CN110006722A - A kind of preparation method and applications of ferroso-ferric oxide/gold structure nano particles - Google Patents
A kind of preparation method and applications of ferroso-ferric oxide/gold structure nano particles Download PDFInfo
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Abstract
The invention discloses a kind of ferroso-ferric oxide/gold structure nano particles preparation method and applications.Ferroso-ferric oxide of the present invention/gold structure nano particles selects 3,3', 5,5'- tetramethyl benzidine (TMB) is used as Raman reporter molecules, by gold-sulphur (Au-S) Covalent bonding together in gold surface, to generate Surface enhanced Raman spectroscopy (SERS).Due to the catalytic action of ferroso-ferric oxide on particle, hydrogen peroxide can quickly aoxidize 3,3', 5,5'- tetramethyl benzidines in detection, according to the variation of SERS signal before and after 3,3', 5,5'- tetramethyl benzidine molecular oxidations, it can be achieved that H2O2The indirect detection of concentration directly detected with concentration of glucose.Advantage is high sensitivity, high specificity, and when detection can avoid the interference of other ingredients in sample, and not need to pre-process, and operating procedure is simpler.Moreover, the method is further upgraded, the H detected in unicellular can be applied to2O2Concentration.
Description
Technical field
The present invention relates to technical field of optical measuring instruments, are related to a kind of system of ferroso-ferric oxide/gold structure nano particles
Preparation Method and its application.
Background technique
The appearance of nano science and the development of nanotechnology provide for the design and building of the analogue enztme based on nano material
New chance.Since analogue enztme has the activity of native enzyme, and easily prepared and purifying, to temperature, acidity and inhibitor etc.
There is more indomitable resistance, there is high-efficient, high specificity and advantage at low cost, therefore, analogue enztme becomes section in recent years
The focus of scholar's research.Fe3O4Nano particle has enzymatic activity similar with natural horseradish peroxidase, so that being based on Fe3O4
The analogue enztme of nano particle becomes the hot fields of scientific research.
Raman spectrum is substance " fingerprint " spectrum, so that the detection based on Raman spectrum typically is provided with excellent specificity；
When raman active molecule is in precious metal surface, the intensity of Raman signal can promote multiple orders of magnitude, this is surface
Enhance Raman spectrum (SERS).SERS signal intensity is high, so that this is based on the detection of SERS but also with high sensitivity
SERS is relative to traditional detection method unique advantage.The unimolecule to substance even may be implemented in detection technique based on SERS
Detection, thus it is widely used in the fields such as chemistry, material and biomedicine.
The method of traditional detection hydrogen peroxide and concentration of glucose includes electrochemical process, spectrophotometry, fluorimetry
Deng.2018, hydrogen peroxide and glucose detected as electrochemical sensor using cobalt nitride nano-array in Xie seminar, right
H2O2Detectable limit reached 1 μM, 50nM has been reached to the detectable limit of glucose, but this method is vulnerable to egg in blood
The interference of white matter, blood color and electrode fouling.2017, Chamaraja et al. used sulfosalicylic acid as colour developing probe, adopted
With Spectrophotometric Determination of Hydrogen Peroxide, to H2O2Detectable limit reached 73nM.But this method is vulnerable to other colored components
Interference, it is desirable that the degree of purity of measured object is higher；2018, Liu seminar was based on using fragrant borate as sensing unit
Imino group coumarin derivative, a kind of fluorescence probe is developed, to H2O2Detectable limit reached 60nM.Although fluorescence is surveyed
Two methods before the method for determining can overcome the problems, such as, but the interference vulnerable to background auto-fluorescence.It is lacked in view of above many
Point, then it is necessary to study go out it is a kind of being capable of the fast high-sensitive method that detects concentration of hydrogen peroxide.
Summary of the invention
For traditional technology, the present invention develops a kind of based on ferroso-ferric oxide/gold structure nano
The method that the SERS hypersensitive of particle quickly detects hydrogen peroxide and concentration of glucose.Ferroso-ferric oxide/gold that the present invention develops
Structure nano I, between 30nm-60nm, ferroso-ferric oxide surface is loaded the partial size of ferroso-ferric oxide by physical absorption
Between 10nm-15nm, the spacing of the adjacent nano gold particle on same ferriferrous oxide particles surface exists nanogold particle partial size
Between 0nm-10nm.
Under physiological condition, H2O2 is a kind of half-life period molecule, and usually concentration is lower, and the present invention utilizes Fe3O4 analogue enztme
Catalytic property, realize quick detection to concentration of hydrogen peroxide, detection time is between 5min-20min.
Using the SERS technology based on nanogold particle, realize to H2O2And the highly sensitive detection of concentration of glucose.It selects
3,3', 5,5'- tetramethyl benzidines (TMB) are used as Raman reporter molecules, by gold-sulphur (Au-S) Covalent bonding together in golden watch
Face, to generate Surface enhanced Raman spectroscopy (SERS).Due to the catalytic action of ferroso-ferric oxide on particle, hydrogen peroxide in detection
3,3', 5,5'- tetramethyl benzidines can quickly be aoxidized, according to SERS before and after 3,3', 5,5'- tetramethyl benzidine molecular oxidations
The variation of signal is, it can be achieved that H2O2The indirect detection of concentration directly detected with concentration of glucose, due to four oxidation three on particle
Iron is magnetic material, and under the action of externally-applied magnetic field, particle aggregation generates coupling effect, forms stronger local electric field hot spot,
To further improve the sensitivity of SERS detection, and its detectable limit can reach 10-9The order of magnitude.
Raman spectrum is substance " fingerprint " spectrum, and TMB can generate wave number 1195cm-1Raman characteristic peak, four oxidation
Under the catalysis of three-iron, redox reaction occurs for hydrogen peroxide and 3,3', 5,5'- tetramethyl benzidines, generates the 3 of oxidation state,
3', 5,5'- tetramethyl benzidines (TMB*), is detected, wave number is in 1195cm by SERS-1The Raman signatures peak intensity at place can subtract
It is weak, and wave number is in 685cm-1New raman characteristic peak can be generated, before and after 3,3', 5,5'- tetramethyl benzidine molecular oxidations
The variation of SERS signal power, so that the detection of the hydrogen peroxide based on Raman spectrum has excellent specificity.
In addition, detection when, under magnetic fields, can ferroso-ferric oxide/gold structure nano I from complex sample
It separates and carries out SERS detection, to avoid the interference of other compositions in sample.
Present invention design and the detection particle of preparation do not need to pre-process, and operating procedure is simpler.Moreover, to this side
Method further upgrades, and can be applied to the H detected in unicellular2O2Concentration.
The technical solution adopted by the present invention is that:
Specific step is as follows for ferroso-ferric oxide of the invention/gold structure nano particles preparation method:
(1)Fe3O4The preparation of nanoparticles solution:
Under logical nitrogen, water bath, polyethylenimine solution, ferrous sulfate solution, potassium nitrate solution, hydrogen is successively added
Sodium hydroxide solution reacts 1-3h, is settled particle with magnet, after deionized water washing, can be prepared by Fe3O4Nanoparticles solution,
The Fe3O4Nano particle diameter is between 30nm-60nm；
(2) preparation of gold nano seed solution:
Configure the mixed solution A of sodium borohydride and sodium citrate；A certain concentration chlorauric acid solution is configured, under magnetic agitation,
Sodium citrate solution is added, adds mixed solution A, obtains gold nano seed solution, the gold nano after reacting a period of time
The partial size of seed is 3nm-5nm；
(3) ferroso-ferric oxide/gold nanoparticle preparation:
Fe prepared by step (1)3O4Nanoparticles solution is mixed with gold nano seed solution prepared by step (2), sufficiently
Stirring, reacts 1-3h, and magnetic separation is washed with deionized to remove excessive gold nano seed, adds polyethyleneimine
Ferroso-ferric oxide/gold kind nanoparticle is made in 55-65 DEG C of reaction 0.5-2h in solution, deionized water washing 1-2 times, and described four
In Fe 3 O/gold nanoparticle, the gap between the nanogold particle on same ferriferrous oxide particles surface is up to 27nm；
(4) one secondary growth of ferroso-ferric oxide/gold nano grain:
Hexadecyltrimethylammonium chloride solution, chlorauric acid solution, potassium bromide solution, AA solution are uniformly mixed, are made
Golden growth-promoting media；Hexadecyltrimethylammonium chloride is added into ferroso-ferric oxide made from step (3)/gold kind nano-particle solution
Solution stirs evenly, and adds golden growth-promoting media, reacts 15-20min；
(5) the multiple regrowth of ferroso-ferric oxide/gold nano grain:
Chlorauric acid solution is added again into step (4) reaction solution, AA solution is then added, reacts 15-20min, gold
Particle regrows；It regrows step to be typically repeated 2-5 times, until in ferroso-ferric oxide/gold nano grain scattering spectrum
The peak LSPR for generating coupling, is washed with deionized 1-2 spare, ferroso-ferric oxide/gold nano of the multiple regrowth
The partial size of grain is in 40nm-75nm.
In step (1), water bath heating temperature is 80-100 DEG C, polyethyleneimine, green vitriol, potassium nitrate, hydrogen
Sodium oxide molybdena molar ratio is 1:115:500:250.
In step (2), the mixed solution A containing mass fraction for 0.075% sodium borohydride and sodium citrate is configured；Magnetic force
Under stirring, aqueous solution of chloraurate and sodium citrate solution are mixed according to the amount of substance concentration of 1:2, solution A is added, Jenner is made
Rice seed solution.
In step (3), mixed according to ferriferrous oxide nano-particle solution with gold nano seed solution volume ratio for 1:45,
Mixing fullys shake, reacts 2h, is washed with deionized 3-5 times, addition and the isometric deionized water of gold nano seed solution,
Mixing fullys shake, adds the polyethylenimine solution of 0-4g/L, can surpass in 55-65 DEG C of reaction 1h if during which assembling
Sound dispersion, deionized water are washed 3-5 times, and ferroso-ferric oxide/gold kind nanoparticle is made.
In step (4), it is according to the ratio between hexadecyltrimethylammonium chloride, gold chloride, potassium bromide, the amount of substance of AA
5000:1.25:1:20 preparing golden growth-promoting media, sufficiently shake up；It is molten to ferroso-ferric oxide made from step (3)/gold kind nanoparticle
The hexadecyltrimethylammonium chloride solution of the amount of same substance is added in liquid, golden growth-promoting media is added to ferroso-ferric oxide/gold
In kind nano-particle solution, ultrasonic 3min sufficiently reacts.
The chlorine gold isometric with chlorauric acid solution in step (4) is added in step (5), in the product that obtains to step (4)
Acid solution, adds the AA solution isometric with AA solution in step (4), and ultrasonic 1min sufficiently reacts.
Ferroso-ferric oxide/gold structure nano particles SERS super sensitivity detection H is utilized the invention proposes a kind of2O2Concentration
Method.
Using ferroso-ferric oxide/gold structure nano particles as probe, 3,3', 5,5'- tetramethyl benzidines are letter for the application
Number molecule, the specific method is as follows:
(1) ferroso-ferric oxide/gold kind nanoparticle probes functionalization:
3,3', 5, the 5'- tetramethyl biphenyl amine aqueous solutions that substance withdrawl syndrome is 80 μm of ol/mL are configured, into the solution
Addition ferroso-ferric oxide/gold structure nano particles solution, ferroso-ferric oxide/gold structure nano particles solution and 3,3', 5,5'- tetra-
The volume ratio of methyl biphenyl amine aqueous solution is 100:1, and normal-temperature reaction 40-60min is separated with magnet, and deionized water washes twice, and adds
Enter deionized water resuspension, obtains SERS probe；
(2) H of SERS probe in detecting various concentration2O2Solution:
Configure a certain concentration gradient (1~10-9mol/L)H2O2The SERS probe of 100 μ L steps (1) preparation is added in solution,
After reacting 5-20min, magnetic force draws probe, is added drop-wise to analysis fine aluminium piece and carries out Raman test.Wherein, the wavelength of raman excitation light
For 633nm, power 10%, using static schema, time for exposure 1s, integral number of times is 2 times.
Ferroso-ferric oxide/gold structure nano particles SERS super sensitivity detection concentration of glucose is utilized the invention proposes a kind of
Method.
Using ferroso-ferric oxide/gold structure nano particles as probe, 3,3', 5,5'- tetramethyl benzidines are letter for the application
Number molecule, the specific method is as follows:
(1) ferroso-ferric oxide/gold kind nanoparticle probes functionalization:
3,3', 5, the 5'- tetramethyl biphenyl amine aqueous solutions that substance withdrawl syndrome is 80 μm of ol/mL are configured, into the solution
Addition ferroso-ferric oxide/gold structure nano particles solution, ferroso-ferric oxide/gold structure nano particles solution and 3,3', 5,5'- tetra-
The volume ratio of methyl biphenyl amine aqueous solution is 100:1, and normal-temperature reaction 40-60min is separated with magnet, and deionized water washes twice, and adds
Enter deionized water resuspension, obtains SERS probe；
(2) enzymatic treatment of different glucose solution:
Configure a certain concentration gradient (1~10-9Mol/L glucose solution), to the different glucose solution of 1mL
The glucose oxidase GOx solution of the 20mg/ml of 20 μ L, 37.5 DEG C of water-bath 30min are added；
(3) SERS detects the glucose solution of various concentration:
To different glucose solution, the above-mentioned SERS probe of 100 μ L is added, after reacting 5-20min, magnetism, which is drawn, to be visited
Needle is added drop-wise to analysis fine aluminium on piece and carries out Raman test.Wherein, the wavelength of raman excitation light is 633nm, and power 10% is adopted
With static schema, time for exposure 1s, integral number of times is 2 times.
The positive effect of the present invention is as follows:
For the detection probe that the present invention develops with 3,3', 5,5'- tetramethyl benzidines for signaling molecule, ferroso-ferric oxide is to urge
Agent, catalyzing hydrogen peroxide aoxidize the reaction of 3,3', 5,5'- tetramethyl benzidines, on the other hand, in externally-applied magnetic field, Fe3O4-
Au structure nano particles can assemble generation coupling, form more SERS hot spots, be conducive to the hydrogen peroxide for detecting lower concentration.
Therefore, the method high sensitivity that the present invention develops, high specificity can avoid the interference of other ingredients in sample when detection, and
It does not need to pre-process, operating procedure is simpler.Moreover, the method is further upgraded, it is slender that detection can be applied to
H intracellular2O2And concentration of glucose.
Detailed description of the invention
Fig. 1 is Fe of the present invention3O4- Au structure nano particles are to H2O2Illustrate with the SERS super sensitivity detection of concentration of glucose
Figure.
Nano particle prepared by the present invention, Fe3O4For catalyst, Fe3O4The Au on surfaceseedsArray can produce " hot spot ", be
Enhance substrate.With Fe3O4-AuseedsBased on the gold particle of composite surface, AuseedsContinuation is grown on ferroso-ferric oxide core,
So that the peak LSPR of nano particle is generated red shift, is convenient for Raman excitation.Herein with 3,3', 5,5'- tetramethyl biphenyl amine molecule
As report molecule, the surface of gold is incorporated in by Au-S key, then under the catalysis of ferroso-ferric oxide, hydrogen peroxide and 3,
3', 5,5'- tetramethyl benzidines occur redox reaction, generate the 3,3' of oxidation state, 5,5'- tetramethyl benzidines
(TMB*), it being detected by SERS, has the generation of new raman characteristic peak, the concentration of hydrogen peroxide is higher, and more 3,3', 5,
5'- tetramethyl benzidine is oxidized to the 3,3' of oxidation state, and the new Raman of 5,5'- tetramethyl benzidines (TMB*), generation is special
The intensity for levying peak is higher.So according to 3,3', the variation of SERS signal power before and after 5,5'- tetramethyl benzidine molecular oxidations,
On the one hand, it can be achieved that H2O2The Sensitive Detection of concentration；It on the other hand, can in the presence of glucose oxidase (GOx)
The Sensitive Detection to concentration of glucose is realized indirectly.
Fig. 2 is Fe of the present invention3O4The aggregation schematic diagram of-Au structure nano particle under the action of an external magnetic field.
Under the action of magnetic field is not added, Fe3O4-Au-TMB is the colloidal solution of uniform dispersion；Under the action of an external magnetic field,
Fe3O4- Au-TMB nano particle carries out reversible aggregation, and intergranular local fields couple, so that " hot spot-effect " is generated,
More SERS hot spots are formed, the hydrogen peroxide for detecting lower concentration is conducive to.Method reported herein relatively before fluorescence
Measuring method, detection sensitivity promote about 1 order of magnitude.
Fig. 3 is to synthesize Fe in the embodiment of the present invention 13O4, Au and Fe3O4- Au nano particle transmission electron microscope figure
(TEM): (a) Fe3O4(M) the TEM figure of nano particle: the Fe of synthesis3O4Nano particles are more uniform, Fe3O4Nano particle
Diameter majority concentrates between 38nm-42nm；(b) the TEM figure of Au nano particle: AuseedsThe partial size most started is mostly distributed in
Between 3-4nm；(c)Fe3O4-AuseedsThe TEM of nano particle schemes: Fe3O4Nano particle is after PEI is modified, with AuseedsOccur even
Connection reaction, generates Fe3O4-Auseeds, such as scheming big ferriferrous oxide particles surface is small AuseedsPartial size is distributed more dilute
It dredges, the gap between the nanogold particle on same ferriferrous oxide particles surface is up to 27nm；(d)Fe3O4- Au nano particle
Add the TEM figure of 1 golden growth-promoting media: after the 1st Secondary Gold, Fe3O4Nano grain surface AuseedsBecome larger close, same four oxygen
The gap changed between the nanogold particle of three-iron particle surface is up to 10nm, at this time AuseedsPartial size integrated distribution in 6-7nm
Between, size is more uniform；(e)Fe3O4- Au nano particle adds the TEM figure of 2 golden growth-promoting medias: after the 2nd Secondary Gold, four oxidations
Three-iron nano grain surface AuseedsFurther increase intensive, AuseedsFor partial size integrated distribution between 8.5-10nm, size is more equal
One；(f)Fe3O4- Au nano particle adds the TEM figure of 3 golden growth-promoting medias: after the 3rd Secondary Gold, ferroso-ferric oxide surface
AuseedsParticle further increases, but size and uneven at this time, and maximum gold particle partial size has reached about 15nm.
Fig. 4 is to synthesize Fe in the embodiment of the present invention 13O4, Au and each Fe3O4The normalized UV- of-Au nanoparticles solution
Vis delustring spectrogram.Wherein, M refers to Fe3O4Nanoparticles solution；AuseedsRefer to Au nano particle；M+AuseedsRefer to Fe3O4-Auseeds
Nano particle；M+Auseeds+ 1 refers to Fe3O4- Au nano particle adds 1 golden growth-promoting media；M+Auseeds+ 2 refer to Fe3O4-AuseedsNanometer
Particle adds 2 golden growth-promoting medias；M+Auseeds+ 3 refer to Fe3O4-AuseedsNano particle adds 3 golden growth-promoting medias.
M+AuseedsCurve is Fe3O4Particle and AuseedsThe linear adduction of particle solution curve.This is because Fe3O4Nanometer
The Au of particle surfaceseedsIt is distributed very sparse, AuseedsBetween spacing it is big, coupling can not be generated.After 1 Secondary Gold liquid is added,
The obvious red shift of Spectral Extinction of grain solution.This is because Fe3O4Particle surface AuseedsDiameter increases, and particle increases, AuseedsBetween
Spacing gradually becomes smaller, AuseedsBetween produce the effect of intercoupling, the Au on ferroso-ferric oxide surfaceseedsArray forms new class
The surface plasmon oscillations mode of shell structure.Again after the raw golden liquid of 1 addition, the further red shift of Spectral Extinction.This is because Fe3O4
Particle surface AuseedsIt further increases and becomes close, the surface plasmon oscillations mode of class shell structure further enhances.3rd time plus
After entering raw golden liquid, red shift occurs for solution Spectral Extinction, but spectral peak width increases.This is because after the raw golden liquid of the 3rd addition, Fe3O4
Particle surface AuseedsPartial size start irregular, partial particulate even forms incomplete shell, particle surface plasma
Mode becomes complicated multiplicity, and peak width is exactly the effect of multi-mode superposition.
Specific embodiment
The following examples combination attached drawing is a further detailed description of the invention.Described concrete measure example is only
The present invention is explained, is not intended to restrict the invention.
Fig. 1 is Fe of the present invention3O4- Au structure nano particles are to H2O2Illustrate with the SERS super sensitivity detection of concentration of glucose
Figure.Fe3O4For catalyst, Fe3O4The Au on surfaceseedsArray can produce " hot spot ", to enhance substrate.With Fe3O4-AuseedsIt is compound
Based on the gold particle on object surface, AuseedsContinuation is grown on ferroso-ferric oxide core, generates the peak LSPR of nano particle red
It moves, is convenient for Raman excitation.It is used as with 3,3', 5,5'- tetramethyl biphenyl amine molecules and reports molecule, hydrogen peroxide and 3,3',
Redox reaction occurs for 5,5'- tetramethyl benzidines, according to SERS before and after 3,3', 5,5'- tetramethyl benzidine molecular oxidations
The detection to concentration of hydrogen peroxide is realized in the variation of signal strength or weakness.
Fig. 2 is Fe of the present invention3O4The aggregation schematic diagram of-Au structure nano particle under the action of an external magnetic field.Magnetic field is being not added
Under the action of, Fe3O4-Au-TMB is the colloidal solution of uniform dispersion；Under the action of an external magnetic field, Fe3O4- Au-TMB nanometers
Grain carries out reversible aggregation, and intergranular local fields couple, to generate " hot spot-effect ", forms more SERS heat
Point is conducive to the hydrogen peroxide for detecting lower concentration.Method reported herein relatively before fluorimetry, detection sensitivity
Promote about 1 order of magnitude.
Embodiment 1
A kind of preparation method of ferroso-ferric oxide/gold structure nano particles, comprising the following steps:
Step 1: Fe3O4The preparation of nano particle: 65mL water being added into 250mL three-necked flask, in the anaerobic of logical nitrogen
Under environment, heating water bath is to 90 DEG C.It weighs 1.280g green vitriol to be dissolved in 10mL deionized water, ferrous sulfate is made
The polyethyleneimine (relative molecular mass 10000, concentration 80mg/mL) of 5mL is successively added in aqueous solution in three-necked flask
(polyethyleneimine ultimate density 4g/L), 10mL ferrous sulfate aqueous solution, 10mL concentration are the potassium nitrate solution of 2.0M, and 10mL is dense
Degree is the sodium hydroxide solution of 1.0M, keeps 2h.Particle is settled with magnet, deionized water is washed 5 times.80mL deionization is added
Spare, the Fe is resuspended in water3O4Nano-particle diameter majority concentrates between 38nm-42nm.
Step 2: the preparation of gold nano seed solution: 1mL1% gold chloride (25mM) is added in 90mL water, stirs 1min
Afterwards, the sodium citrate aqueous solution that 2mL concentration is 38.8mM is added, after stirring 1min, 1mL (0.075%) containing sodium borohydride is added
The 38.8mM sodium citrate aqueous solution of (75mg).After stirring 5min, 4 DEG C are kept in dark place, and gold kind of the particle diameter is mostly distributed
Between 3-4nm.
Step 3: the product of the step of taking 200 μ L to be resuspended one is added in golden kind of the solution of 9mL.Mixing is sufficiently rocked, later
Every 10min interval ultrasound 2min, reacts 2h.Deionized water is washed 5 times.Then, 9mL water is added to be resuspended, adds 1mL's
The PEI aqueous solution of 80mg/mL, 60 DEG C of reaction 1h, if during which assembling, ultrasound makes to disperse.Deionized water 2 times, 2.5mL is added
Deionized water is resuspended.
Step 4: one secondary growth of ferroso-ferric oxide/gold nano grain: the configuration of golden growth-promoting media: taking a 5mL test tube, first
It is 0.2M hexadecyltrimethylammonium chloride solution that 2.5mL concentration is added afterwards, and 125 μ L concentration are the chlorauric acid solution of 10mM, 10 μ
Potassium bromide solution of the L degree for 0.01M, 2.265mL water, AA (0.04M) solution of 50 μ L stir evenly, and gold growth-promoting media is made, to
The hexadecyltrimethylammonium chloride solution that 2.5mL concentration is 0.2M is added in product made from step 3, adds golden growth
Liquid sufficiently shakes up, and reacts 15min.At this point, Fe3O4Nano grain surface AuseedsPartial size integrated distribution between 6-7nm, together
Gap between the nanogold particle on one ferriferrous oxide particles surface is up to 27nm；
Step 5: the multiple regrowth of ferroso-ferric oxide/gold nano grain: 125 μ L being added into the product that step 4 obtains
The AA solution that the chlorauric acid solution and 50 μ L concentration that concentration is 10mM are 0.04M, sufficiently shakes up, ultrasonic 1min, reacts 15min,
Iteration growth；It regrows step to be repeated 1 times, the LSPR of coupling is generated in ferroso-ferric oxide/gold nano grain scattering spectrum
Peak, ferroferric oxide nano granules surface A useedsFor partial size integrated distribution between 8.5-10nm, size is more uniform, uses deionization
Water washing is primary, and 2.5mL deionized water is added and is resuspended.
Step 7: ferroso-ferric oxide/gold nanoparticle probes functionalization: configuration substance withdrawl syndrome is 80 μm of ol/mL
3,3', 5,5'- tetramethyl biphenyl amine aqueous solutions take the ferroso-ferric oxide/gold nanoparticle of 1mL iteration twice, and 10 μ L 3 are added,
3', 5,5'- tetramethyl biphenyl amine aqueous solutions, substance withdrawl syndrome are 80 μm of ol/mL, normal-temperature reaction 40min.Magnet separation, goes
Ion water washing 2 times, 1mL deionized water is added and is resuspended.Ferroso-ferric oxide/gold nano grain after taking a small amount of functionalization, test
Raman spectrum.
(a) in Fig. 3 is the Fe that step 1 is prepared in embodiment 13O4(M) the TEM figure of nano particle, the Fe3O4It receives
Rice grain granularity is more uniform, and diameter majority concentrates between 38nm-42nm；(b) in Fig. 3 is step 2 system in embodiment 1
Standby obtained AuseedsThe TEM of nano particle schemes, AuseedsNano particles are more uniform, partial size be mostly distributed in 3-4nm it
Between；(c) in Fig. 3 is the Fe that step 3 is prepared in embodiment 13O4-AuseedsThe TEM of nano particle schemes, four big oxidations
Three-iron particle surface is small AuseedsParticle, be distributed it is more sparse, the nanogold particle on same ferriferrous oxide particles surface it
Between gap be up to 27nm；(d) in Fig. 3 is the Fe that step 4 is prepared in embodiment 13O4- Au nano particle adds 1 time
The TEM of golden growth-promoting media schemes, Fe3O4Nano grain surface AuseedsBecome larger close, the nanogold on same ferriferrous oxide particles surface
Gap between particle is up to 10nm, at this time AuseedsPartial size integrated distribution between 6-7nm, size is more uniform；In Fig. 3
(e) be step 5 is prepared in embodiment 1 Fe3O4- Au nano particle adds the TEM figure of 2 golden growth-promoting medias, four oxidations three
Iron nano-particle surface A useedsFurther increase intensive, AuseedsFor partial size integrated distribution between 8.5-10nm, size is more equal
One；(f) in Fig. 3 is the Fe that step 5 is prepared in embodiment 13O4- Au nano particle adds the TEM figure of 3 golden growth-promoting medias,
The Au on ferroso-ferric oxide surfaceseedsParticle further increases, but size and uneven at this time, and maximum gold particle partial size has reached
To about 15nm.
Fig. 4 is to synthesize Fe in embodiment 13O4, Au and each Fe3O4The normalized UV-vis delustring of-Au nanoparticles solution
Spectrogram.Wherein, M refers to Fe3O4The UV-vis delustring spectrogram of nanoparticles solution；AuseedsRefer to the UV-vis delustring of Au nano particle
Spectrogram；M+AuseedsRefer to Fe3O4-AuseedsNano particle UV-vis delustring spectrogram, Fe3O4The Au of nano grain surfaceseedsDistribution
It is very sparse, AuseedsBetween spacing it is big, coupling can not be generated；M+Auseeds+ 1 refers to Fe3O4- Au nano particle adds 1 Jin Shengchang
The UV-vis delustring spectrogram of liquid, the Spectral Extinction obviously occur red shift, illustrate Fe3O4Particle surface AuseedsDiameter increases, and particle increases
It is more, AuseedsBetween spacing gradually become smaller, AuseedsBetween produce the effect of intercoupling, the Au on ferroso-ferric oxide surfaceseedsArray
Form the surface plasmon oscillations mode of new class shell structure；M+Auseeds+ 2 refer to Fe3O4-AuseedsNano particle adds 2 times
The UV-vis delustring spectrogram of golden growth-promoting media, the further red shift of the Spectral Extinction.This is because Fe3O4Particle surface AuseedsFurther
Increase and become close, the surface plasmon oscillations mode of class shell structure further enhances；M+Auseeds+ 3 refer to Fe3O4-AuseedsNanometer
Particle adds the UV-vis delustring spectrogram of 3 golden growth-promoting medias, which occurs red shift, but spectral peak width increases.This is because
After the raw golden liquid of 3rd addition, Fe3O4Particle surface AuseedsPartial size start irregular, partial particulate even forms endless
Whole shell, particle surface Plasma mode become complicated multiplicity, and peak width is exactly the effect of multi-mode superposition.
Embodiment 2
Ferroso-ferric oxide/the gold nano grain being prepared using embodiment 1 is as SERS probe, with 3,3', 5,5'- tetra-
Methyl biphenyl amine is report molecule, detects H2O2Concentration the following steps are included:
Step 1: the configuration of a certain concentration gradient hydrogenperoxide steam generator: taking a certain amount of 30% aqueous hydrogen peroxide solution, first
It is made into the aqueous hydrogen peroxide solution of the certain gradient concentration of 1mL afterwards.
Step 2: the hydrogenperoxide steam generator of SERS detection various concentration: for various concentration hydrogenperoxide steam generator, being added
The above-mentioned functionalization probe of 100 μ L, after reacting 15min, magnetism draws probe, is added drop-wise to analysis fine aluminium on piece and carries out Raman test,
Wherein, the wavelength of raman excitation light is 633nm, power 10%, using static schema, time for exposure 1s, integral number of times 2
It is secondary.
Embodiment 3
Ferroso-ferric oxide/the gold nano grain being prepared using embodiment 1 is as SERS probe, with 3,3', 5,5'- tetra-
Methyl biphenyl amine be signaling molecule, detection concentration of glucose the following steps are included:
Step 1: the enzymatic treatment of a certain concentration gradient glucose solution: weighing a certain amount of glucose, be successively made into 1mL
The glucose solution of a certain concentration gradient.The glucose oxidase GOx of the 20mg/mL of 20 μ L, 37.5 DEG C of water-baths are added
30min；
Step 2: the glucose solution of SERS detection various concentration: for a certain concentration gradient (1-10-9Mol/L) grape
The above-mentioned functionalization probe of 100 μ L is added in sugar juice, reacts 15min, and magnetism draws probe, is added drop-wise to analysis fine aluminium on piece and carries out
Raman test.Wherein, the wavelength of raman excitation light is 633nm, power 10%, using static schema, time for exposure 1s, product
Gradation number is 2 times.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of ferroso-ferric oxide/gold structure nano particles preparation method, it is characterised in that: the specific steps of the method are such as
Under:
(1)Fe3O4The preparation of nanoparticles solution:
Under logical nitrogen, water bath, polyethylenimine solution, ferrous sulfate solution, potassium nitrate solution, hydroxide is successively added
Sodium solution reacts 1-3h, is settled particle with magnet, after deionized water washing, can be prepared by Fe3O4Nanoparticles solution, it is described
Fe3O4Nano particle diameter is between 30nm-60nm；
(2) preparation of gold nano seed solution:
Configure the mixed solution A of sodium borohydride and sodium citrate；A certain concentration chlorauric acid solution is configured, under magnetic agitation, is added
Sodium citrate solution adds mixed solution A, obtains gold nano seed solution, the gold nano seed after reacting a period of time
Partial size be 3nm-5nm；
(3) ferroso-ferric oxide/gold nanoparticle preparation:
Fe prepared by step (1)3O4Nanoparticles solution is mixed with gold nano seed solution prepared by step (2), is sufficiently stirred
It mixes, reacts 1-3h, magnetic separation is washed with deionized to remove excessive gold nano seed, it is molten to add polyethyleneimine
Ferroso-ferric oxide/gold kind nanoparticle is made in 55-65 DEG C of reaction 0.5-2h in liquid, and deionized water is washed 1-2 times, four oxygen
Change in three-iron/gold nanoparticle, the gap between the nanogold particle on same ferriferrous oxide particles surface is up to 27nm；
(4) one secondary growth of ferroso-ferric oxide/gold nano grain:
Hexadecyltrimethylammonium chloride solution, chlorauric acid solution, potassium bromide solution, AA solution are uniformly mixed, it is raw that gold is made
Long liquid；It is molten that hexadecyltrimethylammonium chloride is added into ferroso-ferric oxide made from step (3)/gold kind nano-particle solution
Liquid stirs evenly, and adds golden growth-promoting media, reacts 15-20min；
(5) the multiple regrowth of ferroso-ferric oxide/gold nano grain:
Chlorauric acid solution is added again into step (4) reaction solution, AA solution is then added, reacts 15-20min, gold particle
It regrows；It regrows step to be typically repeated 2-5 times, be generated until in ferroso-ferric oxide/gold nano grain scattering spectrum
1-2 spare, ferroso-ferric oxide/gold nano grain of the multiple regrowth is washed with deionized in the peak LSPR of coupling
Partial size is in 40nm-75nm.
2. ferroso-ferric oxide as described in claim 1/gold structure nano particles preparation method, it is characterised in that: step (1)
In, water bath heating temperature is 80-100 DEG C, and polyethyleneimine, green vitriol, potassium nitrate, sodium hydroxide molar ratio are 1:
115:500:250。
3. ferroso-ferric oxide as described in claim 1/gold structure nano particles preparation method, it is characterised in that: step (2)
In, configure the mixed solution A containing mass fraction for 0.075% sodium borohydride and sodium citrate；Under magnetic agitation, by gold chloride
Aqueous solution and sodium citrate solution are mixed according to the amount of substance concentration of 1:2, and solution A is added, gold nano seed solution is made.
4. ferroso-ferric oxide as described in claim 1/gold structure nano particles preparation method, it is characterised in that: step (3)
In, it is mixed according to ferriferrous oxide nano-particle solution with gold nano seed solution volume ratio for 1:45, mixing fullys shake, instead
2h to be answered, is washed with deionized 3-5 times, mixing fullys shake in addition and the isometric deionized water of gold nano seed solution, then
Be added 0-4g/L polyethylenimine solution, in 55-65 DEG C of reaction 1h, if during which assembling, can ultrasonic disperse, deionized water
Ferroso-ferric oxide/gold kind nanoparticle is made in washing 3-5 times.
5. ferroso-ferric oxide as described in claim 1/gold structure nano particles preparation method, it is characterised in that: step (4)
In, it is 5000:1.25:1:20 system according to the ratio between hexadecyltrimethylammonium chloride, gold chloride, potassium bromide, the amount of substance of AA
Standby gold growth-promoting media；The 16 of the amount of same substance are added into ferroso-ferric oxide made from step (3)/gold kind nano-particle solution
Alkyl trimethyl ammonium chloride solution, stirs evenly, and adds golden growth-promoting media, reacts 15-20min.
6. ferroso-ferric oxide as described in claim 1/gold structure nano particles preparation method, it is characterised in that: step (5)
In, the chlorauric acid solution isometric with chlorauric acid solution in step (4) is added in the product that obtains to step (4), add with
The isometric AA solution of AA solution in step (4), reacts 15-20min, and gold particle regrows；Regrow weight as step 1
2-5 times multiple, the peak LSPR until generating coupling in ferroso-ferric oxide/gold nano grain scattering spectrum is washed with deionized
1-2 times spare.
7. ferroso-ferric oxide/gold structure nano particles prepared by the method as described in claim 1-6 are examined for SERS hypersensitive
Survey H2O2Concentration.
8. the use as claimed in claim 7, it is characterised in that: the application with ferroso-ferric oxide/gold structure nano particles is
Probe, 3,3', 5,5'- tetramethyl benzidines are signaling molecule, and the specific method is as follows:
(1) ferroso-ferric oxide/gold nano grain functionalization:
3,3', 5, the 5'- tetramethyl biphenyl amine aqueous solutions that substance withdrawl syndrome is 80 μm of ol/mL are configured, are added into the solution
Ferroso-ferric oxide/gold structure nano particles solution, ferroso-ferric oxide/gold structure nano particles solution and 3,3', 5,5'- tetramethyls
The volume ratio of biphenyl amine aqueous solution is 100:1, and normal-temperature reaction 40-60min is separated with magnet, and deionized water washes twice, and addition is gone
Ionized water is resuspended, and obtains SERS probe；
(2) H of SERS probe in detecting various concentration2O2Solution:
Configure a certain concentration gradient (1~10-9mol/L)H2O2The SERS probe of 100 μ L steps (1) preparation, reaction is added in solution
After 5-20min, magnetic force draws probe, is added drop-wise to analysis fine aluminium piece and carries out Raman test.Wherein, the wavelength of raman excitation light is
633nm, power 10%, using static schema, time for exposure 1s, integral number of times is 2 times.
9. ferroso-ferric oxide/gold structure nano particles prepared by the method as described in claim 1-6 are examined for SERS hypersensitive
Survey the application of concentration of glucose.
10. application as claimed in claim 9, it is characterised in that: the application is with ferroso-ferric oxide/gold structure nano particles
Probe, 3,3', 5,5'- tetramethyl benzidines are signaling molecule, and the specific method is as follows:
(1) with the method (1) in claim 8, SERS probe is prepared.
(2) enzymatic treatment of different glucose solution:
Configure a certain concentration gradient (1~10-9Mol/L glucose solution) is added to the different glucose solution of 1mL
The glucose oxidase GOx solution of the 20mg/ml of 20 μ L, 37.5 DEG C of water-bath 20-40min；
(3) SERS detects the glucose solution of various concentration:
To different glucose solution, the above-mentioned SERS probe of 100 μ L is added, after reacting 5-20min, magnetism draws probe, drop
It is added to analysis fine aluminium on piece and carries out Raman test.Wherein, the wavelength of raman excitation light is 633nm, power 10%, using static state
Mode, time for exposure 1s, integral number of times are 2 times.
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