CN109054812B - Method for preparing near-infrared two-region fluorescent silver sulfide quantum dots in water phase - Google Patents
Method for preparing near-infrared two-region fluorescent silver sulfide quantum dots in water phase Download PDFInfo
- Publication number
- CN109054812B CN109054812B CN201810977601.6A CN201810977601A CN109054812B CN 109054812 B CN109054812 B CN 109054812B CN 201810977601 A CN201810977601 A CN 201810977601A CN 109054812 B CN109054812 B CN 109054812B
- Authority
- CN
- China
- Prior art keywords
- cationic surfactant
- infrared
- silver sulfide
- quantum dots
- sulfide quantum
- 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
Links
Images
Classifications
-
- 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
- C09K11/582—Chalcogenides
-
- 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
- B82Y40/00—Manufacture or treatment of nanostructures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase, which comprises the following steps: the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; step three: and (4) heating the solution obtained in the step two to 35-100 ℃, and reacting to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution. The invention has the advantages that: the preparation method is simple, the conditions are mild, the inert gas protection is not needed, the repeatability is good, the amplification is easy, and the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance and high fluorescence intensity in a near-infrared two-region.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a method for directly preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase.
Background
Due to the characteristics of low price, simple and convenient operation, real-time imaging and the like, optical imaging becomes an important tool for life science research and medical application. The conventional near-infrared fluorescent probe is usually located in the near-infrared region, and the fluorescence emission wavelength is less than 1000 nm. Since the autofluorescence of the living body and the scattering of light by the biological tissue increase with the decrease of the wavelength, although the fluorescent probes in the near infrared region can achieve a better tissue penetration depth to some extent, the imaging result has a poor spatial resolution capability, and is easily interfered by the autofluorescence of the living body, so the application in the field of medical imaging is limited. And the fluorescence imaging of the near-infrared two-region (1000-1700nm) can greatly reduce the spontaneous fluorescence and the scattering of the living body, thereby improving the quality of optical imaging.
The development of imaging technology relies on the development of contrast agents, and there are mainly five classes of near-infrared two-region-emitting fluorescent contrast agents reported at present: small molecular probes, conjugated polymers, quantum dots, single-walled carbon nanotubes and rare earth nanoparticles. The quantum dot probe has the advantages of good stability, high fluorescence quantum yield and the like, and has great advantages when being used as a near-infrared two-region probe. Among various quantum dots, silver sulfide quantum dots have the advantage of good biocompatibility compared with other heavy metal quantum dots such as lead sulfide quantum dots, and have been widely used in animal experiments.
The synthesis of fluorescent silver sulfide quantum dots is generally carried out in an organic phase, and an organic complex of silver is heated at a high temperature in an oil phase or alkyl mercaptan, so that the silver sulfide quantum dots are obtained. The silver sulfide obtained in this way is hydrophobic and needs to be transferred to the aqueous phase by various means for further use, and its colloidal stability in water is still difficult to guarantee. At present, few reports exist on the method for directly preparing the silver sulfide quantum dots in the water phase, the fluorescence quantum yield of the prepared quantum dots is low, and the fluorescence emission wavelength is usually less than 1000 nm. Therefore, the development of a water phase preparation technology is very important for preparing the silver sulfide quantum for near-infrared two-region luminescence.
Disclosure of Invention
The invention aims to provide a method for directly preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase manner, which has the advantages of simple preparation method, mild conditions, no need of inert gas protection, good repeatability and easiness in amplification, and the prepared silver sulfide quantum dots have the advantages of good water solubility, photobleaching resistance, high near-infrared two-zone fluorescence intensity and the like.
In order to achieve the purpose, the invention adopts the following technical scheme: the method for preparing the near-infrared two-zone fluorescent silver sulfide quantum dots in the water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring;
step three: and (4) heating the solution obtained in the step two to 35-100 ℃, and reacting to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
Further, the method for preparing the near-infrared two-region fluorescent silver sulfide quantum dots in the water phase comprises the following steps: in the first step, the cationic surfactant is any one of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride and dihexadecyl dimethyl ammonium bromide.
Further, the method for preparing the near-infrared two-region fluorescent silver sulfide quantum dots in the water phase comprises the following steps: in the first step, the concentration of the cationic surfactant is 0.55-100 mM.
Further, the method for preparing the near-infrared two-region fluorescent silver sulfide quantum dots in the water phase comprises the following steps: in the second step, the molar ratio of the sodium sulfide to the silver nitrate is 0.125: 1-1: 1.
Further, the method for preparing the near-infrared two-region fluorescent silver sulfide quantum dots in the water phase comprises the following steps: in the second step, the concentration of sodium sulfide is 0.05-3 mM.
Further, the method for preparing the near-infrared two-region fluorescent silver sulfide quantum dots in the water phase comprises the following steps: in the third step, the reaction time is 5 min-2 h.
Through the implementation of the technical scheme, the invention has the beneficial effects that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
Drawings
Fig. 1 is a transmission electron microscope image of silver sulfide quantum dots according to an embodiment of the present invention.
Fig. 2 shows the absorption and emission spectra of silver sulfide quantum dots according to an embodiment of the present invention.
Fig. 3 is an absorption and emission spectrum of silver sulfide quantum dots obtained in the fourth embodiment of the present invention.
Fig. 4 is an absorption and emission spectrum of silver sulfide quantum dots obtained in the fifth embodiment of the present invention.
Fig. 5 is an absorption and emission spectrum of silver sulfide quantum dots obtained in the first embodiment of the present invention.
Fig. 6 is an absorption and emission spectrum of silver sulfide quantum dots obtained in the twelfth embodiment of the invention.
Fig. 7 is an absorption and emission spectrum of silver sulfide quantum dots obtained in the thirteenth embodiment of the invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are only used to more clearly illustrate the technical solutions of the present invention, and should not be taken as limiting the scope of the present invention.
The first embodiment is as follows:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is cetyl trimethyl ammonium bromide; the concentration of the cationic surfactant was 1.1 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that the particle size of the obtained silver sulfide quantum dot is less than 10nm as shown in figure 1, the absorption spectrum has no obvious characteristic peak as shown in figure 2, the absorbance is gradually reduced along with the increase of the wavelength, an obvious fluorescence emission peak exists at 1250nm under the excitation of light of 808nm, and the intensity value is high.
The second embodiment is as follows:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is cetyl trimethyl ammonium bromide; the concentration of the cationic surfactant is 100 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that after the concentration of the hexadecyl trimethyl ammonium bromide is greatly increased, the absorption spectrum of the obtained silver sulfide quantum dot is not changed greatly, but the fluorescence emission intensity is greatly reduced.
The third concrete embodiment:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is cetyl trimethyl ammonium bromide; the concentration of the cationic surfactant was 0.55 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that after the concentration of the hexadecyl trimethyl ammonium bromide is reduced, the absorption spectrum of the obtained silver sulfide quantum dot is not changed greatly, but the fluorescence emission intensity is obviously reduced, and the repeatability of the obtained sample is poor. The fourth concrete embodiment:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is cetyl trimethyl ammonium bromide; the concentration of the cationic surfactant was 1.1 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 1: 1; the concentration of sodium sulfide is 2 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that, as shown in fig. 3, after the concentration of sodium sulfide in the reaction system is increased, the absorption spectrum of the obtained silver sulfide quantum dot is not changed greatly, but the fluorescence emission intensity is greatly reduced.
The fifth concrete embodiment:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is cetyl trimethyl ammonium bromide; the concentration of the cationic surfactant is 100 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.25: 1; the concentration of sodium sulfide is 0.5 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that, as shown in fig. 4, after the concentration of sodium sulfide in the reaction system is reduced, the absorbance of the obtained silver sulfide quantum dots is reduced, and the fluorescence emission intensity is also obviously reduced.
The sixth specific embodiment:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is decacetyl trimethyl ammonium bromide; the concentration of the cationic surfactant was 1.1 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 100 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that the absorbance of the obtained silver sulfide quantum dots is improved compared with that of the silver sulfide quantum dots in example 1, but the fluorescence emission intensity is reduced.
The seventh specific embodiment:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is cetyl trimethyl ammonium bromide; the concentration of the cationic surfactant was 1.1 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 35 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that the absorbance of the obtained silver sulfide quantum dots is reduced compared with that of the silver sulfide quantum dots in the embodiment 1, and the fluorescence emission intensity is also obviously reduced.
The eighth embodiment:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is cetyl trimethyl ammonium bromide; the concentration of the cationic surfactant was 1.1 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 2 hours to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that the absorption and emission properties of the obtained silver sulfide quantum dots are similar to those of the first embodiment.
The specific embodiment is nine:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is cetyl trimethyl ammonium bromide; the concentration of the cationic surfactant was 1.1 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 5min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
Experiment results show that the absorption and emission properties of the obtained silver sulfide quantum dots are similar to those of the first embodiment, and the influence of the reaction time on the properties of the obtained silver sulfide quantum dots is small.
The specific embodiment ten:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is dodecyl trimethyl ammonium bromide; the concentration of the cationic surfactant was 1.1 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that, as shown in fig. 5, the short-chain cationic surfactant cannot stabilize the silver sulfide quantum dots well under the same concentration, and the obtained silver sulfide quantum dots are relatively turbid and have very weak fluorescence intensity.
The first specific embodiment:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is dodecyl trimethyl ammonium bromide; the concentration of the cationic surfactant is 11 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
Experimental results show that the short-chain cationic surfactant can well stabilize the silver sulfide quantum dots at a higher concentration, and the obtained silver sulfide quantum dots are clear and transparent and have better fluorescence emission intensity.
The specific example twelve:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is octadecyl trimethyl ammonium bromide; the concentration of the cationic surfactant was 1.1 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental result shows that, as shown in fig. 6, under the same concentration, increasing the length of the alkyl chain in the cationic surfactant has less influence on the absorption spectrum of the obtained silver sulfide quantum dot, but the fluorescence intensity of the silver sulfide quantum dot is improved compared with that of the silver sulfide quantum dot in example 1.
The specific example thirteen:
a method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then reducing the temperature of an aqueous solution of the cationic surfactant to 25-35 ℃; wherein the cationic surfactant is hexadecyl trimethyl ammonium chloride; the concentration of the cationic surfactant was 1.1 mM;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring; wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.45: 1; the concentration of sodium sulfide is 0.9 mM;
step three: and (4) heating the solution obtained in the step two to 90 ℃, and reacting for 30min to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
The invention has the advantages that: according to the invention, the silver sulfide quantum dots with high near-infrared two-zone fluorescence quantum efficiency are directly prepared in the water phase under the conditions of different temperatures and different raw material ratios by using the cationic surfactant as the stabilizer, high temperature and high pressure are not required, and organic solvents and inert gases are not required for protection, so that the defect that most of the traditional silver sulfide quantum dots are prepared at high temperature in the organic phase is overcome, the prepared silver sulfide quantum dots have good water solubility, photobleaching resistance, stable properties, long-time storage and high near-infrared two-zone fluorescence intensity, and various biomolecules containing sulfydryl can be modified on the surface to be used for constructing the target probe; the preparation method is simple, short in preparation period, mild in condition, good in repeatability and easy to amplify and popularize.
The experimental results show that, as shown in fig. 7, under the condition that the lengths of alkyl chains in the surfactant are the same, the change of the anionic species has less influence on the optical properties of the obtained silver sulfide quantum dots, and the absorption and emission spectra are similar to those of the first example.
Claims (4)
1. A method for preparing near-infrared two-zone fluorescent silver sulfide quantum dots in a water phase is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: firstly, adding a cationic surfactant into water, heating until the cationic surfactant is completely dissolved, and then cooling the aqueous solution of the cationic surfactant to 25-35 ℃;
wherein the cationic surfactant is any one of cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and dicetyl dimethyl ammonium bromide;
step two: slowly adding a sodium sulfide solution into the cationic surfactant aqueous solution obtained in the step one, uniformly stirring, and then adding a silver nitrate solution, and uniformly stirring;
wherein the molar ratio of the sodium sulfide to the silver nitrate is 0.125: 1-1: 1;
step three: and (4) heating the solution obtained in the step two to 35-100 ℃, and reacting to obtain the near-infrared two-zone fluorescent silver sulfide quantum dot aqueous solution.
2. The method for preparing the near-infrared two-zone fluorescent silver sulfide quantum dot in the water phase according to claim 1, wherein the method comprises the following steps: in the first step, the concentration of the cationic surfactant is 0.55-100 mM.
3. The method for preparing the near-infrared two-zone fluorescent silver sulfide quantum dot in the water phase according to claim 1, wherein the method comprises the following steps: in the second step, the concentration of sodium sulfide is 0.05-3 mM.
4. The method for preparing the near-infrared two-zone fluorescent silver sulfide quantum dot in the water phase according to claim 1, wherein the method comprises the following steps: in the third step, the reaction time is 5 min-2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810977601.6A CN109054812B (en) | 2018-08-24 | 2018-08-24 | Method for preparing near-infrared two-region fluorescent silver sulfide quantum dots in water phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810977601.6A CN109054812B (en) | 2018-08-24 | 2018-08-24 | Method for preparing near-infrared two-region fluorescent silver sulfide quantum dots in water phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109054812A CN109054812A (en) | 2018-12-21 |
| CN109054812B true CN109054812B (en) | 2021-06-22 |
Family
ID=64757058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810977601.6A Active CN109054812B (en) | 2018-08-24 | 2018-08-24 | Method for preparing near-infrared two-region fluorescent silver sulfide quantum dots in water phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109054812B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609118A (en) * | 2019-01-23 | 2019-04-12 | 南京邮电大学 | A kind of method that mercapto-polyglycol auxiliary prepares silver sulfide quantum dot |
| CN113004889A (en) * | 2021-03-09 | 2021-06-22 | 大连民族大学 | Method for synthesizing near-infrared fluorescence/photothermal/photoacoustic silver sulfide quantum dots |
| CN114702957B (en) * | 2022-04-27 | 2023-10-27 | 东北林业大学 | Preparation of bismuth-doped silver sulfide quantum dot with near infrared two-region fluorescence/photo-thermal property |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887719A (en) * | 2006-07-14 | 2007-01-03 | 哈尔滨师范大学 | Synthesis process of nanometer silver sulfide/copper sulfide in controlled shape |
| CN102701264A (en) * | 2012-04-19 | 2012-10-03 | 吉林大学 | Combining method of Ag2S photoelectric detection material |
| CN102718248A (en) * | 2012-06-13 | 2012-10-10 | 吉林大学 | Method for preparing silver sulfide nanocrystalline with near infrared fluorescence using one-step aqueous phase process |
| CN103991895A (en) * | 2014-05-23 | 2014-08-20 | 南京师范大学 | Preparation method of aptamer-induced Ag2S quantum dots |
| CN106544014A (en) * | 2016-09-22 | 2017-03-29 | 北京化工大学 | A kind of aqueous phase preparation method of ruddiness silver sulfide quantum dot |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277157B (en) * | 2011-05-30 | 2014-06-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Near-infrared silver sulphide quantum dot as well as preparation method and application thereof |
-
2018
- 2018-08-24 CN CN201810977601.6A patent/CN109054812B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887719A (en) * | 2006-07-14 | 2007-01-03 | 哈尔滨师范大学 | Synthesis process of nanometer silver sulfide/copper sulfide in controlled shape |
| CN102701264A (en) * | 2012-04-19 | 2012-10-03 | 吉林大学 | Combining method of Ag2S photoelectric detection material |
| CN102718248A (en) * | 2012-06-13 | 2012-10-10 | 吉林大学 | Method for preparing silver sulfide nanocrystalline with near infrared fluorescence using one-step aqueous phase process |
| CN103991895A (en) * | 2014-05-23 | 2014-08-20 | 南京师范大学 | Preparation method of aptamer-induced Ag2S quantum dots |
| CN106544014A (en) * | 2016-09-22 | 2017-03-29 | 北京化工大学 | A kind of aqueous phase preparation method of ruddiness silver sulfide quantum dot |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of faceted and cubic Ag2S nanocrystals in aqueous solutions;Lihong Dong等;《Journal of Colloid and Interface Science》;20070925;第317卷;第485-492页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109054812A (en) | 2018-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109054812B (en) | Method for preparing near-infrared two-region fluorescent silver sulfide quantum dots in water phase | |
| Wei et al. | Non-enzymatic-browning-reaction: a versatile route for production of nitrogen-doped carbon dots with tunable multicolor luminescent display | |
| Dong et al. | Polyol-mediated C-dot formation showing efficient Tb 3+/Eu 3+ emission | |
| Wang et al. | Microwave assisted one-step green synthesis of cell-permeable multicolor photoluminescent carbon dots without surface passivation reagents | |
| Wang et al. | Oxygen/nitrogen-related surface states controlled carbon nanodots with tunable full-color luminescence: Mechanism and bio-imaging | |
| CN103663412A (en) | Preparation method of carbon quantum dots with adjustable fluorescence colors | |
| CN103232029B (en) | Preparation method and application of green fluorescent carbon dots | |
| Hallaji et al. | Recent advances in the rational synthesis of red-emissive carbon dots for nanomedicine applications: A review | |
| CN102031110A (en) | InP/ZnS core-shell structure quantum dot and preparation method thereof | |
| CN104083771A (en) | Fluorescence resonance energy transfer-based tumor imaging and therapeutic targeting system and construction method thereof | |
| CN111303879B (en) | Efficient single-spectrum band-up-conversion red light nanocrystalline material | |
| CN109423282A (en) | A kind of synthetic method and application of N doping water-solubility fluorescent carbon quantum dot | |
| CN103112882B (en) | Preparation method of targeting near-infrared NaYF4 up-conversion nanocrystal | |
| CN114455567B (en) | Preparation method and application of carbon nano particles | |
| CN103896251A (en) | Preparation method of water-soluble carbon quantum dot biological developing agent | |
| Guo et al. | Novel fluorescence probe based on bright emitted carbon dots for ClO− detection in real water samples and living cells | |
| Gencer et al. | Triggering excitation independent fluorescence in zinc (II) incorporated carbon dots: Surface passivation of carbon dots with zinc (II) ions by microwave assisted synthesis methods | |
| Liao et al. | NIR-II emissive properties of 808 nm-excited lanthanide-doped nanoparticles for multiplexed in vivo imaging | |
| CN110041923B (en) | Preparation method and application of fluorescent carbon quantum dots Phe-CDs | |
| Cheng et al. | In vivo optical bioimaging by using Nd-doped LaF3 luminescent nanorods in the second near-infrared window | |
| CN114015441A (en) | Green solid fluorescent carbon dot and preparation method thereof | |
| Li et al. | Highly stable green and red up-conversion of LiYF4: Yb3+, Ho3+ for potential application in fluorescent labeling | |
| Huang et al. | Transient energy trapping as a size-conserving surface passivation strategy for producing bright ultrasmall upconversion nanoprobes | |
| CN107529514B (en) | Preparation method and application of fluorine ion-doped carbon dots | |
| Mozdbar et al. | The effect of precursor on the optical properties of carbon quantum dots synthesized by hydrothermal/solvothermal method |
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 |