CN110695368B - Eight-fork gold nano-particle, preparation method, application and intermediate thereof - Google Patents

Eight-fork gold nano-particle, preparation method, application and intermediate thereof Download PDF

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CN110695368B
CN110695368B CN201810753194.0A CN201810753194A CN110695368B CN 110695368 B CN110695368 B CN 110695368B CN 201810753194 A CN201810753194 A CN 201810753194A CN 110695368 B CN110695368 B CN 110695368B
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刘堃
常艺馨
张宁宁
陶幸福
孙天盟
张俊虎
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Jilin University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract

The invention discloses eight-fork gold nanoparticles with a ligand A, a preparation method, application and an intermediate. The single-arm length of each branch of the eight-branch gold nanoparticle is 10-30 nm, the single-arm width is 5-20 nm, the preparation method of the eight-branch gold nanoparticle is simple and mild, the reaction rate is high, the repeatability is high, the scale is easy to realize, and the prepared eight-branch gold nanoparticle with the ligand A has the advantages of narrow absorption spectrum peak, high strength, good monodispersity, controllable morphology and good photo-thermal and photo-acoustic properties.

Description

Eight-fork gold nano-particle, preparation method, application and intermediate thereof
Technical Field
The invention discloses eight-fork gold nanoparticles, a preparation method, application and an intermediate thereof.
Background
In the nanoscale, metals exhibit exceptional properties that make them outstanding in a wide range of research applications. Among them, gold nanoparticles have the characteristics of good biological inertia, easy surface modification and the like, so that the gold nanoparticles are widely researched in the biological field. As with other nanomaterials, the size and morphology of gold nanoparticles are two critical parameters that are used to control the properties of the particles to meet different applications. In most cases, particles of different configurations possess different physicochemical properties, so this parameter of morphology is more versatile in adjusting particle properties.
The branch-shaped gold nano-particles have the properties of high specific surface area, enhanced tip electromagnetic field, unique surface plasmon resonance and the like, so that the branch-shaped gold nano-particles have very wide application values in the aspects of catalysis, surface enhanced Raman scattering, photothermal therapy, photoacoustic imaging and the like. Wherein the yield, monodispersity, branch space configuration, repeatability and the like of the branch-shaped gold nanoparticles greatly influence the application performance of the particles.
At present, a plurality of synthesis strategies for constructing branch-shaped gold nanoparticles exist. For example, the Sihai Chen group prepared branched gold nanoparticles for the first time [ J.Am.chem.Soc.2003,125,16186-16187 ], but a series of branched gold nanoparticles with different morphologies, such as four branched particles with one branched, two branched, three branched and planar configurations, existed in the system at the same time. The number of the particle branches synthesized by the method is uncontrollable, so that the monodispersity, the yield and the repeatability of the product are low.
The document [ J.Mater.chem.2012,22, 2244-. However, the peak width at half maximum of the particle spectrum is broad, indicating that the monodispersity of the particles is poor. Moreover, it is known from the electron microscope photographs that the number of branches of the particles is not uniform, and the morphology controllability is poor.
The document [ J.Phys.chem.C 2016,120,20563-20571 ] reports that eight-branched gold nanoparticles are synthesized, but the particles synthesized by the method have short branched arms and unobvious branched morphology, so that the application effect is reduced. At the same time, the broader spectrum illustrates the inhomogeneity in particle size and structure in the system.
In conclusion, the method for conveniently and rapidly synthesizing the branch-shaped gold nanoparticles with high yield, high repeatability, high uniformity and controllable morphology is still a very delicate problem, and the application of the branch-shaped gold nanoparticles is limited to a great extent. Therefore, the method for synthesizing the branch-shaped gold nanoparticles with high yield, good monodispersity and precise and controllable morphology has wide application prospect and commercial value.
Disclosure of Invention
The invention aims to solve the technical problems that the method for preparing the branched gold nanoparticles in the prior art is low in yield and low in repeatability, or the prepared branched gold nanoparticles are uneven in size, uncontrollable in shape or poor in uniformity and the like, so that the eight-branched gold nanoparticles with the ligands A, the preparation method, the application and the intermediates thereof are provided. The eight-fork gold nanoparticles are prepared by adopting a specific seed crystal method. The preparation method is simple and mild, the reaction rate is high, the repeatability is high, the scale is easy to realize, and the prepared octafurcate gold nanoparticles with the ligand A are narrow in absorption spectrum peak, high in strength, good in monodispersity, controllable in shape and good in photo-thermal and photo-acoustic properties.
The present invention solves the above problems by the following means.
The invention provides an eight-branch gold nanoparticle, wherein the eight-branch gold nanoparticle is provided with a ligand A, the length of a single arm of each branch of the eight-branch gold nanoparticle is 10-30 nm, and the width of the single arm is 5-20 nm; the eight branches of the eight-branch gold nano-particles have the same length and width, and the growth direction is<111>Direction and spatial symmetry to OhPoint group;
the ligand A is a cationic surfactant.
In the invention, the width of the single arm refers to the width of the branch corresponding to the position when the length of the single arm is half.
In the present invention, the length of the single arm of the octafurcate gold nanoparticles may be 15.8nm to 22.8nm (e.g., 16.9nm to 18.4nm, and further, 17.5nm to 18.4 nm).
In the present invention, the single-arm width of the octafurcate gold nanoparticles may be 9.3nm to 12.6nm (e.g., 9.9nm to 11.4nm, and further, e.g., 10.3nm to 11.4 nm).
In the present invention, the single-arm length and the single-arm width of the octafurcate gold nanoparticles may be 17.5nm by 9.9nm, 22.8nm by 11.4nm, 15.8nm by 12.6nm, 18.4nm by 9.3nm or 16.9nm by 10.3 nm.
In the present invention, the growth directions of the eight branches of the octafurcate gold nanoparticles can be seen in fig. 3, and for example, the growth directions of the eight branches of the octafurcate gold nanoparticles can be [111], [ -111], [ -1-11 ], [1-11], [11-1], [ -11-1], [ -1-1-1] and [1-1-1] respectively.
In the present invention, the cationic surfactant may be a quaternary ammonium salt, and the quaternary ammonium salt may be one or more selected from the group consisting of cetyltrimethyl ammonium bromide, benzylhexadecyldimethyl ammonium chloride, hexadecyltripropyl ammonium bromide, hexadecyltributyl ammonium bromide, hexadecyltripentyl ammonium bromide and hexadecyltrihexyl ammonium bromide.
The invention also provides a preparation method of the eight-fork gold nanoparticles, which comprises the following steps:
in water, under the condition that the pH value is 7-14 and the action of a weak reducing agent, nano gold seeds with a ligand A and Au are mixed+Reacting the complex;
the Au layer+The complex is prepared by the following method: the method comprises the following steps of reacting Au in water under the action of a ligand A and a strong reducing agent A3+Reduction reaction is carried out to obtain Au+A complex, i.e. a compound;
the strong reducing agent A is Au3+Reduction to Au+Then reduced to Au0In the step (2), the strong reducing agent A is controlled to add Au3+Reduction to Au+
The weak reducing agent is Au capable of reacting3+Reduction to Au+The reducing agent of (1);
the ligand A is as defined above.
In the invention, the strong reducing agent A can be selected from one or more of 4-hydroxyethyl piperazine ethanesulfonic acid, triethylene diamine and 1-methyl pyrrolidine; such as 1-methylpyrrolidine.
In the present invention, the weak reducing agent may be ascorbic acid and/or tartaric acid.
In the invention, the pH value is 7-14, and the pH value can be adjusted by adding the strong reducing agent A or an alkali solution.
In the present invention, the nanogold seed having the ligand A and the Au+The molar ratio of the complex may be 6.7 x 10-9~1.1*10-7E.g. 3.3 x 10-8:1。
In the present invention, the Au is+The concentration of the complex in the reaction solution may be 0.45 to 0.75mM, for example, 0.57 mM.
In the invention, the concentration of the nanogold seed with the ligand A in the reaction solution can be 5.0 to 10-12~5.0*10-11mol/L, e.g. 1.0 x 10-11~3.0*10-11mol/L, e.g. 2.0 x 10-11mol/L。
The reaction solution is prepared by reacting nanogold seeds with ligand A and Au in water under the action of a weak reducing agent under the condition that the pH value is 7-14+Reaction solution in the reaction of the complex.
Au according to the invention+In the preparation method of the complex, the molar using ratio of the weak reducing agent to the ligand A can be 1.25 x 10-30.122, e.g., 0.024: 1.
Au according to the invention+In the preparation method of the complex, the molar ratio of the weak reducing agent to the strong reducing agent A can be 2.5 to 10-30.49, e.g., 0.025: 1.
Au according to the invention+In the preparation method of the complex, the weak reducing agent and the Au3+The molar ratio of (A) to (B) can be 0.67 to 10.8, for example 3.95: 1.
Au according to the invention+In the method for producing a complex, the concentration of the weak reducing agent in the reaction solution may be 5.0 x 10-4~4.88*10-3mol/L, e.g. 2.25 x 10-3mol/L。
Au according to the invention+In the preparation method of the complex, the concentration of the ligand A in the reaction liquid can be 0.04-0.4 mol/L, for example 0.095 mol/L.
Au according to the invention+In the preparation method of the complex, the concentration of the strong reducing agent A in the reaction solution can be 0.01-0.2 mol/L, such as 0.07-0.11 mol/L, and further such as 0.09 mol/L.
Preferably, Au is provided according to the invention+The preparation of the complex is carried out at a pH of greater than 11.
Au according to the invention+In the preparation method of the complex, the Au3+May be present with Au3+In an aqueous solution of, for example, said Au3+Is in the water solution of tetrachloroauric acid, tetrabromo auric acid or potassium chloroaurate.
Au according to the invention+In the preparation method of the complex, the reduction reaction can be carried out at 25-30 DEG CAt a temperature.
Au according to the invention+In the method for producing the complex, the end point of the reaction can be judged by the color change of the reaction solution, for example, when the color of the reaction solution changes to blue or blue-green and the color does not change any more, the end point of the reaction can be determined.
Preferably, the preparation method of the octafurcate gold nanoparticles comprises the following steps: mixing the solution A and the solution B in water under the condition that the pH value is 7-14; the solution A is prepared by mixing a ligand A, a strong reducing agent A and Au3+Mixing to obtain Au with ligand A+A solution; the solution B is obtained by mixing a weak reducing agent and the nanogold seeds; the ligand A, the strong reducing agent A and the weak reducing agent are as defined above.
More preferably, the preparation method of the octafurcate gold nanoparticles comprises the following steps: mixing the solution A and the solution B under the condition that the pH value is 7-14; the solution A is prepared by mixing water, ligand A, strong reducing agent A and Au3+Mixing to obtain Au with ligand A+A solution; the solution B is obtained by mixing water, a weak reducing agent and nanogold seeds; the ligand A, the strong reducing agent A and the weak reducing agent are as defined above.
Wherein, in the solution A, the concentration of the ligand A in the solution A can be 0.084-0.84 mol/L, for example, 0.20 mol/L.
Wherein, in the solution A, the concentration of the strong reducing agent A in the solution A can be 0.021-0.42 mol/L, for example, 0.19 mol/L.
Wherein, in the solution A, the Au is3+The concentration in the solution A may be 0.94 to 1.57 mmol/L, for example, 1.19 mmol/L.
Wherein, in the solution B, the concentration of the weak reducing agent in the solution B can be 0.96-9.33 mmol/L, for example, 4.31 mmol/L.
Wherein, in the solution B, the concentration of the nanogold seeds in the solution B can be 9.6 x 10-12~9.6*10-11mol/L, e.g. 3.8 x 10-11mol/L。
In one embodiment of the present invention, the octafurcate gold nanoparticles can be prepared by the following method (the definition of the unexplained is as described above):
mixing water and ligand A, Au3+And Au is uniformly mixed with the strong reducing agent A until the mixture is colorless+Solution A of (1); uniformly mixing water, a weak reducing agent and the nanogold seeds to obtain a solution B; and mixing the solution A and the solution B uniformly.
In a preferred embodiment of the present invention, the ligand A is present in an aqueous solution of ligand A, and the Au is present in an aqueous solution of ligand A3+Present in a solution containing Au3+The strong reducing agent a is present in an aqueous solution of the strong reducing agent a, and the weak reducing agent is present in an aqueous solution of the weak reducing agent; the nanogold seeds exist in the nanogold seed aqueous solution.
The ligand A aqueous solution, the strong reducing agent A aqueous solution, the Au-containing solution3+The aqueous solution of (A), the aqueous solution of the weak reducing agent and the aqueous solution of the nano-gold seeds are the ligand A, the strong reducing agent A and the Au respectively3+The weak reducing agent and the nano gold seeds are respectively mixed with water to form a solution.
Wherein the concentration of the ligand A in the ligand A aqueous solution can be 0.04-0.5 mol/L, such as 0.4 mol/L.
Wherein, the concentration of the strong reducing agent A in the strong reducing agent A water solution can be 0.01-9.5 mol/L, such as 1 mol/L.
Wherein, the Au is3+In the Au3+The concentration in the aqueous solution may be 1 to 20mmol/L, for example 15 mmol/L.
Wherein the concentration of the weak reducing agent in the weak reducing agent aqueous solution may be 5.0 x 10-41.0mol/L, for example 0.1 mol/L.
Wherein, the concentration of the nanogold seeds in the nanogold seed aqueous solution can be 10-500 nmol/L, such as 100 nmol/L.
The nanogold seed with the ligand A can be prepared according to a conventional method:
for example, the said carrier ligandThe preparation method of the nano gold seed of A comprises the following steps of reacting Au in water under the action of the ligand A and a strong reducing agent3+Carrying out reduction reaction to obtain nanogold seeds with ligands A; the ligand A is as defined above.
The strong reducing agent is Au3+Reducing the metal into Au atoms.
Wherein the solvent may be deionized water.
Wherein the molar volume ratio of the ligand A in the reaction solution can be 0.0077-0.25 mol/L, such as 0.12 mol/L.
Wherein the molar use ratio of the strong reducing agent to the ligand A can be (0.00004-3): 1, e.g. 0.01: 1.
Wherein, the ligand A and the Au3+The molar ratio of (a) to (b) can be 7:1 to 25000:1, for example 251: 1.
Wherein, the Au is3+May be present with Au3+In an aqueous solution of, for example, said Au3+Is present in tetrachloroauric acid aqueous solution, tetrabrominated auric acid aqueous solution or potassium chloroaurate aqueous solution.
Wherein, the strong reducing agent can be sodium borohydride and/or hydrazine.
Wherein the reduction reaction can be carried out at a temperature of 20-30 ℃, for example, 25.5 ℃.
Wherein, the reduction reaction can judge the reaction end point through the color change of the reaction solution, for example, the reaction end point is determined through the color change of the reaction solution from yellow to brown and the color does not change any more.
After the reduction reaction is finished, the prepared gold seed solution can be used after standing, and more preferably, the temperature during standing is 20-30 ℃, for example, 25 ℃.
Preferably, the preparation method of the nanogold seed with the ligand A comprises the following steps: the ligand A and the Au are sequentially added into the solvent3+And the strong reducing agent is subjected to reduction reaction to obtain the nanogold seed.
More preferably, the ligand A is present in an aqueous solution of ligand A, andthe Au3+Present in a solution containing Au3+The strong reducing agent is present in an aqueous solution of the strong reducing agent.
The ligand A solution and the solution containing Au3+The solution of (A) and the solution of the strong reducing agent are the ligand A and the Au respectively3+And solutions of the strong reducing agent and the water, respectively.
Wherein the concentration of the ligand A in the ligand A aqueous solution can be 0.01-0.25 mol/L, such as 0.14 mol/L.
Wherein the concentration of the strong reducing agent in the reducing agent aqueous solution can be 0.001-0.15 mol/L, such as 0.01 mol/L.
Wherein, the Au is3+In the Au3+The concentration of the aqueous solution may be 1 to 15 mmol/L.
The invention also provides the eight-furcate gold nanoparticles prepared by the preparation method.
The invention also provides application of the octa-furcate gold nanoparticles in photothermal therapy and photoacoustic imaging.
The invention also provides Au+A method of preparing a complex comprising the steps of: in water, Au is reacted under the action of ligand A and strong reducing agent A3+Reduction reaction is carried out to obtain Au+A complex, i.e. a compound; the amounts of the ligand A, the strong reducing agent A and the reactants are, for example, as described above.
The invention also provides Au as above+Preparation method of complex and Au prepared by preparation method+A complex compound.
In the present invention, the Au is+The complex is an intermediate for preparing the octafurcate gold nanoparticles.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the eight-furcate gold nanoparticles provided by the invention have narrow absorption spectrum peak, high strength, good monodispersity, controllable morphology and good photo-thermal and photo-acoustic properties; the preparation method is simple and mild, has high reaction rate and high repeatability, and is easy to scale.
(1) The preparation method of the eight-fork gold nanoparticles provided by the invention is simple and mild, and has a high reaction rate; the prepared octabifurcate particles grow on the nanometer seeds, and the prepared octabifurcate gold nanoparticles have narrow absorption spectrum peaks, high strength, good monodispersity, controllable morphology, high repeatability and easy scale production;
(2) the plasma absorption peak position and the size of the branch particles can be adjusted only by adjusting the concentration of the added gold seed particles, and the gold nanoparticles with different plasma absorption peak positions and sizes can be selectively prepared aiming at different applications;
(3) the eight-branch particles provided by the invention can be completely collected only by centrifugation, and are easy to apply;
(4) the octabifurcate particle provided by the invention has good photothermal property, the photothermal conversion efficiency can reach 80.4%, and the octabifurcate particle can be applied to photothermal therapy, photoacoustic imaging and the like.
Drawings
FIG. 1 is a diagram showing an ultraviolet absorption spectrum of the octafurcate gold nanoparticles prepared in example 1;
FIGS. 2 and 3 are TEM images of the octafurcate gold nanoparticles prepared in example 1, and the growth directions of the octafurcate gold nanoparticles obtained are analyzed; and the three-dimensional structure diagram and the length and the width of the eight-branched gold nano particles;
FIG. 4 shows the light absorption intensity (particle concentration) of the octafurcate gold nanoparticle solution prepared in example 1 at 1W/cm2Temperature change curve under 660 nm laser illumination;
FIG. 5 is a photo-acoustic image of the solutions of eight-furcate gold nanoparticles with different absorption intensities (particle concentrations) prepared in example 1.
FIG. 6 is a UV absorption spectrum of four-furcated gold nanoparticles prepared in comparative example 3.
FIGS. 7 and 8 are TEM images of four branches of gold nanoparticles prepared in comparative example 3, and the resulting four branches were analyzed for their growth directions; and the three-dimensional structure diagram and the length and the width of the four-branched gold nanoparticles.
FIG. 9 is a graph of the absorption intensity (particle concentration) of four-branched gold nanoparticle solutions prepared in comparative example 3 at 1W/cm2Temperature change curve under 808 nm laser illumination.
FIG. 10 is a photo-acoustic image of four-furcate gold nanoparticle solutions with different absorption intensities (particle concentrations) prepared in comparative example 3.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Cetyl trimethylammonium bromide, tetrachloroauric acid, 1-methylpyrrolidine, urotropin and ascorbic acid used in the following examples were all purchased from sigma aldrich. Sodium hydroxide was purchased from alatin corporation.
The room temperature is 20-30 ℃.
High resolution transmission electron microscope manufacturer JEOL, model JEM-2100F
The UV-visible spectrophotometer is manufactured by PerkinElmer and Lambda 950;
example 1
1.1 preparation of nanogold seed solution with ligand A:
(1) 3.5mL of hexadecyl trimethyl ammonium bromide aqueous solution with the concentration of 0.14mol/L, 10mL of tetrachloroauric acid solution with the concentration of 15mmol/L and 15mL of sodium borohydride aqueous solution with the concentration of 0.01mol/L are prepared (ice water bath).
(2) To 3.5mL of a 0.14mol/L hexadecyltrimethylammonium bromide aqueous solution, 130. mu.L of a 15mmol/L tetrachloroauric acid aqueous solution was added, and while stirring magnetically (1200rpm) and at room temperature, 500. mu.L of a 0.01mol/L aqueous sodium borohydride solution was added, whereby the color of the solution rapidly changed from yellow to brown. After stirring for 2 minutes, the mixture is placed in a water bath at 25 ℃ for standby.
The nanogold seed solution with the ligand A prepared by the method is about 100 nM.
1.2 preparation of eight-fork gold nanoparticle solution
The preparation method of the eight-fork gold nanoparticle solution comprises the following steps:
10mL of hexadecyl trimethyl ammonium bromide aqueous solution with the concentration of 0.4mol/L, 10mL of 1.0 mol/L1-methyl pyrrolidine aqueous solution, 10mL of tetrachloroauric acid solution with the concentration of 15mmol/L and 5mL of ascorbic acid aqueous solution with the concentration of 0.1mol/L are prepared.
To 2.375mL of a 0.4mol/L hexadecyltrimethylammonium bromide aqueous solution, 1.12mL of an aqueous solution, 380. mu.L of a 15mmol/L tetrachloroauric acid aqueous solution, and 0.9mL of a 1.0 mol/L1-methylpyrrolidine aqueous solution were added, and the mixture was mixed uniformly to change the solution from yellow to colorless (i.e., solution A). At this time, a mixed solution of nanogold seed solution (solution B) prepared from 5.0mL of deionized water, 225. mu.L of ascorbic acid aqueous solution with a concentration of 0.1mol/L, and 2.0. mu.L of 1.1 was added to the above solution. And (3) rapidly and uniformly mixing the solution A and the solution B, and standing in a water bath at 25 ℃ for 5 minutes to obtain blue-green gold nanoparticle octafurcate solution.
The spectra for the synthesized octafurcate gold nanoparticles are measured by an ultraviolet-visible spectrophotometer and characterized by a transmission electron microscope as shown in fig. 1, fig. 2 and fig. 3. As can be seen from FIG. 1, the absorption spectrum peak position 682nm and half-peak width of the synthesized eight-furcate gold nanoparticles are small (76nm), at least 50 particles are counted, the length of a single arm of the eight-furcate particles is 17.5 +/-1.6 nm, the width is 9.9 +/-0.9 nm, and the relative standard deviation is 9.1%, which indicates that the synthesized eight-furcate particles are good in uniformity. The yield of the eight-fork gold nano-particles prepared by the method is as high as 81%. The three-dimensional structure of the prepared octafurcate particle is shown in figures 2 and 3.
As can be seen from fig. 2 and 3, the growth direction <111> direction of the eight branches of the eight-branched gold nanoparticles.
Effect example 1
Photothermal performance of 660 nano-grade light irradiation of eight-furcate gold nanoparticles
Preparing 1mL of eight-fork gold nanoparticle aqueous solution with absorbance of 0.25, respectively placing pure deionized water as reference in a quartz cuvette, and using 660-nanometer laser 1W/cm2And (4) irradiating. Temperature through thermal infrared imager (avoid laser straight)Irradiated) was measured. The photothermal temperature rise curve of the eight-branched gold nanoparticles and the reference is shown in fig. 4.
(reference refers to the temperature rise curve of pure water under the same test conditions)
According to
Figure BDA0001726099620000111
The photothermal conversion efficiency of the gold nano octafurcate particles is calculated to be 80.4% by a calculation formula of photothermal conversion efficiency.
Wherein eta is the photothermal conversion efficiency;
h is the thermal diffusion coefficient;
s is the surface area;
Tmaxthe system can reach a stable highest temperature;
Tsurris ambient temperature;
Q0when the sample does not contain nano particles (in the application, the condition of only deionized water is referred to), the temperature rise power of the cuvette is referenced;
p is the power of the light source;
a is the absorbance value of the nano particles at the wavelength corresponding to the laser.
Effect example 3
Photoacoustic performance of eight-fork gold nanoparticles with ligand A
1mL of an eight-branched gold nanoparticle solution having an absorbance of 5.0 was taken and diluted in this order by 2 times, 4 times, 8 times, and 16 times. Five eight-fork gold nanoparticle aqueous solutions with different absorbances were subjected to photoacoustic imaging test under 680 nm laser, and the results are shown in fig. 5.
Therefore, the eight-branch gold nanoparticles with the ligand A prepared by the method have strong photoacoustic signal intensity, and the photoacoustic signal intensity is in positive correlation with the absorbance (particle concentration) of the eight-branch gold nanoparticles.
Example 2
All the operations were the same as example 1, except that the amount of nanogold seed solution with ligand A added to solution B was 1.0. mu.L (the molar volume concentration of nanogold seed with ligand A in the reaction solution was 1.0X 10)-11mol/L, amount of deionized waterThe total volume of the system was kept to be the same as that of the reaction solution in example 1 by adding 1.0. mu.L, and the size length and width of the obtained octafurcate gold nanoparticles was 22.8. mu.11.4 nm.
Example 3
All the operations were the same as example 1, except that the amount of nanogold seed solution with ligand A added to solution B was 3.0. mu.L (the molar volume concentration of nanogold seed with ligand A in the reaction solution was 3.0X 10)-11mol/L, the amount of deionized water was reduced by 1.0. mu.L to ensure that the total volume of the system was identical to the volume of the reaction solution in example 1, and the size length and width of the obtained octafurcate gold nanoparticles was 15.8X 12.6 nm.
Example 4
All the procedures were the same as in example 1 except that the amount of 1-methylpyrrolidine added to solution A was 0.7mL (the amount of deionized water was adjusted so that the concentration of 1-methylpyrrolidine in the reaction mixture was 0.07 mol/L and the size length and width of the particles was 18.4X 9.3 nm).
Example 5
All the procedures were the same as in example 1 except that 1.1mL of 1-methylpyrrolidine was added to solution A (the amount of deionized water was adjusted so that the concentration of 1-methylpyrrolidine in the reaction mixture was 0.11M and the size length and width of the particles was 16.9X 10.3 nm).
Comparative example 1
All the procedures were as in example 1, except that 1-methylpyrrolidine was replaced with urotropin, and octafurcate gold nanoparticles were not obtained.
Comparative example 2
All the operations were the same as example 1, except that the amount of nanogold seed solution with ligand A added to solution B was 6.0. mu.L (the molar volume concentration of nanogold seed with ligand A in the reaction solution was 6.0 x 10)-11mol/L, the amount of deionized water was reduced by 4.0. mu.L to ensure that the total volume of the system was completely the same as the volume of the reaction solution in example 1, and no eight-furcate gold nanoparticles were obtained.
Comparative example 3
1.1 preparation of nanogold seed solution with ligand A:
(1) 3.5mL of hexadecyl trimethyl ammonium bromide aqueous solution with the concentration of 0.14mol/L, 10mL of tetrachloroauric acid solution with the concentration of 15mmol/L and 15mL of sodium borohydride aqueous solution with the concentration of 0.01mol/L are prepared (ice water bath).
(2) To 3.5mL of a 0.14mol/L hexadecyltrimethylammonium bromide aqueous solution, 130. mu.L of a 15mmol/L tetrachloroauric acid aqueous solution was added, and while stirring magnetically (1200rpm) and at room temperature, 500. mu.L of a 0.01mol/L aqueous sodium borohydride solution was added, whereby the color of the solution rapidly changed from yellow to brown. After stirring for 2 minutes, the mixture is placed in a water bath at 25 ℃ for standby.
The nanogold seed solution with the ligand A prepared by the method is about 100 nM.
1.2 preparation of four-fork gold nanoparticles with ligand A
10mL of hexadecyltrimethylammonium bromide aqueous solution with the concentration of 0.1mol/L, 10mL of urotropine aqueous solution with the concentration of 0.1mol/L, 10mL of tetrachloroauric acid solution with the concentration of 15mmol/L, 5mL of ascorbic acid aqueous solution with the concentration of 0.01mol/L and 1mL of sodium hydroxide aqueous solution with the concentration of 1mol/L are prepared.
Step (1):
adding 400 mu L of tetrachloroauric acid aqueous solution with the concentration of 15mmol/L and urotropine aqueous solution with the concentration of 0.1mol/L into 2mL of hexadecyl trimethyl ammonium bromide aqueous solution with the concentration of 0.1mol/L, uniformly mixing, adding 1mL of ascorbic acid aqueous solution with the concentration of 0.01mol/L, and enabling the solution to be colorless from yellow to prepare Au+Au in Complex solution+The concentration of the complex was 0.81 mmol/L.
Step (2): to the Au prepared in step 1+To the complex solution, 5. mu.L of the mixed solution of the nanogold seed solution with the ligand A, which was prepared in example 1, 1.1 and which contained 6.62mL of deionized water and 0.150mL of a 1mol/L aqueous solution of sodium hydroxide, was added, and the pH was adjusted to 11.85. And (3) after rapid mixing, standing in a water bath at 30 ℃ for 5 minutes to obtain dark green four-branch gold nano-solution.
The spectra for the synthesized four-furcated gold nanoparticles were measured by an ultraviolet-visible spectrophotometer and characterized by a transmission electron microscope as shown in fig. 6, fig. 7 and fig. 8. As can be seen from FIG. 6, the absorption spectrum peak position of the synthesized four-branched gold nanoparticles is 752nm, the half-peak width is small (91nm), at least 50 particles are counted, the particle size length of the four-branched gold nanoparticles is 19.5 +/-1.3 nm, the width of the four-branched gold nanoparticles is 9.7 +/-1.1 nm, and the relative standard deviations are respectively 6.7% and 11.3%, which can indicate that the synthesized four-branched gold nanoparticles are good in uniformity. The yield of the four-fork gold nano-particles prepared by the method is up to 82%. The three-dimensional structure of the prepared quarternary particle is shown in fig. 7 and 8.
As can be seen from FIGS. 7 and 8, the four branches of the four-branched gold nanoparticles all have the growth directions<110>Direction, and spatial symmetry fall under D2dPoint group; the four branches are two groups of branches, each group is provided with two mutually perpendicular branches, and the planes of the two groups of branches are mutually perpendicular. Specifically, the growth directions of the four branches of the four-branch gold nano-particles are respectively [01-1 ]],[101],[0-1-1]And [ -101 ]]。
Comparative effect examples
1. Photothermal performance of 808 nanometer light irradiation of four-fork gold nanoparticles
1mL of the aqueous solution of the four-furcate gold nanoparticles prepared in the comparative example 3 with the absorbance of 0.25 is prepared, pure deionized water is used as a reference and is respectively placed in a quartz cuvette, and a laser with the wavelength of 808 nm is used for 1W/cm2And (4) irradiating. The temperature was measured by thermal infrared imager (avoiding direct laser irradiation). The photothermal temperature rise curve of the four-branched gold nanoparticles and the reference is shown in fig. 9.
(reference refers to the temperature rise curve of pure water under the same test conditions)
According to
Figure BDA0001726099620000141
The photothermal conversion efficiency of the gold nano four-fork particle is calculated to be 53.5 percent by a calculation formula of photothermal conversion efficiency.
Wherein eta is the photothermal conversion efficiency;
h is the thermal diffusion coefficient;
s is the surface area;
Tmaxthe system can reach a stable highest temperature;
Tsurris ambient temperature;
Q0when the sample does not contain nano particles (in the application, the condition of only deionized water is referred to), the temperature rise power of the cuvette is referenced;
p is the power of the light source;
a is the absorbance value of the nanoparticle at different laser values.
2. Photoacoustic performance of four-fork gold nanoparticles with ligand A
1mL of the four-branched gold nanoparticle solution prepared in comparative example 3 having an absorbance of 5.1 was taken and diluted 2 times, 4 times, 8 times, and 16 times in this order. Five aqueous solutions of four-furcated gold nanoparticles with different absorbances were subjected to photoacoustic imaging test under 808 nm laser, and the results are shown in fig. 10.
Therefore, the four-branched gold nanoparticles with the ligand A prepared by the invention have strong photoacoustic signal intensity, and the photoacoustic signal intensity and the absorbance (particle concentration) of the four-branched gold nanoparticles are in a positive correlation.

Claims (34)

1. The eight-branch gold nanoparticle is characterized in that the eight-branch gold nanoparticle is provided with a ligand A, the length of a single arm of each branch of the eight-branch gold nanoparticle is 10-30 nm, and the width of the single arm is 5-20 nm; the eight branches of the eight-branch gold nano-particles have the same length and width, and the growth direction is<111>Direction and spatial symmetry to OhPoint group;
the ligand A is a cationic surfactant.
2. The eight-furcated gold nanoparticles of claim 1, wherein the single arm length of the eight-furcated gold nanoparticles is 15.8nm to 22.8 nm.
3. The eight-furcated gold nanoparticles of claim 2, wherein the single arm length of the eight-furcated gold nanoparticles is 16.9nm to 18.4 nm.
4. The eight-furcated gold nanoparticles of claim 3, wherein the single arm length of the eight-furcated gold nanoparticles is 17.5nm to 18.4 nm.
5. The eight-furcated gold nanoparticles of claim 1, wherein the single-arm width of the eight-furcated gold nanoparticles is 9.3nm to 12.6 nm.
6. The eight-furcated gold nanoparticles of claim 5, wherein the single-arm width of the eight-furcated gold nanoparticles is 9.9nm to 11.4 nm.
7. The eight-furcated gold nanoparticles of claim 6, wherein the single-arm width of the eight-furcated gold nanoparticles is 10.3nm to 11.4 nm.
8. The eight-pronged gold nanoparticles of claim 1, having a single arm length and a single arm width of 17.5nm and 9.9nm, 22.8nm and 11.4nm, 15.8nm and 12.6nm, 18.4nm and 9.3nm, or 16.9nm and 10.3 nm.
9. The eight-branched gold nanoparticle according to claim 1, wherein the eight branches of the eight-branched gold nanoparticle have a growth direction of [111]],
Figure FDA0003374828820000011
Figure FDA0003374828820000012
And
Figure FDA0003374828820000013
10. the eight-furcated gold nanoparticles of claim 1, wherein the cationic surfactant is a quaternary ammonium salt.
11. The eight-furcated gold nanoparticles of claim 10, wherein the quaternary ammonium salt is selected from one or more of cetyl trimethyl ammonium bromide, benzyl cetyl dimethyl ammonium chloride, cetyl tripropyl ammonium bromide, cetyl tributyl ammonium bromide, cetyl tripentyl ammonium bromide, and cetyl trihexyl ammonium bromide.
12. The preparation method of the eight-branch gold nanoparticles is characterized by comprising the following steps:
in water, under the condition that the pH value is 7-14 and the action of a weak reducing agent, nano gold seeds with a ligand A and Au are mixed+Reacting the complex;
the Au layer+The complex is prepared by the following method: the method comprises the following steps of reacting Au in water under the action of a ligand A and a strong reducing agent A3+Reduction reaction is carried out to obtain Au+A complex, i.e. a compound;
the strong reducing agent A is Au3+Reduction to Au+Then reduced to Au0In the step (2), the strong reducing agent A is controlled to add Au3+Reduction to Au+
The weak reducing agent is Au capable of reacting3+Reduction to Au+The reducing agent of (1);
the ligand A is a cationic surfactant.
13. The method for preparing octafurcate gold nanoparticles of claim 12, wherein the cationic surfactant is a quaternary ammonium salt.
14. The method of preparing octafurcate gold nanoparticles of claim 13, wherein the quaternary ammonium salt is selected from one or more of cetyltrimethyl ammonium bromide, benzylhexadecyldimethyl ammonium chloride, hexadecyltripropyl ammonium bromide, hexadecyltributyl ammonium bromide, hexadecyltripentyl ammonium bromide and hexadecyltrihexyl ammonium bromide.
15. The method for preparing octafurcate gold nanoparticles of claim 12, wherein the strong reducing agent a is selected from one or more of 4-hydroxyethylpiperazine ethanesulfonic acid, triethylene diamine, and 1-methylpyrrolidine;
and/or, the weak reducing agent is ascorbic acid and/or tartaric acid;
and/or adjusting the pH value to 7-14 by adding a strong reducing agent A or an alkali solution;
and/or, the nanogold seed with the ligand A and the Au+The molar ratio of the complex used was 6.7 x 10-9~1.1*10-7
And/or, the Au+The concentration of the complex in the reaction solution is 0.45-0.75 mmol/L;
and/or the concentration of the nanogold seed with the ligand A in the reaction solution is 5.0 to 10-12~5.0*10-11mol/L。
16. The method according to claim 15, wherein the octafurcate gold nanoparticles are prepared by the method,
the strong reducing agent is 1-methylpyrrolidine;
and/or, the nanogold seed with the ligand A and the Au+The molar ratio of the complex used was 3.3 x 10-8:1;
And/or, the Au+The concentration of the complex in the reaction solution was 0.57 mmol/L;
and/or the concentration of the nanogold seeds with the ligand A in the reaction solution is 1.0 x 10-11~3.0*10-11mol/L。
17. The method according to claim 16, wherein the nanogold seed having the ligand a has a concentration of 2.0 x 10 in the reaction solution-11mol/L。
18. The method of preparing eight-furcated gold nanoparticles of claim 12, wherein the Au is Au+In the preparation method of the complex, the molar using ratio of the weak reducing agent to the ligand A is 1.25 x 10-3~0.122;
And/or, the Au+In the preparation method of the complex, the molar using ratio of the weak reducing agent to the strong reducing agent A is 2.5 to 10-3~0.49;
And/or, the Au+In the preparation method of the complex, the weak reducing agent and the Au3+The molar use ratio of (A) is 0.67-10.8;
and/or, the Au+In the method for producing the complex, the concentration of the weak reducing agent in the reaction solution is 5.0 x 10-4~4.88*10-3mol/L;
And/or, the Au+In the preparation method of the complex, the concentration of the ligand A in a reaction solution is 0.04-0.4 mol/L;
and/or, the Au+In the preparation method of the complex, the concentration of the strong reducing agent A in a reaction solution is 0.01-0.2 mol/L;
and/or, the Au+The preparation of the complex is carried out at a pH of greater than 11;
and/or, the Au+In the preparation method of the complex, the Au3+Present in a carrier of Au3+In an aqueous solution of (a);
and/or, the Au+In the preparation method of the complex, the reduction reaction is carried out at the temperature of 25-30 ℃;
and/or, the Au+In the preparation method of the complex, the reduction reaction judges the reaction end point through the color change of the reaction solution.
19. The method of preparing eight-furcated gold nanoparticles of claim 18, wherein the Au is Au+In the preparation method of the complex, the molar ratio of the weak reducing agent to the ligand A is 0.024: 1;
and/or, the Au+In the preparation method of the complex, the molar using ratio of the weak reducing agent to the strong reducing agent A is 0.025: 1;
and/or, the Au+In the preparation method of the complex, the weak reducing agent and the Au3+The molar use ratio of (A) to (B) is 3.95: 1;
and/or, the Au+In the preparation method of the complex, the concentration of the weak reducing agent in the reaction solution is 2.25 x 10- 3mol/L;
And/or, the Au+In the preparation method of the complex, the concentration of the ligand A in a reaction solution is 0.095 mol/L;
and/or, the Au+In the preparation method of the complex, the concentration of the strong reducing agent A in a reaction solution is 0.07-0.11 mol/L;
and/or, the Au+In the preparation method of the complex, the Au3+In the aqueous solution of tetrachloroauric acid, tetrabromo auric acid or potassium chloroaurate;
and/or, the Au+In the preparation method of the complex, the reduction reaction can determine the reaction end point by changing the color of the reaction solution into blue and blue-green and when the color does not change any more.
20. The method of preparing eight-furcated gold nanoparticles of claim 19, wherein the Au is Au+In the preparation method of the complex, the concentration of the strong reducing agent A in the reaction liquid is 0.09 mol/L.
21. The method for preparing eight-furcate gold nanoparticles according to claim 12, wherein the eight-furcate gold nanoparticles are prepared by the following method:
mixing water and ligand A, Au3+And Au is uniformly mixed with the strong reducing agent A until the mixture is colorless+Solution A of (1); uniformly mixing water, a weak reducing agent and the nanogold seeds with the ligand A to obtain a solution B; uniformly mixing the solution A and the solution B;
the ligand A is a cationic surfactant;
the strong reducing agent A is Au3+Reduction to Au+Then reduced to Au0The reducing agent of (1); controlling the strong reducing agent A to react with Au3+Reduction to Au+
The weak reducing agent is Au capable of reacting3+Reduction to Au+The reducing agent of (1).
22. The method according to claim 21, wherein the octafurcate gold nanoparticles are prepared by the method,
the cationic surfactant is quaternary ammonium salt.
23. The method of preparing octafurcate gold nanoparticles of claim 22, wherein the quaternary ammonium salt is selected from one or more of cetyltrimethyl ammonium bromide, benzylhexadecyldimethyl ammonium chloride, hexadecyltripropyl ammonium bromide, hexadecyltributyl ammonium bromide, hexadecyltripentyl ammonium bromide and hexadecyltrihexyl ammonium bromide.
24. The method for preparing octafurcate gold nanoparticles of claim 21, wherein the strong reducing agent a is selected from one or more of 4-hydroxyethylpiperazine ethanesulfonic acid, triethylene diamine, and 1-methylpyrrolidine;
and/or the weak reducing agent is ascorbic acid and/or tartaric acid.
25. The method according to claim 24, wherein the strong reducing agent a is 1-methylpyrrolidine.
26. An eight-furcated gold nanoparticle prepared according to the method for preparing eight-furcated gold nanoparticles described in any one of claims 12 to 25.
27. The use of the octafurcate gold nanoparticles of any one of claims 1-11 or claim 26 in photothermal therapy and photoacoustic imaging.
28. Au (gold)+A method for preparing a complex, comprising the steps of: in water, Au is reacted under the action of ligand A and strong reducing agent A3+Reduction reaction is carried out to obtain Au+A complex, i.e. a compound;
the ligand A is a cationic surfactant;
the strong reducing agent A is Au3+Reduction to Au+Then reduced to Au0The reducing agent of (1); controlling the strong reducing agent A to react with Au3+Reduction to Au+
29. The Au of claim 28+The method for producing a complex is characterized in that the cationic surfactant is a quaternary ammonium salt.
30. The Au of claim 29+A process for the preparation of a complex, characterised in that the quaternary ammonium salt is selected from one or more of cetyltrimethylammonium bromide, benzylhexadecyldimethylammonium chloride, hexadecyltripropylammonium bromide, hexadecyltributylammonium bromide, hexadecyltripentylammonium bromide and hexadecyltrihexylammonium bromide.
31. The Au of claim 28+The preparation method of the complex is characterized in that the concentration of the ligand A in a reaction solution is 0.04-0.4 mol/L;
and/or the concentration of the strong reducing agent A in the reaction liquid is 0.01-0.2 mol/L;
and/or, the Au+The preparation of the complex is carried out at a pH of greater than 11;
and/or, the Au3+Present in a carrier of Au3+In an aqueous solution of (a);
and/or the reduction reaction is carried out at a temperature of 25-30 ℃;
and/or judging the reaction end point through the color change of the reaction solution in the reduction reaction.
32. The Au of claim 31+A process for producing a complex, characterized in that the concentration of the ligand A in the reaction solution is 0.095 mol/L;
and/or the concentration of the strong reducing agent A in the reaction liquid is 0.07-0.11 mol/L;
and/or, the saidAu3+In the aqueous solution of tetrachloroauric acid, tetrabromo auric acid or potassium chloroaurate;
and/or, the reaction end point is determined by the time when the color of the reaction solution changes to blue, blue-green, and no longer changes.
33. The Au of claim 32+The method for preparing the complex is characterized in that the concentration of the strong reducing agent A in the reaction liquid is 0.09 mol/L.
34. An Au as claimed in any one of claims 28 to 33+Preparation method of complex and Au prepared by preparation method+A complex compound.
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