CN114229853B - Preparation method of zinc-doped mesoporous silica nanospheres - Google Patents
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- CN114229853B CN114229853B CN202111427213.9A CN202111427213A CN114229853B CN 114229853 B CN114229853 B CN 114229853B CN 202111427213 A CN202111427213 A CN 202111427213A CN 114229853 B CN114229853 B CN 114229853B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/54313—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being characterised by its particulate form
- G01N33/54346—Nanoparticles
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- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/551—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being inorganic
- G01N33/552—Glass or silica
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- G—PHYSICS
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- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/58—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances
- G01N33/585—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances with a particulate label, e.g. coloured latex
- G01N33/587—Nanoparticles
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a preparation method of zinc-doped mesoporous silica nanospheres, which comprises the following steps: firstly synthesizing sulfhydryl functional Mesoporous Silica Nanospheres (MSNs), and then dispersing MSNs samples in Zn (CH) 3 COO) 2 ·2H 2 And (3) in an O aqueous solution, stirring at room temperature after ultrasonic dispersion to generate zinc ion modified mesoporous silica nanospheres, centrifuging the stirred dispersion, repeatedly centrifuging and washing four times by using an ethanol solution, putting the obtained precipitate into a vacuum drying oven at 60 ℃, and taking out to obtain the zinc-mercapto functional modified mesoporous silica nanospheres (MSN (Zn)). The method is simple, the prepared nano-particles have uniform particle size and good dispersibility, the signal amplification effect of MSN (Zn) does not output quantum dots, and the nonspecific adsorption is lower.
Description
Technical Field
The invention belongs to the field of nanoparticle synthesis, and particularly relates to a preparation method of zinc-doped mesoporous silica nanospheres.
Background
Porous materials with pore sizes less than 100nm are collectively referred to as nanomaterials. The porous nanometer material has the characteristics of large external surface area, easy exposure of unit cell, short and regular pore canal, regular framework structure, easy accessibility, improved active site, etc. Based on nanomaterials we can make smaller and lighter devices and the research of nanomaterials is tending to produce higher optical, magnetic, electrical, thermal properties, stronger mechanical property development. In recent years, the research of applying nano materials in the aspects of nano devices, health medicine, aerospace, environmental ecology, energy technology, biotechnology and the like is more and more, and the application prospect of the nano materials is very broad.
Mesoporous silica has a huge specific surface area and good biocompatibility, and has wide application in various fields, and particularly in drug controlled release research, the unique structural property of the mesoporous silica is considered as a drug carrying material with the most prospect. The mesoporous silica has the characteristics of fluorescence, superparamagnetism and the like, and is widely applied, and comprises the steps of modifying organic groups as fluorescent immune labels and marking electrochemical active substances (dyes and metal ions) as electrochemical immunosensors.
At present, the functionalization of mesoporous silica is mainly performed by a copolycondensation method and a post grafting method. The copolycondensation method is to add organic groups and tetraethoxysilane into a system under the action of a template agent, and modify functional groups on the pore wall while preparing mesoporous silica. The mesoporous silica prepared by the method has high organic group load, but can influence the structural molding of the material. The post grafting method is to obtain the formed mesoporous silica material firstly and then modify the surface of the mesoporous silica by a silane coupling agent, and the modification process does not damage the structure of the mesoporous material, so the post grafting method is more widely used.
Therefore, the invention synthesizes zinc-doped mercapto-functionalized mesoporous silica in one step by using an ultrasonic-assisted microemulsion method, has good dispersity and uniform particle size, and can have wide application prospect in the fields of fluorescent immunolabeling and labeling of electrochemical substances.
Disclosure of Invention
The invention aims to provide a preparation method of zinc-doped mesoporous silica nanospheres.
In order to achieve the technical effects, the invention adopts the following technical scheme:
the preparation of the zinc doped mesoporous silica nanospheres comprises the following steps:
(1) Mercapto-functionalized mesoporous SiO 2 The synthesis of nanospheres, namely, transferring 2.5wt% of Cetyl Trimethyl Ammonium Chloride (CTAC), placing the mixture into a beaker, heating the beaker to 60 ℃ in a water bath, taking a certain amount of Triethanolamine (TEA), tetraethyl orthosilicate (TEOS) and 3-mercaptopropionic acid (MPA), heating the mixture in a constant-temperature oil bath at 90 ℃ for 25 minutes without stirring, taking the mixture out of the oil bath, adding a preheated CTAC solution, carrying out ultrasonic reaction on the mixture at room temperature for 3 hours after uniform mixing, adding 50mL of absolute ethyl alcohol solution after finishing, continuing ultrasonic treatment to prevent nanospheres from agglomerating, adding 50mL of absolute ethyl alcohol after the reaction is finished, and carrying out ultrasonic reaction again for 1 hour. Centrifuging the obtained precipitate after the reaction, washing with absolute ethanol, repeating for at least three times to obtain mercapto functional mesoporous SiO 2 Nanospheres (MSNs).
(2) Synthesizing zinc doped mesoporous silica nanospheres: 0.25 mol.L is arranged -1 Zn (CH) 3 COO) 2 ·2H 2 O in water, dispersing the MSNs sample obtained in the step (1) in Zn (CH) 3 COO) 2 ·2H 2 In O aqueous solution, stirring for 12 hours at room temperature after ultrasonic dispersion, and generating zinc ion modified mesoporous SiO 2 A nanosphere. Centrifuging the reacted dispersion liquid, repeatedly washing and centrifuging with absolute ethyl alcohol for four times, and finally drying the obtained precipitate to obtain the zinc doped mesoporous silica nanospheres (MSN (Zn)).
Wherein in step (1) 26.7mL of 2.5wt% CTAC, 1.3mL of TEA, 2.25mL of TEOS and 440. Mu.L of MPA are taken. Centrifugal rotational speeds are 7000 r.min -1 The time was 6min.
It is characterized in that the centrifugal rotational speeds in the step (2) are 6500 r.min -1 The time was 6min. The drying temperature is 60 ℃ and the time is 4 hours.
The further technical scheme is that the mercapto-functionalized mesoporous silica nanospheres adopt a beaker of 150 mL.
The invention provides a preparation method of zinc doped mesoporous silica nanospheres, which is characterized in that 3-mercaptopropionic acid is used as a mercapto source by utilizing an ultrasonic auxiliary microemulsion method, mercapto functional mesoporous silica is synthesized in one step, and then the mercapto functional mesoporous silica is mixed into the zinc doped mesoporous silica nanospheresZn(CH 3 COO) 2 ·2H 2 And (3) in the O aqueous solution, repeatedly centrifuging and washing by using absolute ethyl alcohol to obtain the zinc-mercapto functional modified mesoporous silica nanospheres.
The method has the advantages that:
(1) The preparation method of the zinc-doped mesoporous silica nanospheres is simple and has high output efficiency.
(2) The material prepared by the method not only maintains the high specific surface area and good biocompatibility of the mesoporous silica material, but also has good coordination capacity of the surface modified sulfhydryl.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of doped mesoporous silica nanospheres prepared according to an embodiment of the present invention.
Fig. 2 is a Transmission Electron Micrograph (TEM) of doped mesoporous silica nanospheres prepared in accordance with an embodiment of the present invention.
Detailed Description
Examples
The embodiment is used for explaining the preparation method and the morphology analysis of the zinc-doped mesoporous silica nanospheres.
(1) Mercapto-functionalized mesoporous SiO 2 The synthesis of nanospheres, namely, transferring 2.5wt% of Cetyl Trimethyl Ammonium Chloride (CTAC), placing the mixture into a beaker, heating the beaker to 60 ℃ in a water bath, taking a certain amount of Triethanolamine (TEA), tetraethyl orthosilicate (TEOS) and 3-mercaptopropionic acid (MPA), heating the mixture in a constant-temperature oil bath at 90 ℃ for 25 minutes without stirring, taking the mixture out of the oil bath, adding a preheated CTAC solution, carrying out ultrasonic reaction on the mixture at room temperature for 3 hours after uniform mixing, adding 50mL of absolute ethyl alcohol solution after finishing, continuing ultrasonic treatment to prevent nanospheres from agglomerating, adding 50mL of absolute ethyl alcohol after the reaction is finished, and carrying out ultrasonic reaction again for 1 hour. Centrifuging the obtained precipitate after the reaction, washing with absolute ethanol, repeating for at least three times to obtain mercapto functional mesoporous SiO 2 Nanospheres (MSNs).
(2) Synthesizing zinc doped mesoporous silica nanospheres: 0.25 mol.L is arranged -1 Zn (CH) 3 COO) 2 ·2H 2 Aqueous solution of ODispersing the MSNs sample obtained in the step (1) in Zn (CH) 3 COO) 2 ·2H 2 In O aqueous solution, stirring for 12 hours at room temperature after ultrasonic dispersion, and generating zinc ion modified mesoporous SiO 2 A nanosphere. Centrifuging the reacted dispersion liquid, repeatedly washing and centrifuging with absolute ethyl alcohol for four times, and finally drying the obtained precipitate to obtain the zinc doped mesoporous silica nanospheres (MSN (Zn)).
Wherein in step (1) 26.7mL of 2.5wt% CTAC, 1.3mL of TEA, 2.25mL of TEOS and 440. Mu.L of MPA are taken. Centrifugal rotational speeds are 7000 r.min -1 The time was 6min.
It is characterized in that the centrifugal rotational speeds in the step (2) are 6500 r.min -1 The time was 6min. The drying temperature is 60 ℃ and the time is 4 hours.
The microscopic morphology of the zinc-doped mesoporous silica nanospheres prepared by the invention is studied by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and the prepared nanospheres have good monodispersity and uniform particle size as can be seen from a figure I. The second graph shows that the size difference among the particles is not large, and a clear limit exists among the particles, so that the material has good monodispersity and uniform particle size, and is consistent with the SEM characterization result.
In conclusion, the preparation method of the zinc-doped mesoporous silica nanospheres is simple, the required material is low in price, and the material has large specific surface area and biocompatibility. The material is characterized by good dispersibility and uniform particle size. It is believed that the zinc doped mesoporous silica nanospheres have wide application prospects in the fields of fluorescent immunolabeling and labeling of electrochemical substances.
Claims (1)
1. The preparation method of the zinc-doped mesoporous silica nanospheres comprises the following steps:
(1) Mercapto-functionalized mesoporous SiO 2 The synthesis of nanospheres comprises transferring 2.5. 2.5wt% cetyltrimethylammonium chloride (CTAC) into beaker, heating to 60deg.C in water bath, taking Triethanolamine (TEA), tetraethyl orthosilicate (TEOS), 3-mercaptopropionic acid (MPA) in a certain amount, and heating in 90 deg.C constant temperature oil bathHeating for 25min without stirring, taking out the mixture from an oil bath, adding a preheated CTAC solution, uniformly mixing, carrying out ultrasonic reaction on the mixture at room temperature for 3 hours, adding 50mL of absolute ethyl alcohol solution after the mixture is finished, continuing ultrasonic treatment, preventing nanospheres from agglomerating, adding 50mL of absolute ethyl alcohol after the reaction is finished, and carrying out ultrasonic reaction again for 1 hour; centrifuging the obtained precipitate after the reaction, washing with absolute ethanol, repeating for at least three times to obtain mercapto functional mesoporous SiO 2 Nanospheres (MSNs);
(2) Synthesizing zinc doped mesoporous silica nanospheres: 0.25 mol.L is arranged -1 Zn (CH) 3 COO) 2 ·2H 2 O in water, dispersing the MSNs sample obtained in the step (1) in Zn (CH) 3 COO) 2 ·2H 2 In O aqueous solution, stirring for 12 hours at room temperature after ultrasonic dispersion, and generating zinc ion modified mesoporous SiO 2 A nanosphere; centrifuging the reacted dispersion liquid, repeatedly washing and centrifuging with absolute ethyl alcohol for four times, and finally drying the obtained precipitate to obtain the zinc doped mesoporous silica nanospheres (MSN (Zn));
the method is characterized in that 26.7mL of CTAC with the concentration of 2.5 and wt percent is taken in the step (1), 1.3mL of TEA is taken, 2.25mL of TEOS is taken, and 440 mu L of MPA is taken; centrifugal rotational speeds are r min -1 The time is 6min;
the method is characterized in that the centrifugal rotational speed in the step (2) is 6500r min < -1 >, and the time is 6min; the drying temperature is 60 ℃ and the time is 4 hours.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106689A (en) * | 1985-09-25 | 1987-05-27 | 默克专利股份公司 | Preparing spherical SiO 2 particles |
| US5591797A (en) * | 1993-10-25 | 1997-01-07 | Wacker-Chemie Gmbh | Transition metal-containing hydrophobic silica |
| CN101184803A (en) * | 2005-05-27 | 2008-05-21 | 西巴特殊化学品控股有限公司 | Functionalized nanoparticles |
| CN107982549A (en) * | 2017-12-12 | 2018-05-04 | 湖北工业大学 | A kind of mesoporous silicon dioxide nano particle for being loaded with quantum dot and its preparation method and application |
| CN110217801A (en) * | 2019-05-23 | 2019-09-10 | 首都医科大学 | The mesoporous silicon oxide nanomaterial and the preparation method and application thereof of lipoic acid functionalization |
| EP3653673A1 (en) * | 2018-11-16 | 2020-05-20 | Rhodia Operations | Organosilane-modified precipitated silica |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2789502A1 (en) * | 2011-06-05 | 2012-12-05 | Guangzhou Nacomes New Material Limited Corporation | Fabrication of disordered porous silicon dioxide material and the use of fatty alcohol polyoxyethylene ether in such fabrication |
| EP3744684A1 (en) * | 2019-05-29 | 2020-12-02 | Nouryon Chemicals International B.V. | Porous silica particles |
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- 2021-11-29 CN CN202111427213.9A patent/CN114229853B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106689A (en) * | 1985-09-25 | 1987-05-27 | 默克专利股份公司 | Preparing spherical SiO 2 particles |
| US5591797A (en) * | 1993-10-25 | 1997-01-07 | Wacker-Chemie Gmbh | Transition metal-containing hydrophobic silica |
| CN101184803A (en) * | 2005-05-27 | 2008-05-21 | 西巴特殊化学品控股有限公司 | Functionalized nanoparticles |
| CN107982549A (en) * | 2017-12-12 | 2018-05-04 | 湖北工业大学 | A kind of mesoporous silicon dioxide nano particle for being loaded with quantum dot and its preparation method and application |
| EP3653673A1 (en) * | 2018-11-16 | 2020-05-20 | Rhodia Operations | Organosilane-modified precipitated silica |
| CN110217801A (en) * | 2019-05-23 | 2019-09-10 | 首都医科大学 | The mesoporous silicon oxide nanomaterial and the preparation method and application thereof of lipoic acid functionalization |
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