CN110531061A - A kind of preparation method and its recyclable immune detection application of ferroso-ferric oxide/titanium dioxide/silver core-shell nano material - Google Patents
A kind of preparation method and its recyclable immune detection application of ferroso-ferric oxide/titanium dioxide/silver core-shell nano material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/531—Production of immunochemical test materials
- G01N33/532—Production of labelled immunochemicals
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/536—Immunoassay; Biospecific binding assay; Materials therefor with immune complex formed in liquid phase
- G01N33/537—Immunoassay; Biospecific binding assay; Materials therefor with immune complex formed in liquid phase with separation of immune complex from unbound antigen or antibody
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/54313—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being characterised by its particulate form
- G01N33/54326—Magnetic particles
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a kind of ferroso-ferric oxide/titanium dioxide/silver core-shell nano material preparation method and its directly recyclable immune detection application, feature is that activation triple core-shell nano material combines it with determined antigen, the direct Raman detection of determined antigen is realized using surface enhanced Raman scattering effect, after the completion of Raman detection, ultraviolet lighting degradation antigen is carried out to the nano material of above-mentioned immune combination, magnetic force recycles the nonantigenic existing Fe in surface3O4/TiO2/ Ag core-shell nano material, and it is used for next time in the detection of determined antigen, repeat this Raman detection-catalytic degradation-Raman detection process, realize the directly recyclable immune detection of tumor markers, advantage is that three-layer nuclear shell structure had both had the function of Magnetic Isolation and Raman enhancing, have the function of catalytic degradation tumor markers again, while detecting and limiting low and detectable macromolecular tumor markers.
Description
Technical field
The present invention relates to material engineering and field of nanometer technology, more particularly, to a kind of ferroso-ferric oxide/titanium dioxide/silver
(Fe3O4/TiO2/ Ag) core-shell nano material preparation method and its recyclable immune detection application.
Background technique
In recent years, with the aggravation of environmental pollution, the lasting change of global climate, the generation of crisis in food and people are raw
The increasing of pressure living, cancer take place frequently, and high mortality has become seriously threatening for human health.Therefore, it is developed one
The advanced immunological technique of series, such as chemoluminescence method and enzyme-linked immunosorbent assay biochemistry detection technology visit cancer sufferer
It surveys and treats.But the patient for being in cancer early stage, cancer markers content is lower in blood, is difficult to be sent out early
Now and treated.Surface enhanced Raman scattering immunological technique developed in recent years makes full use of Surface enhanced Raman scattering
The higher Electromagnetic enhancement degree that has and up to unimolecule rank highly sensitive advantage, it can be achieved that tumor markers trace
Amount detection.But Surface enhanced Raman scattering technology based on material be mostly that noble metal nanometer material preparation cost is higher, it is unfavorable
In its practical application in clinical immunization detection.Therefore, it is necessary to develop a kind of circulation immunity detection technique.Titanium dioxide is received
Rice material has excellent photocatalytic activity, is a kind of potential critical material for realizing this recyclable immunoassay technology.Together
When, how to be urged using the light that the diversified nano material with performances such as excellent photoelectromagnetics further increases composite nano materials
Change activity, promoting application of the recyclable immunoassay technology in former field tachysynthesis detection is still the side that researcher is made great efforts
To.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind not only to have had the function of Magnetic Isolation and Raman enhancing, but also tool
There is the detection of catalytic degradation cancer markers to limit low ferroso-ferric oxide/titanium dioxide/silver core-shell nano material preparation method
And its recyclable immune detection application.
The technical scheme of the invention to solve the technical problem is: a kind of ferroso-ferric oxide/titanium dioxide/silver core
The preparation method of shell nanometer material, comprising the following steps:
(1) 1.35-6.75 grams of Iron(III) chloride hexahydrate, 3.6-18.0 grams of sodium acetate and 1.0-5.0 grams of polyethylene glycol are dissolved in 40-
In 200 milliliters of ethylene glycol, after ultrasound is until be completely dissolved, it is transferred in hydrothermal reaction kettle, is reacted 10 hours at 200 DEG C, from
The heart simultaneously collects precipitating after being cleaned with ethyl alcohol to get to Fe3O4Nano particle；
(2) Fe that 50 milligrams of steps (1) obtain is weighed3O4It is that 0.1 mM of every milliliter of hydrochloric acid is water-soluble that nano particle, which is dissolved in concentration,
Ultrasound 15 minutes in liquid, Magnetic Isolation is simultaneously cleaned three times with deionized water；Again after Magnetic Isolation, by Fe3O4Nano particle is dissolved in
120 milliliters by ethyl alcohol and the acetonitrile mixed solution that 3:1 is mixed by volume, after ultrasound makes it completely dissolved, Xiang Qijia
Enter 500 microlitres of ammonium hydroxide, ultrasound is uniformly mixed it；Then 1-6 milliliters of four fourths of metatitanic acid are added dropwise under agitation
Ester, reaction 1.5 hours after, Magnetic Isolation and with ethanol washing three times after to get arrive Fe3O4/TiO2Nano particle；
(3) Fe for taking 81 milligrams of steps (2) to obtain3O4/TiO2Nano particle and 75.4 milligrams of ammonium fluorides be dissolved in 20.45 milliliters by
In the second alcohol and water mixed solution that 13.5:6.95 is mixed by volume, ultrasound puts it by reaction solution after completely dissolution
It is placed in and persistently stirs 1 hour at room temperature, mixing speed is 180-200 rpms, and after the completion of stirring, reaction solution is transferred to
It in reaction kettle, is reacted 24 hours at 180 DEG C, after reaction kettle cooled to room temperature, Magnetic Isolation is simultaneously washed with deionized water
3 times are washed to get the Fe for arriving crystallization3O4/TiO2Nano particle；
(4) Fe for the crystallization for taking 81 milligrams of steps (3) to obtain3O4/TiO2Nano particle is dissolved in 33.4 milliliters of ethyl alcohol, is continued
25 microlitres of 3- aminopropyl trimethoxy siloxanes are added dropwise under stirring, reaction solution is placed at 80 DEG C and is condensed back 4 hours,
After its cooled to room temperature, Magnetic Isolation and with ethanol washing three times to get arrive amidized Fe3O4/TiO2Nanometer
Grain；
(5) 1 gram of polyvinylpyrrolidone (5800 grams every mole of molecular weight) and 28 milligrams of steps (4) are obtained amidized
Fe3O4/TiO2Nano particle is dissolved in 10 ml deionized waters after mixing, and silver ammino solution is added dropwise under mechanical stirring
And be transferred in hydrothermal reaction kettle, sealing, which is placed at 120 DEG C, reacts 11 hours, after reaction kettle cooled to room temperature, magnetic
Property separation and successively with tetrahydrofuran, ethyl alcohol and deionized water wash to get arrive Fe3O4/TiO2/ Ag core-shell nano material, juxtaposition
It is stored in deionized water for use, wherein silver ammino solution is the preparation method comprises the following steps: taking 2 milliliters of concentration is 0.01-0.08 milligrams every milliliter
Silver nitrate aqueous solution, be added excessive ammonium hydroxide until reaction solution become clarification obtain silver ammino solution.
Based on the resulting ferroso-ferric oxide of above-mentioned preparation method/titanium dioxide/silver core-shell nano material tumor markers
Recyclable immunologic detection method, comprising the following steps:
(1) by 15 milligrams of Fe3O4/TiO2/ Ag core-shell nano material is dissolved in 2 milliliters of dimethylformamide (DMF) solutions, then
The DMF solution of 1 milliliter of succinic anhydride is added, after hatching being slowly shaken at 70 DEG C 24 hours, Magnetic Isolation simultaneously uses deionized water
Washing 2 times to get the Fe for arriving carboxylated3O4/TiO2/ Ag core-shell nano material, and be dissolved in 1 milliliter of water, then it is added 1 milliliter
The PBS solution of EDC/NHS is washed with deionized 1 time, then will be after washing after slowly shaking hatching at 30 DEG C 1 hour
Fe3O4/TiO2/ Ag core-shell nano material is dissolved in 1 milliliter by PBS buffer solution and water by isometric mixed solution than mixing
In, the tumor markers solution of 100 micrograms per millilitres is added thereto, in 30 DEG C slowly shake hatching 3.5 hours after, spend from
Sub- water washing is primary, and Magnetic Isolation obtains the Fe for being marked with tumor markers3O4/TiO2/ Ag core-shell nano material, utilizes Raman
Spectrometer, which carries out spectral measurement to it, can detect the content of tumor markers to be measured；
(2) after detecting, the Fe of tumor markers will be marked with3O4/TiO2/ Ag core-shell nano material is dissolved in deionized water,
And be transferred into Clear glass bottles and jars, assemble Fe by the way of small magnet attraction3O4/TiO2/ Ag core-shell nano, is adopted
It is irradiated with the ultraviolet lamp that wavelength is 265 nanometers, until tumor markers degradation completely, then will urge under photocatalysis
Fe after change3O4/TiO2/ Ag core-shell nano material repeats step (1) method and links new tumor markers, can be realized to swollen
The directly recyclable immune detection of tumor markers.
The concentration of succinic anhydride is 10.3 milligrams every milliliter in the DMF solution of succinic anhydride as described in step (1)；It is described
EDC/NHS PBS solution in the concentration of EDC be 10 milligrams every milliliter, the concentration of NHS is 10 milligrams every milliliter.
The tumor markers include prostate-specific antigen PSA, AFP AFP, immune globulin IGg, carbohydrate
Antigens c A199 and Carcinoembryonic Antigen CEA.
Compared with the prior art, the advantages of the present invention are as follows: present invention firstly discloses ferroso-ferric oxide/titanium dioxide/
The preparation method of galactic nucleus shell nanometer material and recyclable immunologic detection method to tumor markers, in three-layer nuclear shell structure
Fe3O4Kernel makes triple core-shell structure have the function of Magnetic Isolation, and sample clean separation can be made more simple and quick.
Simultaneously as Fe3O4The presence of kernel, when the tumor markers combined to core-shell nano material surface carry out photocatalytic degradation
When, it can make core-shell nano material that enrichment of reuniting occur to a certain extent by externally-applied magnetic field, enhance the efficiency of catalysis.
TiO2Subshell has good photocatalytic activity, and mechanism is under ultraviolet lighting, since the energy of photon is greater than TiO2Prohibit
Bandwidth, the electronics (e in valence band-) absorption photon energy is excited on conduction band, while hole (h is left in valence band+).
Work as TiO2There are when surface defect or suitable trapping agent, the compound of electrons and holes is inhibited, will be in TiO2Surface hair
Raw oxidation-reduction reaction.Valence band hole is good oxidant, can be with TiO2The H of adsorption2In O molecule or reaction solution
The OH of dissolution-In conjunction with the hydroxyl radical free radical (OH) for forming oxidisability wave very living.And conduction band electron is good reducing agent, is passed through
With TiO2O that is adsorption or being dissolved in reaction solution2A series of intermediate reactions are carried out, finally can also form oxidisability very
The hydroxyl radical free radical (OH) and Superoxide anion free radical (O of wave living2 -).Hydroxyl radical free radical (OH) and Superoxide anion free radical (
O2 -) various organic matters (including this single chain glycoprotein of prostate-specific antigen PSA) can be oxidized to CO2、H2O etc. is inorganic
Small molecule, and because their oxidability is strong, it can be ensured that oxidation reaction does not stay in intermediate steps generally, does not generate
Between product.Ag shell is made of the Ag nano particle largely to gather, and when there is ambient light photograph, surface electronic can be excited to be formed
Local surface plasmon resonance has TiO around Ag nano particle2In the presence of, electronics a part of these excitations can lead to
It crosses charge transfer process and reaches TiO2Among conduction band, the electrons increased among conduction band remarkably promote TiO2To tumor markers
Catalytic degradation ability.After catalytic degradation, by suitably cleaning, Fe3O4/TiO2/ Ag core-shell nano material can also be recovered benefit
With being detected in conjunction with new determined antigen again, realize a kind of detection of circulation immunity.Meanwhile passing through one step packet of hydro-thermal method
The Ag shell covered is compared to the Ag particle that other methods such as Electrostatic Absorption method synthesizes, in amidized TiO2Adsorption is more tight
It is close and uniform.Be conducive to Ag and TiO2Between charge transfer process facilitation effect, and then significantly increase TiO2Photocatalysis
Activity realizes the catalytic degradation of this kind of macromolecular of tumor markers.Also, its surface electronic causes in excitation light action low-resonance
Local electromagnetic field can significantly increase the specific Raman signals of tumor markers.Ag raman scattering cross section is larger, and enhancing is drawn
Graceful scattering efficiency is higher, and the Surface enhanced Raman scattering base for being advantageously implemented the highly sensitive high specific of tumor markers is direct
Immune detection avoids indirect detection and needs to introduce additional Raman molecular, the cumbersome disadvantage of operating procedure.In short, Fe3O4/
TiO2/ Ag core-shell nano material, not only had the function of Magnetic Isolation, catalytic degradation tumor markers effect but also have enhancing
The effect of tumor markers Raman signal is a kind of novel multi-functional nanometer material.Pass through design synthesis this novel three
Heavy nucleus shell structure especially controls Fe by systematically adjusting reaction condition during the reaction3O4Diameter, TiO2Centre
The closeness of thickness degree and Ag shell, we can comprehensively utilize the respective advantage of above-mentioned three kinds of materials, realize tumor markers
The directly recyclable immune detection of highly sensitive high specific.
Detailed description of the invention
Fig. 1 is the Fe prepared in the embodiment of the present invention 13O4The transmission electron microscope photo of nano material；
Fig. 2 is the Fe prepared in the embodiment of the present invention 13O4/TiO2The transmission electron microscope photo of core-shell nano material；
Fig. 3 is the Fe prepared in the embodiment of the present invention 13O4/TiO2The electron scanning micrograph of/Ag core-shell nano material；
Fig. 4 is that Ag particle is wrapped in Fe prepared by the present embodiment 1 using Electrostatic Absorption method3O4/TiO2Core-shell nano outer surface
The Fe of formation3O4/TiO2The electron scanning micrograph of/Ag triple core-shell nano material；
Fig. 5 is that the Fe prepared in the embodiment of the present invention 1 is respectively adopted3O4/TiO2/ Ag core-shell nano material and Electrostatic Absorption legal system
Standby Fe3O4/TiO2/ Ag triple core-shell nano material urges small molecule 4- mercaptobenzoic acid (0.01 mM every milliliter)
The result of change；
Fig. 6 is the Fe prepared in the embodiment of the present invention 13O4/TiO2/ Ag core-shell nano material is to prostate-specific antigen PSA
The carry out immune detection of (10 micrograms per millilitre) and the result being catalyzed；
Fig. 7 is the Fe prepared using Electrostatic Absorption method3O4/TiO2/ Ag core-shell nano material is to prostate-specific antigen PSA(10
Micrograms per millilitre) carry out immune detection and be catalyzed result；
Fig. 8 is the Fe prepared in the embodiment of the present invention 13O4/TiO2/ Ag core-shell nano material is to prostate-specific antigen PSA's
Directly recyclable immune detection result；
Fig. 9 is the Fe prepared in the embodiment of the present invention 13O4/TiO2/ Ag core-shell nano material is to prostate-specific antigen PSA's
Frequency displacement is 1264 cm in directly recyclable immune middle Raman spectrum-1Feature peak intensity with determined antigen concentration variation diagram；
Figure 10 is the Fe prepared in the embodiment of the present invention 23O4/TiO2/ Ag core-shell nano material is to prostate-specific antigen PSA
It is directly recyclable immune in Raman spectrum frequency displacement be 1264 cm-1Feature peak intensity with determined antigen concentration variation diagram；
Figure 11 is the Fe prepared in the embodiment of the present invention 33O4/TiO2/ Ag core-shell nano material is to prostate-specific antigen PSA
It is directly recyclable immune in Raman spectrum frequency displacement be 1264 cm-1Feature peak intensity with determined antigen concentration variation diagram.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..Unless otherwise specified, embodiment
Used in the conventional means that are well known to those skilled in the art of technological means, raw materials used is commercial goods.Embodiment
Used in Raman spectrum detector BWS415 be purchased from U.S. Bi Da Imtech (B&W Tek Inc.).
Embodiment 1
A kind of Fe3O4/TiO2/ Ag triple core-shell nano material and its to the directly recyclable immune of prostate-specific antigen PSA
Detection method, comprising the following steps:
1、Fe3O4/TiO2The preparation of/Ag triple core-shell nano material
(1) 3.5 grams of Iron(III) chloride hexahydrates, 10.8 grams of sodium acetates and 3 grams of polyethylene glycol are dissolved in 120 milliliters of ethylene glycol, are surpassed
It after sound is until be completely dissolved, is transferred in hydrothermal reaction kettle, is reacted 10 hours at 200 DEG C, be centrifuged and received after being cleaned with ethyl alcohol
Collection precipitates to arrive Fe3O4Nano particle；
(2) Fe that 50 milligrams of steps (1) obtain is weighed3O4It is that 0.1 mM of every milliliter of hydrochloric acid is water-soluble that nano particle, which is dissolved in concentration,
Ultrasound 15 minutes in liquid, Magnetic Isolation is simultaneously cleaned three times with deionized water；Again after Magnetic Isolation, by Fe3O4Nano particle is dissolved in
120 milliliters by ethyl alcohol and the acetonitrile mixed solution that 3:1 is mixed by volume, after ultrasound makes it completely dissolved, Xiang Qijia
Enter 500 microlitres of ammonium hydroxide, ultrasound is uniformly mixed it；Then 3 milliliters of butyl titanates are added dropwise under agitation simultaneously
Reaction 1.5 hours, after reaction, Magnetic Isolation and with ethanol washing three times after to get arrive Fe3O4/TiO2Nano particle；
(3) Fe for taking 81 milligrams of steps (2) to obtain3O4/TiO2Nano particle and 75.4 milligrams of ammonium fluorides be dissolved in 20.45 milliliters by
In the second alcohol and water mixed solution that 13.5:6.95 is mixed by volume, ultrasound puts it by reaction solution after completely dissolution
It is placed in and persistently stirs 1 hour at room temperature, mixing speed is 180-200 rpms, and after the completion of stirring, reaction solution is transferred to
It in reaction kettle, is reacted 24 hours at 180 DEG C, after reaction kettle cooled to room temperature, Magnetic Isolation is simultaneously washed with deionized water
3 times are washed to get the Fe for arriving crystallization3O4/TiO2Nano particle；
(4) Fe for the crystallization for taking 81 milligrams of steps (3) to obtain3O4/TiO2Nano particle is dissolved in 33.4 milliliters of ethyl alcohol, is continued
25 microlitres of 3- aminopropyl trimethoxy siloxanes are added dropwise under stirring, reaction solution is placed at 80 DEG C and is condensed back 4 hours,
After its cooled to room temperature, Magnetic Isolation and with ethanol washing three times to get arrive amidized Fe3O4/TiO2Nanometer
Grain；
(5) 1 gram of polyvinylpyrrolidone (5800 grams every mole of molecular weight) and 28 milligrams of steps (4) are obtained amidized
Fe3O4/TiO2Nano particle is dissolved in 10 ml deionized waters after mixing, and silver ammino solution is added dropwise under mechanical stirring
And be transferred in hydrothermal reaction kettle, sealing, which is placed at 120 DEG C, reacts 11 hours, after reaction kettle cooled to room temperature, magnetic
Property separation and successively with tetrahydrofuran, ethyl alcohol and deionized water wash to get arrive Fe3O4/TiO2/ Ag core-shell nano material, juxtaposition
It is stored in deionized water for use, wherein silver ammino solution is the preparation method comprises the following steps: taking 2 milliliters of concentration is 0.01-0.08 milligrams every milliliter
Silver nitrate aqueous solution, be added excessive ammonium hydroxide until reaction solution become clarification obtain silver ammino solution.
2, it is based on Fe3O4/TiO2The directly recyclable immune detection of the prostate characteristic antigen PSA of/Ag core-shell nano material
(1) by 15 milligrams of Fe3O4/TiO2/ Ag triple core-shell nano material is dissolved in 2 milliliters of dimethylformamide (DMF) solutions,
Then the DMF solution for the succinic anhydride that 1 milliliter of concentration is 10.3 milligrams every milliliter is added, it is small that hatching 24 is slowly shaken at 70 DEG C
Shi Hou, Magnetic Isolation are simultaneously washed with deionized 2 times to get the Fe for arriving carboxylated3O4/TiO2/ Ag core-shell nano material, and it is molten
In 1 milliliter of water, then be added 1 milliliter of EDC/NHS PBS solution, slowly shaken at 30 DEG C hatching 1 hour after, spend from
Sub- water washing 1 time, then by the Fe after above-mentioned washing3O4/TiO2/ Ag core-shell nano material is dissolved in 1 milliliter by PBS buffer solution and water
By in isometric mixed solution than mixing, the prostate-specific antigen PSA that 100 micrograms per millilitres are added thereto is molten
Liquid is washed with deionized once, Magnetic Isolation obtains being marked with PSA's after 30 DEG C slowly shake hatching 3.5 hours
Fe3O4/TiO2/ Ag core-shell nano material is carried out the detectable determined antigen PSA of spectral measurement to it using Raman spectrometer and contained
Amount；
(2) after detecting, the Fe of PSA will be marked with3O4/TiO2/ Ag core-shell nano material is dissolved in deionized water, and by its
It is transferred in Clear glass bottles and jars, assembles nanoparticle by the way of small magnet attraction, use wavelength for 265 nanometers of ultraviolet lamp
It is irradiated, and every the Raman signal of detection in 20 minutes, until the raman characteristic peak of PSA disappears, it was demonstrated that PSA is catalyzed
Degradation is complete；Then by the Fe after above-mentioned catalysis3O4/TiO2/ Ag core-shell nano material, then new PSA is linked, carry out Raman inspection
Ultraviolet lighting is carried out after survey again to be catalyzed, the process of circulating repetition this immune link, Raman detection and photocatalytic degradation is
Directly recyclable immune detection can be achieved.
Fig. 1 shows the Fe prepared in the present embodiment3O4The transmission electron microscope photo of nano material.It can be with from Fig. 1
Find out, prepared Fe3O4Nano material diameter is 240-280 nanometers.
Fig. 2 shows the Fe prepared in the present embodiment3O4/TiO2The transmission electron microscope photo of core-shell nano material, from
It is core-shell structure, TiO that Fig. 2, which can be seen that prepared material,2Shell thickness is 20 nanometers.
Fig. 3 shows the Fe prepared in the present embodiment3O4/TiO2The scanning electron microscope of/Ag core-shell nano material is shone
Piece, from figure 3, it can be seen that prepared Fe3O4/TiO2/ Ag core-shell nano material surface is a large amount of silver nano-grain, arrangement
Closely.
Fig. 4, which is shown, is wrapped in Fe manufactured in the present embodiment for Ag particle using Electrostatic Absorption method3O4/TiO2Core-shell nano material
Expect the Fe that outer surface is formed3O4/TiO2The electron scanning micrograph of/Ag core-shell nano material, from fig. 4, it can be seen that made
Standby Fe3O4/TiO2/ Ag core-shell nano material surface is a small amount of sparse silver nano-grain, silver nano-grain and Fe3O4/TiO2
Outer surface combines more loose and simultaneously uneven.
Fig. 5 is that the Fe prepared in the embodiment of the present invention 1 is respectively adopted3O4/TiO2/ Ag core-shell nano material and Electrostatic Absorption
The Fe of method preparation3O4/TiO2/ Ag core-shell nano material urges small molecule 4- mercaptobenzoic acid (0.01 mM every milliliter)
It is changing as a result, 4- mercaptobenzoic acid is by of the invention real from figure 5 it can be seen that when catalysis time extends to 70 minutes
Apply the Fe prepared in example 13O4/TiO2/ Ag core-shell nano material catalytic degradation is complete, and the Fe of Electrostatic Absorption method preparation3O4/
TiO2That there is no catalytic degradations is complete to 4- mercaptobenzoic acid molecule for/Ag core-shell nano material.Therefore, in the embodiment of the present invention 1
The Fe of preparation3O4/TiO2/ Ag core-shell nano material has higher catalytic activity.
Fig. 6 is the Fe prepared in the embodiment of the present invention 13O4/TiO2/ Ag core-shell nano material is to prostate-specific antigen
PSA(10 micrograms per millilitre) carry out immune detection and catalytic result, from fig. 6 it can be seen that it is immune combine after occur compared with
For apparent Raman spectrum, it was demonstrated that antigen PSA is detected in conjunction with core-shell nano material.After carrying out ultraviolet lighting catalysis,
Characteristic Raman spectral intensity is almost reduced to zero, it was demonstrated that the Fe prepared in the embodiment of the present invention 13O4/TiO2/ Ag core-shell nano material
Determined antigen PSA is catalytically decomposed completely.This is mainly due to the Ag particles using hydro-thermal method cladding in Fe3O4/TiO2
It core-shell nano outer surface cladding more close and is evenly distributed, is conducive to Ag and TiO2Between charge transfer process
Facilitation effect, and then significantly increase TiO2Photocatalytic activity, realize this kind of macromolecular of tumor markers catalytic degradation.
Fig. 7 is the Fe prepared using Electrostatic Absorption method3O4/TiO2/ Ag core-shell nano material is to prostate-specific antigen
PSA(10 micrograms per millilitre) carry out immune detection and catalytic result, it can be seen from figure 7 that it is immune combine after equally occur
More apparent Raman spectrum, it was demonstrated that the Fe of Electrostatic Absorption method preparation3O4/TiO2/ Ag core-shell nano material also has better
The immuno-assays of antigen PSA may be implemented in SERS reinforcing effect.But after carrying out ultraviolet lighting catalysis, it can be found that above-mentioned spy
Sign Raman spectral intensity only has faint reduction, it was demonstrated that the Fe prepared using Electrostatic Absorption method3O4/TiO2/ Ag core-shell nano material is not
Determined antigen PSA can be carried out to catalytic decomposition to fall.This is mainly due to the Ag particles using Electrostatic Absorption method cladding in Fe3O4/
TiO2It core-shell nano outer surface cladding more loose and is unevenly distributed, is unfavorable for realizing to Ag and TiO2Between electricity
The promotion of lotus transmittance process can not enhance TiO2Photocatalytic activity, cannot also realize this kind of macromolecular of tumor markers
Catalytic degradation.Thus, it is received by using the triple core-shell that hydrothermal synthesis method cladding silver nano-grain can obtain well-formed
Rice material, obtains more excellent catalytic activity and circulation immunity catalytic effect.
Fig. 8 is the Fe prepared in the embodiment of the present invention 13O4/TiO2/ Ag core-shell nano material is to prostate-specific antigen
The directly recyclable immune detection result of PSA.As can be seen from Figure 8, every to pass through a Photocatalytic Degradation Process, Raman labels
The Raman spectrum of molecule will disappear, and show that antigen-antibody is complete by catalysis.By eight immune links, Raman detection and
The detectable limit of the cyclic process of photocatalytic degradation, prostate specific antigen (PSA) can reach 100 every milliliter of piks.
Fig. 9 is that frequency displacement is 1264 cm in Raman spectrum-1Feature peak intensity with determined antigen concentration variation diagram, by quasi-
Close as it can be seen that when the concentration of determined antigen is from when changing to 0.1 milligram every milliliter for every milliliter of 100 pik, Raman signatures peak intensity with
Concentration is linear change.Fitting result shows that this variation tendency meets this linear equation of Y=8750+792X, fitting
Degree is 0.985.
Embodiment 2
With above-described embodiment 1, difference is: Fe3O4/TiO2In the preparation of/Ag core-shell nano material: by 1.35 in step (1)
Gram Iron(III) chloride hexahydrate, 3.6 grams of sodium acetates and 1.0 grams of polyethylene glycol are dissolved in 40 milliliters of ethylene glycol, and ultrasound is until completely molten
Xie Hou is transferred in hydrothermal reaction kettle, is reacted 10 hours at 200 DEG C, and precipitating is collected after being centrifuged and being cleaned with ethyl alcohol to get arriving
Fe3O4Nano particle；The volume that butyl titanate is added in step (2) is 1 milliliter.
Figure 10 is that frequency displacement is 1264 cm in Raman spectrum-1Feature peak intensity with determined antigen concentration variation diagram, by quasi-
Close as it can be seen that when the concentration of determined antigen is from when changing to 0.1 milligram every milliliter for every milliliter of 100 pik, Raman signatures peak intensity with
Concentration is linear change.Fitting result shows that this variation tendency meets this linear equation of+806X of Y=8734, fitting
Degree is 0.972.
Embodiment 3
With above-described embodiment 1, difference is: Fe3O4/TiO2In the preparation of/Ag core-shell nano material: by 6.75 in step (1)
Gram Iron(III) chloride hexahydrate, 18.0 grams of sodium acetates and 5.0 grams of polyethylene glycol are dissolved in 200 milliliters of ethylene glycol, and ultrasound is until completely
After dissolution, be transferred in hydrothermal reaction kettle, reacted 10 hours at 200 DEG C, be centrifuged and collect after being cleaned with ethyl alcohol precipitating to get
To Fe3O4Nano particle；The volume that butyl titanate is added in step (2) is 6 milliliters.
Figure 11 is that frequency displacement is 1264 cm in Raman spectrum-1Feature peak intensity with determined antigen concentration variation diagram, by quasi-
Close as it can be seen that when the concentration of determined antigen is from when changing to 0.1 milligram every milliliter for every milliliter of 100 pik, Raman signatures peak intensity with
Concentration is linear change.Fitting result shows that this variation tendency meets this linear equation of Y=8930+840X, degree of fitting
It is 0.981.
In addition to the implementation, tumor markers can also be AFP AFP, immune globulin IGg, sugar antigen
CA199 and Carcinoembryonic Antigen CEA etc..
Above description is not limitation of the present invention, and the present invention is also not limited to the example above.The art it is common
Within the essential scope of the present invention, the variations, modifications, additions or substitutions made also should belong to protection of the invention to technical staff
Range.
Claims (4)
1. a kind of ferroso-ferric oxide/titanium dioxide/silver core-shell nano material preparation method, it is characterised in that including following step
It is rapid:
(1) 1.35-6.75 grams of Iron(III) chloride hexahydrate, 3.6-18.0 grams of sodium acetate and 1.0-5.0 grams of polyethylene glycol are dissolved in 40-
In 200 milliliters of ethylene glycol, after ultrasound is until be completely dissolved, it is transferred in hydrothermal reaction kettle, is reacted 10 hours at 200 DEG C, from
The heart simultaneously collects precipitating after being cleaned with ethyl alcohol to get to Fe3O4Nano particle；
(2) Fe that 50 milligrams of steps (1) obtain is weighed3O4It is 0.1 mM of every milliliter of aqueous hydrochloric acid solution that nano particle, which is dissolved in concentration,
Middle ultrasonic 15 minutes, Magnetic Isolation was simultaneously cleaned three times with deionized water；Again after Magnetic Isolation, by Fe3O4Nano particle is dissolved in
120 milliliters by ethyl alcohol and the acetonitrile mixed solution that 3:1 is mixed by volume, after ultrasound makes it completely dissolved, Xiang Qijia
Enter 500 microlitres of ammonium hydroxide, ultrasound is uniformly mixed it；Then 1-6 milliliters of four fourths of metatitanic acid are added dropwise under agitation
Ester, reaction 1.5 hours after, Magnetic Isolation and with ethanol washing three times after to get arrive Fe3O4/TiO2Nano particle；
(3) Fe for taking 81 milligrams of steps (2) to obtain3O4/TiO2Nano particle and 75.4 milligrams of ammonium fluorides be dissolved in 20.45 milliliters by
In the second alcohol and water mixed solution that 13.5:6.95 is mixed by volume, ultrasound puts it by reaction solution after completely dissolution
It is placed in and persistently stirs 1 hour at room temperature, mixing speed is 180-200 rpms, and after the completion of stirring, reaction solution is transferred to
It in reaction kettle, is reacted 24 hours at 180 DEG C, after reaction kettle cooled to room temperature, Magnetic Isolation is simultaneously washed with deionized water
3 times are washed to get the Fe for arriving crystallization3O4/TiO2Nano particle；
(4) Fe for the crystallization for taking 81 milligrams of steps (3) to obtain3O4/TiO2Nano particle is dissolved in 33.4 milliliters of ethyl alcohol, is continued
25 microlitres of 3- aminopropyl trimethoxy siloxanes are added dropwise under stirring, reaction solution is placed at 80 DEG C and is condensed back 4 hours,
After its cooled to room temperature, Magnetic Isolation and with ethanol washing three times to get arrive amidized Fe3O4/TiO2Nanometer
Grain；
(5) the amidized Fe for obtaining 1 gram of polyvinylpyrrolidone and 28 milligrams of steps (4)3O4/TiO2Nano particle is dissolved in
In 10 ml deionized waters after mixing, silver ammino solution is added dropwise under mechanical stirring and is transferred in hydrothermal reaction kettle,
Sealing, which is placed at 120 DEG C, reacts 11 hours, and after reaction kettle cooled to room temperature, Magnetic Isolation simultaneously successively uses tetrahydro furan
It mutters, ethyl alcohol and deionized water are washed to get Fe is arrived3O4/TiO2/ Ag core-shell nano material, be placed in deionized water storage to
With,
A kind of ferroso-ferric oxide according to claim 1/titanium dioxide/silver core-shell nano material preparation method, it is special
Sign is silver ammino solution described in step (5) the preparation method comprises the following steps: taking 2 milliliters of concentration is 0.01-0.08 milligrams every milliliter of nitre
Excessive ammonium hydroxide is added until reaction solution becomes clarification and obtains silver ammino solution in sour silver aqueous solution.
2. a kind of based on the resulting ferroso-ferric oxide of claims 1 or 2 preparation method/titanium dioxide/silver core-shell nano material
Tumor markers are recycled immunologic detection method, it is characterised in that the following steps are included:
(1) by 15 milligrams of Fe3O4/TiO2/ Ag core-shell nano material is dissolved in 2 milliliters of dimethyl formamide solutions, is then added 1
The DMF solution of milliliter succinic anhydride, after hatching being slowly shaken at 70 DEG C 24 hours, Magnetic Isolation is simultaneously washed with deionized 2
It is secondary to get arrive carboxylated Fe3O4/TiO2/ Ag core-shell nano material, and be dissolved in 1 milliliter of water, 1 milliliter of EDC/ is then added
The PBS solution of NHS is washed with deionized 1 time after slowly shaking hatching at 30 DEG C 1 hour, then by the Fe after washing3O4/
TiO2/ Ag core-shell nano material, which is dissolved in 1 milliliter, to be compared in the mixed solution mixed by PBS buffer solution and water as isometric, to
The tumor markers solution of 100 micrograms per millilitres is wherein added, after 30 DEG C slowly shake hatching 3.5 hours, uses deionized water
It washed once, Magnetic Isolation obtains the Fe for being marked with tumor markers3O4/TiO2/ Ag core-shell nano material, utilizes Raman spectrum
Instrument, which carries out spectral measurement to it, can detect the content of tumor markers to be measured；
(2) after detecting, the Fe of tumor markers will be marked with3O4/TiO2/ Ag core-shell nano material is dissolved in deionized water,
And be transferred into Clear glass bottles and jars, assemble Fe by the way of small magnet attraction3O4/TiO2/ Ag core-shell nano, is adopted
It is irradiated with the ultraviolet lamp that wavelength is 265 nanometers, until tumor markers degradation completely, then will urge under photocatalysis
Fe after change3O4/TiO2/ Ag core-shell nano material repeats step (1) method and links new tumor markers, can be realized to swollen
The directly recyclable immune detection of tumor markers.
3. according to claim 3 can based on ferroso-ferric oxide/titanium dioxide/silver core-shell nano material tumor markers
Circulation immunity detection method, it is characterised in that: the concentration of succinic anhydride in the DMF solution of succinic anhydride as described in step (1)
It is 10.3 milligrams every milliliter；The concentration of EDC is 10 milligrams every milliliter in the PBS solution of the EDC/NHS, and the concentration of NHS is
10 milligrams every milliliter.
4. according to claim 3 can based on ferroso-ferric oxide/titanium dioxide/silver core-shell nano material tumor markers
Circulation immunity detection method, it is characterised in that: the tumor markers include prostate-specific antigen PSA, alpha-fetoprotein
AFP, immune globulin IGg, sugar antigen CA199 and Carcinoembryonic Antigen CEA.
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