CN110231384A - A kind of 3D-rGO/Fe3O4The preparation method and application of-AuNPs/HP- β-CD composite material - Google Patents
A kind of 3D-rGO/Fe3O4The preparation method and application of-AuNPs/HP- β-CD composite material Download PDFInfo
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Abstract
The present invention provides a kind of 3D-rGO/Fe3O4The preparation method and application of-AuNPs/HP- β-CD composite material.The preparation of the composite material is to pass through Fe3O4(3D-rGO/Fe is made to three-dimensional grapheme surface with AuNPs and hydroxypropyl-β-cyclodextrin (HP- β-CD) modification3O4-AuNPs/HP-β-CD).It is fast that the material not only combines 3D-rGO large specific surface area, electron transport rate, Fe3O4The advantages that-AuNPs electro catalytic activity is high, molecule distinguishability also excellent with HP- β-CD confirm Fe by a series of characterizations3O4, AuNPs and HP- β-CD is successfully supported in three-dimensional grapheme structure, and modified glassy carbon electrode surface novel sensing platform is made and be used for detection while guanine and adenine.The result shows that guanine and adenine have obtained lower detection limit under the wider range of linearity, the sensitivity that modified electrode detects two kinds of purine is substantially increased.Sensor prepared by the present invention is also successfully used for detection while guanine and adenine in actual sample milt DNA.
Description
Technical field
The invention belongs to nanocomposites and Electrochemical Detection, and in particular to a kind of 3D-rGO/Fe3O4-AuNPs/HP-
The method that the preparation and its modification of β-CD nanocomposite detect guanine and adenine simultaneously to electrode surface.
Background technique
Guanine (G) and adenine (A) are two kinds of bases important in picodna (DNA) and nucleic acid (RNA).Purine is made
For biomolecule, except have the function of in cell Proliferation it is a variety of it is important in addition to, also with one kind during cell cracking, apoptosis etc.
Danger signal exists.The concentration of base in DNA, will affect the activity of enzyme, by changing normal purine metabolism approach, thus shadow
Immune system is rung, a variety of diseases such as fat and tumor recurrence are caused.Therefore, guanine in biological sample is accurately and efficiently detected
It is significant in bioscience and analytical chemistry field with the content of adenine.Electrochemistry is efficient with it, easy, quick
Advantage is widely used in always the detection of guanine and adenine for many years.
Traditional two-dimensional graphene based composites, although having big specific surface area and good electric conductivity etc.,
In terms of be widely used, but poorly water-soluble.And beta-cyclodextrin (β-CD) is due to close outside its intracavitary hydrophobic, chamber
The structure of water forms super molecular compound in conjunction with various guest molecules, adds its good hydrophilic property, Ke Yiti
The specific recognition and selectivity of high electrode.Therefore after two-dimensional graphene area load β-CD, not only increase it is water-soluble and
To the recognition capability of guest molecule, and chemical property is enhanced, but detection effect is not very significant.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology, provides a kind of 3D-rGO/Fe3O4-AuNPs/HP-β-CD
The method that the preparation and its modification of nano-complex detect guanine and adenine simultaneously to electrode surface, solves the prior art and deposits
The electrode detection range of linearity is narrow, electronics transfer impedance is big and the technical problems such as Monitoring lower-cut height.
The present invention is achieved by the following technical solutions:
A kind of 3D-rGO/Fe3O4The preparation method of-AuNPs/HP- β-CD nanocomposite, comprising the following steps:
1)Fe3O4The preparation of-AuNPs nanoparticle:
First by 49-51mg (preferably 50mg) Fe3O4It is added in 40-60mL (preferably 50mL) ultrapure water, ultrasonic disperse
Afterwards, in N2170-190 μ L (preferably 180 μ L) 3- aminopropyl triethoxysilane (APTES) is added under atmosphere, it is mechanical at room temperature
It stirs 6-8h (preferably 7h), black precipitate ultrapure water and ethyl alcohol wash the simultaneously last vacuum drying of magnetic hysteresis separation repeatedly, obtain ammonia
The Fe of base3O4(Fe3O4-NH2)；Then 19-21mg (preferably 20mg) Fe is taken3O4-NH2It is (excellent that powder ultrasonic is dispersed in 15-25mL
Select 20mL) in ultrapure water, 39-41mg (preferably 40mg) gold nanoparticle (AuNPs) powder is added, 2-4h is stirred at room temperature (preferably
3h), washing and magnetic hysteresis separation repeatedly, 50 DEG C of vacuum drying 7-9h (preferably 8h) are to get to Fe3O4-AuNPs；
2)3D-rGO/Fe3O4The preparation of-AuNPs nano material:
First by graphene oxide (GO) (40mg/20mL) ultrasonication 15-25min (preferably 20min), under ultrasonic dissolution
75-85mg (preferably 80mg) L-cysteine (L-Cys) is added, is rapidly added 550-650 μ L (preferably 600 μ L) ammonium hydroxide, is placed in
It in conical flask, is heated in 95 DEG C of oil bath, reacts 3-5h (preferably 4h), finally filter, be freeze-dried to obtain three-dimensional grapheme
(3D-rGO) black solid powder；3D-rGO 29-31mg (preferably 30mg) obtained is taken again, and ultrasonic disperse is (excellent in 20-40mL
Select 30mg) in water, Fe obtained in 29-31mg (preferably 30mg) step 1) is added3O42-4h is stirred at room temperature (preferably in-AuNPs
3h), repeatedly washing and magnetic hysteresis separation, is freeze-dried and obtains 3D-rGO/Fe3O4-AuNPs；
3)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD composite material:
Take 3D-rGO/Fe obtained in 19-21mg (preferably 20mg) step 2)3O4- AuNPs arrives 50mL conical flask, is added
22.23-24.23mg (preferably 23.23mg) carbodiimide hydrochloride (EDCI) and 12.8-14.8mg (preferably 13.8mg) N- hydroxyl
Hydroxypropyl-β-cyclodextrin (HP- β-CD) 155-165mg is then added in succinimide NHS, mechanical stirring 1-3h (preferably 2h)
(preferably 160mg), after 20-30h (preferably for 24 hours) is stirred at room temperature, magnetic hysteresis is separated and is freeze-dried, and obtains final product 3D-rGO/
Fe3O4-AuNPs/HP-β-CD。
A method of guanine and adenine, including following step are detected simultaneously with three-dimensional grapheme nanocomposite
It is rapid:
1)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD modified electrode:
Glass-carbon electrode is washed and dried, 4-6 μ L (preferably 5 μ L) foregoing 3D-rGO/Fe is pipetted3O4-
AuNPs/HP- β-CD (2mg/mL) drop coating is sufficiently dried under infrared lamp in the surface glass-carbon electrode (GCE), i.e. acquisition 3D-rGO/
Fe3O4The modified electrode of-AuNPs/HP- β-CD；
2) electrochemistry detects guanine and adenine simultaneously:
It first passes through cyclic voltammetry (CV) and Electrode with Electrochemical Impedance Spectroscopy (EIS) and is containing the 5mM potassium ferricyanide and potassium ferrocyanide
Mixture ([Fe (CN)6]3-/4-) and 0.1M KCl-0.1M pH=7 phosphate buffered saline solution PBS in the 3D- prepared
rGO/Fe3O4The glass-carbon electrode of-AuNPs/HP- β-CD modification carries out electrochemical Characterization.It is then immersed in containing 100 μM of guanines and 100
In the PBS pH=3 solution of μM adenine, with differential pulse voltammetry (DPV) detection electric signal come while realizing two kinds of purine
Detection；
3) electrochemistry detects the guanine and adenine in actual sample simultaneously:
First prepare biological sample: the milt DNA for taking 90-110 μ L (preferably 100 μ L) to extract is placed in plastic centrifuge tube, is added
Enter 0.5-1.5mL (preferably 1mL) HCl, 0.5-1.5h (preferably 1h) is heated in boiling water bath and obtains the DNA of denaturation treatment, then plus
Enter 0.5-1.5mL (preferably 1mL) NaOH, and cools down at room temperature；It is settled to finally by the 0.1mol/L PBS of PH=3
20mL；
The constant volume made from 10mL is first taken to be denaturalized milt DNA according to standard addition method, measurement wherein guanine and adenine
Then oxidation current peak takes constant volume made from 10mL to be denaturalized milt DNA again, 50 μM of guanine and adenine is added, surveys again
Measure peak point current, by the difference between measuring twice calculate guanine and adenine concentration, to obtain guanine and gland
The percentage composition of purine further calculates out in milt DNA (G+C)/(A+T) (wherein, C is cytimidine, and T is thymidine)
Ratio is compared with standard value；
4) the interference Journal of Sex Research of G and A is detected simultaneously:
In order to evaluate the selectivity for constructing electrochemical sensor, measure several important biological substances and some metals and
The peak current of guanine and adenine changes in the presence of the interfering substances such as inorganic ions.By the way that 8-12mM (preferably 10mM) is different
Interfering substance 0.1M be added contain 80-120 μM of (preferably 100 μM) guanine and 80-120 μM of (preferably 100 μM) adenine
In PBS pH=3 buffer solution, 3D-rGO/Fe is detected3O4The DPV peak point current of-AuNPs/HP- β-CD/GCE.
Three-dimensional grapheme based nano composite material 3D-rGO/Fe prepared by the present invention3O4- AuNPs/HP- β-CD, modification in
Novel electrochemical sensor is made in the glass-carbon electrode surface (GCE).By differential pulse voltammetry (DPV), with the nano-complex
Modified electrode detects guanine and adenine simultaneously, obtains the wider range of linearity and lower detection limit.
Beneficial effects of the present invention compared with prior art:
(1) three-dimensional graphite alkenyl nano-complex 3D-rGO/Fe prepared by the present invention3O4- AuNPs/HP- β-CD includes four
Kind multifunctional material, can be used for modified electrode.Wherein the unique porous network structure of 3D-rGO assigns the specific surface area of its superelevation
With good electric conductivity, Fe3O4Nanoparticle has good magnetic property, strong catalytic capability and excellent surface-active etc. solely
Property values, AuNPs possess the advantages such as excellent electrocatalysis characteristic and biocompatibility, paste along with HP- β-CD remains β-ring
The cavity structure of essence, while forming super molecular compound in conjunction with various guest molecules, also improves the water-soluble of decorative material
Property and dispersibility.
(2) guanine and adenine are had studied in the electrochemical behavior on modified electrode surface, wider linear by DPV
Lower detection limit has been obtained under range, substantially increases the specific selection recognition reaction that modified electrode detects two kinds of purine
And sensitivity.In addition, the novel sensor is also successfully used for detection while guanine and adenine in milt DNA, also obtain
Satisfied experimental result, this will play an important role in the analysis and research of electrochemical sensor.
Detailed description of the invention
Fig. 1 is 3D-rGO/Fe3O4The SEM (A) of-AuNPs/HP- β-CD, TEM (B) and HRTEM (C) photo；
Fig. 2 is GO, 3D-rGO, 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4Infrared (A) of-AuNPs/HP- β-CD
With Raman (B) spectrum；AuNPs, 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4Ultraviolet (C) of-AuNPs/HP- β-CD and
Fluorescence (D) spectrum；
Fig. 3 is 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4The dynamic light scattering map of-AuNPs/HP- β-CD；
Fig. 4 is (A) GO, 3D-rGO, 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4The XPS of-AuNPs/HP- β-CD
Spectrogram；3D-rGO/Fe3O4The C1s (B) of-AuNPs/HP- β-CD, Fe2p (C) and Au4f (D) XPS spectrum figure；
Fig. 5 is GO, 3D-rGO, 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4- AuNPs/HP- β-CD modified electrode
Containing 5mM [Fe (CN)6]3-/4-With Electrode with Electrochemical Impedance Spectroscopy (EIS) figure (A) and circulation in 0.1M KCl PBS pH=7 solution
Voltammetry (CV) figure (B)；
Fig. 6 is DPV figure of the different modifying electrode in the PBS pH=3 solution that 0.1M contains 100 μM of G and 100 μM of A；
Fig. 7 is the 3D-rGO/Fe in 0.1M PBS pH=33O4The GCE of-AuNPs/HP- β-CD modification deposits 100 μM of G
In the presence of lower various concentration A (A), 100 μM of A various concentration G (B) and simultaneously detect G and A (C) DPV figure；Illustration is corresponding
The peak current of purine bases and the relationship of concentration；(D) it is while detects the corresponding linear graph of G and A；
Fig. 8 is 3D-rGO/Fe in 0.1M PBS pH=3 when other 10mM chaff interferent absence or presences3O4-AuNPs/
Current-responsive figure of the GCE of HP- β-CD modification to 100 μM of G and 100 μM of A.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but embodiment is not intended to limit protection scope of the present invention.
Embodiment 1:
A kind of 3D-rGO/Fe3O4The preparation method of-AuNPs/HP- β-CD nanocomposite, comprising the following steps:
1)Fe3O4The preparation of-AuNPs nanoparticle:
First by the Fe of 50mg3O4It is added in 50mL ultrapure water, after ultrasonic disperse, in N2180 μ L are added under atmosphere
APTES, mechanical stirring 7h, black precipitate ultrapure water and ethyl alcohol wash the simultaneously last vacuum drying of magnetic hysteresis separation repeatedly at room temperature,
Obtain amidized Fe3O4(Fe3O4-NH2).Then 20mg Fe is taken3O4-NH2Powder ultrasonic is dispersed in 20mL ultrapure water, is added
40mg AuNPs powder, is stirred at room temperature 3h, and simultaneously magnetic hysteresis separation, 50 DEG C of vacuum drying 8h obtain Fe for washing repeatedly3O4-AuNPs；
2)3D-rGO/Fe3O4The preparation of-AuNPs nano material:
First by graphene oxide (GO) (40mg/20mL) ultrasonication 20min, 80mg L- half is added under ultrasonic dissolution
Cystine (L-Cys) is rapidly added 600 μ L ammonium hydroxide, is placed in conical flask, heats in 95 DEG C of oil bath, reacts 4h, finally mistake
Filter, is freeze-dried to obtain 3D-rGO black solid powder；3D-rGO 30mg obtained is taken again, and ultrasonic disperse is added in 30mL water
Fe obtained in 30mg step 1)3O43h is stirred at room temperature in-AuNPs, and repeatedly washing and magnetic hysteresis separation, are freeze-dried and obtain 3D-
rGO/Fe3O4-AuNPs；
3)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD composite material:
Take 3D-rGO/Fe obtained in 20mg step 2)3O4- AuNPs arrives 50mL conical flask, and 23.23mg EDCI is added
With 13.8mg NHS, mechanical stirring 2h, HP- β-CD 160mg is then added, after being stirred at room temperature for 24 hours, magnetic hysteresis is separated and freezed dry
It is dry, obtain final product 3D-rGO/Fe3O4- AuNPs/HP- β-CD (see Fig. 1-4)；
As shown in the SEM figure of Figure 1A, it can be clearly seen that three-dimensional porous structure shows to successfully synthesize 3D-rGO, together
When Fe3O4, AuNPs and HP- β-CD introducing, the reticular structure for the nano-complex that do not have an impact.It is further from TEM (Figure 1B)
Observe the apparent fold of 3D-rGO nanometer sheet, and the Fe of black3O4It is in elliposoidal with AuNPs particle, is evenly dispersed in 3D-
Apparent clustering phenomena does not occur for the surface rGO.Fe in the visual field is obtained by HRTEM (Fig. 1 C)3O4With AuNPs nanoparticle
Average diameter respectively may be about 13nm and 7nm.
Fig. 2A is GO, 3D-rGO, 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4The infrared light of-AuNPs/HP- β-CD
Spectrum, in GO curve, 3416cm-1And 1639cm-1The peak at place respectively corresponds the stretching vibration peak of O-H and C=C, 1727cm-1's
Bands of a spectrum then correspond to the flexible peak of C=O.Compared with GO, the disappearance at the peak C=O illustrates that GO is successfully reduced in 3D-rGO curve
rGO.And 3D-rGO/Fe3O4- AuNPs/HP- β-CD and 3D-rGO/Fe3O4- AuNPs spectrogram is in 580cm-1Nearby occurs one
Apparent strong peak, this is because Fe3O4In Fe-O key stretching vibration caused by, this shows Fe3O4Success is modified to three
Tie up graphene surface.Fig. 2 B is GO, 3D-rGO, 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4- AuNPs/HP- β-CD's
Raman spectrum is located at 1350cm-1、1580cm-1And 2750cm-1Peak of prominence respectively correspond D band and G band and 2D band, in graphene
Defect level generally use the intensity at the peak D and the peak G ratio (ID/IG) characterize, the intensity ratio (I at the peak G and the peak 2DG/I2D) show graphite
The number of plies of alkene.Compare the I of GOD/IG(0.90), the I of 3D-rGOD/IG(1.47) increase, this is because GO shape in reduction process
At 3D porous structure, lead to the increase of C vacancy and turbulence.For 3D-rGO/Fe3O4- AuNPs, ID/IGRatio is further
Enhancing, it was confirmed that Fe3O4It is successfully introduced in 3D network with AuNPs nano particle.When with HP- β-CD functionalization 3D-rGO/
Fe3O4When-AuNPs, with 3D-rGO/Fe3O4- AuNPs is compared, ID/IGValue decreases (1.18), this may be chemical modification
The result that segmental defect disappears in journey.I simultaneouslyG/I2D> 1, show 3D-rGO/Fe3O4- AuNPs/HP- β-CD nanocomposite
It is multilayer.The uv absorption spectra of Fig. 2 C, 3D-rGO/Fe3O4- AuNPs/HP- β-CD and 3D-rGO/Fe3O4- AuNPs exists
There is a small peak at 270nm, the ultraviolet absorption peak of corresponding rGO, this sufficiently demonstrates the successful reduction of GO.In addition, comparison
AuNPs, both three-dimensional grapheme based nano-materials do not occur the characteristic absorption peak of gold nanoparticle in 510nm or so,
This may be gold nanoparticle in two kinds of three-dimensional grapheme based composites due to synthesis content it is too low.Fig. 2 D is fluorescence Spectra
Figure, it is obvious that AuNPs, 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4- AuNPs/HP- β-CD exists
There is the characteristic peak of nanogold in 618.5nm, this confirms that AuNPs successfully modifies three-dimensional graphene composite material table again
Face.
Fig. 3 is 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4The dynamic light scattering map of-AuNPs/HP- β-CD, it is right
3D-rGO/Fe3O4- AuNPs/HP- β-CD and 3D-rGO/Fe3O4Two kinds of composite materials of-AuNPs have carried out partial size and have compared.By
Analysis, it is found that the hydration mean particle size of two kinds of materials is respectively 390.8nm and 268.3nm, this illustrates that HP- β-CD is successfully wrapped
It is rolled in three-dimensional grapheme structure, to make 3D-rGO/Fe3O4The partial size of-AuNPs/HP- β-CD increases.
Fig. 4 is XPS spectrum figure.Find there are two kinds of elements of C and O in four kinds of materials in Fig. 4 A, and in 3D-rGO/Fe3O4-
AuNPs/HP- β-CD and 3D-rGO-AuNPs/Fe3O4In there are also Fe and Au element presence.Compared with GO, the peak O1s of 3D-rGO
Value is decreased obviously, and reduction has occurred in this explanation GO during synthesizing 3D-rGO.And 3D-rGO/Fe3O4-AuNPs/HP-
β-CD and 3D-rGO-AuNPs/Fe3O4O1s peak value be apparently higher than 3D-rGO, show the generation of chemical modification process.Fig. 4 B, C
With D respectively to 3D-rGO/Fe3O4The peak C1s, Fe2p and Au4f of-AuNPs/HP- β-CD is fitted, and observes that C1s is composed
There are five types of carbon key C-C (283.5eV), C-N (284.3eV), C-O (285.2eV), C=O (286.3eV), O-C=O altogether in figure
(287.4eV) (Fig. 4 B) has obtained Fe2p in Fe2p spectrogram3/2(710.0eV) and Fe2p1/2Two peaks (723.5eV), and
Au4f in Au4f spectrogram5/2(87.67eV) and Au4f7/2The presence of (84.00eV), all confirmation Fe3O4It is successfully supported on AuNPs
In three-dimensional grapheme structure.
A method of guanine and adenine, including following step are detected simultaneously with three-dimensional grapheme nanocomposite
It is rapid:
1)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD modified electrode:
Glass-carbon electrode is washed and dried, the 5 foregoing 3D-rGO/Fe of μ L are pipetted3O4-AuNPs/HP-β-CD
(2mg/mL) drop coating sufficiently dries under infrared lamp in GCE electrode surface, can be obtained 3D-rGO/Fe3O4-AuNPs/HP-β-
The modified electrode of CD；
2) electrochemistry detects guanine and adenine simultaneously:
It first passes through cyclic voltammetry (CV) and Electrode with Electrochemical Impedance Spectroscopy (EIS) and is containing 5mM [Fe (CN)6]3-/4-And 0.1M
To the 3D-rGO/Fe prepared in the 0.1M pH=7PBS of KCl3O4The glass-carbon electrode of-AuNPs/HP- β-CD modification carries out electrification
Learn characterization.It is then immersed in the PBS pH=3 solution containing 100 μM of guanines and 100 μM of adenines, uses differential pulse voltammetry
(DPV) detection electric signal is come detection while realizing two kinds of purine (see Fig. 5-7)；
Fig. 5 is GO, 3D-rGO, 3D-rGO/Fe3O4- AuNPs and 3D-rGO/Fe3O4- AuNPs/HP- β-CD modified electrode
Containing 5mM [Fe (CN)6]3-/4-With the EIS figure and CV figure in 0.1M KCl PBS pH=7 solution.Fig. 5 A, by EIS with
[Fe(CN)6]3-/4-For redox probe, Impedance Research has been carried out to bare electrode and different modified electrodes.As Nyquist schemes
In, impedance curve includes the semicircle dotted line and the linear dotted line of low frequency range of high frequency region, respectively corresponds the electronics transfer resistance of decorative layer
The diffusion resistance of anti-(Ret) and electrolyte in decorative layer.Fig. 5 B can be seen that compared with bare electrode, the Ret of different modifying electrode
Have reduces to some extent, and has modified 3D-rGO/Fe3O4The electrode impedance value of-AuNPs/HP- β-CD material is minimum, this is
Due to the conductivity of 3D-rGO superelevation, Fe3O4Strong electrocatalysis characteristic and the excellent water solubility of HP- β-CD common are made with AuNPs
Result.
Fig. 6 is DPV figure of the different modifying electrode in the PBS pH=3 solution that 0.1M contains 100 μM of G and 100 μM of A,
There are two apparent oxidation peaks in the potential range of 0.6-1.4V, and independently of each other, do not interfere with each other, this shows these modifications
Material all has electro-chemical activity, both biomolecule of G and A can be carried out while be detected.However comparison naked GCE, 3D-
rGO/GCE、3D-rGO/Fe3O4- AuNPs/GCE, 3D-rGO/Fe3O4- AuNPs/HP- β-CD modification electrode, DPV simultaneously
Highest current responsing signal is shown in detection, this is not only attributed to the fact that the big specific surface area of three-dimensional grapheme and good conduction
Property, also cooperate with Fe3O4Strong catalytic performance and the unique selectivity of HP- β-CD with AuNPs.The above phenomenon shows 3D-
rGO/Fe3O4- AuNPs/HP- β-CD/GCE is selected as while detecting G and A.
Fig. 7 is 3D-rGO/Fe3O4- AuNPs/HP- β-CD/GCE examines G and A in the mixed solution containing G and A
It surveys.In Fig. 7 A, keep guanine concentration constant, to study the trend that the electrochemical signals of adenine change with concentration.As a result it shows
Show, guanine peak current is held essentially constant, and the peak current of adenine is increased with the increase of concentration, and illustration shows that gland is fast
Purine has good linear relationship in 0.5-190 μM of concentration range internal oxidition peak current and concentration, and equation of linear regression is
IP(A)=0.0807cA+0.270(R2=0.999), while the detection of A limit (LODs) is 0.023 μM.Equally obtain in figure 7b
Linear equation and LODs of the G under 0.3-150 μM of the range of linearity, respectively IP(G)=0.078cG+0.780(R2=0.998)
With 0.019 μM.3D-rGO/Fe when Fig. 7 C has also been investigated the concentration of guanine and adenine while having been changed by DPV3O4-AuNPs/
It is detected while HP- β-CD/GCE is to two kinds of purine.Fig. 7 D further obtains guanine in 1-150 μM and 1-190 μM of adenine
Concentration range in equation of linear regression, respectively IP(G)=0.079cG+0.730(R2=0.999) and IP(A)=0.081cA+
0.287(R2=0.999) and the detection limit LODs of two kinds of purine is respectively 0.026 μM and 0.031 μM.The results show that simultaneously
Detection G and A and slope when individually detecting and the range of linearity are not much different, and the two oxidation process is not interfere with each other.It therefore can be with
Use 3D-rGO/Fe3O4- AuNPs/HP- β-CD/GCE simultaneously and individually detect to G and A.
3) electrochemistry detects the guanine and adenine in actual sample simultaneously:
First prepare biological sample: the milt DNA for taking 100 μ L to extract is placed in plastic centrifuge tube, and 1.0mL HCl is added, in
1h is heated in boiling water bath and obtains the DNA of denaturation treatment, adds 1.0mL NaOH, and cool down at room temperature；Finally by PH=3
0.1mol/L PBS be settled to 20mL；
The constant volume made from 10mL is first taken to be denaturalized milt DNA according to standard addition method, measurement wherein guanine and adenine
Then oxidation current peak takes constant volume made from 10mL to be denaturalized milt DNA again, 50 μM of guanine and adenine is added, surveys again
Measure peak point current, by the difference between measuring twice calculate guanine and adenine concentration, to obtain guanine and gland
The percentage composition of purine further calculates out in milt DNA the ratio of (G+C)/(A+T), compares with standard value；
Obtained result is as follows, and the content of guanine and adenine is respectively 21.51% and 28.68%, further calculates
Out the ratio of (G+C)/(A+T) be 0.75, be with standard value 0.77 it is close, this illustrates that the electrochemical sensor that we construct can
It is detected for actual sample.
4) the interference Journal of Sex Research of G and A is detected simultaneously:
In order to evaluate the selectivity for constructing electrochemical sensor, measure several important biological substances and some metals and
The peak current of guanine and adenine changes in the presence of the interfering substances such as inorganic ions.By the way that the different interfering substance of 10mM is added
Enter 0.1M to contain in the PBS pH=3 buffer solution of 100 μM of guanines and 100 μM of adenines, detects 3D-rGO/Fe3O4-
The DPV peak point current of AuNPs/HP- β-CD/GCE (see Fig. 8)；
Fig. 8 is 3D-rGO/Fe in 0.1M PBS pH=3 when other 10mM chaff interferent absence or presences3O4-AuNPs/
HP- β-CD/GCE to the current-responsive figure of 100 μM of G and 100 μM of A, the experimental results showed that, the Na at concentrations up to 100 times+, Ca2 +, Mg2+, K+, Cl-, glucose, L-cysteine detects no apparent interference effect while ascorbic acid is to two kinds of purine,
Is there is oxidation peak apart from adenine and guanine spike potential remote position in dopamine, and peak current is significantly lower than guanine
With the current value of adenine.The above result shows that 3D-rGO/Fe3O4The modified electrode GCE of-AuNPs/HP- β-CD to detecting simultaneously
Guanine and adenine have good anti-interference ability.
Embodiment 2:
A kind of 3D-rGO/Fe3O4The preparation method of-AuNPs/HP- β-CD nanocomposite, comprising the following steps:
1)Fe3O4The preparation of-AuNPs nanoparticle:
First by the Fe of 51mg3O4It is added in 60mL ultrapure water, after ultrasonic disperse, in N2190 μ L are added under atmosphere
APTES, mechanical stirring 8h, black precipitate ultrapure water and ethyl alcohol wash the simultaneously last vacuum drying of magnetic hysteresis separation repeatedly at room temperature,
Obtain amidized Fe3O4(Fe3O4-NH2).Then 21mg Fe is taken3O4-NH2Powder ultrasonic is dispersed in 25mL ultrapure water, is added
41mg AuNPs powder, is stirred at room temperature 4h, and simultaneously magnetic hysteresis separation, 50 DEG C of vacuum drying 9h obtain Fe for washing repeatedly3O4-AuNPs；
2)3D-rGO/Fe3O4The preparation of-AuNPs nano material:
First by graphene oxide (GO) (40mg/20mL) ultrasonication 25min, 85mg L- half is added under ultrasonic dissolution
Cystine (L-Cys) is rapidly added 650 μ L ammonium hydroxide, is placed in conical flask, heats in 95 DEG C of oil bath, reacts 5h, finally mistake
Filter, is freeze-dried to obtain 3D-rGO black solid powder；3D-rGO 31mg obtained is taken again, and ultrasonic disperse is added in 40mL water
31mg step 1) Fe obtained3O44h is stirred at room temperature in-AuNPs, and repeatedly washing and magnetic hysteresis separation, are freeze-dried to obtain 3D-rGO/
Fe3O4-AuNPs；
3)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD composite material:
Take 3D-rGO/Fe obtained in 21mg step 2)3O4- AuNPs arrives 50mL conical flask, and 24.23mg EDCI is added
With 14.8mg NHS, mechanical stirring 3h, HP- β-CD 165mg is then added, after stirring 30h at room temperature, magnetic hysteresis is separated and freezed
It is dry, obtain final product 3D-rGO/Fe3O4-AuNPs/HP-β-CD。
A method of guanine and adenine, including following step are detected simultaneously with three-dimensional grapheme nanocomposite
It is rapid:
1)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD modified electrode:
Glass-carbon electrode is washed and dried, the 6 foregoing 3D-rGO/Fe of μ L are pipetted3O4-AuNPs/HP-β-CD
(2mg/mL) drop coating is sufficiently dried under infrared lamp in GCE electrode surface, i.e. acquisition 3D-rGO/Fe3O4-AuNPs/HP-β-CD
Modified electrode；
2) electrochemistry detects guanine and adenine simultaneously
It first passes through cyclic voltammetry (CV) and Electrode with Electrochemical Impedance Spectroscopy (EIS) and is containing 5mM [Fe (CN)6]3-/4-And 0.1M
To the 3D-rGO/Fe prepared in the 0.1M pH=7PBS of KCl3O4The glass-carbon electrode of-AuNPs/HP- β-CD modification carries out electrification
Learn characterization.It is then immersed in the PBS pH=3 solution containing 100 μM of guanines and 100 μM of adenines, uses differential pulse voltammetry
(DPV) electric signal is detected come detection while realizing two kinds of purine；
3) electrochemistry detects the guanine and adenine in actual sample simultaneously:
First prepare biological sample: the milt DNA for taking 110 μ L to extract is placed in plastic centrifuge tube, and 1.5mL HCl is added, in
1.5h is heated in boiling water bath and obtains the DNA of denaturation treatment, adds 1.5mL NaOH, and cool down at room temperature；Finally by PH
=3 0.1mol/L PBS is settled to 20mL；
The constant volume made from 10mL is first taken to be denaturalized milt DNA according to standard addition method, measurement wherein guanine and adenine
Then oxidation current peak takes constant volume made from 10mL to be denaturalized milt DNA again, 50 μM of guanine and adenine is added, surveys again
Measure peak point current, by the difference between measuring twice calculate guanine and adenine concentration, to obtain guanine and gland
The percentage composition of purine further calculates out in milt DNA the ratio of (G+C)/(A+T), compares with standard value；
4) the interference Journal of Sex Research of G and A is detected simultaneously:
In order to evaluate the selectivity for constructing electrochemical sensor, measure several important biological substances and some metals and
The peak current of guanine and adenine changes in the presence of the interfering substances such as inorganic ions.By the way that the different interfering substance of 12mM is added
Enter 0.1M to contain in the PBS pH=3 buffer solution of 120 μM of guanines and 120 μM of adenines, detects 3D-rGO/Fe3O4-
The DPV peak point current of AuNPs/HP- β-CD/GCE.
Embodiment 3:
A kind of 3D-rGO/Fe3O4The preparation method of-AuNPs/HP- β-CD nanocomposite, comprising the following steps:
1)Fe3O4The preparation of-AuNPs nanoparticle:
First that 49mg is pre-synthesis Fe3O4It is added in 40mL ultrapure water, after ultrasonic disperse, in N2Add again under atmosphere
Enter 170 μ L APTES, at room temperature mechanical stirring 6h, black precipitate ultrapure water and ethyl alcohol wash repeatedly and magnetic hysteresis separation is last true
Sky is dry, obtains amidized Fe3O4(Fe3O4-NH2).Then 19mg Fe is taken3O4-NH2Powder ultrasonic is dispersed in 15mL ultrapure water
In, 39mg AuNPs powder is added, 2h is stirred at room temperature, simultaneously magnetic hysteresis separation, 50 DEG C of vacuum drying 7h obtain Fe for washing repeatedly3O4-
AuNPs；
2)3D-rGO/Fe3O4The preparation of-AuNPs nano material:
First by graphene oxide (GO) (40mg/20mL) ultrasonication 15min, 75mg L- half is added under ultrasonic dissolution
Cystine (L-Cys) is rapidly added 550 μ L ammonium hydroxide, is placed in conical flask, heats in 95 DEG C of oil bath, reacts 3h, finally mistake
Filter, is freeze-dried to obtain 3D-rGO black solid powder；3D-rGO 29mg obtained is taken again, and ultrasonic disperse is added in 20mL water
Fe obtained in 29mg step 1)3O42h is stirred at room temperature in-AuNPs, and repeatedly washing and magnetic hysteresis separation, are freeze-dried and obtain 3D-
rGO/Fe3O4-AuNPs；
3)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD composite material:
Take 3D-rGO/Fe obtained in 19mg step 2)3O4- AuNPs arrives 50mL conical flask, and 22.23mg EDCI is added
With 12.8mg NHS, mechanical stirring 1h, HP- β-CD 155mg is then added, after 20h is stirred at room temperature, magnetic hysteresis is separated and freezed dry
It is dry, obtain final product 3D-rGO/Fe3O4-AuNPs/HP-β-CD。
A method of guanine and adenine, including following step are detected simultaneously with three-dimensional grapheme nanocomposite
It is rapid:
1)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD modified electrode:
Glass-carbon electrode is washed and dried, the 4 foregoing 3D-rGO/Fe of μ L are pipetted3O4-AuNPs/HP-β-CD
(2mg/mL) drop coating is sufficiently dried under infrared lamp in GCE electrode surface, i.e. acquisition 3D-rGO/Fe3O4-AuNPs/HP-β-CD
Modified electrode；
2) electrochemistry detects guanine and adenine simultaneously:
It first passes through cyclic voltammetry (CV) and Electrode with Electrochemical Impedance Spectroscopy (EIS) and is containing 5mM [Fe (CN)6]3-/4-And 0.1M
To the 3D-rGO/Fe prepared in the 0.1M pH=7PBS of KCl3O4The glass-carbon electrode of-AuNPs/HP- β-CD modification carries out electrification
Learn characterization.It is then immersed in the PBS pH=3 solution containing 100 μM of guanines and 100 μM of adenines, uses differential pulse voltammetry
(DPV) electric signal is detected to realize two kinds of purine while detect；
3) electrochemistry detects the guanine and adenine in actual sample simultaneously:
First prepare biological sample: the milt DNA for taking 90 μ L to extract is placed in plastic centrifuge tube, 0.5mL HCl is added, in boiling
0.5h is heated in water-bath and obtains the DNA of denaturation treatment, adds 0.5mL NaOH, and cool down at room temperature；Finally by PH=3
0.1mol/L PBS be settled to 20mL；
The constant volume made from 10mL is first taken to be denaturalized milt DNA according to standard addition method, measurement wherein guanine and adenine
Then oxidation current peak takes constant volume made from 10mL to be denaturalized milt DNA again, 50 μM of guanine and adenine is added, surveys again
Measure peak point current, by the difference between measuring twice calculate guanine and adenine concentration, to obtain guanine and gland
The content of purine further calculates out in milt DNA the ratio of (G+C)/(A+T), compares with standard value；
4) the interference Journal of Sex Research of G and A is detected simultaneously:
In order to evaluate the selectivity for constructing electrochemical sensor, measure several important biological substances and some metals and
The peak current of guanine and adenine changes in the presence of the interfering substances such as inorganic ions.By the way that the different interfering substance of 8mM is added
Enter 0.1M to contain in the PBS pH=3 buffer solution of 80 μM of guanines and 80 μM of adenines, detects 3D-rGO/Fe3O4-AuNPs/
The DPV peak point current of HP- β-CD/GCE.
The above-described embodiments are merely illustrative of preferred embodiments of the present invention, not to structure of the invention
Think and protection scope is defined, without departing from the design concept of the invention, ordinary engineering and technical personnel in this field
Various variations and modifications are made to the technical solution of present aspect, should all fall into protection scope of the present invention.
Claims (10)
1. a kind of 3D-rGO/Fe3O4The preparation method of-AuNPs/HP- β-CD nanocomposite, it is characterised in that: including following
Step:
1)Fe3O4The preparation of-AuNPs nanoparticle:
First by 49-51mg Fe3O4It is added in 40-60mL ultrapure water, after ultrasonic disperse, in N2170- is added under atmosphere
190 μ L3- aminopropyl triethoxysilanes (APTES), simultaneously magnetic hysteresis point is washed in mechanical stirring 6-8h, black precipitate repeatedly at room temperature
From being finally dried in vacuo, obtain amidized Fe3O4(Fe3O4-NH2)；Then 19-21mg Fe is taken3O4-NH2Powder ultrasonic dispersion
In 15-25mL ultrapure water, 39-41mg gold nanoparticle (AuNPs) powder is added, 2-4h is stirred at room temperature, repeatedly washing and magnetic
Stagnant separation, 50 DEG C of vacuum drying 7-9h, obtains Fe3O4-AuNPs；
2)3D-rGO/Fe3O4The preparation of-AuNPs nano material:
First by 40mg/20mL graphene oxide (GO) ultrasonication 15-25min, 75-85mg L- half is added under ultrasonic dissolution
Cystine (L-Cys) is rapidly added 550-650 μ L ammonium hydroxide, is placed in conical flask, heats in 95 DEG C of oil bath, reacts 3-5h,
It finally filters, is freeze-dried to obtain three-dimensional grapheme (3D-rGO) black solid powder；3D-rGO29-31mg obtained is taken again, is surpassed
Sound is dispersed in 20-40mL water, and the Fe that 29-31mg step 1) obtains is added3O42-4h is stirred at room temperature in-AuNPs, repeatedly washs simultaneously
Magnetic hysteresis separation, freeze-drying obtain 3D-rGO/Fe3O4-AuNPs；
3)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD composite material:
Take 3D-rGO/Fe obtained in 19-21mg step 2)3O4- AuNPs arrives 50mL conical flask, and 22.23-24.23mg is added
Then hydroxy propyl-Beta-ring is added in carbodiimide hydrochloride and 12.8-14.8mg n-hydroxysuccinimide, mechanical stirring 1-3h
Dextrin (HP- β-CD) 155-165mg, after 20-30h is stirred at room temperature, magnetic hysteresis is separated and is freeze-dried, and obtains final product 3D-
rGO/Fe3O4-AuNPs/HP-β-CD。
2. the preparation method of nanocomposite according to claim 1, it is characterised in that: in N in the step 1)2Atmosphere
APTES is added under enclosing, the mechanical stirring time is 7h at room temperature.
3. the preparation method of nanocomposite according to claim 1, it is characterised in that: be added in the step 1)
Room temperature mixing time is 3h after AuNPs powder, and 50 DEG C of vacuum drying times are 8h.
4. the preparation method of nanocomposite according to claim 1, it is characterised in that: GO ultrasound in the step 2)
The broken time is 20min, and L-Cys additional amount is 80mg, and ammonium hydroxide additional amount is 600 μ L.
5. the preparation method of nanocomposite according to claim 1, it is characterised in that: in the step 2) in oil bath
The heating reaction time is 4h.
6. the preparation method of nanocomposite according to claim 1, it is characterised in that: room temperature is stirred in the step 2)
Mixing the time is 3h.
7. the preparation method of nanocomposite according to claim 1, it is characterised in that: machinery stirs in the step 3)
Mixing the time is 2h.
8. the preparation method of nanocomposite according to claim 1, it is characterised in that: be added in the step 3)
After HP- β-CD, it is for 24 hours that the time, which is stirred at room temperature,.
9. a kind of electrochemical sensor that nanocomposite the is constructed while method for detecting guanine and adenine, feature exist
In, comprising the following steps:
1)3D-rGO/Fe3O4The preparation of-AuNPs/HP- β-CD modified electrode:
Glass-carbon electrode is washed and dried, the 3D-rGO/Fe described in claim 1 of 4-6 μ L concentration 2mg/mL is pipetted3O4-
AuNPs/HP- β-CD drop coating is sufficiently dried under infrared lamp in glassy carbon electrode surface, i.e. acquisition modified electrode 3D-rGO/Fe3O4-
AuNPs/HP-β-CD/GCE；
2) electrochemistry detects guanine and adenine simultaneously:
Cyclic voltammetry and Electrode with Electrochemical Impedance Spectroscopy are first passed through containing the 5mM potassium ferricyanide and potassium ferrocyanide mixture and 0.1M
To the 3D-rGO/Fe prepared in the 0.1M pH=3 phosphate buffered saline solution PBS of KCl3O4- AuNPs/HP- β-CD/GCE is carried out
Electrochemical Characterization；It is then immersed in the PBS pH=3 solution containing 100 μM of guanines and 100 μM of adenines, uses differential pulse voltammetry
Method detects electric signal come detection while realizing two kinds of purine；
3) electrochemistry detects the guanine and adenine in actual sample simultaneously:
First prepare biological sample: the milt DNA for taking 90-110 μ L to extract is placed in plastic centrifuge tube, and 0.5-1.5mL HCl is added,
0.5-1.5h is heated in boiling water bath and obtains the DNA of denaturation treatment, adds 0.5-1.5mL NaOH, and cool down at room temperature；
20mL is settled to finally by the 0.1mol/L PBS of PH=3；
It is first taken constant volume made from 10mL to be denaturalized milt DNA according to standard addition method, measures the oxidation of wherein guanine and adenine
Then current peak takes constant volume made from 10mL to be denaturalized milt DNA again, 50 μM of guanine and adenine is added, measures peak again
Current value, by the difference between measuring twice calculate guanine and adenine concentration.
10. nanocomposite is constructed according to claim 9 electrochemical sensor while detecting guanine and adenine
Method, it is characterised in that: after HCl is added in the step 3), heating time is 1h in boiling water bath.
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