CN101457139B - High quantum production rate luminescent silicon ball with controllable structure and preparation method thereof - Google Patents
High quantum production rate luminescent silicon ball with controllable structure and preparation method thereof Download PDFInfo
- Publication number
- CN101457139B CN101457139B CN2008100511088A CN200810051108A CN101457139B CN 101457139 B CN101457139 B CN 101457139B CN 2008100511088 A CN2008100511088 A CN 2008100511088A CN 200810051108 A CN200810051108 A CN 200810051108A CN 101457139 B CN101457139 B CN 101457139B
- Authority
- CN
- China
- Prior art keywords
- dye molecule
- add
- organic dye
- positive polarity
- silicon ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The present invention discloses a structure controllable high quantum yield luminous silicon ball and preparation method thereof which belongs to technical field of luminous nano material. The luminous silicon ball takes monodisperse spherical silicon dioxide nanometer particle as base material, wherein organic dye molecule is adulterated; in the structure, distribution state of electropositive organic dye molecule in silicon dioxide nanometer particle is center accumulative, central layer disperse or outer layer accumulative. The preparation method comprises the following steps: take ethyl hydrate as dissolvent; add water and ammoniacal liquor when stirring in 20-40 DEG C; add ethyl orthosilicate and electropositive organic dye molecule for reaction of 9-18 hours; choose to add coloring agent at initial stage, i.e. before nucleation point, or choose to add coloring agent at reaction middle stage, to creat luminous silicon ball of different structure. The difference of adulterated structure makes the invention has different luminous property, the top quantum rate of production can be up to 34.5%, the chemical and colloidal stability good, the preparation method easy and no pollution.
Description
Technical field
The invention belongs to Illuminant nanometer material technology field, particularly high quantum production rate luminescent silicon ball of a kind of controllable structure and preparation method thereof.The said luminescent silicon ball of the present invention promptly is a dyes doping silicon dioxide nano-particle.
Background technology
Because the singularity and the complicacy of living things system have very high requirement to mark with fluorescent probe.In recent years, dyes doping silicon dioxide nano-particle receives much attention as a kind of novel fluorescence probe.Silicon-dioxide not only can provide the protection barrier with chemistry and mechanical stability as the dielectric material of luminescent dye, reduces institute's dopant dye and receives the interference of the environment that comes from the outside, and can improve the light stability of dyestuff, is difficult for by photodegradation or bleaching.Simultaneously, silica dioxide medium can provide the surface of the good and easy functionalization of biocompatibility.But people are also very limited for the understanding of the internal structure of dyes doping silicon dioxide nano-particle at present; Usually people think that dyestuff is evenly to be entrained in silicon ball inside; Go deep into this viewpoint for the too simple (J.Am.Chem.Soc of the description of particle dye inside doped structure along with what study; 2007,129,14251).Moreover, particle dye inside doped structure is also considerably less for the research of luminosity influence.Only rest on the degree that the polystep reaction finishing coats again and can't be implemented in the one pot reaction preparation so people's preparation at present has the dyes doping silicon dioxide nano-particle of controlled inner doped structure; More can't in one pot reaction, realize the controllable doped of dyestuff; This character that causes material particularly optical property and chemicalstability lacks effectively regulation and control and optimization means; Simultaneously also cause the repeatable relatively poor of material prepn, greatly limited application (Langmuir, the Vol.8 of said material; No.12,1992; Langmuir, 2005,21,4277～4280; AdvancedMaterials2004,16,173～176).
The luminescent silicon ball preparation method who has been widely used has microemulsion method (Advanced Materials2004,16,173～176), covalent method (J.Phys.Chem.B, 1999; Vol.103, No.9,1408) and electrostatic method (Langmuir; 2005,21,4277～4280).Common microemulsion method and covalent method prepare the internal structure of product luminescent silicon ball and only think that inside is equally distributed or concentrate on central zone (J.Am.Chem.Soc; 2007; 129,14251), and preparation process loaded down with trivial details, seriously polluted; Especially the particle of microemulsion method preparation dyestuff in depositing is prone to leak, and the preparation process can't realize the regulation and control to dye adulterated structure; The luminescent silicon ball of electrostatic method preparation is difficult to effectively strengthen its luminosity because the luminosity of the positive polarity dyestuff of selecting for use itself is lower than non-polar dyes so the common static method that coats can't be prepared the dye adulterated nanoparticle of controllable structure.
Summary of the invention
The technical issues that need to address of the present invention are; Not quite clear to existing dyes doping silicon dioxide nano-particle doped structure, luminosity is poor, preparation process is loaded down with trivial details, seriously polluted, dyestuff is prone to shortcomings such as leakages, invents that a kind of controllable structure, one pot reaction prepare, high quantum production rate luminescent silicon ball and preparation method thereof.
The present invention selects to have certain polarity water soluble or ethanol and have electropositive organic dye molecule as hotchpotch; Through the adding of the differential responses stage in silicon dioxide granule nucleating growth process dye molecule; Make itself and silicon monomer or oligomer examine surface sediment at silicon with different speed; This just determined between the dye molecule distance and in the inner degree of scatter of silicon ball, thereby obtain the adjustable dyes doping silicon dioxide nano-particle of luminosity, i.e. luminescent silicon ball.
High quantum production rate luminescent silicon ball of a kind of controllable structure of the present invention (being dyes doping silicon dioxide nano-particle) and preparation method thereof, technical scheme mainly comprise the selection and the adding in dye molecule differential responses stage in whole doping process of positive polarity dye molecule.
The selection of said positive polarity dyestuff can be a ruthenium complexe, comprises that chlorination three pyridines couplet ruthenium, chlorination three coffee are coughed up quinoline couplet ruthenium, chlorination one pyridine two coffee are coughed up quinoline and joined ruthenium; Can be the osmium title complex also, comprise that chlorination three pyridines couplet osmium, chlorination three coffee are coughed up quinoline couplet osmium, chlorination one pyridine two coffee are coughed up quinoline and joined osmium.
The adding in said dye molecule differential responses stage in
reaction process; Be meant that dyestuff can be to add before Nano particles of silicon dioxide is assembled nucleation in initial reaction stage; Can be disposable adding or adding in batches after Nano particles of silicon dioxide is assembled nucleation reacting mid-term also, be that tetraethoxysilance hydrolysis monomer is in the adding of silicon nuclear surface sediment growth phase in the reaction later stage perhaps.Because the asynchronism(-nization) that dyestuff adds, roughly can generate the distribution of dye molecule in Nano particles of silicon dioxide is that assemble at the center, the middle layer disperses or the luminescent silicon ball of three kinds of structures of outer accumulative.Wherein, Nano particles of silicon dioxide is that the hydrolysis in organosilicon source and condensation obtain through in the mixing solutions of ethanol, water, ammoniacal liquor.
Concrete technical scheme of the present invention is:
A kind of high quantum production rate luminescent silicon ball of controllable structure; Be to be matrix with monodispersed preparing spherical SiO 2 nanoparticle; The organic dye molecule that wherein mixes, luminescent silicon ball is of a size of 40～100 nanometers, it is characterized in that; Said luminescent silicon ball, the distribution of positive polarity organic dye molecule in Nano particles of silicon dioxide is that assemble at the center or the middle layer disperses or outer accumulative in the structure.
Above-mentioned organic dye molecule is to be dissolvable in water water or alcoholic acid is electropositive fluoresces or the phosphorescence organic dye molecule; The positive polarity organic dye molecule is ruthenium complexe or osmium title complex.
Said organic dye molecule, preferred chlorination three pyridines join ruthenium, chlorination three coffee and cough up quinoline and join ruthenium, chlorination one pyridine two coffee and cough up quinoline and join ruthenium, chlorination three pyridines and join osmium, chlorination three coffee and cough up quinoline and join osmium or chlorination one pyridine two coffee and cough up quinoline and join osmium.
Luminescent silicon ball of the present invention, quantum yield are between 4.24%～34.5%, and luminous peak position is between 579～609 nanometers, and luminescent lifetime is between 0.52～2.86 microsecond.
The preparation method of the high quantum production rate luminescent silicon ball of controllable structure of the present invention is to be solvent with ethanol, and 20～40 ℃ add entry and ammoniacal liquor with stirring down in solvent, add tetraethoxy and positive polarity organic dye molecule again, react to 9～18 hours; By the volumeter of amount of ethanol, water and ammoniacal liquor add-on are water by volume: ammoniacal liquor: ethanol=0.0025～0.05:0.01～0.074:1, the add-on of tetraethoxy are 20～80 milliliters/liter, and the add-on of dyestuff is 10～100 mg/litre;
Described adding tetraethoxy and positive polarity organic dye molecule are to add or add simultaneously the positive polarity organic dye molecule earlier, and forming the distribution of organic dye molecule in Nano particles of silicon dioxide is center accumulative structure; Perhaps, be to add tetraethoxy to add the positive polarity organic dye molecule during 0.2～6 hour, forming the distribution of organic dye molecule in Nano particles of silicon dioxide is the homodisperse structure in middle layer; Perhaps, be to add tetraethoxy to add the positive polarity organic dye molecule greater than 6 hours, forming the distribution of organic dye molecule in Nano particles of silicon dioxide is outer accumulative structure.
Above-mentioned stirring can be stirred with the stirring velocity of 200～600rpm.
The luminescent silicon ball of the various structures that make can pass through dissolution method successively, confirms doping position and the state of aggregation of positive polarity organic dye in the silicon ball.Successively the specific operation process of dissolution method can be referring to embodiment 5.
The selection initial stage just adds dyestuff before the nucleation site; Dyestuff can at first be hydrolyzed monomer or the oligomer protection raises quantum yield; Yet assemble nucleation with hydrolysis monomer or oligomer; Cause dyestuff to be assembled quantum yield is reduced, finally obtain most of dyestuff and accumulate in the nuclear or around the nuclear and outerly be thicker pure silicon dioxide shell.
Be chosen in to react and add dyestuff mid-term; Dye molecule at first also can be by free monomer or oligomer protection; Participate in the banking process on the nuclear surface with monomer or oligomer then, the speed of banking process is the speed that is considerably slower than the gathering nucleation, so can keep certain just effectively preventing because of assembling the cancellation of generation apart from this between the dye molecule; Dye molecule mainly was distributed in subshell part and distributed extensivelyr this moment, and skin has the thin pure silicon dioxide layer of one deck.
Be chosen in reaction later stage adding dyestuff; A spot of free monomer generation electrostatic adsorption in dye molecule and the solution; Because so the less monomer of later stage amount of monomer to the very faint quantum yield increase of the provide protection of free dye molecule seldom; Dye molecule is piled up in silica particle surface with monomer, and it is outer and be affected by the external environment greatlyyer that dye molecule is distributed in luminescent silicon ball with state of aggregation, and quantum yield is very low.
When reaction adds the positive polarity organic dye mid-term,, can add dyestuff in batches for more effectively making the dyestuff uniform distribution.Concrete can be divided into 2～4 addings, and by the volumeter of amount of ethanol, each add-on is 0.1～1.5 mg/litre, each 0.5～2 hour at interval.
The luminescent silicon ball of novel doped structure of the present invention; It is the dyes doping silicon dioxide nano-particle that clearly to distinguish the different dyes distribution that possessed of the first report; Because the difference of its doped structure makes it have different luminosities; The sub-productive rate of maximum amount can reach 34.5%, is that quantum yield is the highest in the dye adulterated luminescent silicon ball of reporting at present of positive polarity.
The preparation method of luminescent silicon ball of the present invention; Utilize the electrostatic interaction of positive polarity organic dye and silicon-dioxide; In silicon dioxide granule nucleating growth process, through the control distribution of dye molecule in silicon dioxide granule and the luminosity of matrix environment Collaborative Control dyestuff.Avoid the pollution of using a large amount of organic solvent, tensio-active agent, silane coupling agent to bring, simplified production stage.The luminescent silicon ball that the present invention finally obtains is monodispersity; The positive polarity of dye molecule is stronger, guarantees that dyestuff in the aftertreatment of luminescent silicon ball with deposit in the process and can not leak, has higher chemicalstability; Particle diameter is even, and chemistry and colloidal stability are good, and the surface is easy to further functionalization.The distribution of controllable dye and matrix environment have increased the controllability of final luminescent silicon ball luminosity greatly; The luminescent silicon ball of different quantum yields, different luminous peak positions and different luminescent lifetimes can be used for different purposes; Also can be used for coded markings simultaneously, have important application value.
Description of drawings
Fig. 1 is the normalized curve that one of the present invention
reaction process synoptic diagram and luminescent silicon ball quantum yield changed with the reaction times.
The curve that the quantum yield that Fig. 2 obtains when being the embodiment of the invention 2 investigation luminescent silicon ball quantum yields changed with the dyestuff joining day.
Fig. 3 is that a kind of structure of the present invention is dye molecule dye distribution scale map by the luminescent silicon ball of middle layer discrete distribution in Nano particles of silicon dioxide.
Fig. 4 is the structural models figure of the luminescent silicon ball of Fig. 3.
Fig. 5 is that a kind of structure of the present invention is the dye distribution scale map of the luminescent silicon ball that in Nano particles of silicon dioxide, assemble to distribute by the center of dye molecule.
Fig. 6 is the structural models figure of the luminescent silicon ball of Fig. 5.
Fig. 7 is that a kind of structure of the present invention is the dye distribution scale map of the luminescent silicon ball that in Nano particles of silicon dioxide, assemble to distribute by skin of dye molecule.
Fig. 8 is the structural models figure of the luminescent silicon ball of Fig. 7.
Embodiment
Embodiment 1
In the 100ml there-necked flask, add 30ml ethanol, ammoniacal liquor 2.2ml, deionized water 0.075ml; 25 ℃ of stirring in water bath, stirring velocity 200rpm adds chlorination three coffee and coughs up quinoline couplet ruthenium 0.3mg; Add tetraethoxy 2.4ml, add for reaction begins, sustained reaction to 12 hour from tetraethoxy.Carry out the absorption spectrum and the fluorescence emission spectrum of real-time monitoring reaction system with reaction, the time dependent normalized curve of quantum yield that absorption that reaction will obtain after finishing and fluorescent emission data computation go out luminescent silicon ball is seen Fig. 1; Be dispersed in the N with the ethanol purification luminescent silicon ball and then with luminescent silicon ball, surveying a minute sample luminescent lifetime is 0.52 microsecond.
Through adding dyestuff when the initial action and whole doping reaction process being carried out the monitoring of quantum yield; Whole
reaction process can be divided into monomer hydrolysis → monomer and form oligomer → oligomer gathering nucleation → oligomer examining surface sediment growth → monomer in the growth of nuclear surface sediment, sees Fig. 1.
Resulting luminescent silicon ball be dyestuff at the center aggregated(particle)structure.
Embodiment 2
In the 100ml there-necked flask, add 30ml ethanol, ammoniacal liquor 2.2ml, deionized water 0.075ml; 25 ℃ of stirring in water bath; Stirring velocity 200rpm adds tetraethoxy 2.4ml, adds from tetraethoxy to be the reaction beginning; Add chlorination three coffee in the time of 0,12 minute, 22 minutes, 1,2,3,4,6 or 8 hour in the reaction beginning respectively and cough up quinoline couplet ruthenium 0.3mg, all continue reaction to 12 hours.Reaction finishes the back and uses the ethanol purification luminescent silicon ball, and then luminescent silicon ball is dispersed in the N, measures sub-productive rate, and the result is as shown in Figure 2.
When chlorination three coffee are coughed up quinoline and are joined ruthenium and add in ethanol, ammoniacal liquor and the aqueous solution simultaneously with tetraethoxy (0 minute adding positive polarity dyestuff), the luminescent silicon ball that obtains be dyestuff at the center aggregated(particle)structure, its quantum yield is relatively low; Reaction beginning adds chlorination three coffee in the time of 12 minutes to 6 hours coughs up quinoline and joins ruthenium, the luminescent silicon ball that obtains be dyestuff in the middle layer dispersed texture, its quantum yield higher relatively (when especially adding dyestuff in 1～6 hour); The reaction beginning adds chlorination three coffee and coughs up quinoline couplet ruthenium in the time of 8 hours, the luminescent silicon ball that obtains is dyestuff strata structure set outside basically, and its quantum yield is relatively low.
Embodiment 3
In the 100ml there-necked flask, add 30ml ethanol; Ammoniacal liquor 2.2ml, deionized water 0.075ml, 25 ℃ of stirring in water bath; Stirring velocity 200rpm; Add tetraethoxy 2.4ml, begin for reacting, add chlorination three coffee when reaction begins 3 hours and cough up 1.5 milligrams of continuation reactions of quinoline couplet ruthenium to 12 hours from the tetraethoxy adding.Reaction finishes the back and uses the ethanol purification luminescent silicon ball, and then luminescent silicon ball is dispersed in the N, and measuring sub-productive rate is 34.5%.Surveying the luminous mean lifetime of 1.5 milligrams of dyestuff add-on final samples is 2.86 microseconds.
Resulting luminescent silicon ball be dyestuff in the middle layer dispersed texture.
Embodiment 4
Other steps are identical with embodiment 3, and the add-on of dyestuff is changed into 3.0 milligrams.Surveying 3.0 milligrams of final quantum yields of dyestuff add-on sample is 15.12%, and mean lifetime is 2.41 microseconds.
Resulting luminescent silicon ball be dyestuff in the middle layer dispersed texture.
In the 100ml there-necked flask, add 30ml ethanol, ammoniacal liquor 2.2ml, deionized water 0.075ml; 25 ℃ of stirring in water bath, stirring velocity 200rpm adds tetraethoxy 2.4ml; Add for reacting beginning from tetraethoxy; The reaction beginning adds chlorination three coffee and coughs up quinoline couplet ruthenium 0.3mg in the time of 3 hours, reaction was to 12 hours, and reaction finishes the back and is dispersed in the water with the ethanol purification luminescent silicon ball and then with luminescent silicon ball.The sodium hydroxide solution of preparation 0.4mol/L; Adding 20mg luminescent silicon ball also picks up counting; The centrifugal 15000rpm that takes a sample at regular intervals, it is quantitatively quantitative with molybdate method free silica that centrifugal back supernatant is cooked dyestuff, till solution is clarified centrifugal nothing fully and precipitated.Obtain luminescent silicon ball dye distribution ratio from the inside to the outside with difference assay normalization method, as shown in Figure 3; Resulting luminescent silicon ball be dyestuff in the middle layer dispersed texture, structural models is as shown in Figure 4.
Embodiment 6
According to embodiment 5, change chlorination three coffee and cough up the quinoline couplet ruthenium joining day, add adding again in 10 hours from tetraethoxy.The same with embodiment 5, through dissolution method successively, confirm doping position and the state of aggregation of dyestuff in luminescent silicon ball.The dye distribution ratio is as shown in Figure 5 from the inside to the outside for luminescent silicon ball, and it is as shown in Figure 6 to obtain structural models, is dyestuff layer accumulative structure outside.
Embodiment 7
According to embodiment 5, changing the ammoniacal liquor add-on is 1.0 milliliters, and the water add-on is 0.975 milliliter; Chlorination three coffee are coughed up the quinoline couplet ruthenium joining day and tetraethoxy adds simultaneously, and reaction was to 12 hours.The luminescent silicon ball that obtains passes through dissolution method successively, confirms doping position and the state of aggregation of dyestuff in luminescent silicon ball.The dye distribution ratio is as shown in Figure 7 from the inside to the outside for luminescent silicon ball, and it is as shown in Figure 8 to obtain structural models, for dyestuff at the center accumulative structure.
Embodiment 8
In the 100ml there-necked flask, add 30ml ethanol; Ammoniacal liquor 0.8ml, deionized water 1.125ml, 20 ℃ of stirring in water bath; Stirring velocity 200rpm; Add tetraethoxy 0.6ml, add for reaction begins from tetraethoxy, the reaction beginning adds chlorination three pyridines and joins ruthenium 0.3mg continuation reaction to 18 hours in the time of 2.5 hours.
Resulting luminescent silicon ball be dyestuff in the middle layer dispersed texture.
Embodiment 9
In the 100ml there-necked flask, add 30ml ethanol; Ammoniacal liquor 0.8ml, deionized water 1.125ml, 40 ℃ of stirring in water bath; Stirring velocity 400rpm; Add tetraethoxy 1.8ml, add for reaction begins from tetraethoxy, the reaction beginning adds chlorination three pyridines and joins ruthenium 0.3mg continuation reaction to 18 hours in the time of 2.5 hours.
Resulting luminescent silicon ball be dyestuff in the middle layer dispersed texture.
In the 100ml there-necked flask, add 30ml ethanol, ammoniacal liquor 0.3ml, deionized water 0.6ml; 30 ℃ of stirring in water bath, stirring velocity 600rpm adds tetraethoxy 1.8ml; Add from tetraethoxy and to be that reaction beginning, reaction beginning add chlorination one pyridine two coffee and cough up quinoline and join osmium 0.1mg in the time of 3 hours, add chlorination one pyridine two coffee in the time of 4 hours and cough up quinoline couplet osmium 0.1mg; Add chlorination one pyridine two coffee in the time of 5 hours and cough up quinoline couplet osmium 0.1mg, continue reaction to 18 hours.
In the present embodiment, the adding of dyestuff is carried out in batches, resulting luminescent silicon ball be dyestuff in the middle layer dispersed texture.
Embodiment 11
In the 100ml there-necked flask, add 20ml ethanol, ammoniacal liquor 0.533ml, deionized water 1.0ml, 40 ℃ of stirring in water bath; Stirring velocity 400rpm adds tetraethoxy 1.2ml, adds from tetraethoxy to be the reaction beginning; The reaction beginning adds chlorination three pyridines and joins ruthenium 0.1mg in the time of 2 hours, 30 minutes at interval, add chlorination three pyridines again and join ruthenium 0.1mg; The interval is 30 minutes again, adds chlorination three pyridines and joins ruthenium 0.1mg, final reaction to 18 hour stopped reaction.
In the present embodiment, the adding of dyestuff is carried out in batches, resulting luminescent silicon ball be dyestuff in the middle layer dispersed texture.
Embodiment 12
In the 100ml there-necked flask, add 50ml ethanol, ammoniacal liquor 3.66ml, deionized water 0.125ml; 25 ℃ of stirring in water bath, stirring velocity 200rpm adds tetraethoxy 4ml; Add for reacting beginning from tetraethoxy, the reaction beginning adds chlorination three coffee and coughs up quinoline couplet ruthenium 1.5mg, 2 hours at interval in the time of 2 hours; Add chlorination three coffee again and cough up quinoline couplet ruthenium 1.5mg, final reaction to 12 hour stopped reaction.
In the present embodiment, the adding of dyestuff is carried out in batches, resulting luminescent silicon ball be dyestuff in the middle layer dispersed texture.
Embodiment 13
In the above-described embodiments, the positive polarity dyestuff all can be other ruthenium complexe or osmium title complex, can prepare the luminescent silicon ball that doped structure and luminosity have nothing in common with each other equally.Preferred ruthenium complexe comprises that chlorination three pyridines couplet ruthenium, chlorination three coffee are coughed up quinoline couplet ruthenium, chlorination one pyridine two coffee are coughed up quinoline and joined ruthenium; Preferred osmium title complex comprises that chlorination three pyridines join osmium, chlorination three coffee and cough up quinoline and join osmium, chlorination one and adjoin pyridine two coffee and cough up quinoline and join osmium.
Claims (5)
1. the high quantum production rate luminescent silicon ball of a controllable structure; Be to be matrix with monodispersed preparing spherical SiO 2 nanoparticle, the organic dye molecule that wherein mixes, luminescent silicon ball is of a size of 40～100 nanometers; It is characterized in that; Said organic dye molecule is to be dissolvable in water water or alcoholic acid fluoresces or the positive polarity organic dye molecule of phosphorescence, and concrete is ruthenium complexe or osmium title complex; Said luminescent silicon ball, the distribution of positive polarity organic dye molecule in Nano particles of silicon dioxide is that assemble at the center or the middle layer disperses or outer accumulative in the structure.
2. according to the high quantum production rate luminescent silicon ball of the described a kind of controllable structure of claim 1; It is characterized in that, said luminescent silicon ball, quantum yield is between 4.24%～34.5%; Luminous peak position is between 579～609 nanometers, and luminescent lifetime is between 0.52～2.86 microsecond.
3. according to the high quantum production rate luminescent silicon ball of claim 1 or 2 described a kind of controllable structure; It is characterized in that; Said positive polarity organic dye molecule is that chlorination three pyridines join ruthenium, chlorination three coffee and cough up quinoline and join ruthenium, chlorination one pyridine two coffee and cough up quinoline and join ruthenium, chlorination three pyridines and join osmium, chlorination three coffee and cough up quinoline and join osmium or chlorination one pyridine two coffee and cough up quinoline and join osmium.
4. the preparation method of the high quantum production rate luminescent silicon ball of the controllable structure of a claim 1; Be to be solvent with ethanol; 20～40 ℃ add entry and ammoniacal liquor with stirring down in solvent, add tetraethoxy and positive polarity organic dye molecule again, react to 9～18 hours; Volumeter by amount of ethanol; Water and ammoniacal liquor add-on are water by volume: ammoniacal liquor: ethanol=0.0025～0.05: 0.01～0.074: 1; The add-on of tetraethoxy is 20～80 milliliters/liter, and the add-on of positive polarity organic dye molecule is 10～100 mg/litre;
Described adding tetraethoxy and positive polarity organic dye molecule are to add or add simultaneously the positive polarity organic dye molecule earlier, and forming the distribution of positive polarity organic dye molecule in Nano particles of silicon dioxide is center accumulative structure; Perhaps, be to add tetraethoxy to add the positive polarity organic dye molecule during 0.2～6 hour, forming the distribution of positive polarity organic dye molecule in Nano particles of silicon dioxide is the homodisperse structure in middle layer; Perhaps, be to add tetraethoxy to add the positive polarity organic dye molecule greater than 6 hours, forming the distribution of positive polarity organic dye molecule in Nano particles of silicon dioxide is outer accumulative structure.
5. according to the preparation method of the high quantum production rate luminescent silicon ball of the described controllable structure of claim 4; It is characterized in that, be that the adding of positive polarity organic dye molecule is carried out in batches in the accumulative configuration process of center forming the distribution of positive polarity organic dye molecule in Nano particles of silicon dioxide; Be divided into 2～4 addings; By the volumeter of amount of ethanol, each add-on is 0.1～1.5 mg/litre, each 0.5～2 hour at interval.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100511088A CN101457139B (en) | 2008-08-22 | 2008-08-22 | High quantum production rate luminescent silicon ball with controllable structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100511088A CN101457139B (en) | 2008-08-22 | 2008-08-22 | High quantum production rate luminescent silicon ball with controllable structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101457139A CN101457139A (en) | 2009-06-17 |
| CN101457139B true CN101457139B (en) | 2012-06-13 |
Family
ID=40768262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100511088A Expired - Fee Related CN101457139B (en) | 2008-08-22 | 2008-08-22 | High quantum production rate luminescent silicon ball with controllable structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101457139B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768437B (en) * | 2010-01-19 | 2012-12-26 | 无锡中德伯尔生物技术有限公司 | SiO2 nano-particle taking positive electrical polyelectrolyte as template and doped with negative electricity dye and preparation method thereof |
| CN103143213A (en) * | 2013-03-29 | 2013-06-12 | 蒋海波 | Air purifying agent |
| CN105419784B (en) * | 2015-12-11 | 2017-06-23 | 吉林大学 | The preparation method of alcohol sensible 9,10 (diphenyl) acetenyl anthracene doped Nano particles of silicon dioxide |
| CN110760301A (en) * | 2018-07-26 | 2020-02-07 | 合皓股份有限公司 | Siloxane organic fluorescent powder and preparation method thereof |
| CN116836698B (en) * | 2023-05-11 | 2024-06-11 | 安徽工业大学 | Silicon dioxide long afterglow luminescent material, preparation method, anti-counterfeiting coating and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040101822A1 (en) * | 2002-11-26 | 2004-05-27 | Ulrich Wiesner | Fluorescent silica-based nanoparticles |
| CN101003729A (en) * | 2007-01-04 | 2007-07-25 | 吉林大学 | Nano incandescnet particles of composite organic dyestuff of silicon dioxide with dual structures, and preparation method |
-
2008
- 2008-08-22 CN CN2008100511088A patent/CN101457139B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040101822A1 (en) * | 2002-11-26 | 2004-05-27 | Ulrich Wiesner | Fluorescent silica-based nanoparticles |
| CN1767941A (en) * | 2002-11-26 | 2006-05-03 | 康乃尔研究基金会有限公司 | Fluorescent silica-based nanoparticles |
| CN101003729A (en) * | 2007-01-04 | 2007-07-25 | 吉林大学 | Nano incandescnet particles of composite organic dyestuff of silicon dioxide with dual structures, and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101457139A (en) | 2009-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101457139B (en) | High quantum production rate luminescent silicon ball with controllable structure and preparation method thereof | |
| CN103990812B (en) | A kind of preparation method of surface enhanced Raman substrate | |
| US8895143B2 (en) | Double core-shell fluorescent materials and preparation methods thereof | |
| CN1215902C (en) | Magnetic fluorescent double functional microballoon with core-shell structure and preparation method thereof | |
| CN101775280B (en) | Water-soluble nuclear-shell magneto-optic dual-function nanoparticle and preparation method thereof | |
| CN102633265B (en) | Preparation method for controllable hollow mesoporous silicon dioxide nanospheres | |
| CN104910917B (en) | A kind of ratio probes of embedding Two Colour Fluorescence quantum dot and preparation method thereof | |
| CN103286312A (en) | Surface-common-enhanced fluorescence surface-enhanced Raman multi-layer core-shell structure composite particles and preparation method of particles | |
| CN113770372B (en) | Preparation method of gold nanoparticle aggregate material | |
| CN103387829A (en) | Phosphorescence silica nanometer probe with core shell composition and preparation method thereof | |
| CN110776916A (en) | Quantum dot dual-emission-ratio fluorescent probe and preparation method and application thereof | |
| CN109047790A (en) | A kind of gold nanorods/zinc oxide/mesoporous silicon oxide yolk shell nanocomposite and preparation method thereof | |
| CN101270281A (en) | Method for preparing hydrophobic dyes doping silicon dioxide nano-particle | |
| CN107383384A (en) | The preparation method and application of zinc protoporphyrin metal organic framework nanometer disk | |
| CN108147456A (en) | A kind of preparation method of monodisperse zirconium dioxide microballoon | |
| CN106221692A (en) | A kind of preparation method of monodisperse silica fluorescent microsphere | |
| CN103497273A (en) | Water-dispersible multicolour fluorescent polymer nanoparticles and preparation method thereof | |
| CN103059835A (en) | Phosphorodiamidate morpholino oligomer (PMO) fluorescent nanoparticle for detecting mercury ion ratio and preparation method thereof | |
| Wang et al. | Multi-stable fluorescent silica nanoparticles obtained from in situ doping with aggregation-induced emission molecules | |
| CN101966978A (en) | Method for preparing multi-metal-oxygen cluster-doped silicon dioxide nanoparticles | |
| CN102433113A (en) | Method for doping amino-reactive dye in silicon dioxide nano-particles | |
| CN104237503A (en) | Mitochondria targeted fluorescent labeling magnetic nano material as well as preparation method and application of mitochondria targeted fluorescent labeling magnetic nano material | |
| CN103862036A (en) | Method for preparing silicon dioxide coated noble metal nanocrystalline | |
| US10995610B2 (en) | Nanotracer for oil recovery and method of preparation thereof | |
| CN103769217A (en) | Loaded type magnetic catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120613 Termination date: 20160822 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |