CN109705840A - The preparation method of high luminescent quantum dot fluorescent microsphere based on affine assembling - Google Patents
The preparation method of high luminescent quantum dot fluorescent microsphere based on affine assembling Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of quantum dot fluorescence microballoon, the method for the present invention is prepared for silica/quantum dot assembly of high load first in organic phase using metal-ligand affinity interaction；Using n-octyl trimethoxy silane/methanol/ammonium hydroxide as hydrolyzation system, realize the silylation modification of the hydrophobic assembly, and ensure silica supports in modification to the high load amount of quantum dot, by organosilan hydrolytic condensation,
Description
(1) technical field
The present invention relates to a kind of systems of composite fluorescence microballoon based on oil-soluble quantum dot and the affine template of silica
Preparation Method, fluorescent microsphere uniform particle diameter made from this method, size is controllable, luminous intensity is high and performance is stablized.
(2) background technique
Quantum dot has the characteristics such as high luminous intensity, wavelength tunability, anti-light bleaching and the polynary transmitting of unitary excitation,
Become the hot spot of field of biomedicine common concern in recent years.Amount with high luminescence energy and monodispersity (excitation purity is high)
Son point is general to be synthesized by high temperature thermal decomposition method.Such quantum dot surface is wrapped up by one layer of organic ligand molecule, in its application
Before biosystem, water-soluble sex modification is inevitable.The water-soluble sex modification strategy of existing oil-soluble quantum dot is main
Including ligand replacement, amphipathic molecule package and silicon dioxide modified etc..Wherein ligand replacement is the earliest modification of exploitation
Method, it is simple and easy, but the fluorescence property loss of quantum dot is serious, and colloid and photochemical stability are all poor；Using two
Parent's property molecular modification can retain the hydrophobic ligand of quantum dot, and then keep its luminescent properties and stability, but the conjunction of polymer
It is high at expense, process is complicated, quantum dot product is difficult to isolate and purify.
Quantum dot and nano-carrier are assembled to the biocompatibility that can be not only effectively improved quantum dot, it can also will be single
The fluorescence signal of quantum dot is effectively amplified, and can inhibit the scintillation of single quantum dot by Statistical Effect.It utilizes
Nanometer, the analysis method set up of quantum dot fluorescence microballoon of micro-meter scale: polynary point for example based on fluorescence-encoded technology
Visual retrieval, the detection of hypersensitive fluorescent marker and fluorescence imaging etc., sense while analysis, intracellular multiple target for Photobiology
Research brings new opportunity.Other function material such as noble metal, magnetic nano-particle etc. is introduced into fluorescent microsphere, it can structure
It builds for medicine multi-modality imaging and diagnosis-treatment Study on Integration functional composite material.
The major defect of the prior art: using polystyrene microsphere as the technical solution of template, will mainly lead to after microspheres swell
Hydrophobic interaction is crossed to load quantum dot, quantum dot is caused to be easy to happen leakage, and polystyrene there are hydrophily difference and
The defects such as optical clarity is low；Using silicon dioxide microsphere as the technical solution of template, covalent coupling or Electrostatic Absorption are mainly utilized
Mode quantum dot is assembled in carrier surface, such as with the carboxyl of carbodiimide activation water-soluble quantum dot after, change with amino
Property silicon dioxide microsphere formed amido bond；Or under certain ph, by carboxylated quantum dot and amination silicon dioxide microsphere
Electrostatic Absorption synthesizes fluorescent microsphere.In the above technology, need to carry out oil-soluble quantum dot phase transfer and carboxylated modification,
It may cause quantum dot reunion or fluorescent quenching；Meanwhile assembling is realized in aqueous phase system, it will be by electrostatic repulsion between quantum dot
Function influence causes packaging efficiency low.
There are two the factor of the decision final brightness of quantum dot fluorescence microballoon is main: one, the intrinsic luminous intensity of quantum dot (amount
Sub- yield)；Two, packaging efficiency of the quantum dot on nano-carrier.In general, it is prepared by organic phase high temperature thermal decomposition method
Quantum dot have it is high shine, fluorescence spectrum is narrow and the characteristics such as excellent in stability, these properties are for optical sensing application all pole
It is important.On the other hand, using the affinity interaction (coordination) between ligand and metal that hydrophobic nano-particles are directly fixed
It is a kind of efficient assemble method to carrier surface.The particles coat density as caused by electrostatic repulsion in being assembled to avoid water phase
The problems such as low and covalent coupling process is to the destruction of quantum dot surface.
Silica optical clarity with higher is readily synthesized and size Control, and can carry out a variety of surface silicons
Alkanisation is modified, therefore is a kind of excellent nano-carrier.The silica of metal compatibility surface (such as mercaptan modification) will be had
Carrier and oil-soluble quantum dot direct-assembling in organic phase have several big advantages: packaging efficiency is high, avoids cumbersome quantum
The pre-treatments such as point phase transfer and the holding for being conducive to quantum yield.Obtain it is high shine and the silica of high load/
After quantum dot microsphere, water-soluble sex modification need to be carried out to hydrophobic assembly, just be able to satisfy biologic applications demand.In microsphere surface packet
Covering another layer of silicon dioxide can effectively improve its water-soluble and stability and is conducive to biological functional, while retain quantum dot table
The hydrophobic ligand in face be the key that it is silicon dioxide modified during determine its luminescent properties.For quantum dot assembly, still
The effective Silicane Method for keeping quantum dot luminous efficiency need to be explored, to guarantee the performance of fluorescent microsphere.
(3) summary of the invention
The invention discloses a kind of preparation method of water-soluble, high luminescent quantum dot fluorescent microsphere, amounts prepared by the present invention
Son point fluorescent microsphere particle monodispersity is good, size is controllable, quantum dot load capacity is high and has the sub- yield of higher amount, can be used for receiving
Rice diagnostic analysis and image probe.The method of the present invention is prepared for first in organic phase using metal-ligand affinity interaction high negative
The silica of load/quantum dot assembly；Using n-octyl trimethoxy silane/methanol/ammonium hydroxide as hydrolyzation system, realizes this and dredge
The silylation modification of water assembly, and ensure that silica supports are to the high load amount of quantum dot in modification.By organic
Silane hydrolyzate condensation,It is compound that growth course is prepared for property stabilization, silica/quantum dot/silica of Gao Faguang
Structure fluorescent microsphere.
Technical scheme is as follows:
A kind of preparation method of quantum dot fluorescence microballoon, the method are as follows:
(1) synthesis of silica template
By ethyl alcohol, water, ammonium hydroxide (25~28wt%), 1:0.06~0.08:0.04~0.05 is mixed by volume, obtains second
The mixed liquor A of alcohol, water, ammonium hydroxide, is warming up to 50 DEG C under stirring, the mixed of ethyl alcohol and ethyl orthosilicate volume ratio 1:0.3~0.4 is added
Solution A is closed, insulated and stirred 5h obtains system A, system A is then added to ethyl alcohol, water, ammonium hydroxide volume ratio 1:0.15~0.2:0.1
It is stirred at 50 DEG C in~0.2 mixed liquid B, the mixed solution B of ethyl alcohol and ethyl orthosilicate volume ratio 1:0.1~0.2 is added dropwise,
Insulated and stirred 5h, is centrifuged later, collects sediment, and washing obtains silicon dioxide microsphere；
The ethyl alcohol, water, the mixed liquor A of ammonium hydroxide and the volume ratio of the mixed solution A of ethyl alcohol and ethyl orthosilicate are 1:0.1
~0.2；
The volume of the system A and the mixed solution B of ethyl alcohol, water, the mixed liquid B of ammonium hydroxide and ethyl alcohol and ethyl orthosilicate
Than for 1:9~10:1~2；
" mixed liquor A of ethyl alcohol, water, ammonium hydroxide ", " mixed liquid B of ethyl alcohol, water, ammonium hydroxide ", not special meaning, mark
It is denoted as " A ", " B " is only intended to the differentiation of identical material in different operation step, " the mixed solution of ethyl alcohol and ethyl orthosilicate
A ", " the mixed solution B of ethyl alcohol and ethyl orthosilicate ", " system A " are similarly；
(2) the sulfhydrylation modification of silica template
Silicon dioxide microsphere obtained by step (1) is distributed in ethyl alcohol, mercaptopropyl trimethoxysilane (MPS), ammonia is added
Water, is stirred at room temperature 12h, and centrifugation, washing obtain sulfhydrylation silicon dioxide microsphere, be dispersed in ethyl alcohol and save in 4 DEG C；
The volumetric usage of the ethyl alcohol is calculated as 80~120mL/g with the quality of silicon dioxide microsphere；
The volumetric usage of the mercaptopropyl trimethoxysilane is calculated as 1~3mL/g with the quality of silicon dioxide microsphere；
The volumetric usage of the ammonium hydroxide is calculated as 2~3mL/g with the quality of silicon dioxide microsphere；
(3) assembling of quantum dot and silicon dioxide microsphere
By the ethanol solution centrifugation of sulfhydrylation silicon dioxide microsphere obtained by step (2), liquid is discarded supernatant, oil-soluble amount is added
Son point solution, ultrasound mix, and sediment is collected in centrifugation, and washing obtains silica/quantum dot compound；
The oil-soluble quantum dot is CdSe/ZnS, and quantum dot surface ligand is in addition to alkyl hydrosulfide (such as 1- lauryl mercaptan)
In addition other commonly use ligand (such as fatty acid, fatty amine, trioctylphosphine oxygen phosphorus), the solvent in the oil-soluble quantum dot solution
For common nonpolar solvent, including toluene, chloroform, hexamethylene, n-hexane etc.；
The concentration of the oil-soluble quantum dot solution is 8~12mg/mL；
The volumetric usage of the oil-soluble quantum dot solution is calculated as 80 with the quality of sulfhydrylation silicon dioxide microsphere~
120mL/g；
(4) silanization of quantum dot assembly and silicon dioxide modified
Silica/quantum dot compound obtained by step (3) is dried in air, n-octyl trimethoxy silane is added
(OTMS), then the mixed liquor of methanol and ammonium hydroxide volume ratio 1:0.02~0.03 is added in ultrasonic dissolution, ultrasound mixes, and is centrifuged, and receives
Collection sediment is simultaneously dispersed in water, and ammonium hydroxide is added, 12h is stirred at room temperature, obtains silica/quantum dot fluorescence microballoon of silanization
Solution, then by the silica of gained silanization/quantum dot fluorescence microspheres solution be added ethyl alcohol and ammonium hydroxide volume ratio 1:0.03~
In 0.04 mixed liquor, ethyl orthosilicate is added portionwise and is stirred to react 6h, is centrifuged later, collect sediment, washing obtains described
Quantum dot fluorescence microballoon；
The volumetric usage of the n-octyl trimethoxy silane is calculated as 2.5 with silica/quantum dot compound quality
~2.7mL/g；
The volumetric usage of the mixed liquor of the methanol and ammonium hydroxide is calculated as 190 with silica/quantum dot compound quality
~210mL/g；
The volumetric usage of the water is calculated as 400~500mL/g with silica/quantum dot compound quality；
The volumetric usage of the ammonium hydroxide is calculated as 0.6~0.7mL/g with silica/quantum dot compound quality；
Mixed liquor, the positive silicic acid second of the silica of the silanization/quantum dot fluorescence microspheres solution and ethyl alcohol and ammonium hydroxide
The volume ratio of ester is 1:4~4.5:0.01~0.03.
The beneficial effects of the present invention are:
1, to quantum dot direct-assembling in organic phase, without carrying out any surface modification and modification to quantum dot.
2, using sulfydryl-metal affinity interaction, realize quantum dot in the high density load of silica surface.
3, the phase of quantum dot microsphere is realized to the cladding (hydrophobic interaction) of quantum dot surface by alkyl silane reagent
Transfer effectively prevents the decline of quantum dot light emitting efficiency caused by conventional ligands replacement method.
4, by organosilan hydrolytic condensation andIt is excellent that silicon dioxide growth can get water-soluble and colloidal stability
Good fluorescent microsphere.
(4) Detailed description of the invention
Fig. 1: the preparation process schematic diagram of quantum dot complex microsphere；
Fig. 2: 200nm silicon dioxide microsphere (a), silica/quantum dot microsphere (using 200nm silicon ball as template, b), two
Silica/quantum dot/SiO 2 composite microsphere (using 200nm silicon ball as template, c) and silica/quantum dot microsphere (with
90nm silicon ball be template, d) transmission electron microscope picture；
Fig. 3: (1 quantum dot, 2 using 200nm silicon ball to be compound micro- made from template for the fluorescence spectrum of quantum dot and complex microsphere
Ball, 3 using 90nm silicon ball as complex microsphere made from template).
(5) specific embodiment
Below by specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in
This.
Embodiment 1:
(1) 80mL ethyl alcohol, 4.85mL water and 3.6mL ammonium hydroxide are mixed and are progressively heated at 50 DEG C.By 8mL ethyl alcohol
And the mixed solution of 3.1mLTEOS rapidly joins reaction flask, in 50 DEG C of stirring 5h.Take the above-mentioned solution of 10mL be added 70mL ethyl alcohol,
It is stirred in 13mL water and 7.5mL ammonium hydroxide.The mixed solution of 1mL TEOS and 10mL ethyl alcohol is added dropwise in reaction flask and stirs 5h
The silica spheres of 90nm can be obtained；Above-mentioned seed growth process is repeated 3 times, acquired solution 10000rpm is centrifuged simultaneously
With ethanol washing 3 times, to prepare the silica spheres of 200nm.
(2) silicon dioxide microsphere of 0.5g after purification is dispersed in 50mL ethyl alcohol, 500 μ L MPS and 1.25mL ammonia is added
12h is stirred at room temperature in water.The silicon dioxide microsphere of sulfhydrylation is centrifuged and can be obtained with ethanol washing 3 times with 10000rpm.By product
It is dispersed to 4 DEG C of preservations in ethyl alcohol.
(3) ethanol solution of sulfhydrylation silicon dioxide microsphere is centrifuged, discards supernatant (precipitating dry weight is 20mg).It is added
The toluene solution 2mL (10mg/mL) of CdSe/ZnS quantum dot, and ultrasound 5min obtains homogeneous phase transparent solution.With 10000rpm from
Heart 5min is by silica/quantum dot complex precipitate.Silica/quantum dot precipitating is washed 1~2 time with toluene to remove
Free CdSe/ZnS quantum dot.
(4) 60 μ L n-octyl trimethoxies are added after suitably drying silica/quantum dot microsphere sediment in air
Precipitating dissolution is obtained homogeneous phase solution under ultrasound condition by base silane.4.5mL methanol and 112 μ L ammonia are added into solution of silane
Water and ultrasound 30min.Silica/quantum dot is centrifuged with 10000rpm and washes away excessive silane reagent with methanol.It will be upper
It states precipitating and is scattered in 10mL water and is added 15 μ L ammonium hydroxide, at least 12h is stirred at room temperature and obtains silica/amount of silanization
Son point fluorescent microsphere.It can pass throughMethod carries out further silicon dioxide growth: 40mL is added in the above-mentioned microspheres solution of 10mL
In ethyl alcohol and 1.25mL ammonium hydroxide, 50 μ L ethyl orthosilicates are added and are stirred to react 3h；Continuously add the reaction of 50 μ L ethyl orthosilicates
And it is stirred to react 3h.Solution is centrifuged and is used ethanol washing 3 times, silica/quantum dot/silica quantum point fluorescence is obtained
Microballoon.
Embodiment 2:
(1) 80mL ethyl alcohol, 4.85mL water and 3.6mL ammonium hydroxide are mixed and are progressively heated at 50 DEG C.By 8mL ethyl alcohol
And the mixed solution of 3.1mLTEOS rapidly joins reaction flask, in 50 DEG C of stirring 5h.Take the above-mentioned solution of 20mL be added 140mL ethyl alcohol,
It is stirred in 26mL water and 15mL ammonium hydroxide.Being added dropwise in reaction flask and stir 5h the mixed solution of 2mL TEOS and 20mL ethyl alcohol can
Obtain the silica spheres of 90nm；Above-mentioned seed growth process is repeated 3 times, acquired solution is centrifuged with 10000rpm and is used in combination
Ethanol washing 3 times, to prepare the silica spheres of 200nm.
(2) silicon dioxide microsphere of 1.0g after purification is dispersed in 100mL ethyl alcohol, 1mL MPS and 2.5mL ammonia is added
12h is stirred at room temperature in water.The silicon dioxide microsphere of sulfhydrylation is centrifuged and can be obtained with ethanol washing 3 times with 10000rpm.By product
It is dispersed to 4 DEG C of preservations in ethyl alcohol.
(3) ethanol solution of sulfhydrylation silicon dioxide microsphere is centrifuged, discards supernatant (precipitating dry weight is 40mg).It is added
The toluene solution 4mL (10mg/mL) of CdSe/ZnS quantum dot, and ultrasound 5min obtains homogeneous phase transparent solution.With 10000rpm from
Heart 5min is by silica/quantum dot complex precipitate.Silica/quantum dot precipitating is washed 1~2 time with toluene to remove
Free CdSe/ZnS quantum dot.
(4) 120 μ L n-octyl trimethoxies are added after suitably drying silica/quantum dot microsphere sediment in air
Precipitating dissolution is obtained homogeneous phase solution under ultrasound condition by base silane.9.0mL methanol and 224 μ L ammonia are added into solution of silane
Water and ultrasound 30min.Silica/quantum dot is centrifuged with 10000rpm and washes away excessive silane reagent with methanol.It will be upper
It states precipitating and is scattered in 20mL water and is added 30 μ L ammonium hydroxide, at least 12h is stirred at room temperature and obtains silica/amount of silanization
Son point fluorescent microsphere.It can pass throughMethod carries out further silicon dioxide growth: 80mL is added in the above-mentioned microspheres solution of 20mL
In ethyl alcohol and 2.5mL ammonium hydroxide, 100 μ L ethyl orthosilicates are added and are stirred to react 3h；Continuously add the reaction of 100 μ L ethyl orthosilicates
And it is stirred to react 3h.Solution is centrifuged and is used ethanol washing 3 times, silica/quantum dot/silica quantum point fluorescence is obtained
Microballoon.
Embodiment 3:
(1) 80mL ethyl alcohol, 4.85mL water and 3.6mL ammonium hydroxide are mixed and are progressively heated at 50 DEG C.By 8mL ethyl alcohol
And the mixed solution of 3.1mLTEOS rapidly joins reaction flask, in 50 DEG C of stirring 5h.Take the above-mentioned solution of 50mL be added 350mL ethyl alcohol,
It is stirred in 65mL water and 37.5mL ammonium hydroxide.The mixed solution of 5mL TEOS and 50mL ethyl alcohol is added dropwise in reaction flask and stirs 5h
The silica spheres of 90nm can be obtained；Above-mentioned seed growth process is repeated 3 times, acquired solution 10000rpm is centrifuged simultaneously
With ethanol washing 3 times, to prepare the silica spheres of 200nm.
(2) silicon dioxide microsphere of 2.5g after purification is dispersed in 250mL ethyl alcohol, 2.5mL MPS and 6.25mL is added
12h is stirred at room temperature in ammonium hydroxide.The silicon dioxide microsphere of sulfhydrylation is centrifuged and can be obtained with ethanol washing 3 times with 10000rpm.It will produce
Product are dispersed to 4 DEG C of preservations in ethyl alcohol.
(3) ethanol solution of sulfhydrylation silicon dioxide microsphere is centrifuged, discards supernatant (precipitating dry weight is 100mg).It is added
The toluene solution 10mL (10mg/mL) of CdSe/ZnS quantum dot, and ultrasound 5min obtains homogeneous phase transparent solution.With 10000rpm from
Heart 5min is by silica/quantum dot complex precipitate.Silica/quantum dot precipitating is washed 1~2 time with toluene to remove
Free CdSe/ZnS quantum dot.
(4) 300 μ L n-octyl trimethoxies are added after suitably drying silica/quantum dot microsphere sediment in air
Precipitating dissolution is obtained homogeneous phase solution under ultrasound condition by base silane.22.5mL methanol and 560 μ L ammonia are added into solution of silane
Water and ultrasound 30min.Silica/quantum dot is centrifuged with 10000rpm and washes away excessive silane reagent with methanol.It will be upper
It states precipitating and is scattered in 50mL water and is added 75 μ L ammonium hydroxide, at least 12h is stirred at room temperature and obtains silica/amount of silanization
Son point fluorescent microsphere.It can pass throughMethod carries out further silicon dioxide growth: the above-mentioned microspheres solution of 50mL is added
In 200mL ethyl alcohol and 6.25mL ammonium hydroxide, 250 μ L ethyl orthosilicates are added and are stirred to react 3h；Continuously add the positive silicic acid second of 250 μ L
Ester reacts and is stirred to react 3h.Solution is centrifuged and is used ethanol washing 3 times, silica/quantum dot/silica quantum is obtained
Point fluorescent microsphere.
Embodiment 4:
(1) 80mL ethyl alcohol, 4.85mL water and 3.6mL ammonium hydroxide are mixed and are progressively heated at 50 DEG C.By 8mL ethyl alcohol
And the mixed solution of 3.1mLTEOS rapidly joins reaction flask, in 50 DEG C of stirring 5h.Take the above-mentioned solution of 10mL be added 70mL ethyl alcohol,
It is stirred in 13mL water and 7.5mL ammonium hydroxide.The mixed solution of 1mL TEOS and 10mL ethyl alcohol is added dropwise in reaction flask and is stirred 5h,
Acquired solution is centrifuged with 10000rpm and is used ethanol washing 3 times, to prepare the silica spheres of 90nm.
(2) silicon dioxide microsphere of 0.5g after purification is dispersed in 50mL ethyl alcohol, 500 μ L MPS and 1.25mL ammonia is added
12h is stirred at room temperature in water.The silicon dioxide microsphere of sulfhydrylation is centrifuged and can be obtained with ethanol washing 3 times with 10000rpm.By product
It is dispersed to 4 DEG C of preservations in ethyl alcohol.
(3) ethanol solution of sulfhydrylation silicon dioxide microsphere is centrifuged, discards supernatant (precipitating dry weight is 20mg).It is added
The toluene solution 2mL (10mg/mL) of CdSe/ZnS quantum dot, and ultrasound 5min obtains homogeneous phase transparent solution.With 10000rpm from
Heart 5min is by silica/quantum dot complex precipitate.Silica/quantum dot precipitating is washed 1~2 time with toluene to remove
Free CdSe/ZnS quantum dot.
(4) 60 μ L n-octyl trimethoxies are added after suitably drying silica/quantum dot microsphere sediment in air
Precipitating dissolution is obtained homogeneous phase solution under ultrasound condition by base silane.4.5mL methanol and 112 μ L ammonia are added into solution of silane
Water and ultrasound 30min.Silica/quantum dot is centrifuged with 10000rpm and washes away excessive silane reagent with methanol.It will be upper
It states precipitating and is scattered in 10mL water and is added 15 μ L ammonium hydroxide, at least 12h is stirred at room temperature and obtains silica/amount of silanization
Son point fluorescent microsphere.It can pass throughMethod carries out further silicon dioxide growth: 40mL is added in the above-mentioned microspheres solution of 10mL
In ethyl alcohol and 1.25mL ammonium hydroxide, 50 μ L ethyl orthosilicates are added and are stirred to react 3h；Continuously add the reaction of 50 μ L ethyl orthosilicates
And it is stirred to react 3h.Solution is centrifuged and is used ethanol washing 3 times, silica/quantum dot/silica quantum point fluorescence is obtained
Microballoon.
Embodiment 5:
(1) 80mL ethyl alcohol, 4.85mL water and 3.6mL ammonium hydroxide are mixed and are progressively heated at 50 DEG C.By 8mL ethyl alcohol
And the mixed solution of 3.1mLTEOS rapidly joins reaction flask, in 50 DEG C of stirring 5h.Take the above-mentioned solution of 20mL be added 140mL ethyl alcohol,
It is stirred in 26mL water and 15mL ammonium hydroxide.The mixed solution of 2mL TEOS and 20mL ethyl alcohol is added dropwise in reaction flask and is stirred 5h,
Acquired solution is centrifuged with 10000rpm and is used ethanol washing 3 times, to prepare the silica spheres of 90nm.
(2) silicon dioxide microsphere of 1.0g after purification is dispersed in 100mL ethyl alcohol, 1mL MPS and 2.5mL ammonia is added
12h is stirred at room temperature in water.The silicon dioxide microsphere of sulfhydrylation is centrifuged and can be obtained with ethanol washing 3 times with 10000rpm.By product
It is dispersed to 4 DEG C of preservations in ethyl alcohol.
(3) ethanol solution of sulfhydrylation silicon dioxide microsphere is centrifuged, discards supernatant (precipitating dry weight is 40mg).It is added
The toluene solution 4mL (10mg/mL) of CdSe/ZnS quantum dot, and ultrasound 5min obtains homogeneous phase transparent solution.With 10000rpm from
Heart 5min is by silica/quantum dot complex precipitate.Silica/quantum dot precipitating is washed 1~2 time with toluene to remove
Free CdSe/ZnS quantum dot.
(4) 120 μ L n-octyl trimethoxies are added after suitably drying silica/quantum dot microsphere sediment in air
Precipitating dissolution is obtained homogeneous phase solution under ultrasound condition by base silane.9mL methanol and 224 μ L ammonium hydroxide are added into solution of silane
And ultrasound 30min.Silica/quantum dot is centrifuged with 10000rpm and washes away excessive silane reagent with methanol.It will be above-mentioned
Precipitating is scattered in 20mL water and is added 30 μ L ammonium hydroxide, and at least 12h is stirred at room temperature and obtains silica/quantum of silanization
Point fluorescent microsphere.It can pass throughMethod carries out further silicon dioxide growth: 80mL second is added in the above-mentioned microspheres solution of 20mL
In alcohol and 2.5mL ammonium hydroxide, 100 μ L ethyl orthosilicates are added and are stirred to react 3h；Continuously add the reaction of 100 μ L ethyl orthosilicates simultaneously
It is stirred to react 3h.Solution is centrifuged and is used ethanol washing 3 times, it is micro- to obtain silica/quantum dot/silica quantum point fluorescence
Ball.
Embodiment 6:
(1) 80mL ethyl alcohol, 4.85mL water and 3.6mL ammonium hydroxide are mixed and are progressively heated at 50 DEG C.By 8mL ethyl alcohol
And the mixed solution of 3.1mLTEOS rapidly joins reaction flask, in 50 DEG C of stirring 5h.Take the above-mentioned solution of 50mL be added 350mL ethyl alcohol,
It is stirred in 65mL water and 37.5mL ammonium hydroxide.The mixed solution of 5mL TEOS and 50mL ethyl alcohol is added dropwise in reaction flask and is stirred
Acquired solution is centrifuged with 10000rpm and is used ethanol washing 3 times, to prepare the silica spheres of 90nm by 5h.
(2) silicon dioxide microsphere of 2.5g after purification is dispersed in 250mL ethyl alcohol, 2.5mL MPS and 6.25mL is added
12h is stirred at room temperature in ammonium hydroxide.The silicon dioxide microsphere of sulfhydrylation is centrifuged and can be obtained with ethanol washing 3 times with 10000rpm.It will produce
Product are dispersed to 4 DEG C of preservations in ethyl alcohol.
(3) ethanol solution of sulfhydrylation silicon dioxide microsphere is centrifuged, discards supernatant (precipitating dry weight is 100mg).It is added
The toluene solution 10mL (10mg/mL) of CdSe/ZnS quantum dot, and ultrasound 5min obtains homogeneous phase transparent solution.With 10000rpm from
Heart 5min is by silica/quantum dot complex precipitate.Silica/quantum dot precipitating is washed 1~2 time with toluene to remove
Free CdSe/ZnS quantum dot.
(4) 300 μ L n-octyl trimethoxies are added after suitably drying silica/quantum dot microsphere sediment in air
Precipitating dissolution is obtained homogeneous phase solution under ultrasound condition by base silane.22.5mL methanol and 560 μ L ammonia are added into solution of silane
Water and ultrasound 30min.Silica/quantum dot is centrifuged with 10000rpm and washes away excessive silane reagent with methanol.It will be upper
It states precipitating and is scattered in 50mL water and is added 75 μ L ammonium hydroxide, at least 12h is stirred at room temperature and obtains silica/amount of silanization
Son point fluorescent microsphere.It can pass throughMethod carries out further silicon dioxide growth: the above-mentioned microspheres solution of 50mL is added
In 200mL ethyl alcohol and 6.25mL ammonium hydroxide, 250 μ L ethyl orthosilicates are added and are stirred to react 3h；Continuously add the positive silicic acid second of 250 μ L
Ester reacts and is stirred to react 3h.Solution is centrifuged and is used ethanol washing 3 times, silica/quantum dot/silica quantum is obtained
Point fluorescent microsphere.
Comparative example:
The prior art: polystyrene microsphere investment prepare quantum dot fluorescent microsphere (bibliography: Nancy Joumaa,
Muriel Lansalot,Alain Theretz,and Abdelhamid Elaissari.Synthesis of Quantum
Dot-Tagged Submicrometer Polystyrene Particles by Miniemulsion
Polymerization.Langmuir 2006,22,1810-1816.)
Preparation process: styrene is mixed with hexadecane and CdSe/ZnS quantum dot first, then with vigorous stirring
This organic is added in water phase (water, lauryl sodium sulfate and sodium bicarbonate).It reacts after ten minutes, by gained mixture
Then obtained microemulsion is led to the deoxygenation of 45min nitrogen, while temperature is risen to 75 DEG C by ultrasound 7 minutes.Finally, over cure is added
Sour aqueous solutions of potassium reacts 5 hours in nitrogen environment.
Quantum dot load factor by the fluorescent microsphere of this method preparation is lower, is unevenly distributed, and fluorescence intensity is not high, from
And the quantum dot fluorescence microballoon is limited in the application of biological field.In contrast, fluorescent microsphere produced by the present invention has height
Uniform load, size uniformity, luminous intensity height, steady performance are imitated, can be applied to medicine multi-modality imaging in-vitro diagnosis
And multi-element biologic analysis.
Claims (2)
1. a kind of preparation method of quantum dot fluorescence microballoon, which is characterized in that the method are as follows:
(1) synthesis of silica template
By ethyl alcohol, water, ammonium hydroxide, 1:0.06~0.08:0.04~0.05 is mixed by volume, obtains the mixing of ethyl alcohol, water, ammonium hydroxide
Liquid A is warming up to 50 DEG C under stirring, the mixed solution A of ethyl alcohol and ethyl orthosilicate volume ratio 1:0.3~0.4, insulated and stirred is added
5h obtains system A, then by system A be added to ethyl alcohol, water, ammonium hydroxide volume ratio 1:0.15~0.2:0.1~0.2 mixed liquid B in
It is stirred at 50 DEG C, mixed solution B, the insulated and stirred 5h of ethyl alcohol and ethyl orthosilicate volume ratio 1:0.1~0.2 is added dropwise, later
Centrifugation, collects sediment, and washing obtains silicon dioxide microsphere；
The volume ratio of the mixed solution A of the ethyl alcohol, water, the mixed liquor A of ammonium hydroxide and ethyl alcohol and ethyl orthosilicate be 1:0.1~
0.2；
The volume ratio of the system A and the mixed solution B of ethyl alcohol, water, the mixed liquid B of ammonium hydroxide and ethyl alcohol and ethyl orthosilicate is
1:9~10:1~2；
(2) the sulfhydrylation modification of silica template
Silicon dioxide microsphere obtained by step (1) is distributed in ethyl alcohol, mercaptopropyl trimethoxysilane, ammonium hydroxide is added, room temperature is stirred
12h is mixed, centrifugation, washing obtain sulfhydrylation silicon dioxide microsphere, be dispersed in ethyl alcohol and save in 4 DEG C；
The volumetric usage of the ethyl alcohol is calculated as 80~120mL/g with the quality of silicon dioxide microsphere；
The volumetric usage of the mercaptopropyl trimethoxysilane is calculated as 1~3mL/g with the quality of silicon dioxide microsphere；
The volumetric usage of the ammonium hydroxide is calculated as 2~3mL/g with the quality of silicon dioxide microsphere；
(3) assembling of quantum dot and silicon dioxide microsphere
By the ethanol solution centrifugation of sulfhydrylation silicon dioxide microsphere obtained by step (2), liquid is discarded supernatant, oil-soluble quantum dot is added
Solution, ultrasound mix, centrifugation, collect sediment, and washing obtains silica/quantum dot compound；
The oil-soluble quantum dot is CdSe/ZnS；
The concentration of the oil-soluble quantum dot solution is 8~12mg/mL；
The volumetric usage of the oil-soluble quantum dot solution is calculated as 80~120mL/g with the quality of sulfhydrylation silicon dioxide microsphere；
(4) silanization of quantum dot assembly and silicon dioxide modified
Silica/quantum dot compound obtained by step (3) is dried in air, n-octyl trimethoxy silane is added, is surpassed
Then the mixed liquor of methanol and ammonium hydroxide volume ratio 1:0.02~0.03 is added in sound dissolution, ultrasound mixes, and sediment is collected in centrifugation
And be dispersed in water, ammonium hydroxide is added, 12h is stirred at room temperature, obtains silica/quantum dot fluorescence microspheres solution of silanization, then
The mixed of ethyl alcohol and ammonium hydroxide volume ratio 1:0.03~0.04 is added in the silica of gained silanization/quantum dot fluorescence microspheres solution
It closes in liquid, ethyl orthosilicate is added portionwise and is stirred to react 6h, is centrifuged later, collect sediment, it is glimmering to obtain the quantum dot for washing
Light microballoon；
The volumetric usage of the n-octyl trimethoxy silane is calculated as 2.5 with silica/quantum dot compound quality~
2.7mL/g；
The volumetric usage of the mixed liquor of the methanol and ammonium hydroxide is calculated as 190 with silica/quantum dot compound quality~
210mL/g；
The volumetric usage of the water is calculated as 400~500mL/g with silica/quantum dot compound quality；
The volumetric usage of the ammonium hydroxide is calculated as 0.6~0.7mL/g with silica/quantum dot compound quality；
The mixed liquor of the silica of the silanization/quantum dot fluorescence microspheres solution and ethyl alcohol and ammonium hydroxide, ethyl orthosilicate
Volume ratio is 1:4~4.5:0.01~0.03.
2. the preparation method of quantum dot fluorescence microballoon as described in claim 1, which is characterized in that in step (3), the oil is molten
Property quantum dot solution in solvent be toluene, chloroform, hexamethylene or n-hexane.
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