Gold nanorods, method for making and use thereof
Gold nanorods were synthesized by seed growth method. By utilizing the balancing effect of CTAB and NaOL surfactants, the problems of low stability and low yield in the synthesis of nanorods in traditional methods were solved, and the uniformity and high purity of the nanorods were achieved, which are suitable for LSPR sensitive units and medical applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-08-08
- Publication Date
- 2026-03-20
AI Technical Summary
Traditional seed-growing methods for synthesizing gold nanorods suffer from poor stability, difficulty in controlling aspect ratio, large axial width, and incomplete reduction of chloroauric acid, resulting in poor experimental repeatability and low yield.
A green, efficient, and controllable seed growth method was adopted, using a binary surfactant formed by mixing hexadecyltrimethylammonium bromide (CTAB) and sodium oleate (NaOL). By controlling the reaction conditions, gold nanospheres with a diameter between 3 and 5 nanometers were synthesized, and the nanospheres were grown with the assistance of silver nitrate to inhibit nanosphere aggregation and achieve uniformity and high purity of nanorods.
This method achieves uniform size and high purity of gold nanorods with controllable aspect ratio, solving the stability and yield problems existing in traditional methods. It is suitable for applications in LSPR sensitive units and the medical field.
Abstract
Description
Technical Field
[0001] This invention relates to the field of nanorod fabrication technology, and in particular to a gold nanorod, its fabrication method, and its applications. Background Technology
[0002] A nanometer is a unit of length between microscopic particles and macroscopic matter, one billionth the size of a meter. Nanomaterials refer to materials whose constituent particles have a size between 1 and 100 nm. When metal particles reach the nanoscale, their size becomes comparable to the wavelength of light, exhibiting coherence. Simultaneously, their surface area and volume increase exponentially, and their surface electronic activity also increases. At this point, traditional mechanical viewpoints are no longer applicable; instead, quantum theory applies. Therefore, they exhibit unique properties that differ from both atoms and molecules, as well as macroscopic matter.
[0003] Therefore, nanomaterials possess both research potential and research value. The synthesis of nanomaterials is the first and most important step in their research. Gold nanorods are nanoparticles with a structure intermediate between gold nanoparticles and gold nanowires. They are generally composed of several gold nanoparticles connected longitudinally, forming a cylinder with its own diameter and length. Methods for synthesizing gold nanorods include template methods, electrochemical synthesis methods, seed growth methods, and seedless growth methods. Among these, the aspect ratio of gold nanorods synthesized by template methods is difficult to control precisely, while electrochemical synthesis methods require a two-electrode electrochemical reaction cell and an ultrasonic environment, taking into account factors such as feasibility and yield.
[0004] However, the traditional seed growth method has several drawbacks: (1) CTAB can prevent seed aggregation but has low stability, resulting in poor reproducibility of the experiment; (2) It is difficult to prepare nanorods with a high aspect ratio. Only gold nanorods with an aspect ratio between 2 and 5 have relatively high uniformity and yield in synthesis; (3) The axial width of the rod is relatively large; (4) Chloroauric acid reduction is incomplete. Summary of the Invention
[0005] The present invention aims to solve at least one of the technical problems existing in the prior art, and proposes a gold nanorod, its fabrication method, and its application.
[0006] In a first aspect, the present invention provides a method for fabricating gold nanorods, the method comprising the following steps;
[0007] Preparation of seed solution: 4mL-6mL of 0.4mM-0.6mM HAuCl4 and 4mL-6mL of 0.1M-0.3M CTAB are mixed for use; 0.5mL-0.7mL of 0.005M-0.015M NaBH4 freshly prepared is diluted with pure water to 0.5mL-1.5ml; 4mL-6mL of prepared NaBH4 solution is injected into the mixed solution of HAuCl4 and CTAB, and after stirring at a preset first speed for a preset first time, it is placed at room temperature for 20min-40min;
[0008] Preparation of growth solution: 7.0g-9.0g of CTAB and a predetermined amount of NaOL are dissolved in 200mL-300mL of warm water, after the solution is cooled to the target temperature, a predetermined amount of 3mM-5mM AgNO3 is added, 200mL-300mL of 0.5mM-1.5mM HAuCl4 is added, the target temperature is maintained and placed for 10min-20min, and stirred at a preset second speed for a preset second time, then a certain volume of 11.1M-13.1M HCl is added to adjust the pH of the solution, and after stirring at a preset third speed for a preset third time, 1mL-1.5mL of 0.054M-0.074M ascorbic acid is added, and stirred for 20s-40s;
[0009] Growth of gold nanorods: a certain amount of the seed solution is added to the growth solution and stirred uniformly; static growth, static at the target temperature for 10h-14h; centrifugation at a preset fourth speed for a preset fourth time, remove the supernatant, and prepare gold nanorods.
[0010] Optionally, in the preparation of the growth solution, the mass of NaOL ranges from 1.234g to 1.543g.
[0011] Optionally, in the preparation of the growth solution, the volume of AgNO3 ranges from 12mL to 18mL.
[0012] Optionally, in the preparation of the growth solution, the volume of HCl ranges from 1mL to 3mL.
[0013] Optionally, in the growth of gold nanorods, the volume of the seed solution ranges from 0.01mL to 0.8mL.
[0014] Optionally, in the preparation of the seed solution, the preparation of NaBH4 includes the following steps:
[0015] 0.0278g-0.0478g NaBH4 is dissolved in 90ml-110ml ice water, stirred uniformly, and prepared into 0.005M-0.015M NaBH4 solution.
[0016] Optionally, the preset first rotating speed ranges from 1100 rpm to 1300 rpm; and / or, the preset first time ranges from 3 min to 5 min.
[0017] Optionally, the temperature of the warm water ranges from 40 DEG C to 60 DEG C, and the target temperature ranges from 20 DEG C to 40 DEG C; and / or,
[0018] The preset second rotating speed ranges from 600 rpm to 800 rpm, and the preset second time ranges from 80 min to 100 min; and / or,
[0019] The preset third rotating speed ranges from 300 rpm to 500 rpm, and the preset third time ranges from 10 min to 20 min; and / or,
[0020] The preset fourth rotating speed ranges from 6000 rpm to 8000 rpm, and the preset fourth time ranges from 30 min to 50 min.
[0021] In the second aspect, the application provides a gold nanorod, which is formed by the method described above.
[0022] In the third aspect, the application provides an application of the gold nanorod, which is formed by the method described above.
[0023] The application has the following advantages:
[0024] The method for making the gold nanorod adopts a green, efficient and controllable synthesis method for gold nanorod, i.e., seed growth method. First, a gold nanosphere with a diameter of 3-5 nm is made, and then the nanosphere is grown in a binary surfactant formed by mixing cetyltrimethylammonium bromide (CTAB) and sodium oleate (NaOL) with the assistance of silver nitrate. The silver nitrate can promote the growth, and the surfactant can inhibit the agglomeration of the nanosphere. The balance between the two can make the size of the grown nanorod uniform and the purity high. DETAILED DESCRIPTION
[0025] The technical solutions of the application will be described clearly and completely below. Obviously, the described embodiments are some of the embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.
[0026] The embodiments of the application relate to a method for making a gold nanorod, which comprises the following steps:
[0027] Preparation of seed solution: 4mL-6mL of 0.4mM-0.6mM HAuCl4 and 4mL-6mL of 0.1M-0.3M CTAB are mixed for use; 0.5mL-0.7mL of 0.005M-0.015M freshly prepared NaBH4 is diluted with pure water to 0.5mL-1.5ml; 4mL-6mL of prepared NaBH4 solution is injected into the mixed solution of HAuCl4 and CTAB, and stirred at 1100rpm-1300rpm for 3min-5min, and then placed at room temperature for 20min-40min;
[0028] Preparation of growth solution: 7.0g-9.0g of CTAB and 1.234g-1.543g of NaOL are dissolved in 200mL-300mL of 40℃-60℃ warm water, after the solution is cooled to 20℃-40℃, 12mL-18mL of 3mM-5mM AgNO3 is added, 200mL-300mL of 0.5mM-1.5mM HAuCl4 is added, the target temperature is maintained and placed for 10min-20min, and stirred at 600rpm-800rpm for 80min-100min, 1mL-3mL of 11.1M-13.1M HCl is added to adjust the pH of the solution, stirred at 300rpm-500rpm for 10min-20min, 1mL-1.5mL of 0.054M-0.074M ascorbic acid is added, and stirred for 20s-40s;
[0029] Growth of gold nanorods: 0.01mL-0.8mL of the seed solution is added to the growth solution and stirred uniformly; static growth, placed at the target temperature for 10h-14h; centrifuged at 6000rpm-8000rpm for 30min-50min, the supernatant is removed, and gold nanorods are prepared.
[0030] Optionally, in the preparation of the seed solution, the preparation of NaBH4 includes the following steps:
[0031] 0.0278g-0.0478g of NaBH4 is dissolved in 90ml-110ml of ice water, stirred uniformly, and 0.005M-0.015M of NaBH4 solution is prepared.
[0032] It should be noted that the growth solution is colorless and transparent, and must be prepared and used immediately, and cannot be stored, because the double surfactant composed of CTAB and sodium oleate can only prevent particle aggregation for a certain period of time, and after three hours, the transparent solution will gradually turn pink, at which time the growth solution has begun to agglomerate, which is not conducive to the growth of nanorods.
[0033] It should be further explained that the growth time of the nanorods must be controlled, and the solution should be centrifuged to remove the growth solution on time, because the gold ion concentration in the growth solution has an influence, if the growth time is too long, the nanorods may be overgrown, at this time, although the aspect ratio of the nanorods basically does not change, the particle size will increase, and even exceed 100 nm, which is beyond the size of nanomaterials, and the growth time should be controlled.
[0034] The method for manufacturing gold nanorods in the embodiments of the present disclosure adopts a green, efficient and controllable synthesis method of gold nanorods, i.e. seed growth method, first, gold nanospheres with a diameter of 3-5 nm are manufactured, then, the nanospheres are grown in a binary surfactant formed by mixing cetyltrimethylammonium bromide (CTAB) and sodium oleate (NaOL) with the assistance of silver nitrate, the silver nitrate can promote the growth, and the surfactant can inhibit the agglomeration of the nanospheres, the balance of the two can make the size of the grown nanorods uniform and the purity high.
[0035] The manufacturing process of the gold nanorods will be described in the following several embodiments.
[0036] Embodiment 1:
[0037] Preparation of seed solution: 5 mL of 0.5 mM HAuCl4 and 5 mL of 0.2 M CTAB are mixed for use; 0.6 mL of 0.01 M NaBH4 prepared freshly is diluted to 1 mL with pure water; 5 mL of the prepared NaBH4 solution is injected into the mixed solution of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, after 2 min, the color of the solution changes from yellow to brownish yellow, after 3-5 min of stirring, the stirring is stopped after 2 min, and the solution is placed at room temperature for 30 min.
[0038] Preparation of growth solution: 7.0 g of CTAB and 1.234 g of NaOL are dissolved in 250 mL of warm water at 50°C, after the solution is cooled to 30°C, 12 mL of 4 mM AgNO3 is added, 250 mL of 1 mM HAuCl4 is added, the solution is kept at 30°C and stirred for 15 min at a speed of 700 rpm, then 1 mL of 12.1 M HCl is added to adjust the pH of the solution, the solution is stirred at a speed of 400 rpm for 15 min, then 1.25 mL of 0.064 M ascorbic acid is added, and stirred for 30 s.
[0039] Growth of gold nanorods: 0.2 mL of the seed solution is added to the growth solution, and stirred uniformly; standing and growth, standing at 30°C for 12 h; centrifugation at a speed of 7000 rpm for 40 min, to remove the supernatant, and gold nanorods are prepared.
[0040] The average length of the gold nanorods prepared in Example 1 was 114.1 ± 6.8 nm, and the average diameter was 63.2 ± 3.4 nm.
[0041] Example 2:
[0042] Preparation of seed solution: 5 mL of 0.5 mM HAuCl4 and 5 mL of 0.2 M CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M NaBH4 was diluted to 1 mL with pure water; 5 mL of the prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, after standing for 2 min, the solution color changed from yellow to brown yellow, after stirring for 3-5 min, stop stirring after 2 min, and stand at room temperature for 30 min.
[0043] Preparation of growth solution: 7.0 g of CTAB and 1.234 g of NaOL were dissolved in 250 mL of warm water at 50°C, after the solution was cooled to 30°C, 12 mL of 4 mM AgNO3 was added, 250 mL of 1 mM HAuCl4 was added, kept at 30°C and stood for 15 min, and stirred at a speed of 700 rpm for 90 min, then 1.5 mL of 12.1 M HCl was added to adjust the pH of the solution, and stirred at a speed of 400 rpm for 15 min, then 1.25 mL of 0.064 M ascorbic acid was added, and stirred for 30 s.
[0044] Growth of gold nanorods: 0.2 mL of seed solution was added to the growth solution and stirred uniformly; standing and growing, standing at 30°C for 12 h; centrifuged at a speed of 7000 rpm for 40 min, remove the supernatant, and prepare gold nanorods.
[0045] The average length of the gold nanorods prepared in Example 2 was 101.7 ± 5.0 nm, and the average diameter was 58.5 ± 2.8 nm.
[0046] Example 3:
[0047] Preparation of seed solution: 5 mL of 0.5 mM HAuCl4 and 5 mL of 0.2 M CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M NaBH4 was diluted to 1 mL with pure water; 5 mL of the prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, after standing for 2 min, the solution color changed from yellow to brown yellow, after stirring for 3-5 min, stop stirring after 2 min, and stand at room temperature for 30 min.
[0048] Preparation of seed solution: 5 mL of 0.5 mM of HAuCl4 and 5 mL of 0.2 M of CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M of NaBH4 was diluted to 1 mL with pure water; 5 mL of prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, and after 2 min of standing, the solution color changed from yellow to brownish yellow, and after 3-5 min of stirring, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0049] Growth of gold nanorods: 0.2 mL of seed solution was added to the growth solution and stirred uniformly; standing growth, standing at 30°C for 12 h; centrifuged at 7000 rpm for 40 min, remove the supernatant, and gold nanorods were prepared.
[0050] The average length of the gold nanorods prepared in Example 3 was 187.2 ± 10.5 nm, and the average diameter was 133.6 ± 6.0 nm.
[0051] Example 4:
[0052] Preparation of seed solution: 5 mL of 0.5 mM of HAuCl4 and 5 mL of 0.2 M of CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M of NaBH4 was diluted to 1 mL with pure water; 5 mL of prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, and after 2 min of standing, the solution color changed from yellow to brownish yellow, and after 3-5 min of stirring, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0053] Preparation of seed solution: 5 mL of 0.5 mM of HAuCl4 and 5 mL of 0.2 M of CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M of NaBH4 was diluted to 1 mL with pure water; 5 mL of prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, and after 2 min of standing, the solution color changed from yellow to brownish yellow, and after 3-5 min of stirring, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0054] Growth of gold nanorods: 0.2 mL of seed solution was added to the growth solution and stirred uniformly; standing growth, standing at 30°C for 12 h; centrifuged at 7000 rpm for 40 min, remove the supernatant, and gold nanorods were prepared.
[0055] The average length of the gold nanorods prepared in Example 4 was 115.4 ± 6.2 nm, and the average diameter was 64.6 ± 3.0 nm.
[0056] Example 5:
[0057] Preparation of seed solution: 5 mL of 0.5 mM HAuCl4 and 5 mL of 0.2 M CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M NaBH4 was diluted to 1 mL with pure water; 5 mL of the prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, after standing for 2 min, the solution color changed from yellow to brown yellow, after stirring for 3-5 min, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0058] Preparation of growth solution: 7.0 g of CTAB and 1.234 g of NaOL were dissolved in 250 mL of warm water at 50°C, after the solution was cooled to 30°C, 18 mL of 4 mM AgNO3 was added, 250 mL of 1 mM HAuCl4 was added, kept at 30°C and stood for 15 min, and stirred at a speed of 700 rpm for 90 min, 1.5 mL of 12.1 M HCl was added to adjust the pH of the solution, and stirred at a speed of 400 rpm for 15 min, 1.25 mL of 0.064 M ascorbic acid was added, and stirred for 30 s.
[0059] Growth of gold nanorods: 0.4 mL of seed solution was added to the growth solution and stirred uniformly; standing and growing, standing at 30°C for 12 h; centrifuged at a speed of 7000 rpm for 40 min, the supernatant was removed, and gold nanorods were prepared.
[0060] The average length of the gold nanorods prepared in Example 5 was 140.0 ± 5.0 nm, and the average diameter was 84.7 ± 3.7 nm.
[0061] Example 6:
[0062] Preparation of seed solution: 5 mL of 0.5 mM HAuCl4 and 5 mL of 0.2 M CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M NaBH4 was diluted to 1 mL with pure water; 5 mL of the prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, after standing for 2 min, the solution color changed from yellow to brown yellow, after stirring for 3-5 min, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0063] Preparation of growth solution: 7.0 g of CTAB and 1.234 g of NaOL were dissolved in 250 mL of warm water at 50 °C, after the solution was cooled to 30 °C, 18 mL of 4 mM of AgNO3 was added, 250 mL of 1 mM of HAuCl4 was added, kept at 30 °C and placed for 15 min, and stirred at 700 rpm for 90 min, 1.5 mL of 12.1 M of HCl was added to adjust the pH of the solution, stirred at 400 rpm for 15 min, 1.25 mL of 0.064 M of ascorbic acid was added, and stirred for 30 s.
[0064] Growth of gold nanorods: 0.2 mL of seed solution was added to the growth solution and stirred uniformly; standing growth, standing at 30 °C for 12 h; centrifuged at 7000 rpm for 40 min, remove the supernatant, and prepare gold nanorods.
[0065] The average length of the gold nanorods prepared in Example 6 was 113.0 ± 4.9 nm, and the average diameter was 59.6 ± 2.6 nm.
[0066] Example 7:
[0067] Preparation of seed solution: 5 mL of 0.5 mM of HAuCl4 and 5 mL of 0.2 M of CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M of NaBH4 was diluted to 1 mL with pure water; 5 mL of prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at 1200 rpm, after standing for 2 min, the solution color changed from yellow to brown yellow, after stirring for 3 min to 5 min, stop stirring after 2 min, and place at room temperature for 30 min.
[0068] Preparation of growth solution: 9.0 g of CTAB and 1.543 g of NaOL were dissolved in 250 mL of warm water at 50 °C, after the solution was cooled to 30 °C, 12 mL of 4 mM of AgNO3 was added, 250 mL of 1 mM of HAuCl4 was added, kept at 30 °C and placed for 15 min, and stirred at 700 rpm for 90 min, 1.0 mL of 12.1 M of HCl was added to adjust the pH of the solution, stirred at 400 rpm for 15 min, 1.25 mL of 0.064 M of ascorbic acid was added, and stirred for 30 s.
[0069] Growth of gold nanorods: 0.8 mL of seed solution was added to the growth solution and stirred uniformly; standing growth, standing at 30 °C for 12 h; centrifuged at 7000 rpm for 40 min, remove the supernatant, and prepare gold nanorods.
[0070] The average length of the gold nanorods prepared in Example 7 was 110.0 ± 8.9 nm, and the average diameter was 69.8 ± 3.8 nm.
[0071] Example 8:
[0072] Preparation of seed solution: 5 mL of 0.5 mM HAuCl4 and 5 mL of 0.2 M CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M NaBH4 was diluted to 1 mL with pure water; 5 mL of the prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, after standing for 2 min, the solution color changed from yellow to brown yellow, after stirring for 3-5 min, stop stirring after 2 min, and placed at room temperature for 30 min.
[0073] Preparation of growth solution: 9.0 g of CTAB and 1.543 g of NaOL were dissolved in 250 mL of warm water at 50°C, after the solution was cooled to 30°C, 12 mL of 4 mM AgNO3 was added, 250 mL of 1 mM HAuCl4 was added, kept at 30°C and stood for 15 min, and stirred at a speed of 700 rpm for 90 min, 1.5 mL of 12.1 M HCl was added to adjust the pH of the solution, and stirred at a speed of 400 rpm for 15 min, 1.25 mL of 0.064 M ascorbic acid was added, and stirred for 30 s.
[0074] Growth of gold nanorods: 0.05 mL of seed solution was added to the growth solution and stirred uniformly; standing and growing, standing at 30°C for 12 h; centrifuged at a speed of 7000 rpm for 40 min, the supernatant was removed, and gold nanorods were prepared.
[0075] The average length of the gold nanorods prepared in Example 8 was 114.2 ± 5.1 nm, and the average diameter was 69.8 ± 3.1 nm.
[0076] Example 9:
[0077] Preparation of seed solution: 5 mL of 0.5 mM HAuCl4 and 5 mL of 0.2 M CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M NaBH4 was diluted to 1 mL with pure water; 5 mL of the prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, after standing for 2 min, the solution color changed from yellow to brown yellow, after stirring for 3-5 min, stop stirring after 2 min, and placed at room temperature for 30 min.
[0078] Preparation of seed solution: 5 mL of 0.5 mM of HAuCl4 and 5 mL of 0.2 M of CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M of NaBH4 was diluted to 1 mL with pure water; 5 mL of prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, and after 2 min of standing, the solution color changed from yellow to brownish yellow, and after 3-5 min of stirring, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0079] Growth of gold nanorods: 0.01 mL of seed solution was added to the growth solution and stirred uniformly; standing growth, standing at 30°C for 12 h; centrifuged at 7000 rpm for 40 min, remove the supernatant, and gold nanorods were prepared.
[0080] The average length of the gold nanorods prepared in Example 9 was 173.7 ± 9.1 nm, and the average diameter was 115.6 ± 4.0 nm.
[0081] Example 10:
[0082] Preparation of seed solution: 5 mL of 0.5 mM of HAuCl4 and 5 mL of 0.2 M of CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M of NaBH4 was diluted to 1 mL with pure water; 5 mL of prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, and after 2 min of standing, the solution color changed from yellow to brownish yellow, and after 3-5 min of stirring, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0083] Preparation of seed solution: 5 mL of 0.5 mM of HAuCl4 and 5 mL of 0.2 M of CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M of NaBH4 was diluted to 1 mL with pure water; 5 mL of prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, and after 2 min of standing, the solution color changed from yellow to brownish yellow, and after 3-5 min of stirring, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0084] Growth of gold nanorods: 0.01 mL of seed solution was added to the growth solution and stirred uniformly; standing growth, standing at 30°C for 12 h; centrifuged at 7000 rpm for 40 min, remove the supernatant, and gold nanorods were prepared.
[0085] The average length of the gold nanorods prepared in Example 10 was 136.0 ± 8.8 nm, and the average diameter was 80.0 ± 5.5 nm.
[0086] Example 11
[0087] Preparation of seed solution: 5 mL of 0.5 mM HAuCl4 and 5 mL of 0.2 M CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M NaBH4 was diluted to 1 mL with pure water; 5 mL of the prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, after standing for 2 min, the solution color changed from yellow to brown yellow, after stirring for 3-5 min, stop stirring after 2 min, and placed at room temperature for 30 min.
[0088] Preparation of growth solution: 9.0 g of CTAB and 1.543 g of NaOL were dissolved in 250 mL of warm water at 50°C, after the solution was cooled to 30°C, 12 mL of 4 mM AgNO3 was added, 250 mL of 1 mM HAuCl4 was added, kept at 30°C and stood for 15 min, and stirred at a speed of 700 rpm for 90 min, then 3.0 mL of 12.1 M HCl was added to adjust the pH of the solution, stirred at a speed of 400 rpm for 15 min, then 1.25 mL of 0.064 M ascorbic acid was added, and stirred for 30 s.
[0089] Growth of gold nanorods: 0.01 mL of seed solution was added to the growth solution and stirred uniformly; standing and growing, standing at 30°C for 12 h; centrifuged at a speed of 7000 rpm for 40 min, remove the supernatant, and prepare gold nanorods.
[0090] The average length of the gold nanorods prepared in Example 11 was 131.3 ± 5.8 nm, and the average diameter was 66.0 ± 3.4 nm.
[0091] Example 12
[0092] Preparation of seed solution: 5 mL of 0.5 mM HAuCl4 and 5 mL of 0.2 M CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M NaBH4 was diluted to 1 mL with pure water; 5 mL of the prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, after standing for 2 min, the solution color changed from yellow to brown yellow, after stirring for 3-5 min, stop stirring after 2 min, and placed at room temperature for 30 min.
[0093] Preparation of seed solution: 5 mL of 0.5 mM of HAuCl4 and 5 mL of 0.2 M of CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M of NaBH4 was diluted to 1 mL with pure water; 5 mL of prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, and after 2 min of standing, the solution color changed from yellow to brownish yellow, and after 3 min to 5 min of stirring, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0094] Growth of gold nanorods: 0.4 mL of seed solution was added to the growth solution and stirred uniformly; standing growth, standing at 30°C for 12 h; centrifuged at a speed of 7000 rpm for 40 min, the supernatant was removed, and gold nanorods were prepared.
[0095] The average length of the gold nanorods prepared in Example 12 was 88.2 ± 4.0 nm, and the average diameter was 40.0 ± 1.6 nm.
[0096] Example 13:
[0097] Preparation of seed solution: 5 mL of 0.5 mM of HAuCl4 and 5 mL of 0.2 M of CTAB were mixed for use; 0.6 mL of freshly prepared 0.01 M of NaBH4 was diluted to 1 mL with pure water; 5 mL of prepared NaBH4 solution was injected into the mixture of HAuCl4 and CTAB, and stirred at a speed of 1200 rpm, and after 2 min of standing, the solution color changed from yellow to brownish yellow, and after 3 min to 5 min of stirring, the stirring was stopped after 2 min, and placed at room temperature for 30 min.
[0098] Preparation of growth solution: 9.0 g of CTAB and 1.543 g of NaOL were dissolved in 250 mL of warm water at 50°C, after the solution was cooled to 30°C, 18 mL of 4 mM of AgNO3 was added, 250 mL of 1 mM of HAuCl4 was added, kept at 30°C and stood for 15 min, and stirred at a speed of 700 rpm for 90 min, then 1.5 mL of 12.1 M of HCl was added to adjust the pH of the solution, stirred at a speed of 400 rpm for 15 min, then 1.25 mL of 0.064 M of ascorbic acid was added, and stirred for 30 s.
[0099] Growth of gold nanorods: 0.4 mL of seed solution was added to the growth solution and stirred uniformly; standing growth, standing at 30°C for 12 h; centrifuged at a speed of 7000 rpm for 40 min, the supernatant was removed, and gold nanorods were prepared.
[0100] The average length of the gold nanorods produced in Example 13 is 105.3 ± 4.5 nm, and the average diameter is 49.9 ± 2.0 nm.
[0101] In a second aspect, the present application provides a gold nanorod produced by the method described above.
[0102] In a third aspect, the present application provides an application of the gold nanorod produced by the method described above.
[0103] One of the applications of the gold nanorods of the present embodiment is to produce LSPR sensitive units, which can enhance the reaction signal of LSPR and make it possible to measure molecules with low concentration and small molecular weight. Another application of the gold nanorods of the present embodiment is in the medical field. Since the longitudinal absorption peak of the gold nanorods is adjustable and the gold nanorods have strong absorption and scattering of light and can emit scattered light efficiently, the gold nanorods after surface modification can be widely used in biological separation, protein detection and medical imaging, with the advantages of accuracy and high efficiency. On the other hand, the gold nanorods have outstanding advantages in cancer treatment. Since cancer cells have the characteristics of fast reproduction and strong mobility, how to accurately find the markers of cancer cells is the primary and fundamental problem. The introduction of modified gold nanorods can accurately locate cancer cells, and it is expected that the absorption of specific wavelength light by the gold nanorods can make the nanorods absorb a large amount of energy in a short time and heat up to kill cancer cells. Although this aspect is still under research, it does have prospects.
[0104] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or make equivalent substitutions for part or all of the technical features; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.
Claims
1. A method for fabricating gold nanorods, characterized in that, The method includes the following steps; Preparation of seed solution: Mix 4 mL to 6 mL of 0.4 mM to 0.6 mM HAuCl4 and 4 mL to 6 mL of 0.1 M to 0.3 M CTAB and set aside; dilute 0.5 mL to 0.7 mL of freshly prepared 0.005 M to 0.015 M NaBH4 with pure water to 0.5 mL to 1.5 mL; add 4 mL to 6 mL of the prepared NaBH4 solution to the HAuCl4 and CTAB mixture, stir at a preset first speed for a preset first time, and then place at room temperature for 20 min to 40 min; Preparation of growth solution: Dissolve 7.0g-9.0g of CTAB and a predetermined amount of NaOL in 200mL-300mL of warm water. After cooling the solution to the target temperature, add a predetermined amount of 3mM-5mM AgNO3 and 200mL-300mL of 0.5mM-1.5mM HAuCl4. Maintain the target temperature and let stand for 10min-20min. Stir at a preset second speed for a preset second time. Add a certain volume of 11.1M-13.1M HCl to adjust the pH of the solution. Stir at a preset third speed for a preset third time. Add 1mL-1.5mL of 0.054M-0.074M ascorbic acid and stir for 20s-40s. Growth of gold nanorods: A quantitative amount of the seed solution is added to the growth solution and stirred evenly; the growth is allowed to proceed under static conditions for 10-14 hours at the target temperature; the supernatant is removed by centrifugation at a preset fourth rotation speed for a preset fourth time to obtain gold nanorods. In the growth of gold nanorods, the volume of the seed solution ranges from 0.01 mL to 0.8 mL; The temperature range of the warm water is 40℃~60℃, and the target temperature range is 20℃~40℃; the preset second rotation speed range is 600rpm~800rpm, and the preset second time range is 80min~100min; the preset third rotation speed range is 300rpm~500rpm, and the preset third time range is 10min~20min; the preset fourth rotation speed range is 6000rpm~8000rpm, and the preset fourth time range is 30min~50min. The mass range of NaOL is 1.234g to 1.543g, the volume range of AgNO3 is 12mL to 18mL, the volume range of HCl is 1mL to 3mL, the preset first rotation speed is 1100rpm to 1300rpm, and the preset first time is 3min to 5min.
2. The method according to claim 1, characterized in that, In preparing the seed solution, the preparation of NaBH4 includes the following steps: dissolving 0.0278g to 0.0478g of NaBH4 in 90ml to 110ml of ice water, stirring evenly to prepare a 0.005M to 0.015M NaBH4 solution.
3. A gold nanorod, characterized in that, It is manufactured using the manufacturing method described in claim 1 or 2.
4. An application of gold nanorods, characterized in that, The gold nanorods are fabricated using the method described in claim 1 or 2.
Citation Information
Patent Citations
Preparation method of gold nanorod material with length-diameter ratio regulated and controlled through hydrochloric acid
CN112743099A