CN112326627A - Preparation and application based on composite magnetic SERS platform - Google Patents
Preparation and application based on composite magnetic SERS platform Download PDFInfo
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- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229960000890 hydrocortisone Drugs 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNLGSMHAJWIINT-UHFFFAOYSA-N [dimethyl(propyl)silyl]methanamine Chemical compound CCC[Si](C)(C)CN DNLGSMHAJWIINT-UHFFFAOYSA-N 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 229940038773 trisodium citrate Drugs 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910021389 graphene Inorganic materials 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000001069 Raman spectroscopy Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract 1
- 239000000427 antigen Substances 0.000 abstract 1
- 102000036639 antigens Human genes 0.000 abstract 1
- 108091007433 antigens Proteins 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 238000011896 sensitive detection Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- MVPUXVBBHWUOFS-UHFFFAOYSA-N 4-sulfanylbenzonitrile Chemical compound SC1=CC=C(C#N)C=C1 MVPUXVBBHWUOFS-UHFFFAOYSA-N 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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]
-
- 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
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- 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
- G01N2021/653—Coherent methods [CARS]
- G01N2021/655—Stimulated Raman
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- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses Fe3O4The preparation method and the application of the @ GO @ Ag and gold nano star SERS substrate comprise the following steps: magnetic ferroferric oxide nano particles are synthesized by an improved solvothermal method, are subjected to amination modification and then are coated with a graphene oxide shell through electrostatic adsorption, and large-specific-surface-area and large-amount oxygen-containing functional groups on the surface of the magnetic ferroferric oxide nano particles can perform in-situ nucleation and growth of silver nano particles to realize a core-shell-satellite structure; the graphene oxide has obvious Raman peaks (G peak, D peak and 2D peak), and can be used as a stable internal standard to reduce experimental errors; the gold nano star is synthesized by simple chemical reduction, is connected with a biological silence area through a gold-sulfur bond and has Raman signal pullingA manbeaconing molecule; the rapid and sensitive detection of the antigen can be realized after the primary antibody and the secondary antibody are respectively modified on the two substrates; the method has the advantages of simple synthesis, easy separation and high sensitivity.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to preparation and potential application of a magnetic SERS substrate and a gold nano-star substrate.
Background
Raman spectroscopy has incomparable advantages in multiplex molecular identification due to its inherently narrow spectrum, but its application is limited due to the low scattering cross-section. The discovery of the Surface Enhanced Raman Scattering (SERS) phenomenon overcomes this limitation and opens the door to applications in trace analyte detection. The main contribution of this enhancement effect comes from the enhanced local electromagnetic field, which is greatly enhanced at the nanocrystal surface, called hot spot, due to the plasmon resonance at the excited noble metal nanocrystal excitation surface, followed by the radiation of dipole fields causing the redistribution of the electromagnetic field in the vicinity of the noble metal. The surface enhanced Raman spectrum can provide abundant fingerprint spectrum information based on molecular structures, has high sensitivity and low detection limit, even can reach the ultrahigh sensitivity of single molecular level, and is widely applied to the fields of material characterization, trace analysis and detection, biomolecule analysis and the like.
The magnetic ferroferric oxide nano material has excellent magnetic enrichment capacity, can quickly separate experimental samples, greatly shortens the tedious post-processing time, reduces the workload, can effectively realize the enrichment of the material, greatly reduces the detection limit, improves the sensitivity, and is frequently used as an SERS substrate material in recent years.
Graphene oxide is a promising nanoscale functional material with excellent performance, and has been receiving attention since the emergence of the materials. The graphene oxide has high specific surface area and abundant functional groups on the surface, can be compounded with most polymers, can form stable dispersion liquid in water, is easy to carry out surface modification, has excellent chemical stability, flexibility and conductivity, and can be used as an excellent carrier material and a multifunctional material for electron or hole transfer. The graphene oxide has wide application and prospect in the fields of photocatalysis, electrocatalysis, preparation of composite materials and the like due to the unique excellent performance of the graphene oxide.
The gold nanoparticles have good stability and bioactivity, and are widely used for preparation and application of SERS substrates, and compared with gold nanospheres and gold nanorods, the gold nanostars can generate more hot spot regions and have stronger Raman signals due to the existence of a plurality of tip structures, so the gold nanostars are gradually concerned and loved by researchers.
Disclosure of Invention
The invention aims to provide a preparation method of a magnetic SERS substrate and a golden nano-star substrate, research and potential application of the preparation method, the substrates have high stability, good uniformity, low sensitivity of SERS signals and good reproducibility, the detection method is simple and convenient to operate, cortisol can be detected by utilizing a handheld Raman instrument, and the preparation method comprises the following specific steps:
（1）Fe3O4preparation of @ GO @ Ag substrate: adding 0.65 g of FeCl 3.6H2O and 0.2 g of trisodium citrate into 20 mL of ethylene glycol, after completely dissolving, adding 1.2 g of anhydrous sodium acetate under stirring, continuously stirring for 0.5H, transferring the mixed solution into a 50 mL polytetrafluoroethylene high-pressure reaction kettle, and reacting for 10H in a 200 ℃ constant temperature box; after the reaction is finished, naturally cooling to room temperature, and separating by using a magnet to obtain black Fe3O4Removing supernatant, washing the product with ethanol for 3-5 times, then washing with water for 3-5 times, and drying in a vacuum drying oven;
taking 1.5 g of the Fe3O4Adding into 50 mL ethanol, performing ultrasonic treatment for 5 min, adding 100 mL Aminopropyltrimethylsilane (APTMS) into the solution, stirring at room temperature for 2h, heating, condensing, refluxing for 2h, naturally cooling, washing with ethanol for several times to remove excessive APTMS, separating with magnet, and drying in a vacuum drying oven;
taking the above Fe3O4dispersing-NH 2 (1.0 g) into 20 mLGO (1.0 mg/mL) solution, heating in water bath to 75 ℃ under mechanical stirring, and reacting for 1h to obtain Fe3O4@ GO solution, washing with ultrapure water 3 times after finishingTo remove excess GO;
dispersing the above solution into 100 ml of LAgNO3Mechanically stirring (10 mM) solution for 30 min to make Ag + reach Fe3O4@ GO surface; then 30 mL (20 mM) of trisodium citrate was added and reacted at 60 ℃ for 6 hours, after which the black precipitate was separated with a magnet, washed three times with ultrapure water and ethanol, and dispersed in 20 mL of ethanol to obtain Fe3O4@ GO @ Ag SERS substrate;
(2) preparing a gold nano-star substrate: adding 10-100 uL of chloroauric acid solution (1%) into 10 mL of water, then sequentially adding 10 uL of 1mol/L hydrochloric acid, 10-300 uL of 0.294mM gold seed solution, 15-30 uL of 23.8mM silver nitrate solution and 30-100 uL of 0.1M ascorbic acid solution, and stirring at room temperature for 10-60 min;
adding 20 uL of 13.56 mM p-mercaptobenzonitrile (4-MBN) solution into 5 mL of the gold nanostar solution, stirring at room temperature for 1h, standing and incubating for 24 h, and washing with water for 2 times after the reaction to remove redundant 4-MBN;
(3) 50 uL of 1 mg/mL monoclonal cortisol antibody to Fe in (1)3O4The SERS substrate solution of @ GO @ Ag is shaken for 2h, then 20 mg/mL BSA solution 50 uL is added, shaken for 1h, to block naked sites, and after 2 times of washing, the substrate is resuspended in 1 mL 10mM PBS buffer solution (pH 7.2);
adding 20 mu L of 0.05 mg/mL cortisol monoclonal antibody into the gold nanostar solution in the step (2), oscillating for 4 h, then adding 20 uL of 1 mg/mL BSA solution, oscillating for 1h to block the naked site, and washing with ultrapure water for 2 times;
(3) and (3) mixing 200 uL of each of the two SERS substrate solutions in the step (2), then adding 200 uL of cortisol with different concentrations, oscillating for 2h, and collecting SERS signals after magnetic separation.
The invention has the beneficial effects that:
(1) the magnetic iron oxide nanoparticles have excellent enrichment capacity, so that the sensitivity of the reaction is greatly improved, the detection limit is reduced, and the heavy centrifugal work is reduced;
(2) the graphene oxide can be used as an internal standard molecule to reduce the interference of uncertain factors and environment on SERS signals and improve the stability and sensitivity of the signals, and can load more silver nanoparticles due to the fact that the graphene oxide has larger specific surface area and functional groups with rich surfaces;
(3) the gold nano star generates more hot spot areas due to more tips, so that the SERS signal is greatly enhanced.
Detailed Description
（1）Fe3O4Preparation of @ GO @ Ag substrate: adding 0.65 g of FeCl 3.6H2O and 0.2 g of trisodium citrate into 20 mL of ethylene glycol, after completely dissolving, adding 1.2 g of anhydrous sodium acetate under stirring, continuously stirring for 0.5H, transferring the mixed solution into a 50 mL polytetrafluoroethylene high-pressure reaction kettle, and reacting for 10H in a 200 ℃ constant temperature box; after the reaction is finished, naturally cooling to room temperature, and separating by using a magnet to obtain black Fe3O4Removing supernatant, washing the product with ethanol for 3-5 times, then washing with water for 3-5 times, and drying in a vacuum drying oven;
taking 1.5 g of the Fe3O4Adding into 50 mL ethanol, performing ultrasonic treatment for 5 min, adding 100 mL Aminopropyltrimethylsilane (APTMS) into the solution, stirring at room temperature for 2h, heating, condensing, refluxing for 2h, naturally cooling, washing with ethanol for several times to remove excessive APTMS, separating with magnet, and drying in a vacuum drying oven;
taking the above Fe3O4dispersing-NH 2 (1.0 g) into 20 mL GO (1.0 mg/mL) solution, heating in water bath to 75 ℃ under mechanical stirring, and reacting for 1h to obtain Fe3O4@ GO solution, washing 3 times with ultrapure water after finishing to remove excess GO;
dispersing the above solution into 100 ml of LAgNO3Mechanically stirring (10 mM) solution for 30 min to make Ag + reach Fe3O4@ GO surface; then 30 mL (20 mM) of trisodium citrate was added and reacted at 60 ℃ for 6 hours, after which the black precipitate was separated with a magnet, washed three times with ultrapure water and ethanol, and dispersed in 20 mL of ethanol to obtain Fe3O4@ GO @ Ag SERS substrate;
(2) preparing a gold nano-star substrate: 40, 60, 80 and 100 uL of chloroauric acid solution (1%) are respectively added into 4 beakers containing 10 mL of ultrapure water, then 10 uL of 1mol/L hydrochloric acid and 100 uL of 0.294mM gold seed solution are sequentially added, 15 and 30uL of 23.8mM silver nitrate solution and 50 uL of 0.1M ascorbic acid solution are respectively added, and the mixture is stirred at room temperature for 10 min;
adding 20 uL of 13.56 mM p-mercaptobenzonitrile (4-MBN) solution into 5 mL of the gold nanostar solution, stirring at room temperature for 1h, standing and incubating for 24 h, and washing with water for 2 times after the reaction to remove redundant 4-MBN;
(3) 50 uL of 1 mg/mL monoclonal cortisol antibody was added to the SERS substrate solution of Fe3O4@ GO @ Ag in (1) with shaking for 2h, followed by addition of 20 mg/mL BSA solution 50 uL with shaking for 1h to block the naked sites, washed 2 times and resuspended in 1 mL of 10mM PBS buffer (pH 7.2);
adding 20 mu L of 0.05 mg/mL cortisol monoclonal antibody into the gold nanostar solution in the step (2), oscillating for 4 h, then adding 20 uL of 1 mg/mL BSA solution, oscillating for 1h to block the naked site, and washing with ultrapure water for 2 times;
(3) and (3) mixing 200 uL of each of the two SERS substrate solutions in the step (2), then adding 200 uL of cortisol with different concentrations, oscillating for 2h, and collecting SERS signals after magnetic separation.
Claims (1)
1. Fe3O4The preparation method and the application of the @ GO @ Ag and gold nano star SERS substrate are characterized by comprising the following steps:
(1) 0.65 g FeCl3·6H2Adding O and 0.2 g of trisodium citrate into 20 mL of ethylene glycol, adding 1.2 g of anhydrous sodium acetate under stirring after complete dissolution, continuously stirring for 0.5 h, transferring the mixed solution into a 50 mL of polytetrafluoroethylene high-pressure reaction kettle, and reacting for 10 h in a 200 ℃ constant temperature box; after the reaction is finished, naturally cooling to room temperature, and separating by using a magnet to obtain black Fe3O4Removing supernatant, washing the product with ethanol for 3-5 times, then washing with water for 3-5 times, and drying in a vacuum drying oven;
(2) taking 1.5 g of the Fe3O4Adding into 50 mL ethanol, performing ultrasonic treatment for 5 min, adding 100 mL Aminopropyltrimethylsilane (APTMS) into the solution, stirring at room temperature for 2h, heating, condensing, refluxing for 2h, naturally cooling, washing with ethanol for several times to remove excessive APTMS, separating with magnet, and drying in a vacuum drying oven;
(3) taking the above Fe3O4-NH2(1.0 g) is dispersed into 20 mL GO (1.0 mg/mL) solution, and the solution is heated to 75 ℃ in a water bath under the mechanical stirring and reacts for 1h to obtain Fe3O4@ GO solution, washing 3 times with ultrapure water after finishing to remove excess GO;
(4) dispersing the above solution into 100 ml of LAgNO3Mechanically stirring (10 mM) solution for 30 min to make Ag+To Fe3O4@ GO surface; then 30 mL (20 mM) of trisodium citrate was added and reacted at 60 ℃ for 6 hours, after which the black precipitate was separated with a magnet, washed three times with ultrapure water and ethanol, and dispersed in 20 mL of ethanol to obtain Fe3O4@ GO @ Ag SERS substrate;
(5) adding 10-100 uL of chloroauric acid solution (1%) into 10 mL of water, then sequentially adding 10 uL of 1mol/L hydrochloric acid, 10-300 uL of 0.294mM gold seed solution, 15-30 uL of 23.8mM silver nitrate solution and 30-100 uL of 0.1M ascorbic acid solution, and stirring at room temperature for 10-60 min;
(6) adding 20 uL of 13.56 mM para-mercaptobenzonitrile (4-MBN) solution into 5 mL of the gold nanostar solution in the step (4), stirring at room temperature for 1h, standing and incubating for 24 h, and washing with water for 2 times after the reaction to remove redundant 4-MBN;
(7) 50 uL of 1 mg/mL monoclonal cortisol antibody to Fe in (4)3O4The SERS substrate solution of @ GO @ Ag is shaken for 2h, then 20 mg/mL BSA solution 50 uL is added, shaken for 1h, to block naked sites, and after 2 times of washing, the substrate is resuspended in 1 mL 10mM PBS buffer solution (pH 7.2);
(8) adding 20 mu L of 0.05 mg/mL cortisol monoclonal antibody into the gold nanostar solution in (5), oscillating for 4 h, then adding 20 uL of 1 mg/mL BSA solution, oscillating for 1h to block the naked site, and washing with ultrapure water for 2 times;
(9) mixing the SERS substrate solutions in the steps (7) and (8) by 200 uL respectively, then adding 200 uL of cortisol with different concentrations, oscillating for 2h, and collecting SERS signals after magnetic separation;
(10) according to the preparation of the gold nano-star in the step (5), the raw materials with different concentrations have great influence on the color, the appearance and the performance of the gold nano-star.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112986211A (en) * | 2021-03-10 | 2021-06-18 | 福建师范大学 | Method for high-precision detection of tumor marker in human blood by aptamer SERS sensor capable of being triggered in targeted mode and self-calibrated mode |
| CN113940361A (en) * | 2021-11-18 | 2022-01-18 | 陕西理工大学 | Core-shell type magnetic nano Fe3O4Preparation method of/Cu/CuO @ Ag composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112986211A (en) * | 2021-03-10 | 2021-06-18 | 福建师范大学 | Method for high-precision detection of tumor marker in human blood by aptamer SERS sensor capable of being triggered in targeted mode and self-calibrated mode |
| CN113940361A (en) * | 2021-11-18 | 2022-01-18 | 陕西理工大学 | Core-shell type magnetic nano Fe3O4Preparation method of/Cu/CuO @ Ag composite material |
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