CN108192596B - Coated carboxylated SiO2Preparation method of fluorescent nanosphere - Google Patents
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Abstract
The invention discloses a coated carboxylated SiO2The preparation method of the fluorescent nanosphere comprises the steps of taking an allyl fluorescent probe with double bonds, methacrylic acid and a silane coupling agent KH151 as raw materials, carrying out polymerization reaction to obtain a fluorescent polymer, and grafting the fluorescent polymer on SiO through the action of chemical bonds2Surface of nanosphere to prepare coated carboxylated SiO2Fluorescent nanospheres. Coated carboxylated SiO prepared by the invention2The fluorescent nanosphere has stable morphological structure, good monodispersity, high luminous efficiency and good biocompatibility, not only has a carboxylation functional group, but also has a firm-Si-O-Si-bond, thereby avoiding the leakage and quenching of the fluorescence of the product.
Description
Technical Field
The invention relates to a preparation method of fluorescent nanospheres, in particular to coated carboxylated SiO2A preparation method of fluorescent nanospheres.
Background
The silicon dioxide microspheres have the advantages of simple preparation, stable property, easy surface modification, good biocompatibility and no degradation under physiological conditions, and are widely applied in the fields of chemistry, engineering, biomedicine and other subjects. Particularly, the functionalized silica fluorescent microspheres not only have excellent optical performance, but also are excellent biological materials, and after the functionalized silica fluorescent microspheres are specifically combined with biological macromolecules through surface functional groups, high-sensitivity and high-selectivity targeted combination can be realized, so that the functionalized silica fluorescent microspheres are applied to the biological fields of molecular tracing, immunoassay, optical instrument correction, drug release and the like.
CN 1782020A discloses a preparation method of a silica fluorescent microsphere containing cadmium telluride fluorescent quantum dots, which physically embeds cadmium telluride as a fluorescent probe in the silica microsphere, and has the advantages of high toxicity, easy leakage and quenching. CN105037662A discloses a preparation method of europium-bonded nano-silica fluorescent microspheres, and documents (Colloids and surfaces B: Biointerfaces, 2017, 157, 286-296) also report that coumarin fluorescent compounds are introduced on the surfaces of aminated silica nanospheres through sulfonamide bonds, however, the surfaces of the two fluorescent microspheres lack functional groups, so that the subsequent researches on biology and the like are inconvenient. The mesoporous silica fluorescent microspheres reported by the Thangqian et al (chemical bulletin, 2010, 68, 18, 1925-1929) are introduced into fluorescein through disulfide bonds, but the disulfide bonds are easily broken in glutathione solution, so that fluorescence leakage is caused.
In addition, the silicon dioxide nanospheres reported in the literature are mostly prepared by adopting a reverse microemulsion method, and the preparation process is long in time consumption.
Disclosure of Invention
The invention aims to provide a coated carboxylated SiO with stable morphological structure, good monodispersity and high luminous efficiency2A preparation method of fluorescent nanospheres.
The coated carboxylated SiO of the invention2The preparation method of the fluorescent nanosphere takes an allyl fluorescent probe with double bonds, methacrylic acid and a silane coupling agent KH151 as raw materials, a fluorescent polymer is obtained through polymerization reaction, and then the fluorescent polymer is grafted on SiO under the action of chemical bonds2Surface of nanosphere to prepare coated carboxylated SiO2Fluorescent nanospheres.
Further, the present invention specifically prepares the coated carboxylated SiO by the following steps2Fluorescent nanospheres.
1) Mixing water, absolute ethyl alcohol and ammonia water uniformly, adding ethyl orthosilicate, stirring and reacting at room temperature, washing a reaction product with water and absolute ethyl alcohol, and drying to obtain SiO2Nanospheres.
2) Adding the allyl fluorescent probe, a silane coupling agent KH151, methacrylic acid and azobisisobutyronitrile into anhydrous methanol, carrying out heating reflux reaction under the protection of inertia, and evaporating to remove a solvent methanol to obtain a carboxylated allyl fluorescent probe-KH 151 polymer.
3) Adding SiO into anhydrous toluene2Heating and refluxing nanospheres and carboxylated allyl fluorescent probe-KH 151 polymer under inert protection to prepare coated carboxylated SiO2Fluorescent nanospheres.
In the preparation method, the allyl fluorescent probe is any one of allyl-4-methylcoumarin, allyl fluorescein, allyl rhodamine B and allyl carbazole.
SiO in step 1) of the invention2In the preparation of the nanosphere, the volume ratio of the water, the absolute ethyl alcohol, the ammonia water and the ethyl orthosilicate is 6-7: 15-16.5: 1.6-1.8: 1.
And then mixing the raw materials, and stirring and reacting for 0.5-3 h at room temperature.
In the preparation of the carboxylated allyl fluorescent probe-KH 151 polymer in the step 2), the mass ratio of the silane coupling agent KH151 to the azobisisobutyronitrile to the allyl fluorescent probe to the methacrylic acid is 1: 0.4-0.7: 0.8-1.8: 1-2.
And then carrying out reflux reaction on the raw materials at 65-70 ℃ for 6-8 h.
In the step 3) of the present invention, it is preferable to react an excess amount of carboxylated allyl fluorescent probe-KH 151 polymer with SiO2The nanospheres are subjected to reflux reaction for 20-24 h at 105-115 ℃.
Further, the invention uses SiO2The reaction product of the reflux reaction of the nanospheres and the carboxylated allyl fluorescent probe-KH 151 polymer is repeatedly washed by water and ethanol until the washing solution does not detect fluorescence any more, and the final coated carboxylated SiO is obtained after drying2Fluorescent nanosphere products.
The invention firstly adopts a free radical polymerization method to polymerize an allyl fluorescent probe, methacrylic acid and KH151 to obtain a carboxylated allyl fluorescent probe-KH 151 polymer, and then the fluorescent polymer is subjected to a high-temperature dehydration condensation method to obtain a carboxylated allyl fluorescent probe-KH 151 polymerChemical bonds of the-Si-bond and in SiO2Obtaining coated carboxylated SiO on the surface of the nanosphere2Fluorescent nanospheres. The fluorescent nanosphere not only has a carboxylation functional group, but also has a firm-Si-O-Si-bond, so that the fluorescent leakage and quenching of the product are avoided.
Compared with the prior art, the preparation method has the following advantages: 1. free radical polymerization is carried out on allyl fluorescent dye, methacrylic acid and vinyl triethoxysilane (KH151) to obtain fluorescent polymer, and the fluorescent polymer is bonded on SiO through chemical bonds2The fluorescent microsphere has carboxyl functional groups on the surface of the nanosphere, the higher overall luminous efficiency of the microsphere is ensured, and the fluorescent dye stably exists and is not easy to leak and quench. 2. The carrier of the fluorescent nanosphere is inorganic material SiO2It has many incomparable properties such as physical rigidity, chemical stability, negligible swelling in solvent, nontoxicity, colloidal stability, high biocompatibility, excellent optical transparency and easy functionalization of surface, especially surface carboxylated SiO2The active carboxyl of the fluorescent nanosphere can react with various inorganic ions or inorganic, organic and biological molecules, and has wide application prospects in the fields of biochemistry, chemical analysis and the like. 3. In the allyl fluorescent dye adopted by the invention, allyl carbazole is a near ultraviolet or deep blue light fluorescent material, allyl fluorescein and allyl coumarin are green light-emitting fluorescent materials, and allyl rhodamine B is a near infrared or red light-emitting fluorescent material, so that the coated carboxylated SiO with blue, green and red fluorescence can be prepared2Fluorescent nanospheres. 4. The invention prepares SiO by adopting a sol-gel method2The nanosphere has short operation time, the fluorescent polymer is introduced by adopting a high-temperature condensation method, the operation is simple and convenient, and the cost for preparing the fluorescent microsphere is low.
Drawings
FIG. 1 is SiO2Scanning Electron Microscopy (SEM) images of nanospheres.
FIG. 2 is SiO2Transmission Electron Microscopy (TEM) images of nanospheres.
FIG. 3 is a carboxylated SiO2Fluorescent nanospheres (a) and SiO2Infrared spectrum of nanosphere (b).
FIG. 4 is a UV (inset) and fluorescence spectra of allyl 4-methylcoumarin of example 1 and SiO thereof2Fluorescence spectrum of the fluorescent nanosphere (ethanol as solvent).
FIG. 5 is a UV spectrum (inset) and a fluorescence spectrum of allylfluorescein of example 2 and SiO thereof2Fluorescence spectrum of fluorescent nanospheres (water as solvent).
FIG. 6 is a UV spectrum (inset) and a fluorescence spectrum of allylfluorescein of example 3 and SiO thereof2Fluorescence spectrum of fluorescent nanospheres (water as solvent).
FIG. 7 is a UV spectrum (inset) and fluorescence spectrum of allylcarbazole of example 4 and SiO thereof2Fluorescence spectrum of the fluorescent nanosphere (ethanol as solvent).
FIG. 8 is a fluorescence microscope photograph of examples 1 to 4.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1.
Adding 28m of distilled water L, 65m of absolute ethyl alcohol L and 7m of ammonia water L into a 100m L three-necked flask, uniformly mixing, adding 4m of Tetraethoxysilane (TEOS) L, magnetically stirring at room temperature to react for 1.5h, centrifugally separating a product, alternately and repeatedly washing with water and absolute ethyl alcohol, and drying in vacuum at 50 ℃ to obtain SiO2Nanospheres.
FIGS. 1 and 2 are SiO as prepared2SEM and TEM images of nanospheres, showing SiO2The nanosphere has good sphericity and good monodispersity, and lays a foundation for preparing the coated carboxylated fluorescent nanosphere.
Weighing 3.3g (30mmol) of resorcinol, slowly adding 60m L concentrated sulfuric acid at normal temperature until the resorcinol is completely dissolved, placing the mixture in an ice water bath, slowly dropwise adding 3.9m L (1.95mmol) of ethyl acetoacetate, continuously reacting for 1h, then heating to room temperature, continuously reacting for 24h, pouring the reaction liquid into ice water of about 300m L, violently stirring, generating off-white precipitate, carrying out suction filtration, recrystallizing with absolute ethyl alcohol, obtaining off-white solid, and drying in a vacuum drying oven at 50 ℃ to obtain 4-methyl-7-hydroxycoumarin.
Weighing 200mg (0.4mmol) of 4-methyl-7-hydroxycoumarin and 0.28g (0.8mmol) of tetrabutylammonium bromide (TBAB), dissolving with 30m L of trichloromethane, adding 0.2g of anhydrous sodium carbonate, a small amount of potassium iodide and 30m L of deionized water, stirring at room temperature for 15min, slowly dropwise adding 0.11m L of 3-bromopropylene, stirring at 30-40 ℃ for about 4h, separating an organic phase by a separating funnel, extracting an aqueous phase with trichloromethane, combining the organic phases, drying with anhydrous sodium sulfate, carrying out rotary evaporation to obtain a yellow-green solid, and carrying out column chromatography to obtain the 4-methyl-7-O-allylcoumarin.
Weighing 0.030g of 4-methyl-7-O-allyl coumarin, 0.0337g of vinyl triethoxysilane (KH151), 0.0337g of methacrylic acid (MAA), 0.0138g of Azobisisobutyronitrile (AIBN) and 10m of anhydrous methanol L, adding into a 100m L three-necked bottle, stirring and heating to 70 ℃ under the protection of nitrogen, carrying out reflux reaction for 7h, evaporating the solvent methanol of the reaction product under vacuum condition to obtain a carboxylated 4-methyl-7-O-allyl coumarin-KH 151 polymer, and filling nitrogen for sealing.
Weighing SiO20.1g of nanosphere, transferring the carboxylated 4-methyl-7-O-allyl coumarin-KH 151 polymer into a three-necked bottle by using anhydrous toluene 10m L, carrying out reflux reaction for 24h under the protection of nitrogen, repeatedly washing the product by using ethanol and water after the reaction is finished until the supernatant does not have fluorescence, and carrying out vacuum drying to obtain the coated carboxylated SiO polymer2Fluorescent nanospheres.
FIG. 4 is a UV (inset) and fluorescence (a) spectra of 4-methyl-7-O-allylcoumarin, and SiO2Fluorescence spectrum of fluorescent nanospheres (b). The fluorescence spectrogram takes ethanol as a solvent and performs measurement at an excitation wavelength of 321 nm. As can be seen from the figure, carboxylated SiO2The fluorescence emission spectrum of the fluorescent nanosphere (b) is reddened relative to 4-methyl-7-O-allyl coumarinBy shifting (13nm), it can be shown that 4-methyl-7-O-allylcoumarin has been successfully grafted onto SiO2The surface of the nanospheres.
Example 2.
Adding distilled water 21m L, absolute ethyl alcohol 48.75m L and ammonia water 5.25m L into a 100m L three-necked flask, uniformly mixing, adding Tetraethoxysilane (TEOS)3m L, magnetically stirring at room temperature to react for 2.5h, centrifugally separating a product, repeatedly washing with water and absolute ethyl alcohol, and drying in vacuum at 50 ℃ to obtain SiO2Nanospheres.
According to a method of a document (J. Mater. chem., 2009, 19, 2018-2025), 2.00g of fluorescein, 2.42g of 3-bromopropylene and 4.97g of anhydrous potassium carbonate are put into a reaction bottle, a solvent DMF 50m L, a catalyst iodine trace amount and a polymerization inhibitor hydroquinone trace amount are added, and the mixture is reacted for 25 hours at 71 ℃ under anhydrous and anaerobic conditions to obtain a yellow crude product of the allylfluorescein, and the yellow crude product is recrystallized from chloroform and is subjected to column chromatography to obtain a pure product of the allylfluorescein.
0.0468g of allyl fluorescein, KH1510.0425g, 0.0526g of MAA, 0.0186g of AIBN and 10m of absolute methanol L are weighed and added into a three-necked bottle with the diameter of 100m L, the mixture is stirred and heated to 70 ℃ under the protection of nitrogen, reflux reaction is carried out for 7h, solvent methanol is evaporated to dryness on a reaction product under the vacuum condition, and the carboxylated allyl fluorescein-KH 151 polymer is obtained and sealed by filling nitrogen.
Weighing SiO20.1g of nanosphere, transferring the carboxylated allyl fluorescein-KH 151 polymer into a three-necked bottle by using anhydrous toluene 10m L, carrying out reflux reaction for 24h under the protection of nitrogen, repeatedly washing the product by using ethanol and water until supernatant does not have fluorescence after the reaction is finished, and carrying out vacuum drying to obtain the coated carboxylated SiO2Fluorescent nanospheres.
FIG. 3(a) is carboxylated allyl fluorescein-KH 151 grafted SiO2Infrared spectrum of fluorescent nanosphere, (b) is SiO2And (4) infrared spectrogram of the nanosphere. (a) Comparing the (a) and (b) at 1300-1750 cm-1Has different peaks in between, and is 1633cm-1Is a characteristic peak of carboxyl, so that the carboxyl is successfully grafted on the SiO2And (4) the surface of the nanosphere.
FIG. 5 is an ultraviolet spectrum (inset) and a fluorescence spectrum (a) of allylfluorescein, and SiO2Fluorescence spectrum of fluorescent nanospheres (b). The fluorescence spectrogram takes water as a solvent and is measured at an excitation wavelength of 454 nm. As can be seen from the figure, carboxylated SiO2The fluorescence emission spectrum of the fluorescent nanosphere (b) is red-shifted (4nm) relative to the allylfluorescein, thereby indicating that the allylfluorescein has been successfully grafted on SiO2The surface of the nanospheres.
Example 3.
Adding 14m of distilled water L, 32.5m of absolute ethyl alcohol L and 3.5m of ammonia water L into a 100m L three-necked flask, uniformly mixing, adding 2m of Tetraethoxysilane (TEOS) L, magnetically stirring at room temperature for reaction for 3h, centrifugally separating a product, alternately and repeatedly washing with water and absolute ethyl alcohol, and drying in vacuum at 50 ℃ to obtain SiO2Nanospheres.
According to a method of a document (J.Mater. chem., 2009, 19, 2018-2025), 240g of rhodamine B, 0.73g of potassium carbonate and 2.65g of 3-bromopropylene are put into a reaction bottle, a solvent DMF 50m L, a trace amount of catalyst iodine and a trace amount of polymerization inhibitor hydroquinone are added, the mixture reacts for 25 hours at 71 ℃ under anhydrous and anaerobic conditions to synthesize a crude product of the allylrhodamine B, and the pure product of the allylrhodamine B is obtained through column chromatography.
Weighing 0.0555g of allyl rhodamine B, KH1510.0486g, 0.0676g of MAA, 0.023g of AIBN and 10m L of anhydrous methanol, adding into a 100m L three-necked bottle, stirring and heating to 70 ℃ under the protection of nitrogen, carrying out reflux reaction for 7h, evaporating the solvent methanol of a reaction product under vacuum condition to obtain a carboxylated allyl rhodamine-KH 151 polymer, and filling nitrogen for sealing.
Weighing SiO20.1g of nanosphere, transferring the carboxylated allyl rhodamine-KH 151 polymer into a three-necked bottle by using anhydrous toluene 10m L, carrying out reflux reaction for 24h under the protection of nitrogen, repeatedly washing the product by using ethanol and water until supernatant does not have fluorescence after the reaction is finished, and carrying out vacuum drying to obtain the coated carboxylated SiO2Fluorescent nanospheres.
FIG. 6 is an ultraviolet spectrum (inset) and a fluorescence spectrum (a) of allylrhodamine B, and SiO2Fluorescence spectrum of fluorescent nanospheres (b). The fluorescence spectrogram takes water as a solvent and is measured at an excitation wavelength of 558 nm. From the figureIt is seen that the carboxylated SiO2The fluorescence emission spectrum of the fluorescent nanosphere (B) is red-shifted (4nm) relative to the allylrhodamine B, thereby indicating that the allylrhodamine B is successfully grafted on SiO2The surface of the nanospheres.
Example 4.
Adding distilled water 35m L, anhydrous ethanol 81.25m L and ammonia water 8.75m L into a 100m L three-necked flask, uniformly mixing, adding Tetraethoxysilane (TEOS)5m L, magnetically stirring at room temperature for reaction for 2h, centrifugally separating a product, alternately and repeatedly washing with water and anhydrous ethanol, and drying in vacuum at 50 ℃ to obtain SiO2Nanospheres.
Putting carbazole, potassium hydroxide and 3-bromopropylene into a reaction bottle, adding a solvent, a catalyst and a polymerization inhibitor, reacting at a certain temperature in the absence of water and oxygen, and performing column chromatography on a crude product to obtain a pure N-allyl carbazole product.
0.0528g of N-allyl carbazole, KH1510.0561g, 0.0612g of MAA, 0.0216g of AIBN and 10m L of anhydrous methanol are weighed and added into a 100m L three-necked bottle, the mixture is stirred and heated to 70 ℃ under the protection of nitrogen, reflux reaction is carried out for 7 hours, a reaction product is subjected to solvent methanol evaporation under the vacuum condition, and a carboxylated allyl carbazole-KH 151 polymer is obtained and is filled with nitrogen for sealing.
Weighing SiO20.1g of nanosphere, transferring the carboxylated allyl carbazole-KH 151 polymer into a three-necked bottle by using anhydrous toluene 10m L, carrying out reflux reaction for 24h under the protection of nitrogen, repeatedly washing the product by using ethanol and water until supernatant does not have fluorescence after the reaction is finished, and carrying out vacuum drying to obtain the coated carboxylated SiO2Fluorescent nanospheres.
FIG. 7 is a UV spectrum (inset) and a fluorescence spectrum (a) of allylcarbazole, and SiO2Fluorescence spectrum of fluorescent nanospheres (b). The fluorescence spectrogram takes ethanol as a solvent and is measured at an excitation wavelength of 293 nm. As can be seen from the figure, carboxylated SiO2The fluorescence emission spectrum of the fluorescent nanosphere (b) is red-shifted (2nm) relative to that of allyl carbazole, thereby indicating that allyl carbazole has been successfully grafted on SiO2The surface of the nanospheres.
FIG. 8 shows fluorescence of examples 1 to 4 in this orderMicroscopic picture. As can be seen from the figure, carboxylated SiO2The fluorescent nanospheres have strong luminescence characteristics, which shows that the allyl fluorescent probe is uniformly grafted on the microsphere surface and has good stability.
Claims (7)
1. Coated carboxylated SiO2The preparation method of the fluorescent nanosphere comprises the steps of taking an allyl fluorescent probe with double bonds, methacrylic acid and a silane coupling agent KH151 as raw materials, carrying out polymerization reaction to obtain a fluorescent polymer, and grafting the fluorescent polymer on SiO through the action of chemical bonds2Surface of nanosphere to prepare coated carboxylated SiO2The fluorescent nanosphere is prepared by the following method:
1) mixing water, absolute ethyl alcohol and ammonia water uniformly, adding ethyl orthosilicate, stirring and reacting at room temperature, washing a reaction product with water and absolute ethyl alcohol, and drying to obtain SiO2Nanospheres;
2) adding the allyl fluorescent probe, a silane coupling agent KH151, methacrylic acid and azobisisobutyronitrile into anhydrous methanol, carrying out heating reflux reaction under the protection of inertia, and evaporating to remove a solvent methanol to obtain a carboxylated allyl fluorescent probe-KH 151 polymer;
3) adding SiO into anhydrous toluene2Heating and refluxing nanospheres and carboxylated allyl fluorescent probe-KH 151 polymer under inert protection to prepare coated carboxylated SiO2Fluorescent nanospheres.
2. The coated carboxylated SiO of claim 12The preparation method of the fluorescent nanosphere is characterized in that the allyl fluorescent probe is any one of allyl-4-methylcoumarin, allyl fluorescein, allyl rhodamine B and allyl carbazole.
3. The coated carboxylated SiO of claim 12The preparation method of the fluorescent nanospheres is characterized in that the volume ratio of the water, the absolute ethyl alcohol, the ammonia water and the ethyl orthosilicate is 6-7: 15-16.5: 1.6-1.8: 1.
4. The coated carboxylated SiO of claim 12The preparation method of the fluorescent nanospheres is characterized in that in the step 1), the reaction is carried out for 0.5-3 hours at room temperature by stirring.
5. The coated carboxylated SiO of claim 12The preparation method of the fluorescent nanosphere is characterized in that the mass ratio of the silane coupling agent KH151 to the azodiisobutyronitrile to the allyl fluorescent probe to the methacrylic acid is 1: 0.4-0.7: 0.8-1.8: 1-2.
6. The coated carboxylated SiO of claim 12The preparation method of the fluorescent nanospheres is characterized in that in the step 2), the reflux reaction is carried out for 6-8 hours at the temperature of 65-70 ℃.
7. The coated carboxylated SiO of claim 12The preparation method of the fluorescent nanosphere is characterized in that excessive carboxylated allyl fluorescent probe-KH 151 polymer and SiO are used2The nanospheres are subjected to reflux reaction for 20-24 h at 105-115 ℃.
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