CN116426279B - H-based 2 O 2 Nano gold composite material mediating carbon quantum dot assembly and preparation method and application thereof - Google Patents

H-based 2 O 2 Nano gold composite material mediating carbon quantum dot assembly and preparation method and application thereof Download PDF

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CN116426279B
CN116426279B CN202310401257.7A CN202310401257A CN116426279B CN 116426279 B CN116426279 B CN 116426279B CN 202310401257 A CN202310401257 A CN 202310401257A CN 116426279 B CN116426279 B CN 116426279B
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cqds
assembly
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composite material
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CN116426279A (en
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刘意
李丹
吴芃晓
付年
陈智峰
江宇
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Guangdong Pharmaceutical University
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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
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • 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
    • 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
    • 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

Abstract

The invention relates to a method based on H 2 O 2 Nano gold composite material for mediating carbon quantum dot assembly and preparation method and application thereof, specifically, aldehyde group-containing carbon quantum dot, dopamine hydrochloride and indole are taken as raw materials, and H is adopted for preparing the nano gold composite material 2 O 2 Is reacted to form the assembly i-N/O-s-CQDs (H) 2 O 2 ) Then reacts with chloroauric acid solution to obtain Au@i-N/O-s-CQDs (H) 2 O 2 ) The method is simple, green and environment-friendly, the obtained nanocomposite has strong fluorescence, stable physical chemistry and good salt tolerance, and the application of the nanocomposite in the aspect of biological imaging can be realized by utilizing the fluorescence characteristic of the nanocomposite.

Description

H-based 2 O 2 Nano gold composite material mediating carbon quantum dot assembly and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano composite materials, and in particular relates to a nano composite material based on H 2 O 2 A nano gold composite material for mediating carbon quantum dot assembly and a preparation method and application thereof.
Background
With the rapid development of nano technology, nano materials are highly focused by a large number of scholars. Compared with the conventional materials, the nano material has special properties mainly in the aspects of light, heat, electricity, magnetism, mechanics and the like, and the special properties determine that the nano material has wide application prospects in various fields. Researchers have now prepared a number of nanomaterials with excellent properties in the light, heat, electricity, magnetism etc. For example, carbon-based nanomaterial-carbon quantum dots are used in various research fields such as biological imaging, biosensing, drug delivery systems, optoelectronics, photovoltaics and photocatalysis due to their excellent properties.
Carbon Quantum Dots (CQDs) are a zero-dimensional carbon nanomaterial with Photoluminescence (PL), and have quantum size effect, small-size effect, surface effect and macroscopic quantum effect, and are widely applied in various fields. However, CQDs are prone to agglomeration and limited in application, and in practical applications, single function materials have failed to meet increasingly complex application requirements. Therefore, the carbon quantum dots and other materials are compounded to form the multifunctional composite material, and the multifunctional composite material has become a hot spot in the field of nano material research.
CQDs are relatively complex in surface, usually with hydroxyl, carboxyl or amino groups, and can coordinate with metal ions and heavy metal ions to cause changes in fluorescence. As disclosed in patent CN115386376a, a nano platinum composite material based on carbon quantum dot assembly is prepared from Polyethylenimine (PEI), dopamine (DA) and aldehyde group-containing carbon quantum dots (CHO-CQDs), and through chemical reaction to form a novel carbon quantum dot assembly (N/O-s-CQDs), which can be used as a closed fluorescent probe for realizing Fe based on fluorescence quenching effect 3+ High sensitivity detection, high sensitivity, good selectivity and strong interference resistance. Wang Shengnan in the carbon quantum dot magnetic fluorescent nanocomposite preparation and its performance research, the preparation of nano magnetic particle Fe is carried out by high pressure reactor and microwave method 3 O 4 The surface is self-assembled layer by layer, and the magnetic Fe is coupled by covalent bonds 3 O 4 And CQDs are compounded to prepare the carbon quantum dot magnetic fluorescent nanocomposite, which has excellent fluorescent property, good dispersibility and uniform particle size, and can meet the application of biological imaging, fluorescent marking and the like in practice.
Although development of carbon quantum dot nano metal composite materials has been advanced to some extent, there are still serious challenges of low quantum yield, poor stability, easy pollution, poor reproducibility and the like. In view of this, development of new carbon quantum dot nano metal composite materials is needed to expand the application.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method based on H 2 O 2 Nano-gold composite material for mediating carbon quantum dot assembly and utilizing H 2 O 2 The structure of the carbon-containing quantum dot, indole and dopamine hydrochloride assembly is regulated and controlled, the obtained composite material has strong fluorescence, good physical and chemical stability, good salt tolerance and small environmental hazard, and the application of the composite material in the aspect of biological imaging can be realized by utilizing the fluorescence characteristic of the composite material.
The technical scheme adopted by the invention for achieving the purpose is as follows:
the invention firstly provides a method based on H 2 O 2 The preparation method of the nano-gold composite material for mediating the assembly of the carbon quantum dots comprises the following steps:
S1、i-N/O-s-CQDs(H 2 O 2 ) Preparation of the Assembly
Aldehyde-containing carbon quantum dots (CHO-CQDs), dopamine hydrochloride (DA) and indole (i-N) are used as raw materials, and are prepared in H 2 O 2 Is reacted to form i-N/O-s-CQDs (H) 2 O 2 ) An assembly;
S2、Au@i-N/O-s-CQDs(H 2 O 2 ) Is prepared from
Reacting chloroauric acid solution with the assembly to obtain Au@i-N/O-s-CQDs (H) 2 O 2 )。
The invention provides the method, which takes CHO-CQDs, DA and indole as raw materials, and successfully prepares the assembly i-N/O-s-CQDs (H) based on the carbon quantum dots under the normal temperature through the mediation of hydrogen peroxide 2 O 2 ) H during the synthesis 2 O 2 The mediating function of the polymer can lead the DA self-polymerization into Polydopamine (PDA) to become controllable, and can also realize the assembly with CHO-CQDs in the DA self-polymerization process, and finally synthesize an assembly i-N/O-s-CQDs(H 2 O 2 ) The method is environment-friendly and successfully introduces high-activity functional groups such as amino groups; and then the residual active groups in the assembly are utilized to lead the gold ions to generate Au-NPs through in-situ reduction and to be relatively uniformly loaded in the assembly, thereby obtaining Au@i-N/O-s-CQDs (H) 2 O 2 ). The preparation method is green and simple, has low cost, overcomes the problems of complex operation and the like of the traditional nano structure, and the obtained composite material has strong fluorescence, high physical and chemical stability, small harm to the environment, high-activity functional groups on the surface, can be specifically combined with heavy metal ions, can realize high-efficiency detection of the heavy metal ions by utilizing the characteristic, and can be applied to fluorescent probes and biological imaging.
Further, the i-N/O-s-CQDs (H 2 O 2 ) The preparation of the assembly specifically comprises the following steps:
1) The CHO-CQDs are ultrasonically dissolved in water to obtain a solution A;
2) DA ultrasonic dissolving into alcohol solvent to obtain solution B;
3) Dropwise adding the solution B into the solution A, and reacting to obtain a solution C;
4) Will H 2 O 2 Dropwise adding the solution and NaOH solution into the solution C, and reacting to obtain a solution D;
5) Adding indole into the solution D, and reacting to obtain a solution E;
6) Dialyzing, filtering and drying the solution E to obtain i-N/O-s-CQDs (H) 2 O 2 ) An assembly.
Preferably, the CHO-CQDs in step 1) are prepared by the following method:
the glutaraldehyde solution is mixed with ethanol, heated for 2-3 hours at 140-155 ℃, and the obtained product is dissolved in ethanol to finally obtain a light yellow CHO-CQDs solution. The concentration of the glutaraldehyde solution is 45-55%, and the mass ratio of the glutaraldehyde solution to the ethanol is 1:1.5-3.
In step 1), the water includes, but is not limited to, purified water, distilled water, drinking water, ultrapure water, purified water, etc., and as a specific embodiment of the present application, the water used is purified water.
Preferably, in step 1), the feed liquid ratio (g/L) of CHO-CQDs to water is 4-12:1, more preferably 6-10:1.
Preferably, in step 2), the alcohol solvent is one or more of methanol, ethanol, ethylene glycol, propanol, isopropanol, n-butanol, propylene glycol, glycerol, ethylene glycol butyl ether, ethylene glycol methyl ether, propylene glycol methyl ether, and propylene glycol ethyl ether, and more preferably ethanol.
Preferably, in step 2), the ratio (g/L) of the DA to the alcohol solvent is 0.25-0.75:1, more preferably 0.4-0.75:1.
Preferably, in step 1), 2), the power of the ultrasound is 100-550W, more preferably 150W.
Preferably, in step 3), the reaction time is from 0.5 to 2 hours, further preferably from 0.5 to 1 hour; the reaction temperature was 25 ℃.
Preferably, in step 4), the concentration of the NaOH solution is 2-8%, further preferably 2-4%; the NaOH solution is added in an amount of 5 to 10% by volume, more preferably 8 to 10% by volume, of the solution C.
Preferably, in step 4), the H 2 O 2 The concentration of the solution is 15-60%, more preferably 50%, H 2 O 2 The amount of (C) added is 0.05 to 0.1% by volume, more preferably 0.08 to 0.1% by volume of the solution C.
Preferably, in step 4), the reaction time is from 1 to 5 hours, further preferably from 1 to 3 hours; the reaction temperature was 25 ℃.
Preferably, in step 5), the feed liquid ratio (g/L) of the added indole to the D solution is 0.03-0.15:1, more preferably 0.038-0.15:1, and the reaction time is 3-6h, more preferably 3-4h; the reaction temperature was 25 ℃.
Preferably, in step 6), the dialysis treatment is performed in a dialysis bag of 1000-2000Da, more preferably a dialysis bag of 1000Da, 2000Da, for a dialysis time of 12-48 hours, more preferably 20-28 hours.
Preferably, in step 6), the filter membrane used in the filtration is an organic-based filter membrane, the organic-based filter membrane is a microporous membrane, more preferably a polyvinylidene fluoride microporous membrane, and the average pore size of the filter membrane is 0.2-0.3 μm, more preferably 0.2-0.25 μm.
Preferably, the freeze drying temperature in step 6) is from-60 to-20 ℃, further preferably from-60 to-40 ℃.
Further, the Au@i-N/O-s-CQDs (H 2 O 2 ) The preparation process of the preparation method specifically comprises the following steps:
1)i-N/O-s-CQDs(H 2 O 2 ) Ultrasonically dissolving the assembly into water to obtain a solution F;
2) Dropwise adding chloroauric acid solution into the solution F, and reacting to obtain a solution G;
3) Dialyzing the solution G in pure water, filtering, and freeze-drying to obtain Au@i-N/O-s-CQDs (H) 2 O 2 )。
Preferably, in step 1), the i-N/O-s-CQDs (H) 2 O 2 ) The ratio of the assembly to water (mg/mL) is 0.125-1:1, more preferably 0.2-0.5:1.
Preferably, in step 2), au in the chloroauric acid solution 3+ The concentration is 12.5-200nmol/L, more preferably 12.5-100nmol/L, and the volume ratio of the addition amount of chloroauric acid solution to solution F is 0.1-0.3:1, more preferably 0.2-0.3:1; the reaction temperature is 0 to 80 ℃, more preferably 50 to 80 ℃, and the reaction time is 4 to 8 hours, more preferably 4 to 6 hours.
Preferably, in step 3), the dialysis treatment is performed in a dialysis bag of 1000-2000Da, more preferably a dialysis bag of 1000Da, 2000 Da; the dialysis time is 12 to 48 hours, more preferably 12 to 24 hours.
The invention also provides the H-based catalyst prepared by the method 2 O 2 A nano-gold composite material mediating carbon quantum dot assembly.
The invention also provides the H-based device 2 O 2 Application of nano gold composite material assembled by mediating carbon quantum dots in biological imaging.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention takes CHO-CQDs, DA and indole as raw materials, and successfully prepares an assembly body i-N/O-s-CQDs (H) based on carbon quantum dots at normal temperature 2 O 2 ) In the process of synthesisJourney H 2 O 2 Plays a mediating role to make DA self-polymerization into PDA controllable, and in the course of DA self-polymerization, it can also implement assembly with CQDs, and the final synthesized assembly i-N/O-s-CQDs (H 2 O 2 ) The high-activity functional groups such as amino are simply and successfully introduced, the method has the advantages of simplicity in operation, lower cost and the like, and the nano material is environment-friendly in synthesis scheme and good in biocompatibility;
2. and then the residual active groups in the assembly are utilized to lead the gold ions to generate Au-NPs through in-situ reduction and to be relatively uniformly loaded in the assembly, thereby obtaining Au@i-N/O-s-CQDs (H) 2 O 2 ) The method comprises the steps of carrying out a first treatment on the surface of the The preparation method is green and simple, has low cost, overcomes the problems of complex operation and the like of the traditional nano structure, and the obtained composite material has strong fluorescence, good physical and chemical stability, good water solubility and small harm to the environment, and can be used as a fluorescent probe and applied to biological imaging; the surface contains high-activity functional groups, can be specifically combined with heavy metal ions, can realize high-efficiency detection of the heavy metal ions by utilizing the characteristic, and can be applied to fluorescent probes and biological imaging.
Drawings
FIG. 1 is H 2 O 2 Concentration pair i-N/O-s-CQDs (H) 2 O 2 ) Schematic of the effect result of the fluorescence properties of (a);
FIG. 2 is a graph of indole addition time versus i-N/O-s-CQDs (H) 2 O 2 ) Schematic of the effect result of the fluorescence properties of (a);
FIG. 3 is NaCl concentration vs. i-N/O-s-CQDs (H) 2 O 2 ) Schematic of the effect result of the fluorescence properties of (a);
FIG. 4 is a pH pair i-N/O-s-CQDs (H) 2 O 2 ) Schematic of the effect result of the fluorescence properties of (a);
FIG. 5 is a schematic diagram of O-s-CQDs, i-N/O-s-CQDs, au@i-N/O-s-CQDs (H) 2 O 2 ) And i-N/O-s-CQDs (H) 2 O 2 ) FTIR plot of (2);
FIG. 6 is a graphical representation of fluorescence intensity test results for different assemblies;
FIG. 7 is an Au@i-N/O-s-CQDs (H) 2 O 2 ) HRTEM image of (2)；
FIG. 8 is an Au@i-N/O-s-CQDs (H) 2 O 2 ) And i-N/O-s-CQDs (H) 2 O 2 ) An XRD pattern of (b);
FIG. 9 is an Au@i-N/O-s-CQDs (H) 2 O 2 ) Fluorescent properties of (C) and Au 3+ Concentration relationship is schematically shown.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. The following is merely exemplary of the scope of the claimed invention and one skilled in the art can make various changes and modifications to the invention of the present application in light of the disclosure, which should also fall within the scope of the claimed invention.
The invention is further illustrated by means of the following specific examples. The various chemical reagents used in the examples of the present invention were obtained by conventional commercial means unless otherwise specified.
Example 1
The present embodiment provides an i-N/O-s-CQDs (H) 2 O 2 ) An assembly prepared by the following method:
1) Ultrasonically dissolving 0.32g of CHO-CQDs in 40mL of pure water, wherein the ultrasonic power is 40kHz, so as to obtain a solution A;
2) Dissolving 0.045g DA in 40mL of ethanol by ultrasonic wave with ultrasonic power of 40kHz to obtain a mixed solution B;
3) Dropwise adding the solution B into the solution A, and reacting for 0.5h at 25 ℃ to obtain a mixed solution C;
4) 0.1mL, 30% H 2 O 2 Adding the solution and 10mL of 4% NaOH solution into the solution C, and reacting for 3 hours at 25 ℃ to obtain a solution D;
5) Adding 0.01g of indole into the solution D, and reacting for 3 hours at 25 ℃ to obtain a solution E;
6) Transferring the solution E into 2000Da dialysis bag, dialyzing for 24 hr, filtering with 0.22 μm filter membrane, spin-evaporating at 60deg.C, freezing at-60deg.C for 4 hr, vacuum drying for 24 hr to obtain orange-red powdered i-N/O-s-CQDs (H) 2 O 2 )。
The preparation method of the CHO-CQDs comprises the following steps: 1.5mL of 50% glutaraldehyde was mixed with 3mL of ethanol, and heated at 150℃for 180min, and the resulting product was dissolved in 5mL of ethanol to finally obtain a pale yellow CHO-CQDs solution.
Examples 2 and 3
The present example provides two other i-N/O-s-CQDs (H 2 O 2 ) An assembly was prepared in substantially the same manner as in example 1, except that H was used in step 4) 2 O 2 The concentration of the solution was varied, H in example 2 2 O 2 The solution concentration was 15%, H in example 2 2 O 2 The concentration of the solution was 60%.
Example 4
This embodiment provides another i-N/O-s-CQDs (H) 2 O 2 ) An assembly prepared by the following method:
1) Ultrasonically dissolving 0.32g of CHO-CQDs in 40mL of pure water, wherein the ultrasonic power is 40kHz, so as to obtain a solution A;
2) Dissolving 0.045g DA in 40mL of ethanol by ultrasonic wave with ultrasonic power of 40kHz to obtain a mixed solution B;
3) Dropwise adding the solution B into the solution A, and reacting for 0.5h at 25 ℃ to obtain a mixed solution C;
4) 0.1mL, 30% H 2 O 2 Adding the solution and 10mL of 4% NaOH solution into the solution C, and reacting for 1h at 25 ℃ to obtain a solution D;
5) Adding 0.01g of indole into the solution D, and reacting for 5 hours at 25 ℃ to obtain a solution E;
6) Transferring the solution E into 2000Da dialysis bag, dialyzing for 24 hr, filtering with 0.22 μm organic filter membrane, spin-evaporating at 60deg.C, freezing at-60deg.C for 4 hr, vacuum drying for 24 hr to obtain orange-red powdered i-N/O-s-CQDs (H) 2 O 2 )。
Example 5
This embodiment provides another i-N/O-s-CQDs (H) 2 O 2 ) An assembly prepared by the following method:
1) Ultrasonically dissolving 0.32g of CHO-CQDs in 40mL of pure water, wherein the ultrasonic power is 40kHz, so as to obtain a solution A;
2) Dissolving 0.045g DA in 40mL of ethanol by ultrasonic wave with ultrasonic power of 40kHz to obtain a mixed solution B;
3) Dropwise adding the solution B into the solution A, and reacting for 0.5h at 25 ℃ to obtain a mixed solution C;
4) 0.1mL, 30% H 2 O 2 Adding the solution and 10mL of 4% NaOH solution into the solution C, adding 0.01g of indole, and reacting at 25 ℃ for 6 hours to obtain a solution E;
5) Transferring the solution E into 2000Da dialysis bag, dialyzing for 24 hr, filtering with 0.22 μm organic filter membrane, spin-evaporating at 60deg.C, freezing at-60deg.C for 4 hr, vacuum drying for 24 hr to obtain orange-red powdered i-N/O-s-CQDs (H) 2 O 2 )。
Comparative example 1
The comparative example provides an O-s-CQDs assembly prepared by the following method:
1) Ultrasonically dissolving 0.16g of CHO-CQDs in 40mL of pure water, wherein the ultrasonic power is 40kHz, so as to obtain a solution A;
2) Dissolving 0.045g DA in 40mL of ethanol by ultrasonic wave with ultrasonic power of 40kHz to obtain a mixed solution B;
3) Dropwise adding the solution B into the solution A, and reacting for 0.5h at 25 ℃ to obtain a mixed solution C;
4) 10mL of 4% NaOH solution is added into the solution C, and the reaction is carried out for 6 hours at 25 ℃ to obtain solution D;
5) Transferring the solution D into 2000Da dialysis bag, dialyzing for 24 hr, filtering with 0.22 μm organic filter membrane, spin-evaporating at 60deg.C, freezing at-60deg.C for 4 hr, vacuum drying for 24 hr to obtain orange-red powdered O-s-CQDs (H) 2 O 2 )。
Comparative example 2
This comparative example provides an O-s-CQDs (H 2 O 2 ) An assembly prepared by the following method:
1) Ultrasonically dissolving 0.16g of CHO-CQDs in 40mL of pure water, wherein the ultrasonic power is 40kHz, so as to obtain a solution A;
2) Dissolving 0.045g DA in 40mL of ethanol by ultrasonic wave with ultrasonic power of 40kHz to obtain a mixed solution B;
3) Dropwise adding the solution B into the solution A, and reacting for 0.5h at 25 ℃ to obtain a mixed solution C;
4) 10mL, 30% H 2 O 2 Adding the solution and 10mL of 4% NaOH solution into the solution C, and reacting for 6 hours at 25 ℃ to obtain a solution D;
5) Transferring the solution D into 2000Da dialysis bag, dialyzing for 24 hr, filtering with 0.22 μm organic filter membrane, spin-evaporating at 60deg.C, freezing at-60deg.C for 4 hr, vacuum drying for 24 hr to obtain orange-red powdered O-s-CQDs (H) 2 O 2 )。
Comparative example 3
This comparative example provides an i-N/O (H 2 O 2 ) An assembly prepared by the following method:
1) Dissolving 0.045g DA in 40mL of ethanol by ultrasonic wave with ultrasonic power of 40kHz to obtain a mixed solution A;
2) Dropwise adding the solution B into the solution A, and reacting for 0.5h at 25 ℃ to obtain a mixed solution B;
3) 0.1mL, 30% H 2 O 2 Adding the solution and 10mL of 2% NaOH solution into the solution B, and reacting for 3 hours at 25 ℃ to obtain a solution C;
4) Adding 0.01g of indole into the solution C, and reacting for 3 hours at 25 ℃ to obtain a solution D;
5) Transferring the solution D into 2000Da dialysis bag, dialyzing for 24 hr, filtering with 0.22 μm organic filter membrane, spin-evaporating at 60deg.C, freezing at-60deg.C for 4 hr, vacuum drying for 24 hr to obtain orange-red powder i-N/O (H) 2 O 2 )。
Comparative example 4
The present comparative example provides an i-N/O-s-CQDs assembly prepared by the following method:
1) Ultrasonically dissolving 0.32g of CHO-CQDs in 40mL of pure water, wherein the ultrasonic power is 40kHz, so as to obtain a solution A;
2) Dissolving 0.045g DA in 40mL of ethanol by ultrasonic wave with ultrasonic power of 40kHz to obtain a mixed solution B;
3) Dropwise adding the solution B into the solution A, and reacting for 0.5h at 25 ℃ to obtain a mixed solution C;
4) 10mL of 4% NaOH solution is added into the solution C, and the reaction is carried out for 3 hours at 25 ℃ to obtain solution D;
5) Adding 0.01g of indole into the solution D, and reacting for 3 hours at 25 ℃ to obtain a solution E;
6) Transferring the solution E into a 2000Da dialysis bag, dialyzing for 24 hours, filtering by using a 0.22 mu m organic filter membrane, performing rotary evaporation at 60 ℃, freezing at-60 ℃ for 4 hours, and performing vacuum drying for 24 hours to obtain brownish red powdery i-N/O-s-CQDs.
Test example 1
i-N/O-s-CQDs (H) obtained in examples 1 to 5 2 O 2 ) The assembly is a sample, the assembly is dissolved in ultrapure water to prepare a solution with the concentration of 0.25mg/mL, and the fluorescence intensity is tested by a fluorescence spectrophotometer under the following test conditions: the excitation wavelength is 370nm, the emission wavelength is 480nm, and the measurement results are shown in figures 1 and 2.
FIG. 1 is a different H 2 O 2 Concentration and i-N/O-s-CQDs (H) 2 O 2 ) As can be seen from an examination of FIG. 1, the relationship between the fluorescence intensities of the assemblies is H 2 O 2 The increase in concentration shows a tendency that the fluorescence intensity increases and decreases, when H 2 O 2 At a concentration of 30%, the fluorescence intensity of the assembly was strongest.
FIG. 2 shows the time of indole addition and the time of i-N/O-s-CQDs (H) 2 O 2 ) As can be seen from the observation of FIG. 2, the total reaction time was 6h, and the fluorescence intensities of the assemblies obtained by introducing indole at 0h, 1h, and 3h after NaOH addition were measured, respectively, and it was found that the indole was immediately added 3h after NaOH addition, and the fluorescence intensity of the obtained assemblies was the strongest.
Test example 2
i-N/O-s-CQDs (H) obtained in example 1 2 O 2 ) For the samples, the fluorescence intensity of the NaC solution under the NaCl solutions with different concentrations is tested, and the concentration of the NaC solution is respectively 2.5mg/mL, 5mg/mL, 7.5mg/mL, 10mg/mL and 12.5mg/mL; the test conditions were the same as in test example 1. The results are shown in FIG. 3.
FIG. 3 is a schematic diagram ofSalt concentration vs. i-N/O-s-CQDs (H) 2 O 2 ) As can be seen from an examination of the effect of the fluorescence intensity of the assembly, when the NaCl concentration was in the range of 2.5-12.5mg/mL, the fluorescence intensity decreased with the increase in the NaCl concentration, but the decrease was not significant, and the NaCl concentration was not significant for i-N/O-s-CQDs (H) 2 O 2 ) Has a slight change in fluorescence intensity, indicating that i-N/O-s-CQDs (H) 2 O 2 ) The assembly has good salt tolerance.
Test example 3
i-N/O-s-CQDs (H) obtained in example 1 2 O 2 ) For the samples, the fluorescence intensity under different pH conditions was measured, the pH range was 2-10, and the measurement conditions were the same as those of test example 1. The results are shown in FIG. 4.
FIG. 4 is a graph of pH vs. i-N/O-s-CQDs (H 2 O 2 ) As can be seen from an examination of the effect of the fluorescence intensity of the assembly, the fluorescence intensity of the assembly gradually increased with increasing pH in the range of ph=2 to 6, and the fluorescence intensity reached the highest at ph=6, and the fluorescence intensity did not change much in the range of ph=4 to 10, i-N/O-s-CQDs (H 2 O 2 ) The assembled body has stable fluorescence intensity and good acid and alkali resistance, and meets the requirement of being used as a fluorescent probe.
Example 6
This example provides an Au@i-N/O-s-CQDs (H 2 O 2 ) Prepared by the following method:
1) 20mg of i-N/O-s-CQDs (H) obtained in example 1 2 O 2 ) Dissolving in 80mL of water to obtain solution F;
2) 20mL of chloroauric acid solution (Au 3+ Dropwise adding 50 nmol/L) of the solution into the solution F, and continuously reacting for 6 hours at 80 ℃ to obtain a mixed solution G;
3) Transferring the solution G into a 2000Da dialysis bag, dialyzing for 12H to obtain solution, spin-steaming at 60deg.C for a certain time, freezing at-60deg.C for 4H, vacuum drying for 24H to obtain yellowish powder Au@i-N/O-s-CQDs (H) 2 O 2 )。
Examples 7 to 11
Examples 7-11 provide a series of Au@i-N/O-s-CQDs (H 2 O 2 ) And a process for its preparationSubstantially the same as in example 6, except that the concentration of chloroauric acid in step 2) was different, au in the chloroauric acid solutions in examples 7 to 11 3+ The concentration was 12.5nmol/L, 25nmol/L, 100nmol/L, 150nmol/L, 200nmol/L in this order.
Test example 4
The products i-N/O-s-CQDs (H) obtained in examples 1, 6 comparative examples 1, 4, respectively 2 O 2 )、Au@i-N/O-s-CQDs(H 2 O 2 ) The O-s-CQDs and i-N/O-s-CQDs are used as samples, and infrared spectrum test is carried out by using a Tensor37 type infrared spectrometer of Bruker Germany, and the scanning range is 4000-500cm -1 Resolution of 4cm -1 The number of scans was 32, and the infrared spectrum (FTIR) was measured as shown in fig. 5.
As can be seen from FIG. 5, in comparison with O-s-CQDs, i-N/O-s-CQDs, au@i-N/O-s-CQDs (H) 2 O 2 ) And i-N/O-s-CQDs (H) 2 O 2 ) At 831cm -1 、745cm -1 There appears a new stretching vibration peak, which is caused by indole and is all attributed to C-H bond on benzene ring, 1078cm -1 The absorption peak at the position is the expansion vibration of C-O bond, 1406cm -1 The stretching vibration at the position is attributed to the C-N key, 1596cm -1 Is caused by dihydroxyindole moiety at 1629cm -1 The stretching vibration at the position is caused by N-H in dopamine, 3500cm -1 The peak at the position shows a divergent peak, and DA self-polymerization is prevented due to the existence of hydrogen peroxide, O-H bond and N-H,3380cm are respectively shown -1 The broad band at the site is attributed to-OH and-NH 2 The absorption peaks of the functional groups, as described above, indicate that CHO-CQDs react with DA and indole (i-N) to form assemblies i-N/O-s-CQDs (H) 2 O 2 ) Is introduced-CONH-. Comparative i-N/O-s-CQDs (H) 2 O 2 ) With Au@i-N/O-s-CQDs (H) 2 O 2 ) Is of the formula (I) Au@i-N/O-s-CQDs (H) 2 O 2 ) At 1354cm -1 The stretching vibration peak belonging to Au-N bond appears at the position of 3420cm -1 The peak at this point is blue shifted by the presence of Au, because of the interaction of amine groups, carbonyl groups, etc. in the assembly with the supported nanogold.
Test example 5
The fluorescence intensity of the assemblies obtained in CHO-CQDs, example 1 and comparative examples 1 to 4 was measured using the same test conditions as in test example 1, and the results are shown in FIG. 6.
FIG. 6 shows Au@i-N/O-s-CQDs (H) 2 O 2 )、i-N/O-s-CQDs(H 2 O 2 )、i-N/O(H 2 O 2 )、O-s-CQDs(H 2 O 2 ) As shown in FIG. 6, the fluorescence intensities of i-N/O-s-CQDs and CHO-CQDs are weak, and after DA and indole are introduced, the fluorescence intensity of the assembly is significantly increased, and on the basis of this, H is present 2 O 2 The fluorescence properties of the resulting assembly are further enhanced by mediation.
Test example 6
As obtained in example 6, au@i-N/O-s-CQDs (H 2 O 2 ) For the samples, a JEM-2100HR transmission electron microscope was used for testing, and the HRTEM chart was shown in FIG. 7.
Looking at FIG. 7, au@i-N/O-s-CQDs (H) 2 O 2 ) The HRTEM images of (a) showed 0.214nm and 0.231nm lattice fringe patterns, corresponding to Au (200) and (111) lattice fringes, indicating that Au (III) was reduced to elemental Au, and was uniformly supported in the assembly.
Test example 7
i-N/O-s-CQDs (H) obtained in example 1 and example 6 2 O 2 )、Au@i-N/O-s-CQDs(H 2 O 2 ) As a sample, XRD patterns of the sample were measured by a SmartLab X-ray diffractometer, and the results are shown in FIG. 8.
As can be seen from an examination of FIG. 8, the XRD patterns of the Au simple substance and the graphene carbon correspond to those of i-N/O-s-CQDs (H 2 O 2 ) The graphene carbon (002) lattice appears in the XRD pattern of (C) at Au@i-N/O-s-CQDs (H) 2 O 2 ) Grapheme carbon (002), (102), (004) lattices and Jin Shanzhi (111), (200) lattices can be found in the XRD patterns of (c), corresponding to the TEM patterns.
Test example 8
Au@i-N/O-s-CQDs (H) obtained in examples 6-11 2 O 2 ) The fluorescence intensity was measured for the sample, and the measurement results are shown in FIG. 9.
FIG. 9 is chlorineAu in the gold acid solution 3+ Concentration vs Au@i-N/O-s-CQDs (H) 2 O 2 ) Influence of fluorescence intensity the test results. As can be seen, with Au 3+ The concentration is increased, the fluorescence spectrum shows the trend of increasing and weakening firstly, and Au in chloroauric acid solution 3+ At a concentration of 50nmol/L, the resulting Au@i-N/O-s-CQDs (H) 2 O 2 ) The fluorescence intensity is highest.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention.

Claims (14)

1. H-based 2 O 2 The preparation method of the nano gold composite material for mediating the assembly of the carbon quantum dots is characterized by comprising the following steps:
S1、i-N/O-s-CQDs(H 2 O 2 ) Preparation of the Assembly
CHO-CQDs, DA and indole as raw materials in H 2 O 2 Is reacted to form i-N/O-s-CQDs (H) 2 O 2 ) An assembly;
S2、Au@i-N/O-s-CQDs(H 2 O 2 ) Is prepared from
Reacting chloroauric acid solution with the assembly to obtain Au@i-N/O-s-CQDs (H) 2 O 2 )；
In the step S1, i-N/O-S-CQDs (H 2 O 2 ) A method of making an assembly comprising the steps of:
(1) The CHO-CQDs are ultrasonically dissolved in water to obtain a solution A;
(2) DA ultrasonic dissolving into alcohol solvent to obtain solution B;
(3) Dropwise adding the solution B into the solution A, and reacting to obtain a solution C;
(4) Will H 2 O 2 Dropwise adding the solution and NaOH solution into the solution C, and reacting to obtain a solution D;
(5) Adding indole into the solution D, and reacting to obtain a solution E;
(6) Dialyzing, filtering and freeze-drying the solution E to obtain i-N/O-s-CQDs (H) 2 O 2 )。
2. The method of claim 1, wherein in step (1), the CHO-CQDs to water feed ratio is 4-12g to 1l.
3. The method of claim 2, wherein in step (1), the CHO-CQDs to water feed ratio is 6-10g:1l.
4. The method according to claim 1, wherein in the step (2), the ratio of the DA to the alcohol solvent is 0.25-0.75 g/1L.
5. The method according to claim 4, wherein in the step (2), the ratio of DA to the alcohol solvent is 0.4-0.75 g/1L.
6. The method according to claim 1, wherein in the step (4), the concentration of the NaOH solution is 2-8%, the addition amount of the NaOH solution is 5-10% of the volume of the solution C, and the H is 2 O 2 The concentration of the solution is 15-60%, H 2 O 2 The addition amount of (C) is 0.05-0.1% of the volume of the solution C.
7. The method of claim 6, wherein in step (4), the concentration of NaOH solution is 2-4%; the addition amount of the NaOH solution is 8-10% of the volume of the solution C; the H is 2 O 2 The concentration of the solution is 50%, H 2 O 2 The addition amount of (C) is 0.08-0.1% of the volume of the solution C.
8. The process of claim 1, wherein in step (5), the feed solution ratio of indole to D solution is 0.03-0.15g:1l.
9. The method of claim 8, wherein in step (5), the feed solution ratio of indole to D solution is 0.038-0.15g:1l.
10. The method according to claim 1, wherein the au@i-N/O-s-CQDs (H 2 O 2 ) The preparation process of (2) comprises the following steps:
①i-N/O-s-CQDs(H 2 O 2 ) Ultrasonically dissolving the assembly into water to obtain a solution F;
(2) dropwise adding chloroauric acid solution into the solution F, and reacting to obtain a solution G;
(3) dialyzing the solution G in pure water, filtering, and freeze-drying to obtain Au@i-N/O-s-CQDs (H) 2 O 2 )。
11. The method of claim 10, wherein in step (2), au in the chloroauric acid solution 3+ The concentration is 12.5-200nmol/L, and the volume ratio of the addition amount of chloroauric acid solution to solution F is 0.1-0.3:1.
12. The method of claim 11, wherein in step (2), au in the chloroauric acid solution 3+ The concentration is 12.5-100nmol/L, and the volume ratio of the addition amount of chloroauric acid solution to solution F is 0.2-0.3:1.
13. H-based 2 O 2 A nano-gold composite material mediating carbon quantum dot assembly, characterized in that it is prepared by the method of any one of claims 1-12.
14. The H-based catalyst of claim 13 2 O 2 Application of nano gold composite material assembled by mediating carbon quantum dots in biological imaging.
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