CN114136958B - High-sensitivity visualization method for regulating and controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres - Google Patents
High-sensitivity visualization method for regulating and controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres Download PDFInfo
- Publication number
- CN114136958B CN114136958B CN202111386678.4A CN202111386678A CN114136958B CN 114136958 B CN114136958 B CN 114136958B CN 202111386678 A CN202111386678 A CN 202111386678A CN 114136958 B CN114136958 B CN 114136958B
- Authority
- CN
- China
- Prior art keywords
- gold
- solution
- nanorod
- etching
- interaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a high-sensitivity visualization method for regulating and controlling gold nanorod etching based on the interaction of a tumor marker and gold nanospheres, which comprises the following steps: (1) Mixing a tumor marker with a gold nanosphere solution, and then catalyzing sodium borohydride to reduce p-nitrophenol to obtain a mixed solution; (2) And (3) adding the mixed solution, the potassium iodate solution and the gold nanorod solution in the step (1) into the B-R buffer solution system, and performing oxidation-reduction reaction to generate the etching agent to regulate and control the etching of the gold nanorod. The method of the invention utilizes the effect of the tumor markers on the surface of the gold nanospheres to form protein corona effect, regulates and controls the performance of the gold nanospheres for catalyzing sodium borohydride to reduce p-nitrophenol, further regulates and controls the etching of the gold nanorods, so that the gold nanorods generate stable color change, is simple and efficient, has rapid color development and high sensitivity, can realize the visualized instant detection of the tumor markers, and has wide application prospect in early prevention and diagnosis of cancer diseases.
Description
Technical Field
The invention relates to the technical field of nanomaterials and detection, in particular to a high-sensitivity visualization method for regulating and controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres.
Background
Colorimetric methods have the advantages of high cost-effectiveness, simple detection, direct readout, and the like, and are widely used for detection of various analytes. It has been reported that the construction of colorimetric sensing based on color change of chromogenic substrates, with a single color being affected by the degree of color recognition by the human population, has limited application. The noble metal nano particles have unique physical and chemical properties, and are widely used in aspects of biological sensing, imaging, clinical diagnosis and the like. And most of anisotropic noble metal nanoparticles show bright colors under visible light due to excellent optical properties of localized surface plasmon resonance, and are widely used for constructing colorimetric sensors. Most conventional dye-based colorimetry methods are generally low in sensitivity and limited by the available analytes, as most organic dyes exhibit low extinction coefficients. In contrast, noble metal nanoparticles have a much higher extinction coefficient, especially gold and silver nanomaterials, 1000 times higher extinction coefficient than organic dyes in the visible region, have a nanoscale (even lower range) sensitivity, and are tunable in dynamic range. These all highlight the great advantage of noble metal nanoparticles in the construction of colorimetric sensors.
Among the numerous colorimetric methods, the methods based on precious metal nanoparticle aggregation are susceptible to interference from the environment and complex samples, generating false positive signals, and have limited applications. The colorimetric method based on etching has stable signals and rich color change, and is very suitable for constructing colorimetric sensors. However, compared with detection methods of other precise instruments, the visual detection method still has disadvantages in sensitivity, so that the construction of the high-sensitivity colorimetric sensing method has very important research and application significance in the fields of biomedicine, chemical analysis and the like.
The Chinese patent document with publication number of CN113030079A discloses a method for detecting pesticide carbaryl based on nano gold etching, which comprises the steps of adding a solution I to be detected containing carbaryl and tetra- (4-pyridyl) zinc porphyrin nanorod into a mixed solution II containing biconical nano gold and hydrogen peroxide, uniformly mixing and fully reacting to obtain a solution system III; according to the color change of a solution system III obtained by introducing the carbofuran before and after reaction or the change of the peak position of the corresponding biconical nano gold LSPR peak, the carbofuran is detected.
The Chinese patent document with publication number of CN107084979A discloses a method for quantitatively detecting organophosphorus pesticide by constructing a colorimetric sensor based on gold nanorod etching, wherein a double-enzyme system is adopted to catalyze acetylcholine chloride to generate hydrogen peroxide, the hydrogen peroxide etches the gold nanorod under the catalysis condition, and the color after the reaction is observed; wherein the double enzyme system is a system containing acetylcholinesterase and choline oxidase simultaneously; the hydrogen peroxide etches the gold nanorods under the action of catalytic conditions, namely the hydrogen peroxide contains Fe 2+ Etching gold nanorods in an acidic solution.
Disclosure of Invention
The invention provides a high-sensitivity visualization method for regulating and controlling gold nanorod etching based on the interaction of tumor markers and gold nanospheres, which is simple and efficient, quick in color development, high in sensitivity and high in color resolution, can realize the visual instant detection of the tumor markers, and has a wide application prospect in early prevention and diagnosis of cancer diseases.
The technical scheme adopted is as follows:
a high-sensitivity visualization method for regulating and controlling gold nanorod etching based on the interaction of tumor markers and gold nanospheres comprises the following steps:
(1) Mixing a tumor marker with a gold nanosphere solution, and then catalyzing sodium borohydride to reduce p-nitrophenol to obtain a mixed solution;
(2) And (3) adding the mixed solution, the potassium iodate solution and the gold nanorod solution in the step (1) into the B-R buffer solution system, and performing oxidation-reduction reaction to generate the etching agent to regulate and control the etching of the gold nanorod.
The tumor markers are rich in cysteine, including but not limited to metallothionein, ribonuclease, transglutaminase or human epididymal protein.
The tumor marker acts on the surface of the gold nanosphere through Au-S bond to form protein corona effect, occupies catalytic sites on the surface of the gold nanosphere, influences the catalytic sodium borohydride to reduce p-nitrophenol, regulates and controls the generation of p-aminophenol, and the p-aminophenol can undergo oxidation-reduction reaction with potassium iodate to generate iodine simple substance with etching effect on the gold nanorod.
Preferably, in the step (1), the gold nanosphere solution is prepared from chloroauric acid, trisodium citrate and tris (hydroxymethyl) aminomethane serving as raw materials by a classical sodium citrate reduction gold chlorate method.
The size of the gold nanospheres determines the performance of catalyzing p-nitrophenol, and the smaller the particle size is, the stronger the catalysis effect is, and preferably, in the step (1), the particle size of the gold nanospheres is 30-50 nm. The gold nanospheres within the particle size range have better capabilities of catalyzing and regulating the etching of gold nanorods, and can realize high-sensitivity visual detection of tumor markers.
Further preferably, the preparation method of the gold nanosphere solution comprises the following steps: adding 5-15 mL of 30-40 mM trisodium citrate into 100-200 mL of deionized water boiling at 500-1500 rpm at 100-150 ℃ for 30-60 min; then 0.5-2 mL of fresh HAuCl with the concentration of 20-30 mM is added rapidly 4 A solution; after 50-70 s, 3-7 mL of 0.05-0.2M tris (hydroxymethyl) aminomethane is added, kept boiling and stirred for 10-20 min at 500-1500 rpm; the temperature is reduced to 90 to 110 ℃, and then 0.5 to 2mL of HAuCl with 20 to 30mM is added rapidly 4 Maintaining the temperature of the solution for 20min; finally, 0.5 to 2mL of 20 to 30mM HAuCl 4 And (3) rapidly injecting and maintaining the temperature for 15-30 min, and naturally cooling to obtain the gold nanosphere solution.
Preferably, in the step (1), the volume ratio of the tumor marker to the gold nanosphere solution is 1-3: 1, a step of; the tumor marker is metallothionein with the concentration of 0-6nM, or the tumor marker is ribonuclease with the concentration of 0-60 nM, or the tumor marker is transglutaminase with the concentration of 0-6.5 nM, or the tumor marker is human epididymis protein with the concentration of 0-2.5 nM. The kind or concentration of the tumor markers has great influence on the catalysis of the gold nanospheres, the etching of the gold nanorods is influenced, and the regulation and control of the etching of the gold nanorods can be realized by regulating the kind or concentration of the tumor markers.
Preferably, in the step (1), the tumor marker and the gold nanosphere solution are uniformly mixed and kept stand for 5-20 min, and then sodium borohydride is catalyzed to reduce p-nitrophenol; the standing process can enable the tumor markers to fully act on the surface of the gold nanospheres to achieve the protein corona effect, occupy the catalytic sites of the gold nanospheres and further reduce the catalytic performance.
Preferably, in the step (1), the volume ratio of the gold nanosphere solution, sodium borohydride and p-nitrophenol is 1:0.25 to 1.5: 0.5-2 mM sodium borohydride, and p-nitrophenol, wherein the concentration of the sodium borohydride is 1.5-9 mM, and the concentration of the p-nitrophenol is 30-120 mu M.
Preferably, in the step (2), the gold nanorod solution is prepared by adopting a classical seed-mediated method and using chloroauric acid, silver nitrate, ascorbic acid, sodium borohydride, hydrochloric acid and cetyl trimethyl ammonium chloride as raw materials.
Preferably, in the step (2), the length-diameter ratio of the gold nanorods is 2-3:1, and the length is 60-80 nm. Gold nanorods with corresponding parameters can generate colorful colors based on LSPR optical properties under the etched condition, and the visual detection sensitivity is high.
Further preferably, the preparation method of the gold nanorod solution comprises the following steps:
(1) preparation of nano gold core: sequentially adding 0.1-0.3 mL of 0.005-0.02M HAuCl 4 NaBH prepared from solution and 0.5-0.7 mL of 0.005-0.02M ice water 4 Sequentially adding the solution into 8-10 ml of 0.05-0.20M CTAB (cetyltrimethylammonium bromide) solution, then vigorously stirring for 1-3 min at the rotating speed of 1100-1300 rpm, and standing the reaction solution at room temperature for at least 1.5-3 h for standby;
(2) sequentially adding 3-5 mL of 0.005-0.02M HAuCl under the conditions of rotating speed 700rpm and water bath at the temperature of 27-32 DEG C 4 0.7-0.9 mL of 0.005-0.02M AgNO 3 Adding 0.5-0.7 ml of 0.05-0.2M ascorbic acid solution and 1-2 ml of 0.5-1.5M HCl solution into 70-90 ml of 0.05-0.2M CTAB solution to obtain mixed solution, adding 60-80 mu L of nano gold core solution prepared in the step (1) into the mixed solution, standing overnight in a water bath at 27-32 ℃, and centrifuging and concentrating to obtain the gold nanorod solution.
Preferably, in the step (2), the volume ratio of the mixed solution, the potassium iodate solution and the gold nanorod solution is 20-75: 1: 8-30, wherein the concentration of the potassium iodate solution is 40-60 mM.
Preferably, in step (2), the pH of the B-R buffer solution system is 2.0, comprising 20-30 mM CTAB and 40-60 mM NaBr.
Preferably, in the step (2), the oxidation-reduction reaction and the etching process are performed at a temperature of 40-60 ℃.
The invention also provides application of the high-sensitivity method for regulating and controlling gold nanorod etching based on the tumor marker-gold nanosphere compound in tumor marker detection.
Mixing a solution to be detected with gold nanospheres, then using the mixed solution to catalyze sodium borohydride to reduce p-nitrophenol, and performing oxidation-reduction reaction according to the method to regulate and control the etching of the gold nanorods; and performing ultraviolet spectrum measurement after etching, photographing a storage picture, and finally calculating according to the longitudinal LSPR peak displacement change to obtain the content of the tumor marker in the solution to be detected.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, a protein corona effect is formed on the surface of the gold nanosphere by utilizing the action of the tumor marker through the Au-S bond, the performance of the gold nanosphere for catalyzing sodium borohydride to reduce p-nitrophenol is regulated and controlled, the generation of an etchant is further influenced, and the etching of the gold nanorod is regulated and controlled, so that stable color change is generated, the visual detection of the tumor marker can be realized, and the method has a wide application prospect in early prevention and diagnosis of cancer diseases.
(2) The method has the advantages of simplicity, high efficiency, low equipment requirement, low cost, quick color development, high color resolution and the like, and can be used for on-site instant detection of tumor markers.
(3) The method can perform ultrasensitive detection of abnormal expression of the concentration of the tumor marker rich in cysteine in a low concentration and narrow range, and the detection limit of metallothionein is as low as 28pM.
Drawings
FIG. 1 is a TEM image of the gold nanosphere solution prepared in example 1, scale 100nm.
FIG. 2 is a TEM image of the gold nanorod solution prepared in example 1, with a scale of 200nm.
Fig. 3 is an ultraviolet spectrogram of the gold nanospheres and gold nanorods in example 1, wherein a is the gold nanospheres and B is the gold nanorods.
FIG. 4 is a TEM effect graph of different concentrations of metallothionein on gold nanorod etching, wherein the concentration of metallothionein in A is 0nM; the concentration of metallothionein in B is 3nM; the metallothionein concentration in C was 4nM; the metallothionein concentration in D was 5nM.
FIG. 5 is a graph showing the effect of metallothionein at different concentrations on longitudinal LSPR peak displacement of gold nanorods.
FIG. 6 is a graph showing the optical effect of different concentrations of metallothionein on gold nanorod etching.
Detailed Description
The invention is further elucidated below in connection with the drawings and the examples. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
Example 1
(1) Preparation of gold nanosphere solution
Trisodium citrate (SC, 10mL,33 mM) was added to 140mL deionized water boiling at 1000rpm (oil bath temperature was maintained at 137 ℃) for 40min. Fresh HAuCl is then added 4 (1 mL,25 mM) was injected rapidly with no significant change in color. After 60 seconds tris (hydroxymethyl) aminomethane (TB, 5mL, 0.1M) was added and the solution color changed rapidly from colorless to pale pink, kept boiling and stirred at 1000rpm for 15min. Subsequently, the temperature is reduced to 100 ℃, HAuCl is added 4 (1 mL,25 mM) was rapidly injected, the color of the solution changed to a reddish wine at about 1min, and the temperature was maintained for 20min. Finally, HAuCl 4 (1 mL,25 mM) was rapidly injected and maintained at the temperature for 20min, and then naturally cooled to obtain a gold nanosphere solution.
The particle size of the obtained gold nanospheres is 30-50 nm, a TEM image is shown in figure 1, an ultraviolet spectrum is shown as A in figure 3, and a longitudinal LSPR peak of the gold nanospheres is at 523 nm.
(2) Preparation of gold nanorod solution
(1) Sequentially adding 0.25mL of 0.01M HAuCl 4 NaBH formulated in solution and 0.60mL of 0.01M ice water 4 Sequentially adding the solutions into 9.75mL 0.10M CTAB solution, and then vigorously stirring at 1200rpm for 2 minutes to obtain nano gold core solution, and standing at room temperature for at least 120 minutes for later use.
(2) First, 4mL of 0.01M HAuCl was sequentially added to the reactor at a rotation speed of 700rpm and a water bath temperature of 28 DEG C 4 Solution, 0.8mL 0.01M AgNO 3 Solution, 0.64ml of 0.1m ascorbic acid solution and 1.6ml of 1m HCl solution were added to 80ml of 0.1m CTAB solution; subsequently, 70. Mu.L of the nano gold core solution prepared in (1) was added to the mixed solution, and after 60 minutes, the color of the solution was gradually changed to red, and after standing overnight in a water bath at 28℃the solution was centrifuged three times at 10000rpm and concentrated to a gold nanorod solution having a concentration of about 1.4 nM.
The length-diameter ratio of the obtained gold nanorods is 2-3:1, the length is 60-80 nm, a TEM image is shown in fig. 2, an ultraviolet spectrum is shown in B in fig. 3, and a longitudinal LSPR peak of the gold nanorods is at 750 nm.
(3) Gold nanorod etching regulation and control based on interaction of tumor markers and gold nanospheres
(1) Adding 320 mu L of deionized water into a 2mL centrifuge tube, adding 25 mu L of gold nanosphere solution prepared in the step (1), adding 50 mu L of metallothionein with different concentrations (0, 1,1.5, 2.5,3,3.5,4,4.5,5,5.5 and 6 nM) respectively, shaking and mixing uniformly, standing for 10min, and sequentially adding 35 mu L of 70 mu M p-nitrophenol and 20 mu L of 4mM NaBH prepared by ice water after standing 4 And 50. Mu.L of a B-R buffer solution of pH 5 were mixed uniformly and allowed to stand for 5min.
(2) 102.5. Mu.L of pH 2B-R buffer solution (containing 20-30 mM CTAB and 40-60 mM NaBr) was added to a 0.5mL centrifuge tube, followed by sequential addition of 125. Mu.L of the mixture after reaction in (1), 2.5. Mu.L of 50mM KIO 3 And 50 mu L of the gold nanorod solution prepared in the step (2), uniformly mixing by vibration, and placing into a water bath kettle at 50 ℃ for water bath for 20min, so as to regulate and control the etching of the gold nanorod.
FIG. 4 is a TEM effect graph of different concentrations of metallothionein on gold nanorod etching, wherein the concentration of metallothionein in A is 0nM; the concentration of metallothionein in B is 3nM; the metallothionein concentration in C was 4nM; the concentration of metallothionein in D is 5nM, and the change of the appearance of the gold nanorod can cause the change of the longitudinal LSPR peak of the gold nanorod, so that the color change is generated.
FIG. 5 is a graph showing the effect of metallothionein on longitudinal LSPR peak displacement of gold nanorods at different concentrations; FIG. 6 is a graph showing the optical effect of different concentrations of metallothionein on gold nanorod etching. As can be seen from the graph, in the presence of metallothionein with the concentration of 0,1,1.5,2,2.5,3,3.5,4,4.5, 5.5,6nM respectively, the longitudinal LSPR peak of the etched gold nanorod gradually shifts blue, the color of the solution gradually changes from pink, purple to purple, indigo to bluish green, gray to brown, and the color is clearly distinguishable, which shows that the method can realize the visual detection of the metallothionein with the concentration of 0-6 nM.
Example 2
(1) Adding 320 μl of deionized water into a 2mL centrifuge tube, adding 25 μl of gold nanosphere solution prepared in example 1, adding 50 μl of ribonuclease with different concentrations (0, 5,10,15,20,25,30,35,40,45,50,60 nM) respectively, shaking and mixing uniformly, standing for 10min, sequentially adding 35 μl of 40 μl of p-nitrophenol and 20 μl of ice water prepared 2mM NaBH 4 And 50. Mu.L of a B-R buffer solution of pH 5 were mixed uniformly and allowed to stand for 5min.
(2) 102.5. Mu.L of pH 2B-R buffer solution (containing 20-30 mM CTAB and 40-60 mM NaBr) was added to a 0.5mL centrifuge tube, followed by sequential addition of 125. Mu.L of the mixture after reaction in (1), 2.5. Mu.L of 40mM KIO 3 And 50 mu L of the gold nanorod solution prepared in the example 1, uniformly mixing by vibration, and placing into a water bath at 45 ℃ for water bath for 20min, so as to regulate and control the etching of the gold nanorod.
Example 3
(1) Adding 320 μl deionized water into 2mL centrifuge tube, adding 25 μl gold nanospheres prepared in example 1, adding 50 μl of different concentrations (3.4, 3.6,3.8,4,4.2,4.4,4.6,4.8,5,5.5,6,6.5 nM) of transglutaminase respectively, shaking and mixing uniformly, standing for 10min, sequentially adding 35 μl of 90 μM p-nitrophenol prepared after standing, and 20 μl ice water prepared 6mM NaBH 4 And 50. Mu.L of a B-R buffer solution of pH 5 were mixed uniformly and allowed to stand for 5min.
(2) 102.5. Mu.L of pH 2B-R buffer solution (containing 20-30 mM CTAB and 40-60 mM NaBr) was added to a 0.5mL centrifuge tube, followed by sequential addition of 125. Mu.L of the mixture after reaction in (1), 2.5. Mu.L of 45mM KIO 3 And 50 mu L of the gold nanorod solution prepared in the example 1, uniformly mixing by vibration, and placing into a water bath at 55 ℃ for water bath for 20min, so as to regulate and control the etching of the gold nanorod.
Example 4
(1) Adding 320 μl deionized water into 2mL centrifuge tube, adding 25 μl gold nanospheres prepared in example 1, adding 50 μl human epididymal proteins with different concentrations (0, 0.2,0.4,0.6,0.8,1,1.2,1.4,1.6,1.8,2,2.5 nM) respectively, shaking and mixing uniformly, standing for 10min, adding 35 μl of 110 μM p-nitrophenol prepared after standing, and adding 20 μl ice water prepared 8mM NaBH 4 And 50. Mu.L of a B-R buffer solution of pH 5 were mixed uniformly and allowed to stand for 5min.
(2) 102.5. Mu.L of pH 2B-R buffer solution (containing 20-30 mM CTAB and 40-60 mM NaBr) was added to a 0.5mL centrifuge tube, followed by sequential addition of 125. Mu.L of the mixture after reaction in (1), 2.5. Mu.L of 55mM KIO 3 And 50 mu L of the gold nanorod solution prepared in the example 1, uniformly mixing by vibration, and placing into a water bath kettle at 60 ℃ for water bath for 20min, so as to regulate and control the etching of the gold nanorod.
Application example 1
The cancer cell sample 500. Mu.L was taken out in a 2mL centrifuge tube, put in a refrigerator at-20℃for 30min for solidification, and then thawed at room temperature, and the freeze thawing was repeated three times. Finally centrifuging at 3000rpm for 5min, taking supernatant, and diluting with PBS buffer solution with pH of 7.4 to obtain supernatant with different cell numbers, thus obtaining sample solution to be tested;
adding 320 mu L of deionized water into a 2mL centrifuge tube, adding 25 mu L of the gold nanosphere solution prepared in the example 1, adding 50 mu L of the sample solution to be measured, vibrating and uniformly mixing, standing for 10min, sequentially adding 35 mu L of 70 mu M p-nitrophenol prepared after standing and 20 mu L of ice water prepared 4mM NaBH 4 And 50 mu L of a B-R buffer solution with pH of 5, and standing for 5min after uniformly mixing;
102.5. Mu.L of pH 2B-R buffer solution (containing 20-30 mM CTAB and 40-60 mM NaBr) was added to a 0.5mL centrifuge tube, followed by sequential addition of 125. Mu.L of the mixture after reaction in (1), 2.5. Mu.L of 50mM KIO 3 And 50 mu L of the gold nanorod solution prepared in the example 1, shaking and mixing uniformly, placing into a water bath kettle at 50 ℃ for water bath for 20min, regulating and controlling etching of the gold nanorod, detecting the metallothionein concentration in the sample solution to be detected through ultraviolet peak shift change, and adopting a commercial kit detection method as a sample solution to be detectedIn contrast, commercial kit detection methods calculate the detection concentration by uv peak absorbance change, and the results are shown in table 1.
Table 1 comparison of commercial kit detection method with tumor marker detection results of the inventive method
The data in the table show that the effect of the method for detecting the content of the tumor markers is similar to the detection result of the commercial kit, and the feasibility and the accuracy of the method for detecting the tumor markers are proved, so that the method has wide application prospect in early prevention and diagnosis of cancer diseases.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A high-sensitivity visualization method for regulating and controlling gold nanorod etching based on the interaction of tumor markers and gold nanospheres is characterized by comprising the following steps:
(1) Mixing a tumor marker with a gold nanosphere solution, and then catalyzing sodium borohydride to reduce p-nitrophenol to obtain a mixed solution; the tumor marker is rich in cysteine, and comprises metallothionein, ribonuclease, transglutaminase or human epididymis protein; the particle size of the gold nanospheres is 30-50 nm;
(2) Adding the mixed solution, the potassium iodate solution and the gold nanorod solution in the step (1) into the B-R buffer solution system, and generating an etchant iodine simple substance by oxidation-reduction reaction in the solution to regulate and control the etching of the gold nanorod;
in the step (1), the volume ratio of the tumor marker to the gold nanosphere solution is 1-3: 1, a step of; the tumor marker is metallothionein with the concentration of 0-6 nM; or the tumor marker is ribonuclease, and the concentration is 0-60 nM; or the tumor marker is transglutaminase, and the concentration is 0-6.5 nM; or the tumor marker is human epididymal protein, and the concentration is 0-2.5 nM.
2. The high-sensitivity visualization method for controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres according to claim 1, wherein the gold nanosphere solution is prepared from chloroauric acid, trisodium citrate and tris (hydroxymethyl) aminomethane as raw materials.
3. The high-sensitivity visualization method for controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres, which is characterized in that the tumor markers and gold nanosphere solution are uniformly mixed and kept stand for 5-20 min to catalyze sodium borohydride to reduce p-nitrophenol.
4. The high-sensitivity visualization method for controlling gold nanorod etching based on the interaction of tumor markers and gold nanospheres according to claim 1, wherein in the step (1), the volume ratio of the gold nanosphere solution, sodium borohydride and p-nitrophenol is 1: 0.25-1.5: 0.5-2 mM, wherein the concentration of sodium borohydride is 1.5-9 mM, and the concentration of p-nitrophenol is 30-120 mu M.
5. The high-sensitivity visualization method for controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres according to claim 1, wherein in the step (2), gold nanorod solution is prepared from chloroauric acid, silver nitrate, ascorbic acid, sodium borohydride, hydrochloric acid and cetyl trimethyl ammonium bromide serving as raw materials, wherein the length-diameter ratio of the gold nanorod is 2-3:1, and the length is 60-80 nm.
6. The high-sensitivity visualization method for controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres according to claim 1, wherein in the step (2), the volume ratio of the mixed solution, the potassium iodate solution and the gold nanorod solution is 20-75: 1: 8-30 mM, wherein the concentration of the potassium iodate solution is 40-60 mM.
7. The high-sensitivity visualization method for controlling gold nanorod etching based on the interaction of tumor markers and gold nanospheres according to claim 1, wherein in the step (2), the oxidation-reduction reaction and the etching process are performed at a temperature of 40-60 ℃.
8. The use of a highly sensitive visualization method for modulating gold nanorod etching based on tumor marker interaction with gold nanospheres according to claim 1 in tumor marker detection, said use being for non-therapeutic and/or diagnostic purposes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111386678.4A CN114136958B (en) | 2021-11-22 | 2021-11-22 | High-sensitivity visualization method for regulating and controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111386678.4A CN114136958B (en) | 2021-11-22 | 2021-11-22 | High-sensitivity visualization method for regulating and controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114136958A CN114136958A (en) | 2022-03-04 |
| CN114136958B true CN114136958B (en) | 2023-08-18 |
Family
ID=80390762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111386678.4A Active CN114136958B (en) | 2021-11-22 | 2021-11-22 | High-sensitivity visualization method for regulating and controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114136958B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114839361A (en) * | 2022-06-10 | 2022-08-02 | 杭州师范大学 | Initial screening method for exfoliated tumor cells |
| WO2024061281A1 (en) * | 2022-09-22 | 2024-03-28 | 宁波大学附属第一医院 | Kit for detecting prostate cancer and use thereof, and kit for detecting bladder cancer and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104407138A (en) * | 2014-11-12 | 2015-03-11 | 济南大学 | Preparation method and application of biosensor based on pine-branch-shaped nano-copper |
| CN105593404A (en) * | 2011-11-22 | 2016-05-18 | 麦克德米德尖端有限公司 | Method for treating metal surfaces |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9201067B2 (en) * | 2003-03-05 | 2015-12-01 | Posco | Size-controlled macromolecule |
| CN110560703B (en) * | 2019-09-18 | 2020-09-18 | 清华大学 | Preparation method and system of gold nanorod with high catalytic activity based on femtosecond laser |
-
2021
- 2021-11-22 CN CN202111386678.4A patent/CN114136958B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105593404A (en) * | 2011-11-22 | 2016-05-18 | 麦克德米德尖端有限公司 | Method for treating metal surfaces |
| CN104407138A (en) * | 2014-11-12 | 2015-03-11 | 济南大学 | Preparation method and application of biosensor based on pine-branch-shaped nano-copper |
Non-Patent Citations (1)
| Title |
|---|
| 基于金纳米材料的可视化生物传感器的研究进展;马小明;孙密;林悦;刘银金;罗芳;郭隆华;邱彬;林振宇;陈国南;;分析化学(01);1-10 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114136958A (en) | 2022-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Facile synthesis of magnetic hierarchical flower-like Co3O4 spheres: Mechanism, excellent tetra-enzyme mimics and their colorimetric biosensing applications | |
| CN114136958B (en) | High-sensitivity visualization method for regulating and controlling gold nanorod etching based on interaction of tumor markers and gold nanospheres | |
| Bai et al. | Strategic synthesis of trimetallic Au@ Ag–Pt nanorattles for ultrasensitive colorimetric detection in lateral flow immunoassay | |
| Feng et al. | Gold–platinum bimetallic nanoclusters with enhanced peroxidase-like activity and their integrated agarose hydrogel-based sensing platform for the colorimetric analysis of glucose levels in serum | |
| Tian et al. | Manganese dioxide nanosheet-mediated etching of gold nanorods for a multicolor colorimetric assay of total antioxidant capacity | |
| Ma et al. | Copper (II) ions enhance the peroxidase-like activity and stability of keratin-capped gold nanoclusters for the colorimetric detection of glucose | |
| Ma et al. | A novel ratiometric fluorescence nanoprobe for sensitive determination of uric acid based on CD@ ZIF-CuNC nanocomposites | |
| Lu et al. | Limitation-induced fluorescence enhancement of carbon nanoparticles and their application for glucose detection | |
| Navarro et al. | Colorimetric-enzymatic determination of tyramine by generation of gold nanoparticles | |
| CN113912134B (en) | Chiral cobalt hydroxide nano particle and preparation method and application thereof | |
| Lin et al. | Multicolor hydrogen sulfide sensor for meat freshness assessment based on Cu2+-modified boron nitride nanosheets-supported subnanometer gold nanoparticles | |
| CN113059175B (en) | Preparation method of Au @ Ag @ AgCl nanoparticles and application of Au @ Ag @ AgCl nanoparticles in ammonia gas colorimetric detection | |
| Zhang et al. | Monodispersed silver-gold nanorods controllable etching for ultrasensitive SERS detection of hydrogen peroxide-involved metabolites | |
| Lu et al. | A novel dual response ratiometric fluorescent probe for the determination of H 2 O 2 and glucose via etching of silver nanoparticles | |
| Zhou et al. | Zeolitic imidazolate framework-8 capped gold nanoclusters as an “on-off-on” fluorescent nanoprobe for sensitive detection of MnO4− and ascorbic acid | |
| He et al. | Facile preparation of Fe3O4@ Pt nanoparticles as peroxidase mimics for sensitive glucose detection by a paper-based colorimetric assay | |
| Wu et al. | Rational design of nanozyme with integrated sample pretreatment for colorimetric biosensing | |
| Sun et al. | Highly sensitive SERS sensors for glucose detection based on enzyme@ MOFs and ratiometric Raman | |
| Fu et al. | Colorimetric detections of iodide and mercuric ions based on a regulation of an Enzyme-Like activity from gold nanoclusters | |
| CN115598082B (en) | Method for detecting organophosphorus pesticide by regulating and controlling gold nanorod etching through double-enzyme cascade reaction based on manganese dioxide nanoflower and alkaline phosphatase | |
| CN113933292B (en) | Method for detecting hemoglobin based on gold nanorod etching multicolor colorimetric method | |
| Li et al. | Highly sensitive quantitative detection of glutathione based on a fluorescence-colorimetric dual signal recognition strategy | |
| Wang et al. | An Au bipyramids@ CuZn MOF core–shell nanozyme enables universal SERS and a colorimetric dual-model bioassay | |
| CN117169201A (en) | Dual-path composite chromogenic sensor based on alkaline phosphatase induction and application thereof | |
| CN116237535A (en) | Platinum-coated gold nano bipyramid synthesized by DNA (deoxyribonucleic acid) mediation and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |