CN111944190A - Quantum dot fluorescent coding microsphere and preparation method thereof - Google Patents
Quantum dot fluorescent coding microsphere and preparation method thereof Download PDFInfo
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- CN111944190A CN111944190A CN202010786761.XA CN202010786761A CN111944190A CN 111944190 A CN111944190 A CN 111944190A CN 202010786761 A CN202010786761 A CN 202010786761A CN 111944190 A CN111944190 A CN 111944190A
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- quantum dot
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- C08J7/16—Chemical modification with polymerisable compounds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a quantum dot fluorescent coding microsphere and a preparation method thereof. The preparation method comprises the following steps: respectively dissolving N quantum dots with different colors in a mixed solution formed by an oil-soluble monomer and a cross-linking agent to obtain N oil phase mixtures, wherein N is more than or equal to 2; sequentially dispersing N kinds of the oil phase mixtures in the same emulsifier solution according to the sequence that the wavelength of the quantum dots dissolved in the oil phase mixtures is from long to short to form quantum dot micelles; adding the quantum dot micelle and an initiator into water, and carrying out polymerization reaction under the protection of nitrogen to obtain quantum dot seed microspheres; and adding a functional monomer into a polymerization reaction system, carrying out grafting reaction on the quantum dot seed microspheres and the functional monomer, and carrying out purification treatment after the reaction is finished to obtain the quantum dot fluorescent coding microspheres.
Description
Technical Field
The invention relates to the technical field of nano biological materials, in particular to a quantum dot fluorescence coding microsphere and a preparation method thereof.
Background
Compared with the traditional fluorescent dye, the quantum dot has the excellent properties of wider excitation wavelength range, narrower emission peak and photobleaching resistance, and is a more ideal fluorescent coding material. However, the quantum dots have the defects of small particle size, high surface energy and low oxygen resistance, so that the application of the quantum dots is limited. The quantum dot fluorescent microspheres obtained by wrapping the quantum dots in the polymer microspheres can obviously improve the optical stability, colloidal stability and biocompatibility of the quantum dots, can amplify detected fluorescent signals and obviously improve the sensitivity of biological detection. Meanwhile, quantum dots with different colors can be embedded in the microsphere, and the obtained quantum dot fluorescent microsphere is excited by light with monomer wavelength, can emit fluorescence with various proportions, and realizes fluorescent coding and high-throughput detection.
In the prior art, the quantum dot fluorescence encoding microsphere prepared based on the swelling method is difficult to be applied to biological detection because the quantum dot is easy to leak out of the interior of the microsphere, so that the fluorescence intensity of the encoding microsphere is unstable. In addition, quantum dots can also be stabilized on the surface of the microsphere by covalent bonding, but this method has the following defects: on one hand, the covalent bonding operation is complicated, on the other hand, the nano material is easy to cause nonspecific adsorption on the surface of the microsphere, if the surface of the microsphere is coated with a polymer or silicon dioxide to reduce the nonspecific adsorption, free radicals are inevitably introduced due to the coated polymer, and can damage the surface of the quantum dot to cause defects and cause obvious fluorescence quenching, and a precursor such as tetraethyl silicate applied when the silicon dioxide is coated has serious influence on a ligand on the surface of the quantum dot and can also cause surface defects to cause the fluorescence quenching of the quantum dot, so that the sensitivity of the quantum dot fluorescence coding microsphere is reduced to a great extent.
Disclosure of Invention
The invention solves the problems that the quantum dot fluorescent coding microsphere prepared based on a swelling method and a covalent bonding mode in the prior art has the defects of unstable fluorescence intensity of the coding microsphere, reduced sensitivity of the fluorescent coding microsphere caused by the reduction of nonspecific adsorption treatment due to strong nonspecific adsorption of the quantum dot microsphere, and the like.
In order to solve at least one aspect of the above problems, the present invention provides a method for preparing quantum dot fluorescent-encoded microspheres, comprising:
respectively dissolving N quantum dots with different colors in a mixed solution formed by an oil-soluble monomer and a cross-linking agent to obtain N oil phase mixtures, wherein N is more than or equal to 2;
sequentially dispersing N kinds of the oil phase mixture in an emulsifier solution according to the sequence that the wavelength of the quantum dots dissolved in the oil phase mixture is from long to short to form quantum dot micelles;
adding the quantum dot micelle and an initiator into water, and carrying out polymerization reaction under the protection of nitrogen to obtain quantum dot seed microspheres;
and adding a functional monomer into a polymerization reaction system, carrying out grafting reaction on the quantum dot seed microspheres and the functional monomer, and carrying out purification treatment after the reaction is finished to obtain the quantum dot fluorescent coding microspheres.
Preferably, the crosslinking agent is an acrylate-containing or methacrylate-containing alcohol ester crosslinking agent.
Preferably, the dispersing N kinds of the oil phase mixtures in the same emulsifier solution in order from long to short wavelength of the quantum dots dissolved therein to form quantum dot micelles includes:
dissolving an emulsifier in water to form emulsion micelles, adding the oil phase mixture in which the first color quantum dots are dissolved in the N oil phase mixtures into the emulsion micelles, and performing ultrasonic dispersion or high-speed homogenization to form first quantum dot micelles;
adding an oil phase mixture in which second color quantum dots are dissolved in the N oil phase mixtures into the first quantum dot micelles, and forming second quantum dot micelles with the outer layers being the second color quantum dots and the inner layers being the first color quantum dots through ultrasonic dispersion or high-speed homogenization, wherein the wavelength of the first color quantum dots is larger than that of the second color quantum dots;
and sequentially emulsifying the quantum dots dissolved in the oil phase mixture from long to short in wavelength until the N oil phase mixtures are completely dissolved in the emulsion micelle to obtain the quantum dot micelle.
Preferably, in the quantum dot beam, the mass concentration of the emulsifier is 0.2% -25%.
Preferably, the oil-soluble monomer comprises one of styrene, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, lauryl acrylate, lauryl methacrylate, isobornyl acrylate and isobornyl methacrylate.
Preferably, the functional monomer comprises one of a carboxyl monomer and a monomer containing a click chemistry derivative group, and the click chemistry derivative group is an epoxy group, an azido group or an aldehyde group.
Preferably, the mass ratio of the oil-soluble monomer to the cross-linking agent in the mixed solution is (1-10): 20.
Preferably, the mass concentration of the quantum dots in the oil phase mixture is 5-50%.
Compared with the prior art, the preparation method of the quantum dot fluorescent microsphere provided by the invention has the following advantages:
according to the invention, through a multiple emulsification mode, quantum dots with different wavelengths in the quantum dot bundle are arranged in a sequence that the wavelengths from the inner layer to the outer layer are shortened, compared with the random distribution of quantum dots with various colors in the microsphere, the self-absorption among the quantum dots is reduced to the greatest extent, the multi-dimensional fluorescence coding is realized, and the purpose that the emission wavelength of each microsphere is more uniform and controllable can be achieved, so that the fluorescence stability of the microsphere is improved.
The invention also introduces the cross-linking agent, utilizes the characteristic that hydrophilic groups of the cross-linking agent migrate to the surface of the microsphere and form hydrogen bonds with water, and forms an ethoxy hydration layer on the surface of the microsphere, so that the surface of the finally prepared quantum dot fluorescence coding microsphere only comprises ethoxy chain segments and functional groups in the cross-linking agent and hardly has hydrophobic groups, thereby the quantum dot fluorescence coding microsphere shows extremely low non-specific adsorption performance, and the sensitivity of the microsphere is improved.
The invention also provides a quantum dot fluorescent coding microsphere, which comprises a microsphere body and a plurality of layers of oil-soluble quantum dots wrapped inside the microsphere body, wherein the oil-soluble quantum dots are distributed in the microsphere body from inside to outside according to the sequence of the wavelength from long to short, and the surface of the microsphere body is modified with a hydration layer comprising an ethoxy chain segment and a functional group connected to the surface of the hydration layer.
The invention also provides application of the quantum dot fluorescence coding microspheres, and the quantum dot fluorescence coding microspheres are applied to the fields of biological labeling, biological separation and/or in-vitro diagnosis.
The application of the quantum dot fluorescent coding microspheres and the preparation method of the quantum dot fluorescent coding microspheres have the same advantages compared with the prior art, and are not repeated herein.
Drawings
FIG. 1 is a flow chart of a method for preparing quantum dot fluorescent encoding microspheres according to an embodiment of the present invention;
fig. 2(a) is an oil-soluble monomer/crosslinker micelle in which red quantum dots are dissolved in example 1 of the present invention, fig. 2(b) is an oil-soluble monomer/crosslinker micelle in which red quantum dots and green quantum dots are dissolved, and fig. 2(c) is a carboxylated quantum dot fluorescent microsphere;
FIG. 3 is a fluorescence spectrum of different quantum dot fluorescence-encoded microspheres in example 3 of the present invention.
Detailed Description
Generally, quantum dots with different particle sizes have different colors, the light emitting color can be changed by changing the size of the quantum dot crystal, and the quantum dots with different particle sizes can emit light with different wavelengths when excited by laser. Compared with the traditional fluorescent dye, the excitation wavelength range of the excited quantum dots is wide and is continuously distributed, so that the quantum dots with different particle sizes can be excited by adopting light with the same wavelength. Because the fluorescence spectrum peak emitted by the excited quantum dots is narrow, the emission spectra do not overlap.
In fluorescent coding, in order to obtain a larger number of codes, one typically uses luminescent materials of multiple colors for coding. Taking two-dimensional coding as an example, red and green two-color quantum dots are embedded in the microsphere. The red light in the visible light has the longest emission wavelength, the green light is the second, and the absorption spectrum of the red quantum dots is wider than that of the green quantum dots, so the red quantum dots can absorb the green light emitted by the green quantum dots. Although the quantum dots have the advantages of wider excitation wavelength range, narrower emission peak and the like, because red and green quantum dots are randomly arranged in the microsphere, light emitted by the green quantum dots embedded in the microsphere can be absorbed by the red quantum dots close to the outside to emit red fluorescence, so that the self-absorption phenomenon among the quantum dots is caused. In addition, because the red and green quantum dots in the microsphere are not uniformly distributed, the fluorescent signals emitted by each sphere may be different, and the sensitivity and the repeatability in use are also reduced.
In order to solve the problems, the invention provides a quantum dot fluorescence coding microsphere and a preparation method thereof, wherein quantum dots with various colors are embedded in the microsphere so as to realize multidimensional coding. The method comprises the steps of respectively dissolving quantum dots with different colors in an oil-soluble monomer to obtain a plurality of oil phase mixtures, respectively dissolving quantum dots with different colors in the plurality of oil phase mixtures, and sequentially emulsifying according to the wavelength of the quantum dots from long to short to obtain the micelle with the plurality of layers of quantum dots, wherein the quantum dot with the longest wavelength is positioned in the inner layer of the micelle, the quantum dot with the shortest wavelength is positioned in the outer layer of the micelle, namely from the inner layer of the micelle to the outer layer of the micelle, and the wavelength of the quantum dot is gradually shortened. And finally, adding a functional monomer by initiation to obtain the quantum dot fluorescent coding microsphere. According to the invention, through a multiple emulsification mode, quantum dots with different wavelengths in the quantum dot bundle are arranged in a sequence that the wavelengths from the inner layer to the outer layer are shortened, compared with the random distribution of quantum dots with various colors in the microsphere, the self-absorption among the quantum dots is reduced to the greatest extent, and the purpose that the emission wavelength of each microsphere is more uniform and controllable can be achieved.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a quantum dot fluorescent coding microsphere, including:
s1, respectively dissolving N quantum dots with different colors in a mixed solution formed by an oil-soluble monomer and a cross-linking agent to obtain N oil phase mixtures, wherein N is more than or equal to 2;
s2, sequentially dispersing the N oil phase mixtures into the same emulsifier solution according to the sequence that the wavelength of the quantum dots dissolved in the oil phase mixtures is from long to short to form quantum dot micelles;
s3, adding the quantum dot micelle and an initiator into water, and carrying out polymerization reaction under the protection of nitrogen to obtain quantum dot seed microspheres;
and S4, adding a functional monomer into the polymerization reaction system to perform grafting reaction, and after the reaction is finished, performing purification treatment to obtain the quantum dot fluorescent coding microspheres.
It should be noted that although the steps in the preparation are described in the forms of S1, S2, S3, S4, etc., this description is only for convenience of understanding, and the forms of S1, S2, S3, S4, etc. do not represent any limitation on the order of the steps.
Wherein the quantum dot is oil soluble quantum dot selected from CdS, CdSe, CdTe, CdP, ZnS, ZnSe, ZnTe, InP, InAs, and CuInS2、AgInS2The quantum dots or the derived alloyed quantum dots composed of the related materials or the alloyed quantum dots composed of the materials and having a core-shell structure.
The oil-soluble monomer comprises one of styrene, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, lauryl acrylate, lauryl methacrylate, isobornyl acrylate and isobornyl methacrylate;
the crosslinking agent includes at least one of ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1, 3-propanediol diacrylate, 1, 3-propanediol dimethacrylate, 1, 3-butanediol diacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, isopentyl tetraacrylate, and isopentyl tetramethacrylate.
In S1, oil-soluble monomers and a cross-linking agent are mixed to form a mixed solution, then oil-soluble quantum dots with two or more colors are respectively dissolved in the mixed solution, and the oil-soluble quantum dots and lipophilic groups in the mixed solution are combined based on a similar compatibility principle to form quantum dot oil-soluble monomer micelles, namely an oil phase mixture. For convenience of description, in this embodiment, quantum dots of two colors of red and green are taken as an example, the red quantum dots are dissolved in the mixed solution to obtain a red oil phase mixture, and the green quantum dots are dissolved in the mixed solution to obtain a green oil phase mixture.
In the embodiment, the cross-linking agent is introduced in the process of forming the quantum dot oil-soluble monomer micelle, the cross-linking agent is preferably an acrylate ester-containing or methacrylate ester-containing cross-linking agent, the cross-linking agent forms a multi-element network structure in the subsequent polymerization process, the quantum dots can be limited in the microspheres, and compared with the quantum dot fluorescent microspheres prepared based on a swelling method in the prior art, the quantum dots are not easy to leak out from the interior of the microspheres, so that the light intensity stability is improved.
In addition, because the oil-soluble monomer such as styrene has stronger hydrophobicity, the hydrophilicity of the introduced cross-linking agent is greater than that of the oil-soluble monomer, so that in the subsequent polymerization reaction with the initiator, the hydrophilic groups in the cross-linking agent gradually migrate to the surface of the microsphere to form a hydrophilic surface on the surface of the microsphere, thereby reducing the non-specific adsorption of the microsphere.
In the subsequent polymerization reaction, the initiator is decomposed to generate free radicals with strong oxidizing property, if the dosage of the cross-linking agent is too high, the reaction rate is obviously improved, and the phenomenon of implosion is possible to occur, so that the free radicals entering the quantum dot micelle in the instantaneous time are too much, the probability that the free radicals act on the surface of the quantum dot is higher, the free radicals can oxidize the surface of the quantum dot, the defect is generated, and the fluorescence efficiency is reduced. Therefore, in order to avoid the generation of defects on the surface structure of the quantum dots caused by the excessive amount of the cross-linking agent, in this example, the mass ratio of the oil-soluble monomer to the cross-linking agent in the mixed solution is (1-10):20, and the mass concentration of the quantum dots dissolved in each oil phase mixture is 5% -50%.
Referring to fig. 2, in S2, sequentially dispersing N oil phase mixtures in the same emulsifier solution to form quantum dot micelles, specifically including:
dissolving an emulsifier in water to form emulsion micelles, adding the oil phase mixture in which the first color quantum dots are dissolved in the N oil phase mixtures into the emulsion micelles, and performing ultrasonic dispersion or high-speed homogenization to form first quantum dot micelles;
adding an oil phase mixture in which second color quantum dots are dissolved in the N oil phase mixtures into the first quantum dot micelles, and forming second quantum dot micelles with the outer layers being the second color quantum dots and the inner layers being the first color quantum dots through ultrasonic dispersion or high-speed homogenization, wherein the wavelength of the first color quantum dots is larger than that of the second color quantum dots;
adding an oil phase mixture in which third color quantum dots are dissolved in the N oil phase mixtures into the second quantum dot micelles, and forming the third quantum dot micelles with the outer layers being the third color quantum dots, the middle layers being the second color quantum dots and the inner layers being the first color quantum dots through ultrasonic dispersion or high-speed homogenization, wherein the wavelength of the second color quantum dots is greater than that of the third color quantum dots;
and dispersing the oil phase mixtures in the emulsifier solution in sequence according to the sequence that the wavelength of the oil-soluble quantum dots dissolved in the N oil phase mixtures is from long to short until the N oil phase mixtures are completely dissolved in the emulsifier solution to obtain the quantum dot micelle.
It should be understood that different colors of light emit at different wavelengths, and thus the wavelength of light represents the color, and in visible light, red light has the longest wavelength, green light has the next shortest wavelength, and blue light has the shortest wavelength. Since the quantum dots with longer emission wavelengths have a wider absorption spectrum than the quantum dots with shorter emission wavelengths, and the shorter the wavelength of light, the higher the photon energy, and the easier it is to be absorbed to excite electrons, the quantum dots with longer emission wavelengths can absorb the light emitted from the quantum dots with shorter emission wavelengths.
By taking quantum dots with two colors of red and green as an example, the emission wavelength of the red quantum dots is greater than that of the green quantum dots, and the red quantum dots can absorb light emitted by the green quantum dots. If the red and green two-color quantum dots are directly mixed and re-emulsified to prepare the quantum dot fluorescent coding microsphere, when the microsphere is used, because the red and green two-color quantum dots are randomly distributed in the microsphere, light emitted by the green quantum dots embedded in the microsphere can be absorbed by the red quantum dots close to the outside, and thus red fluorescence is emitted.
In this embodiment, the emulsification is performed in the order of the emission wavelengths of the quantum dots from long to short, and in the obtained quantum dot bundle, the quantum dots with shorter emission wavelengths are located at the outermost layer of the micelle, and the quantum dots with longer emission wavelengths are located at the innermost layer of the micelle. Thus, the self-absorption phenomenon among the quantum dots is reduced. In addition, the arrangement mode of the quantum dots also enables the emission wavelength of each microsphere to be more uniform and controllable.
The method comprises the steps of taking red and green quantum dots as an example to illustrate the formation mechanism of quantum dot micelles, dissolving the red quantum dots in a mixed solution formed by an oil-soluble monomer and a cross-linking agent to obtain a red oil phase mixture, adding the red oil phase mixture into an emulsifier solution, and forming a red quantum dot micelle solution through ultrasonic dispersion or high-speed homogenization.
In this embodiment, the emulsifier includes at least one of polyacrylic acid, sodium oleate, sodium dodecyl sulfate, polyethylene glycols, polyvinyl alcohols, and polyvinyl pyrrolidones, and preferably, a mixture of a plurality of the foregoing emulsifiers. The main reason is that each emulsifier has a specific hydrophilic-lipophilic balance value (HLB value), and a single emulsifier is often difficult to satisfy the emulsification requirements of a system composed of multiple components, so that a plurality of emulsifiers with different HLB values are usually mixed to form a mixed emulsifier, which can satisfy the requirements of a complex system and greatly enhance the emulsification effect.
Preferably, in order to ensure the emulsifying effect of the emulsifier and form stable micelles more quickly, the mass concentration of the emulsifier in the first color quantum dot micelles is 0.2-25%.
Referring to fig. 2, in S3, the quantum dot micelle containing multiple layers of quantum dots with different colors prepared in S2 and an initiator are added into water, and polymerization is performed under the protection of nitrogen to obtain the quantum dot seed microsphere. The quantum dot micelle has large specific surface area and can adsorb initiator molecules, when the temperature condition is reached, the initiator is decomposed to generate free radicals, and the free radicals initiate oil-soluble monomers to generate chain polymerization reaction. In the polymerization process, molecules continuously and freely move, ethoxy in a cross-linking agent is in contact with water in a reaction system at a certain probability in the movement process, so that a hydrogen bond is formed, the molecules are difficult to move into an oil phase after the hydrogen bond is formed, a hydrophilic ethoxy surface is formed, finally, the whole quantum dot micelle is slowly polymerized and solidified into the quantum dot seed microsphere with the ethoxy on the surface under the action of interfacial tension, and the ethoxy on the surface of the quantum dot seed microsphere is ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, pentaerythritol and the like according to different selected cross-linking agents.
The time of the polymerization reaction has a correlation with the reaction conversion rate of the polymerization reaction, and experimental studies of the inventors find that when the reaction conversion rate of the polymerization reaction is greater than or equal to 95% and the reaction time is less than the half-life of the initiator, the yield and the performance of the finally prepared quantum dot microspheres are the best. Preferably, the mass ratio of the initiator to the quantum dot micelle is (0.1-1):100, the polymerization time is 2h-16h, and the reaction temperature is 60-80 ℃. Therefore, an ethoxy surface with enough thickness can be formed on the surface of the microsphere, and the surface of the microsphere still adsorbs a sufficient amount of initiator capable of initiating subsequent functional monomers, so that the phenomenon that the ethoxy surface is not thick enough due to too short polymerization reaction time is avoided, further, the finally obtained microsphere still has strong nonspecific adsorption, and the phenomenon that the initiator is almost consumed due to too long polymerization reaction time is avoided, the functional monomers cannot be initiated to polymerize when the functional monomers are subsequently added, so that the prepared quantum dot fluorescence coding microsphere surface almost has no functional groups, the subsequent coupling antibody cannot be applied, and if the initiator is subsequently added, water phase nucleation inevitably results, and the functional groups are not uniformly distributed on the surface of the microsphere. Therefore, the mass ratio of the initiator to the quantum dot micelle and the polymerization conditions in this embodiment are set, so that the thickness of the ethoxy surface on the surface of the microsphere is sufficient, and a sufficient amount of initiator for initiating the polymerization of the functional monomer is still adsorbed on the surface of the quantum dot seed microsphere, thereby finally obtaining the quantum dot fluorescence encoding microsphere, wherein a sufficient amount of functional groups are uniformly distributed on the surface of the quantum dot fluorescence encoding microsphere for coupling in later application.
The initiator includes at least one of potassium persulfate, ammonium persulfate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, and azobisisopropylimidazoline, and the initiator is not particularly limited in this embodiment.
And S4, adding a functional monomer into the polymerization reaction system, carrying out grafting reaction on the quantum dot seed microspheres and the functional monomer, and carrying out purification treatment after the reaction is finished to obtain the quantum dot fluorescent coding microspheres.
In this example, when the reaction conversion rate of the grafting reaction is greater than or equal to 95%, the reaction is stopped and the purification treatment is performed. Therefore, the problems that the reaction time is too short, the quantity of grafted functional groups is too small, and the colloid stability of the microspheres and the stability and efficiency of later-stage labeled molecules are influenced can be avoided.
The functional monomer is a carboxyl monomer or a functional monomer containing click chemistry derived groups, which is convenient for coupling various biomolecules in later stage, and the functional monomer containing the click chemistry derived groups is a monomer containing epoxy groups, azido groups or aldehyde groups. Wherein the carboxyl monomer comprises at least one of acrylic acid, methacrylic acid, polyacrylic acid, polymethacrylic acid, itaconic acid and maleic acid. The monomer containing epoxy group, azido group or aldehyde group comprises at least one of glycidyl methacrylate, allyl glycidyl ether, epoxy polyethylene glycol acrylate, epoxy polyethylene glycol methacrylate, azido polyethylene glycol acrylate, azido polyethylene glycol methacrylate, aldehyde polyethylene glycol acrylate, aldehyde polyethylene glycol methacrylate, 4 '-diazide stilbene-2, 2' -disulfonic acid disodium tetrahydrate, acrolein, trans-2-pentenal, 3- (2-furyl) acrolein, 3-dimethylamino acrolein, 2-methylacrolein and cinnamaldehyde.
In addition, because the emulsifier exists on the surface of the prepared quantum dot fluorescent coding microsphere, the emulsifier can be cleaned and taken away by water or other substances capable of dissolving the emulsifier, so that the prepared quantum dot fluorescent coding microsphere can be centrifugally washed and purified after the reaction is finished, and is stored at normal temperature after being concentrated for obtaining the fluorescent coding microsphere with higher quality. The following purification description is given by taking 10mL of quantum dot fluorescent coding microsphere stock solution as an example:
placing the quantum dot fluorescent coding microspheres in a 10mL centrifuge tube, centrifuging at 10000rpm for 10min, then removing supernatant, ultrasonically redissolving with deionized water, repeating for 3 times, wherein the use amount of the redissolved deionized water is gradually reduced, the concentration of the obtained quantum dot fluorescent coding microspheres is gradually increased, and finally the concentrated quantum dot fluorescent coding microspheres are obtained.
In the prior art, quantum dots are stabilized on the surface of microspheres in a covalent bonding mode, and since the nano material is easy to cause nonspecific adsorption on the surface of the microspheres, the surface of the microspheres needs to be coated with polymers or silicon dioxide to reduce the nonspecific adsorption, but obvious fluorescence quenching is caused, thereby reducing the sensitivity of the quantum dot fluorescent coding microsphere, compared with the prior art, the preparation method of the quantum dot fluorescent coding microsphere provided by the embodiment, by introducing the cross-linking agent and utilizing the characteristic that hydrophilic groups of the cross-linking agent migrate to the surface of the microsphere and form hydrogen bonds with water, an ethoxy hydration layer is formed on the surface of the microsphere, so that the surface of the finally prepared quantum dot fluorescence coding microsphere only comprises an ethoxy chain segment and a functional group in a cross-linking agent and hardly has a hydrophobic group, and the quantum dot fluorescence coding microsphere has extremely low non-specific adsorption performance.
In addition, when a plurality of quantum dots with different colors are embedded in the microsphere to obtain a greater variety of encoding microspheres, the oil phase mixture in which the quantum dots with different colors are dissolved is sequentially emulsified according to the sequence of emission wavelengths of the quantum dots from long to short to obtain quantum dot micelles with orderly distributed quantum dots, so that the self-absorption phenomenon among the quantum dots is reduced, the emission wavelength of each microsphere is more uniform, and the sensitivity and the repeatability of the quantum dot fluorescent encoding microsphere during use are improved.
The embodiment of the invention also provides a quantum dot fluorescent microsphere which is prepared according to the preparation method of the quantum dot fluorescent microsphere and comprises a microsphere body and a plurality of layers of oil-soluble quantum dots wrapped inside the microsphere body, wherein the oil-soluble quantum dots are distributed in the microsphere body from inside to outside according to the sequence of the wavelength from long to short, a hydration layer comprising an ethoxy chain segment and a functional group connected to the surface of the hydration layer are modified on the surface of the microsphere body, and the functional group comprises at least one of carboxyl, epoxy, azido and aldehyde.
The embodiment of the invention also provides the application of the quantum dot fluorescent microspheres, and the quantum dot fluorescent coding microspheres are mainly applied to the fields of biological labeling, biological separation and/or in-vitro diagnosis. Taking the application of the red and green two-color coded microspheres in the flow detection technology as an example, one microsphere can pass through a detector, the mass ratio of red and green two-color quantum dots in each microsphere is different, the fluorescent coded microspheres can be prepared in principle when the difference between the emission wavelengths of the two quantum dots is 40nm, and the effective coding can be performed when the mass ratio of the red and green two-color quantum dots is 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1 and 10:0, taking the red (Em ═ 625nm) and green (Em ═ 525nm) as an example. For convenience of explanation, it is assumed that the mass ratio of the two-color red and green quantum dots of the encoded microsphere a1 is 1:2, the mass ratio of the two-color red and green quantum dots of the encoded microsphere a2 is 2:1, the x axis represents the red fluorescence intensity, the y axis represents the green fluorescence intensity, and the flow detection results show that the encoded microsphere a1 appears at the position of the coordinate system (x, y) of (1,2), the encoded microsphere a2 appears at the position of the coordinate system (x, y) of (2,1), and so on.
The invention will be further illustrated with reference to the following specific examples. The quantum dots selected in the following embodiment of the invention are ZnCdSe/ZnS quantum dots, the oil-soluble monomer is styrene, the (methyl) acrylic alcohol ester cross-linking agent is ethylene glycol diacrylate, the functional monomer is polyacrylic acid, the emulsifying agent is sodium dodecyl sulfate, and the initiating agent is potassium peroxodisulfate.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method of quantum dot fluorescent microspheres, which comprises the following specific steps:
1) styrene and ethylene glycol diacrylate were mixed as 5: mixing at a mass ratio of 20 to form a mixed solution, respectively dissolving ZnCdSe/ZnS quantum dots with emission wavelengths of 625nm and 525nm in the mixed solution to prepare a red quantum dot-styrene/ethylene glycol diacrylate solution (namely a red oil phase mixture) with a quantum dot mass concentration of 20% and a green quantum dot-styrene/ethylene glycol diacrylate solution (namely a green oil phase mixture) with a quantum dot mass concentration of 20%;
2) weighing 0.2g of sodium dodecyl sulfate, dissolving the sodium dodecyl sulfate in 100mL of water to form emulsion micelles, adding 4mL of 20% red quantum dot-styrene/ethylene glycol diacrylate solution, namely preparing the emulsifier with the mass concentration of 0.2%, and stirring the mixture at 20 ℃ for 10min to ensure that the red oil phase mixture is uniformly dispersed in the emulsion micelles to form the red quantum dot micelles (as shown in figure 2 (a));
adding 20% of green quantum dot-styrene/ethylene glycol diacrylate solution into the red quantum dot micelle solution, stirring at 20 deg.C for 10min to form micelle with green quantum dot in the outer layer and red quantum dot in the inner layer (as shown in FIG. 2 (b));
3) adding 5mL of styrene and 50mL of 1mg/mL potassium peroxodisulfate aqueous solution into the red and green quantum dot adhesive bundles, uniformly stirring, introducing nitrogen for 30min, removing oxygen in the system, heating to 70 ℃ to perform polymer reaction for 14h, adding 10mL of 0.1g/mL polyacrylic acid, continuing the reaction for 4h, and finally performing centrifugal purification on the product to obtain the carboxylated quantum dot fluorescent coding microspheres (as shown in FIG. 2 (c)).
Example 2
This example differs from example 1 in that:
1) and the mass ratio of the styrene to the ethylene glycol diacrylate in the mixed solution is 1: 20, the mass concentration of the quantum dots in the prepared oil phase mixture is 5 percent;
2) the mass concentration of the emulsifier is 0.2 percent, and the emulsifier is stirred for 20min at the temperature of 0 ℃;
3) the temperature in the polymerization reaction is 60 ℃, and the reaction time is 16 h.
The remaining steps and parameters were the same as in example 1.
Example 3
This example differs from example 1 in that:
1) the mass ratio of styrene to ethylene glycol diacrylate in the mixed solution is 10: 20, the mass concentration of the quantum dots in the prepared oil phase mixture is 50 percent;
2) stirring the emulsifier with the mass concentration of 25% for 2min at 40 ℃;
3) the temperature in the polymerization reaction is 80 ℃, and the reaction time is 2 hours.
The remaining steps and parameters were the same as in example 1.
Example 4
This example differs from example 1 in that:
1) the mass ratio of styrene to ethylene glycol diacrylate in the mixed solution is 10: 20, the mass concentration of the quantum dots in the prepared oil phase mixture is 40 percent;
2) adding oil phase mixtures with different volumes according to the mass concentration of the quantum dots in the oil phase mixtures, wherein the mass ratio of the red and green quantum dots in the quantum dot fluorescent coding microspheres is 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1 and 10: 0; wherein the mass concentration of the emulsifier is 2%, and the emulsifier is stirred for 20min at 40 ℃;
3) the temperature in the polymerization reaction is 80 ℃, and the reaction time is 2 hours.
The other steps and parameters are the same as those in example 1, so that 11 kinds of quantum dot fluorescent coding microspheres are prepared respectively. When the mass ratio of the red and green two-color quantum dots is 0:10, only the green quantum dots are in the coded microspheres, and when the mass ratio of the red and green two-color quantum dots is 10:0, only the red quantum dots are in the coded microspheres. The 11 kinds of coded microspheres have the same steps and parameters except that the mass ratio of red and green quantum dots is different.
The prepared 11 kinds of coded microspheres were subjected to fluorescence test, and the fluorescence spectrum is shown in fig. 3. As can be seen from fig. 3, when laser excitation with the same wavelength is adopted, the microspheres emit red fluorescence and green fluorescence, the intensities of the red fluorescence and the green fluorescence are different, the two colors of red fluorescence and green fluorescence are easy to distinguish, and the corresponding emission spectra of the microspheres with different quantum dot contents of the red and green fluorescence are obviously different, which indicates that the microspheres prepared by the embodiment can not only realize spectrum coding of the red and green fluorescence, but also realize multi-dimensional coding of the red and green fluorescence with different mass/concentration ratios. This is mainly related to the method of twice emulsification adopted in the present embodiment when preparing the encoded microsphere, so that the green quantum dots inside the prepared microsphere are located on the outer layer of the red quantum dots, and the self-absorption between the quantum dots is reduced to the greatest extent. By adjusting the mass/concentration ratio of quantum dots of different colors in the microspheres, more multidimensional coding can be realized.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. A preparation method of quantum dot fluorescent coding microspheres is characterized by comprising the following steps:
respectively dissolving N quantum dots with different colors in a mixed solution formed by an oil-soluble monomer and a cross-linking agent to obtain N oil phase mixtures, wherein N is more than or equal to 2;
sequentially dispersing N kinds of the oil phase mixtures in the same emulsifier solution according to the sequence that the wavelength of the quantum dots dissolved in the oil phase mixtures is from long to short to form quantum dot micelles;
adding the quantum dot micelle and an initiator into water, and carrying out polymerization reaction under the protection of nitrogen to obtain quantum dot seed microspheres;
and adding a functional monomer into a polymerization reaction system, carrying out grafting reaction on the quantum dot seed microspheres and the functional monomer, and carrying out purification treatment after the reaction is finished to obtain the quantum dot fluorescent coding microspheres.
2. The method for preparing the quantum dot fluorescent coding microsphere according to claim 1, wherein the cross-linking agent is an acrylate-containing alcohol ester or methacrylate-containing alcohol ester cross-linking agent.
3. The method for preparing quantum dot fluorescent coding microspheres according to claim 1 or 2, wherein the step of dispersing the N kinds of oil phase mixtures in an emulsifier solution in sequence from long to short wavelengths of the quantum dots dissolved therein to form quantum dot micelles comprises the steps of:
dissolving an emulsifier in water to form emulsion micelles, adding the oil phase mixture in which the first color quantum dots are dissolved in the N oil phase mixtures into the emulsion micelles, and performing ultrasonic dispersion or high-speed homogenization to form first quantum dot micelles;
adding an oil phase mixture in which second color quantum dots are dissolved in N kinds of the oil phase mixtures into the first quantum dot micelles, and forming second quantum dot micelles with the outer layers being the second color quantum dots and the inner layers being the first color quantum dots through ultrasonic dispersion or high-speed homogenization, wherein the wavelength of the first color quantum dots is larger than that of the second color quantum dots;
and sequentially emulsifying the quantum dots dissolved in the oil phase mixture from long to short in wavelength until the N oil phase mixtures are completely dissolved in the emulsion micelle to obtain the quantum dot micelle.
4. The method for preparing the quantum dot fluorescent coding microspheres according to claim 3, wherein the mass concentration of the emulsifier in the quantum dot micelle is 0.2-25%.
5. The method for preparing quantum dot fluorescence-encoded microspheres according to claim 1 or 2, wherein the oil-soluble monomer comprises one of styrene, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, lauryl acrylate, lauryl methacrylate, isobornyl acrylate and isobornyl methacrylate.
6. The method for preparing the quantum dot fluorescent coding microsphere according to claim 1 or 2, wherein the functional monomer comprises one of a carboxyl monomer and a monomer containing a click chemistry derivative group, and the click chemistry derivative group is an epoxy group, an azido group or an aldehyde group.
7. The preparation method of the quantum dot fluorescent coding microsphere as claimed in claim 1 or 2, wherein the mass ratio of the oil-soluble monomer to the cross-linking agent in the mixed solution is (1-10): 20.
8. The preparation method of the quantum dot fluorescent coding microsphere according to claim 1 or 2, wherein the mass concentration of the quantum dots in the oil phase mixture is 5-50%.
9. The quantum dot fluorescence coding microsphere is characterized by comprising a microsphere body and a plurality of layers of oil-soluble quantum dots wrapped inside the microsphere body, wherein the oil-soluble quantum dots are distributed in the microsphere body from inside to outside according to the sequence of wavelength from long to short, and the surface of the microsphere body is modified with a hydration layer comprising an ethoxy chain segment and a functional group connected to the surface of the hydration layer.
10. Use of the quantum dot fluorescence-encoded microsphere according to claim 9 or the quantum dot fluorescence-encoded microsphere prepared by the method according to any one of claims 1 to 8, wherein the quantum dot fluorescence-encoded microsphere is applied to the fields of biological labeling, biological separation and/or in vitro diagnosis.
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