CN116119653A - Multifunctional anti-aggregation quenched carbon nano onion and preparation method and application thereof - Google Patents

Multifunctional anti-aggregation quenched carbon nano onion and preparation method and application thereof Download PDF

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CN116119653A
CN116119653A CN202310081631.XA CN202310081631A CN116119653A CN 116119653 A CN116119653 A CN 116119653A CN 202310081631 A CN202310081631 A CN 202310081631A CN 116119653 A CN116119653 A CN 116119653A
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梁彩珍
谢小保
施庆珊
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Institute of Microbiology of Guangdong Academy of Sciences
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Abstract

The invention discloses a multifunctional anti-aggregation quenched carbon nano onion and a preparation method and application thereof. The invention synthesizes the carbon nano onion with abundant hydrophilic surface functional groups by using histidine and a silane micromolecule compound containing nitrogen as precursors and lanthanide metal salt as a catalyst through a mild one-step hydrothermal or solvothermal method. The preparation process has the characteristics of simplicity, convenience, low cost, environment friendliness and the like; the prepared carbon nano onion has high light stability, water solubility and excellent solid state and dispersion state fluorescence. The carbon nano onion can be used as water-based ink to realize multi-color anti-counterfeiting; the fluorescent probe is used for realizing pathogenic fungus cell imaging; the fluorescent powder is expected to be applied to photoelectric equipment.

Description

Multifunctional anti-aggregation quenched carbon nano onion and preparation method and application thereof
Technical Field
The invention belongs to the technical field of anti-quenching fluorescent carbon nano-materials, and particularly relates to a multifunctional anti-aggregation quenching carbon nano-onion, and a preparation method and application thereof.
Background
Carbon nano onions (Carbon Nano onions, CNOs), also known as onion carbon, a zero-dimensional carbonaceous nanomaterial with a size of about 2-100nm, are emerging members of the fullerene family. The unique graphite carbon shell structure, high chemical stability, excellent electrical, electromagnetic and optical properties and the like show good application prospects in the fields of supercapacitors, microwave absorption, solar cells, electrocatalysts, electron field emitters, lubricant additives, sensors and the like. However, due to the strong hydrophobicity, weak photoluminescence, easy agglomeration and other disadvantages of the carbon nano onion, the application in the fields of water-based anti-counterfeiting ink, biological imaging and the like is challenging. The other zero-dimensional material, namely carbon point, serving as a carbon material is widely applied to information security, biosensing and imaging due to adjustable luminescence property, abundant surface functional groups and the like; however, its tendency to aggregate-quench fluorescence greatly limits its practical use. Therefore, developing the multifunctional fluorescent carbon nano onion with anti-aggregation quenching to expand the application of the multifunctional fluorescent carbon nano onion in the water-based anti-counterfeiting ink and the biological imaging has important scientific significance and value.
Since Ugarte's discovery of carbon nano-onions in 1992, its preparation has been over 20 years old. The preparation method of the carbon nano onion is more and mainly comprises an arc discharge method, a plasma method, an electron beam radiation method, nano diamond vacuum heat treatment, a chemical vapor deposition method, a pyrolysis method, a laser method and the like. However, these methods have complicated process procedures, expensive equipment, low yield, many byproducts, poor controllability, environmental pollution, etc.; in addition, the purification steps of the prepared carbon nano onion are complicated, and a further structural modification method is often required to achieve a specific application target. These drawbacks greatly increase the cost of preparing carbon nano-onions and limit the research on their physicochemical and optical properties. Therefore, there is an urgent need for a strategy for synthesizing multifunctional anti-aggregation quenched carbon nano-onions with simple and convenient design, environmental protection and low cost to expand the application of the multifunctional anti-aggregation quenched carbon nano-onions in information security and biological imaging.
Disclosure of Invention
Aiming at the problems of strong hydrophobicity, easy aggregation quenching optical performance, complex preparation process, high cost, unfriendly environment and the like existing in the prior art, the invention provides a simple, environment-friendly and low-cost method for preparing hydrophilic multifunctional anti-aggregation quenching carbon nano onion, and expands the application of the prepared fluorescent carbon nano onion with excellent optical performance and biocompatibility.
The first object of the invention is to provide a preparation method of a multifunctional anti-aggregation quenching carbon nano onion, which takes histidine and a silane compound containing nitrogen element as raw materials, takes lanthanide metal salt as a catalyst, and prepares the multifunctional anti-aggregation quenching carbon nano onion through a mild hydrothermal or solvothermal method.
The preparation method specifically comprises the following steps:
adding histidine, silane compound containing nitrogen element and lanthanide metal salt into a reaction solvent, stirring until the silane compound and lanthanide metal salt are completely dissolved, transferring into a reaction tank with a polytetrafluoroethylene liner, sealing, placing into a microwave synthesizer, reacting for 0.5-72h at 80-260 ℃, cooling the system, filtering, purifying and drying to obtain the multifunctional anti-aggregation quenching carbon nano onion powder.
Preferably, the mass ratio of the histidine to the nitrogen-containing silane compound is 1:100-100:1, and the mass ratio of the histidine to the lanthanide metal salt is 1:50-50:1; the mass volume ratio of the histidine to the reaction solvent is 1g histidine: 10-300mL of reaction solvent.
Preferably, the silane compound containing nitrogen is one or any combination of 3-aminopropyl triethoxysilane (APTES), N- [3- (trimethoxysilyl) propyl ] ethylenediamine (TMSED) or 3- [2- (2-amino ethylamino) ethylamino ] propyl-trimethoxysilane (AEEA).
Preferably, the silane compound containing nitrogen element is a mixture of APTES and TMSED or AEEA or TMSED and AEEA according to the mass ratio of 1:10-10:1.
Preferably, the lanthanide metal salt is cerium nitrate hexahydrate (Ce (NO 3 ) 3 ·6H 2 O), neodymium nitrate hexahydrate (Nd (NO) 3 ) 3 ·6H 2 O), erbium nitrate hexahydrate (Er (NO) 3 ) 3 ·6H 2 O) or any combination thereof.
Preferably, the reaction solvent is deionized water, ethanol or a mixture thereof. The volume ratio of the ethanol water is 1:9-9:1.
The second object of the present invention is to provide a multifunctional anti-aggregation quenched carbon nano onion prepared by the preparation method.
The third object of the present invention is to provide the application of the multifunctional anti-aggregation quenching carbon nano onion as fluorescent powder.
The multifunctional anti-aggregation quenching carbon nano onion powder has excellent fluorescence performance, so that the multifunctional anti-aggregation quenching carbon nano onion has wider application, including application of fluorescent powder in photoelectric equipment.
The fourth object of the invention is to provide the application of the multifunctional anti-aggregation quenching carbon nano onion in multi-color anti-counterfeiting.
The multifunctional anti-aggregation quenching carbon nano onion can be used for multi-color anti-counterfeiting of water-based ink, and the steps of ink manufacturing and anti-counterfeiting label manufacturing are as follows:
the multifunctional anti-aggregation quenching carbon nano onion powder is dissolved in water to prepare an aqueous solution with any concentration, the aqueous solution is filled into a rigid writing brush, writing is carried out in a non-fluorescent carrier such as filter paper, and the obtained label can show adjustable multi-color fluorescence under the irradiation of ultraviolet lamps with different wavelengths.
A fifth object of the present invention is to provide the use of the multifunctional anti-aggregation quenched carbon nano-onions described above in cell imaging.
The multifunctional anti-aggregation quenching carbon nano onion can be used as a fluorescent probe to realize the application of pathogenic fungus cell imaging, and the identification of living and dead fungus cells can be realized by incubating an aqueous solution of the multifunctional anti-aggregation quenching carbon nano onion with pathogenic candida.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation process is simple and feasible, the cost is low, the reaction condition is milder, the repeatability is good, the synthesis of the carbon nano onion can be realized by utilizing one-step hydrothermal or solvothermal method of the small molecular compound, the reaction time is short, and the multifunctional anti-aggregation quenched carbon nano onion with uniform particle size, excellent water dispersibility and excellent fluorescence performance can be obtained without complex purification process or surface structure functionalization; the preparation process of the invention is to react in a mild and airtight environment, and the reaction solvent is water, ethanol or the combination thereof, and no toxic and harmful gas is discharged, thus the invention has the characteristics of environmental protection.
(2) According to the invention, the nitrogen and silicon elements are directly introduced by using raw materials, so that the prepared multifunctional carbon nano onion has high light stability, fluorescence adjustability and aggregation quenching resistance, and has excellent fluorescence properties in both solid state and dispersion state; the surface of the carbon nano onion has rich hydrophilic functional groups, so that the carbon nano onion has excellent water solubility and biocompatibility.
(3) Due to the excellent adjustable dispersion state fluorescence, water solubility and biocompatibility, the carbon nano onion prepared by the invention can be applied to multi-color anti-counterfeiting made of water-based ink, fluorescent imaging for pathogenic fungi and the like as a fluorescent probe; the unique solid state fluorescence of the prepared carbon nano onion makes the carbon nano onion be used as fluorescent powder and be hopefully applied to photoelectric equipment.
(4) The invention expands the variety of the carbon nano onion and provides technical support for preparing the novel multifunctional anti-quenching fluorescent carbon nano onion.
Drawings
FIG. 1 is a transmission electron microscope image of a multifunctional anti-aggregation quenched carbon nano-onion prepared in example 1 of the present invention.
FIG. 2 shows the IR spectrum (left) and the X-ray photoelectron spectrum (right) of the multifunctional anti-aggregation quenching carbon nano-onion prepared in example 1 of the present invention.
FIG. 3 shows the fluorescence spectrum of the aqueous solution of the multifunctional anti-aggregation quenched carbon nano-onions prepared in example 1 (left) and the fluorescence spectrum of the powder solid (right).
FIG. 4 shows the fluorescence spectrum of the aqueous solution of the multifunctional anti-aggregation quenched carbon nano-onions prepared in example 2 (left) and the fluorescence spectrum of the powder solid (right).
FIG. 5 shows the fluorescence spectrum of the aqueous solution of the multifunctional anti-aggregation quenched carbon nano-onions prepared in example 3 (left) and the fluorescence spectrum of the powder solid (right).
FIG. 6 shows the fluorescence spectrum of the aqueous solution of the multifunctional anti-aggregation quenched carbon nano-onions prepared in example 4 (left) and the fluorescence spectrum of the powder solid (right).
FIG. 7 shows the application of the multifunctional anti-aggregation quenching carbon nano onion prepared in the embodiment 1 of the invention in the aqueous multicolor anti-counterfeiting ink, wherein the font (left) is under the sunlight, the fluorescence (middle) is under the 254nm ultraviolet lamp, and the fluorescence (right) is under the 365nm ultraviolet lamp.
FIG. 8 is a fluorescence microscopic image (top left: bright field; top right: blue channel) of a control group of Candida parapsilosis using the multifunctional anti-aggregation quenched carbon nano-onions prepared in example 1 of the present invention as fluorescent probes in fungal imaging; fluorescence microscopy images of the carbon nano onion treated candida parapsilosis sample group (lower left: bright field; lower right: blue channel).
Detailed Description
The technical scheme of the invention is further described below with reference to specific examples, but the invention is not limited thereto.
Example 1
A preparation method of a multifunctional anti-aggregation quenched carbon nano onion comprises the following steps:
0.5g histidine and 0.5g APTES were weighed separately and dissolved in 150mL deionized water, and 0.1g Ce (NO) was added under magnetic stirring at room temperature 3 ) 3 ·6H 2 After the O solid is completely dissolved, the obtained mixture is mixedThe resultant system is transferred to a reaction tank with a polytetrafluoroethylene liner with a volume of 200mL, sealed and placed in a microwave synthesizer, and the temperature is raised to 180 ℃ at a certain heating rate for reaction for 6h. Cooling to room temperature after stopping the reaction, filtering, dialyzing and drying the obtained product to obtain the multifunctional anti-aggregation quenched carbon nano onion. The obtained carbon nano onion was subjected to morphology characterization by using a transmission electron microscope (see fig. 1), chemical composition and structure characterization by using an infrared spectrum and an X-ray photoelectron spectrum (see fig. 2), and fluorescence characterization by using a fluorescence spectrum (see fig. 3).
Example 2
A preparation method of a multifunctional anti-aggregation quenched carbon nano onion comprises the following steps:
0.11g histidine, 10g APTES and 1g TMSED were each weighed and dissolved in 10mL deionized water/ethanol mixture (V: V=1:9), and 2.7g Ce (NO) was added with magnetic stirring at room temperature 3 ) 3 ·6H 2 O and 2.8g Nd (NO) 3 ) 3 ·6H 2 After the O solid is completely dissolved, the obtained mixture system is transferred into a reaction tank with a polytetrafluoroethylene liner with the volume of 50mL, sealed and placed in a microwave synthesizer, and the temperature is raised to 260 ℃ at a certain heating rate for reaction for 0.5h. Cooling to room temperature after stopping the reaction, filtering, dialyzing and drying the obtained product to obtain the multifunctional anti-aggregation quenched carbon nano onion. The resulting carbon nano-onions were fluorescence characterized using fluorescence spectroscopy (see fig. 4).
Example 3
A preparation method of a multifunctional anti-aggregation quenched carbon nano onion comprises the following steps:
5.5g histidine, 0.05g APTES and 0.5g AEEA were each weighed into 50mL ethanol, and 0.05g Ce (NO) was added with magnetic stirring at room temperature 3 ) 3 ·6H 2 O and 0.06g Er (NO 3 ) 3 ·6H 2 After the O solid is completely dissolved, the obtained mixture system is transferred into a reaction tank with a polytetrafluoroethylene liner to be sealed and placed into a microwave synthesizer, and the temperature is raised to 80 ℃ at a certain heating rate for reaction for 72 hours. To be reactedCooling to room temperature after stopping, filtering, dialyzing and drying the obtained product to obtain the multifunctional anti-aggregation quenched carbon nano onion. The resulting carbon nano-onions were fluorescence characterized using fluorescence spectroscopy (see fig. 5).
Example 4
A preparation method of a multifunctional anti-aggregation quenched carbon nano onion comprises the following steps:
7g histidine, 1g APTES, 3g TMSED and 2g AEEA were weighed separately and dissolved in 100mL deionized water/ethanol mixture (V: V=9:1), and 0.5g Ce (NO) was added with magnetic stirring at room temperature 3 ) 3 ·6H 2 O、0.3g Nd(NO 3 ) 3 ·6H 2 O and 0.2g Er (NO 3 ) 3 ·6H 2 After the O solid is completely dissolved, the obtained mixture system is transferred into a reaction tank with a polytetrafluoroethylene liner to be sealed and placed in a microwave synthesizer, and the temperature is raised to 120 ℃ at a certain heating rate for 4 hours. Cooling to room temperature after stopping the reaction, filtering, dialyzing and drying the obtained product to obtain the multifunctional anti-aggregation quenched carbon nano onion. The resulting carbon nano-onions were fluorescence characterized using fluorescence spectroscopy (see fig. 6).
Example 5
The multifunctional anti-aggregation quenching carbon nano-onions prepared in examples 1, 2, 3 and 4 are used for realizing multi-color anti-counterfeiting application (see figure 7).
1g of the carbon nano onion solid powder prepared in examples 1, 2, 3 and 4 was weighed out, and 1000mL of deionized water was added to completely dissolve to obtain four aqueous inks. Then transferring into a rigid writing brush, writing Chinese (Chinese) and English (CHINA) fonts in non-fluorescent filter paper, naturally airing, and observing the fluorescence change under sunlight and ultraviolet lamp respectively. As shown in fig. 7, the written font was non-fluorescent under sunlight, exhibited white-like fluorescence under 254nm uv lamp irradiation, and exhibited blue-green color under 365nm uv lamp irradiation. The carbon nano onion prepared by the method can be used for multi-color anti-counterfeiting in the preparation of water-based ink.
Example 6
In this example, the multifunctional anti-aggregation quenched carbon nano onion prepared in example 1 was used as a fluorescent probe for fungal cell imaging, and pathogenic candida parapsilosis (Candida parapsilosis) was used as an example (see fig. 8)
Candida parapsilosis (Candida parapsilosis) was removed in liquid Save medium and placed in a dark shaker at 37℃and 180rpm for cultivation. After 3 days, the cultured mixture was boiled for 30min, then centrifuged and washed with phosphate buffer (PBS, 10 mm) having a pH of about 7.4 to collect the inactivated candida parapsilosis cells. The collected candida parapsilosis was incubated in the prepared carbon nano onion solution (PBS, 500 μg/mL) for 30min, and the candida parapsilosis was incubated with the PBS solution as a control treatment, centrifuged and washed to remove carbon nano onions not taken up by candida parapsilosis. The treated candida parapsilosis is then placed on a glass slide and the morphology and fluorescence distribution of the parapsilosis are observed under a 60 x microscope. As can be seen from FIG. 8, the carbon nano onion prepared by the method can be used for fluorescence imaging of pathogenic candida.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.

Claims (10)

1. A preparation method of a multifunctional anti-aggregation quenching carbon nano onion is characterized in that histidine and a silane compound containing nitrogen elements are used as raw materials, lanthanide metal salt is used as a catalyst, and the multifunctional anti-aggregation quenching carbon nano onion is prepared by a mild hydrothermal or solvothermal method.
2. The method of manufacturing according to claim 1, comprising the steps of:
adding histidine, silane compound containing nitrogen element and lanthanide metal salt into a reaction solvent, stirring until the silane compound and lanthanide metal salt are completely dissolved, transferring into a reaction tank with a polytetrafluoroethylene liner, sealing, placing into a microwave synthesizer, reacting for 0.5-72h at 80-260 ℃, cooling the system, filtering, purifying and drying to obtain the multifunctional anti-aggregation quenching carbon nano onion powder.
3. The preparation method according to claim 2, wherein the mass ratio of histidine to the nitrogen-containing silane compound is 1:100-100:1, and the mass ratio of histidine to the lanthanide metal salt is 1:50-50:1; the mass volume ratio of the histidine to the reaction solvent is 1g histidine: 10-300mL of reaction solvent.
4. A process according to any one of claims 1 to 3, wherein the silane compound containing nitrogen is one or any combination of 3-aminopropyl triethoxysilane, N- [3- (trimethoxysilyl) propyl ] ethylenediamine, or 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane.
5. A method according to any one of claims 1 to 3, wherein the lanthanide metal salt is one of cerium nitrate hexahydrate, neodymium nitrate hexahydrate, erbium nitrate hexahydrate or any combination thereof.
6. The method according to claim 2, wherein the reaction solvent is deionized water, ethanol or a mixture thereof.
7. The multifunctional anti-aggregation quenched carbon nano-onions prepared by the preparation method of any one of claims 1-6.
8. The use of the multifunctional anti-aggregation quenched carbon nano-onions as described in claim 7 as fluorescent powder.
9. The use of the multifunctional anti-aggregation quenched carbon nano-onions according to claim 7 in multi-color anti-counterfeiting.
10. The use of the multifunctional anti-aggregation quenched carbon nano-onions of claim 7 in cell imaging.
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