CN114767883B - Preparation method and application of nano composite material based on Au-PbS heterostructure - Google Patents
Preparation method and application of nano composite material based on Au-PbS heterostructure Download PDFInfo
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- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
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Abstract
The invention provides a preparation method and application of a nano composite material based on an Au-PbS heterostructure, which comprises the steps of firstly preparing nano gold particles and sulfur precursors, and then in a high-temperature organic solution, mediating spontaneous epitaxial nucleation and growth of lead sulfide by the nano gold particles so as to obtain the Au-PbS nano particles. The Au-PbS nano-particles synthesized by the method have uniform particle size, good monodispersity, good crystal structure, adjustable fluorescence emission performance in a near infrared II region and good fluorescence quantum yield. The Au-PbS nano particles provided by the invention not only have the performances of nano gold particles and lead sulfide quantum dots, but also have better near infrared light absorption under the synergistic effect of the nano gold particles and the lead sulfide quantum dots, so that the Au-PbS nano particles have good photo-thermal effect, can be used as a photo-thermal conversion agent, and are used for photo-thermal imaging and photo-thermal treatment of tumors. In addition, since the Au-PbS nanoparticles have a large X-ray attenuation coefficient, the Au-PbS nanoparticles can be used as a Computed Tomography (CT) imaging contrast medium for CT imaging.
Description
Technical Field
The invention relates to the technical field of analytical chemistry and nano material preparation, in particular to a preparation method and application of a nano composite material based on an Au-PbS heterostructure.
Background
The PbS quantum dot has long and easily-controlled fluorescence emission wavelength in a second near infrared window (NIR-II, 1000-1700 nm), high fluorescence intensity, lower autofluorescence and deeper tissue penetrability when being used for in-vivo fluorescence imaging, and thus has important application value in the biomedical field. Meanwhile, the nano gold particles are used as a noble metal nano material and have important roles in catalysis, optics, biological diagnosis, treatment and the like. Therefore, the PbS quantum dot and the nano gold particle are combined into one nano structure, so that the novel hybrid material is hopeful to be obtained, the two nano material performances are simultaneously achieved, the performances are better under the synergistic effect, and the novel excellent performances are expanded. However, the synthesis of heterostructure nanoparticles with good crystal structure is very difficult due to the large crystal structure differences that exist for different types of nanomaterials, often resulting in lattice mismatch. On the other hand, in some heterostructure nanoparticle semiconductor-metal nanostructures, the nanoparticle is from a semiconductorThe optical properties of the body, i.e. photoluminescence, are usually quenched by the presence of metal nanoparticles, such as Janus Au-CdSe (Uri Banin, selective Growth of Metal Tips onto Semiconductor Quantum Rods and Tetrapods, science 2004,304,1787-1790), janus Au-CdS (Carsten
Absorption Properties of Metal-Semiconductor Hybrid Nanoparticles, ACS Nano 2011,5,4712-4719), etc., which limits its biomedical applications.
Disclosure of Invention
In order to overcome the problems and obtain the composite nano material with excellent performance, the first aim of the invention is to develop a novel method for preparing the heterostructure composite nano particle containing metal nano gold particles and semiconductor lead sulfide (PbS) quantum dots, so as to solve the problems of fluorescence quenching, imperfect crystal structure, low synthesis efficiency, and other excellent performances of the 'two-sided god' Au-PbS nano particle in the synthesis process of the 'two-sided god' Au-PbS nano particle.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a preparation method of a nano composite material based on an Au-PbS heterostructure comprises the following steps:
step 1, preparing nano gold particles, dispersing the nano gold particles in an organic solvent to prepare a solution A, and dissolving sublimed sulfur in oleylamine to prepare a solution B;
and 4, separating and purifying the nano particles obtained in the step 3 by using a nonpolar organic solvent and absolute ethyl alcohol, so as to obtain the heterostructure Au-PbS nano particles.
Preferably, in the step 1, the specific steps for preparing the nano gold particles are as follows: adding chloroauric acid into room-temperature organic solvent 1,2,3, 4-tetrahydronaphthalene, then adding 1-3mMol of reducer borane-tertiary butylamine or ascorbic acid, and stirring at room temperature for 30-60min to obtain gold nanoparticles.
Preferably, the diameter of the nano gold particles is 1-10nm.
Preferably, in the step 1, the organic solvent is one of normal hexane or chloroform, and the concentration of the gold nanoparticles in the organic solvent is 1-20mg/mL. Both hexane and chloroform are volatile organic solvents that can be easily removed.
Preferably, in the step 1, the concentration of sublimated sulfur in the oleylamine is 1 to 10M. Because the oleylamine is not only used as a simple solvent in a high-temperature organic phase, but also has a certain reducibility, the sulfur precursor prepared by the method has higher reaction activity and is different from pure sulfur. Furthermore, since primary amines in oleylamine can form coordination bonds with cations, oleylamine can also act as a surface ligand of nanoparticles.
Preferably, in the step 2, the lead precursor is lead chloride or lead oleate, the organic solution is a mixed solution of 1-octadecene and oleylamine, wherein the 1-octadecene is used as an experimental reaction solvent, the oleylamine is used as a reducing agent for mediating nucleation and can be used as a surface ligand of nano particles to stabilize the synthesized nano particles, and the volume ratio of the 1-octadecene to the oleylamine is 4-6:1, the concentration of lead precursor in the organic solution is 10-50mM.
Preferably, in the step 3, the temperature is raised to 140-180 ℃, the stirring time of the solution A and the solution B is 5-60min, and the volume ratio of the solution A to the solution B is 5:1-2. In a high-temperature organic solution, the spontaneous epitaxial nucleation and growth of lead sulfide are mediated by the nano gold particles, so that Au-PbS heterostructure nano particles are obtained.
Preferably, in the step 4, the nonpolar organic solvent is n-hexane, the centrifugal speed during purification is 7500-10000r/min, the centrifugal time is 5-10min, and the centrifugation is repeated for 2-4 times.
Preferably, the Au-PbS heterostructure nanoparticles have an absolute fluorescence quantum yield of 2% -40% at an emission wavelength of 1300 nm.
The method provides a brand new lead precursor-lead chloride or lead oleate, improves a preparation method of a sulfur precursor (sublimed sulfur is dissolved in oleylamine), synthesizes a series of Au-PbS heterostructure nano particles with adjustable fluorescence emission wavelength and positioned in a near infrared II region by changing the ratio of the gold nano particles and the lead precursor to the sulfur precursor prepared by adding the improved synthesis method, and has simple operation and high synthesis efficiency. The fluorescence emission wavelength of the Au-PbS heterostructure nano-particles is located in a near infrared II region, the wavelength is in the range of 1000-1700nm, and the quantum yield is high; in addition, the research also discovers that the Au-PbS heterostructure nano-particles synthesized by the method have uniform particle size, good monodispersity, good crystal structure and good fluorescence quantum yield.
The second purpose of the invention aims at providing application of the nano composite material based on the Au-PbS heterostructure prepared by the preparation method in tumor photothermal imaging, photothermal therapy and CT imaging.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method is novel and simple, and the prepared Au-PbS heterostructure nano-particles have the fluorescence performance of a near infrared II region with adjustable emission wavelength and have higher fluorescence quantum yield;
(2) The Au-PbS heterostructure nano-particles prepared by the method have uniform particle size, good monodispersity and good crystal structure;
(3) The Au-PbS heterostructure nano-particles prepared by the method can be used as a Computed Tomography (CT) imaging contrast agent for CT imaging due to the fact that the Au-PbS heterostructure nano-particles have a large X-ray attenuation coefficient;
(4) The Au-PbS heterostructure nano-particles synthesized by the method not only have the performances of nano-gold particles and lead sulfide quantum dots, but also have better near infrared light absorption under the synergistic effect of the nano-gold particles and the lead sulfide quantum dots, so that the Au-PbS heterostructure nano-particles have good photo-thermal effect in a near infrared region, can be used as a photo-thermal conversion agent, and are used for photo-thermal imaging and photo-thermal treatment of tumors.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a schematic representation of the synthesis of Au-PbS heterostructure nanoparticles;
FIG. 2 is an electron microscope image of the gold nanoparticles;
FIG. 3 is a representation of Au-PbS heterostructure nanoparticles, where a is a transmission electron microscopy image of Au-PbS heterostructure nanoparticles according to an embodiment of the present invention; b is a high-resolution electron microscope image of the Au-PbS heterostructure nanoparticle; c is a Scanning Transmission Electron Microscope (STEM) diagram of the Au-PbS heterostructure nanoparticle; d is an X-ray diffraction (XRD) result of the Au-PbS heterostructure nanoparticle polycrystal provided by the embodiment of the invention;
FIG. 4 is a fluorescence property of Au-PbS heterostructure nanoparticles, wherein a is a fluorescence spectrum of Au-PbS heterostructure nanoparticles according to an embodiment of the present invention; b is a bright field photo graph and a fluorescent graph under 808nm laser irradiation of the Au-PbS heterostructure nano-particles;
FIG. 5 is a photo-thermal property of Au-PbS heterostructure nanoparticles, where a is the absorption spectrum of Au-PbS heterostructure nanoparticles (Au-PbS NPs) of the present invention with original gold nanoparticles (Au NPs), lead sulfide quantum dots (PbS QDs), and physical mixtures of Au NPs and PbS QDs (Au NPs/PbS QDs); b is Au NPs, pbS QDs, physical mixtures of Au NPs/PbS QDs, temperature variation of the suspension of Au-PbS heterostructure nanoparticles; c is an infrared thermogram of Au NPs, pbS QDs, physical mixtures thereof and Au-PbS heterostructure nanoparticle suspensions;
FIG. 6 is a CT imaging result of Au-PbS heterostructure nanoparticles, wherein a is an in vitro CT image of Au-PbS heterostructure nanoparticles at different concentrations and a linear fit of HU values of Au-PbS heterostructure nanoparticles at different concentrations; b is in-vivo CT image of 4T1 tumor-bearing mice before and after injection of Au-PbS heterostructure nano-particles with different concentrations, and red circles represent tumor positions.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The experimental reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments, but not limited thereto.
1. Raw material source
The reagents used in the examples of the present invention are as follows:
lead chloride: 98%, shanghai Ala Biochemical technologies Co., ltd;
sublimating sulfur: AR grade, shanghai aladine Biochemical technologies Co., ltd;
trichloromethane: AR grade, tianjin, jieer, chemical industry trade Limited;
borane-t-butylamine: 98%, tianjin Hien Siderurgica, inc.;
1,2,3, 4-tetrahydronaphthalene: AR grade, tianjin Hien Siderurgica, inc.;
chloroauric acid: 48-50% of Au, tianjin Meidema biotechnology Co., ltd;
80-90% of oleylamine, shanghai Ala Biochemical technology Co., ltd;
1-octadecene: 90%, shanghai Ala Biochemical technologies Co., ltd.
2. Examples
Example 1: preparation method of Au-PbS heterostructure nano-particles
(1) Dissolving 0.1g of chloroauric acid in 10mL of 1,2,3, 4-tetrahydronaphthalene at room temperature (25+/-5 ℃), adding 1 millimole of borane-tertiary butylamine, stirring at room temperature, and reacting for 45 minutes to obtain gold nanoparticles;
(2) Dissolving 1 mmol of sublimed sulfur in 10ml of oleylamine to obtain a sulfur precursor B;
(3) 0.321g of lead chloride powder is dissolved in 10mL of nonpolar organic solvent 1-octadecene and oleylamine (volume ratio of 1-octadecene to oleylamine is 5:1) at 120 ℃ to prepare solution C, then 10mg of nano gold seeds are prepared into solution A (5 mg/mL) in organic solvent n-hexane, and then the volume ratio of C to solution A is 5:1, adding the solution A into the solution C, stirring, heating to 160 ℃, then immediately adding the solution B, immediately cooling to 120 ℃, preserving heat for 5 minutes, naturally cooling, and purifying, wherein the volume ratio of n-hexane to absolute ethyl alcohol is 1: and 3, centrifuging, wherein the centrifugal speed is 8000r/min, the centrifugal time is 6min, the centrifuging is repeated for 3 times, and the supernatant is removed to obtain the Au-PbS heterostructure nano-particles.
3. Analysis of results
The structure and properties of the Au-PbS nanoparticles of the present invention are described in detail below with reference to the accompanying drawings.
Experimental example 1
Fig. 1 is a schematic diagram of synthesis of Au-PbS heterostructure nanoparticles, from which the synthesis process of Au-PbS heterostructure nanoparticles can be seen.
Experimental example 2
Fig. 2 is a transmission electron microscope characterization of the nano gold particles according to the embodiment 1 of the present invention, and the result shows that the Au nano particles have uniform particle size and good monodispersity.
Experimental example 3
FIG. 3 is a representation of Au-PbS heterostructure nanoparticles of example 1 of the present invention; in fig. 3 a, a transmission electron microscope image of the Au-PbS heterostructure nanoparticles according to the embodiment of the present invention shows that the Au-PbS nanoparticles are heterostructures, and have uniform particle size and good monodispersity; b is a high-resolution electron microscope image of the Au-PbS heterostructure nanoparticle, and the result shows that each component shows different lattice spacing, wherein the lattice plane spacing in the PbS nanoparticle domain is 0.22nm, corresponding to the 220 crystal face of the galena crystal phase, the lattice plane spacing in the Au nanoparticle domain is 0.24nm, corresponding to the 111 crystal face of Jin Jingxiang, which indicates that the Au-PbS heterostructure nanoparticle has a good crystal structure; c is a Scanning Transmission Electron Microscope (STEM) diagram of the Au-PbS heterostructure nano-particles, and different components on two sides clearly show the heterostructure of the Au-PbS nano-particles; d is the result of X-ray diffraction (XRD) of the polycrystal of the Au-PbS heterostructure nano-particles, and all peaks of the XRD are respectively attributed to crystal phases of PbS (JCPDS: 05-0592) and Au (JCPDS: 04-0784), which shows that the Au-PbS heterostructure nano-particles are successfully prepared.
Experimental example 4
FIG. 4 shows the fluorescence properties of the Au-PbS heterostructure nanoparticles of example 1 of the present invention, and FIG. 4 a shows the fluorescence spectrum of the Au-PbS heterostructure nanoparticles of example 1 of the present invention, and the result shows that the fluorescence emission spectrum of the Au-PbS heterostructure nanoparticles prepared by the method is adjustable, and the fluorescence emission spectrum ranges from 1000nm to 1700nm; b is a bright field photograph of the Au-PbS heterostructure nanoparticle and a fluorescent photograph under 808nm laser irradiation, the concentration of the solution is 0.1mg/mL, the exposure time is 0.05s, and the result in the photograph shows that the Au-PbS heterostructure nanoparticle has bright fluorescent property.
Experimental example 5
Fig. 5 is an absorption spectrum of the Au-PbS heterostructure nanoparticle according to example 1 of the present invention, and fig. 5 a is an absorption spectrum of the Au-PbS heterostructure nanoparticle (Au-PbS NPs) according to the present invention and original Au nanoparticles (Au NPs), lead sulfide quantum dots (PbS QDs), and physical mixtures of Au NPs and PbS QDs (Au NPs/PbS QDs), and changes in the absorption spectrum were analyzed by comparing the absorption spectra of the four nano materials. The original Au NPs showed strong Localized Surface Plasmon Resonance (LSPR) absorption at 521 nm. The original PbS quantum dots have no distinct absorption peaks. Compared with Au NPs, the physical mixture of the Au NPs and the PbS quantum dots has no influence on LSPR absorption at 521nm, but has broadening, which shows that the simple physical mixture of the Au NPs and the PbS quantum dots has little influence on the LSPR absorption position of the Au NPs. However, the LSPR absorbance of the "dihedral" Au-PbS nanoparticles at 553nm exhibited not only a wider and red shift than the original Au NPs, but also significantly enhanced absorption in the near infrared region, indicating that the absorption spectrum of Au-PbS heterostructure nanoparticles is not the sum of the simple homogeneous nanoparticle absorption spectra of the components; FIG. 5 b shows the power density of 1.2W/cm according to the invention 2 For 3 minutes, the temperature changes of the Au NPs, pbS QDs, physical mixtures of Au NPs/PbS QDs, and suspensions of Au-PbS heterostructure nanoparticles, are the same in the figureUnder the conditions of (2), only the Au-PbS heterostructure nanoparticle suspension temperature changes most significantly, and the other groups have little change. FIG. 5 c shows the power density at 1.2W/cm of Au-PbS heterostructure nanoparticles according to example 1 of the present invention 2 Under 808nm laser irradiation, infrared thermograms of Au NPs, pbS QDs, physical mixtures thereof and Au-PbS heterostructure nanoparticle suspensions were obtained. These results indicate that the power density is 1.2W/cm 2 The control temperature was slightly raised by 4.9℃when irradiated with the 808nm laser for 3min, and the Au NPs, pbS QDs and their physical mixtures were raised by 5.8℃at 4.1℃and 10.5℃respectively. However, under the same conditions, the Au-PbS heterostructure nanoparticles increased by 21.1 ℃, indicating that the Au-PbS heterostructure nanoparticles play a key role in enhancing photo-thermal properties.
Experimental example 6
FIG. 6 is a CT image of Au-PbS heterostructure nanoparticles according to an embodiment of the present invention, where a in FIG. 6 is an in vitro CT image of Au-PbS heterostructure nanoparticles of different concentrations and a linear fit of HU values of Au-PbS heterostructure nanoparticles at different concentrations; in fig. 6 b is an in vivo CT image of 4T1 tumor-bearing mice before and after injection of different concentrations of Au-PbS heterostructure nanoparticles, with red circles representing tumor sites. These results indicate that Au-PbS heterostructure nanoparticles may be potential clinical CT contrast agents.
According to the preparation method of the nano composite material based on the Au-PbS heterostructure, borane-tertiary butylamine or ascorbic acid is used as a reducing agent in an organic phase at room temperature to reduce chloroauric acid solution to prepare nano gold particles, then the purified nano gold particles dispersed in an organic solvent are added into a high-temperature organic solution containing lead chloride or lead oleate, after the temperature is raised to a certain temperature, active sulfur precursors are added, and the prepared nano gold particles are Au-PbS heterostructure nano particles. Since the nano-gold particles are added in advance during the preparation of the Au-PbS heterostructure nano-particles, the PbS quantum dots are always formed on the gold nano-particles, which indicates that the nano-gold particles mediate the nucleation and growth of lead sulfide on the nano-gold particles. Moreover, when using smaller amounts of nano-gold particles, a mixture of free PbS quantum dots and "two-sided god" will result. Thus, it was demonstrated that PbS quantum dots preferentially nucleate on the nano-gold particles rather than uniformly nucleating. The final morphology depends on whether the gold surface allows only one nucleation site or multiple nucleation sites. On the other hand, when we change the preparation method of sulfur precursor, namely, sublimated sulfur is dissolved in oleic acid or simple sulfur simple substance is used in the experimental process, experimental results show that Au-PbS heterostructure nano-particles cannot be formed, which shows that the activity of the sulfur precursor plays a key role in the forming process of the Au-PbS heterostructure nano-particles. This has a certain relation to the reducibility of oleylamine.
In addition, the Au-PbS heterostructure nano-particles not only have the performances of nano-gold particles and lead sulfide quantum dots, but also have better near infrared light absorption under the synergistic effect of the nano-gold particles and the lead sulfide quantum dots, so that the Au-PbS heterostructure nano-particles have good photo-thermal effect in a near infrared region, can be used as a photo-thermal conversion agent, and are used for photo-thermal imaging and photo-thermal treatment of tumors. As the Au-PbS heterostructure nano-particles have bright fluorescence emission in a near infrared II region, the background is negligible, the penetration depth is high, and the defect of the penetration depth of photothermal treatment is overcome. The Au-PbS heterostructure nano-particles are successfully used for near infrared II-region fluorescence imaging/photothermal imaging/CT imaging multi-mode guided photothermal therapy (PTT), and good experimental results are obtained.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. A preparation method of a nano composite material based on an Au-PbS heterostructure is characterized by comprising the following steps: the method comprises the following steps:
step 1, preparing nano gold particles, dispersing the nano gold particles in an organic solvent to prepare a solution A, and dissolving sublimed sulfur in oleylamine to prepare a solution B;
step 2, dissolving a lead precursor in an organic solution to prepare a solution C;
step 3, adding the solution A into the solution C, heating, and adding the solution B to obtain nano particles;
and 4, separating and purifying the nano particles obtained in the step 3 by using a nonpolar organic solvent and absolute ethyl alcohol, so as to obtain the heterostructure Au-PbS nano particles.
2. The method for preparing the nanocomposite based on the Au-PbS heterostructure according to claim 1, wherein the method comprises the following steps: in the step 1, the specific steps for preparing the nano gold particles are as follows: adding chloroauric acid into room-temperature organic solvent 1,2,3, 4-tetrahydronaphthalene, then adding 1-3mMol of reducer borane-tertiary butylamine or ascorbic acid, and stirring at room temperature for 30-60min to obtain gold nanoparticles.
3. The method for preparing the nanocomposite based on the Au-PbS heterostructure according to claim 1 or 2, characterized in that: the diameter of the nano gold particles is 1-10nm.
4. The method for preparing the nanocomposite based on the Au-PbS heterostructure according to claim 1, wherein the method comprises the following steps: in the step 1, the organic solvent is one of normal hexane or chloroform, and the concentration of the gold nanoparticles in the organic solvent is 1-20mg/mL.
5. The method for preparing the nanocomposite based on the Au-PbS heterostructure according to claim 1, wherein the method comprises the following steps: in the step 1, the concentration of sublimated sulfur in the oleylamine is 1-10M.
6. The method for preparing the nanocomposite based on the Au-PbS heterostructure according to claim 1, wherein the method comprises the following steps: in the step 2, the lead precursor is lead chloride or lead oleate, the organic solution is a mixed solution of 1-octadecene and oleylamine, and the volume ratio of the lead precursor to the lead oleate is 4-6:1, the concentration of lead precursor in the organic solution is 10-50mM.
7. The method for preparing the nanocomposite based on the Au-PbS heterostructure according to claim 1, wherein the method comprises the following steps: in the step 3, heating to 140-180 ℃, wherein the stirring time of the solution A and the solution B is 5-60min, and the volume ratio of the solution A to the solution B is 5:1-2.
8. The method for preparing the nanocomposite based on the Au-PbS heterostructure according to claim 1, wherein the method comprises the following steps: in the step 4, the nonpolar organic solvent is normal hexane, the centrifugal speed during purification is 7500-10000r/min, the centrifugal time is 5-10min, and the centrifugation is repeated for 2-4 times.
9. The application of the nano composite material based on the Au-PbS heterostructure prepared by the preparation method of any one of claims 1-8 in preparation of tumor photothermal imaging reagents, photothermal therapeutic reagents and CT imaging reagents.
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| Rational Synthesis, Self-Assembly, and Optical Properties of PbS-Au Heterogeneous Nanostructures via Preferential Deposition;Jian Yang等;《J. AM. CHEM. SOC.》;第128卷(第36期);11921-11926 * |
| Sulfur in oleylamine as a powerful and versatile etchant for oxide, sulfide, and metal colloidal nanoparticles;Bin Yuan等;《Phys. Status Solidi A》;1-6 * |
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