CN117384640A - Silver chalcogenide quantum dot and water phase synthesis method thereof - Google Patents
Silver chalcogenide quantum dot and water phase synthesis method thereof Download PDFInfo
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- CN117384640A CN117384640A CN202311292050.7A CN202311292050A CN117384640A CN 117384640 A CN117384640 A CN 117384640A CN 202311292050 A CN202311292050 A CN 202311292050A CN 117384640 A CN117384640 A CN 117384640A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 title claims description 81
- 239000004332 silver Substances 0.000 title claims description 75
- -1 Silver chalcogenide Chemical class 0.000 title claims description 68
- 238000001308 synthesis method Methods 0.000 title abstract description 5
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- 239000000243 solution Substances 0.000 claims description 81
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
- A61K49/0065—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle
- A61K49/0067—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle quantum dots, fluorescent nanocrystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- 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
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention relates to the technical field of quantum dot regulation and control, and provides a silver-chalcogen quantum dot and a water phase synthesis method thereof. Due to the good near infrared two-region fluorescence performance and the good stability in the complex digestive tract, the whole digestive tract organ of the mouse can be imaged.
Description
Technical Field
The invention relates to the technical field of quantum dot regulation and control, in particular to a silver-chalcogenide quantum dot and a water phase synthesis method thereof.
Background
Compared with a noninvasive gastrointestinal tract imaging method, namely an X-ray barium meal method, the near infrared two-region (NIR-II, 1000-1700 nm) fluorescent imaging technology has high sensitivity and high space-time resolutionThe method has the advantages of high rate and high fidelity, and can provide supplementary and detailed information for diagnosis of gastrointestinal diseases. Among them, NIR-II quantum dots are one of the most promising fluorescent materials due to their tunable size dependence on narrow emission, broad absorption, excellent light stability, and ease of functionalization. Silver chalcogenide quantum dots (Ag) with narrow band gap 2 S，Ag 2 Se and Ag 2 Te, etc.) are considered to be a more attractive option for NIR-II fluorescence bioimaging because of their low toxicity and wavelength regulatory range which can cover the near-infrared-region, or even the mid-infrared band.
Currently, silver chalcogenide quantum dots have been widely used for near infrared fluorescence imaging of organs such as living liver, lung and kidney. However, the strongly acidic, complex and enzymatic biological microenvironment of the gastrointestinal tract may result in the fluorescence attenuation or aggregation of most NIR-II quantum dots. Thus, studies on NIR-II fluorescence imaging of the gastrointestinal tract using NIR-II quantum dots have been rarely reported. Gastrointestinal NIR-II fluorescence imaging requires quantum dots as contrast agents that emit in the NIR-II band and are stable.
The optical properties of quantum dots are highly dependent on their size and surface structure. Therefore, the successful synthesis of the acid-resistant and fluorescent-good NIR-II silver chalcogenide quantum dots for gastrointestinal imaging requires precise control of their size, i.e., the growth process of the quantum dots during synthesis, and better passivation of the surface of the quantum dots to enable their surface structure to resist the destruction of complex gastrointestinal environments. However, due to the high reactivity of chalcogen precursor and silver chalcogenide (Ag 2 S、Ag 2 Se and Ag 2 Te), it is difficult to continuously control the emission wavelength of silver-chalcogen quantum dots in the water phase synthesis in an accurate and controllable manner, and meanwhile, it is still a difficult problem to directly synthesize the water phase silver-chalcogen quantum dots emitted in the NIR-II band. In addition, as the size of silver chalcogenide quantum dots increases, the density of surface ligands decreases significantly, resulting in low quantum yield and poor stability of long wavelength silver chalcogenide quantum dots synthesized in aqueous phase. The near infrared two-region bare nuclear quantum dots reported at present are difficult to be used for realizing near infrared two-region fluorescence imaging of gastrointestinal tracts.
Disclosure of Invention
The present invention is directed to solving at least one of the technical problems existing in the related art. Therefore, the invention provides a method for synthesizing silver-chalcogen quantum dots by using water phase, which comprises the following steps:
s1: preparing a chalcogen anion precursor solution under the condition that the pH value is 2-5;
s2: and adding the silver precursor solution into the chalcogen anion precursor solution to react to obtain the silver chalcogenide quantum dots.
According to the method for synthesizing silver chalcogenide quantum dots by using the water phase, the step S1 comprises the following steps:
s11: placing a reducing agent into ultrapure water, stirring to obtain a first mixed solution, and adjusting the pH value of the first mixed solution to 2-5;
s12: adding a first material into the first mixed solution in an inert gas atmosphere to obtain a second mixed solution, and placing the second mixed solution into a constant-temperature shaking incubator with the rotating speed of 30-6000 rpm for reaction for 2-120 min at the temperature of 5-50 ℃ to obtain a third mixed solution;
wherein the first material comprises one of a sulfur source, a selenium source or a tellurium source;
s13: and adding a reducing agent into the third mixed solution, and continuing to perform oscillation reaction for 10-60 s to obtain a chalcogen anion precursor solution.
According to the method for synthesizing silver-chalcogen quantum dots in the aqueous phase, the reducing agent is one of GSH, sodium borohydride, vitamin C or hydrazine hydrate.
According to the method for synthesizing the silver-chalcogen quantum dots by the aqueous phase, the molar ratio of the reducing agent in the step S11 to the reducing agent in the step S12 to the reducing agent in the step S13 is 1:1:1-8:1:1.
According to the method for synthesizing silver chalcogenide quantum dots by using the water phase, the step S2 comprises the following steps:
s21: deoxidizing ultrapure water for 10-420 min in an inert gas atmosphere, and then adjusting the pH value of the ultrapure water to 2-5 at 55-100 ℃;
s22: adding the chalcogen anion precursor solution into ultrapure water, and stirring to obtain a fourth mixed solution;
s23: and adding GSH into the silver salt water solution, stirring to obtain silver precursor solution, adding the silver precursor solution into the fourth mixed solution, and stirring at 50-100 ℃ to obtain the silver chalcogenide quantum dots.
According to the method for synthesizing silver chalcogenide quantum dots by using the aqueous phase, the molar ratio of GSH to silver salt aqueous solution in the step S23 is 1:1-20:1.
The invention also provides a silver chalcogenide quantum dot synthesized by the method for synthesizing the silver chalcogenide quantum dot by the water phase.
According to the silver chalcogenide quantum dot provided by the invention, the silver chalcogenide quantum dot is Ag 2 S quantum dot, ag 2 Se quantum dots or Ag 2 One of the Te quantum dots.
According to the silver-chalcogenide quantum dots provided by the invention, the molar ratio of silver to chalcogen element of the silver-chalcogenide quantum dots is greater than 2:1, a step of; the ligand density of GSH on the surface of the silver chalcogenide quantum dot is 1-8 GSH/nm 2 。
According to the silver chalcogenide quantum dots provided by the invention, the silver chalcogenide quantum dots are applied to near infrared fluorescence imaging of gastrointestinal tracts.
The above technical solutions in the embodiments of the present invention have at least one of the following technical effects:
1. according to the method for synthesizing the silver chalcogenide quantum dots by the aqueous phase, the acid-resistant silver chalcogenide quantum dots are controllably synthesized under the acidic condition, the continuous adjustability of the emission wavelength of the silver chalcogenide quantum dots in a wider range is realized by controlling the synthesis time of the precursor, and the synthesized silver chalcogenide quantum dots are rich in silver on the surfaces and have higher surface ligand density, and have higher colloid stability and fluorescence stability.
2. The silver chalcogenide quantum dot provided by the invention is rich in cations on the surface, and the molar ratio of the cations to anions on the surface is greater than the stoichiometric ratio of 2:1, and has higher ligand density, and the ligand density of GSH on the surface of the silver-chalcogenide quantum dot is 1-8 GSH/nm 2 Not only can resist strongThe acidic environment keeps the stability of the structure and the optical property, thereby being capable of showing consistent fluorescence and colloid stability for a long time in gastric acid simulated liquid and phosphate buffer liquid and not generating agglomeration phenomenon.
3. The silver chalcogenide quantum dot provided by the invention can image the whole digestive tract organ of a mouse due to the good near infrared two-region fluorescence performance and the good stability in the complex digestive tract.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows Ag obtained by the reaction of example 1 according to this invention 2 Emission spectrum diagram of Se quantum dots.
FIG. 2 shows Ag obtained by the reaction at different times in example 1 provided by the present invention 2 Transmission electron microscope image of Se quantum dots.
FIG. 3 shows Ag obtained by the reaction of example 1 according to this invention 2 And counting the corresponding particle size distribution of the Se quantum dots by using a transmission electron microscope image.
FIG. 4 shows an Ag film according to this invention 2 Stability comparison graph of Se quantum dots under different pH conditions.
FIG. 5 shows an Ag film according to this invention 2 And comparing the stability of Se quantum dots at different times under the condition of containing high-concentration hydrogen ions.
FIG. 6 shows an Ag film according to this invention 2 The Se quantum dots were dispersed at surface potentials in PBS and 0.1M HCl aqueous solution, respectively.
FIG. 7 shows Ag obtained in comparative examples 1 to 4 and example 1 provided by the present invention 2 Fluorescence and colloidal stability of Se quantum dots in PBS and SGJ.
FIG. 8 shows the Ag obtained in comparative examples 1 to 4 and example 1 provided by the present invention after 12 hours 2 Fluorescence and colloidal stability of Se quantum dots in PBS and SGJ.
FIG. 9 is a diagram of comparative examples 1-4 and Ag obtained in example 1 provided by the present invention 2 Dispersion of Se quantum dots in PBS and SGJ.
FIG. 10 shows an Ag film according to this invention 2 Se quantum dots are in a near infrared two-region fluorescence imaging diagram of the gastrointestinal tract of the mouse.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The following examples are illustrative of the invention but are not intended to limit the scope of the invention.
Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the embodiments of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The following describes a method for synthesizing silver chalcogenide quantum dots by using water phase in combination with fig. 1 to 10:
the invention provides a method for synthesizing silver-chalcogen quantum dots by using a water phase, which comprises the following steps:
s1: preparing a chalcogen anion precursor solution under the condition that the pH value is 2-5;
s2: and adding the silver precursor solution into the chalcogen anion precursor solution to react to obtain the silver chalcogenide quantum dots.
According to the method for synthesizing silver chalcogenide quantum dots by using the water phase, the step S1 comprises the following steps:
s11: placing a reducing agent into ultrapure water, stirring to obtain a first mixed solution, and adjusting the pH value of the first mixed solution to 2-5;
s12: adding a first material into the first mixed solution in an inert gas atmosphere to obtain a second mixed solution, and placing the second mixed solution into a constant-temperature shaking incubator with the rotating speed of 30-6000 rpm for reaction for 2-120 min at the temperature of 5-50 ℃ to obtain a third mixed solution;
wherein the first material comprises one of a sulfur source, a selenium source or a tellurium source;
s13: and adding a reducing agent into the third mixed solution, and continuing to perform oscillation reaction for 10-60 s to obtain a chalcogen anion precursor solution.
Wherein the sulfur source comprises Na 2 S 2 O 3 Or Na (or) 2 S 2 O 4 Etc.; the selenium source comprises Na 2 S e O 3 Or Na (or) 2 SeO 4 Etc.; tellurium source includes Na 2 TeO 3 Or Na (or) 2 TeO 4 Etc.
Wherein the pH was adjusted using 1M trifluoroacetic acid solution.
The pH values of the first mixed solution, the second mixed solution and the third mixed solution are all 2-5.
Wherein, in the step S11, addThe purpose of the reducing agent is to reduce the sulfur, selenium or tellurium source in a higher valence state to a synthetic lower valence chalcogenide, e.g. to reduce Na by GSH 2 S e O 3 When it is first necessary to make S e O 3 2- Intermediate selenized oxidized glutathione (GSSeSG) necessary for reduction to selenium precursor selenized glutathione (GSSeH);
the purpose of the addition of the reducing agent in step S13 is to further reduce the lower chalcogenides to produce the anionic precursors, such as further reduction of GSSeSG with GSH to produce the reduction product selenium precursor GSSeH.
According to the method for synthesizing silver-chalcogen quantum dots in the aqueous phase, the reducing agent is one of GSH, sodium borohydride, vitamin C or hydrazine hydrate.
According to the method for synthesizing the silver-chalcogen quantum dots by the aqueous phase, the molar ratio of the reducing agent in the step S11 to the reducing agent in the step S12 to the reducing agent in the step S13 is 1:1:1-8:1:1.
According to the method for synthesizing silver chalcogenide quantum dots by using the water phase, the step S2 comprises the following steps:
s21: deoxidizing ultrapure water for 10-420 min in an inert gas atmosphere, and then adjusting the pH value of the ultrapure water to 2-5 at 55-100 ℃;
s22: adding the chalcogen anion precursor solution into ultrapure water, and stirring to obtain a fourth mixed solution;
s23: and adding GSH into the silver salt water solution, stirring to obtain silver precursor solution, adding the silver precursor solution into the fourth mixed solution, and stirring at 50-100 ℃ to obtain the silver chalcogenide quantum dots.
Wherein the aqueous silver salt solution comprises AgNO 3 、AgCH 3 COOH, agCl or other common silver salts.
Wherein, steps S21 and S22 are both performed at 75-100 ℃.
Wherein the pH was adjusted using 1M trifluoroacetic acid solution.
The GSH in step S23 acts as a ligand to serve as a surface ligand of the quantum dot synthesized later, so that the synthesized quantum dot can be well dispersed in an aqueous solution.
And (3) starting to add the silver salt aqueous solution into the fourth mixed solution in the step S23, sampling with time, quantitatively taking 200-1000 mu L of reaction liquid in each time point, placing the reaction liquid in a sample tube, and standing under an ice bath for sudden reaction. And after the sample is restored to room temperature, testing the emission wavelength of the obtained quantum dot and the average particle size of the corresponding silver chalcogenide quantum dot.
According to the method for synthesizing silver chalcogenide quantum dots by using the aqueous phase, the molar ratio of GSH to silver salt aqueous solution in the step S23 is 1:1-20:1.
The invention also provides a silver chalcogenide quantum dot synthesized by the method for synthesizing the silver chalcogenide quantum dot by the water phase.
According to the silver chalcogenide quantum dot provided by the invention, the silver chalcogenide quantum dot is Ag 2 S quantum dot, ag 2 Se quantum dots or Ag 2 One of the Te quantum dots.
According to the silver-chalcogenide quantum dots provided by the invention, the molar ratio of silver to chalcogen element of the silver-chalcogenide quantum dots is greater than 2:1, a step of; the ligand density of GSH on the surface of the silver chalcogenide quantum dot is 1-8 GSH/nm 2 。
Wherein Ag is 2 Se、Ag 2 S and Ag 2 The stoichiometric ratio of Te was 2:1 Ag provided by the invention 2 S quantum dot, ag 2 Se quantum dot and Ag 2 The molar ratio of cations to anions on the surface of the Te quantum dot is greater than 2: and 1, namely the silver chalcogenide quantum dot with the surface rich in cations.
According to the silver chalcogenide quantum dots provided by the invention, the silver chalcogenide quantum dots are applied to near infrared fluorescence imaging of gastrointestinal tracts.
The silver chalcogenide quantum dot is applied to near infrared fluorescence imaging of gastrointestinal tracts, and the imaging process is that capsules containing the silver chalcogenide quantum dot are swallowed by patients, and the good near infrared two-region fluorescence performance and the good stability of the silver chalcogenide quantum dot in complex digestive tracts can be relied on, so that the metabolic process of the silver chalcogenide quantum dot in the intestinal tracts can be detected.
Furthermore, after the silver chalcogenide quantum dots provided by the invention are subjected to functional modification, the silver chalcogenide quantum dots can be used for diagnosis of gastrointestinal diseases, such as in-situ specificity detection of gastric cancer and intestinal cancer, specificity marking of gastrointestinal flora (for example, stomach in-situ marking of helicobacter pylori or specific targeting marking of intestinal flora) and the like.
The following describes a method for synthesizing silver chalcogenide quantum dots in aqueous phase according to examples 1-8.
Example 1
Will be 1.32X10 -5 Mu mol GSH is dissolved by ultrapure water of 1mL, the pH value of the solution is regulated to 2-5 by using 1M trifluoroacetic acid solution, high-purity argon is introduced for 30min to deoxidize, and then 3.3X10 is added -6 Mu mol Na 2 SeO 3 Then the mixture is placed in a constant temperature shaking incubator at 37 ℃ and 180rpm for reaction for 10 min. Finally adding 3.3X10 -6 Mu mol GSH continued to react 30S.
40 Adding mL of ultrapure water into a three-neck flask, introducing high-purity argon gas for 30min for deoxidization, heating to 85 ℃, regulating the pH value of the solution to 2-5 by using 1M trifluoroacetic acid solution, adding the synthesized selenium precursor into a silver precursor, and adding 3.3X10 -5 Mu mol AgNO 3 The aqueous solution is added with 6.6X10 -6 After GSH of (C), the reaction temperature was rapidly lowered to 70℃to continue the reaction. Timing was started after mixing the silver-selenium precursor, samples were taken over time, 500 μl of reaction solution was metered into the sample tube at each time point and placed in an ice bath to quench the reaction.
After the sample was returned to room temperature, the emission of the quantum dots obtained by the reaction for 1min was measured at 620nm, as shown in FIG. 3, at QD 620 Corresponding to Ag 2 The average particle diameter of Se quantum dots is 0.980.28 nm. The same Ag can be obtained by doubling the reaction system 2 Se quantum dots.
When the reaction time is 30min, the Ag is obtained 2 Emission of Se quantum dots at 755nm,as shown in fig. 3, in QD 755 Corresponding to Ag 2 The average particle diameter of Se quantum dots is 1.210.34 nm。
When the reaction time is 1h, the Ag is obtained 2 The emission of Se quantum dots is 880nm, as shown in FIG. 3, at QD 880 Corresponding to Ag 2 The average particle diameter of Se quantum dots is 1.630.42 nm。
When the reaction time is 5h, the Ag is obtained 2 The emission of Se quantum dots is 970nm, as shown in FIG. 3, at QDs 970 Corresponding to Ag 2 The average particle diameter of Se quantum dots is 1.980.52 nm。
The reaction time is 10h, and the obtained Ag 2 The emission of Se quantum dots is 1065 and nm, as shown in FIG. 3, at QDs 1065 Corresponding to Ag 2 The average particle diameter of Se quantum dots is 2.250.62 nm。
As shown in fig. 1, it can be seen that the curves corresponding to reaction 1min, reaction 30min, reaction 1h, reaction 5h, and reaction 10h are respectively from left to right. The method for synthesizing silver-chalcogen quantum dots by using the water phase provided by the invention is illustrated, and Ag can be realized by controlling the synthesis time of precursors 2 The Se quantum dot is continuously adjustable in the emitting wavelength and has high stability.
As shown in fig. 2, from left to right, the emission wavelength was 620nm (QD 620 ) Ag obtained at the site 2 Transmission electron microscopy of Se quantum dots with emission wavelength of 755nm (QD 755 ) Ag obtained at the site 2 Transmission electron microscopy of Se quantum dots with an emission wavelength of 880nm (QD 880 ) Ag obtained at the site 2 Transmission electron microscopy of Se quantum dots at an emission wavelength of 970nm (QD 970 ) Ag obtained at the site 2 Transmission electron microscopy of Se quantum dots and emission wavelength of 1065nm (QD 1065 ) Ag obtained at the site 2 And a transmission electron microscope image of the Se quantum dot, wherein 20nm and 1nm are respectively a scale, and the electron microscope image shown under the scale of 1nm is an enlarged electron microscope image. According to FIG. 2, the present invention provides a water phase synthesis method for Ag 2 The method of Se quantum dots can realize Ag alignment 2 Regulating the size of Se quantum dots, and obtaining Ag 2 The Se quantum dots have uniform particle size and clear lattice structure.
Emission wavelength was 1065nm (QD 1065 ) Ag obtained at the site 2 The silver-selenium ratio of the Se quantum dots is 4:1, the density of surface ligand GSH is 4.7/nm 2 。
Example 2
Will be 1.32X10 -5 Dissolving μmol vitamin C in 1mL ultrapure water, regulating pH to 2-5 with 1M trifluoroacetic acid solution, introducing high-purity argon gas for 30min to remove oxygen, and adding 3.3X10 -6 Mu mol Na 2 SeO 3 Then the mixture is placed in a constant temperature shaking incubator at 21 ℃ and 120 rpm for reaction for 2 min. Finally adding 3.3X10 -6 Mu mol GSH.
40 Adding mL of ultrapure water into a three-neck flask, introducing high-purity argon gas for 30min for deoxidization, heating to 85 ℃, regulating the pH value of the solution to 2-5 by using 1M trifluoroacetic acid solution, immediately adding the synthesized selenium precursor into a silver precursor, and adding 3.3X10 -5 Mu mol AgNO 3 Aqueous solution (AgCH of equal amount of substance) 3 Suspensions of COOH or AgCl may also) and 6.6X10 -6 After GSH of (2), the reaction temperature is rapidly reduced to 65 ℃ to continue the reaction, and Ag is obtained 2 Se quantum dots.
Example 3
Will be 1.32X10 -5 Mu mol sodium borohydride is dissolved by using zero degree ultrapure water of 1mL, the pH value of the solution is regulated to 2-5 by using 1M trifluoroacetic acid solution, high-purity argon is introduced for 30min under ice bath condition to deoxidize, and then 3.3X10 is added -6 Mu mol Na 2 SeO 3 Then the mixture is placed in a constant temperature shaking incubator at 0 ℃ and 80rpm for reaction for 5min. Finally addIn 3.3X10 -6 Mu mol GSH.
40 Adding mL of ultrapure water into a three-neck flask, introducing high-purity argon gas for 30min for deoxidization, heating to 85 ℃, regulating the pH value of the solution to 2-5 by using 1M trifluoroacetic acid solution, adding the synthesized selenium precursor into a silver precursor, and adding 3.3X10 -5 Mu mol AgNO 3 Aqueous solution (AgCH of equal amount of substance) 3 Suspensions of COOH or AgCl may also) and 6.6X10 -6 After GSH of (2), the reaction temperature is rapidly reduced to 65 ℃ to continue the reaction, and Ag is obtained 2 Se quantum dots.
Example 4
Will be 1.32X10 -5 Mu mol sodium borohydride is dissolved by using zero degree ultrapure water of 1mL, the pH value of the solution is regulated to 2-5 by using 1M trifluoroacetic acid solution, high-purity argon is introduced under ice bath condition to deoxidize, and then 3.3 multiplied by 10 is added -6 Mu mol Na 2 S 2 O 3 Then the mixture is placed in a constant temperature shaking incubator at 0 ℃ and 80rpm for reaction for 5min. Finally adding 3.3X10 -6 Mu mol sodium borohydride continued to react 10 s.
40 Adding mL of ultrapure water into a three-neck flask, introducing high-purity argon gas for 30min for deoxidization, heating to 85 ℃, regulating the pH value of the solution to 2-5 by using 1M trifluoroacetic acid solution, adding the synthesized selenium precursor into a silver precursor, and adding 3.3X10 -5 Mu mol AgNO 3 Aqueous solution (AgCH of equal amount of substance) 3 The suspension of COOH or AgCl may be added with 6.6X10 -6 After GSH of (2), the reaction temperature is rapidly reduced to 65 ℃ to continue the reaction, and Ag is obtained 2 S quantum dots.
Example 5
Will be 1.32X10 -5 Mu mol GSH is dissolved by ultrapure water of 1mL, the pH value of the solution is regulated to 2-5 by using 1M trifluoroacetic acid solution, high-purity argon is introduced to deoxidize, and then 3.3X10 is added -6 Mu mol Na 2 TeO 3 Then the mixture is placed in a constant temperature shaking incubator at 37 ℃ and 180rpm for reaction for 15 min. Finally adding 3.3X10 -6 Mu mol GSH continued to react 10 s.
40 Adding mL of ultrapure water into a three-neck flask, and introducing high-purity argon for one periodDeoxidizing, heating to 85deg.C, regulating pH to 2-5 with 1M trifluoroacetic acid solution, adding the synthesized selenium precursor into silver precursor, and adding 3.3X10 -5 Mu mol AgNO 3 Aqueous solution (AgCH of equal amount of substance) 3 COOH or AgCl), and adding 6.6x10 -6 After GSH of (2), the reaction temperature is rapidly reduced to 65 ℃ to continue the reaction, and Ag is obtained 2 Te quantum dots.
Example 6
Ag obtained by reacting one of the reactions provided in example 1 of the present invention for 10 hours 2 The Se quantum dots are placed in buffer solutions with pH values of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13 respectively, the above quantum dot solution is subjected to spectrum scanning by a fluorometer, and the obtained spectrum is subjected to integral treatment to obtain integral area data of fluorescence spectrums of the quantum dots dispersed in the buffer solutions with different pH values, as shown in figure 4, the Ag provided by the invention can be seen 2 The Se quantum dot has the best fluorescence property and the best fluorescence property when the pH value is 2.
Further, the Ag provided by the invention 2 Se quantum dots are placed in an environment with pH of 1 (0.01M HCl aqueous solution), fluorescence spectra of the quantum dot solution are scanned at different time points respectively, and the spectra are integrated, as shown in FIG. 5, ag is obtained after 1day 2 The stability of Se quantum dots is still good, which indicates the Ag provided by the invention 2 Se quantum dots have good fluorescence stability and colloid stability.
Further, the Ag provided by the invention 2 Se quantum dots are respectively placed in 0.1M HCl and PBS, as shown in figure 6, amino groups on a surface ligand GSH of the quantum dots are in a protonated state under a strong acidic environment, so that the surface of the quantum dots has positive charges, and adverse effects caused by damage to the surface structure of the quantum dots by high-concentration hydrogen ions in a gastric acid environment can be resisted.
Comparative example 1
According to literature Biomaterials DOI: the experiment was performed by the method provided by 10.1021/cm202543 m:
will 10mL BAdding diol into a 50mL three-neck flask, introducing Ar gas for 30min to remove oxygen, heating to 110deg.C, adding 100 μl mercaptopropionic acid under stirring, and adding 0.05 mmol AgNO 3 . After continuing to raise the temperature to 145 ℃, continuing to react, stopping stirring and heating, and cooling to room temperature. Adding ultrapure water into the reaction solution, centrifuging after the solution is turbid, and obtaining the Ag by precipitation 2 S quantum dots. The Ag is treated by 2 S quantum dots and other commonly used near infrared quantum dots were dispersed in PBS and SGJ at ph=8, respectively, near infrared two-region imaging was performed on the above solutions at 1h and 12h, respectively, and electron microscopy characterization was performed on the samples at 12 hours. The stability of the quantum dots dispersed in PBS and SGJ is shown in fig. 7 and 8. Synthetic Ag 2 The S quantum dot can well maintain colloid stability and fluorescence stability in neutral PBS. However, when dispersed in a strongly acidic gastric acid mimetic solution, precipitation occurs in a short period of time, and after 12 hours, most of Ag occurs 2 The S quantum dots all precipitate from the solution. And the fluorescence intensity is greatly reduced.
At the same time, ag can be seen in the electron microscope characterization of FIG. 9 2 The S quantum dots can keep better dispersibility in PBS for 12 hours, but can be agglomerated in gastric acid simulated liquid with stronger acidity and can not keep the dispersibility stably.
Comparative example 2
According to document RSC advance DOI: the experiment was carried out by the preparation method provided by 10.1039/C6RA04987G, 10 mmol of selenium powder (790 mg) and 100 mL octadecene were added into a 250 mL three-neck round bottom flask, ar gas was introduced at 110 ℃ for 10 min for deoxidization, and the temperature was raised to 230 ℃ for reaction for 30min to turn the solution into golden yellow. The obtained selenium precursor solution was centrifuged to remove unreacted selenium powder as black precipitate, and then cooled to room temperature and stored in a brown glass bottle. Adding a certain amount of silver acetate and a certain amount of octanethiol into a three-mouth bottle, and heating for 5min at 110 ℃ under an argon atmosphere to remove water and oxygen. And rapidly heating the silver precursor to 160 ℃ and rapidly injecting the prepared Se precursor. The product was mixed with approximately ten volumes of ethanol, centrifuged at 10000rpm for 3 minutes and the precipitate was redispersed in n-hexane. The product was then washed 2 times with a methanol and ethanol mixture (1:1) to substantially remove reaction byproducts and other impurities. When the mol ratio of the silver acetate to Se precursor added into the reaction system is 2:1, the injection temperature is 160 ℃, and the growth is carried out for 20min at 120 ℃, the silver selenide quantum dot with the emission wavelength of 1000 nm is obtained.
The quantum dots were purified twice more and then passed through a 0.22 μm organic phase filter. Dispersing the purified 10 mg quantum dots in chloroform solution, and dispersing the 40 mg octylamine grafted polyacrylic acid with chloroform. The two were then mixed and sonicated for 5min. Followed by spin-drying, adding 10mL of BR buffer (0.05 m, ph=9), followed by transfer into a centrifuge tube and centrifugation at 10000rpm for 3min, and removing the supernatant. Concentrating the converted quantum dot solution to 0.4 KDA ultrafiltration tube mL, adding into size exclusion column, collecting with 7 drops of the solution until the dropped solution has no color. Purified quantum dot 10 mg was dispersed in BR buffer (0.05M, pH 9), 20 mg of mPEG-amine was added followed by 5 mg EDC. The mixture was reacted 2h on a shaking table at 37 ℃. Then purified by a 1000 kDa ultrafiltration tube and concentrated.
The Ag is treated by 2 Se quantum dots and other commonly used near infrared quantum dots were dispersed in PBS and SGJ at ph=8, near infrared two-region imaging was performed on the above solution at 1h and 12h, respectively, and electron microscopy characterization was performed on the sample at 12 hours, and the stability of the quantum dots dispersed in PBS and SGJ is shown in fig. 7 and 8. Ag synthesized by the method 2 The Se quantum dot can well keep colloid stability and fluorescence stability in neutral PBS. However, when it is dispersed in a strongly acidic gastric acid-like liquid, slight agglomeration occurs in a short period of time, and the agglomeration is aggravated for 12 hours. Meanwhile, the fluorescence intensity of the solution is unevenly distributed due to agglomeration.
At the same time, ag can be seen in the electron microscope characterization of FIG. 9 2 The Se quantum dots can keep better dispersibility in PBS for 12 hours, but can be agglomerated in gastric acid simulated liquid with stronger acidity and can not keep the dispersibility stably.
Comparative example 3
Experiments were performed according to the method provided in document JACS DOI: 10.1021/jacs.1c06661: 334 mg AgAc, 1.4 mL OTT, and 10mL ODE were placed in a 25 mL three-necked round bottom flask, and the mixture was stirred at 50deg.C and purged with argon to remove oxygen, at which time the system was in the form of a milky white turbid liquid. This is due to the poor solubility of silver mercaptide in ODE. 50.8. 50.8 mg Te powder was added to a mixed solution of 4 mL OLA and 5.5 mL TBP and sonicated for use. And (3) quickly heating the three-neck flask filled with the Ag precursor to 160 ℃ in an atmosphere continuously introducing argon, taking 1.5 mL tellurium precursor, diluting with 2.5 mL ODE, fully and uniformly mixing, quickly adding the diluted tellurium precursor into the three-neck flask, and growing for 2-30 min at 150 ℃. The water transfer method of the obtained silver telluride was the same as in comparative example 2 described above.
The Ag is treated by 2 Te quantum dots and other commonly used near infrared quantum dots were dispersed in PBS and SGJ at ph=8, respectively, near infrared two-region imaging was performed on the above solutions at 1h and 12h, respectively, and electron microscopy characterization was performed on the samples at 12 hours. The stability of the quantum dots dispersed in PBS and SGJ is shown in FIG. 7 and FIG. 8, and the Ag synthesized by the method 2 Te quantum dots can well maintain colloid stability and fluorescence stability in neutral PBS. However, when it is dispersed in a strongly acidic gastric acid mimetic liquid, a large amount of Ag is formed in a short period of time 2 The Te quantum dots agglomerate. At the same time, the fluorescence intensity of the solution is also due to Ag 2 The Te quantum dots are unevenly distributed due to agglomeration.
At the same time, ag can be seen in the electron microscope characterization of FIG. 9 2 Te quantum dots can keep better dispersibility in PBS for 12 hours, but can be agglomerated in gastric acid simulated liquid with stronger acidity and can not keep the dispersibility stably.
Comparative example 4
According to literature PNAS DOI: the procedure provided by 10.1073/pnas.1806153115 was used for the experiment:
accurately weigh 0.278 g (1 mmol) PbCl 2 The white fine powder was placed in a three-necked flask, and 8mL of oleylamine was taken out by a 10mL syringe and injected into the three-necked flask. The stirrer was turned on at a set speed of 400 rpm, set at 160℃and aerated. Accurately weighing 0.032g of sulfur powder in 10mL of oleylamine, shaking and ultrasonic treatment until the sulfur powder is dissolved to form orange-red transparent liquid (note that the color of the solution is observed), and standing at room temperature for standby. After ventilation for half an hour at 160 ℃, decreaseThe temperature was maintained for 5min at 110 ℃. Note that: the gel formation process and color change were observed. The prepared sulfur precursor solution was aspirated with a 10ml syringe and injected into the 1mLS precursor. After maintaining the temperature at 120℃for 3min, the heating was turned off, 5mL of oleic acid was immediately and rapidly added, and after stirring for 5min, 40 mL absolute ethanol was added. The solution was cooled and then removed to a 50mLEP tube, split into two, and trimmed with ethanol. 10000rpm, and centrifuging for 3min. 2mL of tetrachloroethylene was used for dissolution, ethanol was added for precipitation, and the mixture was purified twice. The water transfer method of the obtained PbS was the same as in comparative example 2.
The PbS quantum dots and other commonly used near infrared quantum dots were dispersed in PbS and SGJ at ph=8, respectively, near infrared two-region imaging was performed on the above solutions at 1h and 12h, respectively, and electron microscopy characterization was performed on the samples at 12 hours. The stability of the quantum dots dispersed in PBS and SGJ is shown in figures 7 and 8, and the PbS quantum dots synthesized by the method can well maintain the colloid stability and fluorescence stability in neutral PBS. However, when the PbS quantum dots are dispersed in a strong acid gastric acid simulated liquid, a large number of PbS quantum dots are agglomerated in a short time. Meanwhile, the fluorescence intensity of the solution is unevenly distributed due to agglomeration of PbS quantum dots.
Meanwhile, in the electron microscope characterization of fig. 9, it can be seen that the PbS quantum dot can maintain good dispersibility in PbS for 12 hours, but can be agglomerated in gastric acid simulated liquid with strong acidity, and the dispersibility of the PbS quantum dot can not be maintained stably.
Example 7
Ag obtained by reacting one of the reactions provided in example 1 for 10 hours 2 The Se quantum dots are placed in a 3500 Da molecular weight cut-off dialysis bag, and stirred and dialyzed under the condition of 50-500 rpm in a 5L ultrapure water system. Fresh ultrapure water is replaced every 2-8 hours, and samples are collected after dialysis for about 24-36 hours. Dialysis of Ag 2 And (3) placing the Se quantum dot aqueous solution into an ultrafiltration tube with a molecular weight cut-off of 50 kDa, centrifuging at 2000-10000 rpm, collecting the lower layer solution of the ultrafiltration tube with the particle size smaller than 50 kDa after every 2-20 min, and simultaneously supplementing ultrapure water into the upper layer concentrated solution of the ultrafiltration tube. After centrifugation until the color of the lower solution is nearly colorless, the solution trapped on the upper layer of the ultrafiltration tube is discarded. Dissolving the collected lower layerPlacing the solution in an ultrafiltration tube of 10 kDa, centrifuging at 2000-10000 rpm, concentrating, and lyophilizing to obtain purified Ag 2 Powder of Se quantum dots.
In FIG. 6, the above Ag was prepared using potassium phthalate as an internal standard 2 Se quantum dot passes through nuclear magnetism 1 The quantitative analysis technology of the H spectrum calculates GSH in Ag 2 The density of the Se quantum dot surface is 1-8 GSH/nm 2 And the surface is a silver-rich (Ag: se=3:1 to 8:1) surface structure (this result is according to literature Zhao, j.y.; wang, z.g.; hu, h.; zhang, z.l.; tang, b.; luo, m.y.; yang, l.l.; wang, b.; pang, d.w. How different are the surfaces of semiconductor Ag) 2 Se quantum dots with various sizes Sci. Bull. 2021, 67 (6), 619-625. Test calculations provided in).
The Ag is prepared by 2 The Se quantum dots and the quantum dots prepared in comparative examples 1, 2, 3 and 4 were respectively dispersed in Phosphate Buffer (PBS) and gastric acid mimetic liquid (SGJ) at pH=8, the above solutions were subjected to near infrared two-region imaging at 1h and 12h, respectively, and the samples at 12 hours were subjected to electron microscopy characterization, and the stability of the quantum dots dispersed in PBS and SGJ was as shown in FIGS. 7 and 8, and the synthesized Ag 2 The S quantum dot can well maintain colloid stability and fluorescence stability in neutral PBS, and when the S quantum dot is dispersed in a strong acid gastric acid simulated liquid, no precipitation occurs, no obvious change occurs after 12 hours, and the fluorescence intensity also does not change.
The first row shown in FIG. 9 is Ag obtained by reacting the quantum dots prepared in comparative examples 1, 2, 3 and 4 with one of the reactions provided in example 1 of the present invention for 10 hours 2 Dispersion of Se Quantum dots in PBS the second row shown in FIG. 9 is Ag obtained by reacting the Quantum dots prepared in comparative examples 1, 2, 3 and 4 with one of the reactions provided in example 1 of the present invention for 10 hours 2 And (3) the dispersion condition of Se quantum dots in gastric acid simulated liquid. As can be seen from fig. 9, the present invention provides an Ag 2 Se quantum dots can simultaneously maintain good dispersibility in phosphate buffer PBS and gastric acid simulation liquid without agglomeration, however, quantum dots obtained in comparative examples 1, 2, 3 and 4 can all maintain good dispersibility in PBSBut they are all subject to severe agglomeration in a more acidic gastric acid mimic environment.
Example 8
The Ag obtained by purification in example 7 2 After Se quantum dots are concentrated to a mass concentration of 1mg/mL, a certain amount of quantum dot solution is infused into the stomach of a mouse according to the weight of the mouse (x/y=0.01, and when the weight of the mouse is y g, the amount of the quantum dot solution used is x milliliters). Near infrared two-region fluorescence imaging of mice was performed at different time points (10 min, 2h, 6 h and 10 h) using a small animal laser imaging system, and the imaging results shown in fig. 10 show that the quantum dot can be smoothly metabolized along the digestive tract organs from stomach (stomach), ileum (ileum), caecum (cecum) to rectum (rectum) after entering the digestive tract of mice, and the Ag provided by the invention was demonstrated through the whole digestive tract 2 The Se quantum dot has good near infrared two-region fluorescence performance and good stability in a complex digestive tract.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The method for synthesizing the silver chalcogenide quantum dots by using the water phase is characterized by comprising the following steps of:
s1: preparing a chalcogen anion precursor solution under the condition that the pH value is 2-5;
s2: and adding the silver precursor solution into the chalcogen anion precursor solution to react to obtain the silver chalcogenide quantum dots.
2. The method for synthesizing silver chalcogenide quantum dots in aqueous phase according to claim 1, wherein said S1 step comprises the steps of:
s11: placing a reducing agent into ultrapure water, stirring to obtain a first mixed solution, and adjusting the pH value of the first mixed solution to 2-5;
s12: adding a first material into the first mixed solution in an inert gas atmosphere to obtain a second mixed solution, and placing the second mixed solution into a constant-temperature shaking incubator with the rotating speed of 30-6000 rpm for reaction for 2-120 min at the temperature of 5-50 ℃ to obtain a third mixed solution;
wherein the first material comprises one of a sulfur source, a selenium source or a tellurium source;
s13: and adding a reducing agent into the third mixed solution, and continuing to perform oscillation reaction for 10-60 s to obtain a chalcogen anion precursor solution.
3. The method of aqueous phase synthesis of silver-chalcogen quantum dots according to claim 2, wherein the reducing agent is one of GSH, sodium borohydride, vitamin C or hydrazine hydrate.
4. The method for synthesizing silver-chalcogen quantum dots by using the aqueous phase according to claim 2, wherein the molar ratio of the reducing agent in the step S11 to the reducing agent in the step S12 to the reducing agent in the step S13 is 1:1:1-8:1:1.
5. The method for synthesizing silver chalcogenide quantum dots in aqueous phase according to claim 1, wherein said step S2 comprises the steps of:
s21: deoxidizing ultrapure water for 10-420 min in an inert gas atmosphere, and then adjusting the pH value of the ultrapure water to 2-5 at 55-100 ℃;
s22: adding the chalcogen anion precursor solution into ultrapure water, and stirring to obtain a fourth mixed solution;
s23: and adding GSH into the silver salt water solution, stirring to obtain silver precursor solution, adding the silver precursor solution into the fourth mixed solution, and stirring at 50-100 ℃ to obtain the silver chalcogenide quantum dots.
6. The method for synthesizing silver-chalcogen quantum dots in aqueous phase according to claim 5, wherein the molar ratio of GSH to silver-salt aqueous solution in the step S23 is 1:1-20:1.
7. Silver-chalcogenide quantum dot synthesized by a method for synthesizing silver-chalcogenide quantum dot in aqueous phase according to any one of claims 1 to 6.
8. The silver-chalcogenide quantum dot of claim 7, wherein the silver-chalcogenide quantum dot is Ag 2 S quantum dot, ag 2 Se quantum dots or Ag 2 One of the Te quantum dots.
9. The silver-chalcogenide quantum dot of claim 7, wherein the molar ratio of silver to chalcogen of the silver-chalcogenide quantum dot is greater than 2:1, a step of; the ligand density of GSH on the surface of the silver chalcogenide quantum dot is 1-8 GSH/nm 2 。
10. The silver-chalcogenide quantum dot according to claim 7, wherein the silver-chalcogenide quantum dot is applied to near infrared fluorescence imaging of gastrointestinal tract.
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