CN102559190B - Dual-mode optical coding probe and preparation method thereof - Google Patents
Dual-mode optical coding probe and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a dual-mode optical coding probe and a preparation method thereof. The probe is in a three-layer core-shell structure, the first-layer core is a gold nano bar, the second-layer shell is silica, the third-layer shell is a cadmium telluride quantum dot, the second-layer shell is wrapped on the outer side of the first-layer core, the third-layer shell covers the outer side ofthe second-layer shell in a sticking mode, and the outer surface of the first-layer core is stuck with Raman molecules which are wrapped by the second-layer shell. The preparation method of the dual-mode optical coding probe comprises the following steps of: 1, preparing an original gold nano bar solution; 2, preparing gold nano bars marked by the Raman molecules; 3, preparing a gold nano bar andsilica metal medium composite nano ball solution; and 4, preparing the dual-mode optical coding probe. The dual-mode optical coding probe has the joint encoding capacity of fluorescence and SERS (Surface Enhanced Raman Scattering), and enhances the optical coding capacity. The preparation method of the dual-mode optical coding probe has a simple process and high repeatability.
Description
Technical field
The present invention relates to field of nanometer material technology, specifically, relate to a kind of double mode optical encoding probe and preparation method thereof, this double mode optical encoding probe possesses the function of fluorescence and Surface enhanced raman spectroscopy combined coding.
Background technology
Along with the continuous improvement of technology of preparing and characterization method, with its unique optical property and undersized characteristics, become the focus that domestic and international researchers pay close attention to based on the optical probe of nano material gradually.The different optical probe of these functions has great application prospect in bio-sensing, bio-imaging and biological detection.
The fluorescence detection technology is quick and simple, is a kind of biological detection means commonly used.There is intrinsic shortcoming in traditional organic dye molecule (fluorophore), is easily bleached as emission spectrum wide ranges, fluorescence etc.The semiconductor-quantum-point material of Chu Xianing has advantages such as spectrum is narrow, light stability is high, the characteristics of luminescence is adjustable in recent years, becomes a kind of novel biological fluorescent labelling thing.Surface enhanced raman spectroscopy (English is " Surface Enhanced Raman Scattering ", in the literary composition be called for short " SERS ") technology spectral line is narrow, be difficult for photobleaching and harmless to biological tissue.The huge Raman humidification that Surface enhanced raman spectroscopy has makes the detection based on Surface enhanced raman spectroscopy can reach very high sensitivity, even can realize the detection of single molecules level.
The optical probe of coding can be used for realizing that various biomolecules detects simultaneously.Usually optical encoding is based on fluorescence signal or SERS signal.Be encoded to example with quantum dot fluorescence, can generate about 10 kinds of sign indicating numbers (10 kinds of colors) at visible region (380-780nm) in theory.But because the influence of spectra overlapping and resonance energy transfer effect, actually can only prepare 3 kinds of distinguishable sign indicating numbers of left and right sides spectrum.And Raman labels molecular structure commonly used is similar, and it is overlapping significantly to make that their SERS spectrum also has, and available spectral range is limited.The feasible independent distinguishable sign indicating number of the spectrum number that generates based on the coded system of fluorescence signal or SERS signal of these unfavorable factors far is inferior to theoretical expectation.
Summary of the invention
Technical matters:Technical matters to be solved by this invention is: a kind of double mode optical encoding probe is provided, this double mode optical encoding probe sets fluorescence and two kinds of optical signallings of SERS are in one, make this double mode optical encoding probe possess the ability of fluorescence and SERS combined coding, strengthened the optical encoding ability.Simultaneously, the present invention also provides a kind of preparation method of double mode optical encoding probe, and this preparation method is simple, and repeatable high, and the optical probe of preparing can provide the strong fluorescence of signal and SERS signal.
Technical scheme:For solving the problems of the technologies described above, double mode optical encoding probe of the present invention, this probe adopts three-layer nuclear shell structure, ground floor nuclear is gold nanorods, and second layer shell is silicon dioxide, and the 3rd layer of shell is cadmium telluride quantum dot, second layer shell is wrapped in the outside of ground floor nuclear, the 3rd layer of shell pastes in the outside of second layer shell, and the outside surface of ground floor nuclear is covered with Raman molecular, and Raman molecular is wrapped up by second layer shell.
The preparation method of double mode optical encoding probe of the present invention may further comprise the steps:
The original gold nanorods solution of step 1. preparation: at first cetyl trimethyl ammonium bromide solution and tetra chlorauric acid solution are mixed, add sodium borohydride solution again, stir, make gold seeds solution; In cetyl trimethyl ammonium bromide solution, add liquor argenti nitratis ophthalmicus, tetra chlorauric acid solution, deionized water, ascorbic acid solution then successively, become colorless to mixed solution, make growth solution; In growth solution, add gold seeds solution at last, make original gold nanorods solution;
The gold nanorods of step 2. preparation Raman molecular mark: with hydro-extractor with the original gold nanorods solution of step 1 preparation carry out centrifugal after, in original gold nanorods solution, form precipitation, extracting this precipitation adds in the deionized water, precipitation is dissolved in the deionized water, form gold nanorods solution, the ethanolic solution that will be dissolved with Raman molecular then adds in the gold nanorods solution, makes the gold nanorods of Raman molecular mark after the stirring;
The double mode optical encoding probe of step 4. preparation: at first the gold nanorods that step 3 is made and silicon dioxide metal medium composite Nano ball solution metal medium composite Nano ball carry out amido modified, then amido modified gold nanorods and silicon dioxide metal medium composite Nano ball solution are mixed stirring with cadmium telluride quantum dot solution, cadmium telluride quantum dot is adsorbed to the surface of gold nanorods and silicon dioxide metal medium composite Nano ball, makes double mode optical encoding probe.
Beneficial effect:Compared with prior art, the present invention has following advantage:
1. integrate two kinds of optical signallings of fluorescence and SERS, make this double mode optical encoding probe possess the ability of fluorescence and SERS combined coding, strengthened the optical encoding ability.In the prior art, the optical encoding probe only has a kind of ability of coding usually, based on fluorescence signal or SERS signal.The optical encoding probe that the technical program provides adopts three-layer nuclear shell structure, ground floor nuclear is gold nanorods, and second layer shell is silicon dioxide, and the 3rd layer of shell is cadmium telluride quantum dot, and the outside surface of ground floor nuclear is covered with Raman molecular, and Raman molecular is wrapped up by second layer shell.This optical encoding probe is under the exciting light irradiation, utilize fluorescence spectrum scope and SERS spectral range simultaneously, can produce fluorescence and SERS signal, possess fluorescence and SERS combined coding ability, the actual sign indicating number number that can generate will increase greatly, possess excellent optical encoding ability.The double mode optical encoding probe of this structure has N the cadmium telluride quantum dot that diameter is different, M different types of Raman molecular 2, the number H=of this optical encoding probe codified so
, enlarged the number of codified.
2. strong, the good stability of the optical encoding probe signals of this structure.Do the SERS substrate with traditional spherical gold grain and compare, the technical program adopts gold nanorods to do the SERS substrate, can obtain stronger SERS signal.Compare as fluorescent material with traditional organic fluorescent dye, the technical program adopts cadmium telluride quantum dot as fluorescent material, has the light stability of narrower emission spectrum and Geng Gao.Utilize silica shell that Raman molecular and cadmium telluride quantum dot are separated, avoid produce power transfer between the two, make Raman molecular and cadmium telluride quantum dot can well keep the spectral characteristic of self.These structures have guaranteed strong, the good operating stability of the signal of optical encoding probe.
3. the preparation method is simple, and repeatable high.The preparation method of double mode optical encoding probe of the present invention only comprises four steps, and process is simple, and is easy to implement.Simultaneously, utilize this preparation method to have repeatable high characteristics.Repeatability is very crucial in a nano material preparation technology factor, and usually character such as the nano material physics for preparing of different batches, chemistry, optics may be different, and is inconsistent as size, spectral characteristic is inconsistent etc.And with the method for this patent, close physics, chemistry, the optical property of probe tool of different batches preparation.
Description of drawings
Fig. 1 is the structural representation of double mode optical encoding probe of the present invention.
Fig. 2 is to be the fluorescence spectrum of the double mode optical encoding probe solution of fluorescent material with the cadmium telluride quantum dot, and excitation wavelength is 400 nm.
Fig. 3 is with 5, (English full name is 5 to 5-two thiobiss (2-nitrobenzoic acid), 5-dithiobis(2-nitro-benzoic acid), be abbreviated as DTNB) molecule is the SERS spectrum of the double mode optical encoding probe particle of Raman molecular, excitation wavelength is 633 nm.
Fig. 4 is to be the SERS spectrum of the double mode optical encoding probe particle of Raman molecular with 4 mercaptobenzoic acids (English full name is 4-mercaptobenzoic acid, is abbreviated as 4MBA) molecule, and excitation wavelength is 633nm.
Fig. 5 is to be the SERS spectrum of the double mode optical encoding probe particle of Raman molecular with 4MBA and DTNB potpourri, and excitation wavelength is 633nm.
Have among the figure: ground floor nuclear 1, Raman molecular 2,3, the three layers of shell 4 of second layer shell.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is described in detail.
As shown in Figure 1, a kind of double mode optical encoding probe of the present invention, this probe adopts three-layer nuclear shell structure, ground floor nuclear 1 is gold nanorods, and second layer shell 3 is silicon dioxide, and the 3rd layer of shell 4 is cadmium telluride quantum dot, second layer shell 3 is wrapped in the outside of ground floor nuclear 1, the 3rd layer of shell 4 pastes in the outside of second layer shell 3, and the outside surface of ground floor nuclear 1 is covered with Raman molecular 2, and Raman molecular 2 is by second layer shell 3 parcels.
The double mode optical encoding probe of this structure is the nano particle based on three-layer nuclear shell structure, and innermost layer has been examined to mark the gold nanorods of Raman molecular 2, its outside parcel silica shell, and outermost layer is cadmium telluride quantum dot.This double mode optical encoding probe can produce fluorescence and SERS signal simultaneously under the exciting light irradiation, possess fluorescence and SERS combined coding ability.
Further, described Raman molecular 2 pastes the outside surface of whole ground floor nuclear 1.When Raman molecular 2 pasted the outside surface of whole ground floor nuclear 1, Raman molecular 2 can provide stronger SERS signal.
Further, described cadmium telluride quantum dot pastes the outside surface of whole second layer shell 3.When cadmium telluride quantum dot pasted the outside surface of whole second layer shell 3, cadmium telluride quantum dot can provide stronger fluorescence signal.
In order to make double mode optical encoding probe have stronger code capacity, the diameter of cadmium telluride quantum dot has two or more.Raman molecular 2 comprises two or more.Raman molecular 2 contains phenyl ring molecule and sulphur atom.When the raman scattering cross section of Raman molecular 2 is more big, just can produce more strong Raman scattering signal.Usually the Raman molecular 2 that contains phenyl ring has bigger raman scattering cross section.Raman molecular 2 is to be easy to be adsorbed onto on the gold nanorods by self sulphur atom and the formation of the gold on gold nanorods gold-sulfide linkage, so Raman molecular 2 preferably contains sulphur atom.Raman molecular 2 preferred 4 mercaptobenzoic acid molecules, 5, the one or any combination in 5-two thiobiss (2-nitrobenzoic acid) molecule, 4 aminothiophenol molecules, 4 methoxybenzenethiol molecules or the 2 thionaphthol molecules.
If the double mode optical encoding probe of this structure has N the cadmium telluride quantum dot that diameter is different, M different types of Raman molecular 2, the number H=of so double mode optical encoding probe codified
For example, adopt two kinds of Raman moleculars and a kind of cadmium telluride quantum dot totally 3 kinds of coding materials prepare double mode optical encoding probe.Two kinds of Raman moleculars are adopted as 5,5-, two thiobiss (2-nitrobenzoic acid) (DTNB) and 4 mercaptobenzoic acids (4MBA), and quantum dot is the water cadmium telluride quantum dot.With the signal on the optical encoding probe among 3 binary codes (xxx) expression the present invention.From left to right, the first bit representation quantum dot; The second bit representation 4MBA; The 3rd bit representation DTNB; " 1 " expression has, and " 0 " expression does not have.Then actual obtainable sign indicating number has (100) (101) (110) (111) (010) (001) (011) totally 7 kinds of sign indicating numbers ((000) sign indicating number is meaningless), and adopt 3 kinds of emission wavelength quantum dots or 3 kinds of Raman moleculars separately, because the influence of spectra overlapping, usually actually can only obtain 3 kinds or 4 kinds of sign indicating numbers, it is very difficult to obtain 7 kinds of sign indicating numbers.
The preparation method of above-mentioned double mode optical encoding probe may further comprise the steps:
The original gold nanorods solution of step 1. preparation: at first cetyl trimethyl ammonium bromide solution and tetra chlorauric acid solution are mixed, add sodium borohydride solution again, stir, make gold seeds solution; In cetyl trimethyl ammonium bromide solution, add liquor argenti nitratis ophthalmicus, tetra chlorauric acid solution, deionized water, ascorbic acid solution then successively, become colorless to mixed solution, make growth solution; In growth solution, add gold seeds solution at last, make original gold nanorods solution;
The gold nanorods of step 2. preparation Raman molecular mark: with hydro-extractor with the original gold nanorods solution of step 1 preparation carry out centrifugal after, in original gold nanorods solution, form precipitation, extracting this precipitation adds in the deionized water, precipitation is dissolved in the deionized water, form gold nanorods solution, the ethanolic solution that will be dissolved with Raman molecular then adds in the gold nanorods solution, makes the gold nanorods of Raman molecular mark after the stirring;
The double mode optical encoding probe of step 4. preparation: at first the gold nanorods that step 3 is made and silicon dioxide metal medium composite Nano ball solution metal medium composite Nano ball carry out amido modified, then amido modified gold nanorods and silicon dioxide metal medium composite Nano ball solution are mixed stirring with cadmium telluride quantum dot solution, cadmium telluride quantum dot is adsorbed to the surface of gold nanorods and silicon dioxide metal medium composite Nano ball, makes double mode optical encoding probe.
Be that SERS strengthens substrate with the gold nanorods, with 5,5-, two thiobiss (2-nitrobenzoic acid) (DTNB) molecule be the SERS label, be fluorescent material with the cadmium telluride quantum dot, prepare double mode optical encoding probe particle, the preparation method comprises the steps:
The original gold nanorods solution of step 1. preparation: at first prepare gold seeds, at room temperature (namely in 23 ~ 30 ℃ temperature range, hereinafter mention room temperature, identical therewith), 2.5mL 0.2M cetyl trimethyl ammonium bromide (abbreviation CTAB) solution is mixed with 1.5mL 1.0mM tetra chlorauric acid solution, vigorous stirring also adds the iced sodium borohydride solution of 0.6mL 0.01M, stops to stir the seed solution that namely gets pale brown look after 2 minutes.Prepare growth solution then, in 50mL 0.2M CTAB solution, add following reagent under the room temperature successively: 2 ~ 4mL 4mM liquor argenti nitratis ophthalmicus, 5mL 15mM tetra chlorauric acid solution, the 45mL deionized water slowly stirs.Adding 1.5mL ~ 3mL 0.08M ascorbic acid to solution subsequently becomes colorless.Add the 1mL seed solution at last, leave standstill 10 ~ 20min and namely get original gold nanorods solution.About 15nm * the 45nm of gained gold nanorods size.
The gold nanorods aqueous solution of step 2. preparation Raman molecular mark: get the original gold nanorods solution of 5mL with 10000 rpm, 30 minutes centrifugal excessive reactant of once removing.Centrifugation is dispersed in the 5mL deionized water, adds 10 ~ 50 μ L 10mM DTNB ethanolic solutions, more than the vigorous stirring 3h.
4) the double mode optical encoding probe of preparation: at first make particle show as electropositivity at gold nanorods and silicon dioxide metal medium composite Nano ball finishing amino, add 20 ~ 100 μ L, 10% polyethyleneimine (being abbreviated as " PEI ", molecular weight 10000) aqueous solution in 1mL gold nanorods and the silicon dioxide metal medium composite Nano ball solution and slowly stir 1h.With 6500 rpm, eccentric cleaning was 3 times in 10 minutes, and gold nanorods and the silicon dioxide metal medium composite Nano ball with amination is dispersed in the 1mL deionized water at last.Water cadmium telluride quantum dot part is mercaptoacetic acid or mercaptopropionic acid, in aqueous solution, show as electronegativity, the gold nanorods that 0.5 ~ 1mL cadmium telluride quantum dot aqueous solution and above-mentioned 1mL is amido modified and silicon dioxide metal medium composite Nano ball solution mixes and slowly stir more than the 3h, eccentric cleaning is removed excessive cadmium telluride quantum dot and is namely got the double mode optical encoding probe that has fluorescence and SERS signal simultaneously.
The fluorescence of this double mode optical encoding probe is surveyed by fluorescence spectrophotometer, and excitation wavelength is 400 nm.When surveying SERS spectrum, this optical encoding probe is dripped on glass sheet, and be fixed on photometry spectrum on the confocal Raman spectra instrument, lasing light emitter is the Argon ion laser of 633 nm, and the irradiation power on the sample is 2.3 mW, and be 60 s integral time.The existing fluorescence of this optical encoding probe (Fig. 2) has the very high SERS signal (Fig. 3) of signal to noise ratio (S/N ratio) again.Quantum dot by changing different emission wavelengths or different SERS labeled molecule can give this probe different optical properties, realize the function of fluorescence and SERS combined coding.The gained sign indicating number is (101) among this embodiment.If medium/metal composite nano-granule sub-surface is not adsorbed cadmium telluride quantum dot, then obtain (001) sign indicating number.If the gold nanorods surface does not connect DTNB, metal medium composite nano-granule sub-surface absorption cadmium telluride quantum dot then gets (100) sign indicating number simultaneously.
Being that SERS strengthens substrate with the gold nanorods, is the SERS label with 4 mercaptobenzoic acids (4MBA) molecule, is fluorescent material with the cadmium telluride quantum dot, prepares double mode optical encoding probe particle, and this method comprises the steps:
Step 1: prepare original gold nanorods solution.Prepare original gold nanorods solution according to the consumption among the embodiment 1 and step.
Step 2: the gold nanorods surface connects the 4MBA molecule.Get the original gold nanorods solution of 5mL with 10000 rpm, 30 minutes centrifugal once to remove excessive reactant.Centrifugation is dispersed in the 5mL deionized water, adds 10 ~ 50 μ L 10mM 4MBA ethanolic solutions, more than the vigorous stirring 3h.
Step 3: connected the gold nanorods surface parcel silicon dioxide of 4MBA molecule, preparation metal medium composite Nano ball solution.With 8000 rpm, 30 minutes once centrifugal with the solution of step 2 preparation, and precipitation is dissipated in 1 ~ 2mL 10mg/mL PAH aqueous solution, slowly stirs behind the 1h with 8000 rpm, and 30 minutes once centrifugal, and precipitation is dissipated in the 5mL deionized water.Add 1 ~ 2mL 25mg/mL PVP aqueous solution, with 8000 rpm, 30min is once centrifugal after the slow stirred overnight, and precipitation is dissipated in the 5mL absolute ethyl alcohol.The ammoniacal liquor that adds 300 ~ 500 μ L 25%, 15 ~ 30 μ L TEOS solution namely get metal medium composite Nano ball more than stirring 6h, and eccentric cleaning is also collected nanosphere in the reactant liquor.This nanosphere is dispersed in the 5mL deionized water the most at last, the about 100nm of nanosphere diameter.
4) metal medium composite nanoparticle surface electrostatic absorption cadmium telluride quantum dot.Add 20 ~ 100 μ L, 10% PEI aqueous solution in the 1mL metal medium composite Nano ball aqueous solution and slowly stir 1h.With 6500 rpm, eccentric cleaning was 3 times in 10 minutes, and the metal medium composite Nano ball with amination is dispersed in the 1mL deionized water at last.The metal medium composite Nano ball solution that 0.5 ~ 1mL cadmium telluride quantum dot aqueous solution and above-mentioned 1mL is amido modified mixes and slowly stirs more than the 3h, and eccentric cleaning is removed excessive cadmium telluride quantum dot and namely got the double mode optical encoding probe that has fluorescence and SERS signal simultaneously.
The fluorescence signal of this probe is seen Fig. 2, and the SERS signal is seen Fig. 4.The fluorescence of this double mode optical encoding probe is surveyed by fluorescence spectrophotometer, and excitation wavelength is 400 nm.When surveying SERS spectrum, this optical encoding probe is dripped on glass sheet, and be fixed on photometry spectrum on the confocal Raman spectra instrument, lasing light emitter is the Argon ion laser of 633 nm, and the irradiation power on the sample is 2.3 mW, and be 60 s integral time.The gained sign indicating number is (110) among this embodiment.If cadmium telluride quantum dot is not adsorbed on metal medium composite Nano ball surface, then obtain (010) sign indicating number.If the gold nanorods surface does not connect 4MBA, metal medium composite nano-granule sub-surface absorption cadmium telluride quantum dot then gets (100) sign indicating number simultaneously.
Being that SERS strengthens substrate with the gold nanorods, is the SERS label with 4MBA and DTNB potpourri, is fluorescent material with the cadmium telluride quantum dot, prepares double mode optical encoding probe particle, and this method comprises the steps:
Step 1: prepare original gold nanorods solution.Prepare original gold nanorods solution according to the consumption among the embodiment 1 and step.
Step 2: the gold nanorods surface connects 4MBA and two kinds of molecules of DTNB.Get the original gold nanorods solution of 5mL with 10000 rpm, 30 minutes centrifugal excessive reactant of once removing.Centrifugation is dispersed in the 5mL deionized water, adds the ethanolic solution that 10 ~ 50 μ L contain 5mM 4MBA and 5mM DTNB, more than the vigorous stirring 3h.
Step 3: the gold nanorods surface parcel silicon dioxide that has connected Raman molecular prepares the metal medium composite nanoparticle.With 8000 rpm, 30 minutes once centrifugal with the solution of step 2 preparation, and precipitation is dissipated in 1 ~ 2mL 10mg/mL PAH aqueous solution, slowly stirs behind the 1h with 8000 rpm, and 30 minutes once centrifugal, and precipitation is dissipated in the 5mL deionized water.Add 1 ~ 2mL 25mg/mL PVP aqueous solution, with 8000 rpm, 30min is once centrifugal after the slow stirred overnight, and precipitation is dissipated in the 5mL absolute ethyl alcohol.The ammoniacal liquor that adds 300 ~ 500 μ L 25%, 15 ~ 30 μ L TEOS solution namely get metal medium composite Nano ball more than stirring 6h, and eccentric cleaning is also collected nanosphere in the reactant liquor.This nanosphere is dispersed in the 5mL deionized water the most at last, the about 100nm of nanosphere diameter.
Step 4: metal medium composite nanoparticle surface electrostatic absorption cadmium telluride quantum dot.Add 20 ~ 100 μ L, 10% PEI aqueous solution in the 1mL metal medium composite nanoparticle aqueous solution and slowly stir 1h.With 6500 rpm, eccentric cleaning was 3 times in 10 minutes, and the metal medium composite nanoparticle with amination is dispersed in the 1mL deionized water at last.The metal medium composite Nano ball solution that 0.5 ~ 1mL cadmium telluride quantum dot aqueous solution and above-mentioned 1mL amination are modified mixes and slowly stirs more than the 3h, and the excessive cadmium telluride quantum dot of eccentric cleaning removal namely gets the double mode optical encoding probe that has fluorescence and SERS signal simultaneously.
This fluorescence probe signal is seen Fig. 2, and the SERS signal is seen Fig. 5.The fluorescence of this double mode optical encoding probe is surveyed by fluorescence spectrophotometer, and excitation wavelength is 400 nm.When surveying SERS spectrum, this optical encoding probe is dripped on glass sheet, and be fixed on photometry spectrum on the confocal Raman spectra instrument, lasing light emitter is the Argon ion laser of 633 nm, and the irradiation power on the sample is 2.3 mW, and be 60 s integral time.The gained sign indicating number is (111) among this embodiment.If cadmium telluride quantum dot is not adsorbed on metal medium composite Nano ball surface, then obtain (011) sign indicating number.
From the spectral line of Fig. 2 to Fig. 5 as can be seen: signal absolute strength numerical value is very big, spectral line is very level and smooth, signal to noise ratio (S/N ratio) is very high, and the probe of this structure has the strong feature of signal.
The above only is preferred implementation of the present invention; be noted that for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. double mode optical encoding probe, it is characterized in that, this probe adopts three-layer nuclear shell structure, ground floor nuclear (1) is gold nanorods, and second layer shell (3) is silicon dioxide, and the 3rd layer of shell (4) is cadmium telluride quantum dot, second layer shell (3) is wrapped in the outside of ground floor nuclear (1), the 3rd layer of shell (4) pastes in the outside of second layer shell (3), and the outside surface of ground floor nuclear (1) is covered with Raman molecular (2), and Raman molecular (2) is wrapped up by second layer shell (3);
Described Raman molecular (2) is 4-mercaptobenzoic acid molecule, 5,5-two thiobiss (2-nitrobenzoic acid) molecule, 4-aminothiophenol molecule, 4-methoxybenzenethiol molecule, the perhaps one or any combination in the 2-thionaphthol molecule.
2. according to the described double mode optical encoding probe of claim 1, it is characterized in that described Raman molecular (2) pastes the outside surface of whole ground floor nuclear (1).
3. according to the described double mode optical encoding probe of claim 1, it is characterized in that described cadmium telluride quantum dot pastes the outside surface of whole second layer shell (3).
4. according to the described double mode optical encoding probe of claim 1, it is characterized in that the diameter of described cadmium telluride quantum dot has two or more.
5. the preparation method of a double mode optical encoding probe as claimed in claim 1 is characterized in that, this preparation method may further comprise the steps:
The original gold nanorods solution of step 1. preparation: at first cetyl trimethyl ammonium bromide solution and tetra chlorauric acid solution are mixed, add sodium borohydride solution again, stir, make gold seeds solution; In cetyl trimethyl ammonium bromide solution, add liquor argenti nitratis ophthalmicus, tetra chlorauric acid solution, deionized water, ascorbic acid solution then successively, become colorless to mixed solution, make growth solution; In growth solution, add gold seeds solution at last, make original gold nanorods solution;
The gold nanorods of step 2. preparation Raman molecular mark: with hydro-extractor with the original gold nanorods solution of step 1 preparation carry out centrifugal after, in original gold nanorods solution, form precipitation, extracting this precipitation adds in the deionized water, precipitation is dissolved in the deionized water, form gold nanorods solution, the ethanolic solution that will be dissolved with Raman molecular then adds in the gold nanorods solution, makes the gold nanorods of Raman molecular mark after the stirring;
Step 3. preparation gold nanorods and silicon dioxide metal medium composite Nano ball solution: at first the gold nanorods surface of the Raman molecular mark that makes by polymer electrolytic confrontation step 2 is carried out close silicon and is handled, gold nanorods with the Raman molecular mark is transferred in the alcoholic solution then, in this alcoholic solution, add ammoniacal liquor and ethyl orthosilicate subsequently, this moment is in the gold nanorods superficial growth layer of silicon dioxide of Raman molecular mark, thus formation gold nanorods and silicon dioxide metal medium composite Nano ball solution;
The double mode optical encoding probe of step 4. preparation: at first the gold nanorods that step 3 is made and silicon dioxide metal medium composite Nano ball solution metal medium composite Nano ball carry out amido modified, then amido modified gold nanorods and silicon dioxide metal medium composite Nano ball solution are mixed stirring with cadmium telluride quantum dot solution, cadmium telluride quantum dot is adsorbed to the surface of gold nanorods and silicon dioxide metal medium composite Nano ball, makes double mode optical encoding probe.
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| US10322194B2 (en) | 2012-08-31 | 2019-06-18 | Sloan-Kettering Institute For Cancer Research | Particles, methods and uses thereof |
| US10105456B2 (en) | 2012-12-19 | 2018-10-23 | Sloan-Kettering Institute For Cancer Research | Multimodal particles, methods and uses thereof |
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