CN101338189A - High voltage electrospinning method for preparing multi-fluorescence-encoded micro-beads - Google Patents
High voltage electrospinning method for preparing multi-fluorescence-encoded micro-beads Download PDFInfo
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- CN101338189A CN101338189A CNA2008100511270A CN200810051127A CN101338189A CN 101338189 A CN101338189 A CN 101338189A CN A2008100511270 A CNA2008100511270 A CN A2008100511270A CN 200810051127 A CN200810051127 A CN 200810051127A CN 101338189 A CN101338189 A CN 101338189A
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Abstract
The invention belongs to the fluorescence-coded technology field and in particular relates to a high voltage electric spinning preparation method of multiplex fluorescence coding microsphere. In the method, fluorescent materials (quantum dots material or fluorescent dyes) with different quantities and different fluorescent characteristics are dispersed in polymer solution (or inorganic matter sol). Then, through the high voltage electric spinning process, the coding microsphere with controllable size and adjustable fluorescent strength and lighting wavelength is obtained. The quantum dots material can be used alone or used in mixing way. The fluorescent material can be used alone or used in mixing way. The flurescent material can also be used together with the quantum dots material. The coding microsphere prepared through the invention can provide fluorescent probes in large quantities for the fields of gene expression, protein-protein interaction, simultaneous detection of various diseases, high throughput screening, combinational chemistry, etc. The method of the invention has the advantages of simple operation, wide application, low cost, stable fluorescence performance, and the like, and is provided with good application and expansion value.
Description
Technical field
The invention belongs to fluorescence-encoded technical field, be specifically related to the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads.
Background technology
In recent years, be accompanied by the development of genomics and proteomics research, particularly the human genome examining order finishes, produced the parallel sequence data of enormous amount, it is a kind of fast to press for searching, effectively the detection analysis technology is screened a large amount of nucleic acid and protein like this, selecting for use the have multiple spectrum feature fluorescence/polymer microsphere of (multi-wavelength and many intensity) that biomacromolecule is carried out parallel coded markings is the effective means that addresses this problem, because in theory, varying strength, the fluorescent substance of different color is united the polymer microsphere that utilization can produce thousands of kinds of optical encodings, connect biomolecules (DNA or albumen) on its surface, so just be equivalent to add a specificity coding to each biomolecules, so only need ten thousand kinds of microballoons of 3-4 just can carry out code identification, thereby make that all genopathies are made rapid detection becomes possibility the full genome of the mankind; Same reason, this microballoon also can connect other molecule, be applied aspect the detection simultaneously of multiple disease, medicament high flux screening and the new drug development, and then driving developing rapidly of gene expression research, proteomics research and association areas such as cytobiology, new medicament screen and pathological diagnosis.
The research group at Nie place is combined into (Nature biotechnology, 2001,19,631) in the middle of the polystyrene porous microsphere to the CdSe/ZnS quanta point material of 3 kinds of colors, 2 kinds of intensity cleverly, and is applied in the middle of the DNA hybridization research.According to their expectation, with 10 kinds of intensity of a kind of wavelength (0,1,2 ... 9) quantum dot can produce 9 kinds of codings, and promptly 10
1-1, with 10 kinds of intensity of 3 kinds of wavelength (0,1,2 ... 9) 999 kinds of codings can be arranged, promptly 10
3-a kind, therefore with m kind wavelength n kind intensity (0,1,2 ... n-1) quantum dot can have n
m-a kind of coding, thereby as long as the coded number that uses 10 kinds of colors, the quanta point material of 6 kinds of intensity to obtain in theory can reach up to a million kinds, remove the part microballoon that can not accurately detect owing to spectra overlapping, available quanta point material microballoon can reach kind more than 40,000, but it is more loaded down with trivial details that this method operates, at first need to prepare the suitable polystyrene microsphere in aperture,, successively quanta point material is absorbed microballoon inside according to from big to small order more then with its swelling in solvent; Along with the increase of quanta point material addition, it is difficulty more that interpolation process more finally becomes, and is difficult to accomplish theoretic heavy addition simultaneously.
We are under the support of project of national nature science fund project, went through for two years, invented a kind of novel method for preparing multi-fluorescence-encoded micro-beads---high pressure electrospinning method, have characteristics simple to operate, quick, with low cost, and by control electrospinning condition, can be easily with the microballoon size control in tens nanometers to several micrometer ranges, the kind of doping fluorescent material and quantity are also unrestricted.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the preparation method of all different multi-fluorescence-encoded micro-beads of a kind of and existing reported in literature is provided---high pressure electrospinning method, change by fluorescent material (quanta point material or fluorescence dye) wavelength and intensity, can obtain the fluorescence labeling probe of enormous amount, thereby satisfy the demand of the extensive coding of association areas such as biomedicine, cytobiology, new medicament screen and pathological diagnosis.
The present invention is that quanta point material or the fluorescence dye that will have different emission band mix with polymer, be made into and have certain density solution, adopt the preparation of high voltage electric spinning technique to have the polymer microsphere of multi-fluorescence spectral quality then, by kind that changes quanta point material and the fluorescent characteristic that quantity changes polymer microsphere, factors such as the concentration by changing macromolecular solution, polymericular weight, electrospinning condition are controlled the form and the size of microballoon.
The high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads of the present invention, its step is as follows:
A: contain the preparation of the electrospinning solution of one or more fluorescent materials:
In air or inert gas atmosphere, the combined ultrasonic of a kind of fluorescent material or multiple fluorescent material is scattered in single solvent or the mixed solvent, solvent should make the fluorescent material ultra-sonic dispersion that sedimentation and quenching of fluorescence do not take place later on, the mass percentage concentration of fluorescent material is 0.001%～10%, then with the macromolecular solution blend, fluorescent material and high molecular mass ratio are 1: 100000～10: 1, through ultrasonic or vibration or stir fluorescent material is scattered in the macromolecular solution uniformly, form homogeneous phase solution or microemulsion;
Or fluorescent material and polymer added in the solvent simultaneously, through ultrasonic or vibration or stir and form homogeneous phase solution or microemulsion.
Fluorescent material comprises quanta point material and fluorescence dye.
Described quanta point material can be II-VI family quanta point material or III-V family quanta point material, or the quanta point material of the nucleocapsid structure of being made up of above-mentioned quanta point material.
Further, quanta point material is for the CdSe series quanta point material based on CdSe, as CdSe, CdSe/ZnS, CdSe/ZnSe, CdSe/CdS, CdSe/CuSe, CdSe/HgTe or CdSe/HgSe/CdSe etc.;
Or based on the serial quanta point material of the CdTe of CdTe, as CdTe, CdTe/ZnS, CdTe/CdS or CdTe/HgS etc.;
Or based on the serial quanta point material of the CdS of CdS, as CdS, CdS/ZnS, CdS/Ag
2S, CdS/PbS, CdS/Cd (OH)
2, CdS/HgS or CdS/HgS/CdS etc.;
Or based on the serial quanta point material of the ZnS of ZnS, as ZnS, ZnS/CdS, ZnS/CdS/ZnS or ZnS/HgS/ZnS/CdS etc.;
Or based on the serial quanta point material of ZnSe, HgS, GaSe, HgSe, HgTe, GdTe, ZnTe, ZnO, PbS, PbSe, CaAs, InP, InAs, InCaAs etc.
Also based on the serial quanta point material of MgS, MgSe, MgTe, CaS, CaTe, SrS, SrSe, SeTe, BaS or BaSe, BaTe.
And by the serial quanta point material of metallic element or nonmetal doping: such as CdS, the CdSe of element dopings such as Mn, Cu, Tb, CdTe, ZnSe, ZnS series quanta point material etc.
Described fluorescence dye is porphyrin, white dyes, nucleic acid dye, acridine, phenanthridines class dyestuff, thiazine and piperazine class dyestuff, BODIPY (boron dipyrromethene difluoride) dyestuff, fluoresceins, rhodamine class, two fluothane boron classes, diphenylethylene, naphthalimide, fluorenes fluorochrome and phthalocyanines dye etc.
Quanta point material can use separately, also can blend use; Fluorescence dye can use separately, also can blend use.Fluorescence dye can also mix use with quanta point material, mixes when using, and the mass ratio between one or more quanta point materials and one or more fluorescence dyes is 0.001: 1～1: 1.
Fluorescent material after the combination can have m kind emission wavelength (m 〉=1) and n kind luminous intensity (0,1,2,3 ... n-1).
Under selected wavelength, with a kind of emission wavelength, 5 kinds of intensity (0,1,2,3,4) can have (1), (2), (3), (4) four kinds of combinations, promptly 5
1-a kind, can form 5
1-a kind of coding form;
Situation with 2 two kinds of wavelength and 2 kinds of intensity (0,1) is an example, and (0:1), (1:0), (1:1) three kinds of combinations can be arranged, promptly 2
2-a kind, can form 2
2-a kind of coding form;
With 2 kinds of wavelength, the situation of 3 kinds of intensity (0,1,2) is an example, and (0:1) can be arranged, (1:0), and (1:1), (0:2), (2:0), (2:1), (1:2), (2:2) eight kinds of combinations, promptly 3
2-a kind;
With 3 kinds of wavelength, the situation of 2 kinds of intensity (0,1) is an example, and (1:1:1) can be arranged, (1:0:1), and (1:1:0), (0:1:1), (0:1:0), (1:0:0), (0:0:1) seven kinds of combinations, promptly 2
3-a kind, can form 2
3-a kind of coding form;
The quantum dot of m kind wavelength n kind intensity can have n by that analogy
m-a kind of type of coding.
Described quanta point material combination is the method according to document (Nature biotechnology, 2001,19,631).
Described solvent is meant and can and all solvents of sedimentation and quenching of fluorescence take place with quantum dot (or fluorescence dye) homodisperse, these solvents can use separately, also can blend use, further comprise chloroform, methylene dichloride, tetracol phenixin, ethylene dichloride, trichloroethane, chloropropane, chlorobutane, benzene, toluene, dimethylbenzene, ethylbenzene, normal hexane, hexanaphthene, methylcyclohexane, heptane, octane, octane-iso, tetrahydrofuran (THF), ethyl acetate, butylacetate, water, methyl alcohol, ethanol, propyl alcohol, isopropylcarbinol, acetone, butanone, ether, butyl ether, amyl ether, acetate, butyric acid, trifluoroacetic acid, acetonitrile, butyronitrile, triethylamine, N, dinethylformamide, N, the N-diethylformamide, dimethyl sulfoxide (DMSO) etc.
Described polymer is the existing all kinds of high molecular polymers that can be used for the high pressure electrospinning, can be the one-component polymer, also can be the various ingredients macromolecule mixture, such as: styrene based copolymers such as polystyrene, styrene/acrylic, styrene/methacrylic acid, styrene/butadiene/styrene; Polymethacrylate multipolymers such as polymethylmethacrylate, methyl methacrylate/vinylformic acid, methyl methacrylate/methacrylic acid; Water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyoxyethylene glycol, polyoxyethylene (PEO), chitosan, polyacrylamide; Biodegradable polymers such as poly(lactic acid), polylactide, poly-(lactic-co-glycolic acid), polycaprolactone; Special engineered polymers such as polyaryletherketone, polyphenylene sulfide, polyether-ether-ketone; Conducting polymer such as polyaniline, Polythiophene; And polyacrylonitrile, polybenzimidazole, polyimide, nylon, poly-4-vinylpyridine, polyurethane, polyethylene, polyvinyl acetate (PVA), sodium alginate, DNA, protein, albumin, polyvinyl carbazole, poly-(ethylene-vinyl acetate), poly-(ethylene-vinyl alcohol), polypropylene, polyvinyl chloride, tetrafluoroethylene (PVDF), polysiloxane, polyoxymethylene, metaldehyde, polycarbonate, poly-hydroxy-butanedioic acid valerate, the poly terephthalic acid phenylenediamine, poly terephthalic acid benzene diester, Mierocrystalline cellulose, polyetherimide, natural rubber, silk, collagen etc.
The mass percent concentration of fluorescent material is directly related with its luminescent properties, can change between 0.001%～10% generally speaking, is preferably 0.001%～1.0%, and more preferably 0.01%～1.0%.
The concentration of macromolecular solution is the key factor that influences electrospinning product form, forms microballoon when concentration is low easily, forms fiber when concentration is high easily, and along with the increase of concentration, electrospinning product form can occur by the variation tendency of microballoon to fiber; Reduction along with concentration, the form of electrospinning product can present the variation tendency from the fiber to the microballoon, after forming microballoon, the size of microballoon can and reduce gradually with the concentration reduction, generally speaking, high molecular mass concentration scope is 0.001%～50% when forming microballoon, and preferred concentration range is 0.001%～20%, and further preferred concentration range is 0.001%～10%.
Fluorescent material and high molecular mass ratio can change between 1: 100000～10: 1, be preferably, and 1: 100000～1: 1, more preferably 1: 100000～1: 1000, more preferably 1: 100000～1: 10000 again.
The raw material that is used for electrospinning can also be various sol systems except that above-mentioned polymer.Be about to all or part of SiO that replaces with of polymer
2Colloidal sol, TiO
2Colloidal sol or SiO
2And TiO
2Mixed sols, when colloidal sol and polymer blended use, the mass ratio of one or more colloidal sols and one-component polymer or various ingredients macromolecule mixture is 1: 99～99: 1.
B: the preparation of multicolor fluorescence polymer microsphere
The electrospinning solution that contains one or more fluorescent materials for preparing in the steps A is imported in the spray fiber tube of electrospinning silk equipment, install shower nozzle additional with 1～3mm bore, and shower nozzle linked to each other with the positive pole of high-voltage power supply (power supply for negative pole output then links to each other with negative pole) is as anode, with metal sheet (or roller, plastics, paper, fabric, water-bath, oil bath etc.) be negative pole, distance is 5～30cm between the positive and negative electrode, regulate the spinning solution rate of flow of fluid at 0.1～10ml/h with the liquid flow rate control device, the high voltage electric that applies 0.5～100,000 volt then on shower nozzle makes the polymers soln body charged, the polymkeric substance drop can overcome surface tension of liquid and form the injection thread, under effect of electric field, the thread splitting, form the uniform multi-fluorescence-encoded polymer microsphere of size, collect on the negative pole.
The coding microball of this patent preparation can provide the fluorescent probe of enormous amount for fields such as genetic expression, protein-protein interaction, the detection simultaneously of multiple disease, high-flux medicaments sifting and combinatorial chemistries by the surface group functionalization.Advantages such as that method provided by the present invention has is simple to operate, suitability wide, cost is lower, photoluminescent property is stable have good application and popularization value.
Description of drawings
Fig. 1: the fluorescence spectrum that contains the double-colored polystyrene microsphere of CdSe/ZnS quanta point material;
Fig. 2: the fluorescence spectrum that contains three look polystyrene microspheres of CdSe/ZnS quanta point material and porphyrin;
Embodiment
Now state as follows in detail to the present invention in conjunction with embodiment:
Following embodiment is to be used for the present invention is further described, but also non exhaustive, the present invention is not imposed any restrictions.
Embodiment 1: contain monochromatic CdSe/ZnS quanta point material polystyrene microsphere
60g vinylbenzene, 6g vinylformic acid, 0.07g Diisopropyl azodicarboxylate mixed dissolution in tetrahydrofuran (THF), are heated 70 ℃ of reactions 10 hours, through sedimentation, washing drying, get polystyrene then, standby;
The 2g polystyrene is dissolved in 18g N, and in the dinethylformamide, making its concentration is 10%;
2 * 10 of maximum absorption will be arranged in the 612nm place
-4G CdSe/ZnS (U.S. Ocean Nanotech product) quanta point material ultra-sonic dispersion is in the 5g chloroform;
N with the 10g polystyrene, dinethylformamide solution mixes with the chloroformic solution of 5g CdSe/ZnS, after stirring, made quanta point material homodisperse in polystyrene solution in ultrasonic 30 minutes, then solution is added in the spin duct of electrospinning silk equipment, install the shower nozzle that diameter is 1mm additional, and shower nozzle linked to each other as anode with the positive pole of high-voltage power supply, with the aluminium foil is negative pole, regulating the positive and negative electrode spacing is 10cm, the shower nozzle flow rate of liquid is 1ml/h, and electrospinning under 1.5kV voltage obtains diameter at quanta point material/polymer microsphere of 1.00 ± 0.25 microns on metal sheet, on this basis, adjust the addition of quanta point material, numerical value of every change will form a kind of coding microball.
Embodiment 2: the polystyrene microsphere that contains double-colored CdSe/ZnS quanta point material
The preparation of polystyrene solution is shown in embodiment 1;
To 4 * 10 of maximum absorption be arranged at 612nm
-4G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 5g chloroform;
3.8 * 10 of maximum absorption will be arranged at the 586nm place
-4G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 5g chloroform;
The chloroformic solution of 10g polystyrene solution with 2.5g CdSe/ZnS (612nm) and 2.5g CdSe/ZnS (586nm) quanta point material mixed, stir 5h, made quanta point material homodisperse in polystyrene solution in ultrasonic 30 minutes, then solution is added in the spin duct, install 1mm diameter shower nozzle additional, and shower nozzle linked to each other as anode with the positive pole of high-voltage power supply, with the aluminium foil is negative pole, regulating the positive and negative electrode spacing is 10cm, the shower nozzle flow rate of liquid is 1ml/h, electrospinning under 1.5kV voltage obtains diameter at double-colored quanta point material/polymer microsphere of 1.00 ± 0.25 microns on metal sheet.
The result of embodiment 2 can find on scheming that as shown in Figure 1 the fluorescent emission wavelength only differs two kinds of quantum dots (586nm and 612nm) of 26nm, after being embedded into the electrospinning microballoon, has realized good spectral separation, and quenching of fluorescence does not take place.
On this basis, change the addition (perhaps stablize a kind of content of wavelength material, change a kind of content of another kind of wavelength material separately) of two kinds of wave band quantum point materials simultaneously, every change once will obtain a kind of coding form.
Embodiment 3: the polystyrene microsphere that contains three look CdSe/ZnS quantum dots
The preparation method of polystyrene such as embodiment 2 methods are implemented;
To 4 * 10 of maximum absorption be arranged at 612nm
-4G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 5g chloroform;
3.8 * 10 of maximum absorption will be arranged at the 586nm place
-4G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 5g chloroform;
3.3 * 10 of maximum absorption will be arranged at the 530nm place
-4G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 5g chloroform;
The 2.0g polystyrene is dissolved in 15.5g N, in the dinethylformamide, standby after stirring;
Get the polystyrene solution of 10g preparation, the chloroformic solution that adds 2.5g CdSe/ZnS (618nm), 2.5gCdSe/ZnS (586nm), 2.5g CdSe/ZnS (530nm) quanta point material then, adopt the implementation process of embodiment 2 to make corresponding polystyrene polychrome microballoon then, its diameter is 0.85 ± 0.20 micron, change the addition of every kind of wavelength quanta point material on this basis, every change once will form a kind of coding.
Embodiment 4: the polystyrene microsphere that contains CdSe/ZnS and CdTe quanta point material
Method according to embodiment 2 obtains polystyrene solution;
With 3.3g CdSe/ZnS (530nm) quantum dot ultra-sonic dispersion in the 5g chloroformic solution;
With 4 * 10
-4G CdTe quantum dot (wavelength of fluorescence is 600nm, U.S. Ocean Nanotech product) ultra-sonic dispersion is in the middle of 5g toluene;
With the 10g polystyrene solution with after the chloroformic solution of 2.5g CdSe/ZnS (530nm), 2.5g CdTe (600nm) quanta point material mixes, adopt the process of embodiment 2 to obtain accordingly by CdSe/ZnS and the adulterated polystyrene microsphere of CdTe two-pack quanta point material, its diameter is 1.00 ± 0.25 microns.On this basis, change the addition of every kind of quanta point material, every change once just can form a kind of coding.
Embodiment 5: the polystyrene microsphere that contains porphyrin
Press the synthetic porphyrin of method of document (SCI, 1997,18,1375) report;
The 0.04g porphyrin is dissolved in 5g N, in the dinethylformamide, stirring, ultrasonic back standby, its fluorescent absorption wavelength is 650nm.
Prepare the 10g polystyrene solution by method among the embodiment 1, join then in the 5g porphyrin solution for preparing above, continue to stir 12 hours acquisition electrospinning solution, can obtain porphyrin/polystyrene microsphere by method in the example 1 then, diameter of micro ball is 0.80 ± 0.20 micron, on this basis, change the addition of porphyrin, every change once will form a kind of coding.
Embodiment 6: the polychrome polystyrene microsphere that contains CdSe/ZnS and porphyrin
The method of pressing embodiment 1 obtains polystyrene;
To 4.3 * 10 of maximum absorption be arranged at 612nm
-4G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 5g chloroform;
To 1.8 * 10 of maximum absorption be arranged at 586nm
-4G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 5g chloroform;
The 10g polystyrene solution is mixed mutually with 2.5g CdSe/ZnS (586nm), the chloroformic solution of 2.5g CdSe/ZnS (612nm) quanta point material, 2.5g porphyrin solution, stirred back ultrasonic 30 minutes, and guaranteed quanta point material homodisperse in macromolecular solution;
Adopt the method for embodiment 1 to prepare the polystyrene microsphere that contains CdSe/ZnS and porphyrin simultaneously, diameter of micro ball is 1.00 ± 0.25 microns.
The experimental result of embodiment 4 is therefrom found as shown in Figure 2, introduces after the porphyrin in quantum dot/polymer microsphere, has realized good spectral separation, does not disturb each other.On this basis, change the addition of every kind of wavelength quanta point material and porphyrin, every change once will form a kind of coding microball.
Embodiment 7: the polystyrene microsphere that contains Mn doping CdSe quanta point material
(J.Phys.Chem.C 2008,112, and 7624-7630) method is synthesized the adulterated CdSe quantum dot of Mn, and its wavelength of fluorescence is 675nm according to document;
According to the synthetic polystyrene microsphere that contains Mn doping CdSe quanta point material of the method for embodiment 1, its diameter is 1.00 ± 0.25, on this basis, changes the addition of quanta point material, and every change once will form a kind of coding.
Embodiment 8: the polychrome silicon dioxide microsphere that contains the CdSe/ZnS quanta point material
In the 7.2g tetrahydrofuran (THF), back flow reaction is 5 hours then with 10.5g tetraethoxy, 2.2g water, 0.25g dissolving with hydrochloric acid, obtains silicon dioxide gel;
Then according to the method for embodiment 2, polystyrene solution is wherein replaced to silicon dioxide gel, the silicon dioxide microsphere that has the CdSe/ZnS quanta point material of multiple optics character again through the acquisition of high pressure electrospinning process, diameter of micro ball is 1.20 ± 0.25 microns, on this basis, change the addition of every kind of wavelength quanta point material, every change once will form a kind of coding.
Embodiment 9: the polychrome polyvinyl alcohol microballoon that contains the CdSe/ZnS quanta point material
With 0.2g polyvinyl alcohol (purchasing) and 0.02g succsinic acid (ethylhexyl) sodium sulfonate (AOT purchases in Adrich) in Beijing Yili Fine Chemicals Co., Ltd., heating for dissolving in 19.8g water, cool to room temperature;
To 4 * 10 of maximum absorption be arranged at 612nm
-3G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 0.5g chloroform;
3.8 * 10 of maximum absorption will be arranged at the 586nm place
-3G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 0.5g chloroform;
3.3 * 10 of maximum absorption will be arranged at the 530nm place
-3G CdSe/ZnS quanta point material ultra-sonic dispersion is in the 0.5g chloroform;
Get the 10g polyvinyl alcohol solution, the chloroformic solution that adds 0.1g CdSe/ZnS (612nm), 0.1g CdSe/ZnS (586nm) and 0.1g CdSe/ZnS (530nm) quanta point material, vigorous stirring and ultrasonic back form microemulsion, obtain to contain the polyvinyl alcohol microballoon of three look quantum dots then according to the process of embodiment 3, its diameter is 500 ± 25nm.On this basis, change the addition of every kind of wavelength quanta point material, every change once will form a kind of coding.
Embodiment 10: the polychrome polylactic acid microsphere that contains the CdSe/ZnS quanta point material
Method according to embodiment 3 is prepared CdSe/ZnS (612nm), CdSe/ZnS (586nm) and CdSe/ZnS (530nm) solution;
1.0g poly(lactic acid) (purchasing in Aldrich) is dissolved in the N of 9.5g chloroform and 9.5g, in the N-diformamide, stirs and be made into 5% solution;
Get the poly(lactic acid) solution of 10g preparation, the chloroformic solution that adds 2.5g CdSe/ZnS (618nm), 2.5g CdSe/ZnS (586nm), 2.5g CdSe/ZnS (530nm) quanta point material, adopt the process of embodiment 3 to make corresponding poly(lactic acid) polychrome microballoon then, its diameter is 0.8 ± 0.15 micron.On this basis, change the addition of every kind of wavelength quanta point material, every change once will form a kind of coding.
Claims (13)
1, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads, its step is as follows:
A, contain the preparation of the electrospinning solution of one or more fluorescent materials:
In air or inert gas atmosphere, the combined ultrasonic of a kind of fluorescent material or multiple fluorescent material is scattered in single solvent or the mixed solvent, solvent should make the fluorescent material ultra-sonic dispersion that sedimentation and quenching of fluorescence do not take place later on, the mass percentage concentration of fluorescent material is 0.001%～10%, then with the macromolecular solution blend, fluorescent material and high molecular mass ratio are 1: 100000～10: 1, through ultrasonic, vibration or stirring make fluorescent material be scattered in the macromolecular solution uniformly, form homogeneous phase solution or microemulsion, promptly obtain containing the electrospinning solution of one or more fluorescent materials;
Or fluorescent material and polymer added in the solvent simultaneously, through ultrasonic, vibration or stir and form homogeneous phase solution or microemulsion, promptly obtain containing the electrospinning solution of one or more fluorescent materials;
The preparation of B, multicolor fluorescence polymer microsphere
The electrospinning solution that contains one or more fluorescent materials for preparing in the steps A is imported in the spray fiber tube of electrospinning silk equipment, install shower nozzle additional with 1～3mm bore, and shower nozzle linked to each other as anode with the positive pole of high-voltage power supply, with the metal sheet is negative pole, distance is 5～30cm between the positive and negative electrode, regulating the spinning solution rate of flow of fluid with the liquid flow rate control device is 0.1～10ml/h, the high voltage electric that applies 0.5～100,000 volt then on shower nozzle makes the polymers soln body charged, the polymkeric substance drop overcomes surface tension of liquid and forms the injection thread, under effect of electric field, the thread splitting forms the uniform multi-fluorescence-encoded polymer microsphere of size, collects on the negative pole.
2, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 1 is characterized in that:
Fluorescent material is quanta point material or fluorescence dye.
3, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 1 or 2 is characterized in that: described multiple fluorescent material combination is meant uses multiple quanta point material blend; Or with multiple fluorescence dye blend use; Or one or more quanta point materials are mixed use with one or more fluorescence dyes, the mass ratio between one or more quanta point materials and one or more fluorescence dyes is 0.001: 1～1: 1.
4, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 2, it is characterized in that: quanta point material is II-VI family quanta point material or III-V family quanta point material, or the quanta point material of the nucleocapsid structure of being made up of above-mentioned quanta point material.
5, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 4 is characterized in that: quanta point material is the serial quanta point material based on CdSe, CdTe, CdS, ZnS, ZnSe, HgS, GaSe, HgSe, HgTe, GdTe, ZnTe, ZnO, PbS, PbSe, CaAs, InP, InAs, InCaAs, MgS, MgSe, MgTe, CaS, CaTe, SrS, SrSe, SeTe, BaS, BaSe or BaTe.
6, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 5 is characterized in that: quanta point material is CdSe, CdSe/ZnS, CdSe/ZnSe, CdSe/CdS, CdSe/CuSe, CdSe/HgTe, CdSe/HgSe/CdSe, CdTe, CdTe/ZnS, CdTe/CdS, CdTe/HgS, CdS, CdS/ZnS, CdS/Ag
2S, CdS/PbS, CdS/Cd (OH)
2, CdS/HgS, CdS/HgS/Cd ZnS, ZnS/CdS, ZnS/CdS/ZnS or ZnS/HgS/ZnS/CdS.
7, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 2 is characterized in that: quanta point material is CdS, CdSe, CdTe, ZnSe or the ZnS series quanta point material of Mn, Cu or Tb element doping.
8, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 2 is characterized in that: fluorescence dye is porphyrin, white dyes, nucleic acid dye, acridine, phenanthridines class dyestuff, thiazine and piperazine class dyestuff, BODIPY dyestuff, fluoresceins dyestuff, rhodamine class dyestuff, two fluothane boron class dyestuffs, stilbene dye, naphthalimide dyestuff, fluorenes fluorochrome or phthalocyanines dye.
9, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 1 is characterized in that: polymer is a polystyrene, styrene/acrylic, styrene/methacrylic acid, styrene/butadiene/styrene, polymethylmethacrylate, methyl methacrylate/vinylformic acid, methyl methacrylate/methacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyoxyethylene glycol, polyoxyethylene, chitosan, polyacrylamide, poly(lactic acid), polylactide, poly-(lactic-co-glycolic acid), polycaprolactone, polyaryletherketone, polyphenylene sulfide, polyether-ether-ketone, polyaniline, Polythiophene, polyacrylonitrile, polybenzimidazole, polyimide, nylon, poly-4-vinylpyridine, polyurethane, polyethylene, polyvinyl acetate (PVA), sodium alginate, DNA, protein, albumin, polyvinyl carbazole, poly-(ethylene-vinyl acetate), poly-(ethylene-vinyl alcohol), polypropylene, polyvinyl chloride, tetrafluoroethylene (PVDF), polysiloxane, polyoxymethylene, metaldehyde, polycarbonate, poly-hydroxy-butanedioic acid valerate, the poly terephthalic acid phenylenediamine, poly terephthalic acid benzene diester, Mierocrystalline cellulose, polyetherimide, natural rubber, silk or collagen.
10, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 1 is characterized in that: with all or part of SiO of replacing with of polymer
2Colloidal sol, TiO
2Colloidal sol or SiO
2And TiO
2Mixed sols, when colloidal sol and polymer blended use, the mass ratio of one or more colloidal sols and one-component polymer or various ingredients macromolecule mixture is 1: 99～99: 1.
11, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 1 is characterized in that: high molecular mass concentration is 0.001%～50% in the macromolecular solution.
12, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 1 is characterized in that: the mass percent concentration of fluorescent material is 0.001%～1.0%.
13, the high voltage electrospinning method for preparing of multi-fluorescence-encoded micro-beads as claimed in claim 1 is characterized in that: fluorescent material and high molecular mass ratio are 1: 100000～1: 1.
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