CN107603591B - A kind of fluorescence microcapsules and preparation method thereof - Google Patents
A kind of fluorescence microcapsules and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of fluorescence microcapsules and preparation method thereof, fluorescence microcapsules of the invention are using polyelectrolyte and graphene quantum dot as cyst material.It is prepared by the layer upon layer electrostatic self-assembly method of cationic polyelectrolyte and electronegative graphene quantum dot.Fluorescent emission properties and good biocompatibility based on graphene quantum dot, the present invention can obtain preparation methods simply, fluorescence radiation stability is good, good biocompatibility fluorescence microcapsules.It solves and needs to carry out cyst material the technical issues of complicated fluorescence derivation can just make it have photoluminescent property in the prior art.
Description
Technical field
The present invention relates to function micro-nano material fields, and in particular to a kind of fluorescence microcapsules and preparation method thereof.
Background technique
Alternating layers (LBL) assembling is carried out on colloid template from scientist in 2000 and removes colloid core obtaining microcapsules
Afterwards, microcapsules have become the material studied extensively over more than 20 years.In recent years, the research of functional microcapsule is very active, science
Family prepared the microcapsules of the primitive containing multiple functions, such as (SiO containing nanoparticle2Nanoparticle, magnetic nano particle
Son, gold nanoparticle, Nano silver grain, carbon nanotube, polymer (dendritic, coordination polymer, pH response polymerization
Object, redox polymers), the functional microcapsule of Prussian blue and large biological molecule (DNA, polypeptide, protein).
In general, microencapsulated forms and size can accurately be controlled by template；Cyst wall composition can be determined by assembled material, thick
Degree can be regulated and controled by changing the deposition number of plies and assembling condition.Therefore, change cyst material, introduce the functionality of novel materials
Microcapsules have potential application prospect in fields such as bioanalysis.
In the research of microcapsules, fluorescent marker is important research method.It, can be with after carrying out fluorescent marker to cyst material
Observe effect microcapsule wall assembling process and change procedure.But complicated approach is generallyd use in the prior art, by organic fluorescence molecule
On marked by fluorescein isothiocyanate to cyst material, but this kind of organic fluorescence molecule is not soluble in water, and label reaction needs organic
Solvent is medium, and method is complicated, stability of photoluminescence is poor, poor biocompatibility.
Graphene quantum dot (Graphene quantum dot) is the nano material of quasi-zero dimension, and internal electron is in each side
Upward movement is all limited to, so quantum confinement effect is particularly significant, has many unique properties, such as stable fluorescence
Transmitting.In addition, its carbon material substrate makes it have excellent biocompatibility.In addition, graphene-structured, which is used as, has a scale
The nanoparticle of degree can simply regard the macromolecular substances of similar polycyclic compound as.So far, it there is no graphene quantum
Point is reported as the research for preparing microcapsule capsule wall material.
Summary of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of fluorescence microcapsules and preparation method thereof, with polyelectrolyte and
Graphene quantum dot is cyst material, and cyst wall is not required to other derivatization and has fluorescent characteristic.The fluorescence microcapsules pass through sun
Cationic polyelectrolyte and electronegative graphene quantum dot are prepared by layer upon layer electrostatic construction from part.
The specific technical solution that the present invention uses is as follows:
A kind of preparation method of fluorescence microcapsules, comprising:
Spherical nuclei even particulate dispersion is assembled in cationic polyelectrolyte solution, centrifuge washing, first layer group
It installs into；Then the fine-particle powder for being assembled with a strata electrolyte is dispersed in electronegative graphene quantum dot solution and is carried out
Assembling, centrifuge washing are so double-deck assembling；It repeats above operation, the composite particles of the different assembling numbers of plies is made；Into
To get the fluorescence microcapsules after one step removal nuclear material.
The present invention selects the graphene quantum dot with negative electrical charge, by it by the preparation condition of control graphene amount point
LBL self-assembly is carried out with cationic polyelectrolyte, prepares microcapsules.Gained microcapsules overcome problems of the prior art,
With stable photoluminescent property and good biocompatibility.
Preferably, the spherical nuclear particle is carbonic acid calcisphere or polystyrene spheres, and partial size is 0.5~20 μm, both
Nuclear material is that current polyelectrolyte multiplayer microcapsule prepares most common nuclear material, and there is simple preparation method, spherical structure, removal to hold
The characteristics of carbon dots that are easy to get.
Preferably, the cationic polyelectrolyte is chitosan, polyallylamine hydrochlorides, diallyl dimethyl chlorine
Change one of ammonium, straight chain or dendroid polyethyleneimine, during the preparation process, the concentration of cationic polyelectrolyte solution is
0.1~5.0mg/ml.
Preferably, the electronegative graphene quantum dot is to be synthesized by existing technology from bottom to top or from top to bottom
Zeta under the conditions of assembling pH be negative value graphene quantum dot.By controlling the preparation condition of graphene amount point, selection tool
There is the graphene quantum dot of negative electrical charge, such as in the prior art, using carbon black as carbon source, the graphene that is obtained after nitric acid oxidation is cut
Quantum dot, surface has a large amount of carboxylic groups, and under conditions of pH > 2, a large amount of electronegative groups of lotus show elecrtonegativity, zeta electricity
Position is negative value；With 1,3,6- trinitro- pyrene for carbon source, the graphene quantum dot synthesized in sodium hydroxide medium, surface is contained greatly
Hydroxyl group is measured, under conditions of pH > 2, a large amount of electronegative groups of lotus show elecrtonegativity, and zeta current potential is negative value.It was preparing
Cheng Zhong, the concentration of electronegative graphene quantum dot solution are 0.1~5.0mg/ml.
Preferably, above-mentioned preparation process carries out at 10~40 DEG C, and each built-up time is 10~30min.
Preferably, in above-mentioned preparation process, centrifuge washing, which refers to, is centrifuged off supernatant, is washed with water/is centrifuged particle 2~5
It is secondary.
Preferably, the method for removing nuclear material is selected according to spherical nuclear particle, with dissolving with hydrochloric acid or ethylenediamine tetrem
The coordination of acid disodium salt and calcium ion removes carbonic acid calcisphere；Removal polystyrene spheres are dissolved with chloroform.
The present invention also provides a kind of fluorescence microcapsules being prepared according to the above method, with polyelectrolyte and graphene
Quantum dot is cyst material, and cyst wall is not required to other derivatization and has fluorescent characteristic.Due to the graphene amount in effect microcapsule wall
Son point is fluorescent material, and when being excited by light, microcapsules have fluorescent characteristic.
Preferably, under 488nm excitation, the fluorescence microcapsules have bright green fluorescence.
Compared with prior art, the beneficial effects of the present invention are:
(1) fluorescence microcapsules of the invention are using polyelectrolyte and graphene quantum dot as cyst material.It is poly- by cation
The preparation of the layer upon layer electrostatic self-assembly method of electrolyte and electronegative graphene quantum dot.
(2) fluorescent emission properties based on graphene quantum dot and good biocompatibility, the present invention can obtain systems
Preparation Method is simple, fluorescence radiation stability is good, good biocompatibility fluorescence microcapsules.It solves and is needed in the prior art to capsule
Wall material carries out the technical issues of complicated fluorescence derivation can just make it have photoluminescent property.
Detailed description of the invention
Fig. 1 is the zeta potential diagram of graphene quantum dot in embodiment 1；
Fig. 2 is Laser Scanning Confocal Microscope photo of the microcapsules under 488nm excitation in embodiment 1；
Fig. 3 is Laser Scanning Confocal Microscope photo of the microcapsules under 488nm excitation in embodiment 2.
Specific embodiment
The invention will be further described with attached drawing combined with specific embodiments below.
Embodiment 1
1, the preparation of fluorescence microcapsules
In the present embodiment, spherical nuclear particle is the electronegative spherical calcium carbonate core that partial size is 4 μm, cationic polyelectrolyte
For diallyl dimethyl ammoniumchloride (PDDA), electronegative graphene quantum dot (GQDs) by the prior art from it is lower and
Upper method synthesis, with 1,3,6 trinitro- pyrene for carbon source, sodium hydroxide is that reaction medium is prepared (referring to Nature
Communication,2014,5,5357)。
The layer upon layer electrostatic self assembling process of PDDA and electronegative GQDs on nuclear material are as follows: at 25 DEG C, by 10mg
The spherical calcium carbonate core that diameter is 4 μm is dispersed in the positively charged PDDA solution that 10mL concentration is 1.0mg/ml and carries out group
Dress, built-up time 30min are centrifuged off supernatant, are washed with water/are centrifuged particle 2 times, first layer is completed；Then will
The fine-particle powder for being assembled with one layer of PDDA, which is dispersed in the electronegative GQDs solution that 10mL concentration is 1.0mg/ml, to be assembled,
Built-up time is 30min, is centrifuged off supernatant, is washed with water/is centrifuged particle 2 times, is so double-deck assembling；It repeats
The above operation, after being assembled into 2 bilayers, is collected by centrifugation composite particles and is washed with water 2 times.
By composite particles be distributed to 10mL concentration be 0.02mol/l disodium EDTA solution in, by with
The coordination of calcium ion further removes spherical calcium carbonate core, is centrifuged off supernatant, is washed with water/is centrifuged 2 times, to completely remove
Spherical calcium carbonate core to get arrive fluorescence microcapsules.
2, it characterizes
The test of zeta current potential is carried out to graphene quantum dot in embodiment 1, as a result as shown in Figure 1；To fluorescence microcapsules
Laser Scanning Confocal Microscope analysis is carried out, as a result as shown in Figure 2.
The present embodiment graphene quantum dot is synthesized by Self-absorption Correction Factor in the prior art, is with 1,3,6 trinitro- pyrene
Carbon source, sodium hydroxide are reaction medium, and the graphene quantum dot of great amount of hydroxy group group is contained on available surface.Fig. 1 can be seen
Out, under conditions of pH > 2, a large amount of electronegative groups of graphene quantum dot lotus, zeta current potential is negative value, shows elecrtonegativity.
Fig. 2 is the Laser Scanning Confocal Microscope photo of the fluorescence microcapsules that prepare under 488nm excitation in embodiment 1.From figure
This it appears that having significant microcapsule structure, under 488nm excitation, microcapsules have bright green fluorescence.
Embodiment 2
1, the preparation of fluorescence microcapsules
In the present embodiment, spherical nuclear particle is the electronegative polystyrene spheres that partial size is 2 μm, and cationic polyelectrolyte is
Dendroid polyethyleneimine (PEI), electronegative graphene quantum dot (GQDs) are closed by top-down methods in the prior art
At, using carbon black as carbon source, be prepared through the cutting of hot nitric acid (referring to Journal of Materials Chemistry, 2012,
22,8764)。
The layer upon layer electrostatic self assembling process of PEI and electronegative GQDs on nuclear material are as follows: at 25 DEG C, by 15mg partial size
It is dispersed in the positively charged PEI solution that 10mL concentration is 0.8mg/ml and is assembled for 2 μm of polystyrene spheres, assembled
Time is 20min, is centrifuged off supernatant, is washed with water/is centrifuged particle 3 times, first layer is completed；Then one will be assembled with
The fine-particle powder of layer PEI is dispersed in the electronegative GQDs solution that 10mL concentration is 0.8mg/ml and is assembled, built-up time
For 20min, it is centrifuged off supernatant, is washed with water/is centrifuged particle 3 times, is so double-deck assembling；It is assembled into 1 pair
After layer, composite particles are collected by centrifugation and are washed with water 3 times.
Composite particles are distributed in 10mL chloroform, polystyrene spheres are dissolved, are centrifuged off supernatant, be washed with water/
Centrifugation 2 times arrives fluorescence microcapsules to completely remove polystyrene spheres.
2, it characterizes
Laser Scanning Confocal Microscope analysis is carried out to the fluorescence microcapsules prepared in embodiment 2, as a result as shown in Figure 3.It can see
Out under 488nm excitation, microcapsules have bright green fluorescence.And it can show polyethyleneimine clearly dendritic morphology.
Claims (7)
1. a kind of preparation method of fluorescence microcapsules characterized by comprising
Spherical nuclei even particulate dispersion is assembled in cationic polyelectrolyte solution, centrifuge washing, first layer group installs
At；Then the fine-particle powder for being assembled with a strata electrolyte is dispersed in electronegative graphene quantum dot solution and carries out group
Dress, centrifuge washing are so double-deck assembling；It repeats above operation, the composite particles of the different assembling numbers of plies is made；Into one
To get the fluorescence microcapsules after step removal nuclear material；
The electronegative graphene quantum dot is by the existing synthesis of technology from bottom to top or from top to bottom in assembling pH
Under the conditions of zeta be negative value graphene quantum dot.
2. the preparation method of fluorescence microcapsules according to claim 1, which is characterized in that the spherical nuclear particle is carbon
Sour calcisphere or polystyrene spheres, partial size are 0.5~20 μm.
3. the preparation method of fluorescence microcapsules according to claim 2, which is characterized in that remove the method for nuclear material according to
Spherical nuclear particle is selected, and removes calcium carbonate with the coordination of dissolving with hydrochloric acid or disodium EDTA and calcium ion
Ball；Removal polystyrene spheres are dissolved with chloroform.
4. the preparation method of fluorescence microcapsules according to claim 1, which is characterized in that the cationic polyelectrolyte
For one in chitosan, polyallylamine hydrochlorides, diallyl dimethyl ammoniumchloride, straight chain or dendroid polyethyleneimine
Kind.
5. the preparation method of fluorescence microcapsules according to claim 1, which is characterized in that during the preparation process, cation
The concentration of polyelectrolyte solution is 0.1~5.0mg/ml.
6. the preparation method of fluorescence microcapsules according to claim 1, which is characterized in that during the preparation process, negatively charged
Graphene quantum dot solution concentration be 0.1~5.0mg/ml.
7. a kind of fluorescence microcapsules that methods described in any item according to claim 1~6 are prepared, which is characterized in that with
Polyelectrolyte and graphene quantum dot are cyst material.
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Effective date of registration: 20211026 Address after: 750000 group 3, Hongxi village, Hongguang Town, Helan County, Yinchuan City, Ningxia Hui Autonomous Region Patentee after: Hao Cong Address before: No.25 Chunhui Road, Zhangguo Town, Xinghua City, Taizhou City, Jiangsu Province Patentee before: Xinghua Lingyi science and Technology Consulting Service Co., Ltd |
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Address after: 750000 group 3, Hongxi village, Hongguang Town, Helan County, Yinchuan City, Ningxia Hui Autonomous Region Patentee after: He Cong Address before: 750000 group 3, Hongxi village, Hongguang Town, Helan County, Yinchuan City, Ningxia Hui Autonomous Region Patentee before: Hao Cong |