CN115466602A - AuNSs in-situ synthesis and application method based on seed-mediated method and portable thermometer - Google Patents

AuNSs in-situ synthesis and application method based on seed-mediated method and portable thermometer Download PDF

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CN115466602A
CN115466602A CN202211287338.0A CN202211287338A CN115466602A CN 115466602 A CN115466602 A CN 115466602A CN 202211287338 A CN202211287338 A CN 202211287338A CN 115466602 A CN115466602 A CN 115466602A
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solution
aqueous solution
concentration
aunss
ascorbic acid
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何悦
王沂雯
刘晏霖
焦必宁
崔永亮
张耀海
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Southwest University
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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    • C09K5/14Solid materials, e.g. powdery or granular
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    • C01G7/00Compounds of gold
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01KMEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
    • G01K11/16Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials

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Abstract

The invention discloses an AuNSs in-situ synthesis and application method based on a seed-mediated method and a portable thermometer. The in-situ synthesis method comprises the following steps: mixing gold seed solution and HAuCl 4 ·4H 2 And adding the aqueous solution of O and hydrochloric acid into deionized water, immediately adding the aqueous solution of silver nitrate and the aqueous solution of ascorbic acid, and quickly mixing at room temperature to obtain the AuNSs. The synthetic method can be applied to the ascorbic acid concentration detection based on a portable thermometer, can solve the problems that a large instrument, a professional technician and a toxic reagent are required in most of the traditional detection, and realizes the rapid and accurate detection of the ascorbic acid.

Description

AuNSs in-situ synthesis and application method based on seed-mediated method and portable thermometer
Technical Field
The invention relates to the technical field of photo-thermal reagents for biosensors, in particular to the technical field of gold nano materials used as photo-thermal reagents.
Background
With the continuous efforts of scientific researchers, thermometers have been used as readout devices for portable biosensors to detect various targets, such as pesticide residues, mycotoxins, micrornas, food-borne pathogens, biomarkers, etc., and one of the key technical problems is the need to accurately establish the relationship between the target concentration and the temperature of the detection solution. One solution commonly used to solve this technical problem is to establish a correlation between the target concentration and the temperature signal by triggering a change in the amount of the photo-thermal agent in the thermometer by reaction of the target molecule.
In the above method for detecting target concentration by the change of photothermal reagent, there are two common detection methods, one is to form a target-aptamer or antigen-antibody specific interaction by the cooperation of photothermal reagent and aptamer or antibody, thereby detecting the change of photothermal reagent amount in solution, but since it needs to perform a plurality of steps of reagent immobilization, labeling and purification, the experimental process is complicated, the conditions are harsh, and it is difficult to apply widely; the other is the direct triggering of the in situ generation or consumption of photothermal agents by the target molecule, which generally does not require a labeling process and is more sensitive and easier to handle. However, most photothermal agents in this manner require complicated reaction processes or harsh reaction conditions (e.g., high temperature or long reaction time) to achieve in situ generation. Therefore, the development of a novel photothermal agent for biosensing, which has an excellent photothermal conversion effect, is easy to synthesize, and preferably does not require any modification, is now urgently needed.
In the aspect of photo-thermal conversion effect, the gold nano material has an extinction coefficient as high as 10 due to the excellent Local Surface Plasmon Resonance (LSPR) characteristic 8 -10 11 M -1 cm -1 And has attracted a great deal of attention. Among various gold nanomaterials, gold nanostars (AuNSs) having various sharp branch structures have higher photo-thermal conversion efficiency due to stronger 'hot spot' effect. Therefore, auNSs has great application potential in novel photo-thermal reagents for biosensing. However, many studies have shown that AuNSs generally exhibit poor performanceStability, a condition in which the particle morphology (remodeling) undergoes a significant change and LSPR blue-shifting in less than 7 days.
AuNSs has been successfully applied to photothermal immunoassay in laboratories, in which the temperature change caused by AuNSs reaches about 30 ℃ which is much higher than that caused by other photothermal reagents, and no antibody needs to be labeled on AuNSs. However, in this method, the silver mediated by the alkaline phosphatase labeled on the antibody is deposited on the AuNSs, which results in a decrease in the photothermal conversion effect of the AuNSs, wherein the preparation process of the AuNSs is also complicated, takes a significant time (more than 24 hours), and the problem of poor stability of the AuNSs is not improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for rapidly synthesizing AuNSs in situ by a seed-mediated method, the reaction process is simple and efficient, the obtained AuNSs material can be prepared and used immediately, has good photo-thermal effect, and can be used as a photo-thermal reagent to further construct a portable temperature detection device and/or a biosensor so as to directly and accurately detect the concentration of target molecules without modification or other treatments.
The technical scheme of the invention is as follows:
the AuNSs in-situ synthesis method based on the seed-mediated method comprises the following steps: mixing gold seed solution and HAuCl 4 ·4H 2 And mixing the O aqueous solution and the hydrochloric acid aqueous solution in deionized water, then adding a silver nitrate aqueous solution and an Ascorbic Acid (AA) aqueous solution, and violently shaking at room temperature to change the color of the mixture into blue, thereby obtaining the gold nano-star material with the multi-branch structure.
According to some preferred embodiments of the invention, the gold seed solution, the HAuCl 4 ·4H 2 The volume ratio of the aqueous O solution to the aqueous hydrochloric acid solution is 1.
According to some preferred embodiments of the present invention, the volume ratio of the aqueous silver nitrate solution to the aqueous ascorbic acid solution is 1:1.
According to some preferred embodiments of the invention, the aqueous hydrochloric acid solution has a concentration of 0.12M.
According to some preferred embodiments of the present invention, the HAuCl 4 ·4H 2 The concentration of the O aqueous solution was 2.5mM.
According to some preferred embodiments of the invention, the concentration of the aqueous solution of silver nitrate is 2mM.
The invention further provides an application method of the synthesis method, which is to apply the synthesis method to the concentration test of a target analyte in a test solution, wherein the test solution is an aqueous solution of the target analyte, and the target analyte is ascorbic acid or other analytes capable of changing the concentration of the ascorbic acid.
According to some preferred embodiments of the invention, the method of applying comprises: mixing the gold seed solution and the HAuCl 4 ·4H 2 And mixing an O aqueous solution and the hydrochloric acid aqueous solution in the deionized water, then adding the silver nitrate aqueous solution and the solution to be tested with different concentrations, shaking violently at room temperature to change the color of the mixture, testing the temperature of the obtained mixture, and obtaining the concentration of the solution to be tested according to the relationship between the temperature of the mixture and the concentration of the ascorbic acid.
According to some preferred embodiments of the invention, the mixture temperature is related to the concentration of the aqueous ascorbic acid solution by: y =0.07196x +0.03305, wherein x represents the concentration of ascorbic acid in the mixture, and y represents the temperature change value of the mixture, i.e. the difference between the test temperature and the test temperature of the mixture of a blank control group without the test solution.
According to the relational expression of the temperature and the concentration, the portable thermometer applying the application method can be further obtained.
The invention has the following beneficial effects:
the preparation method can synthesize AuNSs in situ by a simple and rapid seed-mediated method, and the obtained AuNSs has good photothermal effect and stability.
The preparation method can be further applied to AA detection, and the relation between the concentration of a target solution (AA solution) and the temperature change of AuNSs is established through the obvious temperature change of the AuNSs caused by the AA solutions with different concentrations in the solution to be detected, so that a portable and sensitive thermometer is obtained, and the preparation method can be further applied to a biosensor.
The application method of the invention not only generates the photothermal reagent AuNSs with high photothermal conversion efficiency through in-situ generation, but also does not need to carry out complex and time-consuming synthesis and modification on target molecules in the detection, and has simple detection process and high detection efficiency.
In a further application, the present invention also allows for detection of more analytes by converting analyte concentration to AA concentration, widening the range of analysis.
The application method and the obtained portable thermometer can get rid of the problem that large instruments, professional technicians and toxic reagents are needed in most of the traditional detection, and can realize the on-site rapid detection and analysis of AA.
Drawings
Fig. 1 is a transmission electron microscope of AuNSs particles obtained in example 1.
Fig. 2 is a graph showing an ultraviolet absorption spectrum of AuNSs particles obtained in example 1.
Fig. 3 is a graph showing the temperature dependence of the irradiation time of AuNSs particles obtained in example 1.
Fig. 4 is a graph showing the irradiation time of AuNSs particles obtained in example 2 as a function of the temperature change caused thereby.
Fig. 5 shows the irradiation distance of AuNSs particles obtained in example 2 as a function of the temperature change caused thereby.
Fig. 6 is a graph of the uv absorption spectra of AuNSs particles produced with different amounts of AA obtained in example 2 of the present invention.
Fig. 7 is a graph of the temperature change of AuNSs particles produced with different amounts of AA obtained in example 2.
Fig. 8 is a linear plot of the temperature change of AuNSs particles produced with different amounts of AA from example 2.
Detailed Description
The present invention is described in detail below with reference to the following embodiments and the attached drawings, but it should be understood that the embodiments and the attached drawings are only used for the illustrative description of the present invention and do not limit the protection scope of the present invention in any way. All reasonable variations and combinations that fall within the spirit of the invention are intended to be within the scope of the invention.
According to the technical scheme of the AuNSs synthesis method based on the seed-mediated method, some specific embodiments of the AuNSs synthesis method comprise the following steps:
mixing gold seed solution and HAuCl 4 ·4H 2 And mixing the O aqueous solution and the hydrochloric acid aqueous solution in deionized water, then adding the silver nitrate aqueous solution and the ascorbic acid aqueous solution, and violently shaking at room temperature to change the color of the mixture into blue, thereby obtaining the gold nanostar (AuNSs) material with a multi-branch structure.
Wherein:
preferably, the gold seed solution, HAuCl 4 ·4H 2 The volume ratio of the aqueous O solution to the aqueous hydrochloric acid solution is 1.
Preferably, the volume ratio of the silver nitrate aqueous solution to the ascorbic acid aqueous solution is 1:1.
Preferably, the concentration of the aqueous hydrochloric acid solution is 0.12M.
Preferably, HAuCl 4 ·4H 2 The concentration of the O aqueous solution was 2.5mM
Preferably, the concentration of the silver nitrate aqueous solution is 2mM.
Some embodiments of the method for applying the method for synthesizing AuNSs based on the seed-mediated method according to the present invention include the following steps:
mixing gold seed solution and HAuCl 4 ·4H 2 Mixing an O aqueous solution and a hydrochloric acid aqueous solution in deionized water, then adding a silver nitrate aqueous solution and test solutions with different concentrations, shaking vigorously at room temperature to change the color of the mixture into blue, testing the temperature of the obtained mixture, and obtaining the concentration of the test solution according to the relationship between the temperature of the mixture and the concentration of ascorbic acid, wherein the test solution is an aqueous solution of a target analyte, and the target analyte is ascorbic acid or other analytes capable of changing the concentration of ascorbic acid.
Wherein:
it is preferable thatThe gold seed solution, HAuCl 4 ·4H 2 The volume ratio of the aqueous O solution to the aqueous hydrochloric acid solution is 1.
Preferably, the volume ratio of the silver nitrate aqueous solution to the ascorbic acid aqueous solution is 1:1.
Preferably, the concentration of the aqueous hydrochloric acid solution is 0.12M.
Preferably, HAuCl 4 ·4H 2 The concentration of the O aqueous solution was 2.5mM
Preferably, the concentration of the silver nitrate aqueous solution is 2mM.
The technical solution of the present invention is further shown by the following examples.
Example 1
mu.L of gold seed solution, 8. Mu.L of 2.5mM HAuCl 4 ·4H 2 An aqueous solution of O and 1. Mu.L of 0.12M hydrochloric acid were added to 80. Mu.L of deionized water, immediately followed by the addition of 5. Mu.L of a 2mM aqueous solution of silver nitrate and 5. Mu.L of a 10mM aqueous solution of Ascorbic Acid (AA), and vigorously shaken at room temperature to turn the mixture blue in color.
The AuNSs product is characterized by a transmission electron microscope, and the obtained image is shown in figure 1, so that the gold nanostars (AuNSs) are successfully synthesized in the process, the particle size distribution of the gold nanostars is 65.8 +/-3.8 nm, the gold nanostars are distributed and dispersed, and the gold nanostars are uniform in size.
The obtained AuNSs is subjected to 400-940nm ultraviolet absorption spectrum measurement, the result is shown in figure 2, and the peak value is about 850 nm.
The photo-thermal conversion effect test is performed on the obtained AuNSs, and the blank group and the experimental group are respectively used for comparison, the result is shown in the attached figure 3, it can be seen that the blank group shows an ascending trend of the system temperature along with the extension of the irradiation time, the experimental group shows a descending trend after the system temperature rises, and when the time reaches 90s, the temperature difference between the experimental group and the blank group is the largest.
Example 2
AuNSs synthesis comparisons were performed as experimental versus blank, where:
the preparation process of the experimental group is as follows: mu.L of gold seed solution, 8. Mu.L of 2.5mM HAuCl 4 ·4H 2 An aqueous solution of O and 1. Mu.L of 0.12M hydrochloric acid were added to 80. Mu.L of deionized water, immediately thereafter 5. Mu.L of an aqueous solution of 2mM silver nitrate and 5. Mu.L of aqueous solutions of ascorbic acid of different concentrations were added, and shaken vigorously at room temperature, and the resulting mixture was tested for temperature T and absorption spectrum.
The blank was prepared in the same manner as the experimental group, except that ascorbic acid was not added, and the temperature T of the resulting mixture was measured 0 And an absorption spectrum.
The results of 400-940nm absorption spectrum tests of AuNSs synthesized at different AA concentration in the experimental group are shown in FIG. 6, and it can be seen that the intensity of longitudinal LSPR at 540nm increases as the AA concentration increases from 100 to 600. Mu.M, and then the peak of longitudinal LSPR is observed to shift from 540nm to 870 nm.
Determining the temperature change value delta T of the solution obtained by the reaction of the ascorbic acid according to the change of the concentration of the ascorbic acid according to the data of an experimental group and a blank group, wherein delta T = T-T 0 T represents the temperature of the experimental group, T 0 Representing blank temperature, the results are shown in fig. 7 and 8, and it can be seen that the concentration of the AA aqueous solution is substantially linear with the temperature change of the solution for generating the AuNSs particles, and the relationship is: y =0.07196x +0.03305, wherein x represents the concentration of AA in the mixture and y represents the temperature difference Δ T.
Meanwhile, the temperature change value Δ T, the laser irradiation time and the irradiation distance (the distance from the laser source to the microplate) were measured, and the results are shown in fig. 4 and 5, where it can be seen that Δ T is maximized when the irradiation time is 90s and the irradiation distance is 2 cm.
From the above images, it can be seen that the method based on seed-mediated in situ synthesis of gold nanostars can be successfully applied to the detection of AA concentration or other analyte concentrations whose concentration can be converted to AA concentration. As another example, the concentration of the target can be converted to the concentration of alkaline phosphatase, and different concentrations of alkaline phosphatase can be reacted with the substrate L-ascorbic acid-2-trisodium phosphate of AA to generate different concentrations of AA, so as to perform in-situ synthesis of Venus to realize detection of different targets.
And based on the linear relationship of temperature to AA concentration, it can be used as a sensitive thermometer.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.

Claims (7)

1. The AuNSs in-situ synthesis method based on the seed-mediated method is characterized by comprising the following steps: mixing gold seed solution and HAuCl 4 ·4H 2 And mixing the aqueous solution of O and the aqueous solution of hydrochloric acid in deionized water, then adding the aqueous solution of silver nitrate and the aqueous solution of ascorbic acid, and violently shaking at room temperature to change the color of the mixture into blue, thereby obtaining the gold nano-star material with the branch structure.
2. The method for in situ synthesis of AuNSs based on seed-mediated method according to claim 1, wherein the gold seed solution and the HAuCl are added 4 ·4H 2 The volume ratio of the aqueous O solution to the aqueous hydrochloric acid solution is 1; and/or the volume ratio of the silver nitrate aqueous solution to the ascorbic acid aqueous solution is 1:1.
3. The method for in situ synthesis of AuNSs based on seed-mediated method according to claim 1, wherein the concentration of the aqueous hydrochloric acid solution is 0.12M; and/or, the HAuCl 4 ·4H 2 The concentration of the O aqueous solution is 2.5mM; and/or the concentration of the silver nitrate aqueous solution is 2mM.
4. The method of using the in situ synthesis method of claims 1-3, wherein the synthesis method is applied to the concentration test of target analytes in the test solution, wherein the test solution is an aqueous solution of the target analytes, and the target analytes are ascorbic acid or other analytes capable of changing the concentration of ascorbic acid.
5. Application method according to claim 4, characterized in that it comprises: mixing the gold seed solution and the HAuCl 4 ·4H 2 And mixing an O aqueous solution and the hydrochloric acid aqueous solution in the deionized water, then adding the silver nitrate aqueous solution and the solution to be tested with different concentrations, shaking violently at room temperature to change the color of the mixture, testing the temperature of the obtained mixture, and obtaining the concentration of the solution to be tested according to the relationship between the temperature of the mixture and the concentration of the ascorbic acid.
6. The method of use according to claim 5, wherein the mixture temperature is related to the concentration of the aqueous ascorbic acid solution by: y =0.07196x +0.03305, wherein x represents the concentration of ascorbic acid in the mixture, and y represents the temperature change value of the mixture, i.e., the difference between the test temperature and the test temperature of the mixture of a blank control group without the test solution.
7. A portable thermometer using the method of claim 6.
CN202211287338.0A 2022-10-20 2022-10-20 AuNSs in-situ synthesis and application method based on seed-mediated method and portable thermometer Pending CN115466602A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
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CN101343778A (en) * 2008-08-29 2009-01-14 北京航空航天大学 Process for producing golden nano stick with short length-diameter ratio
CN106077705A (en) * 2016-08-19 2016-11-09 东华大学 A kind of preparation method of gold nanorods
CN109396457A (en) * 2018-12-05 2019-03-01 武汉大学苏州研究院 A kind of shape and the controllable nanogold particle and the preparation method and application thereof of size
CN112641946A (en) * 2021-01-19 2021-04-13 苏州市立医院 Polydopamine-coated gold nano-composite, preparation method thereof and application thereof in multi-modal tumor diagnosis and treatment
CN113770372A (en) * 2021-09-13 2021-12-10 中红外激光研究院(江苏)有限公司 Preparation method of gold nanoparticle aggregate material

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Publication number Priority date Publication date Assignee Title
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CN106077705A (en) * 2016-08-19 2016-11-09 东华大学 A kind of preparation method of gold nanorods
CN109396457A (en) * 2018-12-05 2019-03-01 武汉大学苏州研究院 A kind of shape and the controllable nanogold particle and the preparation method and application thereof of size
CN112641946A (en) * 2021-01-19 2021-04-13 苏州市立医院 Polydopamine-coated gold nano-composite, preparation method thereof and application thereof in multi-modal tumor diagnosis and treatment
CN113770372A (en) * 2021-09-13 2021-12-10 中红外激光研究院(江苏)有限公司 Preparation method of gold nanoparticle aggregate material

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