CN115684126A - Preparation method of equal-ratio SERS (surface enhanced Raman Scattering) nano sensor and application of equal-ratio SERS nano sensor in hydrogen peroxide detection - Google Patents
Preparation method of equal-ratio SERS (surface enhanced Raman Scattering) nano sensor and application of equal-ratio SERS nano sensor in hydrogen peroxide detection Download PDFInfo
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Abstract
The invention relates to the technical field of biosensors, in particular to a preparation method of an equal-ratio SERS nanosensor and application thereof in hydrogen peroxide detection, wherein the equal-ratio SERS nanosensor is prepared by co-modifying an internal standard molecule p-mercaptobenzonitrile 4-MBN and a reporter molecule p-mercaptophenylboronic acid 4-MPBA on gold nanoparticles AuNPs. The boronic acid group in 4-MPBA is capable of responding to hydrogen peroxide H 2 O 2 The generation is 998cm ‑1 Peak intensity change, while in 4-MBN it is located at 2226cm ‑1 The SERS characteristic peak is in a Raman silent region and is not accompanied by H 2 O 2 The concentration changes. According to 998cm ‑1 /2226cm ‑1 Peak intensity ratio achievement of H 2 O 2 Reliable quantitative detection. The method provided by the invention has high sensitivity and high selectivity, the detection limit is 100nM, and H in living cells in the drug stimulation process can be accurately detected in situ, in real time 2 O 2 Horizontal, at and H 2 O 2 Associated clinicHas good practical application prospect in the field of disease diagnosis.
Description
Technical Field
The invention relates to the technical field of biosensors, in particular to a preparation method of an equal-ratio SERS nano sensor and application of the equal-ratio SERS nano sensor in hydrogen peroxide detection.
Background
Hydrogen peroxide H 2 O 2 Is an important intracellular active oxygen molecule, the content of which in vivo changes andthe occurrence and development processes of different diseases are related. Therefore, in order to realize rapid and accurate disease diagnosis and explore related disease regulation and control mechanisms, the development of a high-sensitivity method for realizing high-efficiency, real-time and quantitative detection of in vivo H is urgently needed 2 O 2 And (4) horizontal. To date, researchers have established a number of different H 2 O 2 Detection methods include chemiluminescence, electrochemical sensing, chromatography, and the like. Although these methods can also detect H sensitively 2 O 2 However, they usually cause damage to target cells or tissues, and thus cannot dynamically monitor H in living cells in situ 2 O 2 . Against the above problems, based on H 2 O 2 In response to the fluorescent imaging principle of fluorescent indicators, researchers developed a class of probes directed at H 2 O 2 The in vivo fluorescence detection method has high sensitivity and good biocompatibility. However, the fluorescence imaging signal in the above method is easily interfered by the background of other fluorescent biomolecules in the cell matrix, and in addition, the method has the disadvantages of poor cell membrane penetrability, slow fluorescence response, serious photobleaching and the like, thereby greatly influencing the reliable detection of H in the actual biological sample 2 O 2 The performance of (c).
The Surface Enhanced Raman Spectroscopy (SERS) has high signal enhancement capability, sharp spectral peak (narrow band), low autofluorescence and near-infrared tissue penetration capability, so that the SERS sensor designed based on the noble metal nano material (especially gold nano particles) is expected to solve the problems and realize intracellular H 2 O 2 The accuracy of (3). However, currently developed SERS nanosensors still have difficulty in truly reliably detecting H in biological samples 2 O 2 . The main reasons include: (1) The reproducibility of SERS signals is poor, which is caused by the uneven enhancement of the metal substrate and the irregular distribution of the molecules to be measured on the substrate. (2) The signal of the SERS probe molecule is easily interfered by biological macromolecules such as intracellular protein, amino acid and the like. Based on this, there is an urgent need to develop a reliable SERS sensor with high sensitivity and excellent reproducibility to monitor H in living cells 2 O 2 。
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a preparation method of an equal-ratio SERS nano sensor and application thereof in hydrogen peroxide detection 2 O 2 The signal intensity changes according to 998cm -1 /2226cm -1 Peak intensity ratio realization for intracellular H 2 O 2 The in-situ, real-time and reliable quantitative detection provides a new strategy for developing the application of the SERS biosensor in disease diagnosis.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an equal-ratio SERS nano sensor comprises the following specific steps:
s1, synthesis of gold nanoparticles: synthesizing gold nanoparticles serving as an SERS enhanced substrate by adopting a heating reduction method; the basic principle is that sodium citrate can reduce chloroauric acid to generate gold nanoparticles in a heating state. First, 1.0mL of HAuCl chloroauric acid 4 Adding the solution into 100mL of deionized water, and heating the solution under magnetic stirring to boil the solution; then, rapidly adding 2.0mL of sodium citrate solution, refluxing the reaction solution for 30min until the solution becomes wine red, and stopping heating; gradually cooling to room temperature under magnetic stirring to obtain gold nanoparticles;
s2, preparing an SERS sensor: firstly, powders of a certain amount of 4-MPBA and 4-MBN are respectively dissolved in ethanol to prepare a 4-MPBA solution and a 4-MBN solution with the concentration of 1.0 mM. Sequentially adding the 4-MPBA solution with the concentration of 1.0mM and the 4-MBN solution with the concentration of 1.0mM into the gold nano-particle AuNPs, and magnetically stirring for 12h at room temperature; after the reaction is finished, removing redundant 4-MPBA and 4-MBN which are not modified on the gold nanoparticles by adopting a centrifugal mode, and resuspending the precipitate by using deionized water to obtain the SERS nanosensor Au @4-MPBA &4-MBN.
Preferably, in step S1, the mass fractions of the chloroauric acid solution and the sodium citrate solution are 1.05% and 1.1%, respectively.
Preferably, in step S2, the volumes of the 4-MPBA solution, the 4-MBN solution and the gold nanoparticles are 10. Mu.L, 5. Mu.L and 10mL, respectively.
Preferably, in step S2, the rotational speed and time of the centrifugation are 7500rpm and 10min, respectively.
The invention also provides application of the equal-ratio SERS nano sensor prepared by the preparation method in detection of hydrogen peroxide.
Preferably, the steps are: first, 20. Mu.L of H at various concentrations was added 2 O 2 Respectively adding 180 mu L of the prepared nano sensor solution in parallel, reacting for 1.5h at room temperature, and carrying out SERS detection. The excitation wavelength used was 633nm, the integration time was 5s, and the number of integrations was 1. 998cm in the collected SERS spectrum -1 /2226cm -1 Peak intensity ratio and H 2 O 2 Establishing a relation of concentration to obtain a linear regression equation y =3.618-0.036x and a correlation coefficient R 2 Is 0.989. Then, H to be measured 2 O 2 The solution was run as described above and the corresponding SERS spectra were determined. The peak of the SERS spectrum is 998cm -1 /2226cm -1 And substituting the intensity ratio into the linear regression equation to obtain the concentration of the sample to be measured.
By adopting the technical scheme: and simultaneously modifying the internal standard molecule 4-MBN and the reporter molecule 4-MPBA on the gold nanoparticles to obtain the nano sensor. Wherein 4-MPBA meets H 2 O 2 The change of SERS spectrum occurs, and the 4-MBN is 2226cm -1 The SERS peak is positioned in a Raman silent area, so that the detection of H by other biomacromolecule pairs in cells can be avoided 2 O 2 The interference of (2). Thus, according to 998cm -1 /2226cm -1 The peak intensity ratio can realize intracellular H 2 O 2 Reliable quantitative detection.
Compared with the prior art, the invention has the following beneficial effects:
1. the nano sensor prepared by using the gold nanoparticles as the SERS enhancement substrate has good biocompatibility, strong cell membrane penetrability and excellent SERS enhancement effect, and can detect hydrogen peroxide in cells in situ, in real time and at high sensitivity.
2. The nano sensor prepared by the invention can respond to H to be measured with high sensitivity 2 O 2 Meanwhile, 4-MBN is used as an internal standard molecule to calibrate the SERS signal, so that signal deviation caused by instability of peripheral impurities and instrument test parameters is avoided, and intracellular H is calibrated 2 O 2 And (4) accurate detection.
Drawings
FIG. 1 shows the preparation process and detection H of the equal-ratio SERS nanosensor of the invention 2 O 2 Schematic diagram of (a);
FIG. 2 is a TEM photograph of AuNPs (a) and nanosensors (b) prepared according to the present invention;
FIG. 3 is a graph of the ultraviolet absorption spectra of AuNPs and the nanosensor measured by the ultraviolet spectrometer in example 2 of the invention;
FIG. 4 is a SERS spectrum of AuNPs and the nanosensor measured by the Raman spectrometer in example 2 of the present invention;
FIG. 5 is a graph comparing AuNPs @4-MBN @4-HTP complex (3), nanosensor and H concentration 300mM in accordance with the present invention 2 O 2 SERS spectra before (1) and after (2) solution reaction;
in FIG. 6, (a) shows different concentrations of H 2 O 2 SERS spectra of nanosensors at the time of occurrence, (b) is I 998cm-1 /I 2226cm-1 Intensity ratio of (2) to H 2 O 2 A graph of concentration dependence;
FIG. 7 shows a graph I in example 5 of the present invention 998cm-1 /I 2226cm-1 Intensity ratio with various biologically relevant analytes (concentration 800. Mu.M) and H 2 O 2 (80. Mu.M);
FIG. 8 shows (a) the SERS spectra from randomly selected 30 points on the same sample in example 5 and (b) the corresponding 998cm obtained from data (a) -1 And 2226cm -1 SERS peak intensity of (d);
FIG. 9 (a) is the SERS spectrum of the nanosensor in the cell after the cell was stimulated with PMA of different concentrations in example 6, and (b) is I 998cm-1 /I 2226cm-1 Strength ratioHistogram of the relationship between values and different concentrations of PMA.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention is more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Example 1: the construction of the equal-ratio SERS nano sensor comprises the following steps:
(1) And (3) synthesis of gold nanoparticles: and synthesizing the gold nanoparticles serving as the SERS enhanced substrate by adopting a heating reduction method. The basic principle is that sodium citrate can reduce chloroauric acid to generate gold nanoparticles in a heating state. First, 1.0mL of HAuCl chloroauric acid with a mass fraction of 1.05% 4 Added to 100mL of deionized water and the solution was heated to boiling with magnetic stirring. Then, 2.0mL of a sodium citrate solution with a mass fraction of 1.1% was rapidly added, and the reaction solution was refluxed for 30min until the solution became wine-red in color, and the heating was stopped. And gradually cooling to room temperature under magnetic stirring to obtain the gold nanoparticles.
(2) Preparation of the SERS sensor: firstly, a certain amount of 4-MPBA and 4-MBN powder are respectively dissolved in ethanol to prepare a 4-MPBA solution and a 4-MBN solution with the concentration of 1.0 mM. mu.L of the above 4-MPBA (1.0 mM) solution and 5. Mu.L of 4-MBN (1.0 mM) solution were sequentially added to 10mL of gold nanoparticle AuNPs, and magnetically stirred at room temperature for 12 hours. After the reaction is finished, removing redundant 4-MPBA and 4-MBN which are not modified on the gold nanoparticles by adopting a centrifugal mode (the rotating speed is 7500rpm, and the time is 10 min), and resuspending the precipitate by using deionized water to obtain the SERS nano sensor Au @4-MPBA &4-MBN.
Example 2: characterization of equal-ratio SERS nanosensors
4-MPBA and 4-MBN moleculesThe SERS nanosensor is formed on the surface of AuNPs through Au-S bonds. It can be observed from TEM images of transmission electron microscope, the AuNPs and the nanosensors prepared both have good dispersibility and uniform size (fig. 2a and 2 b), and in addition, the morphology of the AuNPs does not change significantly during the modification of the functional molecules. To demonstrate the successful construction of SERS nanosensors, the uv absorption spectra of AuNPs and nanosensors were compared, as shown in fig. 3, the uv maximum absorption wavelength of AuNPs was 536nm, and the plasma band was slightly red-shifted (540 nm) after modification of the functional molecule, indicating that reporter molecule 4-MPBA and internal standard molecule 4-MBN have been successfully modified on AuNPs. To further demonstrate the successful fabrication of SERS nanosensors, SERS spectra were taken of AuNPs and the nanosensors, respectively (as shown in fig. 4). The result shows that AuNPs have almost no SERS spectral band, and the reporter molecule 4-MPBA (998 cm) is simultaneously generated in the nanosensor -1 ) And the internal standard molecule 4-MBN (2226 cm) -1 ) SERS characteristic peak of (1). The above results show that the response H 2 O 2 The reporter molecule and the internal standard molecule are successfully modified on AuNPs in a self-assembly mode, and the equal-ratio SERS nano sensor is formed.
Example 3: principle feasibility of SERS nano sensor for measuring hydrogen peroxide
To demonstrate SERS sensor detection H 2 O 2 Performance of collecting nanosensor and H 2 O 2 And comparing the SERS spectra before and after the reaction. As shown in FIG. 5, H 2 O 2 The SERS spectrum of oxidized 4-MPBA was almost the same as that of 4-hydroxythiophenol 4-HTP. Wherein, 998cm in the nano sensor -1 And 1021cm -1 The peak intensity of (A) is represented by H 2 O 2 The oxidation is obviously reduced, which shows that the boric acid ester group in 4-MPBA is oxidized into phenolic hydroxyl, and the two peaks can be used as spectral markers to monitor H 2 O 2 . Furthermore, the 4-MBN in the nanosensor is 2226cm -1 (C.ident.N stretching vibration mode) has peak intensity similar to that of H 2 O 2 No changes occurred before and after the reaction (FIG. 5), indicating that it can be used as an internal standard molecule to calibrate H 2 O 2 The measurement of (1). Thus, according to I 998cm-1 And I 2226cm-1 The ratio of (A) can accurately and reliably determine H 2 O 2 。
Example 4: SERS nano sensor for detecting H with different concentrations in aqueous solution 2 O 2
First, different concentrations of H were prepared 2 O 2 An aqueous solution. Collecting different concentrations of H 2 O 2 SERS spectra after reaction with the nanosensor. The results are shown in FIG. 6a, with H 2 O 2 The concentration is increased, and the nano sensor is at 998cm -1 The SERS intensity of (2) gradually decreases and 2226cm -1 The SERS intensity of the (A) is constant, and finally I is caused 998cm-1 /I 2226cm-1 Ratio of (a) to (b) is dependent on H 2 O 2 The concentration increases and gradually decreases. And I 998cm-1 /I 2226cm-1 Ratio of (A) to H 2 O 2 There is a good linear relationship between concentrations (fig. 6 b), resulting in a linear regression equation of y =3.618-0.036x, correlation coefficient R 2 Is 0.989. When the signal-to-noise ratio is 3, the detection limit of the sensor is 100nM, which indicates that the nano sensor is H 2 O 2 The quantitative detection has higher sensitivity.
Example 5: evaluation of detection specificity and reproducibility of nanosensor
To evaluate the nanosensor couple, detect H 2 O 2 The method comprises the steps of reacting various biologically relevant analytes possibly co-existing in living cells with a nanosensor, and collecting SERS spectra after reaction for comparison. As shown in FIG. 7, other biologically relevant analytes (. OH, clO) - 、O 2- TBHP, ATP, PSA and CTnl) in comparison with H 2 O 2 Can cause I in the nanosensor 998cm-1 /I 2226cm-1 The obvious reduction of the ratio indicates that the nano-sensor monitors H in complex biological environment 2 O 2 Has excellent selectivity.
Detection of H for evaluation of nanosensors 2 O 2 The SERS spectrum at each point was collected at 30 randomly selected points on the same sample, and the result is shown in fig. 8 a. 998cm is selected -1 And 2226cm -1 The reproducibility of the two peaks is evaluated, and the relative standard deviation RSD values of Raman signals are 2.52% and 4.63%, respectively, and meet the requirement that the RSD value is less than 20% by the international detection standard. These data indicate that the nanosensor is detecting H 2 O 2 The aspect shows excellent reproducibility.
Example 6: SERS nano sensor dynamic monitoring of intracellular H in drug stimulation process 2 O 2
Nano-sensor for monitoring intracellular H 2 O 2 The concentration of (c) is varied. First, cells planted in a culture dish were cultured in a medium containing 10% fetal bovine serum for 24 hours. Then, phorbol ester PMA with different concentrations was added in parallel to a series of cell culture media, respectively, and incubated for 2.5h. A further nanosensor solution was added at a concentration of 0.42nM and incubated for 2h. And then, washing the culture dish for 3 times by using phosphate buffer, and collecting SERS spectra of the nano sensor in the cells after the action of PMA with different concentrations. The results are shown in FIG. 9a, with PMA-stimulated HepG2 cells at 998cm -1 The SERS intensity of the cells is obviously reduced, indicating that the cells generate H under the stimulation of PMA 2 O 2 . Furthermore, as the concentration of PMA increases, I 998cm-1 /I 2226cm-1 The ratio decreased gradually (as shown in FIG. 9 b), indicating that high concentration of PMA can promote more H production by the cells 2 O 2 Meanwhile, based on the data analysis, the SERS nanosensor constructed in the invention can monitor H in cells in situ, dynamically and accurately 2 O 2 The level changes.
The description and practice of the disclosure herein will be readily apparent to those skilled in the art from consideration of the specification and understanding, and may be modified and modified without departing from the principles of the disclosure. Therefore, modifications or improvements made without departing from the spirit of the invention should also be considered as the protection scope of the invention.
Claims (6)
1. A preparation method of an equal-ratio SERS nano sensor is characterized by comprising the following specific steps:
s1, synthesis of gold nanoparticles: synthesizing gold nanoparticles serving as an SERS enhanced substrate by adopting a heating reduction method; first, 1.0mL of HAuCl chloroauric acid was added 4 Adding the solution into 100mL of deionized water, and heating the solution under magnetic stirring to boil the solution; then, rapidly adding 2.0mL of sodium citrate solution, refluxing the reaction solution for 30min until the solution becomes wine red, and stopping heating; gradually cooling to room temperature under magnetic stirring to obtain gold nanoparticles;
s2, preparing an SERS sensor: sequentially adding a 4-MPBA solution with the concentration of 1.0mM and a 4-MBN solution with the concentration of 1.0mM into the gold nano-particle AuNPs, and magnetically stirring for 12h at room temperature; after the reaction is finished, removing redundant 4-MPBA and 4-MBN which are not modified on the gold nanoparticles by adopting a centrifugal mode, and resuspending the precipitate by using deionized water to obtain the SERS nanosensor Au @4-MPBA &4-MBN.
2. The method for preparing an equal-ratio SERS nanosensor as recited in claim 1, wherein, in step S1, the mass fractions of the chloroauric acid solution and the sodium citrate solution are 1.05% and 1.1%, respectively.
3. The method for preparing an equal-ratio SERS nanosensor as recited in claim 1, wherein in step S2, the volumes of the 4-MPBA solution, the 4-MBN solution and the gold nanoparticles are 10 μ L, 5 μ L and 10mL, respectively.
4. The method for preparing an iso-ratio SERS nanosensor as recited in claim 1, wherein the rotation speed and time of centrifugation in step S2 are 7500rpm and 10min, respectively.
5. The application of the equal-ratio SERS nano sensor prepared by the preparation method of any one of claims 1 to 4 in detecting hydrogen peroxide.
6. The use according to claim 5, wherein 20 μ L of H is added at different concentrations 2 O 2 Are respectively added in parallel with 18Carrying out SERS detection after reacting for 1.5h at room temperature in 0 mu L of the prepared nano sensor solution; the excitation wavelength used was 633nm, the integration time was 5s, the number of integrations was 1; 998cm in the collected SERS spectrum -1 /2226cm -1 Peak intensity ratio and H 2 O 2 Establishing a relation of concentration to obtain a linear regression equation y =3.618-0.036x and a correlation coefficient R 2 Is 0.989; then, H to be measured 2 O 2 The solution is operated according to the steps, and the corresponding SERS spectrum is measured; the peak of the SERS spectrum is 998cm -1 /2226cm -1 And substituting the intensity ratio into the linear regression equation to obtain the concentration of the sample to be measured.
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Citations (5)
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| CN110376379A (en) * | 2019-08-19 | 2019-10-25 | 福建师范大学 | A kind of method that molecular engram combination quiet zone internal standard SERS technology high-precision detects CEA |
| CN112326628A (en) * | 2020-11-19 | 2021-02-05 | 济南大学 | Preparation of ratio-type SERS detection platform based on self-assembly aggregation |
| CN113563222A (en) * | 2021-07-13 | 2021-10-29 | 暨南大学 | Method for detecting hydrogen peroxide based on surface enhanced Raman scattering of silent zone reporter molecule and application |
| CN114689561A (en) * | 2022-05-30 | 2022-07-01 | 南京市食品药品监督检验院 | Method for rapidly detecting bisphenol A in food and environment based on SERS imaging of Raman silent area |
| CN115184331A (en) * | 2022-06-30 | 2022-10-14 | 华南师范大学 | Ratio type composite SERS substrate and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110376379A (en) * | 2019-08-19 | 2019-10-25 | 福建师范大学 | A kind of method that molecular engram combination quiet zone internal standard SERS technology high-precision detects CEA |
| CN112326628A (en) * | 2020-11-19 | 2021-02-05 | 济南大学 | Preparation of ratio-type SERS detection platform based on self-assembly aggregation |
| CN113563222A (en) * | 2021-07-13 | 2021-10-29 | 暨南大学 | Method for detecting hydrogen peroxide based on surface enhanced Raman scattering of silent zone reporter molecule and application |
| CN114689561A (en) * | 2022-05-30 | 2022-07-01 | 南京市食品药品监督检验院 | Method for rapidly detecting bisphenol A in food and environment based on SERS imaging of Raman silent area |
| CN115184331A (en) * | 2022-06-30 | 2022-10-14 | 华南师范大学 | Ratio type composite SERS substrate and preparation method and application thereof |
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