CN116042213A - Near infrared emission gold nanocluster, preparation method and application - Google Patents
Near infrared emission gold nanocluster, preparation method and application Download PDFInfo
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- CN116042213A CN116042213A CN202310061344.2A CN202310061344A CN116042213A CN 116042213 A CN116042213 A CN 116042213A CN 202310061344 A CN202310061344 A CN 202310061344A CN 116042213 A CN116042213 A CN 116042213A
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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
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
- C12Q1/26—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving oxidoreductase
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- 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"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2333/00—Assays involving biological materials from specific organisms or of a specific nature
- G01N2333/90—Enzymes; Proenzymes
- G01N2333/902—Oxidoreductases (1.)
- G01N2333/90219—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10)
- G01N2333/90222—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10) with oxygen as acceptor (1.10.3) in general
- G01N2333/90225—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10) with oxygen as acceptor (1.10.3) in general with a definite EC number (1.10.3.-)
- G01N2333/90229—Catechol oxidase, i.e. Tyrosinase (1.10.3.1)
Abstract
The invention belongs to the technical field of medical detection materials, and discloses a near infrared emission gold nanocluster, a preparation method and application. 2-mercaptobenzoic acid (MBA) reacts with chloroauric acid in aqueous solution to form weak luminescence gold nanoclusters (MBA-AuNCs), and then the near infrared emission gold nanoclusters with compact and ordered luminescence enhancement are formed under the non-covalent bond interaction force by regulating and controlling the pH of the system. The MBA-AuNCs of the invention emit near infrared light, can avoid the interference of autofluorescence, and can reduce the interference of scattering on fluorescence. In addition, MBA-AuNCs have low toxicity and good biocompatibility, and become candidate materials for cell imaging and biological markers. The near infrared emission gold nanocluster prepared by the method has high selectivity and sensitivity for detecting tyrosinase and dopamine, and can observe the change of fluorescence intensity by using a portable ultraviolet lamp, so that the method is simple to operate and easy to realize.
Description
Technical Field
The invention belongs to the technical field of medical detection materials, and particularly relates to a near infrared emission gold nanocluster, a preparation method and application.
Background
Tyrosinase is a polyphenol oxidase with a binuclear copper central structure, and is widely found in microorganisms, animals and plants. Under the action of molecular oxygen, tyrosinase can catalyze and oxidize phenolic substrates to generate quinone compounds so as to regulate and control the generation of melanin in organisms, so that tyrosinase plays a vital role in melanin synthesis by melanocytes. However, excessive melanin deposition causes freckle, brown spot, etc. on human skin, affects beauty, adversely affects body and mind, and abnormal expression of tyrosinase is associated with various diseases such as congenital hypopigmentation, vitiligo, chronic migraine, melanoma, etc. In addition, tyrosinase activity also affects the appearance, mouthfeel, and nutritional value of fruits and vegetables. Therefore, developing a simple and highly sensitive method for detecting tyrosinase activity has great value in the diagnosis and treatment of diseases and in the food industry. Dopamine is an important catecholamine nerve conduction substance in the brain of a human body, plays a very important role in regulating the hormone level, cardiovascular system, kidney function and metabolism of the human body, and is closely related to the emotion, feeling and addictive behaviors of the human body. Abnormality in the concentration of dopamine in the body may cause hypertension, parkinson's disease, schizophrenia, pituitary tumor, etc. Therefore, accurate detection of dopamine concentration is of great clinical significance.
Currently, researchers have developed a variety of methods for detecting tyrosinase activity and dopamine, such as colorimetry, electrochemical analysis, and fluorometry. Wherein the colorimetric method has low detection sensitivity and false positive signals. The electrochemical method improves the sensitivity, but is easy to be interfered by environment, has poor repeatability, and has complicated experimental process and long time consumption. Compared with the two methods, the fluorescence measurement method has the advantages of high sensitivity, high analysis speed, high selectivity, small influence from the outside and the like, and is considered to be a more ideal detection method. In recent years, researchers have developed some fluorescence assays based on inorganic semiconductor quantum dots, carbon quantum dots, metal nanoclusters, but the quantum dot method used has potential toxicity, is unfavorable for detection in biological systems, and few studies on near infrared emission metal nanoclusters remain.
Metal nanoclusters (typically gold, silver, copper) are core-shell structures composed of several to hundreds of metal atoms and organic molecular ligands, typically less than 2nm in size, comparable to the fermi wavelength of electrons, with molecular-like properties such as luminescence, magnetism, chirality, HOMO-LUMO transitions. The metal nanoclusters are used as an emerging atomic-scale nanomaterial, and have wide application prospects in the fields of biomedical imaging, chemical sensing, catalysis, cell labeling, drug delivery and the like due to the accurate structure and unique physicochemical properties. Among them, gold nanoclusters (AuNCs) are widely explored by researchers due to their advantages of simple preparation, high stability, excellent chemical properties, etc., and many patent and literature reports about improving luminescence properties of gold nanoclusters are also available, for example: CN115197694A discloses a preparation method of fluorescent gold nanocluster composite hydrogel, CN112933247a discloses a preparation method of solvent-induced self-assembled gold nanoparticle material, and CN114702950a discloses a preparation method of fluorescent gold nanocluster material, a product and application thereof.
Through the above analysis, the problems and defects existing in the prior art are as follows: the preparation process of most of the luminescence gold nanoclusters reported so far is complex, an organic solvent is required to be introduced for synthesis or assembly, so that serious environmental pollution is caused, the formed aggregate is poor in water solubility, the prepared gold nanoclusters are short in emission wavelength and cannot realize near infrared light emission, and the application of the gold nanoclusters in a biological system is hindered. In addition, the metal nanocluster has small size and high surface energy, the self-assembly process of the metal nanocluster is reasonably controlled, and the preparation of a controllable and uniform nanostructure still faces serious challenges and needs further analysis and breakthrough.
Disclosure of Invention
In order to overcome the problems in the related art, the disclosed embodiments of the invention provide a near infrared emission gold nanocluster, a preparation method and application thereof, and in particular relates to a preparation method of a near infrared emission gold nanocluster and application thereof in tyrosinase and dopamine detection.
The technical scheme is as follows: the preparation method of the near infrared emission gold nanocluster comprises the following steps:
2-mercaptobenzoic acid reacts with chloroauric acid in aqueous solution to form weak-luminescence gold nanoclusters, and then the near infrared-emission gold nanoclusters with compact and ordered luminescence enhancement are formed under the interaction force of non-covalent bonds by regulating and controlling the pH of a system.
The chemical structure of compact ordered, luminescence-enhanced near infrared-emitting gold nanoclusters (ph=6.16) is shown below, with black globules representing gold nuclei.
In one embodiment, the preparation process of the weak luminescence gold nanocluster by reacting 2-mercaptobenzoic acid with chloroauric acid in an aqueous solution comprises:
adding a 2-mercaptobenzoic acid solid reagent into deionized water, and then adding a proper amount of sodium hydroxide solution to completely dissolve the 2-mercaptobenzoic acid solid to obtain a 2-mercaptobenzoic acid solution;
mixing chloroauric acid aqueous solution and 2-mercaptobenzoic acid solution at room temperature, and standing at constant temperature to obtain the weak-luminescence gold nanocluster.
In one embodiment, the molar concentration ratio of 2-mercaptobenzoic acid to chloroauric acid is 1 (2-4).
In one embodiment, the concentration of the sodium hydroxide is 0.05 to 0.15 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The amount of sodium hydroxide added was such that the 2-mercaptobenzoic acid solid was dissolved until complete, yielding a clear solution.
In one embodiment, the gold nanoclusters with weak luminescence are obtained by standing for 8 hours in an incubator at 20 ℃.
In one embodiment, the regulating system pH comprises: weak hairThe addition concentration of the gold nanoclusters is 1 to 30 mmol.L -1 And adjusting the pH value.
In one embodiment, the regulatory system pH comprises: 11.88, 10.47, 9.62, 8.46, 7.43, 6.44, 6.32, 6.24 or 6.16.
Another object of the present invention is to provide a near infrared emission gold nanocluster prepared by the preparation method, the near infrared emission wavelength of which is 650 to 760nm.
The invention further aims to provide an application of the near infrared emission gold nanoclusters in tyrosinase detection.
The invention further aims to provide an application of the near infrared emission gold nanocluster in dopamine detection.
By combining all the technical schemes, the invention has the advantages and positive effects that:
first, aiming at the technical problems existing in the prior art and the difficulty of solving the problems, the technical problems solved by the technical scheme of the invention to be protected, results and data in the research and development process and the like are closely combined, the technical problems solved by the technical scheme of the invention are analyzed in detail and deeply, and some technical effects with creativity brought after the problems are solved are specifically described as follows:
in the invention, the preparation process of the near infrared emission gold nanocluster is creatively obtained through a large number of experiments. If the pH of the system is higher, the formed nano structure has lower order degree, and the near infrared emission nano cluster with strong luminescence can not be obtained.
The material characteristics set forth in the present invention were tested by the following method:
high resolution transmission electron microscopy (HR-TEM). The morphology of the aggregates can be observed by HR-TEM.
Scanning Electron Microscopy (SEM). The morphology of the aggregates can be further observed by SEM.
Fluorescence spectrum. The fluorescence intensity of the sample was measured by a fluorescence spectrophotometer.
Ultraviolet-visible spectroscopy (UV-Vis). The absorption curve of the sample can be determined by UV-Vis.
Secondly, the technical proposal is regarded as a whole or from the perspective of products, and the technical proposal to be protected has the technical effects and advantages as follows:
compared with short wave emission, the near infrared emission is not influenced by the autofluorescence of biological molecules in organisms, reduces background fluorescence, has small damage to tissues and strong tissue penetrating capacity, is suitable for deep tissue imaging, and is favorable for multi-fluorescence staining. These advantages make near infrared fluorescent probes suitable for applications in bioluminescence imaging, particularly medical fluorescence imaging, helping to secret biological processes at the molecular level.
Advantages of the present invention compared to the prior art further include:
the MBA-AuNCs are noble metal clusters, belong to novel inorganic-organic hybrid materials, and have the advantages of novel structure and stable property. And the method of supermolecule self-assembly is utilized to induce MBA-AuNCs to aggregate under specific conditions to form compact ordered nano fibers, so that the fluorescence property in a liquid state is reserved and enhanced.
The preparation method of the MBA-AuNCs is simple, does not need to add a reducing agent or an organic solvent, has no pollution to the environment, and further expands the application prospect of the AuNCs in biological systems.
The MBA-AuNCs of the invention emit near infrared light, can avoid the interference of autofluorescence, and can reduce the interference of scattering on fluorescence. In addition, auNCs has low toxicity and good biocompatibility, and becomes a candidate material for cell imaging and biological marking.
The near infrared emission gold nanocluster prepared by the method has high selectivity and sensitivity for detecting tyrosinase and dopamine, and can observe the change of fluorescence intensity by using a portable ultraviolet lamp, so that the method is simple to operate and easy to realize.
Thirdly, as inventive supplementary evidence of the claims of the present invention, it is also reflected in the following important aspects:
(1) The near infrared emission gold nanocluster prepared by the method has low toxicity and good biocompatibility, is expected to be used for fluorescent marking and biomedical imaging research, provides a new thought for detecting tyrosinase and dopamine, has important significance for diagnosing and treating diseases, and also widens the application of the nanocluster in the field of biological analysis.
(2) Most of the luminescent gold nanoclusters are complicated in preparation process, new additives or organic solvents are required to be introduced, and the prepared gold nanoclusters have shorter emission wavelength and cannot realize near infrared light emission. In addition, the traditional detection method has the defects of complicated steps, expensive equipment and the like, and the fluorescence sensing platform constructed by the method has the advantages of good selectivity, high sensitivity and simplicity in operation.
(3) The invention provides a simple method for preparing near infrared emission gold nanoclusters, and realizes sensitive detection of tyrosinase and dopamine.
(4) The near infrared emission gold nanoclusters prepared by the method can observe the phenomenon by using a portable ultraviolet lamp in the tyrosinase and dopamine detection process, and are simple and convenient to operate.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure;
FIG. 1 is a flow chart of a method for preparing near infrared emission gold nanoclusters according to embodiment 2 of the present invention;
FIG. 2 (a) is a TEM image of MBA-AuNCs provided in example 4 of the present invention;
FIG. 2 (b) is a photoluminescence spectrum according to FIG. 2 (a) provided in example 4 of the present invention;
FIG. 3 (a) is a TEM image of a near infrared emission gold nanocluster provided in example 5 of the present invention;
FIG. 3 (b) is a photoluminescence spectrum of FIG. 3 (a) provided in example 5 of the present invention;
FIG. 4 (a) is a TEM image of a near infrared emission gold nanocluster provided in example 6 of the present invention;
FIG. 4 (b) is an SEM image of near infrared emission gold nanoclusters provided in example 6 of the present invention;
FIG. 4 (c) is a photoluminescence spectrum of FIG. 4 (a) and FIG. 4 (b) provided in example 6 of the present invention;
FIG. 5 is a diagram showing the excitation spectrum, emission spectrum and absorption spectrum of the near infrared emission gold nanoclusters provided in example 6 of the present invention;
FIG. 6 is a graph showing the survival rate of cells incubated with HeLa cells for 24 hours in the near infrared emitting gold nanoclusters of Experimental example 1 of the present invention;
FIG. 7 is a laser confocal image of the incubation of near infrared emitting gold nanoclusters with HeLa cells in experimental example 1 of the present invention;
FIG. 8 is a graph showing the emission spectrum of the near infrared emission gold nanoclusters of the present invention after tyrosinase, dopamine, tyrosinase and dopamine are added.
FIG. 9 shows measurement of 1.0 mmol.L by ultraviolet-visible spectrophotometer in Experimental example 2 of the present invention -1 Dopamine, 2.5unit mL -1 Tyrosinase, 1.0 mmol.L -1 Dopamine and 2.5unit mL -1 Ultraviolet-visible absorption spectrum of tyrosinase;
FIG. 10 is a graph showing the emission spectrum of a sample in which different concentrations of dopamine were added and transferred to a quartz cuvette and tested using a fluorescence spectrophotometer according to experiment example 3 of the present invention;
FIG. 11 is a graph showing the variation of the normalized photoluminescence intensity of the near infrared emission gold nanoclusters according to the present invention as provided in experimental example 3 with different concentrations of dopamine;
FIG. 12 is a graph showing the linear relationship between the normalized photoluminescence intensity of the near infrared emission gold nanoclusters and dopamine of different concentrations provided in Experimental example 3 of the present invention;
FIG. 13 is a graph showing the emission spectrum of a sample according to the invention in which the sample provided in Experimental example 3 was transferred into a quartz cuvette and the sample was tested using a fluorescence spectrophotometer;
FIG. 14 is a graph showing the emission spectrum of a sample in which tyrosinase of different concentrations was added and transferred to a quartz cuvette and tested by using a fluorescence spectrophotometer according to the present invention provided in Experimental example 4;
FIG. 15 is a graph showing the variation of the normalized photoluminescence intensity of the near infrared emission gold nanoclusters according to the present invention as measured by experimental example 4 with tyrosinase at different concentrations;
FIG. 16 is a graph showing the linear relationship between the normalized photoluminescence intensity of the near infrared emission gold nanoclusters and tyrosinase at different concentrations provided in experimental example 4 of the present invention;
FIG. 17 is a graph showing the emission spectrum of a sample according to Experimental example 4 of the present invention, which was transferred to a quartz cuvette and tested by using a fluorescence spectrophotometer.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Description of the terminology:
MBA-AuNCs: is a nano cluster which takes gold atoms as cores and 2-mercaptobenzoic acid (MBA for short) as a reducing agent and a capping ligand. The periphery of MBA contains-COOH groups, and photoluminescence enhancement can be realized by reasonably controlling the pH of the system and adjusting the aggregation behavior of nanoclusters.
The structure of the weakly luminescent gold nanoclusters (MBA-AuNCs) is as follows, wherein black globules represent gold nuclei.
The raw materials used in the embodiment of the invention are conventional raw materials and commercially available products, wherein: chloroauric acid, sodium hydroxide and nitric acid are purchased from the national pharmaceutical group chemical reagent company, MBA is purchased from the Shanghai A Ding Shenghua technology company, tyrosinase and dopamine hydrochloride are purchased from the Shanghai A microphone Lin Shenghua company, and the product is directly used without treatment before use.
1. Explanation of the examples:
example 1
The embodiment of the invention provides a near infrared emission gold nanocluster, wherein 2-mercaptobenzoic acid (MBA) and chloroauric acid react in an aqueous solution to form a weak luminescence gold nanocluster (MBA-AuNCs), and then the near infrared emission gold nanocluster with compact and ordered structure and enhanced luminescence is formed under the interaction force of non-covalent bonds by regulating and controlling the pH of a system.
The chemical structure of compact ordered, luminescence-enhanced near infrared-emitting gold nanoclusters (ph=6.16) is shown below, with black globules representing gold nuclei.
In the embodiment of the invention, preferably, the molar concentration of the chloroauric acid is: 5 to 15 mmol.L -1 。
In the embodiments of the present invention, preferably, the molar concentration of the 2-mercaptobenzoic acid (MBA): 10 to 35 mmol.L -1 。
The invention endows luminescence enhancement and near infrared emission functions on the weak luminescence gold nanoclusters (MBA-AuNCs) and can detect tyrosinase and dopamine, wherein the MBA-AuNCs is an inorganic-organic hybrid material, gold is an inner core, the periphery is an organic ligand, and the ligand is MBA.
Example 2
As shown in fig. 1, the preparation method of the near infrared emission gold nanocluster provided by the embodiment of the invention includes:
s101, preparation of MBA-AuNCs: adding a 2-mercaptobenzoic acid (MBA) solid reagent into deionized water, and then adding a proper amount of sodium hydroxide solution to completely dissolve the 2-mercaptobenzoic acid (MBA) solid to obtain a 2-mercaptobenzoic acid MBA solution; mixing chloroauric acid aqueous solution and 2-mercaptobenzoic acid (MBA) solution at room temperature, gradually changing the color of the mixture into pale yellow, standing for 8 hours in a constant temperature box at 20 ℃, and changing the color of the solution from pale yellow into colorless and transparent to obtain MBA-AuNCs;
s102, preparing near infrared emission gold nanoclusters: adding a nitric acid solution into the MBA-AuNCs, and reasonably regulating and controlling the pH value of the MBA-AuNCs to obtain the near infrared emission gold nanocluster.
In the embodiment of the present invention, preferably, in step S101, the AuNCs: MBA concentration ratio of 1 (mmol.L) -1 ):2～4(mmol·L -1 ) Most preferably 1 (mmol.L) -1 ):2.5(mmol·L -1 )。
In the embodiment of the present invention, preferably, in step S101, the concentration of the sodium hydroxide is 0.05 to 0.15mol·l -1 Preferably, the concentration of sodium hydroxide is 0.1 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The amount of sodium hydroxide added was such that the MBA solids were completely dissolved, resulting in a clear solution.
In the embodiment of the present invention, it is preferable that in step S101, the concentration of the aqueous chloroauric acid solution is 10 mmol.L -1 Concentration of MBA solution 25 mmol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of chloroauric acid to MBA is 1:2.5.
in the embodiment of the present invention, it is preferable that the concentration is 1 to 30 mmol.L in step S102 -1 The pH of the control system is 11.88, 10.47, 9.62, 8.46, 7.43, 6.44, 6.32, 6.24 and 6.16, the luminous intensity is best when the pH=6.16, the emission wavelength is 650-760 nm, and the pH=6.16 is more preferable in the near infrared region.
Example 3
Based on the preparation method of the near infrared emission gold nanocluster provided in embodiment 2 of the present invention, further, the present embodiment provides a preparation method of a near infrared emission gold nanocluster, which is different in that:
synthesis of MBA-AuNCs: 0.0370g of MBA reagent is accurately weighed into a test tube, 3.76mL of deionized water is added, and then 240 mu L of 5 mol.L is added -1 MBA was completely dissolved by NaOH to give 4mL of 60 mmol.L -1 MBA solution. 4mL of 20 mmol.L -1 Adding chloroauric acid solution into the prepared MBA solution, gradually changing the color of the mixture into pale yellow, standing for 8 hours in a constant temperature box at 20 ℃, and changing the color of the solution from pale yellow into colorless and transparent to obtain MBA-AuNCs.
Example 4
Based on the preparation method of the near infrared emission gold nanocluster provided in embodiment 2 of the present invention, further, the present embodiment provides a preparation method of a near infrared emission gold nanocluster, which is different in that:
synthesis of MBA-AuNCs: accurately weighing 0.0308g of MBA reagent into a test tube, adding 3.84mL of deionized water, and then adding 160 mu L of 5 mol.L -1 MBA was completely dissolved by NaOH to give 4mL of 50 mmol.L -1 MBA solution. 4mL of 20 mmol.L -1 Adding chloroauric acid solution into the prepared MBA solution, gradually changing the color of the mixture into pale yellow, standing in a constant temperature box at 20 ℃ for 8 hours, and changing the color of the solution from pale yellow into colorless and transparent to obtain MBA-AuNCs with the pH value of 11.88.
A TEM image of MBA-AuNCs obtained in this example is shown in FIG. 2 (a). As can be seen from FIG. 2 (a), MBA-AuNCs appear as nanodot states. The luminous intensity is very weak as shown in fig. 2 (b).
Example 5
Based on the preparation method of the near infrared emission gold nanocluster provided in embodiment 2 of the present invention, further, the present embodiment provides a preparation method of a near infrared emission gold nanocluster, which is different in that:
preparation of near infrared emission gold nanoclusters: using HNO 3 Regulating the pH of the MBA-AuNCs to 8.46, and standing for 24 hours in a constant temperature box at 20 ℃ to obtain the product.
The TEM image of the near infrared emission gold nanoclusters obtained in this example is shown in fig. 3 (a). As can be seen from fig. 3 (a), the near infrared emission gold nanoclusters are in a nanorod state. The luminescence is slightly enhanced but still weaker as shown in fig. 3 (b).
Example 6
Based on the preparation method of the near infrared emission gold nanocluster provided in embodiment 2 of the present invention, further, the present embodiment provides a preparation method of a near infrared emission gold nanocluster, which is different in that:
preparation of near infrared emission gold nanoclusters: using HNO 3 Regulating the pH of the MBA-AuNCs to 6.16, and standing for 24 hours in a constant temperature box at 20 ℃ to obtain the product.
TEM and SEM images of the near infrared emission gold nanoclusters obtained in this example are shown in FIG. 4 (a) and FIG. 4 (b), respectively. As can be seen from fig. 4 (a) and 4 (b), the near-infrared emission gold nanoclusters are in a nanofiber state. The compactness and the order degree of the aggregate are increased, and the luminescence is obviously enhanced, as shown in fig. 4 (c).
The excitation spectrum, the emission spectrum and the absorption spectrum of the near infrared emission gold nanoclusters obtained in this embodiment are shown in fig. 5. The bottom right illustration is an optical photograph of the near infrared emitting gold nanoclusters obtained in this example under a fluorescent lamp and an ultraviolet lamp, respectively.
Example 7
Based on the preparation method of the near infrared emission gold nanocluster provided in embodiment 2 of the present invention, further, the present embodiment provides a preparation method of a near infrared emission gold nanocluster, which is different in that:
preparation of near infrared emission gold nanoclusters: the gold nanoclusters obtained in example 6 were diluted four times with deionized water to a final concentration of 2.5 mmol.L -1 Near infrared emission performance is still better maintained.
In the foregoing embodiments, the descriptions of the embodiments are emphasized, and in part, not described or illustrated in any particular embodiment, reference is made to the related descriptions of other embodiments.
2. Application examples:
application example
The application of the near infrared emission gold nanocluster provided by the embodiment of the invention in tyrosinase and dopamine detection comprises the following steps:
MBA is used as a stabilizer and a reducing agent, and reacts with chloroauric acid through Au-S coordination to form MBA-AuNCs. The MBA ligand contains-COOH active sites outside, the pH of the system is controllably regulated, the nanoclusters are self-assembled into ordered nanofibers, and under the pushing of non-covalent bond interaction force, the intramolecular vibration and rotation of the MBA ligand are limited, the non-radiative transition is reduced, and the excellent near infrared luminescence characteristic is shown. When tyrosinase and dopamine are added simultaneously, tyrosinase can catalyze and oxidize dopamine to generate o-quinone, so that luminescence of the nanoclusters is quenched, and tyrosinase and dopamine are detected.
3. Evidence of example related effects:
experimental example 1
Used forThe ionized water was diluted to a concentration of 0.25, 0.75, 1.0 mmol.L, respectively, in the near infrared emission gold nanoclusters obtained in example 6 -1 HeLa cells were then incubated with different concentrations of gold nanoclusters for 24h and cytotoxicity was assessed using the MTT assay, the experimental results are shown in FIG. 6. HeLa cells and gold nanoclusters were co-incubated in cell culture medium and laser confocal results are shown in FIG. 7.
Experimental example 2
To the near infrared emission gold nanoclusters obtained in example 7, a concentration of 1.0 mmol.L was added, respectively -1 Is 2.5unit mL in concentration -1 The concentration of tyrosinase in (2.5 unit mL) -1 Tyrosinase and 1.0 mmol.L -1 Is placed in an incubator at 20 ℃. After the complete reaction, the samples were transferred to quartz cuvettes, respectively, and the emission spectra of the samples were measured using a fluorescence spectrophotometer, as shown in fig. 8.
Determination of 1.0 mmol.L using an ultraviolet-visible spectrophotometer -1 Dopamine, 2.5unit mL -1 Tyrosinase, 1.0 mmol.L -1 Dopamine and 2.5unit mL -1 The UV-visible absorption spectrum of tyrosinase was shown in FIG. 9.
MBA-AuNCs still maintain the original luminescence property after aggregation to form nanofibers under the non-covalent bond interaction. As can be seen from fig. 8, only when tyrosinase and dopamine are simultaneously added, luminescence of the nanoclusters can be quenched, which illustrates that the near infrared emission gold nanoclusters prepared by the present invention can be used for detecting tyrosinase and dopamine.
Experimental example 3
To the near infrared emission gold nanoclusters obtained in example 7, a concentration of 2.5unit mL was added -1 Then adding different amounts of dopamine solution to make the concentration of dopamine from 0 to 6.0 mmol.L -1 Placing in a constant temperature box at 20 ℃ for cultivation. After the complete reaction, the samples added with different concentrations of dopamine were transferred to a quartz cuvette, and the emission spectrum of the samples was tested using a fluorescence spectrophotometer, and the results are shown in fig. 10.
Contains a fixed TYR content (2.5 unit·mL -1 ) The curve of normalized photoluminescence intensity at 713nm of the near infrared emission gold nanoclusters obtained in example 7 of (1) with different concentrations of dopamine is shown in fig. 11. Wherein, the upper right top and bottom inserts are respectively provided with fixed TYR content (2.5 unit mL) of dopamine with different concentrations under fluorescent lamp and ultraviolet lamp -1 ) Near infrared emitting gold nanocluster photomicrographs obtained in example 7 of (c). Contains a fixed TYR content (2.5 unit mL) -1 ) The linear relationship between normalized photoluminescence intensity at 713nm and different concentrations of dopamine of the near infrared emitting gold nanoclusters obtained in example 7 of (a) is shown in fig. 12.
0 to 0.25 mmol.L -1 A good linear relationship between normalized luminescence intensity and dopamine concentration was observed. The linear regression equation is: normalized photoluminescence intensity=1.0-2.59 [ dopamine ]]，R 2 =0.989. Based on N/s=3, the detection limit of dopamine is calculated to be 2.1 μmol·l -1 。
To the near infrared emission gold nanoclusters obtained in example 7, a concentration of 2.5unit mL was added -1 Then adding tyrosinase with concentration of 1.0 mmol.L respectively -1 K of (2) + 、Na + 、Ca 2+ 、Ba 2+ 、Mg 2+ L-ascorbic acid (L-asc), L-tyrosine (L-tyr), L-histidine (L-his), D-histidine (D-his) D-phenylalanine (D-phe) and dopamine were incubated in an incubator at 20 ℃. After the complete reaction, the above samples were transferred to a quartz cuvette, and the luminescence intensity of the samples was measured using a fluorescence spectrophotometer, and the photoluminescence intensity at 713nm was as shown in fig. 13. Continuously adding 1.0 mmol.L to the sample -1 Is placed in an incubator at 20 ℃. After the complete reaction, the above samples were transferred to a quartz cuvette, and the luminescence intensity of the samples was measured using a fluorescence spectrophotometer, and the photoluminescence intensity at 713nm was as shown in fig. 13.
Experimental example 4
The near infrared emission gold nanoclusters obtained in example 7 were added to a concentration of 1.0 mmol.L -1 Is then added with different amounts of dopamineThe concentration of tyrosine is from 0 to 4.0unit mL -1 Placing in a constant temperature box at 20 ℃ for cultivation. After the reaction was completed, the samples added with tyrosinase at different concentrations were transferred to a quartz cuvette, and the emission spectrum of the samples was measured using a fluorescence spectrophotometer, and the results are shown in fig. 14.
Contains fixed dopamine content (1.0 mmol.L) -1 ) The curve of normalized photoluminescence intensity at 713nm of the near infrared emission gold nanoclusters obtained in example 7 of (1) with tyrosinase at different concentrations is shown in fig. 15. Wherein, the upper right top and bottom inserts are respectively provided with different concentration tyrosinase pairs under a fluorescent lamp and an ultraviolet lamp, and the concentration of the tyrosinase pairs contains fixed dopamine (1.0 mmol.L -1 ) Near infrared emitting gold nanocluster photomicrographs obtained in example 7 of (c). Contains fixed dopamine content (1.0 mmol.L) -1 ) The linear relationship between normalized photoluminescence intensity at 713nm and tyrosinase at different concentrations of near infrared emitting gold nanoclusters obtained in example 7 of (1) is shown in fig. 16.
At 0 to 0.2unit mL -1 A good linear relationship between normalized luminescence intensity and tyrosinase concentration was observed. The linear regression equation is: normalized photoluminescence intensity=0.99-1.42 [ tyrosinase]，R 2 =0.992. Based on N/S=3, the detection limit of tyrosinase is calculated to be 0.0357 unit.mL -1 。
The near infrared emission gold nanoclusters obtained in example 7 were added to a concentration of 1.0 mmol.L -1 Then K with the concentration of 0.005mg/mL is added respectively + 、Na + 、Ca 2+ 、Ba 2+ 、Mg 2+ L-ascorbic acid (L-asc), L-tyrosine (L-tyr), L-histidine (L-his), D-histidine (D-his), D-phenylalanine (D-phe) and a concentration of 2.5unit mL -1 Is placed in an incubator at 20 ℃. After the complete reaction, the above samples were transferred to a quartz cuvette, and the luminescence intensity of the samples was measured using a fluorescence spectrophotometer, and the photoluminescence intensity at 713nm was as shown in fig. 17. Continuously adding 2.5unit mL to the sample -1 Is placed inCulturing in an incubator at 20 ℃. After the complete reaction, the above samples were transferred to a quartz cuvette, and the luminescence intensity of the samples was measured using a fluorescence spectrophotometer, and the photoluminescence intensity at 713nm was as shown in fig. 17.
Experiments show that
The invention provides a preparation method of near infrared emission gold nanoclusters and application of the near infrared emission gold nanoclusters in tyrosinase and dopamine detection. By controllably adjusting the pH of the system, the nanoclusters self-assemble into compact ordered nanostructures, exhibiting near infrared luminescence enhancement. The near infrared luminescent nanocluster provided by the invention has the advantages of simple preparation method, no need of introducing an organic solvent, low toxicity and good biocompatibility, and can be used as a candidate material for cell imaging and fluorescent marking. After tyrosinase and dopamine are added, luminescence is obviously quenched, so that the detection is convenient, and sensitive detection of tyrosinase and dopamine can be realized.
While the invention has been described with respect to what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the near infrared emission gold nanocluster is characterized by comprising the following steps of: 2-mercaptobenzoic acid reacts with chloroauric acid in aqueous solution to form weak-luminescence gold nanoclusters, and the near infrared-emission gold nanoclusters are formed under the interaction force of non-covalent bonds by regulating and controlling the pH of a system.
2. The method for preparing the near infrared emission gold nanoclusters according to claim 1, wherein the preparation process of reacting 2-mercaptobenzoic acid with chloroauric acid in an aqueous solution to form the weak luminescence gold nanoclusters comprises: adding a 2-mercaptobenzoic acid solid reagent into deionized water, and then adding a sodium hydroxide solution to completely dissolve the 2-mercaptobenzoic acid solid to obtain a 2-mercaptobenzoic acid solution;
mixing chloroauric acid aqueous solution and 2-mercaptobenzoic acid solution at room temperature, and standing at constant temperature to obtain the weak-luminescence gold nanocluster.
3. The method for preparing near infrared emission gold nanoclusters according to claim 2, wherein the molar concentration ratio of 2-mercaptobenzoic acid to chloroauric acid is 1 (2-4).
4. The method for preparing near infrared emission gold nanoclusters according to claim 2, characterized in that the concentration of sodium hydroxide is 0.05 to 0.15 mol.l -1 The method comprises the steps of carrying out a first treatment on the surface of the The amount of sodium hydroxide added was such that the 2-mercaptobenzoic acid solid was dissolved until complete, yielding a clear solution.
5. The method for preparing near infrared emission gold nanoclusters according to claim 2, characterized in that said standing at constant temperature is: standing in a constant temperature cabinet at 20 ℃ for 8h.
6. The method for preparing near infrared emission gold nanoclusters according to claim 1, wherein the pH of the control system includes: adding nitric acid solution with the concentration of 1-30 mmol/L into the weak luminescence gold nanocluster, and regulating and controlling the pH value to obtain the gold nanocluster with enhanced luminescence and near infrared emission.
7. The method of claim 6, wherein the pH is 11.88, 10.47, 9.62, 8.46, 7.43, 6.44, 6.32, 6.24, or 6.16.
8. A near infrared emission gold nanocluster prepared by the method for preparing a near infrared emission gold nanocluster according to any one of claims 1 to 7, the near infrared emission wavelength of the near infrared emission gold nanocluster being 650nm to 760nm.
9. Use of the near infrared emitting gold nanoclusters of claim 8 in tyrosinase detection.
10. Use of the near infrared emitting gold nanoclusters of claim 8 in dopamine detection.
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