CN210237528U - Long afterglow luminous particle with rod-shell structure - Google Patents
Long afterglow luminous particle with rod-shell structure Download PDFInfo
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- CN210237528U CN210237528U CN201920611804.3U CN201920611804U CN210237528U CN 210237528 U CN210237528 U CN 210237528U CN 201920611804 U CN201920611804 U CN 201920611804U CN 210237528 U CN210237528 U CN 210237528U
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Abstract
The utility model discloses a excellent shell structure long afterglow luminous particle, excellent shell structure long afterglow luminous particle's size is the nanometer, excellent shell structure long afterglow luminous particle includes: a spherical shell; and the rod-shaped long afterglow light emitting unit is positioned inside the spherical shell. The long afterglow luminous particle with the rod-shell structure provided by the utility model can be used as a carrier with a marking function.
Description
Technical Field
The utility model relates to a luminous technical field especially relates to excellent shell structure long persistence light-emitting particle.
Background
The long afterglow luminescent material can absorb natural light, lamplight and the like, store energy and can continuously emit light after the light source is removed. The long-afterglow luminescent material is commonly used as a marker of a target drug object due to the long-afterglow performance of the long-afterglow luminescent material.
However, the current drug carriers with labeling effect are generally prepared by preparing long afterglow luminescent materials into porous structures, and carrying out drug adsorption through the porous structures, so that the drug-loading rate is small.
The above is only for the purpose of assisting understanding of the technical solutions of the present invention, and does not represent an admission that the above is the prior art.
SUMMERY OF THE UTILITY MODEL
The utility model mainly aims at providing a long afterglow luminous particle with a rod-shell structure, which aims at providing a carrier with marking function.
In order to realize the utility model discloses a purpose, the utility model provides a excellent shell structure long afterglow luminescent particle, excellent shell structure long afterglow luminescent particle's size is the nanometer, excellent shell structure long afterglow luminescent particle includes:
a spherical shell;
and the rod-shaped long afterglow light emitting unit is positioned inside the spherical shell.
Preferably, the inner diameter of the spherical shell is 55nm to 65nm, and the thickness of the spherical shell is 8nm to 12 nm.
Preferably, the length of the rod-shaped long afterglow luminescent unit is 50nm to 65 nm.
Preferably, the cross-sectional diameter of the rod-shaped long afterglow luminescent unit is 18nm to 22 nm.
Preferably, the rod-shaped long afterglow light emitting unit passes through the spherical center of the spherical shell.
Preferably, both ends of the rod-shaped long afterglow light emitting unit are abutted against the spherical shell.
Preferably, the spherical shell is composed of a light-transmitting material.
Preferably, the spherical shell is a silica spherical shell.
Preferably, the rod-shaped long afterglow luminescent unit comprises europium, dysprosium-doped strontium aluminate or chromium-doped zinc gallate.
The embodiment of the utility model provides a excellent shell structure long afterglow luminous granule, excellent shell structure long afterglow luminous granule includes: a spherical shell; and the rod-shaped long afterglow light emitting unit is positioned inside the spherical shell. The utility model provides a long afterglow luminous granule of excellent shell structure because there is the vacant part inside the casing, can deposit medicine etc. and long afterglow luminescence unit can provide the marking function, and luminous granule's size is the nanometer, can be phagocytosed by the cell, consequently can regard as a carrier that has the marking function.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a rod-shell structure long-afterglow luminescent particle provided by the present invention;
FIG. 2 is a transmission electron microscope image of the hollow mesoporous silica spheres prepared according to the embodiment of the present invention;
FIG. 3 is a transmission electron microscope image of the rod-shell structure long-afterglow luminescent particles prepared by the embodiment of the present invention;
FIG. 4 is a diagram of excitation and emission spectra of a long-afterglow luminescent material with a rod-shell structure prepared by the embodiment of the present invention;
fig. 5 is an afterglow attenuation diagram of the rod-shell structure long-afterglow luminescent material prepared by the embodiment of the present invention.
The reference numbers illustrate:
the objects, features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
It should be noted that, if directional indications (such as up, down, left, right, front, back, horizontal, vertical … …) are involved in the embodiment of the present invention, the directional indications are only used to explain the relative position relationship between the components, the motion situation, etc. in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indications are changed accordingly.
In addition, if there is a description relating to "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The utility model provides a long afterglow luminescent particle with a rod-shell structure, in particular to a nano-sized long afterglow luminescent particle with a rod-shell structure.
As shown in fig. 1, the utility model provides a long afterglow luminescent particle of rod-shell structure, the size of long afterglow luminescent particle of rod-shell structure is the nanometer, rod-shell structure long afterglow luminescent particle includes spherical shell 100 and rod-like long afterglow luminescence unit 200, rod-like long afterglow luminescence unit 200 is located inside spherical shell 100.
Referring to fig. 1, the present invention provides a long-afterglow luminescent particle with a rod-shell structure, wherein the spherical shell 100 is a silica spherical shell. The utility model provides a rod-shaped in long afterglow luminous particle with rod-shell structureThe composition of the long-afterglow luminescent unit 200 can be any one of the compositions of long-afterglow luminescent materials, and preferably, the composition of the rod-shaped long-afterglow luminescent unit 200 is europium and dysprosium doped strontium aluminate (SrAl)2O4:Eu2+,Dy3+)。
Referring to fig. 1, the present invention provides a long afterglow luminescent particle with a rod-shell structure, which is a nano-scale particle, preferably, the inner diameter of the spherical shell 100 is 55nm to 65nm, and the thickness is 8nm to 12 nm. The length of the rod-shaped long afterglow luminescent unit 200 is 50nm to 65nm, and the cross section diameter of the rod-shaped long afterglow luminescent unit 200 is 18nm to 22 nm.
With reference to fig. 1, the present invention provides a rod-shell structure long-afterglow luminescent particle, preferably, the rod-shaped long-afterglow luminescent unit 200 passes through the spherical center (not labeled in the figure) of the spherical shell 100; preferably, both ends of the rod-shaped long afterglow light emitting unit 200 are in contact with the spherical shell 100.
The utility model provides a long afterglow luminous particle of excellent shell structure, spherical shell 100 and bar-shaped long afterglow luminescence unit 200, bar-shaped long afterglow luminescence unit 200 is located inside spherical shell 100.
The utility model provides a long afterglow luminous granule of excellent shell structure because there is the vacant part inside the casing, can deposit medicine etc. and long afterglow luminescence unit can provide the marking function, and luminous granule's size is nanometer level, consequently can regard as a carrier that has the marking effect. For example, the utility model provides a when excellent shell structure long afterglow luminescent particle uses as the drug carrier, can be right ball shell 100 carries out the target modification to pour into the medicine into the inside vacant space of ball shell 100, thereby obtain the excellent shell structure long afterglow luminescent particle who carries the medicine, the long afterglow luminescent property of long afterglow luminescence unit 200 among the excellent shell structure long afterglow luminescent particle can provide the mark function for this drug carrier, and because the excellent shell structure long afterglow luminescent particle size that this embodiment provided is the nanometer, can be phagocytized by the cell, can send into the medicine effectively in the cell.
By way of specific example, the following is a silica spherical shell 100 and the silica spherical shell 100Rod-shell structure (SrAl) composed of rod-shaped europium and dysprosium doped strontium aluminate2O4:Eu2+,Dy3+@ HMS) as an example, the preparation method and the luminescence property of the rod-shell structure long afterglow luminescent particle provided by the utility model are further explained.
Method in the embodiment of the present invention, first, hollow mesoporous Silica (SiO) is prepared2) Nanospheres (HMS). Then preparing europium and dysprosium doped strontium aluminate (SrAl) by using an impregnation method (under the vacuum condition)2O4:Eu2+,Dy3+) The ion mixed solution of the required raw materials and PEG10000 are injected into the hollow structure of the hollow mesoporous silica nanosphere. Then drying is carried out, the concentration of PEG10000 in the mixed solution is rapidly increased along with the gradual reduction of water molecules in the drying process, and the PEG tends to aggregate into micelles after the concentration of the PEG exceeds a critical concentration, so that rod-shaped SrAl is formed in a hollow structure2O4:Eu2+,Dy3+And (4) forming. Then calcining in the air to remove PEG10000, and further calcining in a reducing atmosphere to obtain a silica spherical shell 100 and rod-shell structure composite particles (SrAl) consisting of rod-shaped europium and dysprosium doped strontium aluminate in the silica spherical shell 1002O4:Eu2+,Dy3+@HMS)。
The preparation method comprises the following steps:
(1) preparation of Polystyrene (PS) spheres
390mL of water, 1.3mL of methacryloyloxyethyltrimethyl ammonium chloride (AETAC, 75 wt% in water), 44mL of styrene (polystyrene generally contains hydroquinone as a polymerization inhibitor, styrene is stirred in concentrated NaOH solution for 2h before use to remove hydroquinone as a polymerization inhibitor, and after standing for 24h, the upper layer of styrene is taken out for use), stirred for 30min, and introduced with nitrogen (N)2) And 20 min. In N2Heating the mixture in an oil bath at 90 ℃ under protection, adding 10mL of 2, 2-azobis (2-methylimidazole) dihydrochloride aqueous solution (containing 1.0g of 2, 2-azobis (2-methylimidazole) dihydrochloride), and reacting for 24h to obtain the nano polystyrene spheres. In the embodiment of the utility model, the polystyrene sphere is used as a template for preparing the hollow mesoporous silica sphere,it is understood that the nano-polystyrene spheres can also be purchased directly for use.
(2) Preparation of hollow mesoporous silica spheres (HMS)
5mL of the prepared PS sphere solution was dispersed in 50mL of absolute ethanol, ultrasonically dispersed for 20min, 40mL of ultrapure water was added to obtain a dispersion, 1.4578g of cetyltrimethylammonium Bromide (CTAB) and 18mL of concentrated ammonia water were added to the dispersion, and then stirred on a magnetic stirrer for 2 h. 2mL Tetraethyl orthosilicate (TEOS) was added dropwise and the reaction was stirred for 24 h. And after the reaction is finished, standing the reaction liquid for 2h, removing supernatant, centrifuging the lower layer mixture for 5min at the rotating speed of 5000r/min, drying the precipitate obtained by centrifugation at 80 ℃, and calcining the dried precipitate in air at 550 ℃ for 2h to obtain the hollow mesoporous silica spheres. Referring to fig. 2, fig. 2 is the utility model discloses preparation the utility model discloses the transmission electron microscope picture of the hollow mesoporous silica ball that the preparation obtained can be seen from, the embodiment of the utility model provides a hollow mesoporous silica spherule footpath that the preparation obtained is evenly distributed, and the complete flawless of spherical shell 100, spherical shell 100 internal diameter about 55nm ~ 65nm, spherical shell 100 thickness about 8nm ~ 12 nm.
(3) Preparation of rod-shell structured long-afterglow luminescent particles (rod-shell structured SrAl2O4: Eu)2+,Dy3+@ HMS composite particle
2.5mL of strontium nitrate (Sr (NO)3)2) 5mL of aluminum nitrate (Al (NO) in an aqueous solution (molar concentration: 0.5M)3)3) 0.5M, 0.25M europium nitrate (Eu (NO)3)3) 0.05M and 0.5mL dysprosium nitrate (Dy (NO)3)3) The aqueous solution (molar concentration: 0.05M) of (D) was mixed as an aqueous phase. Adding 0.5mL of glycerol, 10mL of absolute ethanol and 2g of PEG10000 (polyethylene glycol 10000, polyethylene glycol with molecular weight of 8600-10500) into the water phase, and stirring for 1 h. Adding 0.2g of hollow mesoporous silica spheres, ultrasonically dispersing for 30min, then putting the reaction system into a vacuum oven, vacuumizing for 30min to inject a solution containing each reactant into the hollow mesoporous silica spheres, and then continuously stirring and reacting for 24 h.
And after the reaction is finished, centrifuging the reaction solution at the rotating speed of 6000r/min for 10min, drying the precipitate obtained by centrifugation at 80 ℃, and calcining the dried precipitate in a muffle furnace (in air) at 600 ℃ for 2h to obtain the precursor. Calcining the precursor in a tube furnace in a weak reducing atmosphere to obtain the long-afterglow luminescent particles, wherein the calcining temperature (highest temperature) is 1100 ℃, the calcining time is 4 hours, the heating rate is 5 ℃/min, and the atmosphere gas is 5% H2And 95% N2The mixed gas of (1).
In the embodiment of the present invention, Sr (NO) is contained3)2And Al (NO)3)3Formation of SrAl2O4，Eu(NO3)3、Dy(NO3)3Injecting the mixed solution of PEG and Sr (NO) into the silicon dioxide spherical shell by an impregnation method3)2And Al (NO)3)3Reaction to form SrAl2O4，Eu(NO3)3And Dy (NO)3)3Providing doped europium ions and dysprosium ions, taking PEG as a guiding agent, wherein the concentration of PEG in a mixed solution in the hollow mesoporous silica nanosphere is rapidly increased along with the gradual reduction of water molecules in the drying process, and the PEG tends to be aggregated into micelles after the concentration of the PEG exceeds the critical concentration, so that rod-shaped SrAl is formed in the spherical shell2O4:Eu2+,Dy3+(namely the rod-shaped long afterglow luminescent unit), sintering to remove PEG and reducing to obtain rod-shell structure long afterglow luminescent particles, wherein the rod-shell structure long afterglow luminescent particles are rod-shell structure composite particles (SrAl) composed of a silicon dioxide spherical shell and rod-shaped europium and dysprosium doped strontium aluminate in the silicon dioxide spherical shell2O4:Eu2+,Dy3+@ HMS). In addition, PEG also serves as a polymerization inhibitor to form steric hindrance, so that the hollow spheres are prevented from being fully contacted with each other in the drying process, the sintering degree of the hollow mesoporous silica nanospheres is effectively reduced, and the hollow mesoporous silica nanospheres can keep the hollow structure intact in the calcining process. When PEG is not added, no rod-shaped structure is formed in the hollow structure, and the hollow mesoporous silica nanospheres are directly and fully contacted in the drying process and are calcinedIn the process, serious sintering occurs, the hollow structure of the material is damaged to a great extent, and the hollow structure of a part of hollow mesoporous silica spheres in the finally obtained material is incomplete. The PEG guide effect is related to the molecular weight, the embodiment of the utility model provides an, the PEG of chooseing for use is PEG10000 (the PEG of molecular weight 8600 ~ 10500), and when the PEG molecular weight undersize that uses, PEG can't gather into micelle, SrAl in the material that finally obtains2O4:Eu2+,Dy3+The silicon dioxide nano spherical shell is in an irregular dispersion state; when the molecular weight of PEG used is too large, SrAl in the finally obtained material2O4:Eu2+,Dy3+The silicon dioxide nanometer spherical shell is flocculent, and rod-shaped SrAl can not be formed in the silicon dioxide spherical shell2O4:Eu2+,Dy3+。
Referring to fig. 3, fig. 3 is a transmission electron microscope image of the rod-shell structure long-afterglow luminescent particles prepared according to the embodiment of the present invention, as is apparent from fig. 3, the long-afterglow luminescent particles prepared according to the embodiment of the present invention have a rod-shell structure, the spherical shell 100 composed of silica is kept intact, and the rod-shaped long-afterglow luminescent unit 200 composed of europium and dysprosium doped strontium aluminate is located in the spherical shell 100. The length of the rod-shaped long afterglow luminescent unit 200 is about 50nm to 65nm, and the diameter of the cross section is 18nm to 22 nm. Most of the rod-shaped long afterglow light emitting units 200 pass through the center of the spherical shell 100, and both ends thereof are in contact with the spherical shell 100.
Referring to fig. 4, fig. 4 is an excitation and emission spectrogram of the rod-shell structure long-afterglow luminescent material prepared according to the embodiment of the present invention, and it can be seen that the emission peak of the prepared rod-shell structure long-afterglow luminescent material is about 520nm, and the material can be excited by light of 310nm to 360nm, and the rod-shell structure long-afterglow luminescent material prepared according to the embodiment has an obvious excitation luminescence property.
Further, referring to fig. 5, fig. 5 is an afterglow attenuation diagram of the rod-shell structure long-afterglow luminescent material prepared according to the embodiment of the present invention, and the rod-shell structure long-afterglow luminescent material prepared according to the embodiment has typical long afterglow performance, and still has strong light intensity after being attenuated for 2 hours.
The above only is the preferred embodiment of the present invention, not limiting the scope of the present invention, all the equivalent structure changes made by the contents of the specification and the drawings under the inventive concept of the present invention, or the direct/indirect application in other related technical fields are included in the patent protection scope of the present invention.
Claims (8)
1. The long-afterglow luminescent particles with the rod-shell structure are characterized in that the size of the long-afterglow luminescent particles with the rod-shell structure is nanoscale, and the long-afterglow luminescent particles with the rod-shell structure comprise:
a spherical shell;
and the rod-shaped long afterglow light emitting unit is positioned inside the spherical shell.
2. The rod-shell structured long-afterglow luminescent particle according to claim 1, wherein the inner diameter of the spherical shell is 55nm to 65nm, and the thickness is 8nm to 12 nm.
3. The rod-shell structured long-afterglow luminescent particle of claim 2, wherein the length of the rod-shaped long-afterglow luminescent unit is 50nm to 65 nm.
4. The rod-shell structured long-afterglow luminescent particle of claim 1, wherein the rod-shaped long-afterglow luminescent unit has a cross-sectional diameter of 18nm to 22 nm.
5. The rod-shell structured long-afterglow luminescent particle according to claim 1, wherein said rod-shaped long-afterglow luminescent unit passes through the spherical center of said spherical shell.
6. The rod-shell structured long-afterglow luminescent particle of claim 1, wherein both ends of the rod-shaped long-afterglow luminescent unit are abutted against the spherical shell.
7. The rod-shell structured long-afterglow luminescent particle according to any of claims 1 to 6, wherein said spherical shell is a silica spherical shell.
8. The rod-shell structured long-afterglow luminescent particle according to any one of claims 1 to 6, wherein the rod-shaped long-afterglow luminescent unit is strontium aluminate or zinc gallate material.
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| CN116836698A (en) * | 2023-05-11 | 2023-10-03 | 安徽工业大学 | Silicon dioxide long afterglow luminescent material, preparation method, anti-counterfeiting coating and application |
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| CN116836698A (en) * | 2023-05-11 | 2023-10-03 | 安徽工业大学 | Silicon dioxide long afterglow luminescent material, preparation method, anti-counterfeiting coating and application |
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