-GSH nanoparticles, it is 1mmol/ to add 5mL~50mL concentration ranges
The E2- ethanol solutions of L~20mmol/L, 1~20h of reaction time.
3. the preparation method of estradiol magnetic molecule marking nanoparticle electrochemical sensing film according to claim 1, it is special
Levy is that in step a), the time for adding aniline-HCl solution to lead to nitrogen is 1~50min.
4. the preparation method of estradiol magnetic molecule marking nanoparticle electrochemical sensing film according to claim 1, it is special
Levy is that in step a), the volume range of aniline and HCl is 1：The concentration range of 10~20, HCl be 0.05mol/L~
5mol/L。
5. the preparation method of estradiol magnetic molecule marking nanoparticle electrochemical sensing film according to claim 1, it is special
Levy is that in step a), the reaction temperature of whole process is 5~50 DEG C.
6. the preparation method of estradiol magnetic molecule marking nanoparticle electrochemical sensing film according to claim 1, it is special
It is the every Fe containing 5mg~20mg in step b) to levy3O4In the pre-assembled solution of molecular imprinting of@Au-GSH nanoparticles, add
Concentration range is the ammonium persulfate solution 0.1mL~5mL of 10mmol/L~500mmol/L.
7. the preparation method of estradiol magnetic molecule marking nanoparticle electrochemical sensing film according to claim 1, it is special
It is that in step b), polymerization reaction time is 2~20h to levy, and reaction temperature is 0~50 DEG C.
8. the preparation method of estradiol magnetic molecule marking nanoparticle electrochemical sensing film according to claim 1, it is special
It is that in step c), the concentration range of HCl- ethanol solutions is 0.05mol/L~2.0mol/L to levy, process time be 5min~
2h。
9. the preparation method of estradiol magnetic molecule marking nanoparticle electrochemical sensing film according to claim 1, it is special
Levy is that in step d), the concentration of E2-PBS is 0.01~2.0mol/L, and mixing time is 5min~5h.
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| CN102323323A (en) * | 2011-07-12 | 2012-01-18 | 南京医科大学 | Preparation method for 17 beta-estradiol molecular imprinting film electrochemical sensor |
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| CN102323323A (en) * | 2011-07-12 | 2012-01-18 | 南京医科大学 | Preparation method for 17 beta-estradiol molecular imprinting film electrochemical sensor |
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