Preparation method of luminescent microspheres
During the preparation of luminescent microspheres, SiO2 microspheres are combined with dyes or luminescent agents, and layer-by-layer assembly is achieved through polymer modification, which solves the problems of poor luminescent stability and low biocompatibility of existing luminescent microspheres, and achieves more efficient luminescent stability and biocompatibility.
Patent Information
- Application Number
- CN202411907278.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-24
- Publication Date
- 2025-04-04
AI Technical Summary
The existing luminescent microspheres have poor luminescence stability and low biocompatibility, and no effective solution has been available.
By mixing water, ethanol and ammonia water at 56:16:0.1, adding cetyl trimethylammonium bromide and dissolving, a solution with a concentration of 0.5% to 1.5%, adding a silicon source to the solution to make the solution concentration 5% to 15%, reacting at 60°C for 1 hour to 24 hours to obtain SiO2 microspheres; removing the template in the SiO2 microspheres to obtain mesoporous SiO2 microspheres with a size of 100 nm to 4000 nm; combining mesoporous SiO2 microspheres with dye, luminescent agent or fluorescent agent to obtain mesoporous SiO2 luminescent microspheres, and combining them with polymers such as polyethyleneimine to undergo group modification to achieve layer-by-layer assembly.
The chemiluminescence stability and biocompatibility of luminescence microspheres are improved, and efficient luminescence microspheres are constructed through self-assembly layers, solving the problems of poor luminescence stability and low biocompatibility.
Smart Images
Figure CN119752435A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of nanomaterials, and in particular to a method for preparing luminescent microspheres. Background Art
[0002] Chemiluminescence is a type of molecular luminescence spectroscopy. It is mainly based on the principle that the concentration of the analyte in the chemical detection system and the chemiluminescence intensity of the system are linearly quantitatively related under certain conditions. It uses instruments to detect the chemiluminescence intensity of the system to determine the content of the analyte. Luminescent microspheres are luminescent materials commonly used in chemiluminescence detection.
[0003] In the prior art, the preparation methods of luminescent microspheres mainly include solvent diffusion method, aqueous phase polymerization method and organic-inorganic hybrid method, but most of them have the problems of low luminescence efficiency, poor luminescence stability and low biocompatibility.
[0004] With regard to the problems of poor luminescence stability and low biocompatibility of luminescent microspheres in the prior art, no effective solution has been proposed yet. Summary of the invention
[0005] Based on this, it is necessary to provide a method for preparing luminescent microspheres in order to solve the problems of poor luminescent stability and low biocompatibility of luminescent microspheres in related technologies.
[0006] In a first aspect, an embodiment of the present application provides a method for preparing luminescent microspheres, the method comprising the following steps:
[0007] Mix water, ethanol and ammonia water in a ratio of 56:16:0.1, add hexadecyltrimethylammonium bromide and stir to dissolve to obtain a solution with a concentration of 0.5% to 1.5%, add a silicon source to the solution to make the solution concentration of 5% to 15%, react at 60°C for 1 hour to 24 hours to obtain SiO2 microspheres; remove the template in the SiO2 microspheres to obtain mesoporous SiO2 microspheres with a size of 100nm to 4000nm;
[0008] The mesoporous SiO2 microspheres are combined with at least one of a dye, a luminescent agent or a fluorescent agent to obtain mesoporous SiO2 luminescent microspheres; the mesoporous SiO2 luminescent microspheres are redissolved in a solution containing at least one of linear polyethyleneimine, branched polyethyleneimine or polyacrylic acid, and the surface of the mesoporous SiO2 luminescent microspheres is modified with different groups; this step is repeated until layer-by-layer assembled luminescent microspheres are obtained.
[0009] In one embodiment, the removing of the template from the SiO2 microspheres comprises the following steps:
[0010] Add 6 mg / ml ammonium nitrate ethanol solution to the SiO2 microspheres to remove the template by ion exchange;
[0011] Alternatively, the SiO2 microspheres are calcined at 550°C for 5 to 24 hours.
[0012] In one embodiment, the step of combining the mesoporous SiO2 microspheres with at least one of a dye, a luminescent agent or a fluorescent agent comprises the following steps:
[0013] The mesoporous SiO2 microspheres are combined with at least one of the dye, the luminescent agent or the fluorescent agent by physical adsorption, chemical adsorption or electrostatic adsorption.
[0014] In one embodiment, the silicon source is selected from one or more of silicic acid, tetraethyl silicate, butyl silicate, 3-aminopropyltriethoxysilane, octadecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane or 3-mercaptopropyltrimethoxysilane.
[0015] In one embodiment, the dye is selected from one or more of amido black, Ponceau red or Coomassie brilliant blue.
[0016] In one embodiment, the luminescent agent is selected from one or more of acridinium ester, luminol or AMPPD.
[0017] In one embodiment, the fluorescent agent is selected from one or more of carbon quantum dots or cadmium telluride quantum dots.
[0018] The above-mentioned method for preparing luminescent microspheres comprises the following steps: uniformly mixing water, ethanol and ammonia water in a ratio of 56:16:0.1, adding hexadecyltrimethylammonium bromide and stirring to dissolve to obtain a solution with a concentration of 0.5% to 1.5%, adding a silicon source to the solution to make the solution concentration of 5% to 15%, reacting at 60°C for 1 hour to 24 hours to obtain SiO2 microspheres; removing the template in the SiO2 microspheres to obtain mesoporous SiO2 microspheres with a size of 100nm to 4000nm; combining the mesoporous SiO2 microspheres with at least one of a dye, a luminescent agent or a fluorescent agent to obtain mesoporous SiO2 luminescent microspheres; redissolving the mesoporous SiO2 luminescent microspheres in a solution containing at least one of linear polyethyleneimine, branched polyethyleneimine or polyacrylic acid, and modifying the surface of the mesoporous SiO2 luminescent microspheres with different groups; and repeating this step until layer-by-layer assembled luminescent microspheres are obtained. The present application improves the stability of chemiluminescence by embedding dyes, luminescent agents or fluorescent agents in mesoporous SiO2 microspheres, and based on the fact that linear polyethyleneimine, branched polyethyleneimine and polyacrylic acid have abundant functional groups, such as amino, carboxyl and hydroxyl groups, the surface of mesoporous SiO2 luminescent microspheres can be modified with different groups, thereby effectively improving the adsorption capacity and biocompatibility of the mesoporous SiO2 luminescent microspheres, and constructing luminescent microspheres through layer-by-layer self-assembly, effectively solving the problems of poor luminescent stability and low biocompatibility of the luminescent microspheres. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:
[0020] Figure 1 It is a schematic diagram of a flow chart of a method for preparing luminescent microspheres provided in an embodiment of the present application. DETAILED DESCRIPTION
[0021] In order to make the purpose, technical solutions and advantages of the present application clearer, the present application is described and illustrated below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not intended to limit the present application. Based on the embodiments provided in the present application, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present application.
[0022] Obviously, the drawings described below are only some examples or embodiments of the present application. For ordinary technicians in this field, the present application can also be applied to other similar scenarios based on these drawings without creative work. In addition, it can also be understood that although the efforts made in this development process may be complicated and lengthy, for ordinary technicians in this field related to the content disclosed in this application, some changes in design, manufacturing or production based on the technical content disclosed in this application are just conventional technical means, and should not be understood as insufficient content disclosed in this application.
[0023] Reference to "embodiments" in this application means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those of ordinary skill in the art that the embodiments described in this application may be combined with other embodiments without conflict.
[0024] Unless otherwise defined, the technical terms or scientific terms involved in this application should be understood by people with ordinary skills in the technical field to which this application belongs. The words "one", "a", "a", "the" and the like involved in this application do not indicate a quantity limitation, and may indicate the singular or plural. The terms "include", "comprise", "have" and any of their variations involved in this application are intended to cover non-exclusive inclusions; for example, a process, method, system, product or device that includes a series of steps or modules (units) is not limited to the listed steps or units, but may also include steps or units that are not listed, or may also include other steps or units inherent to these processes, methods, products or devices. The words "connect", "connected", "coupled" and the like involved in this application are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. The "multiple" involved in this application refers to two or more. "And / or" describes the association relationship of associated objects, indicating that there may be three relationships, for example, "A and / or B" can mean: A exists alone, A and B exist at the same time, and B exists alone. The character " / " generally indicates that the objects before and after are in an "or" relationship. The terms "first", "second", "third", etc. involved in this application are only used to distinguish similar objects and do not represent a specific ordering of the objects.
[0025] The present invention provides a method for preparing luminescent microspheres, which comprises the following steps:
[0026] Step S101, mix water, ethanol and ammonia water in a ratio of 56:16:0.1, add hexadecyltrimethylammonium bromide and stir to dissolve to obtain a solution with a concentration of 0.5% to 1.5%, add a silicon source to the solution to make the solution concentration of 5% to 15%, react at 60°C for 1 hour to 24 hours to obtain SiO2 microspheres; remove the template in the SiO2 microspheres to obtain mesoporous SiO2 microspheres with a size of 100nm to 4000nm.
[0027] Specifically, the role of hexadecyl trimethyl ammonium bromide in the present application is to emulsify the solution as an emulsifier. In addition, 6 mg / ml ammonium nitrate ethanol solution can be added to the SiO2 microspheres to remove the template through ion exchange; or the SiO2 microspheres can be calcined at 550°C for 5 to 24 hours.
[0028] In addition, in order to make the finally prepared luminescent microspheres better for chemiluminescence detection, preferably, the size of the mesoporous SiO2 microspheres is 100-300nm.
[0029] Step S102, combining the mesoporous SiO2 microspheres with at least one of a dye, a luminescent agent or a fluorescent agent to obtain mesoporous SiO2 luminescent microspheres; redissolving the mesoporous SiO2 luminescent microspheres in a solution containing at least one of linear polyethyleneimine (PEI), branched polyethyleneimine (BPEI) or polyacrylic acid (PAA), and modifying the surface of the mesoporous SiO2 luminescent microspheres with different groups; repeating this step until the layer-by-layer assembled luminescent microspheres are obtained.
[0030] Specifically, the mesoporous SiO2 microspheres can be combined with at least one of a dye, a luminescent agent or a fluorescent agent by utilizing physical adsorption, chemical adsorption or electrostatic adsorption.
[0031] In addition, the silicon source in the present application is selected from one or more of silicic acid, tetraethyl silicate, tetrabutyl silicate, 3-aminopropyltriethoxysilane, octadecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane or 3-mercaptopropyltrimethoxysilane.
[0032] The dye in the present application is selected from one or more of amido black, Ponceau red or Coomassie brilliant blue.
[0033] The luminescent agent in the present application is selected from one or more of acridinium ester, luminol or AMPPD.
[0034] The fluorescent agent in the present application is selected from one or more of carbon quantum dots or cadmium telluride quantum dots.
[0035] Figure 1 The schematic diagram of the process for preparing the luminescent microspheres provided in this application is as follows: Figure 1 As shown, a silicon source is hydrolyzed and emulsified in a solution mixed with water, ethanol, ammonia water and hexadecyltrimethylammonium bromide to obtain SiO2 microspheres, and a 6 mg / ml ammonium nitrate ethanol solution is added to the SiO2 microspheres to remove the template through ion exchange; or the SiO2 microspheres are calcined at 550°C for 5 to 24 hours to obtain mesoporous SiO2 microspheres; the mesoporous SiO2 microspheres are combined with at least one of a dye, a luminescent agent or a fluorescent agent to obtain mesoporous SiO2 luminescent microspheres; the mesoporous SiO2 luminescent microspheres are redissolved in a solution containing at least one of linear polyethyleneimine, branched polyethyleneimine or polyacrylic acid, and the surface of the mesoporous SiO2 luminescent microspheres is modified with different groups; the above steps are repeated until layer-by-layer assembled luminescent microspheres are obtained.
[0036] In the prior art, the preparation methods of luminescent microspheres mainly include solvent diffusion method, aqueous phase polymerization method and organic-inorganic hybrid method, but most of them have the problems of low luminescence efficiency, poor luminescence stability and low biocompatibility.
[0037] In order to solve the above problems, the present application provides a method for preparing luminescent microspheres, which comprises mixing water, ethanol and ammonia water in a ratio of 56:16:0.1, adding hexadecyltrimethylammonium bromide and stirring to dissolve to obtain a solution with a concentration of 0.5% to 1.5%, adding a silicon source to the solution to make the solution concentration of 5% to 15%, and reacting at 60°C for 1 hour to 24 hours to obtain SiO2 microspheres; removing the template in the SiO2 microspheres to obtain mesoporous SiO2 microspheres with a size of 100nm to 4000nm; combining the mesoporous SiO2 microspheres with at least one of a dye, a luminescent agent or a fluorescent agent to obtain mesoporous SiO2 luminescent microspheres; redissolving the mesoporous SiO2 luminescent microspheres in a solution containing at least one of linear polyethyleneimine, branched polyethyleneimine or polyacrylic acid, and modifying the surface of the mesoporous SiO2 luminescent microspheres with different groups; repeating this step until layer-by-layer assembled luminescent microspheres are obtained. The present application improves the stability of chemiluminescence by embedding dyes, luminescent agents or fluorescent agents in mesoporous SiO2 microspheres, and based on the fact that linear polyethyleneimine, branched polyethyleneimine and polyacrylic acid have abundant functional groups, such as amino, carboxyl and hydroxyl groups, the surface of mesoporous SiO2 luminescent microspheres can be modified with different groups, thereby effectively improving the adsorption capacity and biocompatibility of the mesoporous SiO2 luminescent microspheres, and constructing luminescent microspheres through layer-by-layer self-assembly, effectively solving the problems of poor luminescent stability and low biocompatibility of the luminescent microspheres.
[0038] It should be understood that the specific embodiments described herein are only used to explain the application, rather than to limit it. Based on the embodiments provided in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the protection scope of this application.
[0039] Obviously, the drawings are only some examples or embodiments of the present application. For ordinary technicians in the field, the present application can also be applied to other similar situations based on these drawings without creative work. In addition, it is understandable that although the work done in this development process may be complicated and lengthy, for ordinary technicians in the field, certain changes in design, manufacturing or production based on the technical content disclosed in this application are only conventional technical means and should not be regarded as insufficient content disclosed in this application.
[0040] The term "embodiment" in this application refers to a specific feature, structure or characteristic described in conjunction with the embodiment that can be included in at least one embodiment of the present application. The appearance of this phrase in various locations in the specification does not necessarily mean the same embodiment, nor does it mean that it is mutually exclusive with other embodiments and is independent or optional. It is clearly or implicitly understood by those of ordinary skill in the art that the embodiments described in this application can be combined with other embodiments without conflict.
[0041] The above embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of patent protection. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the scope of protection of the present application. Therefore, the scope of protection of the present application shall be subject to the attached claims.
Claims
1. A method for preparing luminescent microspheres, characterized in that: The method comprises the following steps: Mix water, ethanol and ammonia water in a ratio of 56:16:0.1, add hexadecyltrimethylammonium bromide and stir to dissolve to obtain a solution with a concentration of 0.5% to 1.5%, add a silicon source to the solution to make the solution concentration of 5% to 15%, react at 60°C for 1 hour to 24 hours to obtain SiO2 microspheres; remove the template in the SiO2 microspheres to obtain mesoporous SiO2 microspheres with a size of 100nm to 4000nm; The mesoporous SiO2 microspheres are combined with at least one of a dye, a luminescent agent or a fluorescent agent to obtain mesoporous SiO2 luminescent microspheres; the mesoporous SiO2 luminescent microspheres are redissolved in a solution containing at least one of linear polyethyleneimine, branched polyethyleneimine or polyacrylic acid, and the surface of the mesoporous SiO2 luminescent microspheres is modified with different groups; this step is repeated until layer-by-layer assembled luminescent microspheres are obtained.
2. The method for preparing luminescent microspheres according to claim 1, characterized in that: The method of removing the template from the SiO2 microspheres comprises the following steps: Add 6 mg / ml ammonium nitrate ethanol solution to the SiO2 microspheres to remove the template by ion exchange; Alternatively, the SiO2 microspheres are calcined at 550°C for 5 to 24 hours.
3. The method for preparing luminescent microspheres according to claim 1, characterized in that: The step of combining the mesoporous SiO2 microspheres with at least one of a dye, a luminescent agent or a fluorescent agent comprises the following steps: The mesoporous SiO2 microspheres are combined with at least one of the dye, the luminescent agent or the fluorescent agent by physical adsorption, chemical adsorption or electrostatic adsorption.
4. The method for preparing luminescent microspheres according to claim 1, characterized in that: The silicon source is selected from one or more of silicic acid, tetraethyl silicate, butyl silicate, 3-aminopropyltriethoxysilane, octadecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane or 3-mercaptopropyltrimethoxysilane.
5. The method for preparing luminescent microspheres according to claim 1, characterized in that: The dye is selected from one or more of amido black, Ponceau red or Coomassie brilliant blue.
6. The method for preparing luminescent microspheres according to claim 1, characterized in that: The luminescent agent is selected from one or more of acridinium ester, luminol or AMPPD.
7. The method for preparing luminescent microspheres according to claim 1, characterized in that: The fluorescent agent is selected from one or more of carbon quantum dots or cadmium telluride quantum dots.