CN105001851B - A kind of fluorescent microsphere with micella particle interlayer and surface carboxyl groups and preparation method thereof - Google Patents
A kind of fluorescent microsphere with micella particle interlayer and surface carboxyl groups and preparation method thereof Download PDFInfo
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- CN105001851B CN105001851B CN201510269771.5A CN201510269771A CN105001851B CN 105001851 B CN105001851 B CN 105001851B CN 201510269771 A CN201510269771 A CN 201510269771A CN 105001851 B CN105001851 B CN 105001851B
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Abstract
The invention discloses a kind of fluorescent microsphere with micella particle interlayer and surface carboxyl groups and preparation method thereof, belong to fluorescent sensing material technical field.By poly- (styrene) block copolymer self assembly in the mixed solvent of tetrahydrofuran and water, poly- (styrene) polymer micelle particle solution is obtained；Polystyrene divinylbenzene crosslinked microsphere with sulfonic acid surfactant base is as core, on the surface of core by static-electronic driving, LBL self-assembly alternating deposit is to phenylenevinylenes presoma and poly- (styrene) micella particle, it is thermally treated again, obtain to phenylenevinylenes/poly- (styrene) micellar shell.The fluorescent microsphere that the present invention is provided, its maximum emission wavelength is 510~520 nm；Fluorescent microsphere Stability Analysis of Structures, surface topography and good dispersion property；Preparation process is simple, it is easy to operate, it is suitable for industrialized production, product can be applied to the fields such as biological detection, medical diagnosis.
Description
Technical field
The present invention relates to a kind of high molecular fluorescent microballoons and preparation method thereof, more particularly to a kind of band micella particle interlayer and
Fluorescent microsphere of surface carboxyl groups and preparation method thereof, belongs to fluorescent sensing material technical field.
Background technology
Used as the core sensing element of liquid phase suspension chip technology, functional fluorescence coding microball carries molecular recognition
With the task of signal representation.Therefore, the chemistry on the microsphere supported surface of research and development is excellent with biological modification method, processability
Different functional fluorescence microballoon, is the important content for building high sensitivity and high selectivity liquid phase suspension chip technology.Using quiet
Conjugated polyelectrolytes are adsorbed onto microsphere surface this method by electro ultrafiltration, main by the use of the colloidal spheres of organic or inorganic as material
, by the Electrostatic Absorption on its surface, in the way of alternating deposit can be coated to the polyelectrolyte of oppositely charged by matrix
Matrix microspheres surface, is assembled into the fluorescent microsphere of core shell structure.Can without cumbersome surface-functionalized process using the method
To obtain multilayered fluorescent microballoon of the surface with differential responses group.But, because polyelectrolyte is after microsphere surface is deposited to
The interspersed effect of chain can occur, self-quenching phenomenon closely occurs so as to cause fluorescent material to be piled up, influence the fluorescence of thus obtained microsphere
Can, limit its application in some fields.
The content of the invention
The chain of the polyelectrolyte that the present invention exists for the fluorescent microsphere of existing utilization electrostatic interaction assembling core shell structure is worn
Insert and fluorescence self-quenching problem, there is provided one kind can effectively overcome the deficiencies in the prior art, and preparation process is simple, product
Stability Analysis of Structures, pattern are good, fluorescent microsphere with micella particle interlayer and surface carboxyl groups and preparation method thereof.
Realizing the technical scheme of the object of the invention, to be to provide a kind of fluorescence with micella particle interlayer and surface carboxyl groups micro-
Ball, described microballoon is nucleocapsid structure, and core is polystyrene-divinylbenzene crosslinked microsphere of the surface containing sulfonic group functionalization,
On the surface of core by static-electronic driving, LBL self-assembly, alternating deposit is to phenylenevinylenes presoma and poly- (acrylic acid-benzene
Ethene) micella particle, then after heat treatment, obtain to phenylenevinylenes/poly- (acrylicstyrene) micellar shell.
Described fluorescent microsphere is in monodispersity, and average grain diameter is 5~35 μm；Its excitation wavelength is 330~410nm, most
Big launch wavelength is 510~520nm.
Technical solution of the present invention also includes that a kind of fluorescence with micella particle interlayer and surface carboxyl groups as described above is micro-
The preparation method of ball, comprises the following steps：
1st, during NaCl is added to phenylenevinylenes precursor water solution, it is 0.05M~0.4M's to be configured to concentration
To phenylenevinylenes precursor salt solution, pre-PPV salting liquids are denoted as；
2nd, poly- (acrylicstyrene) is dissolved in tetrahydrofuran, then is slowly added dropwise deionized water thereto, through dialysis
After obtain poly- (acrylicstyrene) micella particle solution, be denoted as PAA-b-PS solution；
3rd, the polystyrene-divinylbenzene crosslinked microsphere of sulfonic acid surfactant base is scattered in deionized water, is alternately added
Enter step（1）The pre-PPV salting liquids and step of preparation（2）The PAA-b-PS solution of preparation；A kind of solution is often added, to reaction
Liquid carries out concussion treatment 0.5~1 hour, after centrifuge washing, adds another solution；
4th, will react and finish the microballoon that obtains and carry out freeze-drying, then be heat-treated under conditions of being 80~120 DEG C in temperature,
Obtain the fluorescent microsphere with micella particle interlayer and surface carboxyl groups.
Principle of the invention is：On the surface of core by static-electronic driving, LBL self-assembly alternating deposit it is sub- to phenylene
Ethene presoma（pre-PPV）With poly- (acrylicstyrene) micella particle（PAA-b-PS）, thermally treated, pre-PPV heat disappears
Turn into PPV after removing, the micella particle interlayer of introducing can effectively reduce polyelectrolyte layer and the interspersed effect of the chain of interlayer, make on microballoon
The fluorescent emission kind polyparaphenylene Asia ethene of load is not susceptible to fluorescence self-quenching.
Compared with prior art, the beneficial effects of the present invention are：
1st, the present invention introduces the carboxyl functional group for having bioactivity using the method modification microsphere surface of LBL self-assembly,
Preparation technology is simplified, it is easy to operate without cumbersome chemical reaction, it is suitable for industrialized production.
2nd, the technical scheme provided using the present invention, introduces micella particle, so as to form a kind of band to microsphere surface
The structure of micella particle interlayer, significantly reduces layer and the interspersed effect of the chain of interlayer, makes the fluorescent emission kind loaded on microballoon
Polyparaphenylene Asia ethene is not susceptible to fluorescence self-quenching.
3rd, the fluorescent microsphere that the present invention is provided good dispersion property in water and various organic solvents, is that it is further participated in
Other chemical reactions can be applied to the fields such as biological detection, medical diagnosis there is provided possible.
Brief description of the drawings
Fig. 1 is the principle schematic that the present invention prepares the fluorescent microsphere with micella particle interlayer and surface carboxyl groups；
Fig. 2 is the scanning electricity of the fluorescent microsphere with micella particle interlayer and surface carboxyl groups that the embodiment of the present invention 1 is provided
Sub- microphotograph；
Fig. 3 is the fluorescence light of the fluorescent microsphere with micella particle interlayer and surface carboxyl groups that the embodiment of the present invention 1 is provided
Spectrogram；
Fig. 4 is that the streaming of the fluorescent microsphere with micella particle interlayer and surface carboxyl groups that the embodiment of the present invention 1 is provided is thin
Born of the same parents' data.
Specific embodiment
Technical solution of the present invention is further elaborated with reference to the accompanying drawings and examples.
Embodiment 1
The present embodiment provides a kind of fluorescent microsphere with micella particle interlayer and surface carboxyl groups, and its preparation process is as follows：
Step 1：Prepare polyparaphenylene Asia ethene precursor salt solution
Reference literature Macromol. Rapid Commun. 2013,34,102-108, synthesis polyparaphenylene Asia second
Alkene presoma：Under the catalysis of oxygen-free environment and sodium hydrate aqueous solution, reacted to phenylenevinylenes monomer in ice-water bath
After one hour, dialysed 5~6 times with deionized water and can obtain polyparaphenylene Asia ethene precursor water solution.Use liquid-transfering gun
2.5mL polyparaphenylenes Asia ethene precursor water solution is measured, 0.02925g sodium chloride is added thereto to, vibration is dissolved,
Obtain the polyparaphenylene Asia ethene precursor salt solution of water white transparency.
Step 2：Prepare poly- (acrylicstyrene) micella particle solution
Weigh 1 mg amphipathic nature block polymers poly- (acrylicstyrene)（ PAA-b-PS）It is placed in 10 mL tetrahydrochysene furans
In muttering, stirring and dissolving exists to without obvious solid matter, then is filtered with 0.22 μm of organic phase polysulfoxides ether filter, with
Remove wherein a small amount of insoluble impurities.Then 1.5 are dropwise slowly added dropwise in the solution with micro-injection pump while stirring
ML deionized waters（Account for the 13% of total solvent）, this process about needs lasting 3 hours.Finally, it is by solution loading molecular cut off
Dialysed 5~6 times with deionized water in 14000 bag filter, be used to the organic solvent in removing system, and further stablized certainly
Micellar structure obtained by assembling.Gained Micellar Solution Which Is be placed in refrigerator refrigerate it is standby.
Step 3：Prepare the fluorescent microsphere with micella particle interlayer and surface carboxyl groups
Weigh the polystyrene-divinylbenzene crosslinking of 75mg sulfonic acid surfactant bases（PSDVB）Microballoon（Micro- life is received by Suzhou
Thing Science and Technology Ltd. provides）It is placed in test tube, resulting solution 2.5mL in being slowly added to 1 in concussion vibrates 30 points under normal temperature
Clock, after reaction terminates, mixture is centrifuged（2000 revs/min）, microballoon is washed three times with deionized water then（First shake：
1000 revs/min, then be centrifuged：2000 revs/min, supernatant is removed, then add deionized water to repeat concussion, centrifugation）.Repeat above-mentioned
Step adds the micella particle solution 2.5mL of gained in 2.Said process be alternately repeated 2 times after through freeze-drying, at 80 DEG C heat
Treatment 1 hour, obtains the fluorescent microsphere with micella particle interlayer and surface carboxyl groups.
Referring to accompanying drawing 1, it is that the principle for preparing the fluorescent microsphere with micella particle interlayer and surface carboxyl groups of the invention is shown
It is intended to；On the surface of core by static-electronic driving, LBL self-assembly alternating deposit to phenylenevinylenes presoma（pre-PPV）
With poly- (acrylicstyrene) micella particle（PAA-b-PS）, and after heat treatment pre-PPV eliminates into PPV.The micella of introducing
Particle interlayer can be effectively reduced layer and the interspersed effect of the chain of interlayer, make the fluorescent emission kind polyparaphenylene loaded on microballoon
Sub- ethene is not susceptible to fluorescence self-quenching.
Referring to accompanying drawing 2, it is sweeping for the fluorescent microsphere with micella particle interlayer and surface carboxyl groups that the present embodiment is provided
Retouch electron micrograph；As seen from Figure 2, the fluorescent microsphere regular appearance, uniform particle diameter, surface uniform load micella grain
Son, average grain diameter is about 10 μm.
In preparing fluorescent microsphere, step 3 by the same procedure of the present embodiment, the alternating weight of step 1 and step 2 solution is added
Again number is respectively 0.5,1,1.5,2,2.5,3, and referring to accompanying drawing 3, it is the different cladding number of plies band micellas that the present embodiment is provided
The fluorescence spectrum comparison diagram of the fluorescent microsphere of particle interlayer and surface carboxyl groups；As seen from Figure 3, the maximum fluorescence hair of microballoon
Ejected wave is long in 515 nm or so, and the cladding number of plies is on the launch wavelength and peak shape of microballoon substantially without influence.
Referring to accompanying drawing 4, it is that the difference that the present embodiment is provided coats the numbers of plies with micella particle interlayer and surface carboxyl groups
The flow cytometry data of fluorescent microsphere；As seen from Figure 4, after PPV outer claddings PAA-b-PS micella particles, microsphere fluorescence intensity
Slightly reduce, but as the number of plies increases, its fluorescence intensity is serrated rising.
Claims (4)
1. a kind of fluorescent microsphere with micella particle interlayer and surface carboxyl groups, it is characterised in that：Described microballoon is core-shell structure copolymer knot
Structure, core is polystyrene-divinylbenzene crosslinked microsphere of the surface containing sulfonic group functionalization, is driven by electrostatic force on the surface of core
Dynamic, LBL self-assembly, alternating deposit to phenylenevinylenes presoma and poly- (acrylicstyrene) micella particle, then through heat
After treatment, polyparaphenylene Asia ethene and poly- (acrylicstyrene) micellar shell are obtained.
2. a kind of fluorescent microsphere with micella particle interlayer and surface carboxyl groups according to claim 1, it is characterised in that：
The fluorescent microsphere is in monodispersity, and average grain diameter is 5~35 μm.
3. a kind of fluorescent microsphere with micella particle interlayer and surface carboxyl groups according to claim 1, it is characterised in that：
The excitation wavelength of the fluorescent microsphere is 330~410nm, and maximum emission wavelength is 510~520nm.
4. a kind of preparation method of the fluorescent microsphere with micella particle interlayer and surface carboxyl groups as claimed in claim 1, its
It is characterised by comprising the following steps：
（1）During NaCl is added to phenylenevinylenes precursor water solution, it is 0.05M~0.4M to Asia to be configured to concentration
Phenylene vinylene precursor salt solution, is denoted as pre-PPV salting liquids；
（2）Poly- (acrylicstyrene) is dissolved in tetrahydrofuran, then is slowly added dropwise deionized water thereto, after dialysis
Poly- (acrylicstyrene) micella particle solution is obtained, PAA-b-PS solution is denoted as；
（3）The polystyrene-divinylbenzene crosslinked microsphere of sulfonic acid surfactant base is scattered in deionized water, is alternately added
Step（1）The pre-PPV salting liquids and step of preparation（2）The PAA-b-PS solution of preparation；A kind of solution is often added, to reaction solution
Concussion treatment 0.5~1 hour is carried out, after centrifuge washing, another solution is added；
（4）To react and finish the microballoon that obtains and carry out freeze-drying, then be heat-treated under conditions of being 80~120 DEG C in temperature, obtain
To the fluorescent microsphere with micella particle interlayer and surface carboxyl groups.
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| CN103275700A (en) * | 2013-06-03 | 2013-09-04 | 南京工业大学 | Method for preparing polymer fluorescent microsphere |
| CN104371708B (en) * | 2014-11-10 | 2016-05-18 | 苏州大学 | A kind of surperficial carboxylic fluorescent microballoon with crosslinked shell structure and preparation method thereof |
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