CN117659414A - Synthesis of rigid-flexible amphiphilic polyarylether block copolymer and preparation of fluorescent composite microspheres thereof - Google Patents
Synthesis of rigid-flexible amphiphilic polyarylether block copolymer and preparation of fluorescent composite microspheres thereof Download PDFInfo
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Abstract
A rigid-flexible amphiphilic polyarylether segmented copolymer synthesis and a preparation method of fluorescent composite microspheres belong to the technical field of high polymer materials. The invention synthesizes and obtains the rigid-flexible amphiphilic poly (arylene ether nitrile) -poly (ethylene glycol) segmented copolymer (PENG) through nucleophilic substitution polycondensation reaction of a hydrophilic poly (ethylene glycol) (PEG) soft segment and a hydrophobic poly (arylene ether nitrile) (PEN) hard segment, and the copolymer has hydrophilic/biological compatibility from the PEG soft segment and hydrophobic interaction/pi-pi effect from the PEN hard segment. The above characteristics enable PENG to be used as a macromolecular surfactant, and water-dispersible fluorescent composite microspheres with different particle sizes and morphologies are obtained through co-assembly with oil-soluble QDs in an oil-in-water limited emulsion system, so that the PENG has important application value in the fields of in-vitro diagnosis and biological imaging.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a rigid-flexible amphiphilic polyarylether block copolymer and a method for embedding quantum dots into the same to form fluorescent composite microspheres.
Background
Fluorescent microspheres are particles having a diameter of between a few nanometers and tens of micrometers and being loaded with fluorescent substances on the surface or inside, capable of emitting fluorescent signals when excited by photons of a certain energy. Compared with single fluorescent molecules, the fluorescent microsphere has relatively stable luminescence behavior and morphological structure, and thus has wide application prospect in the fields of biological medicine, photoelectric devices and the like. Among a plurality of fluorescent microspheres, fluorescent composite microspheres based on high molecular compounds and semiconductor Quantum Dots (QDs) have the advantages of easy control of morphology and size, rich surface functionalization paths, narrow fluorescence emission peak, wide excitable wavelength range, strong fluorescence stability and the like, and are widely applied to the detection technical fields of fluorescent immunochromatography, labeling and tracing, biosensors, liquid-phase chips, microfluidics and the like.
The polymer/quantum dot fluorescent composite microspheres can be divided into natural polymer fluorescent microspheres and synthetic polymer fluorescent microspheres according to different polymer carriers, wherein the microspheres with small particle size can reach several nanometers, and the diameters of the microspheres with large particle size can even reach hundreds of micrometers. Although natural polymers generally have good biocompatibility, the structural composition is complex, so that the natural polymer-based fluorescent composite microsphere still has the defect of poor batch stability. In comparison, the synthetic polymer has the advantages of clear segment structure, controllable molecular weight, strong molecular design and the like, and has unique advantages in preparing the fluorescent composite microsphere with adjustable shape and size and controllable surface functional groups. Polystyrene (PS) -divinylbenzene is a common synthetic polymer system for preparing fluorescent composite microspheres, and fluorescent composite microspheres with uniform size can be prepared by different compositing modes of PS and quantum dots, but the surface reactive functional groups of the microspheres are limited, so that subsequent biological functionalization paths are limited. Aiming at the problem, researchers synthesize a series of amphiphilic block copolymers as a high molecular carrier through chain polymerization reaction of functionalized olefin monomers, and then prepare the high molecular fluorescent composite microspheres with different particle sizes and surfaces rich in functional groups (amino, carboxyl, hydroxyl and the like) by means of the co-assembly process of the high molecular fluorescent composite microspheres and semiconductor quantum dots, and the fluorescent composite microspheres have great application value in the field of in-vitro diagnosis due to the rich biological functionalization strategies.
Although the co-assembly of amphiphilic block copolymer based on olefin monomer and semiconductor quantum dot has become an effective method for preparing high molecular fluorescent composite microsphere, the solvent resistance and long-term stability of the fluorescent composite microsphere still need to be further improved due to the flexible segment characteristic of the olefin polymer carrier. Therefore, the block copolymer with a special molecular chain structure is designed and synthesized, and the co-assembly technology of the block copolymer and the quantum dots is developed, so that the novel polymer fluorescent composite microsphere is hopeful to be prepared.
Disclosure of Invention
The invention aims at solving the problems in the background technology and provides a method for synthesizing a rigid-flexible amphiphilic polyarylether segmented copolymer and embedding oil-soluble quantum dots to prepare fluorescent composite microspheres. The invention synthesizes and obtains the rigid-flexible amphiphilic poly (arylene ether nitrile) -poly (ethylene glycol) segmented copolymer (PENG) through nucleophilic substitution polycondensation reaction of a hydrophilic poly (ethylene glycol) (PEG) soft segment and a hydrophobic poly (arylene ether nitrile) (PEN) hard segment, and the copolymer has hydrophilic/biological compatibility from the PEG soft segment and hydrophobic interaction/pi-pi effect from the PEN hard segment. The characteristics enable PENG to be used as a macromolecular surfactant, and water-dispersible fluorescent microspheres with different particle sizes and morphologies are obtained through co-assembly with oil-soluble QDs in an oil-in-water limited emulsion system, so that the PENG has important application value in the fields of in-vitro diagnosis and biological imaging.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a rigid-flexible amphiphilic polyarylether segmented copolymer is a polyarylether nitrile-polyethylene glycol segmented copolymer (PENG), is obtained by nucleophilic substitution reaction of a hydroxyl-terminated polyethylene glycol hydrophilic soft segment and a fluorine-terminated rigid hydrophobic segment, and has the following structural formula:
wherein,
or->Or alternatively，m＝30～60，n＝90～120。
A method for synthesizing a rigid-flexible amphiphilic polyarylether segmented copolymer comprises the following steps:
step 1, adding 26.82 to 26.83 parts by mass of bisphenol Ar monomer, 13.97 to 13.98 parts by mass of 2, 6-difluorobenzonitrile and 20.73 parts by mass of potassium carbonate into a reaction bottle, and uniformly mixing;
step 2, adding 56.75 parts by mass of NMP (N-methylpyrrolidone) and 16.04 parts by mass of toluene into the mixed solution in the step 1, stirring and refluxing for 2-4 hours at 140-150 ℃, and then heating to 180 ℃ and continuously stirring and refluxing for 1-2 hours to obtain a mixed solution A;
step 3, heating the mixed solution A in the step 2 to 190 ℃; dissolving 15-20 parts by mass of polyethylene glycol monomethyl ether in 20.56 parts by mass of NMP, adding into the mixed solution A after complete dissolution, and then introducing N 2 Reacting for 2-3 h; after the reaction is completed, the obtained melt is poured into ethanol to be rapidly cooled and purified, and then dried in a blast oven at 60 ℃ to obtain the rigid-flexible amphiphilic polyarylether segmented copolymer.
Wherein the bisphenol Ar monomer in the step 1 isOr->Or alternatively
A method for preparing fluorescent composite microspheres based on the rigid-flexible amphiphilic polyarylether segmented copolymer comprises the following steps:
step 1, adding 10 parts by mass of deionized water into a reaction bottle to obtain a mixed solution B;
step 2, sequentially adding 0.002-0.015 part (mass) of the rigid-flexible amphiphilic polyarylether segmented copolymer, 94.8 parts (mass) of N, N-dimethylformamide, 0.2 part (mass) of quantum dots and 1192.5 parts (mass) of methylene dichloride into another reaction bottle to obtain a mixed solution C;
step 3, adding the mixed solution C obtained in the step 2 into the mixed solution B obtained in the step 1, sealing, magnetically stirring for 6 hours, and then opening a reaction bottle until the dichloromethane is completely volatilized;
and step 4, separating the reaction liquid obtained in the step 3, and cleaning the obtained product to obtain the fluorescent composite microsphere.
Further, the quantum dots are oil-soluble semiconductor fluorescent quantum dots.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention obtains the poly (arylene ether nitrile) -poly (ethylene glycol) segmented copolymer (PENG) with rigid-flexible amphiphilic molecular structure characteristics through nucleophilic substitution reaction between hydrophilic poly (ethylene glycol) and hydrophobic poly (arylene ether nitrile), which not only maintains the water solubility and biocompatibility of poly (arylene ether nitrile), but also has the characteristic of dipole interaction between the rigid chain segment and molecular chain of poly (arylene ether nitrile), so that the copolymer can be used as a macromolecular surfactant to participate in emulsion restricted self-assembly; meanwhile, the synthetic method of the PENG segmented copolymer is simple and efficient, and industrialization is easy to realize.
2. The PENG embedded oil-soluble quantum dot fluorescent composite microsphere prepared by the invention does not use other surfactants in the preparation process, the particle size of the microsphere can be flexibly regulated and controlled between 10nm and 1000nm, and the preparation method is simple, safe and environment-friendly, easy to control and has good application prospect in the fields of biological imaging and in-vitro diagnosis.
Drawings
FIG. 1 is an infrared spectrum of a poly (arylene ether nitrile) -poly (ethylene glycol) block copolymer obtained in example 1 and example 2 of the present invention;
FIG. 2 is a DSC (differential scanning calorimeter) of a poly (arylene ether nitrile) -poly (ethylene glycol) block copolymer obtained in example 1 and example 2 of the present invention;
FIG. 3 shows the TGA (thermogravimetric analyzer) of the poly (arylene ether nitrile) -poly (ethylene glycol) block copolymers obtained in examples 1 and 2 of the present invention;
FIG. 4 shows SEM (scanning electron microscope) corresponding to the supernatant of the dispersion of poly (arylene ether nitrile) -poly (ethylene glycol) microspheres obtained in examples 3 and 4 of the present invention, which correspond to large-sized microspheres; wherein, (a) corresponds to PENG-7K of example 3 and (b) corresponds to PENG-12K of example 4;
FIG. 5 shows TEM (transmission electron microscope) corresponding to the supernatant of the PENG/quantum dot fluorescent composite microsphere dispersion obtained in example 3 and example 4 of the present invention, which corresponds to small-sized microspheres; wherein, (a) corresponds to PENG-7K of example 3 and (b) corresponds to PENG-12K of example 4;
FIG. 6 shows fluorescence emission spectra corresponding to supernatants of PENG/quantum dot fluorescent composite microsphere dispersions obtained in examples 3 and 4 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to be limiting, and various modifications and alterations can be made by those skilled in the art based on the basic idea of the invention without departing from the scope thereof.
Example 1
Step 1, adding 26.82 to 26.83 parts by mass of bisphenol A monomer, 13.97 to 13.98 parts by mass of 2, 6-difluorobenzonitrile and 20.73 parts by mass of potassium carbonate into a reaction bottle, and uniformly mixing;
step 2, adding 56.75 parts by mass of NMP (N-methylpyrrolidone) and 16.04 parts by mass of toluene into the mixed solution in the step 1, stirring and refluxing for 2-4 hours at 140-150 ℃, and then heating to 180 ℃ and continuously stirring and refluxing for 1-2 hours to obtain a mixed solution A;
step 3, heating the mixed solution A in the step 2 to 190 ℃; dissolving 15-20 parts by mass of polyethylene glycol monomethyl ether in 20.56 parts by mass of NMP, adding into the mixed solution A after complete dissolution, and then introducing N 2 Reacting for 2h; after the reaction is finished, the obtained melt is poured into ethanol to be rapidly cooled and purified, and then dried in a blast oven at 60 ℃ to obtain the rigid-flexible amphiphilic polyarylether segmented copolymer PENG-7K, and the obtained product is ground for standby。
Example 2
Step 1, adding 26.82 to 26.83 parts by mass of bisphenol A monomer, 13.97 to 13.98 parts by mass of 2, 6-difluorobenzonitrile and 20.73 parts by mass of potassium carbonate into a reaction bottle, and uniformly mixing;
step 2, adding 56.75 parts by mass of NMP (N-methylpyrrolidone) and 16.04 parts by mass of toluene into the mixed solution in the step 1, stirring and refluxing for 2-4 hours at 140-150 ℃, and then heating to 180 ℃ and continuously stirring and refluxing for 1-2 hours to obtain a mixed solution A;
step 3, heating the mixed solution A in the step 2 to 190 ℃; dissolving 15-20 parts by mass of polyethylene glycol monomethyl ether in 20.56 parts by mass of NMP, adding into the mixed solution A after complete dissolution, and then introducing N 2 Reacting for 2.5h; after the reaction is finished, the obtained melt is poured into ethanol to be rapidly cooled and purified, and then dried in a blast oven at 60 ℃ to obtain the rigid-flexible amphiphilic polyarylether segmented copolymer PENG-12K, and the obtained product is ground for standby.
The rigid-flexible amphiphilic poly (arylene ether nitrile) -poly (ethylene glycol) block copolymers synthesized in example 1 and example 2 were characterized by infrared (FITR) and the results are shown in fig. 1. The poly (arylene ether nitrile) -poly (ethylene glycol) block copolymers synthesized from example 1 and example 2 were prepared at 2969cm -1 The vibration peak of the methyl C-H in bisphenol A is 2230cm -1 Is characterized by the characteristic absorption peak of cyano group on benzene ring, 1245cm -1 1021cm -1 The transmission peaks appearing at the positions are asymmetric stretching vibration and symmetric stretching vibration peaks of the aromatic ether bond Ar-O-Ar, which indicate that the polyethylene glycol monomethyl ether and the polyarylether nitrile form a block copolymer.
DSC characterization is performed on the rigid-flexible amphiphilic poly (arylene ether nitrile) -poly (ethylene glycol) block copolymer synthesized in example 1 and example 2, and the results are shown in FIG. 2. The molecular weight of the poly (arylene ether nitrile) -polyethylene glycol block copolymer synthesized in the example 1 is 7kDa, no obvious glass transition is seen in a DSC test temperature range, the copolymer starts to decompose at 250 ℃, absorbs energy, starts to release heat, and the curve is in an ascending trend; the poly (arylene ether nitrile) -poly (ethylene glycol) block copolymer synthesized from example 2 had a molecular weight of 12kDa and a glass transition temperature of 126.6 ℃. This is probably due to the fact that the glass transition temperature becomes smaller after adding polyethylene glycol monomethyl ether.
The rigid-flexible amphiphilic poly (arylene ether nitrile) -poly (ethylene glycol) block copolymers synthesized in example 1 and example 2 were subjected to TGA characterization, and the results are shown in fig. 3. The carbon residue of PENG-7K of example 1 was 62.95%; the carbon residue of PENG-12 is 37.8%, which shows that PENG-7K has better thermal stability, and the microspheres prepared by the method have better thermal stability and optical stability in combination with the subsequent optical characterization.
GPC characterization was performed on the rigid-flexible amphiphilic poly (arylene ether nitrile) -polyethylene glycol block copolymers synthesized in example 1 and example 2, and the results are shown in Table 1. Table 1 shows the number average molecular weights (Mn), weight average molecular weights (Mw) and PD values of the poly (arylene ether nitrile) -poly (ethylene glycol) block copolymers obtained in examples 1 and 2, respectively, by GPC (normal temperature gel permeation chromatography), PENG-7K and PENG-12K random copolymers, as shown in Table 1, and by controlling the introduction of N 2 The subsequent reaction time can respectively obtain PENG with weight average molecular weight of 7kDa and 12kDa, which indicates that N is controlled to be introduced 2 The molecular weight of synthesized PENG can be effectively regulated and controlled by the reaction time.
TABLE 1
Comparative example 1
The difference between this comparative example and example 1 is that: in step 3, N is introduced 2 After 2h of reaction, obtaining a melt, and injecting the melt into water for rapid cooling; the remaining steps were the same as in example 1. When the melt is injected into water for cooling, the melt is dissolved in water due to the hydrophilicity of PEG, and a solid target product cannot be obtained.
Comparative example 2
The difference between this comparative example and example 1 is that: in step 3, N is introduced 2 After 2h of reaction, obtaining a melt, and injecting the melt into cyclohexanone for rapid cooling; the remaining steps were the same as in example 1. When the melt is injected into cyclohexanone for cooling, the cyclohexanone is not polar organic solvent and can not form polar interaction with PEG, so that the cyclohexanone is difficult to separate out.
Example 3
Step 1, adding 10 parts by mass of deionized water into a reaction bottle to obtain a mixed solution B;
step 2, sequentially adding 0.002-0.015 part (mass) of the poly (arylene ether nitrile) -polyethylene glycol block copolymer prepared in the example 1, 94.8 parts (mass) of N, N-dimethylformamide, 0.2 part (mass) of quantum dots and 1192.5 parts (mass) of methylene dichloride into another reaction bottle to obtain a mixed solution C;
step 3, adding the mixed solution C obtained in the step 2 into the mixed solution B obtained in the step 1, sealing, magnetically stirring for 6 hours, and then opening a reaction bottle until the dichloromethane is completely volatilized;
and step 4, separating the reaction liquid obtained in the step 3, and cleaning the obtained product to obtain the PENG-7K microsphere dispersion liquid.
Example 4
Step 1, adding 10 parts by mass of deionized water into a reaction bottle to obtain a mixed solution B;
step 2, sequentially adding 0.002-0.015 part (mass) of the poly (arylene ether nitrile) -polyethylene glycol block copolymer prepared in the example 2, 94.8 parts (mass) of N, N-dimethylformamide, 0.2 part (mass) of quantum dots and 1192.5 parts (mass) of methylene dichloride into another reaction bottle to obtain a mixed solution C;
step 3, adding the mixed solution C obtained in the step 2 into the mixed solution B obtained in the step 1, sealing, magnetically stirring for 6 hours, and then opening a reaction bottle until the dichloromethane is completely volatilized;
and step 4, separating the reaction liquid obtained in the step 3, and cleaning the obtained product to obtain the PENG-12K microsphere dispersion liquid.
Dispersing the PENG/quantum dot composite fluorescent microsphere dispersion liquid prepared in the embodiment 3 and the embodiment 4 in deionized water to obtain a dispersion liquid with the mass concentration of 0.5 mg/mL; setting the wavelength of emitted light to 522nm, the width of a slit to 10nm, the voltage of a PMT to 400V, and the response time to 0.1s, and obtaining the excitation spectrum of the composite fluorescent microsphere dispersion liquid through wavelength scanning; the excitation light wavelength is set to 365nm, the slit width is 10nm, the PMT voltage is 400V, the response time is 0.1s, and the fluorescence emission spectrum under 365nm excitation is obtained through wavelength scanning.
As shown in fig. 4, SEM corresponding to the supernatant of the PENG/quantum dot composite fluorescent microsphere dispersion obtained in example 3 and example 4 of the present invention corresponds to large-sized microspheres; from the SEM micro morphology graph, fluorescent composite microspheres prepared by adopting PENG with different molecular weights have different morphologies: fluorescent composite microspheres prepared from PENG-7K copolymer exhibit a complete spherical structure, as shown in FIG. 4 (a); whereas fluorescent composite microspheres prepared with PENG-12K copolymers generally have an open cell structure, as shown in FIG. 4 (b).
As shown in fig. 5, TEM pictures of the supernatants of the PENG/quantum dot composite fluorescent microsphere dispersions obtained in example 3 and example 4 of the present invention, which correspond to small-sized microspheres; as shown in fig. 5 (a), a TEM image and a particle size distribution histogram of the PENG-7K microsphere supernatant, which have an average particle size of 3.85 nm; as shown in FIG. 5 (b), the TEM image and the particle size distribution histogram of the supernatant of PENG-12K microspheres have an average particle size of 10.61 nm. The fluorescent composite microsphere prepared by embedding the similar QDs into the block copolymer with larger molecular weight is shown to increase in average particle size.
As shown in FIG. 6, the fluorescence emission spectra corresponding to the supernatants of the PENG/quantum dot composite fluorescent microsphere dispersions prepared in examples 3 and 4 of the present invention were obtained, and the emission wavelength was 522nm. From the spectrum, the PENG/quantum dot composite fluorescent microsphere has characteristic emission peaks of oil-soluble quantum dots at 522nm under excitation of 365nm, which indicates that the synthesized rigid-flexible amphiphilic PENG segmented copolymer can be used as a macromolecular surfactant to realize water phase transfer of the oil-soluble quantum dots, so that the macromolecular fluorescent composite microsphere can be prepared under the condition that other small molecular surfactants are not added, and the fluorescence intensity of the prepared fluorescent composite microsphere can be regulated and controlled by the molecular weight of the PENG segmented copolymer.
Claims (4)
1. The rigid-flexible amphiphilic polyarylether segmented copolymer is characterized in that the copolymer is obtained by nucleophilic substitution reaction of hydroxyl-terminated polyethylene glycol and fluorine-terminated polyarylether nitrile, and has the following structural formula:
wherein,or->Or alternatively，m＝30～60，n＝90～120。
2. The synthesis method of the rigid-flexible amphiphilic polyarylether segmented copolymer is characterized by comprising the following steps of:
step 1, adding 26.82 to 26.83 parts by mass of bisphenol Ar monomer, 13.97 to 13.98 parts by mass of 2, 6-difluorobenzonitrile and 20.73 parts by mass of potassium carbonate into a reaction bottle, and uniformly mixing;
step 2, adding 56.75 parts by mass of NMP and 16.04 parts by mass of toluene into the mixed solution in the step 1, stirring and refluxing for 2-4 hours at 140-150 ℃, and then heating to 180 ℃ and continuously stirring and refluxing for 1-2 hours to obtain a mixed solution A;
step 3, heating the mixed solution A in the step 2 to 190 ℃; dissolving 15-20 parts by mass of polyethylene glycol monomethyl ether in 20.56 parts by mass of NMP, adding into the mixed solution A after complete dissolution, and then introducing N 2 Reacting for 2-3 h; after the reaction is completed, the obtained melt is poured into ethanol for rapid cooling, and purified and dried, so that the rigid-flexible amphiphilic polyarylether segmented copolymer is obtained.
3. A method for preparing fluorescent composite microspheres based on the rigid-flexible amphiphilic polyarylether block copolymer according to claim 1, comprising the following steps:
step 1, adding 10 parts by mass of deionized water into a reaction bottle to obtain a mixed solution B;
step 2, sequentially adding 0.002-0.015 part by mass of the rigid-flexible amphiphilic polyarylether block copolymer in claim 1, 94.8 parts by mass of N, N-dimethylformamide, 0.2 part by mass of quantum dots and 1192.5 parts by mass of methylene dichloride into another reaction bottle to obtain a mixed solution C;
step 3, adding the mixed solution C obtained in the step 2 into the mixed solution B obtained in the step 1, sealing, magnetically stirring for 6 hours, and then opening a reaction bottle until the dichloromethane is completely volatilized;
and step 4, separating the reaction liquid obtained in the step 3, and cleaning the obtained product to obtain the fluorescent composite microsphere.
4. A method for preparing fluorescent composite microspheres based on the rigid-flexible amphiphilic polyarylether block copolymer obtained by the method according to claim 2, comprising the following steps:
step 1, adding 10 parts by mass of deionized water into a reaction bottle to obtain a mixed solution B;
step 2, sequentially adding 0.002-0.015 part by mass of the rigid-flexible amphiphilic polyarylether segmented copolymer obtained by the method of claim 2, 94.8 parts by mass of N, N-dimethylformamide, 0.2 part by mass of quantum dots and 1192.5 parts by mass of dichloromethane into another reaction bottle to obtain a mixed solution C;
step 3, adding the mixed solution C obtained in the step 2 into the mixed solution B obtained in the step 1, sealing, magnetically stirring for 6 hours, and then opening a reaction bottle until the dichloromethane is completely volatilized;
and step 4, separating the reaction liquid obtained in the step 3, and cleaning the obtained product to obtain the fluorescent composite microsphere.
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