CN110666160B - Preparation method and obtained product of self-assembled composite nanostructure of side-by-side gold nanorods coated with polydopamine - Google Patents
Preparation method and obtained product of self-assembled composite nanostructure of side-by-side gold nanorods coated with polydopamine Download PDFInfo
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 42
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000001338 self-assembly Methods 0.000 claims abstract description 51
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 27
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 229960003638 dopamine Drugs 0.000 claims description 16
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- 239000000047 product Substances 0.000 description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 21
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Abstract
本发明涉及一种聚多巴胺包覆的肩并肩金纳米棒自组装复合纳米结构的制备方法及所得产品,该方法以异丙醇和聚丙烯酸诱导金纳米棒肩并肩自组装，进而利用聚多巴胺包覆金纳米棒自组装结构，所得金纳米棒沿轴向有序排列组装，形成金纳米棒肩并肩自组装结构。本发明操作简单、重复性好、成本低廉，所得聚多巴胺包覆的肩并肩金纳米棒自组装复合纳米结构具有较好的等离子体共振光学性质，表现出良好的光热效应及表面增强拉曼散射效应，光热转换效率好、自身耐热性好，在纳米光热诊疗剂及光学传感领域具有较好的应用前景。
The invention relates to a preparation method of a polydopamine-coated side-by-side gold nanorod self-assembled composite nanostructure and the obtained product. The method uses isopropanol and polyacrylic acid to induce the side-by-side self-assembly of gold nanorods, and then uses polydopamine to coat A gold nanorod self-assembled structure, the obtained gold nanorods are arranged and assembled in an orderly axial direction to form a side by side self-assembled structure of gold nanorods. The method has the advantages of simple operation, good repeatability and low cost, and the obtained polydopamine-coated side-by-side gold nanorod self-assembled composite nanostructure has good plasmonic resonance optical properties, and exhibits good photothermal effect and surface-enhanced Raman scattering. It has good photothermal conversion efficiency and good heat resistance, and has good application prospects in the fields of nanophotothermal diagnosis and treatment agents and optical sensing.
Description
Technical Field
The invention relates to a preparation method of a nano composite structure taking polydopamine as a shell and a gold nanorod self-assembly structure as a core and an obtained product, in particular to a preparation method of a polydopamine-coated shoulder by shoulder (side by side) orderly-arranged gold nanorod self-assembly composite nano structure and an obtained product, belonging to the field of functional nano materials.
Background
In recent years, gold nanorods have potential application value in the field of optical sensing due to unique adjustable optical properties and geometric structures, and are widely concerned by many researchers. The gold nanorods have surface plasma resonance absorption peaks which are continuously adjustable from a visible light region to a near-infrared light region along with the change of the length-diameter ratio, extremely high surface electric field intensity enhancement effect, extremely large optical absorption and scattering cross section, and continuously adjustable photothermal conversion efficiency from 50% to 100%, and have good application prospects in the fields of optical sensing, biomedical treatment and the like. The gold nanorods are used as a photo-thermal conversion substrate, the micro morphology is easy to change by heat after the photo-thermal conversion is carried out by receiving near infrared light irradiation, and the surface coating becomes one of the methods for keeping the stability of the gold nanorods. Polydopamine is widely applied to the field of functional material research due to its unique surface modification function and good biocompatibility. The assembly of gold nanorods can be assembled and aggregated in a head-to-end (end-to-end) or shoulder-by-shoulder (side by side) form through molecular induction. The assembled gold nanorods are easy to form a hot spot effect and have a surface enhanced Raman scattering effect on Raman reporter molecules. However, the current method for self-assembling and coating the gold nanorods has the defects of complicated steps, complex used reagents and difficult control of the assembly form, so that the use of the gold nanorods is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a polydopamine-coated shoulder-to-shoulder gold nanorod self-assembly composite nanostructure and an obtained product.
The invention is realized by the following measures:
the invention provides a simple and convenient preparation method of a polydopamine-coated shoulder-side gold nanorod self-assembly composite nanostructure with a special appearance, which comprises the following steps:
(1) preparing gold nanorods by adopting a seed growth method, centrifugally cleaning the obtained gold nanorods for 2 times, and then dispersing the gold nanorods into water to obtain a high-concentration gold nanorod solution for later use;
(2) adding the gold nanorod solution obtained in the step (1) into water, then adding polyacrylic acid, adjusting the pH to 7-8, ultrasonically mixing for 1-2h, and then dropwise adding isopropanol to complete self-assembly of the gold nanorods;
(3) and (3) ultrasonically mixing the mixture obtained in the step (2) with an isopropanol aqueous solution, then adjusting the pH value to 8-9, and adding dopamine to react to obtain the polydopamine-coated shoulder-side gold nanorod self-assembled composite nanostructure.
The method comprises the steps of firstly synthesizing a gold nanorod self-assembly structure, and then coating a polydopamine shell layer on the surface of the morphological self-assembly structure to obtain the final polydopamine-coated shoulder-side-by-shoulder gold nanorod self-assembly composite nano structure. The gold nanorods in the gold nanorod self-assembly structure are orderly arranged side by side, can be prepared by adopting a seed growth method, and can be prepared into the gold nanorods with different sizes according to the method recorded in the literature by the technicians in the field, so that the details are not repeated. Based on the consideration of photothermal effect and surface enhanced Raman scattering effect, the diameter of the gold nanorod is 10-15 nanometers, and the length-diameter ratio is about 4-5: 1.
The gold nanorods are prepared by a classical seed growth method, and because a surfactant is required to be added in the preparation process to control the growth of the gold nanorods in a reaction solution, the surface of the prepared gold nanorods is attached with the surfactant. In order to normally carry out the subsequent reaction, in the step (1), the obtained gold nanorods are centrifuged and cleaned, and the concentration of the surfactant on the gold nanorods is reduced. The washing is carried out with pure water, and the number of washing is selected according to the concentration of the surfactant, and generally 2 times is sufficient.
In a specific embodiment of the invention, the gold nanorod solution prepared by the seed growth method is centrifuged to remove the supernatant, then water is added for cleaning, the supernatant is centrifuged after cleaning, and then water is added for centrifugal cleaning once. The gold nanorods after being cleaned are dispersed into a small amount of water for convenience of subsequent use to prepare a high-concentration solution for later use.
Further, in the step (2), the gold nanorod solution in the step (1) is added into water, and then polyacrylic acid and isopropanol are added, so that self-assembly is completed under the combined action of the polyacrylic acid and the isopropanol. The self-assembled gold nanorods can be orderly arranged and are arranged in parallel side by side on the same horizontal plane, and the adjacent gold nanorods are contacted with each other and are in a shoulder-to-shoulder shape, which can also be called as orderly arranged gold nanorod cluster structures. The self-assembly morphology has good plasma resonance optical property, shows good photothermal effect and surface enhanced Raman scattering effect, and has good application prospect in the fields of nano photothermal diagnosis and treatment agents and optical sensing.
Further, in the step (2), polyacrylic acid and isopropanol are added in the form of aqueous solution for convenient addition and better dispersion mixing, and the concentration of the aqueous solution can be adjusted according to specific conditions as long as the concentration of the gold nanorods and the concentration of polyacrylic acid in the final mixed system meet certain conditions.
Preferably, in the step (2), in a mixed system composed of gold nanorods, polyacrylic acid, isopropanol and water (the mixed system refers to a mixed system finally formed after dropping isopropanol), the final concentration of the gold nanorods in the mixed system is 1-3 μmol/L, and the final concentration of polyacrylic acid in the mixed system is 0.6 × 10%-4 ~4×10-4mg/mL, volume ratio of water to isopropanol of 1: 1.5-8.
Further, in the step (2), ammonia water is adopted to adjust the pH, the concentration of the ammonia water can be selected at will, and the amount of water brought in by other materials can be properly adjusted according to the condition of the water brought in by the ammonia water, so that the concentration of each substance in the mixed system and the volume ratio of water to isopropanol meet the requirements.
Further, in the step (2), the ultrasound can be realized by using conventional ultrasound equipment in a laboratory. After the ultrasonic treatment, isopropanol is dropped, the isopropanol is preferably dropped in the form of an aqueous solution, and the solution changes from red to blue along with the dropping of the isopropanol, which indicates that the gold nanorods are completely self-assembled.
Further, in the step (3), the polydopamine shell is coated after the self-assembly is finished. Wherein the volume concentration of the isopropanol aqueous solution is 45-55%, and the volume ratio of the mixture obtained after the reaction in the step (2) to the isopropanol aqueous solution is 2-4:1 under the volume concentration. And (3) mixing the mixture obtained in the step (2) with an isopropanol aqueous solution, then mixing for 20-30min under ultrasound, and then adjusting the pH value to 8-9, wherein the ultrasound is performed by adopting conventional laboratory ultrasound equipment. After the pH is adjusted, dopamine is added for reaction, preferably in the form of an aqueous solution for better dispersion and mixing. The concentration of the solution can be adjusted according to the needs, and the effect on the result is not great. The amount of dopamine added is dependent on the desired thickness of the polydopamine shell.
In one embodiment of the present invention, the concentration of dopamine in the mixed system is 0.03-0.08 mg/mL.
Further, in the step (3), the reaction temperature is 45-55 ℃, and the reaction time is more than 3h, preferably 3-6 h.
Further, in the step (3), the pH can be adjusted by ammonia water, and the concentration of ammonia water to be used can be arbitrarily selected, and is preferably the same as the concentration of ammonia water in the step (2) in order to reduce the cost.
The gold nanorod self-assembly composite nanostructure coated with polydopamine is composed of a gold nanorod self-assembly structure and polydopamine, wherein the gold nanorods in the gold nanorod self-assembly structure are arranged in parallel side by side, adjacent gold nanorods are in contact with each other and are in a shoulder-by-shoulder shape, and the polydopamine is coated on the surface of the gold nanorod self-assembly structure. The product takes a side-by-side gold nanorod self-assembly structure as a core and polydopamine as a shell, has excellent photo-thermal effect and surface enhanced Raman scattering effect, improves the heat resistance of the gold nanorods during photo-thermal response after being coated with the polydopamine shell, and has good application prospect. Therefore, the polydopamine-coated shoulder-by-shoulder gold nanorod self-assembly composite nanostructure obtained by the method is also within the protection range.
The invention explores a method for inducing the shoulder-to-shoulder self-assembly of the gold nanorods by polyacrylic acid and isopropanol and further coating the self-assembly structure of the gold nanorods by utilizing polydopamine, the method is simple to operate, good in repeatability and low in cost, can stably and efficiently obtain the self-assembly of the gold nanorods, and has important guiding significance for the preparation and application research of the gold nanomaterials and composite materials thereof. The obtained poly-dopamine-coated shoulder-side gold nanorod self-assembly composite nanostructure has good plasma resonance optical property, shows good photothermal effect and surface enhanced Raman scattering effect, has good photothermal conversion efficiency and good heat resistance, and has good application prospect in the fields of nano photothermal diagnosis and treatment agents and optical sensing.
Drawings
Fig. 1 is a transmission electron micrograph of the polydopamine-coated shoulder-by-shoulder gold nanorod self-assembled composite nanostructure synthesized in example 1 of the present invention.
Fig. 2 is a transmission electron microscope photograph of the polydopamine-coated shoulder-by-shoulder gold nanorod self-assembly composite nanostructure synthesized in example 2 of the present invention.
FIG. 3 is a transmission electron micrograph of a product obtained in comparative example 1 of the present invention.
FIG. 4 is a transmission electron micrograph of a product obtained in comparative example 2 of the present invention.
FIG. 5 is a transmission electron micrograph of a product obtained in comparative example 3 of the present invention.
FIG. 6 is a surface enhanced Raman scattering spectrum of the product obtained by the present invention.
FIG. 7 is a line graph showing the change of photothermal conversion temperature of the product obtained by the present invention.
Detailed Description
The present invention will be further illustrated by the following examples, which are intended to be merely illustrative and not limitative.
Example 1
1.1 preparation and pretreatment of gold nanorods: preparing gold nanorods by adopting a classical seed growth method, centrifuging the obtained reaction solution at the rotating speed of 10000 r/min for 20 minutes, removing supernatant, adding water to precipitate for cleaning, centrifuging after cleaning to remove supernatant, and then adding centrifugal cleaning once to obtain the gold nanorods, wherein the diameter of the gold nanorods is 12 nm, and the length-diameter ratio of the gold nanorods is 4.5: 1, dispersing the gold nanorods into a proper amount of water to prepare a concentrated high-concentration gold nanorod solution (the tenfold absorbance of the solution is 1.0 after dilution, and the absorption peak is positioned at 815 nm) for later use.
1.2 formation of "side-by-side" self-assembly: taking 2 mL of the gold nanorod solution in the step 1), adding 3mL of water, 30 microliters of polyacrylic acid PAA solution (0.2 mg/mL) and 45 microliters of ammonia water (2 mol/L), ultrasonically mixing for 1 hour, and then dropwise adding 55 mL of isopropanol solution (water: isopropanol volume ratio 1: 10), the solution turns blue in color, and self-assembly occurs.
1.3 mixing 30 mL of the solution prepared in the step 2) with 10 mL of isopropanol/water solvent (volume ratio is 1: 1), carrying out ultrasonic treatment for 20 minutes, adding ammonia water (2 mol/L) to adjust the pH value of the solution to 8.5, then adding 40 microliter of dopamine aqueous solution with concentration of 0.05 g/mL, reacting at 50 ℃ for 3.5 hours to obtain a dark brown solution, and carrying out centrifugal cleaning to obtain the poly-dopamine-coated shoulder-side-by-side gold nanorod self-assembled composite nanostructure.
The transmission electron microscope photo of the obtained product is shown in fig. 1, and it can be seen from the figure that the gold nanorods are orderly arranged side by side and self-assembled into a side-by-side structure, and the polydopamine is wrapped on the surface of the self-assembled structure.
FIG. 6 is the surface enhanced Raman scattering spectrum of the resulting product versus Raman reporter crystal violet, as can be seen: the simple crystal violet solution does not detect an obvious Raman scattering peak under the irradiation of a 785 nm laser, and the obtained product is used as an enhancement substrate, and the crystal violet with the same concentration shows a stronger Raman scattering peak, which indicates that the obtained product can be used as a good surface enhanced Raman scattering material.
Fig. 7 is a line graph showing the change in photothermal conversion temperature of the resulting product, and it can be seen that: compared with a single gold nanorod, the gold nanorod assembly coated with the polydopamine shows better photothermal response, and the obtained product has certain application potential in the aspect of cancer photothermal treatment.
Example 2
2.1 preparation and pretreatment of gold nanorods: the same as in example 1.
2.2 formation of the "side-by-side" self-assembly: taking 4 mL of the gold nanorod solution in the step 1), adding 6 mL of water, 60 microliters of polyacrylic acid (PAA) (0.2 mg/mL) and 90 microliters of ammonia water (2 mol/L), adjusting the pH of the solution to 7.5, ultrasonically mixing for 1 hour, and then dropwise adding 110 mL of isopropanol solution (water: isopropanol volume ratio 1: 10), the solution turns blue in color, and self-assembly occurs.
2.3 mixing 60 mL of the solution prepared in the step 2) with 20 mL of isopropanol/water solvent (volume ratio is 1: 1), performing ultrasonic treatment for 20 minutes, adding ammonia water (2 mol/L) to adjust the pH value of the solution to 8.5, then adding 80 microliter of dopamine aqueous solution with concentration of 0.05 g/mL, reacting for 4 hours at 50 ℃ to obtain a dark brown solution, and performing centrifugal cleaning to obtain the poly-dopamine-coated shoulder-shoulder gold nanorod self-assembled composite nanostructure.
The transmission electron microscope photo of the obtained product is shown in fig. 2, and it can be seen from the figure that the gold nanorods are orderly arranged side by side and self-assembled into a side-by-side structure, and the polydopamine is wrapped on the surface of the self-assembled structure.
Example 3
3.1 preparation and pretreatment of gold nanorods: the same as in example 1.
3.2 formation of the "side-by-side" self-assembly: taking 2 mL of the gold nanorod solution in the step 1), adding 50 microliters (0.2 mg/mL) of polyacrylic acid PAA and 90 microliters of ammonia water (2 mol/L), adjusting the pH of the solution to 7.5, ultrasonically mixing for 1 hour, and dropwise adding 110 mL of isopropanol solution (water: isopropanol volume ratio 1: 10), the solution turns blue in color, and self-assembly occurs.
2.3 mixing 60 mL of the solution prepared in the step 2) with 20 mL of isopropanol/water (volume ratio 1: 1) solvent, performing ultrasonic treatment for 20 minutes, adding ammonia water (2 mol/L) to adjust the pH value of the solution to 8.5, then adding 80 microliter of dopamine aqueous solution with the concentration of 0.05 g/mL, reacting at 45 ℃ for 5 hours to obtain a dark brown solution, and performing centrifugal cleaning to obtain the poly-dopamine-coated shoulder-shoulder gold nanorod self-assembly composite nanostructure. The obtained product is of a core-shell structure, gold nanorods are orderly arranged side by side and self-assembled into a side-by-side structure, and polydopamine is wrapped on the surface of the self-assembled structure.
Example 4
4.1 preparation and pretreatment of gold nanorods: the same as in example 1.
4.2 formation of the "side-by-side" self-assembly: taking 2 mL of the gold nanorod solution in the step 1), adding 3mL of water, 30 microliters (0.2 mg/mL) of polyacrylic acid PAA and 90 microliters of ammonia water (2 mol/L), adjusting the pH of the solution to 7.5, ultrasonically mixing for 1 hour, and dropwise adding 85 mL of isopropanol solution (water: isopropanol volume ratio 1: 10), the solution turns blue in color, and self-assembly occurs.
4.3 taking 45 mL of the solution prepared in the step 2), mixing with 15 mL of isopropanol/water (volume ratio 1: 1) solvent, carrying out ultrasonic treatment for 20 minutes, adding ammonia water (2 mol/L) to adjust the pH value of the solution to 8.5, then adding 80 microliter of dopamine aqueous solution with the concentration of 0.05 g/mL, reacting at 55 ℃ for 4 hours to obtain a dark brown solution, and carrying out centrifugal cleaning to obtain the poly-dopamine-coated shoulder-shoulder gold nanorod self-assembled composite nanostructure. The obtained product is of a core-shell structure, gold nanorods are orderly arranged side by side and self-assembled into a side-by-side structure, and polydopamine is wrapped on the surface of the self-assembled structure.
Example 5
5.1 preparation and pretreatment of gold nanorods: the same as in example 1.
5.2 formation of the "side-by-side" self-assembly: taking 2 mL of the gold nanorod solution in the step 1), adding 3mL of water, 30 microliters (0.2 mg/mL) of polyacrylic acid PAA and 90 microliters of ammonia water (2 mol/L), adjusting the pH of the solution to 7.5, ultrasonically mixing for 1 hour, and dropwise adding 10 mL of isopropanol solution (water: isopropanol volume ratio 1: 10), the solution turns blue in color, and self-assembly occurs.
5.3, mixing 15 mL of the solution prepared in the step 2) with 5 mL of isopropanol/water (volume ratio is 1: 1) solvent, carrying out ultrasonic treatment for 20 minutes, adding ammonia water (2 mol/L) to adjust the pH value of the solution to 8.5, then adding 40 microliter of dopamine aqueous solution with the concentration of 0.05 g/mL, reacting at 50 ℃ for 6 hours to obtain a dark brown solution, and carrying out centrifugal cleaning to obtain the poly-dopamine-coated shoulder-side-by-side gold nanorod self-assembled composite nanostructure. The obtained product is of a core-shell structure, gold nanorods are orderly arranged side by side and self-assembled into a side-by-side structure, and polydopamine is wrapped on the surface of the self-assembled structure.
Comparative example 1
1. Preparing and pretreating gold nanorods: the same as in example 5.
The formation process of "side-by-side" self-assembly: the formation process of the "side-by-side" self-assembly: taking 2 mL of the gold nanorod solution in the step 1), adding 30 microliters (0.2 mg/mL) of polyacrylic acid PAA and 90 microliters of ammonia water (2 mol/L), ultrasonically mixing for 1 hour, and dropwise adding 1 mL of isopropanol solution (water: isopropanol volume ratio of 1: 10), the brick red of the monodisperse gold nanorods is kept in the solution and does not turn blue, and the gold nanorods are not assembled because of improper addition of isopropanol.
3. Mixing the solution prepared in the step 2) with 10 ml of isopropanol/water (volume ratio is 1: 1) solvent, and performing ultrasonic treatment for 20 minutesAdding ammonia water (2 mol/L) to adjust the pH of the solution to 8.5, adding 40 microliter dopamine aqueous solution with the concentration of 0.05 g/mL at 50oAfter the reaction is carried out for 30 minutes, the polymerization time is too short, the color of the solution has no obvious change, a transmission electron microscope photo of the obtained product is shown in figure 3, and the gold nanorods of the obtained product are not subjected to self-assembly and polydopamine coating.
Comparative example 2
1. Preparing and pretreating gold nanorods: the same as in example 5.
The formation process of "side-by-side" self-assembly: the same as in example 5.
3. Taking the solution prepared in the step 2), mixing with 5 mL of isopropanol/water (volume ratio is 1: 1) solvent, carrying out ultrasonic treatment for 20 minutes, adding ammonia water (2 mol/L) to adjust the pH value of the solution to 8.5, then adding 40 microliters of dopamine aqueous solution with concentration of 0.05 g/mL, reacting for 1 hour at 50 ℃, keeping the solution blue, and carrying out transmission electron microscopy on the obtained product as shown in figure 4 because the polymerization time is too short, wherein the gold nanorods are subjected to side-by-side ordered self-assembly, but the dopamine is not subjected to polymerization coating.
Comparative example 3
1. Preparing and pretreating gold nanorods: the same as example 5, except that: and 4 times of washing, and over-washing leads to the concentration of the gold nanorod surfactant being substantially 0.
The formation process of "side-by-side" self-assembly: taking 2 mL of the gold nanorod solution in the step 1), adding 3mL of water, 30 microliters (0.2 mg/mL) of polyacrylic acid PAA and 90 microliters of ammonia water (2 mol/L), adjusting the pH of the solution to 7.5, ultrasonically mixing for 1 hour, and dropwise adding 10 mL of isopropanol solution (water: isopropanol volume ratio 1: 10), the solution did not turn blue.
3. Taking 15 mL of the solution prepared in the step 2), mixing with 5 mL of isopropanol/water (volume ratio is 1: 1) solvent, carrying out ultrasonic treatment for 20 minutes, adding ammonia water (2 mol/L) to adjust the pH of the solution to 8.5, then adding 40 microliters of dopamine aqueous solution with the concentration of 0.05 g/mL, reacting at 50 ℃ for 6 hours to obtain a dark brown solution, carrying out centrifugal cleaning, and obtaining a transmission electron microscope photo of the product as shown in figure 5.
Comparative example 4
1. Preparing and pretreating gold nanorods: the same as in example 5.
The formation process of "side-by-side" self-assembly: the same as example 5, except that: polyacrylic acid is replaced by polyacrylamide, the color of the solution does not turn blue, and self-assembly does not occur.
Comparative example 5
1. Preparing and pretreating gold nanorods: the same as in example 5.
The formation process of "side-by-side" self-assembly: the same as example 5, except that: after 5. mu.l (0.2 mg/mL) of polyacrylic acid PAA was added, the solution did not turn blue in color and no self-assembly occurred.
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