CN111004628B - Core-shell structure chalcogenide quantum dot, and preparation method and application thereof - Google Patents
Core-shell structure chalcogenide quantum dot, and preparation method and application thereof Download PDFInfo
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- CN111004628B CN111004628B CN201911347868.8A CN201911347868A CN111004628B CN 111004628 B CN111004628 B CN 111004628B CN 201911347868 A CN201911347868 A CN 201911347868A CN 111004628 B CN111004628 B CN 111004628B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052981 lead sulfide Inorganic materials 0.000 claims abstract description 14
- 229940056932 lead sulfide Drugs 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 238000003384 imaging method Methods 0.000 claims abstract description 10
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 10
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- 238000011282 treatment Methods 0.000 claims abstract description 8
- 239000011669 selenium Substances 0.000 claims description 22
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
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- 239000002798 polar solvent Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 3
- 229910021608 Silver(I) fluoride Inorganic materials 0.000 claims description 2
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- 125000000217 alkyl group Chemical group 0.000 claims description 2
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 2
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- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 claims description 2
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- 239000002253 acid Substances 0.000 claims 1
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- 239000000126 substance Substances 0.000 claims 1
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- 238000007306 functionalization reaction Methods 0.000 abstract description 4
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- 239000013078 crystal Substances 0.000 abstract description 2
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- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 8
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- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 4
- YRXWPCFZBSHSAU-UHFFFAOYSA-N [Ag].[Ag].[Te] Chemical compound [Ag].[Ag].[Te] YRXWPCFZBSHSAU-UHFFFAOYSA-N 0.000 description 4
- 229910052946 acanthite Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 229910052798 chalcogen Inorganic materials 0.000 description 4
- 150000001787 chalcogens Chemical class 0.000 description 4
- KDSXXMBJKHQCAA-UHFFFAOYSA-N disilver;selenium(2-) Chemical compound [Se-2].[Ag+].[Ag+] KDSXXMBJKHQCAA-UHFFFAOYSA-N 0.000 description 4
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
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- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
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- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
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- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000013399 early diagnosis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
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- FQVPFGDPYSIWTM-UHFFFAOYSA-N tributyl(sulfanylidene)-$l^{5}-phosphane Chemical compound CCCCP(=S)(CCCC)CCCC FQVPFGDPYSIWTM-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/661—Chalcogenides
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- 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
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
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- 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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- 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
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Abstract
The invention discloses a core-shell structure chalcogenide quantum dot, a preparation method and application thereof. The chalcogenide quantum dot with the core-shell structure comprises a lead sulfide quantum dot serving as a core and a shell layer coated on the core, wherein the shell layer is made of silver chalcogenide Ag 2 X is selected from S, se or Te. The preparation method comprises the following steps: lead sulfide quantum dots are used as crystal nuclei, and in a reaction system with a coordination surfactant, a chalcogenide source is added as a precursor of a chalcogenide anion, and a silver source is used as a precursor of silver for exogenous growth. The chalcogenide quantum dot with the core-shell structure has the advantages of high fluorescence yield, uniform size, good stability and the like, can perform real-time living body imaging of biological tissues through surface biological functionalization treatment, and has the advantages of simple and easy operation of preparation process, mild reaction conditions, short preparation period, good repeatability, easy control and suitability for large-scale production.
Description
Technical Field
The invention relates to a quantum dot, in particular to a lead sulfide quantum dot core-shell structure with high fluorescence intensity and low toxicity, a preparation method and biological application thereof, belonging to the technical field of material chemistry and biology.
Background
The biological fluorescence imaging technology has the characteristics of fast feedback, multiple optical channels, high sensitivity, high resolution, no ionizing radiation and the like, and has important application prospects in the aspects of early diagnosis, treatment and prognosis evaluation of diseases. Of these, near infrared two-domain (NIR-II, 1000-1700 nm) quantum dots are of interest due to their higher tissue penetration depth and lower autofluorescence. Compared with NIR-I (750-900 nm) quantum dots, blood and tissues have low absorption and scattering of NIR-II, so that the NIR-II has deeper penetrating power for living tissues and presents higher signal-to-back ratio when being used for in-vivo imaging. Therefore, the near-infrared two-region quantum dot has greater advantages in the aspects of biological detection and in-vivo imaging.
Among the numerous near-infrared two-region quantum dots, lead sulfide (PbS) quantum dots have a high fluorescence quantum yield of about 40%, can achieve a strong fluorescence emission intensity, a small forbidden bandwidth of about 0.41ev, and a large bohr radius of about 18nm, can cover the entire NIR-ii region and be continuously tunable, and can also achieve a large stokes shift and a narrow half-peak width of about 80nm (Multigram Scale, solventless, and Diffusion-Controlled Route to high half-peak monocrystalline. J. Ph. Ys. Chem. B2006, 110,671-673. However, the solubility product constant of PbS quantum dots is large (8.4X 10) -28 ) And has heavy metal Pb 2 + This greatly hinders the biological applications of PbS quantum dots. However, most of the reports in the literature relate to the biological application of the CdS quantum dots, wherein the cadmium sulfide quantum dots are mostly coated by a cation exchange method, and cadmium ions serving as heavy metals have biological toxicity.
Disclosure of Invention
The invention mainly aims to provide a core-shell structure chalcogenide quantum dot, a preparation method and application thereof, thereby overcoming the defects in the prior art.
The embodiment of the invention provides a chalcogenide quantum dot with a core-shell structure, which comprises a lead sulfide quantum dot serving as a core and a shell layer coated on the core, wherein the shell layer is composed of a chalcogenide of silver.
Further, the chalcogenide of silver is Ag 2 X, wherein X is selected from S, se or Te.
Furthermore, the fluorescence emission peak of the chalcogenide quantum dot with the core-shell structure is positioned between 950 nm and 1800 nm.
The embodiment of the invention also provides a preparation method of the chalcogenide quantum dot with the core-shell structure, which comprises the following steps: heating a reaction system containing lead sulfide quantum dots, a sulfur family source, ligand molecules and a solvent to 25-120 ℃ in a closed environment, adding a silver source, and fully reacting.
In some embodiments, the method of making further comprises: and after the reaction is finished, naturally cooling the obtained mixed reaction system to room temperature, adding a polar solvent, washing and centrifuging to obtain the hydrophobic chalcogenide quantum dot with the core-shell structure.
In some embodiments, the method of making further comprises: and performing surface biological functionalization treatment on the chalcogenide quantum dots with the core-shell structure.
The embodiment of the invention also provides application of any one of the chalcogenide quantum dots with the core-shell structure in preparation of a bioluminescent imaging product.
Compared with the prior art, the chalcogenide quantum dot with the core-shell structure provided by the embodiment of the invention has the advantages of high fluorescence yield, uniform size, good stability and the like, can perform real-time living body imaging on biological tissues through surface biological functionalization treatment, and has the advantages of simple and easy operation of preparation process, mild reaction conditions, short preparation period, good repeatability, easy control and suitability for large-scale production.
Drawings
FIG. 1 is the hydrophobic PbS @ Ag of example 1 2 A transmission electron microscope photograph of Se quantum dots;
FIG. 2 is the hydrophobic in example 1Sex PbS quantum dot, pbS @ Ag 2 A near-infrared fluorescence spectrum of the Se quantum dots;
FIG. 3 shows the hydrophilic PbS quantum dots, pbS @ Ag in example 1 2 A near-infrared fluorescence spectrum of the Se quantum dots;
FIG. 4 is the hydrophilic PbS @ Ag in example 1 2 Photograph of Se quantum dot vessel imaging.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made long-term research and numerous experiments to propose the technical scheme of the present invention. The technical scheme mainly uses lead sulfide quantum dots as crystal nuclei, and obtains the low-toxicity near-infrared silver chalcogenide compound coated lead sulfide quantum dots (PbS @ Ag for short) with high fluorescence yield by externally adding a chalcogenide source as a chalcogenide anion precursor and a silver source as a silver precursor for exogenous growth in a reaction system with a coordination surfactant 2 X, X = S, se or Te), which has the advantages of high fluorescence yield, fluorescence stability, uniform dimension, simple preparation process, etc., and has better stability compared to PbS quantum dots, and also has good biocompatibility through further surface biofunctionalization treatment, which can be applied to bioimaging, especially to real-time in vivo imaging of biological tissues, and exhibits excellent bioimaging performance. The technical solution of the present invention will be explained in more detail as follows.
One aspect of the embodiments of the present invention provides a chalcogenide quantum dot with a core-shell structure (i.e., the aforementioned pbs @ ag) 2 X) comprising lead sulphide quantum dots as a core and a shell layer coated on the core, said shell layer consisting of a silver chalcogenide.
Further, the chalcogenide of silver is Ag 2 X, wherein X is selected from S, se or Te.
Furthermore, the fluorescence emission peak of the chalcogenide quantum dot with the core-shell structure is positioned between 950 nm and 1800 nm.
Further, the diameter of the lead sulfide quantum dot is 3-7nm.
Further, the thickness of the shell layer is 0.25-2.5nm.
The chalcogenide quantum dot with the core-shell structure provided by the embodiment of the invention takes the silver chalcogenide quantum dot as the protective shell layer of the PbS quantum dot, and has an extremely low concentration product constant<10 -50 Low toxicity, good stability, and the like, and can effectively prevent Pb 2+ And the exudation can be cooperated with the PbS quantum dots serving as the core to show higher fluorescence yield, better fluorescence stability and better biological safety.
Another aspect of the embodiments of the present invention also provides a method for preparing a chalcogenide quantum dot with a core-shell structure, including: heating a reaction system containing lead sulfide quantum dots, a sulfur family source, ligand molecules and a solvent to 25-120 ℃ in a closed environment to enable the sulfur family source to be adsorbed on the surface of lead ions, and further adding a silver source and fully reacting according to the principle of epitaxial growth.
In some embodiments, the preparation method further comprises: and after the reaction is finished, naturally cooling the obtained mixed reaction system to room temperature, adding a polar solvent, washing and centrifuging to obtain the hydrophobic chalcogenide quantum dot with the core-shell structure.
In some embodiments, the molar ratio of the lead sulfide quantum dots, the chalcogen source, the ligand molecules and the silver source is 1 (1-20): 1-10000): 2-60.
In some embodiments, the diameter of the lead sulfide quantum dots may be of different sizes, for example, the diameter may be 3.5-6.2nm, more specifically, 3.5, 4.6, 5.8, or 6.2nm, but is not limited thereto.
In some embodiments, the silver source comprises any one or combination of silver nitrate, silver acetate, silver trifluormethyl mercaptan, silver diethyldithiocarbamate, silver monofluoride, silver octadecanoate, silver oleylamine, without limitation.
In some embodiments, the chalcogen source comprises any one or combination of octadecenylsulfur, octadecenylselenium, octadecenyltellurium, trioctylphosphine sulfur, trioctylphosphine selenium, trioctylphosphine tellurium, tributylphosphine sulfur, tributylphosphine selenium, tributylphosphine tellurium, and is not limited thereto.
In some embodiments, the ligand molecule includes any one or a combination of long chain alkyl amines, long chain alkyl acids, and long chain thiols, without limitation.
Preferably, the chain length of the ligand molecule is in the range of C12-C24.
In some embodiments, the solvent includes any one or a combination of octadecene, N-methylpyrrolidone, and dimethylsulfoxide, without limitation.
In some embodiments, the preparation method further comprises: and mixing and reacting the hydrophobic chalcogenide quantum dot with the core-shell structure and a hydrophilic modification reagent in a solvent to obtain the hydrophilic chalcogenide quantum dot with the core-shell structure.
In some embodiments, the hydrophilic modification agent includes any one or a combination of thioglycol, aminopolyglycol, thioglycolic acid, and is not limited thereto.
In some embodiments, the molar ratio of the hydrophobic chalcogenide quantum dots with core-shell structure to the hydrophilic modification agent is 1 (10-100000), and is not limited thereto.
In some embodiments, the polar organic solvent includes any one or a combination of more of ethanol, methanol, acetone, and 1-methyl-2-pyrrolidone, and is not limited thereto.
In the foregoing embodiment, when the chalcogen source is the same, such as selenium source, the thickness of the silver selenide shell layer on the surface can be controlled by using different silver sources, different reaction temperatures and different reaction times, for example, the shell layer can be thickened by increasing the temperature and prolonging the reaction time.
In the foregoing embodiment, when the silver sources are the same, the use of different chalcogen sources can result in lead sulfide quantum dots coated with chalcogenides having different silver shells, for example, if trioctylphosphine selenium is used, the result is silver selenide coated lead sulfide quantum dots.
The preparation method of the chalcogenide quantum dot with the core-shell structure provided by the embodiment of the invention has the advantages of simple operation, mild reaction conditions and short preparation periodGood repeatability and easy control, and the prepared PbS @ Ag 2 The X quantum dots have high fluorescence yield, uniform size and good stability.
In some embodiments, the preparation method further comprises: the operation of the step of performing surface biofunctionalization treatment on the chalcogenide quantum dots with the core-shell structure is known to those skilled in the art, and can be referred to numerous documents in the field, for example, reference can be made to "surface functionalization of quantum dots and application research thereof in the biomedical field", biochemistry, 2019, stage 2, and the like. By subjecting the PbS @ Ag 2 The X quantum dots are subjected to surface biological functionalization treatment, so that the biological tissue real-time in-vivo imaging can be performed, and an excellent imaging effect is shown.
The embodiment of the invention also provides application of any one of the chalcogenide quantum dots with the core-shell structure in preparation of a bioluminescence imaging product.
In another aspect, the embodiments of the present invention further provide a product, which is applied to a bioluminescence imaging method, where the product includes any one of the chalcogenide quantum dots with a core-shell structure; and, the bio-fluorescence imaging method includes: and performing real-time in vivo imaging on the biological tissue by using the core-shell structure chalcogenide quantum dots.
In another aspect of the embodiments of the present invention, there is provided a bioluminescence imaging method including: and carrying out real-time in vivo imaging on the biological tissue by using any one of the core-shell structure chalcogenide quantum dots. Including but not limited to living blood vessels and the like.
The invention is further illustrated by the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Unless otherwise specified, various reagents used in the following examples are well known to those skilled in the art and available from commercial sources and the like. However, the experimental methods in the following examples, in which specific conditions are not specified, are generally performed under conventional conditions or under conditions recommended by the manufacturers.
Example 1: 1mg of a sulfur compound having a diameter of 6.2nmLead quantum dots, 10g of octanethiol, 10mL of dimethyl sulfoxide and 0.3mL (0.016M) of trioctylphosphine selenium are mixed and placed in a three-neck flask, the temperature is raised to 50 ℃ in the air, then 0.3mL (0.032M) of silver acetate solution is added for keeping for 30min, finally 50mL of absolute ethyl alcohol is added after the solution is naturally cooled to room temperature, the solution is centrifuged, washed and dispersed in toluene, and the obtained sample is identified as silver selenide coated lead sulfide core-shell structure quantum dots (the diameter is 6.6nm and the shell thickness is 0.2nm as shown in figure 1) by a transmission electron microscope and X-ray diffraction, so that a good near infrared fluorescence emission spectrum (the light emission wavelength is 1400-1800nm as shown in figure 2) is obtained, and the fluorescence has red shift compared with PbS quantum dots; adding 0.15g of sulfhydryl polyethylene glycol into the toluene, adding absolute ethyl alcohol with the same volume, performing ultrasonic treatment in an ultrasonic cleaner for 4h, centrifuging, and washing with deionized water to obtain water-soluble PbS @ Ag with particle size of about 6.6nm and shell thickness of 0.2nm 2 The Se quantum dots have obviously reduced fluorescence emission compared with the oil phase due to the absorption of water; but at the same concentration, compared with the aqueous phase PbS alone, the fluorescence is higher, the fluorescence is more stable, and the fluorescence is stable and unchanged after being placed for 10 days. (as shown in fig. 3). Mixing the above PbS @ Ag 2 Se quantum dots are dispersed in deionized water, and then 10mg of amino polyethylene glycol (PEG-NH) 2 ) Adding the solution; then 50. Mu.L of an aqueous solution containing 0.01mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 50. Mu.L of an aqueous solution containing 0.01mmol of N-hydroxysuccinimide (NHS) were added to the above mixed solution, wrapped with aluminum foil, and stirred for 4 hours in the dark. The product was centrifuged, washed with phosphate buffered saline (PBS, pH = 7.4), and resuspended in phosphate buffered saline to give 1mg/mL PEG-modified PBS @ ag concentration 2 Se quantum dots, and injecting the 200 mu L solution into tail veins of mice; the laser with 808nm is used for excitation, the filter with 1400nm is used for taking a picture by using a 2D InGaAs camera, and PbS @ Ag can be clearly seen 2 The Se quantum dots emit light in the blood vessels of the mice, and the positions of the blood vessels of the mice are clearly seen (as shown in figure 4).
Example 2: 1mg of lead sulfide quantum dots with a diameter of 3.5nm, 5g of oleylamine, 5g of dodecanethiol, 10mL of octadecene and 0.5mL (0.016M) of tributylphosphine sulfide were mixed and placed in three portsHeating the flask to 90 ℃ in the air, adding 0.5mL (0.032M) of silver acetate oleylamine solution, keeping for 1h, naturally cooling the solution to room temperature, adding 50mL of absolute ethyl alcohol, centrifuging, washing, dispersing in toluene, and identifying the obtained sample as silver sulfide-coated lead sulfide core-shell structure quantum dots by a transmission electron microscope and X-ray diffraction, wherein the diameter of the silver sulfide-coated lead sulfide core-shell structure quantum dots is 4.3nm, the thickness of a shell layer of the silver sulfide-coated lead sulfide core-shell structure quantum dots is 0.4nm, the silver sulfide-coated lead sulfide core-shell structure quantum dots also have good near-infrared fluorescence emission spectrum, and the emission wavelength is 850-1300nm; adding 0.2g thioctic acid into the toluene, adding absolute ethyl alcohol with the same volume, stirring for 24h, centrifuging, washing with deionized water to obtain water-soluble PbS @ Ag with shell thickness of about 0.4nm 2 The fluorescence emission of the S quantum dots is slightly reduced compared with that of the oil phase due to the absorption of water; but at the same concentration, compared with the aqueous phase PbS alone, the fluorescence is higher, the fluorescence is more stable, and the fluorescence is stable and unchanged after being placed for 10 days. Mixing the above PbS @ Ag 2 Dispersing the S quantum dots in deionized water, and then adding 10mg of amino polyethylene glycol (PEG-NH) 2 ) Adding the solution; then 50. Mu.L of an aqueous solution containing 0.01mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 50. Mu.L of an aqueous solution containing 0.01mmol of N-hydroxysuccinimide (NHS) were added to the above mixed solution, wrapped with aluminum foil, and stirred for 4 hours in the dark. The product was centrifuged, washed with phosphate buffered saline (PBS, pH = 7.4), and resuspended in phosphate buffered saline to give 1mg/mL PEG-modified PBS @ ag concentration 2 S quantum dots, and carrying out tail vein injection on the mouse by taking 200 mu L of the solution; the laser with 808nm is used for excitation, the filter with 1000nm is used for taking a picture by using a 2D InGaAs camera, and PbS @ Ag can be clearly seen 2 Se quantum dots emit light in the blood vessels of the mice, and the positions of the blood vessels of the mice are clearly seen.
Example 3: mixing 1mg of lead sulfide quantum dots with the diameter of 4.6nm, 5g of oleic acid, 5g of octadecylamine, 10mL of N-methylpyrrolidone and 1.5mL (0.016M) of octadecenylselenium, putting the mixture into a three-neck flask, heating the mixture in the air to 110 ℃, adding 1mL (0.032M) of silver acetate oleylamine solution for keeping the temperature for 1h, finally adding 50mL of absolute ethyl alcohol after the solution is naturally cooled to the room temperature, centrifuging, washing, dispersing in toluene, and using a transmission electron microscope and an X-ray diffraction to obtain a sampleThe quantum dots are identified as silver selenide coated lead sulfide core-shell structure quantum dots, the diameter is 6.2nm, the shell layer thickness is 0.8nm, the quantum dots also have good near-infrared fluorescence emission spectrum, and the emission wavelength is 1100-1500nm; (ii) a Adding 0.1g mercaptopropionic acid into the toluene, adding absolute ethyl alcohol with the same volume, oscillating for 8h on an oscillator, centrifuging, and washing with deionized water to obtain water-soluble PbS @ Ag with shell thickness of about 0.8nm 2 Se quantum dots, the fluorescence emission of which is reduced compared with that of oil phase due to the absorption of water; but at the same concentration, compared with the aqueous phase PbS alone, the fluorescence is higher, the fluorescence is more stable, and the fluorescence is stable and unchanged after being placed for 10 days. Mixing the above PbS @ Ag 2 Se quantum dots are dispersed in deionized water, and then 10mg of aminopolyethylene glycol (PEG-NH) is added 2 ) Adding the solution; then 50. Mu.L of an aqueous solution containing 0.01mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 50. Mu.L of an aqueous solution containing 0.01mmol of N-hydroxysuccinimide (NHS) were added to the above mixed solution, wrapped with aluminum foil, and stirred for 4 hours in the dark. The product was centrifuged, washed with phosphate buffered saline (PBS, pH = 7.4), and resuspended in phosphate buffered saline to give 1mg/mL PEG-modified PbS @ Ag 2 Se quantum dots, and carrying out tail vein injection on the mice by taking 200 mu L of the solution; the laser with 808nm is used for excitation, the filter with 1400nm is used for taking a picture by using a 2D InGaAs camera, and PbS @ Ag can be clearly seen 2 The Se quantum dots emit light in the blood vessels of the mice, and the positions of the blood vessels of the mice are clearly seen.
Example 4: mixing 1mg of lead sulfide quantum dots with the diameter of 5.8nm, 5g of oleic acid, 5g of tetradecylthiol, 10mL of octadecene and 100 mu L (0.016M) of trioctylphosphine tellurium, putting the mixture into a three-neck flask, heating the mixture to 120 ℃ in the air, heating the mixture to 120 ℃ in the Ar atmosphere, adding 100 mu L (0.032M) of silver acetate oleylamine solution, keeping the mixture for 1.5h, finally, naturally cooling the solution to room temperature, adding 50mL of absolute ethyl alcohol, centrifuging, washing, dispersing in toluene, and identifying the obtained sample as the silver telluride-coated lead sulfide core-shell structure quantum dots by using a transmission electron microscope and X-ray diffraction, wherein the diameter of the silver telluride-coated lead sulfide quantum dots is 7.8nm, the shell thickness of the silver telluride-coated lead sulfide quantum dots is 1.0nm, the silver telluride-shell layer has a good near-infrared fluorescence emission spectrum, and the emission wavelength of the silver telluride-coated lead sulfide is 1200-1600nm; (ii) a 0.15g of thioglycolic acid was addedAdding anhydrous ethanol with the same volume into the toluene, stirring for 24h, centrifuging, and washing with deionized water to obtain water-soluble PbS @ Ag with shell thickness of about 1.0nm 2 Te quantum dots, the fluorescence emission of which is greatly reduced compared with the oil phase due to the absorption of water; but under the same concentration, compared with the aqueous phase PbS alone, the PbS has higher fluorescence, more stable fluorescence and stable and unchanged fluorescence after being placed for 10 days. Mixing the above PbS @ Ag 2 Te quantum dots are dispersed in deionized water, and then 10mg of amino polyethylene glycol (PEG-NH) is added 2 ) Adding the solution; then, 50. Mu.L of an aqueous solution containing 0.01mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 50. Mu.L of an aqueous solution containing 0.01mmol of N-hydroxysuccinimide (NHS) were added to the above mixed solution, wrapped with aluminum foil, and stirred for 4 hours in the dark. The product was centrifuged, washed with phosphate buffered saline (PBS, pH = 7.4), and resuspended in phosphate buffered saline to give 1mg/mL PEG-modified PbS @ Ag 2 Se quantum dots, and carrying out tail vein injection on the mice by taking 200 mu L of the solution; the sample is excited by a laser with 808nm, a filter with 1400nm and a 2D InGaAs camera are used for photographing, and PbS @ Ag can be seen 2 The Se quantum dots emit light in the blood vessels of the mice, and the positions of the blood vessels of the mice are seen.
In addition, the inventors of the present invention also synthesized another series of PbS @ Ag using other raw materials and reaction conditions according to the present specification with reference to the above examples 1 to 4 2 And the X quantum dots and the performance of the core-shell structure quantum dots are tested, and the results are ideal.
The above description is only a representative example of the many possible applications of the present invention, and should not be construed as limiting the scope of the present invention. All technical solutions formed by equivalent transformation or equivalent replacement fall within the protection scope of the present invention.
Claims (12)
1. A chalcogenide quantum dot with a core-shell structure is characterized by comprising a lead sulfide quantum dot as a core and a shell layer coated on the core; the diameter of the lead sulfide quantum dot is 3-7 nm; the shell layer has a thickness of 0.25-2.5nm and is composed of a silver chalcogenideThe substance is Ag 2 X, wherein X is selected from S, se or Te; and the fluorescence emission peak of the chalcogenide quantum dot with the core-shell structure is positioned between 950 nm and 1800 nm.
2. The preparation method of the chalcogenide quantum dot with the core-shell structure according to claim 1, which is characterized by comprising the following steps: heating a reaction system containing lead sulfide quantum dots, a sulfur family source, ligand molecules and a solvent to 25-120 ℃ in a closed environment, adding a silver source, and fully reacting;
wherein, the molar ratio of the lead sulfide quantum dots, the chalcogenide source, the ligand molecules and the silver source is 1 (1-20) to (1-10000) to (2-60);
the sulfur group source comprises any one or combination of more of octadecenylsulfur, octadecenylselenium, octadecenyltellurium, trioctylphosphine sulfur, trioctylphosphine selenium, trioctylphosphine tellurium, tributylphosphine sulfur, tributylphosphine selenium and tributylphosphine tellurium;
the ligand molecule comprises any one or more of long-chain alkylamine with chain length of C12-C24, long-chain alkyl acid and long-chain thiol.
3. The production method according to claim 2, characterized in that: the silver source comprises any one or combination of silver nitrate, silver acetate, silver trifluoromethanesulfonate, silver diethyldithiocarbamate, silver monofluoride, silver octadecanoate and silver oleylamine.
4. The production method according to claim 2, characterized in that: the solvent comprises any one or more of octadecene, N-methyl pyrrolidone and dimethyl sulfoxide.
5. The method of claim 2, further comprising: and after the reaction is finished, naturally cooling the obtained mixed reaction system to room temperature, adding a polar solvent, washing and centrifuging to obtain the hydrophobic chalcogenide quantum dot with the core-shell structure.
6. The method of claim 5, wherein: the polar solvent comprises any one or combination of ethanol, methanol, acetone and 1-methyl-2-pyrrolidone.
7. The method of claim 5, further comprising: and mixing the hydrophobic chalcogenide quantum dots with the core-shell structure with a hydrophilic modification reagent in a solvent for reaction to obtain the hydrophilic chalcogenide quantum dots with the core-shell structure.
8. The method for producing according to claim 7, characterized in that: the hydrophilic modification reagent comprises one or more of sulfhydryl polyethylene glycol, amino polyethylene glycol and sulfhydryl acetic acid.
9. The method for producing according to claim 7, characterized in that: the molar ratio of the hydrophobic chalcogenide quantum dots with the core-shell structure to the hydrophilic modification reagent is 1 (10-100000).
10. The preparation method according to any one of claims 2 to 9, further comprising a step of performing surface biofunctionalization treatment on the chalcogenide quantum dots with the core-shell structure.
11. The use of the core-shell chalcogenide quantum dots according to claim 1 in the preparation of bioluminescent imaging products.
12. A bioluminescent imaging method comprising: the core-shell structure chalcogenide quantum dots of claim 1 are utilized for real-time in vivo imaging of biological tissues.
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