CN117247775A - Luminescent composite nano material and preparation method and application thereof - Google Patents
Luminescent composite nano material and preparation method and application thereof Download PDFInfo
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- CN117247775A CN117247775A CN202311489393.2A CN202311489393A CN117247775A CN 117247775 A CN117247775 A CN 117247775A CN 202311489393 A CN202311489393 A CN 202311489393A CN 117247775 A CN117247775 A CN 117247775A
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 71
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 33
- 230000005284 excitation Effects 0.000 claims abstract description 24
- 125000003277 amino group Chemical group 0.000 claims abstract description 22
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims description 52
- 239000011701 zinc Substances 0.000 claims description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- 238000000799 fluorescence microscopy Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 3
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
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- 239000000463 material Substances 0.000 description 15
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- 230000004048 modification Effects 0.000 description 4
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- 239000002073 nanorod Substances 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/661—Chalcogenides
- C09K11/662—Chalcogenides with zinc or cadmium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
- G01N21/6456—Spatial resolved fluorescence measurements; Imaging
- G01N21/6458—Fluorescence microscopy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses a luminescent composite nanomaterial and a preparation method and application thereof, wherein the luminescent composite nanomaterial comprises carbon quantum dots with carboxyl modified surfaces and long afterglow nanoparticles with amino modified surfaces; the carbon quantum dots with carboxyl groups modified on the surfaces are connected with the long afterglow nano particles with amino groups modified on the surfaces through amide bonds; the saidThe molecular formula of the long afterglow nano particles is Zn 2 GeO 4 :Mn 2+ Wherein Zn 2+ With Mn 2+ The molar ratio of (3) is 95-99.5: 0.5-5; the mass ratio of the long afterglow nano particles with the amino groups modified on the surfaces to the carbon quantum dots with the carboxyl groups modified on the surfaces is 1 (1-3). According to the luminescent composite nanomaterial, under the excitation wavelength of 350-400 nm, 440-500 nm has a blue light emission peak; under the excitation wavelength of 250-260 nm, 530-560 nm has green light emission peak, can be applied to the fields of anti-counterfeiting, fluorescent imaging and temperature sensing, has simple preparation process and low cost, and is beneficial to realizing industrialized mass production.
Description
Technical Field
The invention relates to the technical field of luminescent composite nano materials, in particular to a luminescent composite nano material, a preparation method and application thereof.
Background
The information disclosed in the background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an admission or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
At present, anti-counterfeiting is used in various aspects of daily life, but aiming at some special fields, the existing anti-counterfeiting materials are difficult to meet the requirements, for example, the problems that a single material printing anti-counterfeiting technology is easy to imitate, complicated images and texts are difficult to identify and the like exist.
In order to improve the anti-counterfeiting level, double anti-counterfeiting attracts attention of researchers. Patent CN 113736465B (publication date: 2022.09.23) discloses a dual mode fluorescent nanoparticle composite material made of up-conversion luminescent nanoparticles and EuSe semiconductor material, wherein the EuSe semiconductor material uniformly coats the surface of the up-conversion luminescent nanoparticles to form a heterogeneous particle structure, and the composite structure is formed by physical coating. However, physical coating tends to cause delamination between different nanoparticles during purification processes (e.g., high-speed centrifugation, etc.), affecting the yield and stability of the nanoparticle composites. In addition, in order to improve the hydrophilicity of the nanoparticle composite material so that the nanoparticle composite material can be dispersed in an aqueous solution, the PVP hydrophilic macromolecules are coated on the outer surface of the nanoparticle composite material, so that the steps are complicated, and the luminescence of the composite material can be influenced.
Therefore, there is a need to provide a dual anti-counterfeiting nanoparticle composite material with good stability and hydrophilicity.
Disclosure of Invention
In view of the above, the invention provides a luminescent composite nanomaterial, a preparation method and application thereof, which solves the problems that an anti-counterfeiting mark is easy to imitate and complex anti-counterfeiting images and texts are difficult to identify in the prior art, and the luminescent composite nanomaterial has good stability and hydrophilicity and good dispersibility in aqueous solution.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the invention provides a luminescent composite nanomaterial comprising carbon quantum dots with carboxyl groups modified on the surfaces and long-afterglow nanoparticles with amino groups modified on the surfaces, wherein the long-afterglow nanoparticles with amino groups modified on the surfaces are obtained by reacting the long-afterglow nanoparticles with 3-aminopropyl triethoxysilane in an aqueous solution; the molecular formula of the long afterglow nano particles is Zn 2 GeO 4 :Mn 2+ Wherein Zn 2+ With Mn 2+ The molar ratio of (3) is 95-99.5: 0.5-5; the carbon quantum dots with carboxyl groups modified on the surfaces are connected with the long afterglow nano particles with amino groups modified on the surfaces through amide bonds formed by dehydration condensation of the carboxyl groups and the amino groups; the mass ratio of the long afterglow nano particles with the amino groups modified on the surfaces to the carbon quantum dots with the carboxyl groups modified on the surfaces is 1 (1-3).
In a second aspect, the present invention provides a method for preparing the above luminescent composite nanomaterial, comprising the steps of:
reacting the long afterglow nano-particles with 3-aminopropyl triethoxysilane in water to obtain the long afterglow nano-particles with amino groups modified on the surfaces;
and (3) carrying out dehydration condensation reaction on the carboxyl and amino on the carbon quantum dot with the carboxyl modified surface and the amino long afterglow nano particles with the amino modified surface.
In a third aspect, the invention provides an application of the luminescent composite nanomaterial in dual anti-counterfeiting, temperature sensing or fluorescence imaging.
Compared with the prior art, the invention has the following beneficial effects:
(1) The luminescent composite nanomaterial provided by the invention emits blue light under the excitation wavelength of 350-400 nm and emits green light under the excitation wavelength of 250-260 nm, so that double anti-counterfeiting can be realized, and meanwhile, the luminescent composite nanomaterial also has long afterglow luminescent performance, and the imitation risk of anti-counterfeiting marks is reduced;
(2) The luminescent composite nanomaterial provided by the invention has smaller particle size and higher fluorescence emission intensity, can have obvious luminescent effect only by adding a small amount of the luminescent composite nanomaterial for mixing, has a simple detection mode, and can effectively reduce industrial detection flow;
(3) The luminescent composite nano material provided by the invention has good hydrophilicity, is easy to disperse in water, does not need to be coated with a hydrophilic modifier for hydrophilic modification, and has unaffected luminous intensity; meanwhile, the aqueous dispersion is more environment-friendly, and the harmful influence of the organic solvent on the environment and human body is avoided;
(4) The luminescent composite nanomaterial provided by the invention has the advantages of simple preparation process and low cost, and is beneficial to realizing industrial mass production; meanwhile, the preparation process is finished in an aqueous solution, and the preparation process is environment-friendly;
(5) The luminescent composite nanomaterial prepared by the invention not only can be applied to anti-counterfeiting, but also can be applied to the fields of temperature measurement, fluorescence imaging and the like, and has wide application range.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. It will be obvious to those skilled in the art that other figures may be obtained from these figures without the inventive effort.
FIG. 1 is a Transmission Electron Microscope (TEM) image of a carbon quantum dot of example 1 of the present invention;
FIG. 2 is an emission spectrum of the carbon quantum dots of example 1 of the present invention;
FIG. 3 is a Zn film prepared in example 2 of the present invention 2 GeO 4 :Mn 2+ Scanning electron microscope images of the nano particles;
FIG. 4 shows Zn prepared in example 2 of the present invention 2 GeO 4 :Mn 2+ X-ray diffraction pattern of nanoparticles;
FIG. 5 shows Zn prepared in example 2 of the present invention 2 GeO 4 :Mn 2+ Nanoparticles and amino-modified Zn prepared in example 3 2 GeO 4 :Mn 2+ An emission spectrum of the nanoparticle;
FIG. 6 shows CDs-Zn prepared in example 3 of the present invention 2 GeO 4 :Mn 2+ Is a transmission electron microscope image;
FIG. 7 shows CDs-Zn prepared in example 3 of the present invention 2 GeO 4 :Mn 2+ Is a graph of the emission spectrum of (2);
FIG. 8 shows CDs-Zn prepared in example 3 of the present invention 2 GeO 4 :Mn 2+ Photograph of the luminous pattern under 254nm laser excitation;
FIG. 9 shows CDs-Zn prepared in example 3 of the present invention 2 GeO 4 :Mn 2+ Photograph of luminous pattern under 365nm laser excitation;
FIG. 10 shows CDs-Zn prepared in example 3 of the present invention 2 GeO 4 :Mn 2+ A photo of the luminous pattern is obtained after the laser source is removed by irradiation of 254nm laser for 5 s; a graph a is a light-emitting pattern photograph at 0s, B is a light-emitting pattern photograph at 0.1s, and C is a light-emitting pattern photograph at 0.2 s;
FIG. 11 shows CDs-Zn prepared in example 3 of the present invention 2 GeO 4 :Mn 2+ Emission spectra irradiated with 365nm laser at different temperatures;
FIG. 12 is a bright field chart (A) of Hela cells and CDs-Zn of application example 3 of the present invention 2 GeO 4 :Mn 2+ Fluorescent imaging (B-panel), hela cell bright field and CDs-Zn 2 GeO 4 :Mn 2+ Superimposed images of the fluorescence imaging images (panel C).
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As described in the background art, the existing single anti-counterfeiting material is easy to copy, and the complex anti-counterfeiting pattern is difficult to identify, so that there is a need for an anti-counterfeiting material which is easy to identify and difficult to copy. The existing double anti-counterfeiting nanoparticle composite material is poor in stability and hydrophilicity, hydrophilic modification is needed to disperse in water, the steps are complicated, and the fluorescence intensity is inevitably affected.
In view of the above, the present invention provides a light-emitting composite nano-meterThe material comprises carbon quantum dots with carboxyl modified surfaces and long-afterglow nano particles with amino modified surfaces, wherein the long-afterglow nano particles with amino modified surfaces are obtained by reacting the long-afterglow nano particles with 3-aminopropyl triethoxysilane in an aqueous solution; the molecular formula of the long afterglow nano particles is Zn 2 GeO 4 :Mn 2+ Wherein Zn 2+ With Mn 2+ The molar ratio of (1) to (99.5) is (0.5 to 5); the carbon quantum dots with carboxyl groups modified on the surfaces are connected with the long afterglow nano particles with amino groups modified on the surfaces through amide bonds formed by dehydration condensation of the carboxyl groups and the amino groups; the mass ratio of the long afterglow nano particles with the amino groups modified on the surfaces to the carbon quantum dots with the carboxyl groups modified on the surfaces is 1 (1-3).
In the invention, the surface of the carbon quantum dot is rich in carboxyl, the surface of the long afterglow nanoparticle contains more hydroxyl groups, and the surface of the long afterglow nanoparticle is rich in amino groups after being modified by amino groups, so that the luminescent composite nanomaterial has rich hydrophilic groups, is extremely easy to disperse in water, and does not need to be modified by adding other hydrophilic substances.
The 3-aminopropyl triethoxy silane (APTES) contains three hydrolyzable groups (ethoxy), silanol is generated by hydrolysis in the reaction, and the silanol is unstable and is very easy to combine with hydroxyl groups on the surfaces of the long-afterglow nano particles for dehydration, so that the silanol is connected with the long-afterglow nano particles through chemical bonds. The carbon quantum dot surface has rich carboxyl, so the carbon quantum dot can be used for long afterglow nano particle Zn with amino modified on the surface 2 GeO 4 :Mn 2+ Is connected with the amino through an amide bond formed by dehydration condensation of carboxyl and amino. The carbon quantum dots are extremely unstable and easy to aggregate, and the phenomenon of fluorescence quenching is easy to occur due to secondary aggregation, and the invention adopts the chemical bond connection mode to ensure that the prepared carbon quantum dots-long afterglow nano particles (CDs-Zn) 2 GeO 4 :Mn 2+ ) The luminescent composite nano material has better stability in the subsequent purification step and application process, and the carbon quantum dots are uniformly dispersed, so that the phenomenon of fluorescence quenching caused by secondary convergence is avoided.
In the luminescent composite nanomaterial, the particle size of the carbon quantum dot with the carboxyl modified on the surface is 2-5 nm, and the long afterglow nanoparticle with the amino modified on the surface is in the shape of a nano rod, and the length of the long afterglow nanoparticle is 40-100 nm, and the width of the long afterglow nanoparticle is 15-25 nm.
According to the luminescent composite nanomaterial, under the excitation wavelength of 350-400 nm, 440-500 nm has a blue light emission peak; at an excitation wavelength of 250-260 nm, 530-560 nm has a green emission peak.
In another embodiment of the present invention, a method for preparing the above luminescent composite nanomaterial is provided, including the steps of:
reacting the long afterglow nano-particles with 3-aminopropyl triethoxysilane in water to obtain the long afterglow nano-particles with amino groups modified on the surfaces;
and (3) carrying out dehydration condensation reaction on the carboxyl and amino on the carbon quantum dot with the carboxyl modified surface and the amino long afterglow nano particles with the amino modified surface.
In the invention, during dehydration condensation reaction, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) are added to activate carboxyl groups on the surfaces of carbon quantum dots, and then the carboxyl groups react with amino groups to generate amide bonds. The activation time is preferably 1-3 h.
The preparation method of the long afterglow nano-particles comprises the following steps: mixing manganese salt, zinc salt and dilute nitric acid, and adding Na 2 GeO 3 And (3) adding NaOH solution into the aqueous solution to adjust the pH value to 7.2-7.9, performing hydrothermal synthesis reaction, and purifying to obtain the aqueous solution.
The hydrothermal synthesis reaction conditions of the invention are as follows: the temperature is 210-230 ℃, preferably 220 ℃, and the time is 12-24 hours, preferably 16-h; the molar ratio of the zinc salt to the manganese salt is (95-99.5): (0.5-5), preferably 99:1.Mn (Mn) 2+ The concentration will be to Zn 2 GeO 4 :Mn 2+ The luminous intensity of (2) is affected.
The purification method of the long afterglow nano particles is not particularly limited, and the purification method is common in the field, and the purification method is that liquid after hydrothermal synthesis reaction is subjected to centrifugation, water washing and drying, so that the long afterglow nano particles are obtained.
The preparation method of the carbon quantum dot with the carboxyl modified surface is not particularly limited, and the carbon quantum dot with the carboxyl modified surface is prepared by adopting a hydrothermal method common in the field. The preparation process of the carbon quantum dot comprises the following steps: dripping ethanolamine into an aqueous solution dissolved with citric acid, vigorously stirring until the solution is clear, performing hydrothermal synthesis reaction for 5-8 hours at 170-200 ℃, and purifying to obtain the aqueous solution. The temperature of the hydrothermal synthesis reaction is preferably 180 ℃ and the time is preferably 6 hours.
In the invention, the mol ratio of ethanolamine to citric acid is 1.8-2.2:1, preferably 2:1. The carbon quantum dot synthesized by adopting the ethanolamine and the citric acid with the molar ratio as raw materials has good luminous performance.
In another embodiment of the present invention, there is provided the use of the luminescent composite nanomaterial described above in dual anti-counterfeiting, fluorescence imaging or temperature sensing.
The luminescent composite nanomaterial prepared by the invention can realize fluorescence emission of different colors under excitation of excitation lights (254 nm and 365 nm) with different wavelengths, thereby realizing double anti-counterfeiting function; the material is dispersed in liquid and only used as a fixed pattern, so that the fluorescent imaging function can be realized. Under 365nm laser excitation, the material is heated (28-61 ℃), and the fluorescence intensity of the material is reduced along with the temperature rise, so that the temperature measurement function can be realized. After the prepared luminescent composite nano material is incubated with cells for 2 hours, the composite nano material can enter the cells, so that fluorescent imaging in the cells is realized.
The source of the reagents in the examples is not particularly limited and commercially available products known to those skilled in the art may be used.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
The embodiment provides preparation of carbon quantum dots (CDs), comprising the following steps:
(1) 19.212g of citric acid is weighed, added into a beaker, 20mL of water is added and stirred uniformly to obtain an aqueous solution of citric acid (0.1 mol), 11.98mL of aqueous solution of ethanolamine (0.2 mol) is added dropwise into the aqueous solution of citric acid, and the solution is stirred vigorously until the solution is clear.
(2) Sealing the clear solution in a reaction kettle, heating to 180 ℃ and keeping for 6 hours, and naturally cooling to room temperature to obtain reddish brown liquid.
(3) Adding the reddish brown liquid into a dialysis bag with 3500 molecular weight cutoff for dialysis, changing water every 4 hours, dialyzing for three days, and removing excessive micromolecular products and impurities to obtain purified CDs aqueous solution.
The Transmission Electron Microscope (TEM) image of the obtained carbon quantum dots was measured, as shown in fig. 1. As can be seen from the figure, CDs are spherical and have a size of about 3 nm.
And taking 0.2mL of carbon dots of the purified CDs aqueous solution, adding 6.4mL of water to dilute the carbon dots, and measuring an emission spectrum diagram of the carbon quantum dots, wherein the emission peak is 456nm, and the excitation light source is 365nm and the power is 4W as shown in figure 2.
Example 2
This example provides long afterglow nanoparticle Zn 2 GeO 4 :Mn 2+ Comprises the following steps:
(1) Zn (NO) was added to the beaker 3 ) 2 (1.98mmol)，MnCl 2 (0.02 mmol) and 300. Mu.L of 1% (by mass) dilute nitric acid and 20mL of water were added thereto and stirred.
(2) Dissolving 10mmol NaOH in 10mL water solution until NaOH is completely dissolved, and taking 2mmol GeO 2 Adding the above-mentioned materials, stirring so as to obtain Na 2 GeO 3 A solution. 5.5mL of the above solution was added to the solution in step (1) by syringe, and the mixed solution was stirred for 30 minutes.
(3) The pH of the solution was adjusted to 7.58 with 1% by mass of sodium hydroxide and stirred for 30 minutes. Transferring the mixture into a hydrothermal reaction kettle and keeping the temperature at 220 ℃ for 16 hours.
(4) Centrifuging the reacted solution at 10000r/min×10min to obtain Zn 2 GeO 4 : Mn 2+ The nanoparticles were washed with water and dried.
FIG. 3 shows Zn prepared in this example 2 GeO 4 :Mn 2+ Scanning electron microscope pictures of nano particles, as can be seen from the pictures, zn 2 GeO 4 :Mn 2+ The nano particles are rod-shaped, the particle length is about 100nm, and the particle width is about 35 nm.
FIG. 4 shows Zn prepared in this example 2 GeO 4 :Mn 2+ X-ray diffraction pattern of nanoparticles, zn 2 GeO 4 :Mn 2+ The XRD pattern of the nanoparticles was completely consistent with that of the standard card (JCPLDS#11-0687), indicating that Zn was prepared 2 GeO 4 :Mn 2+ The nanoparticles are pure phase and free of any impurities.
FIG. 5 shows Zn prepared in this example 2 GeO 4 :Mn 2+ The emission spectrum of the nano particle has a main emission peak of 544nm corresponding to Mn 2+ A kind of electronic device 4 T 1 → 6 A 1 The transition is carried out by using 254nm excitation light source and 4W power.
Example 3
The present example provides CDs-Zn 2 GeO 4 :Mn 2+ The preparation of the nano-particles comprises the following specific steps:
(1) 2.5mg of long afterglow nanoparticle (Zn) 2 GeO 4 :Mn 2+ ) Dissolving in 15mL of water, adding 1mL of APTES, and stirring for 12h to obtain the amino modified long-afterglow nanoparticle. The solution after the above reaction was centrifuged (10000 r/min. Times.10 min) and dispersed with 15mL of water.
(2) 100mg EDC,50mg NHS was dissolved in 20mL of water, and the diluted CDs solution of example 1 (containing 7mg CDs) was added thereto and stirred for 2 hours to activate carboxyl groups on CDs.
(3) Taking the activated CDs solution and Zn modified by amino in the step (1) 2 GeO 4 :Mn 2+ Is stirred for 12 hours, centrifuged at 12000r/min, washed once with water and dispersed in 15mL of water to obtain CDs-Zn 2 GeO 4 :Mn 2+ An aqueous solution of luminescent composite nanomaterial.
FIG. 5 provides an emission spectrum of the amino-modified long persistence nanoparticle prepared in this example, and it can be seen that after the amino group is modified, the light-emitting position and the light-emitting intensity are not significantly changed, which indicates that the modified amino group does not affect the light-emitting performance.
FIG. 6 shows CDs-Zn prepared in this example 2 GeO 4 :Mn 2+ Can be observed in Zn by transmission electron microscopy 2 GeO 4 The surface of the nano rod has a large number of carbon dots distributed, the size of the nano rod is 40-100 nm, and the width of the nano rod is 15-25 nm.
FIG. 7 shows CDs-Zn prepared in this example 2 GeO 4 :Mn 2+ The emission spectrum graph excited at 254nm,365nm and 390nm has excitation power of 4W, main emission peak at 254nm excitation wavelength of 544nm and emits green light, which indicates Zn in the luminescent composite nano material 2 GeO 4 :Mn 2+ Is a fluorescent property of (a). At an excitation wavelength of 365nm, the main emission peak is 456nm; under the excitation wavelength of 390nm, the main emission peak is 495nm, and blue light is emitted, which shows the fluorescence property of the carbon quantum dots in the luminescent composite nano material.
Application example 1
The material in example 3 was used for anti-counterfeiting experiments, and the specific steps were as follows:
(1) 0.1g of polyvinyl alcohol was weighed, and 5mL of CDs-Zn dispersed therein was added 2 GeO 4 :Mn 2+ The aqueous solution of the luminescent composite nano material is uniformly stirred, and the mixed solution becomes a viscous colloid.
(2) Preparing proper paperboard, covering a hollow template with proper size, coating the obtained colloid, drying and removing the hollow template to obtain corresponding patterns, and exciting with different wavelengths (254 nm,365nm and 390 nm) to obtain pattern photos of fig. 8 and 9. FIG. 8 shows CDs-Zn prepared in example 3 2 GeO 4 :Mn 2+ Light-emitting pattern photo of light-emitting composite nano material, wherein the excitation light source is 254nm and the power is 4W, which shows CDs-Zn 2 GeO 4 :Mn 2+ Zn in luminous composite nano material 2 GeO 4 Is a fluorescent property of (a). FIG. 9 shows CDs-Zn prepared in example 3 2 GeO 4 :Mn 2+ Light-emitting pattern photo of light-emitting composite nano material, wherein the excitation light source is 365nm and the power is 1W, which shows CDs-Zn 2 GeO 4 :Mn 2+ Fluorescence of CDs in composite nanomaterialQuality is high.
In addition, CDs-Zn 2 GeO 4 :Mn 2+ The luminescent composite nano material has long afterglow luminescence property, and FIG. 10 is a photograph of luminescent patterns of the luminescent composite nano material at 0s, 0.1s and 0.2s after the excitation light source is removed by adopting 254nm laser irradiation for 5 s.
Application example 2
The materials of example 3 were used in temperature sensing experiments, with the following specific steps:
(1) 3mL of CDs-Zn was taken 2 GeO 4 :Mn 2+ Placing the aqueous solution of the composite nano material in a standard cuvette of 1cm multiplied by 1cm, and placing the cuvette in a liquid temperature measuring device;
(2) Heating the cuvette by a temperature changing device, and testing CDs-Zn by a spectrometer under 365nm laser irradiation 2 GeO 4 :Mn 2+ The fluorescence spectrum of the composite nano material is obtained to obtain a change curve of the fluorescence spectrum along with the temperature, and the temperature in the environment where the composite material is positioned can be calculated by using the curve, as shown in figure 11, the excitation light source is 365nm, the power is 4W, which indicates CDs-Zn 2 GeO 4 :Mn 2+ Fluorescent properties of CDs at different temperatures in the composite nanomaterial.
Application example 3
The material of example 3 was used in a fluorescence imaging experiment, the specific procedure being as follows:
(1) CDs-Zn prepared by ultraviolet lamp pair 2 GeO 4 :Mn 2+ The composite nanomaterial (5 mL) was sterilized and dispersed in 15mL of Hela cell culture Medium DMEM.
(2) HeLa cells were grown at 5X 10 3 Density of individual/wells was seeded in 96-well plates at 5% co 2 Incubation overnight at 37℃to ensure cell attachment was performed with 200. Mu.L of CDs-Zn per well 2 GeO 4 :Mn 2+ The DMEM culture medium of the composite nano material is incubated for 2 hours.
(3) Cell fixation by 4% paraformaldehyde and observation of CDs-Zn by inverted fluorescence microscopy 2 GeO 4 :Mn 2+ Fluorescent imaging of composite nanomaterial in cells.
Respectively shooting cell bright field and material fluorescence image, and combining the two to obtain superimposed image, as shown in figure 12, the excitation light source is 365nm, which shows CDs-Zn 2 GeO 4 :Mn 2+ Fluorescent properties of composite nanomaterials in cell imaging.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The luminescent composite nano material is characterized by comprising carbon quantum dots with carboxyl modified surfaces and long-afterglow nano particles with amino modified surfaces, wherein the long-afterglow nano particles with amino modified surfaces are obtained by reacting the long-afterglow nano particles with 3-aminopropyl triethoxysilane in an aqueous solution; the molecular formula of the long afterglow nano particles is Zn 2 GeO 4 :Mn 2 + Wherein Zn 2+ With Mn 2+ The molar ratio of (3) is 95-99.5: 0.5-5; the carbon quantum dots with carboxyl groups modified on the surfaces are connected with the long afterglow nano particles with amino groups modified on the surfaces through amide bonds formed by dehydration condensation of the carboxyl groups and the amino groups; the mass ratio of the long afterglow nano particles with the amino groups modified on the surfaces to the carbon quantum dots with the carboxyl groups modified on the surfaces is 1 (1-3).
2. The luminescent composite nanomaterial of claim 1, wherein the carbon quantum dots with carboxyl groups modified on the surface have a particle size of 2-5 nm; the long afterglow nano particles with amino groups modified on the surfaces have the following sizes: the length is 40-100 nm, and the width is 15-25 nm.
3. The luminescent composite nanomaterial of claim 1, wherein the luminescent composite nanomaterial has a blue emission peak at an excitation wavelength of 350-400 nm at 440-500 nm; at an excitation wavelength of 250-260 nm, 530-560 nm has a green emission peak.
4. The method for preparing the luminescent composite nanomaterial according to any one of claims 1 to 3, characterized by comprising the steps of:
reacting the long afterglow nano-particles with 3-aminopropyl triethoxysilane in water to obtain the long afterglow nano-particles with amino groups modified on the surfaces;
and (3) carrying out dehydration condensation reaction on the carboxyl and amino on the carbon quantum dot with the carboxyl modified surface and the amino long afterglow nano particles with the amino modified surface.
5. The method according to claim 4, wherein the carboxyl group is activated by adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide during the dehydration condensation reaction, and the activation time is 1 to 3 hours.
6. The method of preparing the long persistence nanoparticle of claim 4, comprising the steps of: mixing manganese salt, zinc salt and dilute nitric acid, and adding Na 2 GeO 3 And (3) adding NaOH solution into the aqueous solution to adjust the pH value to 7.2-7.9, performing hydrothermal synthesis reaction, and purifying to obtain the aqueous solution.
7. The method of claim 4, wherein the hydrothermal synthesis reaction conditions are: the temperature is 210-230 ℃ and the time is 12-24 hours; the molar ratio of zinc salt to manganese salt is 95-99.5: 0.5 to 5.
8. The method of preparing the carbon quantum dot according to claim 4, wherein the preparation process of the carbon quantum dot with the carboxyl group modified on the surface comprises the following steps: dripping ethanolamine into an aqueous solution dissolved with citric acid, vigorously stirring until the solution is clear, performing hydrothermal synthesis reaction for 5-8 hours at 170-200 ℃, and purifying to obtain the aqueous solution.
9. The method of claim 8, wherein the molar ratio of ethanolamine to citric acid is 1.8-2.2:1.
10. The use of a luminescent composite nanomaterial according to any of claims 1-3, characterized in that the use comprises the use of the luminescent composite nanomaterial in dual anti-counterfeiting, temperature sensing or fluorescence imaging.
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