CN1306002C - Silicon dioxide fluorescent microball containing cadmium telluride fluorescence quantum point - Google Patents
Silicon dioxide fluorescent microball containing cadmium telluride fluorescence quantum point Download PDFInfo
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- CN1306002C CN1306002C CNB2004100099418A CN200410009941A CN1306002C CN 1306002 C CN1306002 C CN 1306002C CN B2004100099418 A CNB2004100099418 A CN B2004100099418A CN 200410009941 A CN200410009941 A CN 200410009941A CN 1306002 C CN1306002 C CN 1306002C
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- silicon dioxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 234
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 117
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 70
- 239000011806 microball Substances 0.000 title 1
- 239000004005 microsphere Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 32
- 239000002096 quantum dot Substances 0.000 claims abstract description 32
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
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- 239000003495 polar organic solvent Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 9
- 125000002091 cationic group Chemical group 0.000 claims abstract description 6
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 62
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- 239000000243 solution Substances 0.000 claims description 47
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- 238000006243 chemical reaction Methods 0.000 claims description 20
- -1 siloxanes Chemical class 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 7
- 229920006317 cationic polymer Polymers 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
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- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 claims description 4
- FPOSCXQHGOVVPD-UHFFFAOYSA-N chloromethyl(trimethoxy)silane Chemical compound CO[Si](CCl)(OC)OC FPOSCXQHGOVVPD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- SRFACLNNATVRAT-YUDCMIJISA-N (2s)-2-[[(e)-2-carboxyethenyl]amino]-3-methyl-3-sulfinobutanoic acid Chemical compound OS(=O)C(C)(C)[C@H](C(O)=O)N\C=C\C(O)=O SRFACLNNATVRAT-YUDCMIJISA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
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- 230000005540 biological transmission Effects 0.000 description 9
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 6
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 6
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- AGBQKNBQESQNJD-SSDOTTSWSA-N (R)-lipoic acid Chemical compound OC(=O)CCCC[C@@H]1CCSS1 AGBQKNBQESQNJD-SSDOTTSWSA-N 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- AGBQKNBQESQNJD-UHFFFAOYSA-N alpha-Lipoic acid Natural products OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
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- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- PBFKVYVGYHNCGT-UHFFFAOYSA-N 1-sulfanylpropane-1,2,3-triol Chemical compound OCC(O)C(O)S PBFKVYVGYHNCGT-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000011953 bioanalysis Methods 0.000 description 3
- PSIBWKDABMPMJN-UHFFFAOYSA-L cadmium(2+);diperchlorate Chemical compound [Cd+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PSIBWKDABMPMJN-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 230000008878 coupling Effects 0.000 description 2
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
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- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
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- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
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- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
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Abstract
The present invention relates to a silicon dioxide fluorescent microsphere which comprises one or more cadmium telluride fluorescent quantum dots and a preparing method for the silicon dioxide fluorescent microsphere. The method comprises the following steps: a reverse microemulsion is formed by using a mixture of water soluble cadmium telluride fluorescent quantum dots and ammonium hydroxide as a water phase, a non-polar organic solvent as an oil phase and a non-ionic surface-active agent as an emulsifier; siloxane is hydrolyzed at a normal temperature; siloxane is hydrolyzed at a room temperature by adopting a reverse microemulsion method; silicon dioxide fluorescent microsphere with a core-shell structure is obtained by a one-step reaction; then a silicon dioxide microsphere with one cadmium telluride fluorescent quantum dot is obtained after deposition and separation. The particle diameter of the silicon dioxide fluorescent microsphere can be regulated in a range of 30 to 100 nanometers by controlling experiment conditions; a silicon dioxide fluorescent microsphere with a plurality of cadmium telluride quantum dots can be obtained by changing the type of siloxane or by adding cationic polyelectrolyte. In addition, the number of cadmium telluride quantum dots in the silicon dioxide microsphere can be controlled by changing the dosage of cationic polyelectrolyte.
Description
Technical field
The present invention relates to silica fluorescent microballoon that contains the cadmium telluride fluorescence quantum and preparation method thereof.More particularly, adopt the method for reverse micro emulsion that the water soluble cadmium telluride fluorescence quantum is compound in the silicon dioxide microsphere, prepare silica fluorescent microballoon, control the number of cadmium telluride quantum dot in the silica fluorescent microballoon simultaneously with single or a plurality of cadmium telluride quantum dots.
Background technology
The unique fluorescence size adjustable of II-VI family fluorescent nano particles (being called fluorescence quantum again) makes it at aspects such as bioanalysis and biological studies great application prospect be arranged as a kind of marker material.The material that serves as a mark improves its chemical stability thereby fluorescence quantum requires to coat one deck inert material on its surface.Silicon-dioxide is undoubtedly a kind of desirable selection, and it not only can stop the diffusion of photo-generated carrier and oxygen, thereby improves the fluorescent stability of quantum dot effectively; And can stop the gathering of nanoparticle at aqueous phase.The more important thing is that the chemistry of silicones development is very ripe, this just provides great convenience for the biological functional on fluorescence quantum surface.Therefore, the silicon dioxide microsphere that contains single or a plurality of cadmium telluride quantum dots can be easily and the biomolecules coupling, is expected to be used for external, body internal labeling biomolecules, and great application prospect is arranged in bioanalysis.Yet up to the present to the control of fluorescent quantum number of spots in the microballoon, the maintenance of photoluminescent property, the preparation that especially only contains the silica fluorescent microballoon of a fluorescence quantum remains the technical barrier in the application.
The preparation method who is coated with the silicon dioxide microsphere of inorganic nanoparticles mainly contains two kinds: a kind of St of being based on ber method.This procedure is loaded down with trivial details, need through ligand exchange, progressively process such as growth just can obtain the silicon dioxide microsphere (50～120 nanometer) of greater particle size, utilize this method not only to be difficult to obtain having only the silicon dioxide microsphere (Chem.Mater.2000 of single cadmium telluride quantum dot, 12,2676～2685), and can not control the number of quantum dot in the silicon dioxide microsphere.Second method is exactly a reverse microemulsion process.A.Asher etc. (J.Am.Chem.Soc.1994,116,6739-6744) mode that adopts this method to form Cadmium Sulfide (CdS) by original position has obtained containing the silicon dioxide microsphere of single CdS fluorescent nano particles.Compare with preceding a kind of method, the prepared by reverse microemulsion method method is simple, and the silicon ball of size range in 30～150 nanometers has narrower granularity to disperse than St ber method.But the CdS nanoparticle size distribution that adopts in-situ method to prepare is wide, degree of crystallinity is low, simultaneously the bad control of its photoluminescent property.
In the quantum dot family of II-VI family, what fluorescence had a strong size-dependent has only cadmium selenide and cadmium telluride.Up to the present, also do not see the report that adopts reverse micro emulsion method control preparation to contain single or a plurality of cadmium telluride quantum dot silicon dioxide microspheres.
Summary of the invention
One of purpose of the present invention provides the silica fluorescent microballoon that contains single or a plurality of cadmium telluride fluorescence quantums, and its fluorescence efficiency is not less than 10%, and microballoon has good biocompatibility, can be used in the mark biomolecules.
Two of purpose of the present invention provides a kind of preparation method who contains the silica fluorescent microballoon of single or multiple cadmium telluride fluorescence quantums.
Three of purpose of the present invention provides a kind of method of reverse micro emulsion that adopts the water soluble cadmium telluride fluorescence quantum is compound in the silicon dioxide microsphere, prepare the silica fluorescent microballoon that contains single or a plurality of cadmium telluride quantum dots, control the number of cadmium telluride quantum dot in the silica fluorescent microballoon simultaneously.
The present invention at first prepares the clear and definite cadmium telluride quantum dot of photoluminescent property (fluorescence efficiency is the highest can to reach 85%) at aqueous phase, be water with water soluble cadmium telluride fluorescence quantum, ammonia water mixture then, non-polar organic solvent is an oil phase, nonionic surface active agent is that emulsifying agent forms reverse micro emulsion, water at normal temperature is separated siloxanes, then through obtaining having the silicon dioxide microsphere of single cadmium telluride fluorescence quantum after precipitation, the separation.Change the type of siloxanes or add cationic polyelectrolyte, can access silica fluorescent microballoon with a plurality of cadmium telluride quantum dots.And, can control the number of cadmium telluride quantum dot in the silicon dioxide microsphere to a certain extent by the consumption that changes cationic polyelectrolyte.
The silica fluorescent microballoon that contains single cadmium telluride fluorescence quantum of the present invention is a nuclear with the cadmium telluride fluorescence quantum, and silicon-dioxide is shell.The cadmium telluride fluorescence quantum is positioned at the center of silicon dioxide microsphere, fluorescent emission center peak position is between 510～650 nanometers, the particle diameter of cadmium telluride fluorescence quantum is 2.5～4 nanometers, and the silica shell layer thickness is 14～50 nanometers, and fluorescence efficiency is not less than 10%.
The silica fluorescent microballoon that contains a plurality of cadmium telluride fluorescence quantums of the present invention, cadmium telluride quantum dot is dispersed in the silicon dioxide microsphere, and fluorescent emission center peak position is between 510～650 nanometers, and the particle diameter of cadmium telluride fluorescence quantum is 2.5～4 nanometers; The particle diameter that contains the silica fluorescent microballoon of a plurality of cadmium telluride fluorescence quantums is 30～100 nanometers, and the number of described a plurality of cadmium telluride quantum dots is controlled in 2～100 scopes, and fluorescence efficiency is not less than 10%.
The preparation method who contains the silica fluorescent microballoon of single or a plurality of cadmium telluride fluorescence quantums of the present invention, this method may further comprise the steps:
(1) the cadmium telluride fluorescence quantum prepares (M.Y.Gao et al according to existing document, J.Phys.Chem., 1998,102,8360), detailed process is as follows: cadmium salt (comprising Cadmium chloride fine powder, cadmium acetate, cadmium perchlorate) is mixed with 0.001mol/L～0.15mol/L, solution between preferred 0.005mol/L～0.05mol/L, (mol ratio of cadmium salt and sulfydryl modification agent is between 1: 1～1: 3 to add the sulfydryl modification agent subsequently, between preferred 1: 2.0～1: 2.5), regulate its pH value and transfer to 10～13, preferred 10.5～11.4.With excessive dilution heat of sulfuric acid and tellurium aluminium (Al
2Te
3) H that generates of reaction
2Te directly feeds in the above-mentioned cadmium solution (mol ratio of cadmium and tellurium between 1: 0.2～1: 0.8, preferred 1: 0.4～1: 0.6), stirs 10～20 minutes post-heating this solution that refluxes.Control return time, obtain the CdTe fluorescence quantum of fluorescent emission center peak position any modulation between 510 nanometer to 650 nanometers.
(2) in the water soluble cadmium telluride fluorescence quantum aqueous solution, add ammoniacal liquor, mix and form quantum dot and ammoniacal liquor mixing solutions, wherein the volume ratio of the cadmium telluride aqueous solution and ammoniacal liquor is between 1: 0.1～1: 10, preferred 1: 0.5～1: 8, the concentration of cadmium telluride solution is between 0.00013～0.04mol/L, between preferred 0.0013～0.013mol/L; Ammonia concn is at 25wt%～28wt%.
(3) mixing solutions that step (2) is obtained mixes with nonionic surface active agent (can further add assistant for emulsifying agent), non-polar organic solvent, form water-in-oil-type (W/O) reverse micro emulsion, wherein the mol ratio of Total Water in the mixing solutions that obtains of step (2) and nonionic surface active agent is between 4: 1～12: 1, the Total Water in the mixing solutions that step (2) obtains and the volume ratio of non-polar organic solvent are between 1: 15～1: 21, and the volume ratio of assistant for emulsifying agent and nonionic surface active agent is 0～1: between 8; Add tetraethoxysilane, tetramethoxy-silicane, TSL 8330, aminopropyltriethoxywerene werene, propyl trimethoxy silicane, propyl-triethoxysilicane, chloromethyl Trimethoxy silane, chloromethyl triethoxyl silane, sulfydryl sec.-propyl Trimethoxy silane or sulfydryl sec.-propyl triethoxyl silane again, wherein the mol ratio of the Total Water in the mixing solutions that obtains of step (2) and above-mentioned any one siloxanes is between 4: 1～100: 1; Behind the stirring reaction 1～7 day, add acetone, wherein the volume of acetone is 2～5 times of reverse micro emulsion volume; Be settled out the silica fluorescent microballoon, through the alcohol washing, be dispersed in again after the centrifugation in the water again, form the stable silica fluorescent microballoon water solution system that contains single cadmium telluride quantum dot; Or
The mixing solutions of step (2) is joined in the cationic polymers ionogen, and wherein the volume ratio of the mixing solutions that obtains of step (2) and cationic polyelectrolyte solution is between 480: 1～24: 1, and the electrolytical concentration of cationic polymers is 1.61 * 10
-4Wt%～1.61 * 10
-2Between the wt%, add nonionic surface active agent (can further add assistant for emulsifying agent), non-polar organic solvent again, form water-in-oil-type (W/O) reverse micro emulsion, wherein the mol ratio of Total Water in the mixing solutions that obtains of step (2) and nonionic surface active agent is between 4: 1～12: 1, the Total Water in the mixing solutions that step (2) obtains and the volume ratio of non-polar solvent are between 1: 15～1: 21, and the volume ratio of assistant for emulsifying agent and nonionic surface active agent is 0～1: between 8; Add tetraethoxysilane, tetramethoxy-silicane, TSL 8330, aminopropyltriethoxywerene werene, propyl trimethoxy silicane, propyl-triethoxysilicane, chloromethyl Trimethoxy silane, chloromethyl triethoxyl silane, sulfydryl sec.-propyl Trimethoxy silane or sulfydryl sec.-propyl triethoxyl silane again, wherein the mol ratio of the Total Water in the mixing solutions that obtains of step (2) and above-mentioned any one siloxanes is between 4: 1～100: 1; Behind the stirring reaction 1～7 day, add acetone, wherein the volume of acetone is 2～5 times of reverse micro emulsion volume; Be settled out the silica fluorescent microballoon, through the alcohol washing, be dispersed in again after the centrifugation in the water again, form the stable silica fluorescent microballoon water solution system that contains a plurality of cadmium telluride quantum dots; Or
The mixing solutions that step (2) is obtained mixes with nonionic surface active agent (can add assistant for emulsifying agent), non-polar organic solvent, form water-in-oil-type (W/O) reverse micro emulsion, wherein the mol ratio of Total Water in the mixing solutions that obtains of step (2) and nonionic surface active agent is between 4: 1～12: 1, the Total Water in the mixing solutions that step (2) obtains and the volume ratio of non-polar organic solvent are between 1: 15～1: 21, and the volume ratio of assistant for emulsifying agent and nonionic surface active agent is 0～1: between 8; The mixture (both volume ratios are between 10: 1～1: 10) that adds tetramethoxy-silicane or tetraethoxysilane and TSL 8330 or aminopropyltriethoxywerene werene again, wherein the mol ratio of the mixture of the Total Water in the mixing solutions that obtains of step (2) and above-mentioned any one siloxanes is between 4: 1～100: 1; Behind the stirring reaction 1～7 day, add acetone, wherein the volume of acetone is 2～5 times of reverse micro emulsion volume; Be settled out the silica fluorescent microballoon, through the alcohol washing, be dispersed in again after the centrifugation in the water again, form the stable silicon dioxide microsphere that contains a plurality of cadmium telluride fluorescence quantums.
The mixture of one or more in described water soluble cadmium telluride fluorescence quantum coating materials selected from mercapto acetate, thiohydracrylic acid, mercapto glycerol, the Thioctic Acid.
Described nonionic surface active agent comprises dodecyl Soxylat A 25-7 (polyoxyethylene-(n)-dodecyl ether, as dodecyl four oxygen Vinyl Ethers), nonyl phenyl Soxylat A 25-7 (polyoxyethylene-(n)-nonylphenyl ether, as Triton N-42 (n=4), Triton N-57 (n=5), Triton N-60 (n=6), Triton N-101 (n=9～10)), octyl phenyl Soxylat A 25-7 (polyoxyethylene-(n)-octylphenyl ether, as Triton X-15 (n=1), Triton X-35 (n=3), Triton X-45 (n=5), Triton X-100 (n=9～10)), dodecylphenyl Soxylat A 25-7 (polyoxyethylene-(n)-dodecylphenyl ether is as DP-6 (n=6)) or 1-oleic acid sorbose acid anhydrides ester (as span 80).
Described assistant for emulsifying agent is n-hexyl alcohol, amylalcohol or butanols etc.
Described alcohol is n-hexyl alcohol, amylalcohol, butanols, Virahol or ethanol etc.
Described non-polar organic solvent comprises normal heptane, hexanaphthene, normal hexane, pentane, benzene, chlorobenzene, toluene, trichloromethane or methylene dichloride.
Described cationic polymers ionogen comprises diallyl dimethyl ammoniumchloride (Poly (diallyldimethylammonium chloride)), polymine (Poly (ethyleneimine) or their mixture.
The silicon dioxide microsphere particle diameter that contains single cadmium telluride fluorescence quantum among the present invention is controlled, and structure is clear and definite, and fluorescence efficiency is not less than 10%.Preparation method's process is simple, and is easy to operate, can obtain having the silica fluorescent microballoon of single or a plurality of cadmium telluride quantum dots at high quality water soluble cadmium telluride quantum point surface coated silica shell; The number of cadmium telluride quantum dot is controlled in 1～100 scope in the silicon dioxide microsphere.
Preparation process of the present invention is simple, and the silica fluorescent microballoon that obtains has the biocompatibility of height, very easily carries out biological coupling, and huge using value is arranged in biomarker and bioanalysis.
Description of drawings
The fluorescence spectrum figure of Fig. 1 embodiment of the invention 1 gained water soluble cadmium telluride fluorescence quantum.
Transmission electron microscope (TEM) photo of Fig. 2 embodiment of the invention 5 gained fluorescent silicon dioxide microballoons.
The uv-absorbing and the fluorescence spectrum figure of Fig. 3 embodiment of the invention 5 gained fluorescent silicon dioxide microballoon aqueous solution.
Transmission electron microscope (TEM) photo of Fig. 4 embodiment of the invention 6 gained fluorescent silicon dioxide microballoons.
Transmission electron microscope (TEM) photo of Fig. 5 embodiment of the invention 7 gained fluorescent silicon dioxide microballoons.
Transmission electron microscope (TEM) photo of Fig. 6 embodiment of the invention 15 gained fluorescent silicon dioxide microballoons.
Transmission electron microscope (TEM) photo of Fig. 7 embodiment of the invention 16 gained fluorescent silicon dioxide microballoons.
Transmission electron microscope (TEM) photo of Fig. 8 embodiment of the invention 19 gained fluorescent silicon dioxide microballoons.
Embodiment
Embodiment 1:
Take by weighing 1.405g cadmium perchlorate (Cd (ClO
4)
26H
2O) join in the secondary deionized water of 150mL deoxygenation, add 0.56mL mercapto glycerol and 0.12mL Thiovanic acid stablizer subsequently, with the NaOH aqueous solution its pH value is transferred to 11.2 again, form the solution that contains sulfhydryl compound and cadmium ion.On the other hand, getting 30mL 0.5M sulphuric acid soln is injected into and fills 0.39g tellurium aluminium (Al
2Te
3) flask in, with the H that generates
2Te all feeds in the above-mentioned cadmium-ion solution, stirs after 15 minutes, and reflux 10 minutes to 10 days obtains mercapto glycerol and Thiovanic acid jointly stabilizing, the fluorescent emission center peak position cadmium telluride fluorescence quantum aqueous solution between 510～650 nanometers.Fluorescence spectrum is seen Fig. 1.
Embodiment 2:
Take by weighing 1.315g cadmium perchlorate (Cd (ClO
4)
26H
2O) join in the secondary deionized water of 150mL deoxygenation, add the 0.55mL Thiovanic acid subsequently, its pH value is transferred to 11.2, form the solution that contains sulfhydryl compound and cadmium ion as stablizer.All the other steps are with embodiment 1, obtain that Thiovanic acid is stable, the cadmium telluride quantum dot aqueous solution of fluorescent emission center peak position between 510～650 nanometers.
Embodiment 3:
Take by weighing 1.031g Cadmium chloride fine powder (CdCl
22.5H
2O) join in the secondary deionized water of 150mL deoxygenation, add the 0.55mL thiohydracrylic acid subsequently, its pH value is transferred to 11.2, form the solution that contains sulfhydryl compound and cadmium ion as stablizer.All the other steps are with embodiment 1, obtain that thiohydracrylic acid is stable, the cadmium telluride quantum dot aqueous solution of fluorescent emission center peak position between 510～650 nanometers.
Embodiment 4:
Take by weighing 1.031g Cadmium chloride fine powder (CdCl
22.5H
2O) join in the secondary deionized water of 150mL deoxygenation, add the 0.65mL Thioctic Acid subsequently, its pH value is transferred to 11.2, form the solution that contains sulfhydryl compound and cadmium ion as stablizer.All the other steps are with embodiment 1, obtain that Thioctic Acid is stable, the cadmium telluride quantum dot aqueous solution of fluorescent emission center peak position between 510～650 nanometers.
Embodiment 5:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 610 nanometers) the 50 μ L of mercapto glycerol-Thiovanic acid finishing of embodiment 1, mix with 250 μ L ammoniacal liquor (concentration is 25wt%) after being diluted to 250 μ L.Add Triton X-100 1.77mL simultaneously, hexanaphthene 7.5mL, n-hexyl alcohol 1.8mL mixing obtains transparent system, and the mixed solution 480 μ L with cadmium telluride and ammoniacal liquor join in the above-mentioned system then, stir to obtain transparent reverse micro emulsion.Adding 100 μ L tetraethoxysilanes at last continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere,, remove de-emulsifier, be dispersed in the water at last with butanols, Virahol, washing with alcohol, centrifugal.By transmission electron microscope photo Fig. 2 of gained as can be known, have only a cadmium telluride fluorescence quantum in the silicon dioxide microsphere, the median size of silicon dioxide microsphere is 72 nanometers, narrowly distributing.From the uv-absorbing of the silicon dioxide microsphere aqueous solution and fluorescence spectrum Fig. 3 as can be known, prepared silicon dioxide microsphere has kept the photoluminescent property of cadmium telluride fluorescence quantum, and fluorescence efficiency is 10%.
Embodiment 6:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 630 nanometers) the 50 μ L of the Thiovanic acid finishing of embodiment 2, be diluted to 250 μ L, mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Add Triton X-100 1.77mL simultaneously, hexanaphthene 7.5mL, n-hexyl alcohol 1.8mL mixing obtains transparent system, and the mixed solution 480 μ L with cadmium telluride and ammoniacal liquor join in the above-mentioned system then, stir to obtain transparent reverse micro emulsion.Add the continuous stirring of 100 μ L tetraethoxysilanes at last.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere,, remove de-emulsifier, be dispersed in aqueous phase at last with butanols, Virahol, washing with alcohol, centrifugal.By transmission electron microscope photo Fig. 4 of gained as can be known, have only a cadmium telluride fluorescence quantum in the silicon dioxide microsphere, the median size of silicon dioxide microsphere is 78 nanometers.
Embodiment 7:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in the 630 nanometers) aqueous solution 1mL of the Thiovanic acid finishing of embodiment 2, be concentrated to 0.15mL, add 0.14mL ammoniacal liquor (concentration is 25wt%) again.Get Triton X-100 1.52mL simultaneously, hexanaphthene 19mL, n-hexyl alcohol 0.45mL mixing obtains transparent system, and the mixed solution with cadmium telluride and ammoniacal liquor joins in the above-mentioned system then, stirs to obtain transparent reverse micro emulsion.Adding the 0.67mL tetraethoxysilane continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere, centrifugal with butanols, Virahol, washing with alcohol, remove de-emulsifier.Be dispersed in aqueous phase at last.By transmission electron microscope photo Fig. 5 of gained as can be known, have only a cadmium telluride fluorescence quantum in the silicon dioxide microsphere, the median size of silica fluorescent microballoon is 38 nanometers.
Embodiment 8:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 530 nanometers) the 50 μ L of the Thiovanic acid finishing of embodiment 2, be diluted to 250 μ L, mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Add Triton N-101 2mL simultaneously, normal heptane 10mL mixes obtaining transparent system, and the mixed solution with cadmium telluride and ammoniacal liquor joins in the above-mentioned system then, stirs to obtain transparent reverse micro emulsion.Adding 100 μ L tetramethoxy-silicanes continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere, centrifugal with butanols, Virahol, washing with alcohol, remove de-emulsifier, be dispersed in aqueous phase at last, thereby obtain having the silica fluorescent microballoon of single cadmium telluride quantum dot.
Embodiment 9:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 580 nanometers) the 100 μ L of the thiohydracrylic acid finishing of embodiment 3, be diluted to 500 μ L, get 350 μ L and mix with 150 μ L ammoniacal liquor (concentration is 28wt%).Get DP-6 1.8mL simultaneously, normal heptane 10mL mixes obtaining transparent system, and the mixed solution with cadmium telluride/ammoniacal liquor joins in the above-mentioned system then, stirs to obtain transparent reverse micro emulsion.Adding 200 μ L tetraethoxysilanes continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere, centrifugal with butanols, Virahol, washing with alcohol, remove de-emulsifier, be dispersed in aqueous phase at last, thereby obtain having the silica fluorescent microballoon of single cadmium telluride quantum dot.
Embodiment 10:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 620 nanometers) the 100 μ L of the Thioctic Acid finishing of embodiment 4, be diluted to 500 μ L, get 400 μ L and mix with 100 μ L ammoniacal liquor (concentration is 25wt%).Get dodecyl four oxygen Vinyl Ether 1.8mL simultaneously, toluene 10mL mixes obtaining transparent system, and the mixed solution with cadmium telluride/ammoniacal liquor joins in the above-mentioned system then, stirs to obtain transparent reverse micro emulsion.Adding 100 μ L tetramethoxy-silicanes continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere, centrifugal with butanols, Virahol, washing with alcohol, remove de-emulsifier, be dispersed in aqueous phase at last, thereby obtain having the silica fluorescent microballoon of single cadmium telluride quantum dot.
Embodiment 11:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 620 nanometers) the 150 μ L of the Thiovanic acid finishing of embodiment 2, be diluted to 450 μ L, get 300 μ L and mix with 200 μ L ammoniacal liquor (concentration is 25wt%).Get 1-oleic acid sorbose acid anhydrides ester 2 grams simultaneously and be dissolved in the 11mL trichloromethane, the mixed solution with cadmium telluride/ammoniacal liquor joins in the above-mentioned system then, stirs to obtain transparent reverse micro emulsion.Adding 100 μ L tetramethoxy-silicanes continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere, centrifugal with butanols, Virahol, ethanol Shen Di, remove de-emulsifier, be dispersed in aqueous phase at last, thereby obtain having the silicon dioxide microsphere of single cadmium telluride quantum dot.
Embodiment 12:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 630 nanometers) the 100 μ L of the Thiovanic acid finishing of embodiment 2, be diluted to 500 μ L, get 250 μ L and mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Add Triton X-100 1.77mL simultaneously, hexanaphthene 7.5mL, n-hexyl alcohol 1.8mL mixing obtains transparent system, and the mixed solution 480 μ L with cadmium telluride/ammoniacal liquor join in the above-mentioned system then, stir to obtain transparent reverse micro emulsion.Adding 100 μ L allyl groups, three second methoxy silane at last continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere,, remove de-emulsifier, be dispersed at last in the ethanol, obtain having the silicon dioxide microsphere of single cadmium telluride quantum dot with butanols, Virahol, washing with alcohol, centrifugal.
Embodiment 13:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 630 nanometers) the 100 μ L of the Thiovanic acid finishing of embodiment 2, be diluted to 500 μ L, get 250 μ L and mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Add Triton X-100 1.77mL simultaneously, hexanaphthene 7.5mL, n-hexyl alcohol 1.8mL mixing obtains transparent system, and the mixed solution 480 μ L with cadmium telluride/ammoniacal liquor join in the above-mentioned system then, stir to obtain transparent reverse micro emulsion.Adding 100 μ L TSL 8330 at last continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere,, remove de-emulsifier, be dispersed in aqueous phase at last, obtain having the silicon dioxide microsphere of single cadmium telluride quantum dot with butanols, Virahol, washing with alcohol, centrifugal.
Embodiment 14
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 630 nanometers) the 100 μ L of the Thiovanic acid finishing of embodiment 2, be diluted to 500 μ L, get 250 μ L and mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Add Triton X-100 1.77mL simultaneously, hexanaphthene 7.5mL, n-hexyl alcohol 1.8mL mixing obtains transparent system, and the mixed solution 480 μ L with cadmium telluride/ammoniacal liquor join in the above-mentioned system then, stir to obtain transparent reverse micro emulsion.Adding 100 μ L sulfydryl sec.-propyl Trimethoxy silanes at last continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere,, remove de-emulsifier, be dispersed in aqueous phase at last, obtain having the silicon dioxide microsphere of single cadmium telluride quantum dot with butanols, Virahol, washing with alcohol, centrifugal.
Embodiment 15:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 610 nanometers) the 100 μ L of mercapto glycerol-Thiovanic acid finishing of embodiment 1, be diluted to 500 μ L, get 250 μ L and mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Add the 5 μ L diallyl dimethyl ammoniumchloride aqueous solution in mixed solution, its concentration is 4 * 10
-3Wt%.Get Triton X-100 1.77mL simultaneously, hexanaphthene 7.5mL, n-hexyl alcohol 1.8mL mixing obtains transparent system, and the mixed solution that will be mixed with the cadmium telluride/ammoniacal liquor of diallyl dimethyl ammoniumchloride then joins in the above-mentioned system, stirs and obtains transparent reverse micro emulsion.Adding 100 μ L tetraethoxysilanes continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere, centrifugal with butanols, Virahol, washing with alcohol, remove de-emulsifier, obtain having the silica fluorescent microballoon of a plurality of cadmium telluride fluorescence quantums.By can seeing among electromicroscopic photograph Fig. 6,8 of the number average out to of cadmium telluride fluorescence quantum in silicon dioxide microsphere.
Embodiment 16:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 610 nanometers) the 100 μ L of mercapto glycerol-Thiovanic acid finishing of embodiment 1, be diluted to 500 μ L, get 250 μ L and mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Adding 10 μ L concentration in mixed solution is 4 * 10
-3Wt% diallyl dimethyl ammoniumchloride solution, all the other operations are identical with the step of specific embodiment 11.From electromicroscopic photograph Fig. 7 of gained as can be known the silicon dioxide microsphere cadmium telluride fluorescent quantum count out manyly than the number that obtains by embodiment 11, be approximately 20.
Embodiment 17:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 610 nanometers) the 100 μ L of mercapto glycerol-Thiovanic acid finishing of embodiment 1, be diluted to 500 μ L, get 250 μ L and mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Add 5 μ L polyethyleneimine: amine aqueous solutions in mixed solution, its concentration is 1.0 * 10
-2Wt%.Get Triton X-100 1.8mL simultaneously, hexanaphthene 8mL, n-hexyl alcohol 1.8mL mixing obtains transparent system, and the mixed solution that will be mixed with the cadmium telluride/ammoniacal liquor of polymine then joins in the above-mentioned system, stirs to obtain transparent reverse micro emulsion.Adding 150 μ L tetraethoxysilanes continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere, centrifugal with butanols, Virahol, washing with alcohol, remove de-emulsifier, obtain having the silica fluorescent microballoon of a plurality of cadmium telluride fluorescence quantums, the number of quantum dot is about 28 in silica fluorescent microballoon.
Embodiment 18:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 610 nanometers) the 100 μ L of mercapto glycerol-Thiovanic acid finishing of embodiment 1, be diluted to 500 μ L, get 250 μ L and mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Add 10 μ L polyethyleneimine: amine aqueous solutions in mixed solution, its concentration is 6.4 * 10
-3Wt%; Add 10 μ L diallyl dimethyl ammoniumchloride solution again, its concentration is 6.4 * 10
-3Wt%; Get Triton X-100 1.8mL simultaneously, hexanaphthene 8mL, n-hexyl alcohol 1.8mL mixing obtains transparent system, and the mixed solution with polymine/diallyl dimethyl ammoniumchloride/cadmium telluride/ammoniacal liquor joins in the above-mentioned system then, stirs and obtains transparent reverse micro emulsion.Adding 150 μ L tetraethoxysilanes continues to stir.Finish reaction after three days, add acetone precipitation and go out silicon dioxide microsphere, centrifugal with butanols, Virahol, washing with alcohol, remove de-emulsifier, obtain having the silica fluorescent microballoon of a plurality of cadmium telluride fluorescence quantums, the number of quantum dot is about 40 in silica fluorescent microballoon.
Embodiment 19:
Get cadmium telluride fluorescence quantum (fluorescent emission center peak position is in 610 nanometers) the 100 μ L of mercapto glycerol-Thiovanic acid finishing of embodiment 1, be diluted to 500 μ L, get 250 μ L and mix with 250 μ L ammoniacal liquor (concentration is 25wt%).Add Triton X-100 1.77mL simultaneously, hexanaphthene 7.5mL, n-hexyl alcohol 1.8mL mixing obtains transparent system, and the mixed solution 480 μ L with cadmium telluride/ammoniacal liquor join in the above-mentioned system then, stir to obtain transparent reverse micro emulsion.Add 100 μ L tetraethoxysilanes, 100 μ L TSL 8330 continue to stir, and after 3 days, go out silicon dioxide microsphere with acetone precipitation, behind the flush away emulsifying agent, silicon dioxide microsphere are dispersed in aqueous phase.From electromicroscopic photograph Fig. 8 of gained, as can be known, about 80 cadmium telluride fluorescence quantums are arranged in the silicon dioxide microsphere.
From above-mentioned each embodiment and remaining experiment, we can draw to draw a conclusion: (1) adopts identical prescription the cadmium telluride fluorescence quantum that the different surfaces modifier is modified can be compound in the silicon dioxide microsphere, and has only a cadmium telluride fluorescence quantum in a silicon dioxide microsphere.(2) proportioning that simply changes reverse micro emulsion can be controlled the particle diameter of silicon dioxide microsphere; (3) add the cationic polymers ionogen, obtain having the silica fluorescent microballoon of a plurality of cadmium telluride fluorescence quantums, change the number that electrolytical add-on can be regulated cadmium telluride fluorescence quantum in the silicon dioxide microsphere; (4) mixture of hydrolysis tetraethoxysilane and TSL 8330 can have the silica fluorescent microballoon of a plurality of cadmium telluride fluorescence volume quantum dots.
Claims (12)
1. silica fluorescent microballoon that contains the cadmium telluride fluorescence quantum, it is characterized in that: in the silica fluorescent microballoon, contain single or multiple cadmium telluride fluorescence quantums, fluorescent emission center peak position is between 510～650 nanometers, and the particle diameter of cadmium telluride fluorescence quantum is 2.5～4 nanometers.
2. microballoon according to claim 1, it is characterized in that: the silica fluorescent microballoon that contains single cadmium telluride fluorescence quantum, with the cadmium telluride fluorescence quantum is nuclear, silicon-dioxide is shell, the cadmium telluride fluorescence quantum is positioned at the center of silicon dioxide microsphere, and the silica shell layer thickness is 14～50 nanometers.
3. microballoon according to claim 1, it is characterized in that: the silica fluorescent microballoon that contains a plurality of cadmium telluride fluorescence quantums, cadmium telluride quantum dot is dispersed in the silicon dioxide microsphere, and the particle diameter that contains the silica fluorescent microballoon of a plurality of cadmium telluride fluorescence quantums is 30～100 nanometers.
4. according to claim 1,2 or 3 described microballoons, it is characterized in that: the described fluorescence efficiency that contains the silica fluorescent microballoon of cadmium telluride fluorescence quantum is not less than 10%.
5. according to claim 1 or 3 described microballoons, it is characterized in that: the number of described a plurality of cadmium telluride fluorescence quantums is 2～100.
6. preparation method who contains the silica fluorescent microballoon of cadmium telluride fluorescence quantum according to claim 1 is characterized in that this method may further comprise the steps:
(1) add ammoniacal liquor in the water soluble cadmium telluride fluorescence quantum aqueous solution, mix forming quantum dot and ammoniacal liquor mixing solutions, wherein the volume ratio of the cadmium telluride aqueous solution and ammoniacal liquor is between 1: 0.1～1: 10; The concentration of cadmium telluride solution is between 0.00013～0.04mol/L, and ammonia concn is at 25wt%～28wt%;
(2) mixing solutions that step (1) is obtained mixes with nonionic surface active agent, non-polar organic solvent, form the water-in-oil-type reverse micro emulsion, wherein the mol ratio of Total Water in the mixing solutions that obtains of step (1) and nonionic surface active agent is between 4: 1～12: 1, and the Total Water in the mixing solutions that step (1) obtains and the volume ratio of non-polar organic solvent are between 1: 15～1: 21; Add tetraethoxysilane, tetramethoxy-silicane, TSL 8330, aminopropyltriethoxywerene werene, propyl trimethoxy silicane, propyl-triethoxysilicane, chloromethyl Trimethoxy silane, chloromethyl triethoxyl silane, sulfydryl sec.-propyl Trimethoxy silane or sulfydryl sec.-propyl triethoxyl silane again, wherein the mol ratio of the Total Water in the mixing solutions that obtains of step (1) and above-mentioned any one siloxanes is between 4: 1～100: 1; Stirring reaction adds acetone, and wherein the volume of acetone is 2～5 times of reverse micro emulsion volume; Be settled out the silica fluorescent microballoon, through the alcohol washing, be dispersed in again after the centrifugation in the water again, form the stable silica fluorescent microballoon water solution system that contains single cadmium telluride quantum dot; Or
The mixing solutions of step (1) is joined in the cationic polymers ionogen, wherein the volume ratio of the mixing solutions that obtains of step (1) and cationic polyelectrolyte solution is between 480: 1～24: 1, add nonionic surface active agent, non-polar organic solvent again, form the water-in-oil-type reverse micro emulsion, wherein the mol ratio of Total Water in the mixing solutions that obtains of step (1) and nonionic surface active agent is between 4: 1～12: 1, and the Total Water in the mixing solutions that step (1) obtains and the volume ratio of non-polar solvent are between 1: 15～1: 21; Add tetraethoxysilane, tetramethoxy-silicane, TSL 8330, aminopropyl triethoxy brick alkane, propyl trimethoxy silicane, propyl-triethoxysilicane, chloromethyl Trimethoxy silane, chloromethyl triethoxyl silane, sulfydryl sec.-propyl Trimethoxy silane or sulfydryl sec.-propyl triethoxyl silane again, wherein the mol ratio of the Total Water in the mixing solutions that obtains of step (1) and above-mentioned any one siloxanes is between 4: 1～100: 1; Stirring reaction adds acetone, and wherein the volume of acetone is 2～5 times of reverse micro emulsion volume; Be settled out the silica fluorescent microballoon, through the alcohol washing, be dispersed in again after the centrifugation in the water again, form the stable silica fluorescent microballoon water solution system that contains a plurality of cadmium telluride quantum dots; Or
The mixing solutions that step (1) is obtained mixes with nonionic surface active agent, non-polar organic solvent, form the water-in-oil-type reverse micro emulsion, wherein the mol ratio of Total Water in the mixing solutions that obtains of step (1) and nonionic surface active agent is between 4: 1～12: 1, and the Total Water in the mixing solutions that step (1) obtains and the volume ratio of non-polar organic solvent are between 1: 15～1: 21; The mixture that adds tetramethoxy-silicane or tetraethoxysilane and TSL 8330 or aminopropyltriethoxywerene werene again, wherein the volume ratio of tetramethoxy-silicane or tetraethoxysilane and TSL 8330 or aminopropyltriethoxywerene werene is between 10: 1～1: 10, and the mol ratio of the Total Water in the mixing solutions that step (1) obtains and the mixture of above-mentioned any one siloxanes is between 4: 1～100: 1; Stirring reaction adds acetone, and wherein the volume of acetone is 2～5 times of reverse micro emulsion volume; Be settled out the silica fluorescent microballoon, through the alcohol washing, be dispersed in again after the centrifugation in the water again, form the stable silicon dioxide microsphere that contains a plurality of cadmium telluride fluorescence quantums.
7. method according to claim 6, it is characterized in that: the mixing solutions that described step (2) obtains further adds assistant for emulsifying agent with nonionic surface active agent, when non-polar organic solvent mixes, and the volume ratio of assistant for emulsifying agent and nonionic surface active agent is 0～1: between 8.
8. method according to claim 6 is characterized in that: described cationic polymers ionogen comprises diallyl dimethyl ammoniumchloride, polymine or their mixture.
9. according to claim 6 or 8 described methods, it is characterized in that: the electrolytical concentration of described cationic polymers is 1.61 * 10
-4Wt%～1.61 * 10
-2Between the wt%.
10. method according to claim 7 is characterized in that: described assistant for emulsifying agent is n-hexyl alcohol, amylalcohol or butanols.
11. method according to claim 6 is characterized in that: described non-polar organic solvent is normal heptane, hexanaphthene, normal hexane, pentane, benzene, chlorobenzene, toluene, trichloromethane or methylene dichloride.
12. method according to claim 6 is characterized in that: described nonionic surface active agent comprises dodecyl Soxylat A 25-7, nonyl phenyl Soxylat A 25-7, octyl phenyl Soxylat A 25-7, dodecylphenyl Soxylat A 25-7 or 1-oleic acid sorbose acid anhydrides ester.
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