CN113440623B - Au NRs @ Gd 2 O 3 Method for preparing composite material - Google Patents

Au NRs @ Gd 2 O 3 Method for preparing composite material Download PDF

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CN113440623B
CN113440623B CN202110181668.0A CN202110181668A CN113440623B CN 113440623 B CN113440623 B CN 113440623B CN 202110181668 A CN202110181668 A CN 202110181668A CN 113440623 B CN113440623 B CN 113440623B
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polyacrylic acid
water
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CN113440623A (en
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张树泉
张兴华
张燕
杨建峰
王子武
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Tianjin Hospital Of Itcwm Nankai Hospital
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Abstract

The invention provides Au NRs @ Gd 2 O 3 The preparation method of the composite material comprises the steps of firstly, synthesizing polyacrylic acid modified ultra-small Gd by using gadolinium nitrate, ammonia water and polyacrylic acid as raw materials 2 O 3 A nanoparticle; then, au NRs with different length-diameter ratios are synthesized by using chloroauric acid as an Au source, cetyl trimethyl ammonium bromide as a surfactant, sodium borohydride as a reducing agent and silver nitrate as a growth guiding agent; the positive and negative charges of different surfactants are used for electrostatic attraction to modify Gd of polyacrylic acid 2 O 3 Mixing and oscillating nano particle concentrated solution and hexadecyl trimethyl ammonium bromide modified Au NRs dispersion solution to synthesize Au NRs @ Gd 2 O 3 A composite material. The synthetic operation process is simple, and the synthesized Au NRs @ Gd 2 O 3 The composite material is non-toxic and pollution-free, has good water dispersibility and stability, and has higher T 1 MRI performance, and has wide application prospect in the biomedical field.

Description

Au NRs @ Gd 2 O 3 Method for preparing composite material
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to Au NRs @ Gd 2 O 3 A preparation method of (gold nanorod loaded gadolinium oxide nanoparticle) composite material.
Background
Malignant tumors seriously endanger human life and health, so that accurate diagnosis of tumors at an early stage is necessary. Magnetic resonance imaging is an important means for tumor diagnosis, but the imaging effect is limited, and contrast agents are required to enhance the imaging effect. Currently commercially available T 1 Magnetic resonance contrast agents are chelates of gadolinium-diethylenetriamine pentaacetic acid (Gd-DTPA), but gadolinium chelate contrast agents have been warned by the U.S. food and drug administration of the risk of causing nephrogenic systemic fibrosis.
Gadolinium-based nanoparticles as a nanoThe rice material has better T 1 Magnetic Resonance (MRI) imaging capabilities are widely studied. In order to further accurately image tumors, a plurality of imaging means are often used for assisting each other to make up for the defects of various imaging modes, so that it is particularly necessary to develop a composite nano material with multi-modal imaging potential. Gold nanorods (Au NRs) have good CT imaging potential and good photoacoustic imaging potential due to good infrared absorption capability. The gadolinium oxide nano-particles have a good magnetic resonance imaging effect, the gold nano-rods and the gadolinium oxide nano-particles are compounded, and the compounded nano-materials have the potential of multi-modal imaging.
At present, people generally prepare gold and gadolinium oxide composite nano-materials by a solvothermal method, but the method has complex operation process, needs high-temperature and high-pressure environment, and the imaging effect of the synthesized gold and gadolinium oxide composite materials is poor. Therefore, it is especially necessary to develop a preparation method of the gold and gadolinium oxide composite material with simple process and good imaging effect.
Disclosure of Invention
The invention aims to provide an Au NRs @ Gd for overcoming the defects of complex preparation process and poor imaging performance of the existing gold and gadolinium oxide composite material 2 O 3 A simple preparation method of the composite material.
The method takes water as a solvent, gadolinium nitrate as a Gd source and polyacrylic acid (PAA) as a surfactant to modify Gd 2 O 3 Nanoparticles, adopting chloroauric acid as Au source, modifying Au NRs by Cetyl Trimethyl Ammonium Bromide (CTAB), and synthesizing Au NRs @ Gd by electrostatic interaction between PAA and CTAB 2 O 3 A composite material. The method has simple synthesis process, and the synthesized Au NRs @ Gd 2 O 3 The composite material has higher T 1 MRI performance, good water solubility and stability due to the wrapping of polyacrylic acid, and filling up the existing Au NRs @ Gd 2 O 3 A blank of composite material synthesis technology.
The technical scheme of the invention is as follows:
the invention provides Au NRs @ Gd 2 O 3 Preparation method of composite materialThe method comprises the following steps: firstly, gadolinium nitrate, ammonia water and polyacrylic acid are used as raw materials to synthesize Gd modified by polyacrylic acid 2 O 3 A nanoparticle; then, au NRs are synthesized by using chloroauric acid as an Au source, cetyl trimethyl ammonium bromide as a surfactant, sodium borohydride as a reducing agent and silver nitrate as a growth guiding agent; then modifying polyacrylic acid with Gd 2 O 3 Mixing and oscillating nano particle concentrated solution and hexadecyl trimethyl ammonium bromide modified Au NRs dispersion solution to synthesize Au NRs @ Gd 2 O 3 A composite material.
Specifically, the Au NRs @ Gd 2 O 3 The preparation method of the composite material comprises the following steps:
1): adding polyacrylic acid into water, and stirring for 40-60min under argon atmosphere to obtain polyacrylic acid aqueous solution; then heating the polyacrylic acid aqueous solution to 60-100 ℃, then adding gadolinium nitrate and ammonia water, heating and stirring for 40min, and naturally cooling to room temperature; adding the obtained product into dialysis bag for dialysis for 48-72h, and centrifuging and concentrating with ultrafiltration tube to obtain Gd 2 O 3 Concentrating the solution for later use;
2): cetyl Trimethyl Ammonium Bromide (CTAB) was dissolved in water and chloroauric acid solution (HAuCl) was added 4 ) Rapidly adding ice-cold sodium borohydride (NaBH) 4 ) The solution is stirred vigorously for 110s to form a gold seed solution; adding CTAB into water, and sequentially adding HAuCl 4 Solution of AgNO 3 And adding an ascorbic acid solution and a gold seed solution into the solution after stirring, stirring the solution at normal temperature for 12-16h to obtain Au NRs, washing the Au NRs by deionized water, and dispersing the Au NRs in the deionized water to obtain an Au NRs dispersion solution for later use.
3): mixing Au NRs dispersion solution with Gd 2 O 3 Mixing the concentrated solutions, shaking for 4-6h, centrifuging, washing with deionized water, and dispersing in deionized water to obtain Au NRs @ Gd 2 O 3 A composite material.
Specifically, the Au NRs @ Gd 2 O 3 The preparation method of the composite material comprises the following steps:
1): 240mg of polyacrylic acid were added to 40mL of water inStirring for 40-60min under argon atmosphere to obtain polyacrylic acid aqueous solution; then heating the polyacrylic acid aqueous solution to 60-100 ℃, then adding 90mg of gadolinium nitrate and 2mL of 25% ammonia water, heating and stirring for 40min, and naturally cooling to room temperature; adding the obtained product into dialysis bag (molecular weight cut-off 3500 Da) for dialysis treatment for 48-72h, and then dialyzing with M w Centrifugal concentration is carried out in an ultrafiltration tube of =3000Da to obtain Gd 2 O 3 Concentrating the solution for later use;
2): 0.364g of cetyltrimethylammonium bromide (CTAB) was dissolved in 9.5mL of water, and 1mL of a 2.5mmol/L chloroauric acid solution (HAuCl) was added 4 ) 0.5mL of ice-cold sodium borohydride (NaBH) at a concentration of 0.012mol/L was added rapidly 4 ) The solution was stirred vigorously for 110s to form a gold seed solution. 3.842g CTAB was added to 80mL water followed by 2mL HAuCl at 2.5mmol/L 4 Solution, 2-6mL AgNO with concentration of 4mmol/L 3 And stirring the solution for 10min, adding 0.7mL of ascorbic acid solution with the concentration of 0.0778mol/L and 120 mu L of gold seed solution, stirring at normal temperature for 12-16h to obtain Au NRs, washing with deionized water, and dispersing in 10mL of deionized water to obtain Au NRs dispersion solution for later use.
3): 2mL of Au NRs dispersion solution and 1-2mL of Gd are respectively taken 2 O 3 Mixing the concentrated solutions, shaking for 4-6h, centrifuging at 15000r/min, washing with deionized water, and dispersing in deionized water to obtain Au NRs @ Gd 2 O 3 A composite material.
The invention also provides Au NRs @ Gd 2 O 3 A composite material prepared by the method.
The invention also provides the Au NRs @ Gd 2 O 3 Use of a composite material, the Au NRs @ Gd 2 O 3 The composite material acts as a contrast agent.
In the above application, the Au NRs @ Gd 2 O 3 Use of composite materials as contrast agents for T 1 In Magnetic Resonance (MRI) imaging.
The invention has the beneficial effects that:
the invention has simple synthetic operation process and does not need high-temperature high-pressure stripsBecause the surface of the element is coated by PAA with better biocompatibility, the synthesized Au NRs @ Gd 2 O 3 The composite material has better biocompatibility, water dispersibility and stability, and better T 1 MRI imaging performance, CT imaging and photoacoustic imaging application potential, and wide application prospect in the biomedical field.
Drawings
FIG. 1 is Gd prepared using polyacrylic acid as a surfactant in example 1 2 O 3 Transmission electron microscopy of nanoparticles.
FIG. 2 is a transmission electron micrograph of Au NRs1 prepared in example 1.
FIG. 3 is a transmission electron micrograph of Au NRs2 prepared in example 2.
FIG. 4 is a transmission electron micrograph of Au NRs3 prepared in example 3.
FIG. 5 shows Au NRs1@ Gd obtained in example 4 2 O 3 Transmission electron microscopy of the composite.
FIG. 6 is Au NRs2@ Gd obtained in example 5 2 O 3 Transmission electron microscopy images of the composite.
FIG. 7 shows Au NRs3@ Gd obtained in example 6 2 O 3 Transmission electron microscopy of the composite.
FIG. 8 is Au NRs @ Gd in examples 4 to 6 2 O 3 Zeta potential map of the composite.
FIG. 9 shows Au NRs1@ Gd obtained in example 4 2 O 3 Magnetic resonance imaging and relaxation rate r of composite material 1 Figure (a).
FIG. 10 is Au NRs2@ Gd obtained in example 5 2 O 3 Magnetic resonance imaging and relaxation rate r of composite material 1 Figure (a).
FIG. 11 shows Au NRs3@ Gd obtained in example 6 2 O 3 Magnetic resonance imaging and relaxation rate r of composite material 1 Figure (a).
FIG. 12 shows Au NRs3@ Gd obtained in example 7 2 O 3 -2 transmission electron microscopy of the composite.
FIG. 13 shows Au NRs3@ Gd obtained in example 8 2 O 3 -3 transmission electron microscopy of the composite.
FIG. 14 is Au NRs3@ Gd in examples 6-8 2 O 3 Zeta potential map of the composite.
FIG. 15 shows Au NRs3@ Gd obtained in example 7 2 O 3 -2 magnetic resonance imaging and relaxation rate r of the composite material 1 Figure (a).
FIG. 16 shows Au NRs3@ Gd obtained in example 8 2 O 3 -3 magnetic resonance imaging and relaxation rate r of composite material 1 Figure (a).
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Au NRs @ Gd prepared by utilizing technical scheme of the invention 2 O 3 The material was subjected to transmission electron microscopy (JEOL, 2100)), zeta potential (laser granulometer (SURPASS 3)) and magnetic resonance imaging performance (nuclear magnetic resonance scanner (prism 3.0T), with magnetic resonance test parameters of 200ms repetition time, 12ms echo time, 20cm × 5cm imaging field, 128 × 128 phase encoding matrix).
1. Different AgNO 3 Au NRs were prepared under the condition of addition amount.
Example 1:
step 1: adding 240mg of polyacrylic acid into 40mL of water, and stirring for 40min under an argon environment; heating the polyacrylic acid aqueous solution to 60 ℃, adding 90mg of gadolinium nitrate and 2mL of 25% ammonia water, heating and stirring for 40min, and naturally cooling to room temperature; adding the obtained product into dialysis bag (molecular weight cut-off 3500 Da) for dialysis treatment for 48h, and then dialyzing with M w Centrifugal concentration is carried out in an ultrafiltration tube of =3000Da to obtain Gd 2 O 3 The solution was concentrated for use.
Step 2: 0.364g of cetyltrimethylammonium bromide was dissolved in 9.5mL of water, and 1mL of HAuCl was added at a concentration of 2.5mmol/L 4 The solution was rapidly added 0.5mL of ice-cold NaBH at a concentration of 0.012mol/L 4 The solution was stirred vigorously for 110s to form a gold seed solution. 3.842g CTAB was added to 80mL of water followed by 2mL of 2.5mmol/L HAuCl 4 Solution, 2mL concentrationIs 4mmol/L AgNO 3 The solution is stirred for 10min, then 0.7mL ascorbic acid solution with the concentration of 0.0778mol/L and 120 mu L gold seed solution are added, the solution is stirred for 12h at normal temperature to obtain Au NRs1, and then the Au NRs1 is washed by deionized water and dispersed in 10mL deionized water for standby.
Example 2:
the other steps are the same as example 1, except for the AgNO in step 2 3 The volume was changed from 2mL to 4mL to obtain Au NRs2.
Example 3:
the other steps are the same as example 1 except that AgNO in step 2 3 The volume was changed from 2mL to 6mL to obtain Au NRs3.
And (3) testing results:
FIG. 1 is Gd prepared using polyacrylic acid 2 O 3 The transmission electron microscope image of the nano-particles shows that the nano-particles have good dispersibility and the particle size is about 1.4 nm.
By changing AgNO 3 The Au NRs with different sizes are prepared according to the addition amount, and transmission electron microscope tests are carried out on the Au NRs, and the test results are respectively shown in FIGS. 2 to 4. FIG. 2 is a transmission electron micrograph of Au NRs1 prepared in example 1, and the result shows that the aspect ratio of the prepared Au NRs1 is about 2.5. FIG. 3 is a transmission electron micrograph of Au NRs2 prepared in example 2, and the result shows that the aspect ratio of the prepared Au NRs2 is about 3.2. FIG. 4 is a transmission electron micrograph of Au NRs3 prepared in example 3, and the result shows that the aspect ratio of the prepared Au NRs3 is about 3.7. As can be seen from the results of transmission electron microscopy, agNO was observed 3 The aspect ratio of Au NRs is gradually increased by increasing the adding amount.
2. Using Gd 2 O 3 The nano particles are coated with Au NRs with different length-diameter ratios to obtain Au NRs @ Gd 2 O 3 A composite material.
Example 4:
step 1: adding 240mg of polyacrylic acid into 40mL of water, and stirring for 50min under an argon environment; heating the polyacrylic acid aqueous solution to 80 ℃, then adding 90mg of gadolinium nitrate and 2mL of 25% ammonia water, heating and stirring for 40min, and naturally cooling to room temperature; adding the obtained product into dialysis bag (molecular weight cut-off 3500 Da) for permeationSeparating for 60h, and then treating with M w Centrifugal concentration in ultrafiltration tube of =3000Da to obtain Gd 2 O 3 The solution was concentrated for use.
Step 2: 0.364g of cetyltrimethylammonium bromide was dissolved in 9.5mL of water, and 1mL of HAuCl was added at a concentration of 2.5mmol/L 4 The solution was quickly added 0.5mL of ice-cold NaBH at a concentration of 0.012mol/L 4 The solution was stirred vigorously for 110s to form a gold seed solution. 3.842g CTAB was added to 80mL of water followed by 2mL of 2.5mmol/L HAuCl 4 Solution, 2mL of AgNO with a concentration of 4mmol/L 3 The solution is stirred for 10min, then 0.7mL of ascorbic acid solution with the concentration of 0.0778mol/L and 120 mu L of gold seed solution are added, the solution is stirred for 14h at normal temperature to obtain Au NRs1, and then the Au NRs1 is washed by deionized water and dispersed in 10mL of deionized water for later use.
And step 3: 2mL of Au NRs1 dispersion solution and 1mL of Gd were respectively taken 2 O 3 Mixing the concentrated solutions, shaking for 4h, centrifuging at 15000r/min, washing with deionized water, and dispersing in deionized water to obtain Au NRs1@ Gd 2 O 3 A composite material.
Example 5:
the other steps are the same as example 4 except that AgNO in step 2 3 Changing 2mL into 4mL to obtain Au NRs2@ Gd 2 O 3 A composite material.
Example 6:
the other steps are the same as example 4 except that AgNO in step 2 3 Changing 2mL into 6mL to obtain Au NRs3@ Gd 2 O 3 A composite material.
And (3) testing results: FIGS. 5 to 7 are each Gd 2 O 3 Au NRs1@ Gd compounded by nano particles and Au NRs with different length-diameter ratios 2 O 3 、Au NRs2@Gd 2 O 3 、Au NRs3@Gd 2 O 3 Transmission electron micrograph of the composite showing Gd 2 O 3 The nano particles are compactly wrapped on the periphery of the Au NRs.
FIG. 8 shows Gd 2 O 3 After the nano particles are compounded with Au NRs, the Zeta potential on the surface of the composite material is changed from positive electrical property to negative electrical property and the value is changedLarger indicates Gd 2 O 3 The nano particles are successfully compounded with Au NRs, the electronegative PAA is coated on the outer layer of the composite material, and the PAA has better biological cell compatibility, so that Au NRs @ Gd 2 O 3 Has better biocompatibility and stability. FIGS. 9-11 are Gd 2 O 3 Au NRs1@ Gd compounded by nano particles and Au NRs with different length-diameter ratios 2 O 3 、Au NRs2@Gd 2 O 3 、Au NRs3@Gd 2 O 3 Magnetic resonance imaging map and magnetic resonance relaxation rate r of composite material 1 And a fitted curve thereof. As can be seen, the magnetic resonance imaging graphs thereof all become brighter with the increase of Gd concentration, and with the increase of the aspect ratio of Au NRs, au NRs1@ Gd 2 O 3 Relaxation rate r of 1 42.46mM -1 s -1 ，Au NRs2@Gd 2 O 3 Relaxation rate r of 1 42.66mM - 1 s -1 ，Au NRs3@Gd 2 O 3 Relaxation rate r of 1 43.64mM -1 s -1 . The results show that Au NRs @ Gd 2 O 3 Relaxation rate r of composite material 1 The aspect ratio of Au NRs is slightly improved along with the increase of the aspect ratio of Au NRs.
3. Modification of Gd 2 O 3 The nano-particle loading is Au NRs @ Gd 2 O 3 A composite material.
Example 7:
step 1: adding 240mg of polyacrylic acid into 40mL of water, and stirring for 60min under an argon environment; heating the polyacrylic acid aqueous solution to 100 ℃, then adding 90mg of gadolinium nitrate and 2mL of 25% ammonia water, heating and stirring for 40min, and naturally cooling to room temperature; adding the obtained product into dialysis bag (molecular weight cut-off 3500 Da) for dialysis treatment for 72h, and then dialyzing with M w Centrifugal concentration is carried out in an ultrafiltration tube of =3000Da to obtain Gd 2 O 3 The solution was concentrated for use.
And 2, step: 0.364g of cetyltrimethylammonium bromide was dissolved in 9.5mL of water, and 1mL of HAuCl was added at a concentration of 2.5mmol/L 4 The solution was rapidly added 0.5mL of ice-cold NaBH at a concentration of 0.012mol/L 4 Solution, vigorously stirringStirring for 110s to form a gold seed solution. 3.842g CTAB was added to 80mL of water followed by 2mL of 2.5mmol/L HAuCl 4 Solution, 6mL of AgNO with a concentration of 4mmol/L 3 The solution is stirred for 10min, then 0.7mL ascorbic acid solution with the concentration of 0.0778mol/L and 120 mu L gold seed solution are added, the solution is stirred for 16h at normal temperature to obtain Au NRs3, and then the Au NRs3 is washed by deionized water and dispersed in 10mL deionized water for standby.
And step 3: 2mL of Au NRs3 dispersion and 1.5mL of Gd were separately added 2 O 3 Mixing the concentrated solutions, shaking for 6h, centrifuging at 15000r/min, washing with deionized water, and dispersing in deionized water to obtain Au NRs3@ Gd 2 O 3 -2 composite material.
Example 8:
the other procedure was the same as in example 7 except that Gd was used in step 3 2 O 3 Changing the concentration solution from 1.5mL to 2mL to obtain Au NRs3@ Gd 2 O 3 -3 composite material.
And (3) testing results: FIGS. 12-13 show the modification of Gd 2 O 3 Supported Au NRs3@ Gd 2 O 3 Transmission electron micrograph of the composite showing Gd dependence 2 O 3 Increased amount of added Au NRs3 external Gd 2 O 3 The amount of load of (b) increases.
FIG. 14 shows Au NRs3 and Gd 2 O 3 After compounding, the Zeta potential of the composite material is changed from positive to negative, and the composite material has better stability.
FIGS. 15-16 are graphs showing increased Gd 2 O 3 Au NRs3@ Gd after loading 2 O 3 -2 and Au NRs3@ Gd 2 O 3 -3 magnetic resonance imaging chart, relaxation rate and fitting curve thereof, wherein the magnetic resonance imaging chart becomes brighter gradually along with the increase of Gd concentration, and the relaxation rate r thereof 1 Respectively 49.66mM -1 s -1 And 49.88mM -1 s -1 . The results show that with Gd 2 O 3 Has an increased loading, the relaxation rate r of the composite material 1 The value increases.
From the above results, it can be seen that Au NRs @ Gd proposed by the present invention 2 O 3 The preparation method of the composite material is simple and pollution-free, and has higher T 1 MRI performance, and T 1 MRI performance can be adjusted through load amount, has great application potential, and fills up Au NRs @ Gd 2 O 3 A blank of composite material synthesis technology.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
The invention is not the best known technology.

Claims (5)

1. Au NRs @ Gd 2 O 3 The preparation method of the composite material is characterized by comprising the following steps: firstly, gadolinium nitrate, ammonia water and polyacrylic acid are used as raw materials to synthesize polyacrylic acid modified Gd 2 O 3 A nanoparticle; then, au NRs are synthesized by using chloroauric acid as an Au source, cetyl trimethyl ammonium bromide as a surfactant, sodium borohydride as a reducing agent and silver nitrate as a growth guiding agent; then modifying polyacrylic acid with Gd 2 O 3 Mixing and oscillating nano particle concentrated solution and hexadecyl trimethyl ammonium bromide modified Au NRs dispersion solution to synthesize Au NRs @ Gd 2 O 3 A composite material.
2. Au NRs @ Gd according to claim 1 2 O 3 The preparation method of the composite material is characterized by comprising the following steps: the method comprises the following steps:
1): adding polyacrylic acid into water, and stirring for 40-60min under argon atmosphere to obtain polyacrylic acid aqueous solution; then heating the polyacrylic acid aqueous solution to 60-100 ℃, then adding gadolinium nitrate and ammonia water, heating and stirring for 40min, and naturally cooling to room temperature; adding the obtained product into dialysis bag for dialysis treatment for 48-72h, and centrifuging and concentrating with ultrafiltration tube to obtain Gd 2 O 3 Concentrating the solution for later use;
2): dissolving cetyl trimethyl ammonium bromide in water, adding chloroauric acidRapidly adding an ice-cold sodium borohydride solution into an acid solution, and violently stirring for 110s to form a gold seed solution; CTAB is added into water, HAuCl is added in sequence 4 Solution of AgNO 3 Adding an ascorbic acid solution and a gold seed solution into the solution after stirring, stirring for 12-16h at normal temperature to obtain Au NRs, washing with deionized water, and dispersing in the deionized water to obtain an Au NRs dispersion solution for later use;
3): mixing Au NRs dispersion solution with Gd 2 O 3 Mixing the concentrated solutions, oscillating for 4-6h, centrifuging, washing with deionized water, and dispersing in deionized water to obtain Au NRs @ Gd 2 O 3 A composite material.
3. Au NRs @ Gd according to claim 2 2 O 3 The preparation method of the composite material is characterized by comprising the following steps: the method comprises the following steps:
1): adding 240mg of polyacrylic acid into 40mL of water, and stirring for 40-60min under an argon environment to obtain a polyacrylic acid aqueous solution; then heating the polyacrylic acid aqueous solution to 60-100 ℃, then adding 90mg of gadolinium nitrate and 2mL of 25% ammonia water, heating and stirring for 40min, and naturally cooling to room temperature; adding the obtained product into dialysis bag with molecular weight cut-off of 3500Da for dialysis treatment for 48-72h, and then dialyzing with M w Centrifugal concentration is carried out in an ultrafiltration tube of =3000Da to obtain Gd 2 O 3 Concentrating the solution for later use;
2): dissolving 0.364g of hexadecyl trimethyl ammonium bromide in 9.5mL of water, adding 1mL of 2.5mmol/L chloroauric acid solution, quickly adding 0.5mL of 0.012mol/L ice-cold sodium borohydride solution, and violently stirring for 110s to form a gold seed solution; 3.842g CTAB was added to 80mL of water followed by 2mL of 2.5mmol/L HAuCl 4 Solution of 2-6mL AgNO with concentration of 4mmol/L 3 Stirring the solution for 10min, adding 0.7mL of ascorbic acid solution with the concentration of 0.0778mol/L and 120 mu L of gold seed solution, stirring at normal temperature for 12-16h to obtain Au NRs, washing with deionized water, and dispersing in 10mL of deionized water to obtain Au NRs dispersion solution for later use;
3): 2mL of Au NRs dispersion solution and 1-2mL of Gd are respectively taken 2 O 3 Mixing the concentrated solutions, shaking for 4-6h, centrifuging at 15000r/min, washing with deionized water, and dispersing in deionized water to obtain Au NRs @ Gd 2 O 3 A composite material.
4. Au NRs @ Gd 2 O 3 A composite material characterized by: the composite material is prepared by the method of any one of claims 1 to 3.
5. The Au NRs @ Gd of claim 4 2 O 3 Preparation of composite Material 1 Use in contrast agents for magnetic resonance imaging.
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