CN112986561A - Multimode immune instant analysis excited by nano titanium carbide hybrid - Google Patents

Multimode immune instant analysis excited by nano titanium carbide hybrid Download PDF

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CN112986561A
CN112986561A CN202110215768.0A CN202110215768A CN112986561A CN 112986561 A CN112986561 A CN 112986561A CN 202110215768 A CN202110215768 A CN 202110215768A CN 112986561 A CN112986561 A CN 112986561A
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戴宏
魏洁
陈妍洁
张书培
皇怡甜
任卉竹
李秀华
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Fujian Normal University
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Abstract

The invention discloses multimode immune real-time analysis excited by a nano titanium carbide hybrid. The plasma nano hybrid Ti3C2The @ CuNCs has good photo-thermal conversion performance and can cause the SED temperature of the flexible conductive substrate to rise under the excitation of near infrared light. Further, Ti3C2The high catalyst activity of @ CuNCs can also catalyze the oxidation of a colorimetric reagent Lecuo-MB to generate blue methylene blue MB, so that the color of a substrate is changed from light blue to deep blue. Methylene blue MB also has excellent photo-thermal properties, Ti3C2The synergistic effect of @ CuNCs and MB photothermal effect further enhances light absorption and amplifies the temperature signal. At the same time, the continuously increased heat also accelerates the migration of charge inside the SED, and the charge migration caused by the temperature rise can be monitored in real time through the digital multimeterThe resistance changes, and the temperature signal can be converted into an electric signal. The method realizes high sensitivity and multi-signal immunodetection of human anti-ASGPR, has great potential in clinical diagnosis of malignant diseases, and opens up a new way for point-of-care detection.

Description

Multimode immune instant analysis excited by nano titanium carbide hybrid
Technical Field
The invention belongs to the technical field of novel functional materials and biosensing detection, and particularly relates to a multi-mode immunoassay method for detecting human asialoglycoprotein receptor (asialoglycoprotein receptor) human anti-ASGPR (acute respiratory syndrome) by using a photothermal chemical sensor based on a nano titanium carbide hybrid.
Background
The latent period of the etiology of many malignant diseases is long, the early diagnosis is difficult, the lack of effective preventive measures and other problems seriously threaten public health, and therefore, the design of a reliable early monitoring means is necessary for reducing the threat of malignant diseases to human health. The discovery of biomarkers in recent years provides important reference for early diagnosis of various malignant tumors. However, since the cost and complexity of biomarker detection are high, the need for professional operators and the like limit the popularization and promotion of ELISA in remote areas. The method is combined with ELISA, so that economic and effective daily health care service is provided under the condition of limited resources.
Photothermal chemical detection uses light as an excitation signal and heat generated by light radiation as a detection signal. Higher sensitivity can be obtained by using different forms of energy changes caused by the local temperature rise of the substrate caused by the light radiation as detection signals. MXene is an emerging multifunctional two-dimensional photothermal material, and shows huge application potential in photothermal biosensing. Wherein, Ti3C2Tx MXene is the easiest to prepare and relatively inexpensive, its unique semiconductor and electromagnetic properties make Ti3C2Tx exhibitsAnd the plasma absorption peak shows strong near infrared absorption and photo-thermal conversion efficiency under laser irradiation. Furthermore, studies have shown that the incorporation of metal plasmons can effectively improve the light-to-heat conversion efficiency, since the tunable Localized Surface Plasmon Resonance (LSPR) peak of the metal nanoparticles may effectively absorb NIR light and convert it to heat, which can be transferred to the ambient environment, causing a significant temperature rise.
In this experiment ionic nano-hybrid Ti3C2@ CuNCs has good photothermal conversion properties and is used as a signal reporter, and can cause the temperature of a flexible conductive Substrate (SED) to rise under the excitation of near infrared light. Further, Ti3C2The high catalyst activity of @ CuNCs can also catalyze the oxidation of a colorimetric reagent Lecuo-MB to generate blue MB, so that the color of a substrate is changed from light blue to deep blue. As an effective near-infrared dye, MB also has excellent photo-thermal properties, Ti3C2The stacking of @ CuNCs with MB photothermal effect further enhances light absorption and amplifies the temperature rise signal. Meanwhile, the continuously increased heat also accelerates the migration of charges inside the SED, so that the conductivity change caused by the temperature rise can be monitored in real time through a digital multimeter, and further, the temperature signal is successfully converted into an electric signal. The method realizes the multi-signal immunodetection with high sensitivity and high accuracy for human anti-asialoglycoprotein receptor human anti-ASGPR, the innovative multi-signal reading instant detection sensing platform has great potential in clinical diagnosis of malignant diseases, and a new way is opened for point-of-care detection.
Disclosure of Invention
The invention aims to provide a multimode immune instant analysis method excited by a nano titanium carbide hybrid, which is used for instant detection of a biomarker.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
(1) preparation of SED/Ab modified substrate: 0.5 polyvinyl alcohol PVA solid was dissolved in 10 mL of ultrapure water, 2mL of glycerin was added and heated for 20 minutes with continuous stirring to finally obtain a homogeneous hydrosol. Then, the hydrosol was treated with 1 mL of 0.5 mol/L NaOH solution at 40 ℃ for 1 hour, and 1 mL of 1% by mass cyanuric chloride was added to the mixture to react for 1 hour. Then, an acetic acid solution with the mass fraction of 3% is dropped to neutralize the excess alkali. And then transferring the hydrosol to a 96-well plate with each well being 100 mu L, and cooling to room temperature to obtain the PVA hydrogel used as the SED (flexible temperature-sensitive conductive device). In order to further enlarge the adsorption volume, 30 μ L of 10% by mass HCl was added to the surface of the SED in a flexible temperature-sensitive conductive apparatus to etch for 10 minutes and washed several times with PH 7.4 phosphoric acid buffer solution. Then, 5. mu.L of an antibody against human asialoglycoprotein receptor human anti-ASGPR (Shanghai Jianglai Biotech Co., Ltd.) was added thereto at a concentration of 1.6U/mL, and the mixture was incubated at 4 ℃ for 40 min to wash out the unsuccessfully adsorbed antibody with a phosphate buffer solution of pH 7.4. Blocking the nonspecific sites with bovine serum albumin BSA solution with the concentration of 1.0 wt.% to obtain an SED/Ab modified substrate;
（2）SED/Ab/ Ag-Ti3C2preparation of @ CuNCs modified substrate: adding 250 mu L of Ti3C2The @ CuNCs complex was dispersed in 250. mu.L of 10mM 1-aminoethyl-3-methylimidazolium bromide solution and sonicated for 30min for Ti3C2The @ CuNCs complex is subjected to surface amination treatment. Then, 50. mu.L of human asialoglycoprotein receptor human anti-ASGPR (Shanghai Jianglai Biotech Co., Ltd.) at a concentration of 1.6U/mL and 10. mu.L of 25 wt% glutaraldehyde were added dropwise to the surface-aminated Ti3C2@ CuNCs solution, stirred at room temperature for 12 h. Finally, the mixture is centrifuged at 5000r/min for 10min, the supernatant is removed, the weakly bound molecules are separated and redispersed with 250 μ LpH 7.4.4 phosphoric acid buffer solution to obtain Ag-Ti3C2@ CuNCs probe; different concentrations of human anti-asialoglycoprotein receptor human anti-ASGPR standard solution (Shanghai Jianglai Biotech limited) and a labeled probe Ag-Ti3C2Dropping the mixed solution of @ CuNCs into the SED/Ab modified substrate prepared in the step 1), incubating for 40 min at 4 ℃, and combining the antibody fixed on the surface of the SED of the flexible temperature-sensitive conductive equipment by using a competitive reaction; washing the surface of the substrate with a phosphate buffer solution with pH 7.4 and naturally drying at room temperature to obtain SED/Ab/Ag-Ti3C2@ CuNCs modified substrate;
(3) human body resistance removingDetection of the sialoglycoprotein receptor human anti-ASGPR: dripping 30 mu L of developer Leuco-MB on the SED/Ab/Ag-Ti prepared in the step 2)3C2The reaction is carried out for 90s on the substrate modified by @ CuNCs, so that the developer Leuco-MB is oxidized to generate methylene blue MB to obtain SED/Ab/Ag-Ti3C2Modification of substrate with @ CuNCs/MB, and observation of 1X 10-6U/mL-1×10-2Color change between U/mL; collecting SED/Ab/Ag-Ti at different concentrations through smart phone3C2@ CuNCs/MB modifies the photograph of the substrate and converts it into red, green and blue RGB images using the professional drawing software PowerPoint, calculates 1X 10-6 U/mL–1×10-2Color values between U/mL. The color change may be defined by: color value = red value (R) + green value (G) × 256 + blue value (B) × 65536; using 808nm laser at optical power density of 5W cm-2The following pairs SED/Ab/Ag-Ti3C2Irradiating the modified substrate of @ CuNCs/Leuco-MB for 1min, and measuring by 1 × 10 with electronic thermometer-8 U/mL–1×10-3Temperature change between U/mL; subjecting SED/Ab/Ag-Ti3C2The @ CuNCs/Leuco-MB modified substrate is connected with a digital multimeter, and 808nm laser is used for measuring the optical power density at 5W cm-2For SED/Ab/Ag-Ti3C2Irradiating the modified substrate of @ CuNCs/Leuco-MB for 1min, recording 1X 10-8 U/mL–1×10-2Resistance change between U/mL; drawing a working curve by recording different temperature changes, resistance changes and color value changes generated before and after 808nm laser radiation; and replacing the human asialoglycoprotein receptor (asialoglycoprotein receptor) anti-ASGPR standard solution with the sample solution to be detected for detection, and checking the detection result through a working curve.
The above Ti3C2The @ CuNCs complex is prepared by the following method:
250 μ L of 5mg/mL Ti3C2MXene nanoplatelets were dissolved in N, N-dimethylformamide and 100uL of 100mM CuCl was injected2And 20uL of 50mM ascorbic acid AA, stirred well. Subsequently, 20 μ L of 0.25mg/mL copper nanocluster CuNCs was added to the mixture and refluxed at 100 ℃ for 12h until the mixture color changed from gray to brown. Then, will obtainThe mixture was centrifuged at 5000r/min for 10min, the precipitate was collected and the free ions were washed off with deionized water. Dissolving the precipitate with 250 μ L deionized water to obtain Ti3C2@ CuNCs plasma nano hybrid.
The Ti3C2The MXene nanosheet material is prepared by the following method:
50mg of Ti3AlC2 MXene powder (Shanghai Michelin reagent Co., Ltd.) was dissolved in 3mL of 50 wt% hydrofluoric acid HF and stirred at room temperature for 48 hours. The resulting solution was centrifuged at 10000 r/min for 10 minutes to remove the supernatant and harvest the product, which was then sonicated and washed with 0.5M NaOH to neutralize excess acid. The collected precipitate was then washed several times with deionized water until the solution became neutral. Drying the product at 70 ℃ overnight to obtain Ti3C2MXene nano-sheet.
The copper nanocluster Cu NCs material is prepared by the following method:
100 mg of yeast extract was dissolved in 8mL of ultrapure water and mixed with 2mL of 100mM CuCl2Mixing the solutions at room temperature, and stirring for 2-3 min; refluxing the mixture at 100 deg.C for 12h until the solution changes color from light blue to dark green; and finally, centrifuging the obtained sample for 10min under 10000rmp, and taking supernatant to obtain a purified copper nanocluster Cu NCs solution.
The Leuco-MB developer is prepared by the following method:
mixing 5 mM of methylene blue MB and 50mM of ascorbic acid AA according to the volume of 1:1, and shaking for 20min until the color of the solution is changed from dark blue to light blue, thus obtaining the Leuco-MB color developing agent
A multimode immune instant analysis sensor excited by nano titanium carbide hybrid is characterized in that SED/Ab/Ag-Ti3C2The @ CuNCs substrate is prepared by the following method: 1) preparation of SED/Ab modified substrate: 0.5 polyvinyl alcohol PVA solid was dissolved in 10 mL of ultrapure water, 2mL of glycerin was added and heated for 20 minutes with continuous stirring to finally obtain a homogeneous hydrosol. Then, the hydrosol was treated with 1 mL of 0.5 mol/L NaOH solution at 40 ℃ for 1 hour, and 1 mL of 1% by mass cyanuric chloride was added to the mixture to react for 1 hour. Then dropping the mixture into the solutionThe excess base was neutralized by 3% strength acetic acid solution. Subsequently, the hydrosol is transferred to a 96-well plate with 100 μ L of each well, and is cooled to room temperature to obtain the PVA hydrogel which is used as the SED (temperature sensitive conductive device). To further expand the adsorption volume, 30 μ L of 10% HCl by mass was added to the SED surface and etched for 10 minutes and rinsed several times with pH 7.4 phosphate buffer. Then, 5. mu.L of a human anti-asialoglycoprotein receptor human anti-ASGPR antibody (Shanghai Jianglai Biotech Co., Ltd.) was added thereto at a concentration of 1.6U/mL, and the mixture was incubated at 4 ℃ for 40 min to wash out unsuccessfully adsorbed antibody with a phosphate buffer solution of pH 7.4. Blocking the non-specific sites with 1.0 wt.% bovine serum albumin BSA solution to obtain SED/Ab modified substrate, 2) adding 250. mu.L Ti3C2The @ CuNCs complex was dispersed in 250. mu.L of 10mM 1-aminoethyl-3-methylimidazolium bromide solution and sonicated for 30min for Ti3C2The @ CuNCs complex is subjected to surface amination treatment. Then, 50. mu.L of human asialoglycoprotein receptor human anti-ASGPR (Shanghai Jianglai Biotech Co., Ltd.) at a concentration of 1.6U/mL and 10. mu.L of 25 wt% glutaraldehyde were added dropwise to the surface-aminated Ti3C2@ CuNCs solution, stirred at room temperature for 12 h. Finally, the mixture is centrifuged at 5000r/min for 10min, the supernatant is removed, the weakly bound molecules are separated and redispersed with 250 μ LpH 7.4.4 phosphoric acid buffer solution to obtain Ag-Ti3C2@ CuNCs probe; different concentrations of human anti-asialoglycoprotein receptor human anti-ASGPR standard solution and labeled probe Ag-Ti3C2Dropping the mixed solution of @ CuNCs into the SED/Ab modified substrate prepared in the step 1), incubating for 40 min at 4 ℃, and binding the antibody fixed on the SED surface by using a competitive reaction; washing the surface of the substrate with a phosphate buffer solution with pH 7.4 and naturally drying at room temperature to obtain SED/Ab/Ag-Ti3C2@ CuNCs modified substrate;
a multimode immune instant analysis method excited by a nano titanium carbide hybrid is characterized by comprising the following steps: 1) 30 μ L of Leuco-MB was dropped on the SED/Ab/Ag-Ti3C2The reaction is carried out for 90s on the substrate modified by @ CuNCs, so that the developer Leuco-MB is oxidized to generate methylene blue MB to obtain SED/Ab/Ag-Ti3C2Modifying a substrate with @ CuNCs/MB, and laser irradiating SED/Ab/Ag-Ti with 808nm3C2Irradiating a @ CuNCs/MB modified substrate; 2) measurement of human anti-asialoglycoprotein receptor human anti-ASGPR: photos of SED under different concentrations are collected through a smart phone, converted into red, green and blue RGB images through professional drawing software PowerPoint, and 1 x 10 is calculated-6 U/mL–1×10-2Color values between U/mL. The color change may be defined by: color value = red value (R) + green value (G) × 256 + blue value (B) × 65536; using 808nm laser to SED/Ab/Ag-Ti3C2@ CuNCs/MB modified substrate radiation for 1min (optical power density 5W cm)-2) 1X 10 measured with an electronic thermometer-8 U/mL–1×10-3Temperature change between U/mL; subjecting SED/Ab/Ag-Ti3C2The @ CuNCs/MB modified substrate is connected with a digital multimeter, and SED/Ab/Ag-Ti is subjected to laser alignment at 808nm3C2@ CuNCs/MB modified substrate radiation for 1min (optical power density 5W cm)-2) Recording 1X 10 by portable fluorescence spectrometer-8 U/mL–1×10-2Resistance change between U/mL; drawing a working curve by recording different temperature changes, resistance changes and color value changes generated before and after 808nm laser radiation; replacing human anti-asialoglycoprotein receptor human anti-ASGPR standard solution with to-be-detected sample solution for detection, and checking the detection result through a working curve
The invention has the following remarkable advantages:
(1)Ti3C2the synergistic effect between MXene and copper nanoclusters CuNCs can obviously improve Ti3C2The photo-thermal property of the @ CuNCs nano hybrid causes the temperature of a reaction interface to be sharply increased under the excitation of near infrared light.
(2)Ti3C2The @ CuNCs nano hybrid has good catalytic activity, can catalyze the Lecuo-MB solution to change color and regenerate blue methylene blue MB, and further amplifies a thermal signal by the photothermal effect of the methylene blue MB under the irradiation of near infrared.
(3) The flexible conductive electronic device SED based on the polyelectrolyte hydrogel can convert the temperature change on a reaction interface into an electric signal, thereby realizing the ultra-sensitive and multi-mode analysis of a target object.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the human asialoglycoprotein receptor-resistant human anti-ASGPR multimode chemical sensor.
FIG. 2A is a graph of the change in fluorescence intensity after laser irradiation of substrates modified with different concentrations of human anti-asialoglycoprotein receptor human anti-ASGPR.
FIG. 2B is a graph of the linear relationship between the resistance change of the sensing substrate under laser irradiation and the concentration of human anti-asialoglycoprotein receptor human anti-ASGPR standard solution.
FIG. 3A is a graph of the color change of substrates modified with different concentrations of human anti-asialoglycoprotein receptor human anti-ASGPR after addition of Lecuo-MB solution.
FIG. 3B is a linear relationship of color change versus concentration of human anti-asialoglycoprotein receptor human anti-ASGPR standard solution.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
A multimode immune instant analysis method excited by nano titanium carbide hybrid (as shown in figure 1):
1) dissolving 0.5 of polyvinyl alcohol (PVA) solid in 10 mL of ultrapure water, adding 2mL of glycerol, and heating for 20 minutes under continuous stirring to finally obtain uniform hydrosol;
2) then, the hydrosol was treated with 1 mL of 0.5 mol/L NaOH solution at 40 ℃ for 1 hour, and 1 mL of 1% by mass cyanuric chloride (dissolved in 1, 4-dioxane) was added to react for 1 hour. Then, acetic acid solution with the mass fraction of 3% is dripped to neutralize the redundant alkali;
3) then transferring the hydrosol to a 96-pore plate with each pore being 100 mu L, and cooling to room temperature to obtain polyvinyl alcohol hydrogel used as a flexible temperature-sensitive conductive device SED;
4) adding 30 mu L of HCl with the mass fraction of 10% to the surface of the SED of the flexible temperature-sensitive conductive equipment, etching for 10 minutes, and washing for several times by using a phosphoric acid buffer solution with the pH of 7.4;
5) the unsuccessfully adsorbed antibody was washed away by adding 5. mu.L of a human anti-asialoglycoprotein receptor human anti-ASGPR antibody (Shanghai Jianglai Biotech Co., Ltd.) and incubating at 4 ℃ for 40 min with a phosphate buffer solution of pH 7.4. Blocking the nonspecific sites with bovine serum albumin BSA solution with the concentration of 1.0 wt.% to obtain an SED/Ab modified substrate;
6）SED/Ab/ Ag-Ti3C2preparation of a @ CuNC modified substrate: adding 250 mu L of Ti3C2The @ CuNCs complex was dispersed in 250. mu.L of 10mg/mL 1-aminoethyl-3-methylimidazolium bromide solution (manufactured by the institute for chemical and physical, Lanzhou, Mich.) and sonicated for 30min for Ti3C2The @ CuNCs complex is subjected to surface amination treatment. Then, 50. mu.L of human asialoglycoprotein receptor human anti-ASGPR (Shanghai Jianglai Biotech Co., Ltd.) at a concentration of 1.6U/mL and 10. mu.L of 25 wt% glutaraldehyde were added dropwise to the surface-aminated Ti3C2@ CuNCs solution, stirred at room temperature for 12 h. Finally, the mixture is centrifuged at 5000r/min for 10min, the supernatant is removed, the weakly bound molecules are separated and redispersed with 250 μ LpH 7.4.4 phosphoric acid buffer solution to obtain Ag-Ti3C2@ CuNCs probe; different concentrations of human anti-asialoglycoprotein receptor human anti-ASGPR standard solution (Shanghai Jianglai Biotech limited) and a labeled probe Ag-Ti3C2Dropping the mixed solution of @ CuNCs into the SED/Ab modified substrate prepared in the step 1), incubating for 40 min at 4 ℃, and binding the antibody fixed on the SED surface by using a competitive reaction; washing the surface of the substrate with a phosphate buffer solution with pH 7.4 and naturally drying at room temperature to obtain SED/Ab/Ag-Ti3C2@ CuNCs modifies the substrate.
The above Ti3C2The @ CuNCs complex is prepared by the following method: 250 μ L of Ti with a concentration of 5mg/mL3C2MXene nanoplatelets were dissolved in N, N-dimethylformamide and 100uL of 100mM CuCl was injected2And 20uL of ascorbic acid (vitamin C, abbreviated as AA) at a concentration of 50mM, and sufficiently stirred; subsequently, 20. mu.L of 0.25mg/mL of the above copper nanoclusters CuNCs were addedAdding into the mixture, and refluxing at 100 deg.C for 12h until the mixture changes color from gray to brown; then, centrifuging the obtained mixture for 10min at 5000r/min, collecting the precipitate, and washing away free ions by using deionized water; dissolving the precipitate with 250 μ L deionized water to obtain Ti3C2@ CuNCs plasma nano hybrid;
the Ti3C2The MXene nanosheet material is prepared by the following method:
50mg of Ti3AlC2 MXene (Shanghai Michelin reagent Co., Ltd.) powder was dissolved in 3mL of 50 wt% hydrofluoric acid and stirred at room temperature for 48 hours; centrifuging the resulting solution at 10000 r/min for 10 minutes to remove supernatant and harvest the product, and washing with 0.5M NaOH after sonication to neutralize excess acid; then, washing the collected precipitate with deionized water for multiple times until the solution becomes neutral; drying the product at 70 ℃ overnight to obtain Ti3C2MXene nano-sheet.
The copper nanocluster Cu NCs material is prepared by the following method:
100 mg of yeast extract was dissolved in 8mL of ultrapure water and mixed with 2mL of 100mM CuCl2Mixing the solutions at room temperature, and stirring for 2-3 min; refluxing the mixture at 100 deg.C for 12h until the solution changes color from light blue to dark green; and finally, centrifuging the obtained sample for 10min under 10000rmp, and taking supernatant to obtain a purified copper nanocluster Cu NCs solution.
The Leuco-MB developer is prepared by the following method:
mixing 5 mM of methylene blue MB and 50mM of ascorbic acid AA according to the volume of 1:1, and shaking for 20min until the color of the solution is changed from dark blue to light blue, thus obtaining the Leuco-MB color developing agent.
Example 2
A multimode immune instant analysis method excited by a nano titanium carbide hybrid comprises the following steps:
1) dropping 30 μ L of Leuco-MB developer on SED/Ab/Ag-Ti3C2Reaction on a @ CuNC modified substrate for 90s to obtain SED/Ab/Ag-Ti3C2Modifying a substrate with @ CuNCs/MB, and laser irradiating SED/Ab/Ag-Ti with 808nm3C2Irradiating a @ CuNCs/MB modified substrate;
2) measurement of human anti-asialoglycoprotein receptor human anti-ASGPR: collecting SED/Ab/Ag-Ti at different concentrations through smart phone3C2@ CuNCs/MB modifies the photograph of the substrate and converts it into red, green and blue RGB images using the professional drawing software PowerPoint, calculates 1X 10-6 U/mL–1×10-2Color values between U/mL. The color change may be defined by: color value = red value (R) + green value (G) × 256 + blue value (B) × 65536; using 808nm laser to SED/Ab/Ag-Ti3C2@ CuNCs/Leuco-MB modified substrate radiation for 1min (optical power density 5W cm)-2) 1X 10 measured with an electronic thermometer-8 U/mL–1×10-3Temperature change between U/mL; subjecting SED/Ab/Ag-Ti3C2The @ CuNCs/MB modified substrate is connected with a digital multimeter, and SED/Ab/Ag-Ti is subjected to laser alignment at 808nm3C2@ CuNCs/MB modified substrate radiation for 1min (optical power density 5W cm)-2) Recording 1X 10 by digital multimeter-8 U/mL–1×10-2Resistance change between U/mL; drawing a working curve by recording different temperature changes, resistance changes and color value changes generated before and after 808nm laser radiation;
3) and replacing the human asialoglycoprotein receptor (asialoglycoprotein receptor) anti-ASGPR standard solution with the sample solution to be detected for detection, and checking the detection result through a working curve.

Claims (4)

1. A multimode immune instant analysis method excited by a nano titanium carbide hybrid is characterized by comprising the following steps:
preparation of SED/Ab modified substrate: dissolving 0.5 of polyvinyl alcohol (PVA) solid in 10 mL of ultrapure water, adding 2mL of glycerol, and heating for 20 minutes under continuous stirring to finally obtain uniform hydrosol; then, treating the hydrosol with 1 mL of NaOH solution with the concentration of 0.5 mol/L for 1 h at 40 ℃, adding 1 mL of cyanuric chloride with the mass fraction of 1 percent dissolved in 1, 4-dioxane, and reacting for 1 h; then, acetic acid solution with the mass fraction of 3% is dripped to neutralize the redundant alkali; then transferring the hydrosol to a 96-pore plate with each pore being 100 mu L, and cooling to room temperature to obtain PVA hydrogel used as a flexible temperature-sensitive conductive device SED; in order to further enlarge the adsorption volume, 30 μ L of HCl with the mass fraction of 10% is added on the surface of the SED of the flexible temperature-sensitive conductive equipment for etching for 10 minutes and is washed for a plurality of times by phosphoric acid buffer solution with the pH value of 7.4; then 5. mu.L of human anti-asialoglycoprotein receptor human anti-ASGPR antibody at a concentration of 1.6U/mL was added and incubated at 4 ℃ for 40 min to wash away unsuccessfully adsorbed antibody Ab with phosphate buffered solution pH 7.4; blocking the nonspecific sites with bovine serum albumin BSA solution with the concentration of 1.0 wt.% to obtain an SED/Ab modified substrate;
SED/Ab/Ag-Ti3C2preparation of @ CuNCs modified substrate: adding 250 mu L of Ti3C2The @ CuNCs complex was dispersed in 250. mu.L of 1-aminoethyl-3-methylimidazolium bromide solution at a concentration of 10mg/mL and sonicated for 30min for Ti3C2Carrying out surface amination treatment on the @ CuNCs compound; then, 50. mu.L of human anti-asialoglycoprotein receptor human anti-ASGPR at a concentration of 1.6U/mL and 10. mu.L of glutaraldehyde at a concentration of 25 wt% were added dropwise to the surface-aminated Ti3C2Stirring at room temperature for 12h in a @ CuNCs solution; finally, the mixture was centrifuged at 5000r/min for 10min, the supernatant removed to separate weakly bound molecules and redispersed in 250 μ LpH 7.4.4 phosphate buffer to obtain Ag-Ti3C2@ CuNCs probe; different concentrations of human anti-asialoglycoprotein receptor human anti-ASGPR standard solution and labeled probe Ag-Ti3C2Dropping the mixed solution of @ CuNCs into the SED/Ab modified substrate prepared in the step 1), incubating for 40 min at 4 ℃, and combining the antibody fixed on the surface of the SED of the flexible temperature-sensitive conductive equipment by using a competitive reaction; washing the surface of the substrate with a phosphate buffer solution with pH 7.4 and naturally drying at room temperature to obtain SED/Ab/Ag-Ti3C2@ CuNCs modified substrate;
(3) detection of human anti-asialoglycoprotein receptor human anti-ASGPR: dripping 30 mu L of developer Leuco-MB on the SED/Ab/Ag-Ti prepared in the step 2)3C2The reaction is carried out for 90s on the substrate modified by @ CuNCs, so that the Leuco-MB developer is oxidized to generate methylene blue MB to obtain SED/Ab/Ag-Ti3C2Modification of substrate with @ CuNCs/MB, and observation of 1X 10-6 U/mL–1×10-2Color change between U/mL; collecting SED/Ab/Ag-Ti at different concentrations through smart phone3C2@ CuNCs/MB modifies the photograph of the substrate and converts it into a red, green and blue RGB image using professional drawing software PowerPoint, calculates 1 × 10-6 U/mL–1×10-2Color values between U/mL; the color change is defined by: color value = red value (R) + green value (G) × 256 + blue value (B) × 65536; using 808nm laser at optical power density of 5W cm-2The following pairs SED/Ab/Ag-Ti3C2Irradiating the modified substrate of @ CuNCs/Leuco-MB for 1min, and measuring by 1 × 10 with electronic thermometer-8 U/mL–1×10-3Temperature change between U/mL; subjecting SED/Ab/Ag-Ti3C2The @ CuNCs/MB modified substrate is connected with a digital multimeter, and 808nm laser is used for measuring the optical power density at 5W cm-2The following pairs SED/Ab/Ag-Ti3C2Irradiating the modified substrate of @ CuNCs/MB for 1min, recording 1X 10-8 U/mL–1×10-2Resistance change between U/mL; drawing a working curve by recording different temperature changes, resistance changes and color value changes generated before and after 808nm laser radiation; and replacing the human asialoglycoprotein receptor (asialoglycoprotein receptor) anti-ASGPR standard solution with the sample solution to be detected for detection, and checking the detection result through a working curve.
2. The method of claim 1, wherein said Ti is3C2The @ CuNCs complex is prepared by the following method: 250 μ L of Ti with a concentration of 5mg/mL3C2MXene nanosheets were dissolved in N, N-dimethylformamide and 100uL of CuCl with a concentration of 100mM was injected2And 20uL of ascorbic acid AA with a concentration of 50mM, and stirring well; subsequently, 20. mu.L of copper nanocluster CuNCs having a concentration of 0.25mg/mL are added to the mixture and refluxed at 100 ℃ for 12h until the mixture changes color from gray to brown; then, centrifuging the obtained mixture for 10min at 5000r/min, collecting the precipitate, and washing away free ions by using deionized water; dissolving the precipitate with 250 μ L deionized waterCan prepare Ti3C2@ CuNCs plasma nano hybrid;
the Ti3C2The MXene nanosheet material is prepared by the following method:
50mg of Ti3AlC2 MXene powder was dissolved in 3mL of 50 wt% hydrofluoric acid HF and stirred at room temperature for 48 hours; centrifuging the resulting solution at 10000 r/min for 10 minutes to remove supernatant and harvest the product, and washing with 0.5M NaOH after sonication to neutralize excess acid; then, washing the collected precipitate with deionized water for multiple times until the solution becomes neutral; drying the product at 70 ℃ overnight to obtain Ti3C2MXene nanosheets;
the copper nanocluster Cu NCs are prepared by the following method:
100 mg of yeast extract was dissolved in 8mL of ultrapure water and mixed with 2mL of 100mM CuCl2Mixing the solutions at room temperature, and stirring for 2-3 min; refluxing the mixture at 100 deg.C for 12h until the solution changes color from light blue to dark green; finally, centrifuging the obtained sample for 10min under 10000rmp, and taking supernatant to obtain a purified copper nanocluster Cu NCs solution;
the Leuco-MB developer is prepared by the following method:
mixing 5 mM of methylene blue MB and 50mM of ascorbic acid AA according to the volume of 1:1, and shaking for 20min until the color of the solution is changed from dark blue to light blue, thus obtaining the Leuco-MB color developing agent.
3. A multimode immune instant analysis sensor excited by nano titanium carbide hybrid is characterized by comprising SED/Ab/Ag-Ti3C2@ CuNCs modified substrate, SED/Ab/Ag-Ti3C2The @ CuNCs modified substrate is prepared by the following method: 1) preparation of SED/Ab modified substrate: dissolving 0.5 of polyvinyl alcohol (PVA) solid in 10 mL of ultrapure water, adding 2mL of glycerol, and heating for 20 minutes under continuous stirring to finally obtain uniform hydrosol; then, treating the hydrosol with 1 mL of NaOH solution with the concentration of 0.5 mol/L for 1 h at 40 ℃, and adding 1 mL of cyanuric chloride with the mass fraction of 1% for reaction for 1 h; then dropping 3 percent of the mixture by massNeutralizing the excess base with acetic acid solution; then transferring the hydrosol to a 96-pore plate with each pore being 100 mu L, and cooling to room temperature to obtain PVA hydrogel used as a flexible temperature-sensitive conductive device SED; to further expand the adsorption volume, 30 μ L of 10% by mass HCl was added to the SED surface and etched for 10 minutes and washed several times with pH 7.4 phosphate buffer; then 5. mu.L of a human anti-asialoglycoprotein receptor human anti-ASGPR antibody (Shanghai Jianglai Biotech Co., Ltd.) was added thereto at a concentration of 1.6U/mL, and incubated at 4 ℃ for 40 min to wash out unsuccessfully adsorbed antibody with a phosphate buffer solution of pH 7.4; blocking the non-specific sites with 1.0 wt.% bovine serum albumin BSA solution to obtain SED/Ab modified substrate, 2) adding Ti to 250. mu.L3C2The @ CuNCs complex was dispersed in 250. mu.L of 10mM 1-aminoethyl-3-methylimidazolium bromide solution and sonicated for 30min for Ti3C2Carrying out surface amination treatment on the @ CuNCs compound to obtain Ti with aminated surface3C2@ CuNCs solution; then, 50. mu.L of human asialoglycoprotein receptor human anti-ASGPR (Shanghai Jianglai Biotech Co., Ltd.) at a concentration of 1.6U/mL and 10. mu.L of glutaraldehyde at a concentration of 25 wt% were dropped to the surface-aminated Ti3C2Stirring at room temperature for 12h in a @ CuNCs solution; finally, the mixture is centrifuged at 5000r/min for 10min, the supernatant is removed and the weakly bound molecules are separated and redispersed with 250 μ L of pH 7.4 phosphate buffer to obtain Ag-Ti3C2@ CuNCs probe; different concentrations of human anti-asialoglycoprotein receptor human anti-ASGPR standard solution (Shanghai Jianglai Biotech limited) and a labeled probe Ag-Ti3C2Dropping the mixed solution of @ CuNCs into the SED/Ab modified substrate prepared in the step 1), incubating for 40 min at 4 ℃, and binding the antibody fixed on the surface of the SED/Ab modified substrate by using a competitive reaction; washing the SED/Ab modified substrate surface with phosphate buffer solution with pH 7.4, and naturally drying at room temperature to obtain SED/Ab/Ag-Ti3C2@ CuNCs modifies the substrate.
4. A multimode immune real-time analysis method excited by nano titanium carbide hybrid is characterized by comprising the following stepsThe following: 1) dropping 30. mu.L of Leuco-MB developer on the SED/Ab/Ag-Ti of claim 33C2The reaction is carried out for 90s on the substrate modified by @ CuNCs, so that the developer Leuco-MB is oxidized to generate methylene blue MB to obtain SED/Ab/Ag-Ti3C2Modifying a substrate with @ CuNCs/MB, and laser irradiating SED/Ab/Ag-Ti with 808nm3C2Irradiating a @ CuNCs/MB modified substrate; 2) measurement of human anti-asialoglycoprotein receptor human anti-ASGPR: collecting SED/Ab/Ag-Ti at different concentrations through smart phone3C2@ CuNCs/MB modifies the photograph of the substrate and converts it into red, green and blue RGB images using the professional drawing software PowerPoint, calculates 1X 10-6 U/mL–1×10-2Color values between U/mL; the color change may be defined by: color value = red value (R) + green value (G) × 256 + blue value (B) × 65536; using 808nm laser to SED/Ab/Ag-Ti3C2@ CuNCs/MB modified substrate with optical power density of 5W cm-2Irradiating for 1min, and measuring by electronic thermometer to obtain 1 × 10-8 U/mL–1×10-3Temperature change between U/mL; subjecting SED/Ab/Ag-Ti3C2The @ CuNCs/MB modified substrate is connected with a digital multimeter, and SED/Ab/Ag-Ti is subjected to laser alignment at 808nm3C2@ CuNCs/MB modified substrate with optical power density of 5W cm-2Irradiating for 1min, and recording with digital multimeter to obtain 1 × 10-8 U/mL–1×10-2Resistance change between U/mL; drawing a working curve by recording different temperature changes, resistance changes and color value changes generated before and after 808nm laser radiation; and replacing the human asialoglycoprotein receptor (asialoglycoprotein receptor) anti-ASGPR standard solution with the sample solution to be detected for detection, and checking the detection result through a working curve.
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