CN110951479B - Preparation method of PEG (polyethylene glycol) coated porous rare earth phosphate fluorescent nano material - Google Patents
Preparation method of PEG (polyethylene glycol) coated porous rare earth phosphate fluorescent nano material Download PDFInfo
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Abstract
The invention discloses a preparation method of a PEG (polyethylene glycol) coated porous rare earth phosphate fluorescent nano material, belonging to the technical field of nano materials; the method adopts PEG with the average molecular weight of 1000-3000, and the PEG is coated on the surface of the porous rare earth phosphate nano-particles to prepare the fluorescent nano-composite material with the core-shell structure, and the material has excellent luminous performance, water solubility and biocompatibility, thereby solving the bottleneck problem for the application of the rare earth fluorescent nano-material in the aspects of biology, medicine and the like, and the method has the advantages of mild preparation conditions, simple process and no need of special environment; the water-soluble core-shell structure fluorescent nano material prepared by the invention has potential application prospects in the aspects of fluorescent labeling, photothermal treatment, drug carriers, immunoassay, biochips, detection of germs and microorganisms in food and environment, photo-biological imaging and the like.
Description
Technical Field
The invention relates to a coating method of porous nano particles, in particular to a preparation method of a PEG (polyethylene glycol) coated porous rare earth phosphate fluorescent nano material with good fluorescent property; belongs to the technical field of nano materials.
Background
At present, the surfaces of rare earth luminescent nanoparticles synthesized by conventional methods (e.g., high-temperature thermal decomposition method, precipitation method, water/solvent thermal method, sol-gel method, etc.) are hydrophobic; in recent years, although researchers have adopted various methods to prepare rare earth nano materials with different morphologies, uniform particle size and controllable size, the researchers still have difficulty in obtaining good water solubility and biocompatibility, and limit the application of the rare earth nano materials in the field of biomedicine, so that the surfaces of the rare earth nano materials need to be modified after the nano particles are synthesized; therefore, the selection of a proper surface coating and modification reagent has important significance for the surface functional modification and application of the rare earth nano luminescent particles.
Polyethylene glycol (PEG) is a nonionic surfactant, has excellent water solubility and stability, and is not easily affected by electrolyte, acid and alkali; its molecular formula is HO (CH) 2 CH 2 O) n H, only two hydrophilic groups of hydroxyl and ether are used, and a hydrophobic group is not used; it has a serpentine shape in aqueous solution, overall showing considerable hydrophilicity; polyethylene glycol (PEG) is widely used in the biomedical field, food additives, melting aids, analytical reagents, softeners, lubricants and the like; the core-shell structure nano composite material obtained by coating the surface of the porous rare earth phosphate fluorescent nano particle with polyethylene glycol (PEG) has the advantages of the polyethylene glycol (PEG) and the porous rare earth phosphate fluorescent nano particle, and has excellent luminous performance, water solubility and biocompatibility, so the core-shell structure nano composite material has wider application prospect.
There are also many related technologies for PEG coating, such as chinese patent publication No.: (CN 109847095A, application number: 201811620520.7), discloses a preparation method of PEG-coated photosensitizer IR780 modified calcium phosphate bone cement; the Chinese patent invention discloses the following numbers: (CN 101903290A, application number: 200880114641.2), discloses a PEG-coated core-shell silicon dioxide nano-particle and a preparation method thereof; the Chinese patent invention discloses: (CN 108671233A, application number: 201810545666.3), discloses a preparation method of a polyethylene glycol-polycaprolactone-polyethylene glycol coated silica/polypyrrole/mesoporous silica drug-loaded material; the Chinese patent invention grant number: (CN 103705932B, application number: 201310747523.8), discloses a preparation method of polylactic acid-polyethylene glycol coated florfenicol nanofiber, successfully solves the problems of drug loading, drug burst release, short action time and poor water solubility; the Chinese patent invention discloses the following numbers: (CN 106983874A, application number: 201710233210.9), discloses a gold nanorod/polyethylene glycol/carbon dot nano hybrid imaging contrast material and a preparation method thereof. The authorization number of the Chinese patent: (CN 103405790B, application number: 201310302421.5), discloses a method for preparing a polymer in-situ modified superparamagnetic particle, which successfully solves the problems of low crystallinity, small saturation magnetization and poor MRI imaging effect of the existing commercial contrast agent; the Chinese patent invention discloses: (CN 11001629A, application number: 20190301352.3) discloses an antibacterial polishing solution based on stone polishing and a preparation method thereof; the Chinese patent invention discloses: (CN 107723833A, application number: 201710962010.7) discloses a preparation method of an alpha-nano alumina modified polyester fiber.
At present, no report that PEG-coated porous rare earth doped phosphate fluorescent nanoparticles have stable and good fluorescence properties is found.
Disclosure of Invention
The invention provides a preparation method of a PEG-coated porous rare earth phosphate fluorescent nano material, which adopts PEG with the average molecular weight of 1000-3000 to coat the PEG on the surface of a porous rare earth phosphate nano particle to prepare the core-shell structure fluorescent nano composite material.
The technical scheme adopted by the invention is as follows: a method for preparing PEG-coated porous rare earth phosphate fluorescent nano material by ultrasonic dispersion treatment of YPO 4 :Sm 3+ A porous nano luminescent material, which is prepared by performing surface coating and modification reaction by using PEG with the molecular weight of 1000 to 3000 in a microwave reactor to synthesize a core-shell structure nano luminescent material containing hydrophilic surface functional groups; comprises the following steps.
The method comprises the following steps: preparing porous rare earth doped phosphate fluorescent nanoparticles by a hydrothermal method;
(1) Mixing Sm 2 O 3 、Y 2 O 3 Dissolving in nitric acid with the molar concentration of 3-6 mol/L to obtain Sm (NO) with the molar concentration of 0.02-0.5 mol/L 3 ) 3 Solutions A and Y (NO) 3 ) 3 Solution B;
(2) Sm (NO) 3 ) 3 Solutions A and Y (NO) 3 ) 3 Mixing the solution B to obtain a mixed solution C, wherein the molar ratio of the solution A to the solution B is (1); adding H of 2 to 5mol/L into the mixed solution C 3 PO 4 Obtaining a reaction system D, wherein the molar ratio of the cation to the anion in the reaction system D is 1 to 1;
(3) Adjusting the pH value of the reaction system D to be less than or equal to 2 by using NaOH solution, wherein obvious precipitation is generated; strongly stirring for 10 to 30min, and then carrying out ultrasonic treatment for 10 to 30min to fully mix the components to obtain a reaction system E;
(4) Transferring the reaction system E into a reaction kettle with polytetrafluoroethylene, sealing, putting into a drying box, and reacting for 6 to 24h within the temperature range of 120 to 240 ℃; naturally cooling to room temperature, and centrifuging by using a centrifugal machine to separate a solid product; washing the solid product with deionized water for 2 to 4 times, and then washing with absolute ethyl alcohol for 2 to 3 times; then putting the mixture into a forced air drying oven for drying for 8 to 12h, wherein the drying temperature is 80 to 120 ℃; and finally, grinding and grinding by using agate to obtain the porous rare earth doped phosphate fluorescent nano-particles.
Step two: preparing PEG (1000 to 3000) coated porous rare earth phosphate core-shell structure fluorescent nanoparticles by a microwave method;
(1) Dissolving 0.08 to 0.8g of PEG (1000 to 3000) in deionized water to obtain 0.08 to 0.8g/L of PEG solution A;
(2) Dissolving the porous rare earth doped phosphate fluorescent nano-particles prepared in the step one in deionized water, and carrying out ultrasonic treatment for 40 to 60min to obtain 0.002 to 0.01mol/L suspension B;
(3) Putting the suspension B into a microwave reactor at the temperature ranging from 50 to 80 ℃, and then dripping the PEG solution A into the suspension B which is continuously stirred at the speed of 4 to 8 drops per second, wherein the volume ratio of the suspension B to the PEG solution A is 1; after the PEG solution A is dripped, cooling the reaction system to room temperature to obtain a reaction system C; adding n-hexane with the same volume as that of the reaction system C, aging for 12-36h, and centrifuging by using a high-speed centrifuge to separate a solid product, wherein the centrifugal rate of the high-speed centrifuge is 8000-10000r/min; then washing the solid product with absolute ethyl alcohol for 3 to 5 times; then placing the mixture into a forced air drying oven for drying, wherein the drying temperature is 60 to 80 ℃, and the drying time is 20 to 30h; and finally, grinding by using agate to obtain the porous rare earth phosphate core-shell structure fluorescent nanoparticles coated by PEG (1000 to 3000).
In the first step, lanthanum or gadolinium is used to replace yttrium in the rare earth ions, and any one of cerium, europium, terbium and dysprosium is used to replace samarium.
The invention has the beneficial effects that: the invention coats PEG (1000 to 3000) on the surface of the porous rare earth phosphate fluorescent nano-particles to prepare the fluorescent nano-composite material with a core-shell structure, the material has excellent fluorescence property, water solubility and biocompatibility, and key technical problems are solved for the application of the rare earth nano-luminescent material in the aspects of biology, medicine and the like.
The method used by the invention has the advantages of mild preparation conditions, simple process and no need of special environment. The water-soluble core-shell structure porous fluorescent nano material prepared by the invention has potential application prospects in the aspects of fluorescent labeling, photothermal treatment, drug carriers, immunoassay, biochips, detection of germs and microorganisms in food and environment, photo-biological imaging and the like.
Drawings
FIG. 1 is an SEM photograph of the porous rare earth-doped phosphate fluorescent nanoparticles prepared in step one of example 1 of the present invention.
FIG. 2 is an SEM photograph of the PEG-coated porous rare earth phosphate core-shell structure fluorescent nanoparticles prepared in example 1 of the present invention.
FIG. 3 is a TEM photograph of the porous rare earth-doped phosphate fluorescent nanoparticles prepared in step one of example 1 of the present invention.
FIG. 4 is a TEM photograph of the PEG-coated porous rare earth phosphate core-shell structure fluorescent nanoparticles prepared in example 1 of the present invention.
Fig. 5 is an X-ray diffraction (XRD) pattern of the porous rare earth-doped phosphate fluorescent nanoparticle prepared in example 1 and the PEG-coated porous rare earth phosphate core-shell structure fluorescent nanoparticle prepared in the present invention.
Fig. 6 is an infrared spectrum of the porous rare earth-doped phosphate fluorescent nanoparticle prepared in example 1 of the present invention and the PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticle prepared in example 1.
Fig. 7 is an excitation spectrum of the porous rare earth-doped phosphate fluorescent nanoparticles and the PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticles prepared in examples 1, 3, and 4 of the present invention.
Fig. 8 is an emission spectrum of the porous rare earth-doped phosphate fluorescent nanoparticles and PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticles prepared in examples 1, 3, and 4 of the present invention.
Fig. 9 is an emission spectrum of the porous rare earth-doped phosphate fluorescent nanoparticle prepared in example 2 of the present invention and the PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticle.
Fig. 10 is an excitation spectrum of the porous rare earth-doped phosphate fluorescent nanoparticle and the PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticle prepared in example 2 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the following embodiments and the accompanying drawings, which are only used for illustrating the technical solution of the present invention and not for limiting the same.
Example 1
The method comprises the following steps: preparing porous rare earth doped phosphate fluorescent nanoparticles by a hydrothermal method;
(1) Mixing Sm 2 O 3 、Y 2 O 3 Dissolving in nitric acid with a molar concentration of 3.6mol/L to obtain Sm (NO) with a molar concentration of 0.05mol/L 3 ) 3 Solution A and 0.5mol/L Y (NO) 3 ) 3 Solution B;
(2) Mixing Sm (NO) 3 ) 3 Solutions A and Y (NO) 3 ) 3 Mixing the solution B in a volume ratio of 2; 3mol/L of H is added to the solution C 3 PO 4 Obtaining a reaction system D, wherein the molar ratio of the cations to the anions in the reaction system D is 1;
(3) Adjusting the pH value of the reaction system D to 1 by using NaOH solution, strongly stirring for 30min, and carrying out ultrasonic treatment for 30min to fully mix the reaction system D and the reaction system E to obtain a reaction system E;
(4) Transferring the reaction system E into a reaction kettle with polytetrafluoroethylene, sealing, placing in a drying oven, and reacting for 12h at the temperature of 200 ℃; naturally cooling to room temperature, and centrifuging by using a centrifugal machine to separate a solid product; then washing the solid product with deionized water for 3 times, and then washing with absolute ethyl alcohol for 3 times; then putting the mixture into a blast drying oven to be dried for 12 hours, wherein the drying temperature is 80 ℃; and finally, grinding and grinding by using agate to obtain the porous rare earth doped phosphate fluorescent nano-particles.
Step two: preparing PEG (1000) coated porous rare earth phosphate core-shell structure fluorescent nanoparticles by a microwave method;
(1) 0.2g PEG with molecular weight of 1000 is dissolved in deionized water to obtain 0.2g/L PEG solution A;
(2) Dissolving the porous rare earth doped phosphate fluorescent nano-particles prepared in the step one in deionized water, and performing ultrasonic treatment for 60min to obtain 0.004mol/L suspension B;
(3) Suspension B was placed in a microwave reactor at a temperature in the range of 65 ℃ and PEG solution a was then added dropwise at a rate of 7 drops per second to continuously stirred suspension B: the volume ratio of the PEG solution A is 1; after the solution A is dripped, cooling to room temperature to obtain a reaction system C; aging 50mL of reaction system C and n-hexane with the same volume for 12h, and centrifuging by using a high-speed centrifuge to separate a solid product, wherein the centrifugation rate of the high-speed centrifuge is 8000-10000r/min; then washing the solid product with absolute ethyl alcohol for 4 times; then putting the mixture into a forced air drying oven for drying at the drying temperature of 60 ℃ for 24 hours; and finally, grinding by using agate to obtain the PEG (1000) coated porous rare earth phosphate core-shell structure fluorescent nanoparticles.
FIG. 1 is a SEM photograph of the porous rare earth-doped phosphate fluorescent nanoparticles prepared in the first step of example 1; FIG. 2 shows an SEM photograph of the PEG-coated porous rare earth phosphate core-shell structured fluorescent nanoparticles prepared in example 1; comparing the two SEM photographs, the surface of the coated nanoparticle (shown in figure 2) is smoother than that of the nanoparticle (shown in figure 1) before coating, the coating thickness is 5-10 nm, and the dispersibility is better.
FIG. 3 is a TEM photograph of the porous rare earth-doped phosphate fluorescent nanoparticles obtained in the first step of example 1; from this photograph, it can be seen that the rare earth doped phosphate fluorescent nanoparticles are porous.
FIG. 4 shows a TEM image of the PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticles prepared in example 1; the success of PEG coating can be confirmed by comparing two TEM photographs in figure 1 and figure 2; the coating thickness is 5 to 10nm, and the dispersibility is good.
FIG. 5 shows X-ray diffraction (XRD) patterns of the porous rare earth-doped phosphate fluorescent nanoparticles prepared in example 1 and the PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticles prepared in example 1; it can be seen from the figure that the crystal structure of the nanoparticle after coating is the same as that before coating, which indicates that the coating agent PEG does not affect the crystal structure of the porous nano rare earth phosphate.
FIG. 6 shows the IR spectra of the porous rare earth-doped phosphate fluorescent nanoparticles prepared in example 1 and the PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticles prepared in example 1; as can be seen from the figure, the PEG successfully coats the rare earth doped phosphate porous fluorescent nanoparticles.
FIG. 7 shows the excitation spectra of the porous rare earth-doped phosphate fluorescent nanoparticles prepared in example 1 and the PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticles; as shown in fig. 8, the emission spectra of the porous rare earth-doped phosphate fluorescent nanoparticles prepared in example 1 and the PEG-coated porous rare earth phosphate core-shell fluorescent nanoparticles are shown, and it can be seen by comparing the two fluorescence spectra that the excitation spectrum and the emission spectrum of the coated porous rare earth phosphate core-shell fluorescent nanoparticles have the same peak positions and peak types as those before coating, except that the luminescence intensity of the coated porous rare earth phosphate core-shell fluorescent nanoparticles is obviously enhanced by more than 1 time than that before coating.
Example 2
The method comprises the following steps: preparing porous rare earth doped phosphate fluorescent nanoparticles by a hydrothermal method;
(1) Eu is mixed 2 O 3 、Y 2 O 3 Dissolving in nitric acid with a molar concentration of 3.6mol/L to obtain Eu (NO) with a molar concentration of 0.05mol/L 3 ) 3 Solution A and 0.5mol/L Y (NO) 3 ) 3 Solution B;
(2) Eu (NO) 3 ) 3 Solutions A and Y (NO) 3 ) 3 Mixing the solution B in a volume ratio of 8; adding 3mol/L H into the mixed solution C 3 PO 4 Obtaining a reaction system D, wherein the molar ratio of the cations to the anions in the reaction system D is 1;
(3) Adjusting the pH value of the reaction system D to 1 by using a NaOH solution, strongly stirring for 30min, and carrying out ultrasonic treatment for 30min to fully mix the mixture to obtain a reaction system E;
(4) Transferring the reaction system E into a reaction kettle with polytetrafluoroethylene, sealing, placing in a drying oven, and reacting for 12h at the temperature of 200 ℃; naturally cooling to room temperature, and centrifuging by using a centrifugal machine to separate a solid product; then washing the solid product with deionized water for 3 times, and then washing with absolute ethyl alcohol for 3 times; then putting the mixture into a blast drying oven to be dried for 12 hours, wherein the drying temperature is 80 ℃; and finally, grinding and grinding by using agate to obtain the porous rare earth doped phosphate fluorescent nano-particles.
Step two: preparing PEG (3000) coated porous rare earth phosphate core-shell structure fluorescent nanoparticles by a microwave method;
(1) 0.5g of PEG with the molecular weight of 3000 is dissolved in deionized water to obtain 0.5g/L of PEG solution A;
(2) Dissolving the porous rare earth doped phosphate fluorescent nano-particles prepared in the step one in deionized water, and performing ultrasonic treatment for 60min to obtain 0.004mol/L suspension B;
(3) The suspension B was placed in a microwave reactor at a temperature in the range of 65 ℃ and then the PEG solution a was added dropwise at a rate of 7 drops per second to the continuously stirred suspension B: the volume ratio of the PEG solution A is 1; after the solution A is dripped, cooling to room temperature to obtain a reaction system C; aging 50mL of reaction system C and n-hexane with the same volume for 12h, and centrifuging by using a high-speed centrifuge to separate a solid product, wherein the centrifugation rate of the high-speed centrifuge is 8000-10000r/min; then washing the solid product with absolute ethyl alcohol for 4 times; then putting the mixture into a forced air drying oven for drying at the drying temperature of 60 ℃ for 24 hours; and finally, grinding by using agate to obtain the PEG (3000) coated porous rare earth phosphate core-shell structure fluorescent nanoparticles.
Example 2 using europium instead of samarium, the SEM and TEM photographs, X-ray diffraction (XRD) patterns, and ir spectra of the prepared porous rare earth-doped phosphate fluorescent nanoparticles and the prepared PEG-coated porous rare earth phosphate core-shell structure fluorescent nanoparticles were substantially the same as those of example 1 except for the emission and excitation spectra, as shown in fig. 9 and 10, and comparing the two spectra, it was found that the excitation and emission spectra of the coated porous rare earth phosphate core-shell structure fluorescent nanoparticles were exactly the same as those before coating, except that the emission intensity was enhanced by more than 1 fold as compared to that before coating.
Example 3
The method comprises the following steps: preparing porous rare earth doped phosphate fluorescent nanoparticles by a hydrothermal method;
(1) Mixing Sm 2 O 3 、Y 2 O 3 Dissolving in nitric acid with a molar concentration of 3.0mol/L to obtain Sm (NO) with a molar concentration of 0.05mol/L 3 ) 3 Solution A and 0.5mol/L Y (NO) 3 ) 3 Solution B;
(2) Sm (NO) 3 ) 3 Solutions A and Y (NO) 3 ) 3 Mixing the solution B in a volume ratio of 2; adding 3mol/L of H into the mixed solution C 3 PO 4 Obtaining a reaction system D, wherein the molar ratio of the cations to the anions in the reaction system D is 1;
(3) Adjusting the pH value of the reaction system D to 2 by using NaOH solution, strongly stirring for 30min, and then carrying out ultrasonic treatment for 30min to fully mix the reaction system D and the reaction system E to obtain a reaction system E;
(4) Transferring the reaction system E into a reaction kettle with polytetrafluoroethylene, sealing, placing in a drying oven, and reacting for 12h at the temperature of 200 ℃; naturally cooling to room temperature, and centrifuging by using a centrifuge to separate a solid product; then washing the solid product with deionized water for 3 times, and then washing with absolute ethyl alcohol for 3 times; then placing the mixture into a forced air drying oven for drying for 12 hours, wherein the drying temperature is 80 ℃; and finally, grinding and grinding by using agate to obtain the porous rare earth doped phosphate fluorescent nano-particles.
Step two: preparing PEG (1000) coated porous rare earth phosphate core-shell structure fluorescent nanoparticles by a microwave method;
(1) 0.3g of PEG with the molecular weight of 1000 is dissolved in deionized water to obtain 0.3g/L of PEG solution A;
(2) Dissolving the porous rare earth doped phosphate fluorescent nano-particles prepared in the step one in deionized water, and performing ultrasonic treatment for 60min to obtain 0.004mol/L suspension B;
(3) Suspension B was placed in a microwave reactor at a temperature in the range of 65 ℃ and PEG solution a was then added dropwise at a rate of 7 drops per second to continuously stirred suspension B: the volume ratio of the PEG solution A is 1; after the solution A is dripped, cooling to room temperature to obtain a reaction system C; then, taking 50mL of reaction system C and n-hexane with the same volume for aging for 12h, and centrifuging by adopting a high-speed centrifuge to separate a solid product, wherein the centrifugal rate of the high-speed centrifuge is 8000-10000r/min; then washing the solid product with absolute ethyl alcohol for 4 times; then putting the mixture into a forced air drying oven for drying at the drying temperature of 60 ℃ for 24 hours; and finally, grinding by using agate to obtain the PEG (1000) coated porous rare earth phosphate core-shell structure fluorescent nanoparticles.
SEM and TEM photographs, X-ray diffraction (XRD) patterns, and infrared spectrograms of the porous rare earth-doped phosphate fluorescent nanoparticles prepared in example 3 and the PEG-coated rare earth phosphate core-shell structure porous fluorescent nanoparticles prepared in example 1 were substantially the same, except for the intensities of fluorescence emission and excitation spectra, as shown in fig. 7 and 8; comparing the two spectrograms, the excitation spectrum and the emission spectrum of the coated porous rare earth phosphate core-shell structure fluorescent nano particle have the same peak position and peak type as those before coating, and the difference is that the luminous intensity is enhanced by more than 2 times compared with that before coating.
Example 4
The method comprises the following steps: preparing porous rare earth doped phosphate fluorescent nanoparticles by a hydrothermal method;
(1) Mixing Sm 2 O 3 、Y 2 O 3 Dissolving in nitric acid with a molar concentration of 3.6mol/L to obtain molSm (NO) at a concentration of 0.05mol/L 3 ) 3 Solution A and 0.5mol/L Y (NO) 3 ) 3 Solution B;
(2) Mixing Sm (NO) 3 ) 3 Solutions A and Y (NO) 3 ) 3 Mixing the solution B in a volume ratio of 2; adding 3mol/L H into the mixed solution C 3 PO 4 Obtaining a reaction system D, wherein the molar ratio of the cations to the anions in the reaction system D is 1: 2;
(3) Adjusting the pH value of the reaction system D to 1.5 by using NaOH solution, strongly stirring for 30min, and then carrying out ultrasonic treatment for 30min to fully mix the reaction system D and the reaction system E to obtain a reaction system E;
(4) Transferring the reaction system E into a reaction kettle with polytetrafluoroethylene, sealing, placing in a drying oven, and reacting for 12h at the temperature of 200 ℃; naturally cooling to room temperature, and centrifuging by using a centrifuge to separate a solid product; then washing the solid product with deionized water for 3 times, and then washing with absolute ethyl alcohol for 3 times; then putting the mixture into a blast drying oven to be dried for 12 hours, wherein the drying temperature is 80 ℃; and finally, grinding and grinding by using agate to obtain the porous rare earth doped phosphate fluorescent nano-particles.
Step two: preparing PEG (1000) coated porous rare earth phosphate core-shell structure fluorescent nanoparticles by a microwave method;
(1) 0.5g PEG with molecular weight of 1000 is dissolved in deionized water to obtain 0.5g/L PEG solution A;
(2) Dissolving the porous rare earth doped phosphate fluorescent nanoparticles prepared in the first step in deionized water, and performing ultrasonic treatment for 60min to obtain 0.004mol/L suspension B;
(3) The suspension B was placed in a microwave reactor at a temperature in the range of 65 ℃ and then the PEG solution a was added dropwise at a rate of 8 drops per second to the continuously stirred suspension B: the volume ratio of the PEG solution A is 1; after the solution A is dripped, cooling to room temperature to obtain a reaction system C; then, aging 50mL of reaction system C and n-hexane with the same volume for 12h, and centrifuging by using a high-speed centrifuge to separate a solid product, wherein the centrifugal rate of the high-speed centrifuge is 8000-10000r/min; then washing the solid product with absolute ethyl alcohol for 4 times; then putting the mixture into a forced air drying oven for drying at the drying temperature of 60 ℃ for 24 hours; and finally, grinding by using agate to obtain the PEG (1000) coated porous rare earth phosphate core-shell structure fluorescent nano particle.
SEM and TEM photographs, X-ray diffraction (XRD) patterns, and infrared spectrograms of the porous rare earth-doped phosphate fluorescent nanoparticles prepared in example 4 and the PEG-coated porous rare earth phosphate core-shell structure fluorescent nanoparticles prepared in example 1 were substantially the same, except for the intensities of fluorescence emission and excitation patterns, as shown in fig. 7 and 8. Comparing two fluorescence spectrograms, the excitation spectrum and the emission spectrum of the coated porous rare earth phosphate core-shell structure fluorescent nano particle have the same peak position and peak type as those before coating, and the difference is that the luminous intensity is enhanced by more than 4 times compared with that before coating.
The water solubility of the PEG-coated porous rare earth phosphate core-shell structured fluorescent nanoparticles prepared in examples 1, 3, and 4 was studied; the products obtained in examples 1, 3 and 4 were dissolved in water in amounts of 0.01g/L, 0.02g/L, 0.03g/L, 0.04g/L and 0.05g/L, and the water solubility and water dissolution time were visually observed in Table 1,
TABLE 1
According to the table, the concentration of the PEG solution has obvious influence on the water solubility of the prepared PEG-coated porous rare earth phosphate core-shell structure fluorescent nanoparticles, and the concentration increase of the PEG solution A can shorten the water-soluble time according to the existing experiment; the larger the concentration of the PEG-coated porous rare earth phosphate core-shell structure fluorescent nanoparticles is, the shorter the dissolution time in water is.
It should be understood that the above-mentioned examples are only for illustrating the technical solutions of the present invention more clearly, and are not intended to limit the embodiments of the present invention. Variations in the forms described above will occur to those skilled in the art upon consideration of the foregoing description. It is not possible to list all embodiments of the invention herein. But any obvious variations that are extensible and which fall within the technical solutions proposed by the present invention will still fall within the scope of protection of the present invention.
Claims (3)
1. A preparation method of a PEG-coated porous rare earth phosphate fluorescent nano material is characterized by comprising the following steps:
the method comprises the following steps: preparing porous rare earth doped phosphate fluorescent nanoparticles by a hydrothermal method;
mixing Sm 2 O 3 、Y 2 O 3 Dissolving in nitric acid with the molar concentration of 3-6 mol/L to obtain Sm (NO) with the molar concentration of 0.02-0.5 mol/L 3 ) 3 Solutions A and Y (NO) 3 ) 3 Solution B;
mixing Sm (NO) 3 ) 3 Solutions A and Y (NO) 3 ) 3 Mixing the solution B to obtain a mixed solution C, wherein the molar ratio of the solution A to the solution B is 1 to 99 to 10; adding H of 2 to 5mol/L into the mixed solution C 3 PO 4 Obtaining a reaction system D, wherein the molar ratio of cations to anions in the reaction system D is 1 to 1;
adjusting the pH value of the reaction system D to be less than or equal to 2 by using NaOH solution, and having obvious precipitation; strongly stirring for 10 to 30min, and then carrying out ultrasonic treatment for 10 to 30min to fully mix the components to obtain a reaction system E;
transferring the reaction system E into a reaction kettle with polytetrafluoroethylene, sealing, putting into a drying box, and reacting for 6 to 24h at the temperature of 120 to 240 ℃; naturally cooling to room temperature, and centrifuging by using a centrifugal machine to separate a solid product; washing the solid product with deionized water for 2 to 4 times, and then washing with absolute ethyl alcohol for 2 to 3 times; then putting the mixture into a forced air drying oven for drying for 8 to 12h, wherein the drying temperature is 80 to 120 ℃; finally, grinding by using agate to obtain porous rare earth doped phosphate fluorescent nano particles;
step two: preparing PEG 1000-3000 coated porous rare earth phosphate core-shell structure fluorescent nanoparticles by a microwave method;
dissolving 0.08 to 0.8g of PEG1000 to 3000 in deionized water to obtain a PEG solution A of 0.08 to 0.8 g/L;
dissolving the porous rare earth doped phosphate fluorescent nano-particles prepared in the step one in deionized water, and carrying out ultrasonic treatment for 40 to 60min to obtain 0.002 to 0.01mol/L suspension B;
putting the suspension B into a microwave reactor at the temperature ranging from 50 to 80 ℃, and then dripping the PEG solution A into the suspension B which is continuously stirred at the speed of 4 to 8 drops per second to ensure that the volume ratio of the suspension B to the PEG solution A is 1; after the PEG solution A is dripped, cooling the reaction system to room temperature to obtain a reaction system C; then adding n-hexane with the same volume as that of the reaction system C, aging for 12-36h, and centrifuging by using a high-speed centrifuge to separate a solid product, wherein the centrifugal rate of the high-speed centrifuge is 8000-10000r/min; then washing the solid product with absolute ethyl alcohol for 3 to 5 times; then putting the mixture into a forced air drying oven for drying at the drying temperature of 60-80 ℃ for 20-30h; and finally, grinding by using agate to obtain the PEG 1000-3000 coated porous rare earth phosphate core-shell structure fluorescent nanoparticles.
2. The preparation method of the PEG-coated porous rare earth phosphate fluorescent nanomaterial according to claim 1, characterized in that: the samarium oxide in the first step can be replaced by europium oxide.
3. The application of the PEG-coated porous rare earth phosphate fluorescent nano material prepared by the method according to claim 1 or 2 is characterized in that: it can be used for detecting pathogenic bacteria and microorganisms in food and environment.
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