CN108998004A - A kind of preparation method of high stability quantum dot microsphere - Google Patents
A kind of preparation method of high stability quantum dot microsphere Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of high stability quantum dot microsphere, belong to technology of quantum dots field, preparation method is using oil-soluble fluorescent quantum dot as initial raw material, prepare the quantum dot of hydrophily and surface coated silica, amidated silane coupling agent is prepared again and modifies the quantum dot of hydrophily and surface coated silica with it, obtains amidated quantum dot microsphere.With the quantum dot microsphere that preparation method provided by the present invention obtains, product stability is high, and granularity is uniform, and shape is uniform, and fluorescence intensity is high, and preparation is simple, and yield is high, can be widely applied to biology and medicine detection and analysis field.
Description
Technical field
The invention belongs to technology of quantum dots fields, and in particular to a kind of preparation method of high stability quantum dot microsphere.
Background technique
Quantum dot, partial size are generally several nanometers to tens nanometer, are that a kind of fluorescence emission peak is relatively narrow, can pass through control
Grain size control fluorescence peak position one kind material, composition can be ZnSe/ZnS, CdSe/ZnS, InP/ZnS, PbS,
CuInS2、CuInSe2、Cu2ZnSnSe4、CuIn(Ga)S2、CuIn(Ga)Se2Deng.Quantum dot, due to its quantum size effect
With the controllable characteristic of fluorescence emission wavelengths, exciting light spectrum width and continuous, Same Wavelength can excite a variety of different colours simultaneously
Fluorescence quantum.Compared with traditional fluorescent reagent, fluorescence quantum yield is high, anti-light Bleachability strong, solar battery,
The fields such as light emitting diode, which have been obtained, to be widely applied.
Quantum dot is since its property stable in the air is lower, after being synthesized generally under hydrophobic environment, the long hydrocarbon of surface connection
Oleic acid, oleyl amine of chain etc. lead to its hydrophily and poor biocompatibility, are typically only capable to stabilization and are stored in organic reagent, surface
It needs to be protected from its oxidation with oleyl amine, oleic acid etc., limits it in the potential application of biomolecule identification and marker field.?
In medical treatment detection, quantum dot can be used to labelled antigen concentration, but problem to be solved is how to be translated into hydrophilic loop
How the particle of energy stable dispersion, control the homogeneity and yield of its partial size under border.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of high stability quantum dot microsphere, can be by oil-soluble quantum
Point changes water-soluble quantum dot, and stability is high, and granularity is uniform, and shape is uniform, and fluorescence intensity is high, and preparation is simple, and yield is high.
The present invention provides the following technical solutions:
A kind of preparation method of high stability quantum dot microsphere, comprising the following steps:
S1: oil-soluble fluorescent quantum dot is diluted with solvent, keeps its evenly dispersed, hydrophilic and oleophilic is then added into solution
Solvent and deionized water；
S2: to the S1 mixed solution and dripping silicon source obtained and alkali source saturated solution；
S3: being centrifuged the solution after the completion of hydrolyzing in S2 to obtain sediment, be washed with solvent, is continued centrifugation and is consolidated
The quantum dot of body sediment, i.e. hydrophily and surface coated silica；
S4: succinic anhydride and solvent being added in the three neck round bottom flask equipped with constant pressure funnel, is filled with nitrogen protection,
Under the conditions of ice-water bath, the mixture of silane coupling agent and the solvent is added dropwise, it is small that 0.5-2 is stirred under the conditions of ice-water bath
When, the reaction was continued at room temperature 24-48 hours, removes the solvent after completion of the reaction, obtains faint yellow thick oil product, i.e.,
Amidated silane coupling agent；
S5: the solid sediment that S3 is obtained disperses to obtain quantum dot dispersion liquid with polar solvent, then will obtain in S4
Amidated silane coupling agent and alkali source are added drop-wise in the quantum dot dispersion liquid, are hydrolyzed at room temperature；
S6: being centrifuged the solution after the completion of hydrolyzing in S5 to obtain sediment, be washed with solvent, and continuing centrifugation, to obtain solid heavy
Starch, as amidated quantum dot microsphere, is finally dispersed with polar solvent.
Preferably, the S1 oil-soluble fluorescence quantum be core-shell type quantum point or inorganic perovskite fluorescence quantum,
Cost is relatively low for it, be readily synthesized and property stabilization, quantum efficiency are high.The core-shell type quantum point be using ZnS as the quantum dot of shell,
Preferably CdSe/ZnS or CdTe/ZnS；The inorganic perovskite fluorescence quantum is that the inorganic perovskite of CsPbClxBryIz is glimmering
Light quanta point, wherein x+y+z=1.
It preferably, is toluene, chloroform, methylene chloride, four for the diluted solvent of oil-soluble fluorescent quantum dot in the S1
One of hydrogen furans, hexamethylene, octane, ketone and ethers or a variety of mixing；Hydrophilic and oleophilic solvent is dehydrated alcohol, isopropyl
One of alcohol, ethyl acetate, n,N-Dimethylformamide, dimethyl sulfoxide, ketone, ethers, tetrahydrofuran and second cyanogen are more
The mixing of kind.
Preferably, in the S1 hydrophilic and oleophilic solvent and dilution after quantum dot solution volume ratio 0.5:1-10:1.
Preferably, silicon source is silicate class or with dehydrated alcohol, isopropanol, ethyl acetate, N, N- diformazan in the S2
The esters of silicon acis of one of base formamide, dimethyl sulfoxide, ketone, ethers, tetrahydrofuran and second cyanogen or a variety of mixed dilutings, institute
The mixing that silicate class is preferably one or both of methyl orthosilicate and ethyl orthosilicate is stated, it can by changing silicon source composition
Adjust hydrolysis rate and pattern.
Preferably, alkali source is alkali compounds, preferably one of ammonium hydroxide, sodium hydroxide and potassium hydroxide in the S2
Or a variety of mixing, the dissolution of the alkali source and retarder thinner are water, dehydrated alcohol, isopropanol, ethyl acetate, N, N- dimethyl
One of formamide, dimethyl sulfoxide, ketone, ethers, tetrahydrofuran and second cyanogen or a variety of mixing, the pH value of the alkali source
For 8-13, adjustable hydrolysis rate is formed by changing alkali source.
Preferably, silicon source in the S2, alkali source saturated solution, mixed solvent volume ratio be 0.1-2:0.001-0.1:1-
100, keep its hydrolysis rate appropriate, gained granular size, pattern are more uniform.
Preferably, the hydrolysis temperature in the S2 is -1 DEG C -40 DEG C, and hydrolysis time is 0.1-12 hours, makes its hydrolysis speed
Rate is appropriate, and gained granular size, pattern are more uniform.
Preferably, it is deionized water, dehydrated alcohol, acetone, N, N- dimethyl that solvent used is washed in the S3 and S6
One of formamide or dimethyl sulfoxide or a variety of mixing.
Preferably, the molar ratio of succinic anhydride and silane coupling agent is 1.2:1-0.9:1 in the S4, has reacted it
Entirely.
Preferably, solvent is one of chloroform, methylene chloride and tetrahydrofuran or a variety of mixing in the S4.
Preferably, alkali source is alkali compounds, preferably one of ammonium hydroxide, sodium hydroxide and potassium hydroxide in the S5
Or a variety of mixing, the dissolution of the alkali source and retarder thinner are water, dehydrated alcohol, isopropanol, ethyl acetate, N, N- dimethyl
One of formamide, dimethyl sulfoxide, ketone, tetrahydrofuran and second cyanogen or a variety of mixing, the pH value of the alkali source are 8-
13, the volume ratio of the alkali source and the polar solvent is 0.0001:1-0.1:1.
Preferably, amidated silane coupling agent is exclusive use in the S5, or with dehydrated alcohol, isopropanol, second
One of acetoacetic ester, n,N-Dimethylformamide, dimethyl sulfoxide, ketone, ethers, tetrahydrofuran and second cyanogen are a variety of mixed
It closes and dilutes, the mass ratio of the amidated silane coupling agent and quantum dot dispersion liquid is 0.002:1-0.1:1, makes its hydrolysis speed
Rate is moderate.
Preferably, the polar solvent in the S5 is in dehydrated alcohol, n,N-Dimethylformamide and dimethyl sulfoxide
One or more mixing, the time of hydrolysis are 0.1-8 hours.
Preferably, the polar solvent in the S6 is in dehydrated alcohol, n,N-Dimethylformamide and dimethyl sulfoxide
One or more mixing keeps the quantum dot microsphere of surface hydrophilic evenly dispersed.
The beneficial effects of the present invention are:
(1) present invention chooses different-grain diameter size, the fluorescence quantum with different emission spectrum characteristics, passes through silicon source
Hydrolysis and the hydrolysis of silane coupling agent of carboxylated are surface modified, and complete quantum dot from oil-soluble to water-soluble transformation,
Stability is high, and validity period can increase by 50% or more.
(2) particle size range for the quantum dot microsphere that the present invention prepares is 40-500nm, and granularity and pattern are uniform.
(3) preparation method provided by the present invention is simple, easy to operate, and the yield of the quantum dot microsphere of acquisition is big.
(4) fluorescence intensity of the prepared quantum dot microsphere obtained of the present invention is high, by the amount of the different wave length prepared
Son point marks different antibodies respectively, generates multicolor fluorescence quantum dot probe, is calculated according to the fluorescence signal intensity of quantum dot probe
The not content of synantigen realizes the synchronous detection of multiple groups antigen-antibody in same pipe.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the transmission electron microscope figure for the quantum dot microsphere that embodiment 1 obtains；
Fig. 2 is the stability test result figure of quantum dot microsphere in embodiment 1.
Specific embodiment
Embodiment 1
It chooses a kind of red CdSe/ZnS quantum dot to be surface modified, obtains the preparation side of high stability quantum dot microsphere
Method, comprising the following steps:
S1: it takes the red CdSe/ZnS core-shell type quantum point 0.25mL of 100mg/mL in a round bottom flask, and is added
The toluene solution of 12.5mL is diluted, and ultrasonic 30min keeps its evenly dispersed；
S2: dehydrated alcohol 125mL and ammonium hydroxide 4.2mL (NH is added in the solution obtained under stirring condition into S13Content is
1%-15%), the TEOS of 6mL is added dropwise under intense agitation dropwise, hydrolyzes 3h at 25 DEG C；
S3: being centrifuged 5min with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once, continues centrifugation and obtains sediment；
S4: succinic anhydride 5.25g and methylene chloride are added in the three neck round bottom flask equipped with constant pressure funnel
100mL, is filled with nitrogen protection, under the conditions of ice-water bath, be added silane coupling agent 3- aminopropyl diethoxymethylsilane 9.57g and
Methylene chloride 100mL is added dropwise dropwise in constant pressure funnel, and 1h is stirred under the conditions of ice-water bath, continues the reaction at room temperature for 24 hours,
Revolving removes methylene chloride, obtains faint yellow thick oil product 3- aminopropyl diethoxymethylsilane -4- ketobutyric acid, instead
Answer process as follows:
S5: the sediment obtained in S3 is dispersed in the ethanol solution of 125mL, and ultrasonic 30min dispersion continues to add
The ammonium hydroxide 7.5mL for entering mass fraction 5% is vigorously stirred the amidated silane coupling agent 3- aminopropyl two prepared in lower addition S4
(ethoxymethyl) base silane -4- ketobutyric acid 0.815g, hydrolyzes 3h at room temperature；
S6: being centrifuged 5min for the solution after the completion of hydrolyzing in S5 with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once,
Continue centrifugation acquisition and finally modify the quantum dot microsphere finished, is dispersed with the dehydrated alcohol of 25mL, ultrasonic 30min is spare.
Above-mentioned quantum dot microsphere is marked into a kind of antibody to match with tested antigen, prepares the spy of quantum dot labelled antibody
Needle establishes test method.
If Fig. 1 is the transmission electron microscope figure of the quantum dot microsphere of the present embodiment acquisition, it can be seen that quantum dot is micro-
The granularity and shape of ball are uniform.
Such as the stability test result figure that Fig. 2 is quantum dot microsphere, it is unattenuated to be positively retained at fluorescence intensity in one month
More than 20%.
Embodiment 2
It chooses a kind of red CdSe/ZnS quantum dot to be surface modified, obtains the preparation side of high stability quantum dot microsphere
Method, comprising the following steps:
S1: it takes the red CdSe/ZnS core-shell type quantum point 0.25mL of 100mg/mL in a round bottom flask, and is added
The toluene solution of 12.5mL is diluted, and ultrasonic 30min keeps its evenly dispersed；
S2: dehydrated alcohol 125mL and ammonium hydroxide 1.25mL (NH3 mass are added in the solution obtained under stirring condition into S1
Score is 1%), the TEOS of 0.8mL to be added dropwise under intense agitation dropwise, hydrolyzes 3h at 10 DEG C；
S3: being centrifuged 5min with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once, continues centrifugation and obtains sediment；
S4: succinic anhydride 5.25g and methylene chloride are added in the three neck round bottom flask equipped with constant pressure funnel
100mL, is filled with nitrogen protection, under the conditions of ice-water bath, be added silane coupling agent 3- aminopropyl diethoxymethylsilane 9.57g and
Methylene chloride 100mL is added dropwise dropwise in constant pressure funnel, and 1h is stirred under the conditions of ice-water bath, continues the reaction at room temperature for 24 hours,
Revolving removes methylene chloride, obtains faint yellow thick oil product 3- aminopropyl diethoxymethylsilane -4- ketobutyric acid, instead
Answer process as follows:
S5: the sediment obtained in S3 is dispersed in the ethanol solution of 125mL, and ultrasonic 30min dispersion continues to add
The ammonium hydroxide 5.5mL for entering mass fraction 5% is vigorously stirred the amidated silane coupling agent 3- aminopropyl two prepared in lower addition S4
(ethoxymethyl) base silane -4- ketobutyric acid 0.815g, hydrolyzes 3h at room temperature；
S6: being centrifuged 5min for the solution after the completion of hydrolyzing in S5 with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once,
Continue centrifugation acquisition and finally modify the quantum dot microsphere finished, is dispersed with the dehydrated alcohol of 25mL, ultrasonic 30min is spare.
Above-mentioned quantum dot microsphere is marked into a kind of antibody to match with tested antigen, prepares the spy of quantum dot labelled antibody
Needle establishes test method.
Embodiment 3
It chooses a kind of red CdSe/ZnS quantum dot to be surface modified, obtains the preparation side of high stability quantum dot microsphere
Method, comprising the following steps:
S1: it takes the red CdSe/ZnS core-shell type quantum point 0.25mL of 100mg/mL in a round bottom flask, and 20mL is added
Toluene solution be diluted, ultrasonic 30min keeps its evenly dispersed；
S2: dehydrated alcohol 10mL, acetone 50ml and ammonium hydroxide 0.025mL are added in the solution obtained under stirring condition into S1
(NH3 mass fraction be 1%) is added dropwise the TEOS of 0.1mL under intense agitation dropwise, hydrolyzes 8h at 0 DEG C；
S3: being centrifuged 5min with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once, continues centrifugation and obtains sediment；
S4: succinic anhydride 5.25g and methylene chloride are added in the three neck round bottom flask equipped with constant pressure funnel
100mL, is filled with nitrogen protection, under the conditions of ice-water bath, be added silane coupling agent 3- aminopropyl diethoxymethylsilane 9.57g and
Methylene chloride 100mL is added dropwise dropwise in constant pressure funnel, and 1h is stirred under the conditions of ice-water bath, continues the reaction at room temperature for 24 hours,
Revolving removes methylene chloride, obtains faint yellow thick oil product 3- aminopropyl diethoxymethylsilane -4- ketobutyric acid, instead
Answer process as follows:
S5: the sediment obtained in S3 is dispersed in dehydrated alcohol/acetone 1:4 mixed solution of 50mL, ultrasound
30min dispersion, continuously adds the ammonium hydroxide 0.05mL of mass fraction 1%, is vigorously stirred the amidated silicon prepared in lower addition S4
Alkane coupling agent 3- aminopropyl diethoxymethylsilane -4- ketobutyric acid 0.815g, hydrolyzes 8h at room temperature；
S6: being centrifuged 5min for the solution after the completion of hydrolyzing in S5 with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once,
Continue centrifugation acquisition and finally modify the quantum dot microsphere finished, is dispersed in the water of 25mL, ultrasonic 30min is spare.
Above-mentioned quantum dot microsphere is marked into a kind of antibody to match with tested antigen, prepares the spy of quantum dot labelled antibody
Needle establishes test method.
Embodiment 4
It chooses a kind of red CdSe/ZnS quantum dot to be surface modified, obtains the preparation side of high stability quantum dot microsphere
Method, comprising the following steps:
S1: it takes the red CdSe/ZnS core-shell type quantum point 0.25mL of 100mg/mL in a round bottom flask, and 50mL is added
Toluene solution be diluted, ultrasonic 30min keeps its evenly dispersed；
S2: dehydrated alcohol 12mL and ammonium hydroxide 2mL (NH is added in the solution obtained under stirring condition into S13Mass fraction
For the TEOS of 2mL 1%), is added dropwise under intense agitation dropwise, 0.2h is hydrolyzed at 20 DEG C；
S3: being centrifuged 5min with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once, continues centrifugation and obtains sediment；
S4: succinic anhydride 5.25g and methylene chloride are added in the three neck round bottom flask equipped with constant pressure funnel
100mL, is filled with nitrogen protection, under the conditions of ice-water bath, be added silane coupling agent 3- aminopropyl diethoxymethylsilane 9.57g and
Methylene chloride 100mL is added dropwise dropwise in constant pressure funnel, and 1h is stirred under the conditions of ice-water bath, continues the reaction at room temperature for 24 hours,
Revolving removes methylene chloride, obtains faint yellow thick oil product 3- aminopropyl diethoxymethylsilane -4- ketobutyric acid, instead
Answer process as follows:
S5: the sediment obtained in S3 is dispersed in the ethanol solution of 50mL, and ultrasonic 30min dispersion continues to add
The ammonium hydroxide 1mL for entering mass fraction 1% is vigorously stirred the amidated silane coupling agent 3- aminopropyl diethyl prepared in lower addition S4
Oxygroup methyl-monosilane -4- ketobutyric acid 2g, hydrolyzes 0.2h at room temperature；
S6: being centrifuged 5min for the solution after the completion of hydrolyzing in S5 with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once,
Continue centrifugation acquisition and finally modify the quantum dot microsphere finished, is dispersed with the dehydrated alcohol of 25mL, ultrasonic 30min is spare.
Above-mentioned quantum dot microsphere is marked into a kind of antibody to match with tested antigen, prepares the spy of quantum dot labelled antibody
Needle establishes test method.
Embodiment 5
Choose a kind of green phosphor perovskite quantum dot CsPbBr3It is surface modified, it is micro- to obtain high stability quantum dot
The preparation method of ball, comprising the following steps:
S1: the green CsPbBr of 14.05mg/mL is taken3In a round bottom flask, and the first of 12.5mL is added in quantum dot 1.78mL
Benzole soln is diluted, and ultrasonic 30min keeps its evenly dispersed；
S2: dehydrated alcohol 125mL, deionized water 0.5mL and ammonium hydroxide are added in the solution obtained under stirring condition into S1
0.25mL(NH3Content is 25%-28%), the TEOS of 6mL is added dropwise under intense agitation dropwise, hydrolyzes 3h at room temperature；
S3: being centrifuged 5min with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once, continues centrifugation and obtains sediment；
S4: succinic anhydride 5.25g and methylene chloride are added in the three neck round bottom flask equipped with constant pressure funnel
100mL, is filled with nitrogen protection, under the conditions of ice-water bath, be added silane coupling agent 3- aminopropyl diethoxymethylsilane 9.57g and
Methylene chloride 100mL is added dropwise dropwise in constant pressure funnel, and 1h is stirred under the conditions of ice-water bath, continues the reaction at room temperature for 24 hours,
Revolving removes methylene chloride, obtains faint yellow thick oil product 3- aminopropyl diethoxymethylsilane -4- ketobutyric acid, instead
Answer process as follows:
S5: the sediment obtained in S3 is dispersed in the ethanol solution of 125mL, and ultrasonic 30min dispersion continues to add
Enter deionized water 0.5mL, ammonium hydroxide 1.25mL, is vigorously stirred the 3- aminopropyl diethoxymethylsilane-prepared in lower addition S4
4- ketobutyric acid 0.815g, hydrolyzes 3h at room temperature；
S6: being centrifuged 5min for the solution after the completion of hydrolyzing in S5 with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once,
Continue centrifugation acquisition and finally modify the quantum dot microsphere finished, is dispersed with the dehydrated alcohol of 25mL, ultrasonic 30min is spare.
By a kind of above-mentioned quantum dot-labeled antibody to match with tested antigen, quantum dot labelled antibody probe is prepared, is built
Vertical test method.
Embodiment 6
The CdSe/ZnS quantum dot for choosing three kinds of wavelength is surface modified, and obtains the preparation of high stability quantum dot microsphere
Method, comprising the following steps:
S1: the yellow of red (618nm) CdSe/ZnS core-shell type quantum point 0.25mL, 8mg/mL of 100mg/mL are taken respectively
Green (505nm) CdSe/ZnS core-shell type quantum point of (565nm) CdSe/ZnS core-shell type quantum point 8.333mL and 8mg/mL
In three round-bottomed flasks, the toluene solution for being separately added into 12.5mL is diluted 8.333mL, and ultrasonic 30min divides it uniformly
It dissipates；
S2: dehydrated alcohol 125mL, deionized water 6.25mL and ammonium hydroxide are added in the solution obtained under stirring condition into S1
0.25mL(NH3Content is 25%-28%), the TEOS of 6mL is added dropwise under intense agitation dropwise respectively, hydrolyzes 3h at room temperature；
S3: being centrifuged 5min with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once, continues centrifugation and obtains sediment；
S4: succinic anhydride 5.25g and methylene chloride are added in the three neck round bottom flask equipped with constant pressure funnel
100mL, is filled with nitrogen protection, under the conditions of ice-water bath, be added silane coupling agent 3- aminopropyl diethoxymethylsilane 9.57g and
Methylene chloride 100mL is added dropwise dropwise in constant pressure funnel, and 1h is stirred under the conditions of ice-water bath, continues the reaction at room temperature for 24 hours,
Revolving removes methylene chloride, obtains faint yellow thick oil product 3- aminopropyl diethoxymethylsilane -4- ketobutyric acid, instead
Answer process as follows:
S5: the sediment obtained in S3 is dispersed in the ethanol solution of 125mL, and ultrasonic 30min dispersion continues to add
Enter deionized water 6.25mL, ammonium hydroxide 1.25mL, is vigorously stirred the 3- aminopropyl diethoxymethylsilane-prepared in lower addition S4
4- ketobutyric acid 0.815g, hydrolyzes 3h at room temperature；
S6: being centrifuged 5min for the solution after the completion of hydrolyzing in S5 with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once,
Continue centrifugation acquisition and finally modify the quantum dot microsphere finished, is dispersed with the dehydrated alcohol of 25mL, ultrasonic 30min is spare.
By a kind of above-mentioned quantum dot-labeled antibody to match with tested antigen, quantum dot labelled antibody probe is prepared, is built
Vertical test method.
Embodiment 7
The CdSe/ZnS quantum dot for choosing two kinds of wavelength carries out blending surface modification, obtains high stability quantum dot microsphere
Preparation method, comprising the following steps:
S1: the green of red (618nm) CdSe/ZnS core-shell type quantum point 0.200mL and 10mg/mL of 100mg/mL are taken
(the sub- point mass ratio of two amounts can in practice in three round-bottomed flasks by (505nm) CdSe/ZnS core-shell type quantum point 0.500mL
To be 0:10,2:8,5:5,8:2,10:0 etc.), the toluene solution that 12.5mL is added is diluted, ultrasonic 30min, makes it uniformly
Dispersion；
S2: dehydrated alcohol 125mL, deionized water 6.25mL and ammonium hydroxide are added in the solution obtained under stirring condition into S1
0.25mL(NH3Content is 25%-28%), the TEOS of 6mL is added dropwise under intense agitation dropwise respectively, hydrolyzes 3h at room temperature；
S3: being centrifuged 5min with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once, continues centrifugation and obtains sediment；
S4: succinic anhydride 5.25g and methylene chloride are added in the three neck round bottom flask equipped with constant pressure funnel
100mL, is filled with nitrogen protection, under the conditions of ice-water bath, be added silane coupling agent 3- aminopropyl diethoxymethylsilane 9.57g and
Methylene chloride 100mL is added dropwise dropwise in constant pressure funnel, and 1h is stirred under the conditions of ice-water bath, continues the reaction at room temperature for 24 hours,
Revolving removes methylene chloride, obtains faint yellow thick oil product 3- aminopropyl diethoxymethylsilane -4- ketobutyric acid, instead
Answer process as follows:
S5: the sediment obtained in S3 is dispersed in the ethanol solution of 125mL, and ultrasonic 30min dispersion continues to add
Enter deionized water 6.25mL, ammonium hydroxide 1.25mL, is vigorously stirred the 3- aminopropyl diethoxymethylsilane-prepared in lower addition S4
4- ketobutyric acid 0.815g, hydrolyzes 3h at room temperature；
S6: being centrifuged 5min for the solution after the completion of hydrolyzing in S5 with 10000 revs/min of revolving speed, and dehydrated alcohol is washed once,
Continue centrifugation acquisition and finally modify the quantum dot microsphere finished, is dispersed with the dehydrated alcohol of 25mL, ultrasonic 30min is spare.
By a kind of above-mentioned quantum dot-labeled antibody to match with tested antigen, quantum dot labelled antibody probe is prepared, is built
Vertical test method.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (15)
1. a kind of preparation method of high stability quantum dot microsphere, which comprises the following steps:
S1: oil-soluble fluorescent quantum dot being diluted with solvent, keeps its evenly dispersed, and hydrophilic and oleophilic solvent is then added into solution
And deionized water；
S2: to the S1 mixed solution and dripping silicon source obtained and alkali source saturated solution；
S3: being centrifuged the solution after the completion of hydrolyzing in S2 to obtain sediment, be washed with solvent, and continuing centrifugation, to obtain solid heavy
The quantum dot of starch, i.e. hydrophily and surface coated silica；
S4: succinic anhydride and solvent are added in the three neck round bottom flask equipped with constant pressure funnel, is filled with nitrogen protection, ice water
Under the conditions of bath, the mixture of silane coupling agent and the solvent is added dropwise, is stirred 0.5-2 hours under the conditions of ice-water bath, room
Temperature is lower, and the reaction was continued 24-48 hours, removes the solvent after completion of the reaction, obtains faint yellow thick oil product, i.e. amide
The silane coupling agent of change；
S5: the solid sediment that S3 is obtained disperses to obtain quantum dot dispersion liquid, then the amide that will be obtained in S4 with polar solvent
The silane coupling agent and alkali source of change are added drop-wise in the quantum dot dispersion liquid, are hydrolyzed at room temperature；
S6: being centrifuged the solution after the completion of hydrolyzing in S5 to obtain sediment, be washed with solvent, continues centrifugation and obtains solid precipitating
Object, as amidated quantum dot microsphere, is finally dispersed with polar solvent.
2. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that in the S1
Oil-soluble fluorescent quantum dot is core-shell type quantum point or inorganic perovskite fluorescence quantum, and the core-shell type quantum point is with ZnS
For the quantum dot of shell；The inorganic perovskite fluorescence quantum is the inorganic perovskite fluorescence quantum of CsPbClxBryIz,
Middle x+y+z=1.
3. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that in the S1
It is toluene, chloroform, methylene chloride, tetrahydrofuran, hexamethylene, octane, ketone for the diluted solvent of oil-soluble fluorescent quantum dot
With one of ethers or a variety of mixing；Hydrophilic and oleophilic solvent is dehydrated alcohol, isopropanol, ethyl acetate, N, N- dimethyl
One of formamide, dimethyl sulfoxide, ketone, ethers, tetrahydrofuran and second cyanogen or a variety of mixing.
4. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that in the S1
The volume ratio 0.5:1-10:1 of quantum dot solution after hydrophilic and oleophilic solvent and dilution.
5. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that in the S2
Silicon source is silicate class or with dehydrated alcohol, isopropanol, ethyl acetate, n,N-Dimethylformamide, dimethyl sulfoxide, ketone
The esters of silicon acis of one of class, ethers, tetrahydrofuran and second cyanogen or a variety of mixed dilutings.
6. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that in the S2
Alkali source is alkali compounds, and the dissolution of the alkali source and retarder thinner are water, dehydrated alcohol, isopropanol, ethyl acetate, N, N- bis-
One of methylformamide, dimethyl sulfoxide, ketone, ethers, tetrahydrofuran and second cyanogen or a variety of mixing, the alkali source
PH value is 8-13.
7. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that in the S2
Silicon source, alkali source saturated solution, mixed solvent volume ratio be 0.1-2:0.001-0.1:1-100.
8. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that in the S2
Hydrolysis temperature be -1 DEG C -40 DEG C, hydrolysis time be 0.1-12 hours.
9. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that the S3 and
It is one in deionized water, dehydrated alcohol, acetone, n,N-Dimethylformamide or dimethyl sulfoxide that solvent used is washed in S6
Kind or a variety of mixing.
10. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that the S4
The molar ratio of middle succinic anhydride and silane coupling agent is 1.2:1-0.9:1.
11. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that the S4
In solvent be one of chloroform, methylene chloride and tetrahydrofuran or a variety of mixing.
12. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that the S5
Middle alkali source is alkali compounds, and the dissolution of the alkali source and retarder thinner are water, dehydrated alcohol, isopropanol, ethyl acetate, N, N-
One of dimethylformamide, dimethyl sulfoxide, ketone, tetrahydrofuran and second cyanogen or a variety of mixing, the pH of the alkali source
Being worth is 8-13, and the volume ratio of the alkali source and the polar solvent is 0.0001:1-0.1:1.
13. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that the S5
In amidated silane coupling agent be to be used alone, or with dehydrated alcohol, isopropanol, ethyl acetate, N, N- dimethyl formyl
One of amine, dimethyl sulfoxide, ketone, ethers, tetrahydrofuran and second cyanogen or a variety of mixed dilutings use, the amidation
Silane coupling agent and quantum dot dispersion liquid mass ratio be 0.002:1-0.1:1.
14. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that the S5
In polar solvent be one of dehydrated alcohol, n,N-Dimethylformamide and dimethyl sulfoxide or a variety of mixing, hydrolysis
The time of reaction is 0.1-8 hours.
15. a kind of preparation method of high stability quantum dot microsphere according to claim 1, which is characterized in that the S6
In polar solvent be one of dehydrated alcohol, n,N-Dimethylformamide and dimethyl sulfoxide or a variety of mixing.
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