CN115645555A - Water-soluble isotope silver sulfide quantum dot for tracing and preparation method thereof - Google Patents
Water-soluble isotope silver sulfide quantum dot for tracing and preparation method thereof Download PDFInfo
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Images
Abstract
The invention discloses a water-soluble isotope silver sulfide quantum dot for tracing and a preparation method thereof. The preparation method of the water-soluble isotope silver sulfide quantum dot comprises the following steps: in an inert atmosphere, heating and preserving heat of a system consisting of an isotope silver source, 3-mercaptopropionic acid, 11-mercaptoundecanoic acid and an organic solvent, and obtaining the water-soluble isotope silver sulfide quantum dot after the reaction is finished. The preparation method of the water-soluble isotope silver sulfide quantum dot is simple, the isotope silver sulfide quantum dot can be directly dissolved in water by virtue of the sulfur source and the surface ligand, and the isotope silver sulfide quantum dot has the advantages of uniform size, good stability and good monodispersity. The isotope silver sulfide quantum dot of the invention does not have the defects of strong background interference, dye leakage, photobleaching, difficult accurate quantification and the like of the traditional fluorescence labeling method, and can simultaneously track the distribution rules and characteristics of two kinds of silver sulfide quantum dots after different administration time, thereby reasonably designing and optimizing the administration dosage and the administration time interval.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a water-soluble isotope silver sulfide quantum dot for tracing and a preparation method thereof.
Background
The unique optical and biological characteristics of quantum dots enable the quantum dots to be widely applied to the field of biomedicine. And silver sulfide quantum dots (Ag) 2 S QDs) has wide application prospect and great potential value in the aspects of cell marking, molecular detection, biological imaging, optical diagnosis and treatment and the like due to the characteristics of high quantum yield, adjustable emission wavelength, good light stability, good biocompatibility and the like. Therefore, to meet the special requirements of biomedical applications, water-soluble Ag with high stability is prepared 2 S QDs have become a hot spot for research in recent years.
At present, ag 2 The preparation method of the S QDs mainly comprises thermal cracking, thermal injection, phase transfer, hydrothermal treatment and the like. Du et al by [ (C) 2 H 5 ) 2 NCS 2 Ag]The precursor thermal cracking method prepares about 10.2nm Ag 2 S QDs, which has good dispersibility in non-polar solvents (e.g., cyclohexane) (j.am. Chem. Soc.2010,132, 1470). Jiang et al utilized a hot injection method to rapidly inject hexamethyldisilazane into a mixed solvent containing silver acetate, myristic acid, 1-Octylamine (OA) and 1-octadecene, resulting in small size (. About.1.5 nm) Ag that can be dispersed in organic solvents 2 S QDs (chem. Mater.2012,24, 3). Zhao et al use of dodecylamine (DDA) to react Ag + Transferring the DDA mixture from the aqueous phase to toluene, drying, redispersing in oleylamine, and mixing with sulphur powder at 150 ℃ for 1 hour to obtain DDA-coated 3.7nm Ag 2 S QDs(Mater.Lett.2014,126,78)。
The above method is mainly small-sized Ag 2 S QDs, and Ag produced 2 S QDs can only be dispersed in organic phase, which seriously hinders the direct application in the biomedical field. Although, researchers have replaced Ag with hydrophilic ligands by ligand exchange methods 2 Hydrophobic ligands of S QDs to obtain water soluble Ag 2 S QDs. However, this method is cumbersome, costly, inefficient, and wasteful of materials and Ag after exchange 2 The S QDs fluorescence quantum yield decreases. Although, the water-soluble Ag was prepared by means of a hydrothermal method 2 S QDs, but this process is complicated, small in size and serious in agglomeration. In addition, stable isotopes are widely used in many fields by virtue of their radiopacity, non-decay and ready availability, but no isotope nanoparticles are currently available for tracking cells and animalsStudy of different dosing and dosing intervals in vivo. And compared with the defects of strong background interference, dye leakage, photobleaching, difficult precise quantification and the like of the traditional fluorescence labeling method, the isotope nano-particles can simultaneously track the distribution rules and characteristics of two silver sulfide quantum dots after different administration time, thereby reasonably designing and optimizing the administration dosage and the administration time interval and ensuring the highest accumulation amount of the medicine on the affected part. Therefore, the water-soluble isotope Ag which has high stability and good monodispersity and can be used for tracing is prepared by a simple method 2 The S QDs are particularly important.
Disclosure of Invention
The invention aims to provide a water-soluble isotope silver sulfide quantum dot for tracing and a preparation method thereof 2 The S QDs can be directly dissolved in water, have uniform size and good stability and monodispersity, and can simultaneously track the distribution rule and characteristics of two isotope silver sulfide quantum dots after different administration times.
The invention provides a preparation method of water-soluble isotope silver sulfide quantum dots, which comprises the following steps:
in an inert atmosphere, heating and preserving heat of a system consisting of an isotope silver source, 3-mercaptopropionic acid (MPA), 11-mercaptoundecanoic acid (MUA) and an organic solvent, and obtaining the water-soluble isotope silver sulfide quantum dot after the reaction is finished.
In the above production method, the molar ratio of the isotope silver source, the 3-mercaptopropionic acid, and the 11-mercaptoundecanoic acid may be (2 to 10): (200-300): (50 to 100), specifically 5: (200-300): (50 to 100), 5:287: (50 to 100), 5: (200-300): 69 or 5:287:69;
the ratio of the isotope silver source to the organic solvent is 0.05mmol:10mL.
In the above preparation method, the isotopic silver source is selected from isotopic silver nitrate (silver nitrate)) ( 107 AgNO 3 Or 109 AgNO 3 ) Isotope of silver acetate (CH) 3 COO 107 Ag or CH 3 COO 109 Ag), isotope of silver citrate (C) 6 H 5 107 Ag 3 O 7 Or C 6 H 5 109 Ag 3 O 7 ) Any one of (a) to (b);
the organic solvent is ethylene glycol.
In the preparation method, the heating and heat preservation comprises the first heating and heat preservation and the second heating and heat preservation;
the first heating and heat preservation can be heating to 100-120 ℃ (such as 110 ℃) and heat preservation for 30-60 min (such as 30 min);
the second heating and holding may be heating to 140-150 deg.C (e.g. 145 deg.C) and holding for 1.5-3 h (e.g. 1.5 h).
In the above preparation method, the heating and the heat preservation are performed under stirring, and the rotation speed of the stirring may be 600r/s.
In the above preparation method, after the reaction is completed, the method may further include the steps of:
cooling the system after the reaction is finished, washing the system by using an organic solvent, centrifuging the system, and collecting the precipitate;
and dispersing the precipitate in deionized water, cleaning, centrifuging, and collecting the precipitate to obtain the water-soluble isotope silver sulfide quantum dot.
Further, the organic solvent for cleaning can be a mixed solution of ethylene glycol and ethanol; in the mixed solution of ethylene glycol and ethanol, the volume ratio of ethylene glycol to ethanol may be specifically 1:4.
further, the centrifugal force of the centrifugation can be 8000-10000 g, and the time can be 5-15 min.
In the above preparation method, the method for preparing the system consisting of the isotope silver source, the 3-mercaptopropionic acid, the 11-mercaptoundecanoic acid and the organic solvent comprises the following steps:
adding the organic solvent into the 11-mercaptoundecanoic acid, and introducing inert gas for exhausting to obtain an organic solution of the 11-mercaptoundecanoic acid; and sequentially adding the 3-mercaptopropionic acid and the isotope silver source into the organic solution of the 11-mercaptoundecanoic acid to obtain a system consisting of the isotope silver source, the 3-mercaptopropionic acid, the 11-mercaptoundecanoic acid and the organic solvent.
In the invention, the particle size of the isotope silver sulfide quantum dots can be specifically controlled according to the time of the second heating and heat preservation.
The invention further provides the water-soluble isotope silver sulfide quantum dot prepared by the preparation method.
The isotopic silver sulfide quantum dots can be 107 Ag 2 S or 109 Ag 2 S。
The water-soluble isotope silver sulfide quantum dots are spherical silver sulfide quantum dots, and the outer layer is blocked by carboxyl;
the particle size of the water-soluble isotope silver sulfide quantum dot can be 15-32 nm.
The invention also protects the application of the water-soluble isotope silver sulfide quantum dot in preparing a product for optimizing a drug administration scheme; the isotope silver sulfide quantum dot is 107 Ag 2 S QDs and 109 Ag 2 S QDs。
in the above-mentioned application, the administration regimen comprises the administration time interval and/or the administration dosage.
In the above application, the optimized dosing regimen comprises the following steps: adding quantum dots into the cells or tissues after administration for incubation according to the conditions after incubation 107 Ag 2 S QDs and 109 Ag 2 the ratio of S QDs, and the dosage scheme.
The cells can be specifically Hep G2 cells;
the tissue may be spleen or liver;
the incubation temperature is 37 ℃, and the incubation time can be 6-24 h;
in particular, it can be determined by ICP-MS 107 Ag 2 S QDs and 109 Ag 2 the ratio of S QDs.
The invention has the following beneficial effects:
(1) The isotope silver sulfide quantum dot is prepared by using isotope silver nitrate (silver nitrate) 107 AgNO 3 And 109 AgNO 3 ) Is silver source, 3-mercaptopropionic acid (MPA) and 11-mercaptoundecanoic acid (MUA) are sulfur source and surface ligand, ethylene Glycol (EG) is used as reaction solvent, and carboxyl-terminated water-soluble isotope is obtained under the heating condition 107 Ag 2 S and 109 Ag 2 s QDs. Compared with the traditional preparation method, on one hand, the preparation method is simple and easy, consumes less materials, needs less complex factors to be controlled, and has no advantages of time consumption, complex ligand exchange process and the like in the traditional preparation method; on the other hand, it is assisted by MPA and MUA, so that 107 Ag 2 S and 109 Ag 2 the S QDs can be directly dissolved in water, and have uniform size, good stability and good monodispersity.
(2) The isotope silver sulfide quantum dot of the invention does not have the defects of strong background interference, dye leakage, photobleaching, difficult accurate quantification and the like of the traditional fluorescence labeling method, and can simultaneously track the distribution rules and characteristics of two kinds of silver sulfide quantum dots after different administration time, thereby reasonably designing and optimizing the administration dosage and the administration time interval and ensuring the highest accumulation amount of the medicine on the affected part.
Drawings
Fig. 1 is a transmission electron micrograph, a size distribution diagram and an energy spectrum of the water-soluble isotope silver sulfide quantum dot in example 1.
Fig. 2 is a silver ion release curve of the water-soluble isotope silver sulfide quantum dot in example 1.
FIG. 3 is a transmission electron micrograph of the water-soluble isotope silver sulfide quantum dot of example 1 after two months of storage.
FIG. 4 shows the content of isotope Ag in the cells in the Hep G2 cell uptake trace in example 1.
FIG. 5 is the isotopic Ag content in mouse spleen and liver as followed by the tissue level in example 1.
FIG. 6 is a transmission electron micrograph of water-soluble silver sulfide quantum dots of example 2.
FIG. 7 is a transmission electron micrograph of the water-soluble silver sulfide quantum dots of example 3.
Fig. 8 is a transmission electron micrograph of silver sulfide quantum dots in comparative example 1.
Fig. 9 is a transmission electron micrograph of silver sulfide quantum dots in comparative example 2.
Fig. 10 is a transmission electron micrograph of silver sulfide quantum dots in comparative example 3.
FIG. 11 is a transmission electron micrograph of silver sulfide in comparative example 4.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
The ICP-MS test conditions in the examples below are shown in Table 1.
TABLE 1 ICP-MS test conditions
Example 1 preparation of water-soluble isotopic silver sulfide Quantum dots for tracing
Preparing water-soluble isotope silver sulfide quantum dots for tracing according to the following steps:
1、 107 AgNO 3 and 109 AgNO 3 preparation of
0.2g of 107 Ag and 0.2g 109 The Ag silver blocks are cut into pieces as much as possible, added into a crucible and placed in a metal bath heater for heating, the metal bath heater is heated to 75 ℃, 1mL (69 wt%) of concentrated nitric acid is measured, and the concentrated nitric acid is added into the crucible for reaction in a small amount for multiple times. Stirring with a glass rod, drying the product and grinding it into powderAnd (4) powder. The product was stored protected from light.
2. Water-soluble isotope silver sulfide quantum dot 107 Ag 2 S and 109 Ag 2 preparation of S QDs
Placing 150mg (0.69 mmol) of 11-mercaptoundecanoic acid (MUA) in a 50mL three-neck flask, adding 10mL of Ethylene Glycol (EG), introducing Ar gas flow, and exhausting for 30 min; while stirring at room temperature, 250. Mu.L (2.87 mmol) of 3-mercaptopropionic acid (MPA) was added, and after stirring for 5min, 8.5mg (0.05 mmol) were added 107 AgNO 3 Or 109 AgNO 3 Stirring for 10min; heating to 110 deg.C, maintaining for 30min, heating to 145 deg.C, maintaining the temperature for 1.5h, and stopping stirring and heating; placing the reaction solution in ice water to cool to room temperature, adding 20mL of ethanol into 5mL of EG solution, centrifuging at 10000g for 5min, and washing twice; then the mixture is dispersed in deionized water and washed twice under the same condition to obtain the high-stability water soluble isotope 107 Ag 2 S and 109 Ag 2 S QDs。
3. characterization of
Will be provided with 107 Ag 2 S and 109 Ag 2 after drying the S QDs on a copper mesh, they were observed by high-power transmission microscope and analyzed for particle size by ImageJ statistics. And simultaneously performing energy spectrum characterization. The results of the experiment are shown in FIG. 1. As can be seen from the TEM images and the particle size distribution, 107 Ag 2 s and 109 Ag 2 s QDs size 15nm; as can be seen from the energy spectrum data, ag: S = 2.
4. Silver ion release
107 Ag 2 S and 109 Ag 2 s QDs 80. Mu.g was dispersed in 8mL of PBS buffer (pH = 7.4), incubated at 37 ℃ for various times, 1mL of the solution was collected at various time intervals, the filtrate was centrifuged using an ultrafiltration tube (5 kD), and digested at 95 ℃ (HNO) 3 ：H 2 SO 4 =9: 1) And (5) carrying out ICP-MS detection for 12 h. The silver ion release rate after incubation for 0-120h is shown in figure 2, and it can be seen that the silver ion release is basically 0 and the stability is good. The two transmission electron microscope images are shown in fig. 3, and it can be seen that the size of the quantum dot is still not obviously changed after two months.
5. Use of
(1) Cellular uptake tracking
107 Ag 2 S QDs (10. Mu.g) incubation of Hep G2 cells (initial plating number 9X 10) 5 One) after 3h, the incubation medium was washed off in PBS buffer and an equal dose was added 109 Ag 2 S QDs were incubated, and after 3h, the cells were harvested by centrifugation (800g, 5 min), washed twice with PBS buffer, and digested at 95 deg.C (HNO) 3 ：H 2 SO 4 =9: 1) After 12h, ICP-MS measures the content of isotope Ag to obtain the non-incubated Ag 2 Cells of S QDs serve as controls. The results of the experiment are shown in FIG. 4, and the data show that cells can be tracked by ICP-MS 107 Ag 2 S and 109 Ag 2 the uptake of S QDs is different, and the uptake ratio is about 107 Ag 2 S： 109 Ag 2 S＝2.56。
(2) Tissue level tracking
Equal amount for tail vein injection 107 Ag 2 S and 109 Ag 2 s QDs (0.2 mg/kg), 48h later, mice were euthanized, spleens and livers were then weighed and digested at 95 ℃ (HNO) 3 ：H 2 SO 4 =9: 1) And measuring the content of the isotope Ag by ICP-MS after 12 hours. The results of the experiment are shown in FIG. 5. It can be seen that ICP-MS is used to track the distribution of the two particles in the liver and spleen respectively, and the in vivo proportion stability is better after equal amount of material is injected.
Example 2
Ag was prepared according to the procedure of example 1 2 S QDs, except that the Ag is maintained at 145 ℃ for 2h 2 The size of S QDs is 20nm, and a TEM image is shown in FIG. 6.
Example 3
Ag was prepared according to the procedure of example 1 2 S QDs, except that the Ag is maintained at 145 ℃ for 3h 2 The size of S QDs is 32nm, and a TEM image is shown in FIG. 7.
Comparative example 1
Preparation procedure As in example 1, ag was prepared by replacing only 0.69mmol of 11-mercaptoundecanoic acid (MUA) with mercaptopropionic acid 2 Of S QDsThe TEM photograph is shown in FIG. 8. As can be seen from fig. 8, the silver sulfide prepared in this comparative example has non-uniform size distribution and serious agglomeration.
Comparative example 2
The preparation procedure was the same as in example 1 except that the amount of the silver source was adjusted to 0.01mmol, the amount of 3-mercaptopropionic acid was adjusted to 0.25mmol, and the total amount of 11-mercaptoundecanoic acid was adjusted to 0.12mmol, to prepare Ag 2 TEM images of S QDs are shown in FIG. 9. As can be seen from FIG. 9, ag obtained in this comparative example 2 The size distribution of S QDs is not uniform and the dispersibility is not good.
Comparative example 3
The preparation procedure was the same as in example 1 except that the amount of the silver source was adjusted to 0.1mmol, the amount of 3-mercaptopropionic acid was adjusted to 8.6mmol, and the total amount of 11-mercaptoundecanoic acid was adjusted to 2.4mmol, to prepare Ag 2 TEM images of S QDs are shown in FIG. 10. As can be seen from FIG. 10, ag obtained in this comparative example 2 The size distribution of the S QDs is not uniform, and agglomeration is severe.
Comparative example 4
The preparation steps are the same as example 1, the step of raising the temperature to 110 ℃ and keeping the temperature for 30min is not carried out only in the process of raising the temperature and keeping the temperature, the temperature of the system is directly raised to 145 ℃ and kept at the temperature for 1.5h, and the obtained Ag 2 TEM images of S QDs are shown in FIG. 11. As can be seen from FIG. 11, ag obtained in this comparative example 2 No obvious particles are seen in the S QDs, and the agglomeration is serious.
The present invention has been described in detail above. It will be apparent to those skilled in the art that the invention can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with reference to specific examples, it will be appreciated that the invention may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. The use of some of the essential features is possible within the scope of the claims attached below.
Claims (10)
1. A preparation method of water-soluble isotope silver sulfide quantum dots comprises the following steps:
in an inert atmosphere, heating and preserving heat of a system consisting of an isotope silver source, 3-mercaptopropionic acid, 11-mercaptoundecanoic acid and an organic solvent, and obtaining the water-soluble isotope silver sulfide quantum dot after the reaction is finished.
2. The method of claim 1, wherein: the molar ratio of the isotope silver source to the 3-mercaptopropionic acid to the 11-mercaptoundecanoic acid is (2-10): (200-300): (50-100);
the ratio of the isotope silver source to the organic solvent is 0.05mmol:10mL.
3. The method according to claim 1 or 2, characterized in that: the isotope silver source is selected from any one of isotope silver nitrate, isotope silver acetate and isotope silver citrate;
the organic solvent is ethylene glycol.
4. The method according to any one of claims 1-3, wherein: the heating and heat preservation comprises first heating and heat preservation and second heating and heat preservation;
the first heating and heat preservation is to heat the mixture to 100-120 ℃ and preserve the mixture for 30-60 min;
and the second heating and heat preservation is carried out for 1.5-3 h when the temperature is raised to 140-150 ℃.
5. The method according to any one of claims 1-4, wherein: the method also comprises the following steps after the reaction is finished:
cooling the system after the reaction is finished, washing the system by using an organic solvent, centrifuging the system, and collecting the precipitate;
and dispersing the precipitate in deionized water, cleaning, centrifuging, and collecting the precipitate to obtain the water-soluble isotope silver sulfide quantum dot.
6. The water-soluble isotope silver sulfide quantum dot prepared by the preparation method of any one of claims 1 to 5.
7. The water-soluble isotopic silver sulfide quantum dot of claim 6, wherein: the water-soluble isotope silver sulfide quantum dots are spherical silver sulfide quantum dots, and the outer layer is blocked by carboxyl;
the particle size of the water-soluble isotope silver sulfide quantum dot is 15-32 nm.
8. Use of the water-soluble isotopic silver sulfide quantum dots of claim 6 or 7 in the manufacture of a product for optimizing a dosing regimen; the isotope silver sulfide quantum dot is 107 Ag 2 S QDs and 109 Ag 2 S QDs。
9. use according to claim 8, characterized in that: the dosing regimen comprises a time interval of administration and/or a dose of administration.
10. A product for optimizing a dosing regimen comprising the water-soluble isotopic silver sulfide quantum dots of claim 6 or 7.
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| CN102643641A (en) * | 2012-04-17 | 2012-08-22 | 武汉大学 | Preparation method for water-soluble Ag2S quantum dot |
| CN102849779A (en) * | 2012-10-11 | 2013-01-02 | 吉林大学 | Preparation method of silver sulfide quantum dots |
| CN107418562A (en) * | 2017-09-06 | 2017-12-01 | 东北大学 | The synthetic method of near-infrared silver sulfide quantum dot |
| CN112964775A (en) * | 2021-02-01 | 2021-06-15 | 中国地质大学（武汉） | Manufacturing method of target for LA-ICP-MS analysis |
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| CN102643641A (en) * | 2012-04-17 | 2012-08-22 | 武汉大学 | Preparation method for water-soluble Ag2S quantum dot |
| CN102849779A (en) * | 2012-10-11 | 2013-01-02 | 吉林大学 | Preparation method of silver sulfide quantum dots |
| CN107418562A (en) * | 2017-09-06 | 2017-12-01 | 东北大学 | The synthetic method of near-infrared silver sulfide quantum dot |
| CN112964775A (en) * | 2021-02-01 | 2021-06-15 | 中国地质大学（武汉） | Manufacturing method of target for LA-ICP-MS analysis |
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