CN107828008B - Preparation method and application of double-fluorescent-channel polymer microspheres - Google Patents
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Abstract
The invention relates to a preparation method of a novel polymer microsphere with double fluorescence channels, which comprises the following steps of (a) preparing a poly (divinylbenzene-co-p-vinylphenylboronic acid) microsphere with a fluorescence channel by a solvothermal method; (b) the polymer microsphere with double fluorescent channels is prepared by a self-assembly mode with fluorescent materials. The invention has the beneficial effects that: (1) the poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres prepared by the method have good fluorescence performance and regular morphology, and can specifically recognize D-fructose and generate fluorescence quenching. (2) The prepared polymeric microspheres are easy to color, and can be used for fluorescence ratio detection and multicolor fluorescence imaging by self-assembly with different types of fluorescent materials.
Description
Technical Field
The invention belongs to the research field of polymer microspheres, and relates to a preparation method and application of a double-fluorescence-channel polymer microsphere.
Background
In the past research on the phenylboronic acid fluorescent material, researchers often improve the fluorescence of the phenylboronic acid by introducing a large conjugated group into the phenylboronic acid, so that the phenylboronic acid is used as a suitable fluorescent probe. However, these works often require a better synthetic base and a more complicated design scheme, which brings much inconvenience to the development of the phenylboronic acid fluorescent material and also raises the research threshold.
The weak functionality of commercial polymeric microspheres, such as polystyrene microspheres, severely limits the applicability of the polymeric microspheres. Researchers often need to perform complex chemical modifications on polystyrene microspheres to improve their functionality.
The conventional double-fluorescent-channel material has complicated synthesis steps. The prepared double-fluorescence channel microsphere has narrow double-fluorescence channel spacing and mutual interference of the double-fluorescence channels. When the double-fluorescence channel microsphere is applied to fluorescence detection, a proper target object is difficult to select, and meanwhile, the emission band of the double-fluorescence channel has no controllability, so that the applicability of the double-fluorescence channel microsphere is greatly reduced.
Disclosure of Invention
A poly (divinylbenzene-co-p-vinylphenylboronic acid) microsphere is prepared by a simple free radical polymerization mode, and can be applied to fluorescence detection of D-fructoses. The synthesis method is simple and does not need complex design. Meanwhile, the microsphere has good appearance and fluorescence characteristic. Can be excited at 258nm and emit at 323.5 nm. In the development and application of the microsphere, the microsphere is found to have better quenching effect with D-fructose, and has weaker fluorescence response with other saccharides such as D-glucose, sucrose, galactose and maltose. The microsphere is proved to be used for fluorescence detection of D-fructose. Meanwhile, the combination of the microsphere and saccharide can generate a new ultraviolet absorption peak, and the ultraviolet absorption peak and the concentration show a better linear relationship, which shows that the material can be used as a saccharide ultraviolet detection color developing agent. In the subsequent research, the characteristic that poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres are easy to color is utilized, and the poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres are self-assembled with fluorescent materials such as quantum dots and carbon dots to serve as double-fluorescence-channel fluorescent microspheres and colorful fluorescent imaging materials.
The specific technical scheme provided by the invention is as follows:
a preparation method of a double-fluorescent-channel polymer microsphere comprises the following steps:
(a) preparing mono-fluorescent poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres by a solvothermal method;
(b) the polymer microsphere with double fluorescent channels is prepared by a method of self-assembly with fluorescent materials.
Further, the step (a) of preparing the mono-fluorescent poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres is performed as follows:
(1) dissolving a functional monomer and a cross-linking agent in acetonitrile;
(2) adding an initiator into the solution prepared in the step (1), introducing nitrogen, and sealing under the condition of nitrogen;
(3) polymerizing for 8 hours in a reaction kettle at the temperature of 110 ℃ to initiate the solution prepared in the step (2);
(4) and (4) centrifuging the solution prepared in the step (3) to remove the reaction solvent, washing with acetonitrile and methanol in sequence, and then drying in vacuum.
Further, the functional monomer is 4-vinyl phenylboronic acid, and the using amount is 5 mmol. ,
further, the crosslinking agent is divinylbenzene, and the dosage is 5 mmol.
Further, the initiator is azobisisobutyronitrile; the dosage is 30 mg.
Further, the dosage of the acetonitrile is 80 mL.
Further, the polymerization temperature is 110 ℃ and the polymerization time is 8 hours.
Further, the step (b) of preparing the polymer microsphere with double fluorescence channels comprises the following steps:
(1) dissolving the mono-fluorescent poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres obtained in the step (a) into 10mL of ethanol solution, and carrying out ultrasonic treatment for 30 minutes;
(2) adding a fluorescent material into the solution obtained in the step (1), and magnetically stirring for 8 hours;
(3) and (3) centrifuging the solution obtained in the step (2) to remove the trans-ethanol, washing with methanol for 3 times, and drying in vacuum.
Further, the amount of the monofluorescent poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres was 50 mg.
Further, the fluorescent materials are quantum dots (CdSe/ZnS, lambda)ex:360nm/λem500-700nm) or carbon dots (carbon source: citric acid,. lambda.ex:365nm/λem500-700nm) in an amount of 200. mu.L.
The invention adopts a simple self-assembly mode to prepare the double-fluorescence-channel microsphere, the synthesis is simple, the second fluorescence channel can be adjusted by adjusting the type of the doped fluorescent material, and the corresponding second fluorescence channel can be selected according to the performance of the detection target object.
The double-fluorescence-channel polymer microsphere is applied to detection of D-fructose.
The conventional polymer microsphere has no fluorescence property and limited applicability. The poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres prepared by the invention have fluorescence property, can specifically identify D-fructose, and are quenched by fluorescence. The prepared polymer microsphere with double fluorescent channels simplifies the synthesis steps of the double fluorescent materials by the self-assembly of the poly (divinylbenzene-co-p-vinylphenylboronic acid) microsphere with the single fluorescent channel and the fluorescent materials. The method has universality, and can prepare different types of double-fluorescence-channel polymer microspheres by self-assembly with different types of fluorescent materials, thereby expanding the applicability of the double-fluorescence-channel microspheres in the detection field.
The solvothermal method is developed on the basis of a hydrothermal method, and refers to a synthetic method in which an original mixture is reacted in a closed system such as an autoclave by using an organic or non-aqueous solvent as a solvent at a certain temperature and under the autogenous pressure of the solution. It differs from hydrothermal reactions in that the solvent used is organic rather than water. Hydrothermal methods are often only suitable for the preparation and treatment of oxide functional materials or a few chalcogenides which are not sensitive to water, and the preparation and treatment of three-dimensional framework materials involving some water-sensitive compounds (reactive, hydrolytic, decomposing or unstable with water), such as iii-V semiconductors, carbides, fluorides, novel arsenate molecular sieves, are not suitable, which has prompted the development and development of solvothermal methods.
The invention has the beneficial effects that:
(1) the poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres prepared by the method have good fluorescence performance and regular morphology, and can specifically recognize D-fructose and generate fluorescence quenching.
(2) The prepared polymeric microspheres are easy to color, and can be used for fluorescence ratio detection and multicolor fluorescence imaging by self-assembly with different types of fluorescent materials.
Description of the drawings:
FIG. 1: scanning electron micrographs of poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres
FIG. 2: ultraviolet absorption and fluorescence emission spectra of poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres, (a) ultraviolet-visible absorption spectrum (b) fluorescence emission spectrum
FIG. 3: influence of addition amount of D-fructose on fluorescence quenching of polymer microspheres (pH 9.0)
FIG. 4: Lineweaver-Burk double reciprocal diagram of polymer microsphere-fructose system
FIG. 5 shows the fluorescence diagram of the interaction between water-soluble quantum-double fluorescent channel microspheres and D-fructose
FIG. 6 is a drawing of a dual fluorescent channel-transmitting polymeric material under 356nm UV lamp (from left to right: carbon dots, oil-soluble quantum dots, water-soluble quantum dots)
Detailed Description
In order that the above features and advantages of the present invention will be readily understood and appreciated, embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
Example 1
Preparation method of double-fluorescent-channel polymer microspheres
(1) Solvothermal method for preparing poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres with single fluorescent channel
4-Vinylphenylboronic acid (735mg, 5mmol) and divinylbenzene (710. mu.L, 5mmol) (basic alumina column to remove polymerization inhibitor) were added to 80mL of acetonitrile and dissolved thoroughly with sonication. 30mg of azobisisobutyl (recrystallization) was added to the above solution, and the reaction mixture was placed in a 100mL reaction vessel and reacted at 110 ℃ for 8 hours. After the polymerization reaction, the reaction solvent was removed by centrifugation, washed three times with methanol, and dried for use.
The results of fig. 1 show that the synthesized polymer microspheres have good morphology, and the size of the synthesized polymer microspheres reaches submicron level.
FIG. 2(a) is a graph of the UV absorption of poly (divinylbenzene-co-p-vinylphenylboronic acid) with polymeric microspheres having a maximum UV absorption peak at 258 nm. 258nm is taken as the generation wavelength of the polymer microsphere, the fluorescence emission spectrum of the polymer microsphere in the figure 2(b) is obtained, and the spectrum shows that the synthesized polymer microsphere has the maximum emission wavelength of 323.5 nm.
(2) Fluorescent material-polymer microsphere self-assembly preparation dual-fluorescent-channel fluorescent microsphere
Adding 50mg of the microspheres obtained in the step (1) into a screw reagent bottle filled with 10mL of ethanol, carrying out ultrasonic treatment for 30min, adding 200 mu L of water-soluble quantum dots, carrying out magnetic stirring for 8 h, centrifuging to remove a reaction solvent, washing with methanol for three times, and carrying out vacuum drying.
Example 2
Action of single fluorescent channel polymeric microsphere and D-fructose
Detection conditions are as follows: preparing aqueous solutions (pH: 3, 5, 7, 9, 11) with different pH values by using a sodium hydroxide solution and a hydrochloric acid adjusting solution, dissolving poly (divinylbenzene-co-p-vinylphenylboronic acid) polymer microspheres (1mg) in 10mL of the solution, diluting the solution by 10 times, and preparing the aqueous solution with the concentration of 1 × 10-2mg/mL of aqueous solutions of poly (divinylbenzene-co-p-vinylphenylboronic acid) at various pH values. Weighing sugar with different masses, dissolving with the solution by ultrasonic wave, and detecting the fluorescence type and ultraviolet signal. The fluorescence setting conditions are that the excitation wavelength is 258nm, the generation wavelength is 285-480nm, the excitation and emission slit is 10nm, the voltage is 400v, and the response time is 2.0 s.
The results in FIG. 3 show that the microsphere with a single fluorescent channel has the strongest quenching response at a pH value of 9.0, has the widest application range, and can realize the detection of fructose within the range of 0.25-100 mg/mL.
The results in FIG. 4 show that the quenching mode between the polymer microsphere with a single fluorescence channel and D-fructose belongs to static quenching, and a related complex is formed between the fluorescent polymer microsphere and D-fructose, thereby causing fluorescence quenching of the polymer microsphere. And establishing a Lineweaver-Burk double reciprocal curve, obtaining a corresponding straight line, fitting to obtain a correlation coefficient of 0.98793, and enabling the result to accord with a static quenching rule.
Example 3
Action of double-fluorescence channel polymeric microspheres and D-fructose
Dissolving polymer microsphere (1mg) self-assembled with water-soluble quantum dot in 10mL of solution, diluting the solution by 10 times to obtain a solution with concentration of 1 × 10-2mg/mL of Poly (diethyl ether) of different pHAlkenylbenzene-co-p-vinylphenylboronic acid) aqueous solution (pH 9.0). Weighing a certain amount of D-fructose, ultrasonically dissolving the D-fructose by using the solution, and detecting the fluorescent type and the ultraviolet signal of the D-fructose. The fluorescence setting conditions are that the excitation wavelength is 258 and 360nm, the generation wavelength is 480 and 500-800nm, the excitation and emission slit is 10nm, the voltage is 700v, and the response time is 2.0 s.
The results of fig. 5 show that the synthesized poly (divinylbenzene-co-p-vinylphenylboronic acid) can self-assemble with the fluorescent material in a short time. By self-assembling with the fluorescent material, the original fluorescent single-channel polymer microsphere is converted into a material with double fluorescent channels. The double fluorescence channels are not interfered with each other, and the method can be applied to the detection of D-fructose by a fluorescence ratio method, and the fluorescence ratio detection method is more sensitive and accurate compared with a single fluorescence detection method.
The result of FIG. 6 shows that the microsphere with double fluorescence channels prepared by self-assembly can be used for multicolor fluorescence imaging, and the applicability of the microsphere with double fluorescence channels is improved.
Example 4
Preparation method of double-fluorescent-channel polymer microspheres
(1) Solvothermal preparation of Mono-fluorescent channeled poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres 4-vinylphenylboronic acid (735mg, 5mmol) and divinylbenzene (710. mu.L, 5mmol) (basic alumina column to remove inhibitor) were added to 80mL acetonitrile and dissolved thoroughly with ultrasound. 30mg of azobisisobutyl (recrystallization) was added to the above solution, and the reaction mixture was placed in a 100mL reaction vessel and reacted at 110 ℃ for 8 hours. After the polymerization reaction, the reaction solvent was removed by centrifugation, washed three times with methanol, and dried for use.
(2) Fluorescent material-polymer microsphere self-assembly preparation dual-fluorescent-channel fluorescent microsphere
Adding 50mg of the microspheres obtained in the step (1) into a screw reagent bottle filled with 10mL of ethanol, performing ultrasonic treatment for 30min, and adding carbon dots (carbon source: citric acid, lambda)ex:365nm/λem500-700nm) 200. mu.L, magnetically stirring for 8 hours, centrifuging to remove the reaction solvent, washing with methanol three times, and vacuum drying.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (2)
1. A preparation method of a double-fluorescent-channel polymer microsphere is characterized by comprising the following steps:
(a) preparing mono-fluorescent poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres by a solvothermal method;
(b) preparing polymer microspheres with double fluorescent channels by a method of self-assembly with fluorescent materials;
the procedure of the step (a) for preparing the monofluorescent poly (divinylbenzene-co-p-vinylphenylboronic acid) microspheres is as follows:
adding 5mmol of 4-vinylphenylboronic acid and 5mmol of divinylbenzene into 80mL of acetonitrile, carrying out ultrasonic full dissolution, adding 30mg of azobisisobutyronitrile into the solution, placing the reaction solution into a 100mL reaction kettle, reacting for 8 hours at 110 ℃, centrifuging to remove the reaction solvent after the polymerization reaction is finished, washing with methanol for three times, and drying for later use;
the process for preparing the polymer microsphere with the double fluorescent channels in the step (b) is as follows:
adding 50mg of the microspheres obtained in the step (1) into a screw reagent bottle filled with 10mL of ethanol, performing ultrasonic treatment for 30min, adding a fluorescent material, performing magnetic stirring for 8 hours, centrifuging to remove a reaction solvent, washing with methanol for three times, and performing vacuum drying;
the fluorescent materials are respectively lambdaex:360nm/λem500-700nm CdSe/ZnS quantum dots or lambda prepared by using citric acid as carbon sourceex:365nm/λem500-700nm carbon dots, and the amount of the fluorescent material is 200 μ L.
2. The application of the polymer microsphere with double fluorescence channels, which is obtained by the preparation method according to claim 1, is characterized in that the microsphere is applied to the detection of D-fructose.
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| CN103304735A (en) * | 2012-03-14 | 2013-09-18 | 中国科学院大连化学物理研究所 | Method for preparing polymeric microsphere in alcohol-water mixed solvent |
| CN103937486A (en) * | 2014-01-26 | 2014-07-23 | 南京大学 | Fluorescent nanoprobes, and preparation method and applications thereof |
| CN104497236A (en) * | 2014-12-16 | 2015-04-08 | 湖南科技大学 | Copolymer modified fluorescent carbon nanoparticles with pH response |
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Patent Citations (5)
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| US3864166A (en) * | 1972-06-15 | 1975-02-04 | Boehringer Mannheim Gmbh | Process for the separation of sugars |
| CN102516458A (en) * | 2011-12-13 | 2012-06-27 | 南京大学 | Molecularly imprinted polymer specially combined with specified glycoprotein and preparation method and application of molecularly imprinted polymer |
| CN103304735A (en) * | 2012-03-14 | 2013-09-18 | 中国科学院大连化学物理研究所 | Method for preparing polymeric microsphere in alcohol-water mixed solvent |
| CN103937486A (en) * | 2014-01-26 | 2014-07-23 | 南京大学 | Fluorescent nanoprobes, and preparation method and applications thereof |
| CN104497236A (en) * | 2014-12-16 | 2015-04-08 | 湖南科技大学 | Copolymer modified fluorescent carbon nanoparticles with pH response |
Non-Patent Citations (1)
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| "Facile synthesis of magnetic poly(styrene-co-4-vinylbenzene-boronic acid) microspheres for selective enrichment of glycopeptides";Wang Mengyi et al.,;《PROTEOMICS》;20150731;第15卷(第13期);第2158-2165页 * |
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Address after: No.9, 13th Street, economic and Technological Development Zone, Binhai New Area, Tianjin Patentee after: Tianjin University of Science and Technology Address before: 300222 No. 1038 South Dagu Road, Tianjin, Hexi District Patentee before: Tianjin University of Science and Technology |