CN110591702B - Preparation method and application of aggregation-induced luminescent silver nanocluster - Google Patents

Preparation method and application of aggregation-induced luminescent silver nanocluster Download PDF

Info

Publication number
CN110591702B
CN110591702B CN201910888226.2A CN201910888226A CN110591702B CN 110591702 B CN110591702 B CN 110591702B CN 201910888226 A CN201910888226 A CN 201910888226A CN 110591702 B CN110591702 B CN 110591702B
Authority
CN
China
Prior art keywords
aggregation
induced luminescent
silver
induced
luminescent silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910888226.2A
Other languages
Chinese (zh)
Other versions
CN110591702A (en
Inventor
张彦
吕玫
高鹏飞
李天栋
双少敏
张国梅
董川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi University
Original Assignee
Shanxi University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi University filed Critical Shanxi University
Priority to CN201910888226.2A priority Critical patent/CN110591702B/en
Publication of CN110591702A publication Critical patent/CN110591702A/en
Application granted granted Critical
Publication of CN110591702B publication Critical patent/CN110591702B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/58Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N2021/6417Spectrofluorimetric devices
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432Quenching

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Biophysics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a preparation method and application of aggregation-induced luminescent silver nanoclusters, wherein the preparation method comprises the following steps: mixing 5-17.5 parts by volume of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20 parts by volume of 2.5mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 60-80 ℃, refluxing for 12-48h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanoclusters, wherein the fluorescence quantum yield can be as high as 0.44. The preparation method is simple in preparation process, simple in reaction condition and environment-friendly, and the prepared aggregation-induced luminescent silver nanocluster has good aggregation-induced luminescent property, high fluorescence quantum yield, microsecond-level long service life and high content of Ag (I). The aggregation-induced luminescent silver nanocluster prepared by the invention can be used for detecting tetracycline.

Description

Preparation method and application of aggregation-induced luminescent silver nanocluster
Technical Field
The invention relates to preparation of silver nanoclusters, in particular to a preparation method and application of aggregation-induced luminescent silver nanoclusters.
Background
Tetracycline (TC) is a broad spectrum antibacterial drug found in the middle of the 20 th century. Because tetracycline has the advantages of various antibacterial properties, low cost, good oral absorption and the like, the tetracycline is widely applied to the industries such as the medical industry, the breeding industry, the meat processing industry and the like. However, as a result of investigation, when tetracycline circulates in the environment, on one hand, ecological pollution is caused, and on the other hand, after the tetracycline is contacted with microorganisms or bacteria in the environment, the microorganisms or bacteria generate resistance genes, so that the inhibition capability of the tetracycline to the bacteria is reduced. More seriously, the microorganisms producing antibiotic resistance can directly or indirectly enter the human body through the ecological cycle, resulting in reduced antibiotic action and threat to human health. Common tetracycline detection methods include Capillary Electrophoresis (CE), High Performance Liquid Chromatography (HPLC), spectrophotometry, and Chemiluminescence (CL). However, these methods have the disadvantages of being time-consuming, expensive in apparatus and cumbersome to operate. In recent years, fluorescence analysis methods have been widely studied in the field of analytical detection due to the advantages of easy operation, high sensitivity, fast signal response, low cost, real-time detection, almost no damage to samples, and the like. Therefore, it is very important to construct a high-selectivity and high-accuracy fluorescence analysis method for detecting tetracycline.
Organic fluorophores with conjugated structures cause quenching effects in the aggregated state, whereas luminescent materials with aggregation-induced emission may emit strong light in the aggregated state or in the solid state. In recent years, the unique properties of such luminescent materials have made them overcome the drawbacks of the aggregation quenching effect of conventional luminescent materials, and such aggregation-induced luminescent materials have attracted attention from a wide range of researchers. Currently, most of the research on aggregation-induced emission phenomenon focuses on organic molecules such as tetraphenylethylene and hexaphenylsilole. In recent years, there have been reports of nanocluster aggregation-induced emission materials, and Jiezhou et al adopted Au3+The prepared silver nanoclusters are induced to obtain aggregation type silver nanoclusters (Talanta,2018,188, 623-629) with strong luminescence, and after the nanoclusters are aggregated, intramolecular vibration and rotation of the ligand can be inhibited, so that the non-radiative relaxation behavior of an excited state related to the ligand is inhibited, and the luminescence performance of the silver nanoclusters is obviously enhanced. However, an aggregate having long-life properties is obtainedInducing luminescent materials is very challenging. In a recent study (Journal of Materials Chemistry B,2018,6, 3927-3933), Saifei Pan et al prepared hydrophobic silver nanoclusters protected by thiosalicylic acid under the protection of nitrogen and self-assembled at 0 ℃ to obtain aggregation-induced emission nanomaterials, the quantum yield was 0.25 and the fluorescence lifetime was 7.65 μ s. Although the aggregation-induced emission material with long service life is obtained, the whole process not only needs the protection of nitrogen, but also needs self-assembly at 0 ℃, and the process is complicated.
Disclosure of Invention
In view of this, the present invention aims to provide a preparation method and an application of aggregation-induced luminescent silver nanoclusters, which aim to overcome the defects of complicated preparation process, low fluorescence quantum yield and short fluorescence lifetime existing in the existing preparation process of silver nanoclusters.
In order to achieve the purpose of the invention, the following technical scheme is adopted:
a preparation method of aggregation-induced luminescent silver nanoclusters comprises the following steps: mixing 5-17.5 parts by volume of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20 parts by volume of 2.5mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 60-80 ℃, refluxing for 12-48h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanoclusters.
Preferably, the method comprises the following steps: mixing 5-12.5 parts by volume of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20 parts by volume of 2.5mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 70-80 ℃, refluxing for 12-36h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanoclusters.
More preferably, the method comprises the following steps: mixing 5 parts by volume of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20 parts by volume of 2.5mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 24 hours, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster.
The aggregation-induced luminescent silver nanocluster prepared by the invention is applied to detection of tetracycline.
The invention has the beneficial effects that:
(1) the invention adopts N-acetyl-L-cysteine as a reducing agent and a ligand protective agent to prepare the aggregation-induced luminescent silver nanocluster with good luminescence property, the preparation process is simple and environment-friendly, the addition of chemical reagents such as common reducing agents of sodium borohydride, ascorbic acid, a surfactant and the like is avoided, the prepared aggregation-induced luminescent silver nanocluster has the characteristics of aggregation-induced luminescence and can generate strong fluorescence, the fluorescence emission peak of the aggregation-induced luminescent silver nanocluster is about 490nm, when the aggregation-induced luminescent silver nanocluster is observed by a black background under ultraviolet light, the strong blue-green fluorescence is presented, and the fluorescence quantum yield can be as high as 0.44.
(2) The aggregation-induced luminescent silver nanocluster prepared by the invention has the advantages of average particle size of 1.36nm, small size, uniform particle size distribution and good photobleaching resistance.
(3) The aggregation-induced luminescent silver nanocluster prepared by the invention has high sensitivity and selectivity on tetracycline, can be applied to tetracycline detection, and has the detection limit of 0.47 mu M.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a process of forming aggregation-induced luminescent silver nanoclusters;
fig. 2 is a transmission electron microscope photograph of aggregation-induced luminescent silver nanoclusters of example 8;
fig. 3 is an ultraviolet absorption spectrum and fluorescence excitation and emission spectrum of aggregation-induced luminescent silver nanoclusters of example 8;
fig. 4 is a graph of the photostability of aggregation-induced luminescent silver nanoclusters of example 8;
FIG. 5 is an X-ray photoelectron spectrum of aggregation-induced luminescent silver nanoclusters of example 8;
fig. 6 is a transmission electron microscope photograph of comparative example silver nanoclusters.
Fig. 7(a) is a working curve of the aggregation-induced luminescent silver nanoclusters of example 8 in response to tetracycline;
FIG. 7(b) is a linear relationship between the change value of the fluorescence intensity in logarithm of the aggregation-induced luminescent silver nanocluster of example 8 and the tetracycline concentration;
FIG. 8 is a bar graph of fluorescence of aggregation-induced luminescent silver nanoclusters of example 8 after interaction with various small molecules;
fig. 9 is a bar graph of fluorescence of aggregation-induced luminescent silver nanoclusters of example 8 after interaction with various metal ions.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
As shown in fig. 1, the formation process of the aggregation-induced luminescent silver nanoclusters of the present invention is: firstly, N-acetyl-L-cysteine (NAC) is coordinated with monovalent silver Ag (I) through sulfydryl (-SH) under stirring at room temperature to form Ag (I) -thiolate complex, or Ag (I) is coordinated with other groups-X (-COOH/NO) in solution2 -) Coordination occurs to form a coordination compound; then under the heating reflux condition of 60-80 ℃, N-acetyl-L-cysteine selectively reduces Ag (I) into Ag (0) due to the high affinity between Ag (I) and zero-valent silver Ag (0), and the Ag (0) is separated from Ag (I) -thiolate complex by NAC to form Ag (0) -Ag (I) -thiolate intermediate; ag (0) -Ag (I) -S when the reflux is carried out under the condition of continuously controlling the heating temperature to be 60-80 DEG CThe alkoxide intermediates are slowly aggregated by Ag (0) collision and fusion to form Ag (0) core and shell structure of Ag (i) -thiolate complex, forming aggregation-induced emission type silver nanoclusters as shown in fig. 2. The luminescence behavior of the silver nanoclusters is caused by charge transfer from a ligand to silver and from the ligand to monovalent silver and then to zero-valent silver, after the silver nanoclusters are aggregated, the vibration and rotation in ligand N-acetyl-L-cysteine molecules are inhibited, so that the excited state non-radiative relaxation behavior related to the ligand is inhibited, the luminescence performance of the silver nanoclusters is obviously enhanced, and after the silver nanoclusters are aggregated, the charge transfer can be carried out among different clusters, so that the fluorescence performance of the silver nanoclusters is further enhanced.
Example 1
A preparation method of aggregation-induced luminescent silver nanoclusters comprises the following steps: mixing 5mL of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20mL of 2.5mmol/L silver nitrate aqueous solution, uniformly stirring the mixed solution, controlling the heating temperature to be 60 ℃ and refluxing for 24h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster. The fluorescence emission peak of the aggregation-induced luminescent silver nanocluster is about 516nm, and when the aggregation-induced luminescent silver nanocluster is observed on a black background under ultraviolet light, relatively strong green fluorescence is presented, the quantum yield is 0.35, and the fluorescence lifetime is 9.15 mu s.
Example 2
A preparation method of aggregation-induced luminescent silver nanoclusters comprises the following steps: mixing 5mL of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20mL of 2.5mmol/L silver nitrate aqueous solution, uniformly stirring the mixed solution, controlling the heating temperature to be 70 ℃ and refluxing for 24h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster. The fluorescence emission peak of the aggregation-induced luminescent silver nanocluster is about 494nm, and the aggregation-induced luminescent silver nanocluster presents strong blue-green fluorescence when observed with a black background under ultraviolet light, wherein the quantum yield is 0.40, and the fluorescence lifetime is 10.55 mu s.
Example 3
A preparation method of aggregation-induced luminescent silver nanoclusters comprises the following steps: mixing 17.5mL of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20mL of 2.5mmol/L silver nitrate aqueous solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 48h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster. The fluorescence emission peak of the aggregation-induced luminescent silver nanocluster is about 492nm, and when the aggregation-induced luminescent silver nanocluster is observed on a black background under ultraviolet light, intense blue-green fluorescence is presented, the quantum yield is 0.39, and the fluorescence lifetime is 9.22 mu s.
Example 4
A preparation method of aggregation-induced luminescent silver nanoclusters comprises the following steps: mixing 15mL of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20mL of 2.5mmol/L silver nitrate aqueous solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 36h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster. The fluorescence emission peak of the aggregation-induced luminescent silver nanocluster is about 492nm, and when the aggregation-induced luminescent silver nanocluster is observed on a black background under ultraviolet light, intense blue-green fluorescence is presented, the quantum yield is 0.40, and the fluorescence lifetime is 9.85 microseconds.
Example 5
A preparation method of aggregation-induced luminescent silver nanoclusters comprises the following steps: mixing 12.5mL of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20mL of 2.5mmol/L silver nitrate aqueous solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 24h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster. The fluorescence emission peak of the aggregation-induced luminescent silver nanocluster is about 492nm, and when the aggregation-induced luminescent silver nanocluster is observed on a black background under ultraviolet light, intense blue-green fluorescence is presented, the quantum yield is 0.41, and the fluorescence lifetime is 10.20 mu s.
Example 6
A preparation method of aggregation-induced luminescent silver nanoclusters comprises the following steps: mixing 10mL of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20mL of 2.5mmol/L silver nitrate aqueous solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 24h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster. The fluorescence emission peak of the aggregation-induced luminescent silver nanocluster is about 490nm, and when the aggregation-induced luminescent silver nanocluster is observed under ultraviolet light on a black background, intense blue-green fluorescence is presented, the quantum yield is 0.42, and the fluorescence lifetime is 10.55 mu s.
Example 7
A preparation method of aggregation-induced luminescent silver nanoclusters comprises the following steps: mixing 7.5mL of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20mL of 2.5mmol/L silver nitrate aqueous solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 12h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster. The fluorescence emission peak of the aggregation-induced luminescent silver nanocluster is about 490nm, and when the aggregation-induced luminescent silver nanocluster is observed under ultraviolet light and a black background, intense blue-green fluorescence is presented, the quantum yield is 0.42, and the fluorescence lifetime is 10.65 microseconds.
Example 8
A preparation method of aggregation-induced luminescent silver nanoclusters comprises the following steps: mixing 5mL of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20mL of 2.5mmol/L silver nitrate aqueous solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 24h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster.
The size and shape of the synthesized aggregation-induced luminescent silver nanoclusters (AgNCs) were characterized by a Transmission Electron Microscope (TEM), and as shown in fig. 2, the synthesized aggregation-induced luminescent silver nanoclusters exhibited an aggregated state, and their luminescent aggregates consisted of smaller silver nanoclusters with an average particle size of 1.36nm, indicating that the strong luminescent properties of the synthesized aggregation-induced luminescent silver nanoclusters were caused by aggregation induction.
500. mu.L of BR buffer solution (50mmol/L, pH 5), 500. mu.L of ethanol mixed solution system and 100. mu.L of aggregation-induced luminescent silver nanocluster solution were added to a fluorescence cuvette, and its ultraviolet absorption spectrum and fluorescence excitation and emission spectrum were measured, as shown in FIG. 3, with the fluorescence emission peak of the aggregation-induced luminescent silver nanocluster being 494 nm.
The aggregation-induced luminescent silver nanocluster solution is subjected to a photobleaching resistance experiment, as shown in fig. 4, the aggregation-induced luminescent silver nanocluster solution can maintain good luminescent performance within 30min, which indicates that the photobleaching resistance is good.
The aggregation-induced luminescent silver nanocluster shows strong blue-green fluorescence when observed with a black background under ultraviolet light, the quantum yield is 0.44, and the fluorescence lifetime is 11.08 microseconds.
The chemical valence state of the synthesized aggregation-induced luminescent silver nanoclusters was characterized by X-ray photoelectron spectroscopy (XPS), and fig. 5 is an XPS spectrogram of Ag3d, showing Ag3d5/2And Ag3d3/2The maximum peak values of the binding energy of (a) are 367.68eV and 373.68eV, respectively. 367.68eV is between 367.5eV (Ag (I)) and 368.2eV (Ag (0)), the synthesized aggregation-induced luminescent silver nanoclusters are deduced to be composed of Ag (I) and Ag (0), and the ratio of Ag (I) to Ag (0) of the synthesized aggregation-induced luminescent silver nanoclusters can be deduced to be 2.25:1 by further peak separation of XPS as shown in FIG. 5.
Comparative example:
a method for preparing silver nanoclusters, comprising the steps of:
mixing 20mL of 1mmol/L silver nitrate solution and 80mL of 0.125mmol/L N-acetyl-L-cysteine aqueous solution to form a mixed solution, and then stirring the mixed solution vigorously to obtain 8.8mg of NaBH4Adding into the mixed solution to obtain yellow silver colloid solution. Stirring the obtained yellow silver colloid solution for 2 hours at room temperature in the dark to ensure that the N-acetyl-L-cysteine is self-assembled on the surface of the silver cluster, and then storing the yellow silver colloid solution at 4 ℃ and keeping out of the sun overnight to obtain the silver nanocluster. The silver nanoclusters were prepared as a 0.1mg/mL aqueous solution of silver nanoclusters, and the aqueous solution was dropped on a copper mesh with a carbon film, vacuum-dried, and then subjected to TEM testing, as shown in fig. 6, where the silver nanoclusters had a particle diameter of about 12nm and exhibited no fluorescence when observed on a black background under ultraviolet light.
This comparative example is a comparative example to example 8, which is further illustrated by the use of NaBH in order to further illustrate the advantages of the process of the present invention4AgNO as reducing agent3The monovalent silver Ag (I) is reduced to zero-valent silver Ag (0), and N-acetyl-L-cysteine is used as a ligand to synthesize the silver nanocluster. By comparison, with NaBH4The preparation method of the reducing agent can not obtain the fluorescent nano material.
Example 9
Use of aggregation-induced luminescent silver nanoclusters prepared as in example 8 in the detection of tetracycline.
The aggregation-induced luminescent silver nanoclusters prepared in example 8 were configured into 0.1mg/mL aggregation-induced luminescent silver nanocluster solution, 500 μ L of ethanol, 500 μ L of BR buffer solution (50mmol/L, pH 5), and 100 μ L of aggregation-induced luminescent silver nanocluster solution were injected into a fluorescence cuvette, stirred until uniform mixing was achieved, and after no bubble was generated, the tetracycline solution was added to the fluorescence cuvette in the order of concentration from small to large, and the fluorescence spectra thereof were measured with 386nm as the excitation wavelength, respectively. As shown in fig. 7(a), as the concentration of tetracycline increases, the fluorescence of the silver nanoclusters is gradually quenched; as shown in FIG. 7(b), the logarithmic change in fluorescence intensity was plotted as Log (F) against the concentration of tetracycline0is/F) wherein F0And F respectively represent the fluorescence intensity of the silver nanoclusters in the absence and presence of tetracycline, and the detection limit of tetracycline is 0.47 μ M (calculated according to the formula LOD ═ 3 σ/k, σ is standard deviation of the fluorescence intensity values of the silver nanoclusters for 11 times, and the k value is the slope of the fitted straight line in fig. 7 (b)). The regression equation of the silver nanoclusters obtained by linear fitting is: y is 0.0139+0.004X, and the linear coefficient is R20.997. Based on the method, the aggregation-induced luminescent silver nanocluster can be applied to detection of tetracycline in milk.
Example 10
The aggregation-inducible luminescent silver nanoclusters prepared in example 8 were configured into an aggregation-inducible luminescent silver nanocluster solution of 0.1mg/mL, 500 μ L of ethanol, 500 μ L of BR buffer solution (50mmol/L, pH 5), and 100 μ L of the aggregation-inducible luminescent silver nanocluster solution were injected into a fluorescence cuvette, and first, tetracycline was added thereto to measure the fluorescence intensity thereof as a blank; secondly, respectively adding 20 common anions and cations and 15 common micromolecules (the concentration of the coexisting ions is 20 times that of the tetracycline) and other potential interference substances, measuring and recording the fluorescence intensity value; tetracycline was added to the solution, and the fluorescence intensity was measured and recorded. Measuring fluorescence spectra with 386nm as excitation wavelength, respectively, and drawing a bar graph of fluorescence intensity at 494nm corresponding to different small molecules, as shown in FIG. 8; the different ions were plotted against the intensity of the fluorescence at 494nm as shown in FIG. 9. Experiments prove that other small molecules and ions do not interfere the detection of the system on the tetracycline.
The 15 small molecules are DL-cysteine (DL-Cys), DL-histidine (DL-His), L-glutamine (L-Glu), tyrosine (Tyr), phenylalanine (Phe), Glutathione (GSH), vitamin C, vitamin B1, vitamin B2, vitamin B6, glucose (Glc), sorbic acid (Sorbicic), citric acid (Citricacid), DL-mandelic acid (DL-Mandelicacid) and erythromycin (E), respectively. 20 kinds of anions and cations are respectively PO4 3-、CO3 2-、HCO3 -、F-、SO4 2-、Cl-、NO2 -、Ac-、SCN-、C2O4 2-、Ca2+、Mg2+、K+、Zn2+、Mn2+、Na+、Sn2+、Al3+、Fe3+And Cu2+
The preparation method is simple in preparation process, simple in reaction condition and environment-friendly, and the prepared aggregation-induced luminescent silver nanocluster has good aggregation-induced luminescent property, high fluorescence quantum yield, microsecond-level long service life and high content of Ag (I). The aggregation-induced luminescent silver nanocluster prepared by the invention can be used for detecting tetracycline.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement or combination made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (3)

1. A preparation method of aggregation-induced luminescent silver nanoclusters is characterized by comprising the following steps: mixing 5-17.5 parts by volume of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20 parts by volume of 2.5mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 60-80 ℃, refluxing for 12-48h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanoclusters.
2. The method for preparing aggregation-induced luminescent silver nanoclusters according to claim 1, comprising the steps of: mixing 5-12.5 parts by volume of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20 parts by volume of 2.5mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 70-80 ℃, refluxing for 12-36h, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanoclusters.
3. The method for preparing aggregation-induced luminescent silver nanoclusters according to claim 1 or 2, comprising the steps of: mixing 5 parts by volume of 20mmol/L N-acetyl-L-cysteine aqueous solution and 20 parts by volume of 2.5mmol/L silver nitrate solution, uniformly stirring the mixed solution, controlling the heating temperature to be 80 ℃ and refluxing for 24 hours, cooling, taking out, and freeze-drying to obtain the aggregation-induced luminescent silver nanocluster.
CN201910888226.2A 2019-09-19 2019-09-19 Preparation method and application of aggregation-induced luminescent silver nanocluster Active CN110591702B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910888226.2A CN110591702B (en) 2019-09-19 2019-09-19 Preparation method and application of aggregation-induced luminescent silver nanocluster

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910888226.2A CN110591702B (en) 2019-09-19 2019-09-19 Preparation method and application of aggregation-induced luminescent silver nanocluster

Publications (2)

Publication Number Publication Date
CN110591702A CN110591702A (en) 2019-12-20
CN110591702B true CN110591702B (en) 2021-07-27

Family

ID=68861313

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910888226.2A Active CN110591702B (en) 2019-09-19 2019-09-19 Preparation method and application of aggregation-induced luminescent silver nanocluster

Country Status (1)

Country Link
CN (1) CN110591702B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111606932A (en) * 2020-06-28 2020-09-01 浙江师范大学 Forty-five-core silver nanocluster with metal core containing chlorine ions and synthesis method thereof
CN112916863B (en) * 2021-01-19 2022-05-20 山西大学 Water-soluble luminescent silver nanocluster and preparation method and application thereof
CN113237934B (en) * 2021-05-24 2024-04-09 常州大学 Chiral silver sulfide quantum dot/few-layer carbon nitride compound capable of being used for electrochemiluminescence chiral recognition and preparation method thereof
CN114558569B (en) * 2022-01-27 2023-06-16 山西大学 Gold-silver bimetallic nanocluster and preparation method and application thereof
CN116463118B (en) * 2023-03-15 2024-01-30 河南大学 Silver cluster with aggregation-induced emission effect and preparation method and application thereof
CN117025209B (en) * 2023-08-09 2024-02-09 湖北大学 Orange silver fluorescent probe for detecting tetracycline antibiotics and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103822889A (en) * 2014-01-15 2014-05-28 江南大学 Colorimetric detection method for Cl<->, Br<-> and I<-> based on silver nano-cluster hydrogel
CN104227013A (en) * 2014-09-13 2014-12-24 福建医科大学 N-acetyl-L-cysteine-gold nanocluster fluorescent material and preparation method thereof
CN107375993A (en) * 2017-08-15 2017-11-24 重庆科技学院 A kind of preparation method of copper silver nanoclusters composite aquogel
CN108372312A (en) * 2018-03-23 2018-08-07 山西大学 A kind of green fluorescence ag nano-cluster and the preparation method and application thereof
CN108992464A (en) * 2018-09-30 2018-12-14 苏州大学 A kind of polypeptide-ag nano-cluster compound and the preparation method and application thereof
CN109810694A (en) * 2019-01-23 2019-05-28 山西大学 A kind of water-soluble copper namo fluorescence probe and the preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103822889A (en) * 2014-01-15 2014-05-28 江南大学 Colorimetric detection method for Cl<->, Br<-> and I<-> based on silver nano-cluster hydrogel
CN104227013A (en) * 2014-09-13 2014-12-24 福建医科大学 N-acetyl-L-cysteine-gold nanocluster fluorescent material and preparation method thereof
CN107375993A (en) * 2017-08-15 2017-11-24 重庆科技学院 A kind of preparation method of copper silver nanoclusters composite aquogel
CN108372312A (en) * 2018-03-23 2018-08-07 山西大学 A kind of green fluorescence ag nano-cluster and the preparation method and application thereof
CN108992464A (en) * 2018-09-30 2018-12-14 苏州大学 A kind of polypeptide-ag nano-cluster compound and the preparation method and application thereof
CN109810694A (en) * 2019-01-23 2019-05-28 山西大学 A kind of water-soluble copper namo fluorescence probe and the preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Colorimetric detection of iron ions (III) based on the highly sensitive plasmonic response of the N-acetyl-L-cysteine-stabilized silver nanoparticles;Xiaohui Gao等;《Analytica Chimica Acta》;20150403;第879卷;第118-125页 *
Valence States Effect on Electrogenerated Chemiluminescence of Gold Nanocluster;Huaping Peng等;《ACS Appl.Mater.Interfaces》;20170411;第9卷;第14929-14934页 *

Also Published As

Publication number Publication date
CN110591702A (en) 2019-12-20

Similar Documents

Publication Publication Date Title
CN110591702B (en) Preparation method and application of aggregation-induced luminescent silver nanocluster
Liu et al. Highly fluorescent Ag nanoclusters: microwave-assisted green synthesis and Cr3+ sensing
Shang et al. Microwave-assisted rapid synthesis of luminescent gold nanoclusters for sensing Hg 2+ in living cells using fluorescence imaging
Sun et al. Synthesis of thiolated Ag/Au bimetallic nanoclusters exhibiting an anti-galvanic reduction mechanism and composition-dependent fluorescence
CN108372312B (en) Green fluorescent silver nanocluster and preparation method and application thereof
Chen et al. Functionalized CdS quantum dots-based luminescence probe for detection of heavy and transition metal ions in aqueous solution
Bo et al. A new determining method of copper (II) ions at ng ml− 1 levels based on quenching of the water-soluble nanocrystals fluorescence
Sotelo-Gonzalez et al. Mn-doped ZnS quantum dots for the determination of acetone by phosphorescence attenuation
Wang et al. One-step hydrothermal synthesis of thioglycolic acid capped CdS quantum dots as fluorescence determination of cobalt ion
Amjadi et al. Gold nanostar-enhanced chemiluminescence probe for highly sensitive detection of Cu (II) ions
Desai et al. Fluorescence enhancement of bovine serum albumin gold nanoclusters from La3+ ion: detection of four divalent metal ions (Hg2+, Cu2+, Pb2+ and Cd2+)
WO2020147753A1 (en) Preparation of metal nanocluster wrapped with sericin protein and fluorescence probe
CN110862820A (en) Preparation method and application of cysteine-gold nanocluster
Wang et al. A simple and sensitive assay of gallic acid based on localized surface plasmon resonance light scattering of silver nanoparticles through modified Tollens process
CN108500286A (en) A kind of preparation method of novel fluorescence gold nano cluster
Lan et al. One-pot hydrothermal synthesis of orange fluorescent silver nanoclusters as a general probe for sulfides
Lian et al. Copper nanoclusters as a turn-on fluorescent probe for sensitive and selective detection of quinolones
CN109307664A (en) The fluorescent detection probe of metal ion in a kind of detectable living cells
CN101851502B (en) Ru(bpy)3-doped Ag@SiO2 fluorescent nano particles and preparation method thereof
Zhang et al. Synthesis of Ag nanoclusters by a pH-dependent etching method in aqueous solution
Jana et al. Fluorescence enhancement via varied long-chain thiol stabilized gold nanoparticles: A study of far-field effect
CN101186815A (en) Preparation method for fluorescence metal nano particles
CN106520126B (en) Mercury ion probe and its synthetic method based on Doped ions luminous mechanism and application
Jiang et al. A rhodamine-based sensing probe excited by upconversion NaYF4: Yb3+/Er3+ nanoparticles: the realization of simple Cu (II) detection with high sensitivity and unique selectivity
Cruz Enríquez et al. Enhanced resonance light scattering properties of gold nanoparticles due to cooperative binding

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant