CN111175369B - MALDI-TOF MS matrix for small molecule detection and application thereof - Google Patents
MALDI-TOF MS matrix for small molecule detection and application thereof Download PDFInfo
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Abstract
The invention discloses a MALDI-TOF MS matrix for small molecule detection and application thereof, wherein the matrix is a gold nanoparticle-covalent organic framework composite material, and the matrix is prepared by reducing gold ions on a covalent organic framework material into gold nanoparticles through the interaction of Au-S bonds by taking the covalent organic framework material with thioether as a substrate. The gold nanoparticle-covalent organic framework composite material is used as a MALDI-TOF MS matrix, can be used for rapidly detecting small molecular compounds such as nucleosides, nucleic acid, environmental organic pollutants, drug small molecules, estrogen, amino acid and other organic small molecules, and has low detection limit and higher sensitivity.
Description
Technical Field
The invention belongs to the technical field of detection of small molecular compounds, and particularly relates to a gold nanoparticle-covalent organic framework composite material formed by reaction of a covalent organic framework material with a thioether cantilever and gold ions, which is used as a MALDI-TOF MS matrix and application thereof in detection of small molecular compounds.
Background
A novel soft ionization biological mass spectrum, namely matrix assisted laser desorption/ionization time-of-flight mass spectrum (MALDI-TOF MS) developed in the end of the 80 s has the advantages of high sensitivity, simplicity in operation, strong impurity resistance and the like, and is widely applied to analysis and identification of various molecules such as polypeptide, protein, macromolecule and the like at present. According to previous studies, in MALDI-TOF mass spectrometry, conventional matrices such as a-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (2,5-DHB) have been widely used for large molecule detection, but have rarely been used for small molecule identification for the following reasons: on one hand, signals of the traditional organic matrix can inhibit or overlap with target signals in a low-quality area, and cause serious interference on small molecule analysis; on the other hand, due to the heterogeneous co-crystallization of the analyte with a matrix (e.g., 2,5-dihydroxybenzoic acid (DHB)) to form a "hot spot", the detection requires selection within the sample spot, resulting in less reproducible analyte detection.
Inorganic materials can also be used for matrixes of MALDI materials, and documents report that graphene oxide is added into a common matrix to assist matrix excitation, and the addition of small-concentration graphene oxide can help the common matrix to form uniform crystals, but the graphene oxide splashes under a vacuum state to pollute an MALDI instrument, and documents report that inorganic nanoparticles are used as the MALDI matrix, and the nanoparticles have strong ionization capacity and high energy transfer speed and are suitable for ionization and desorption of small molecules, but the nanoparticles are easy to fall off under the vacuum of the MALDI instrument to pollute the instrument and generate interference peaks, so that the immobilization of the nanoparticles becomes an important problem. Therefore, the development of a new matrix is of great significance for the detection of small-molecule compounds by MALDI-TOF mass spectrometry.
Disclosure of Invention
The invention aims to solve the technical problems of large interference and low sensitivity of the traditional MALDI-TOF MS matrix on small molecule analysis, and provides the MALDI-TOF MS matrix which can be used for detecting small molecule substances, has high detection selectivity and sensitivity and can enhance the mass spectrum signals of the small molecules.
The substrate used for solving the technical problems is a gold nanoparticle-covalent organic framework composite material formed by incubating a covalent organic framework material with thioether cantilevers and a chloroauric acid aqueous solution at room temperature and reducing gold ions on the covalent organic framework material into gold nanoparticles through the interaction of Au-S bonds, wherein the mass fraction of the gold nanoparticles is 6-24%.
The structural units of the covalent organic framework material with thioether cantilevers are shown as follows:
the compound is prepared according to the method disclosed in the literature "Zhiming Z, wanfu Z, kaixun C, et al. A. A. Organic frame bearing sulfur nutrient areas for selective detection and recovery of Au front-low communication a. Solutions [ J ]. Chemical Communications,2018, 10.1039.C8C 05369C-", and the specific preparation method is as follows: 30mg of 2, 5-bis (2- (ethylthio) ethoxy) terephthaloyl hydrazine and 8mg of 1,3, 5-mesitylene triformal are added into a mixed solvent of 1.2mL1, 4-dioxane, 1,3,5 trimethylbenzene and acetic acid with the volume ratio of 5.
In the matrix, the mass fraction of gold nanoparticles is preferably 14% to 20%.
The incubation time at room temperature is preferably 10 to 15 hours.
The MALDI-TOF MS matrix is used for detecting small molecules, wherein the small molecules are any one of nucleosides, nucleic acids, environmental organic pollutants, drug small molecules, estrogen and amino acids.
The nucleoside is any one of cytidine, adenosine, guanosine, uridine and the like, the nucleic acid is any one of adenine, guanine, urine and the like, the environmental organic pollutant is any one of thiabendazole, melamine, pyrene derivatives and the like, the drug micromolecule is any one of norfloxacin, folic acid, artemisinin and the like, and the estrogen is any one of diethylstilbestrol, estradiol, estriol, estrone and the like.
When the MALDI-TOF MS matrix is used for detecting small molecules, the mass ratio of the matrix to the small molecules is preferably 1-1:1, wherein the matrix is dissolved by acetonitrile, and the small molecules are dissolved by any one of water, methanol, ethanol and acetonitrile.
The invention has the following beneficial effects:
the gold nanoparticles are combined with the covalent organic framework material with thioether cantilevers to form the gold nanoparticle-covalent organic framework composite material, the composite material is used as a MALDI-TOF MS matrix, wherein the covalent organic framework material has the advantages of small background interference, good salt resistance, high desorption/ionization efficiency and the like when being used as the MALDI matrix due to the large specific surface, good stability and strong pi-pi stacking interaction of the covalent organic framework material, and the gold nanoparticles have strong ultraviolet absorption capacity and can rapidly transfer laser energy to ionize analytes in MALDI detection. The gold nanoparticles combined on the covalent organic framework through gold-sulfur bonds are not easy to fall off under the vacuum of MALDI, the influence of citrate as a reducing agent on the preparation of the gold nanoparticles is reduced, the rapid transfer of energy enhances the ionization analysis of covalent organic framework materials on small molecules, and the gold nanoparticle-covalent organic framework composite material has low detection limit and higher sensitivity when used as a MALDI-TOF MS matrix on small molecule compounds, such as nucleosides, nucleic acids, nitrogen-containing heterocycles, estrogens and the like, and simultaneously enhances mass spectrum signals of the small molecules in the MALDI.
Drawings
FIG. 1 is a structural diagram of Au-COF.
FIG. 2 is XPS comparison of TTB-COF with 16.45% Au-COF.
FIG. 3 is XPS comparison of TTB-COF with 16.45% Au-COF.
FIG. 4 is an environmental scanning electron microscope image of 16.45% Au-COF.
FIG. 5 is a mass spectrum of 16.45% Au-COF as MALDI-TOF MS matrix in example 1.
FIG. 6 is a graph showing the trend of mass spectrum intensity of Au-COF formed by adding chloroauric acid at different concentrations as MALDI-TOF MS matrix for detecting cytidine.
FIG. 7 is a mass spectrum of TTB-COF and 16.45% Au-COF as MALDI-TOF MS matrix for detection of cytidine.
FIG. 8 is a mass spectrum of TTB-COF and 16.45% Au-COF as MALDI-TOF MS matrix for adenosine detection.
FIG. 9 is a mass spectrum of TTB-COF and 16.45% Au-COF as MALDI-TOF MS matrix for detection of adenine.
FIG. 10 is a mass spectrum of TTB-COF and 16.45% Au-COF as MALDI-TOF MS matrix for the detection of thiabendazole.
FIG. 11 is a mass spectrum of TTB-COF with 16.45% Au-COF as MALDI-TOF MS matrix for detection of melamine.
FIG. 12 is a mass spectrum of TTB-COF and 16.45% Au-COF as MALDI-TOF MS matrix for detection of diethylstilbestrol.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Ultrasonically dispersing 5mg of TTB-COF in 1mL of acetonitrile, adding 19mL of chloroauric acid aqueous solution, uniformly mixing to ensure that the concentration of TTB-COF in the mixed solution is 0.25mg/mL and the concentrations of chloroauric acid are 0.12, 0.20, 0.30, 0.40, 0.50 and 0.60mmol/L respectively, incubating at room temperature for 12 hours, washing with acetonitrile for multiple times to remove the chloroauric acid which is not completely reacted, and obtaining the gold nanoparticle-covalent organic framework composite material (Au-COF), wherein the structural unit is shown in figure 1.
And testing the gold ion concentration in the supernatant obtained after incubation of the TTB-COF and chloroauric acid with different concentrations by using an ultraviolet absorption spectrometer to obtain the mass fraction of the gold nanoparticles in the gold nanoparticle-covalent organic framework composite material, wherein the results are shown in table 1.
Table 1 shows the gold adsorption amount and mass fraction when Au-COF is formed by adding chloroauric acid solutions with different concentrations and incubating
The results of XPS, SEM, and MALDI-TOF MS with respect to the prepared gold nanoparticles having a mass fraction of 16.45% of Au-COF (hereinafter referred to as 16.45% Au-COF) at a TTB-COF and chloroauric acid concentration of 0.40mmol/L were shown in FIGS. 2 to 5. As is clear from FIGS. 2 and 3, 16.45% by weight of Au-COF showed significant gold-sulfur bonds, 16.45% by weight of Au-COF showed significant gold nanoparticles, and FIG. 5 showed that it itself served as a substrate and had few hetero peaks in a low molecular weight region, and thus it was very advantageous for the detection of small molecules. Tests show that the Au-COF formed by incubating TTB-COF with chloroauric acid at other concentrations is used as a substrate, and has few hetero peaks in a low molecular weight region, so that the method is very favorable for detecting small molecules.
Example 2
Application of Au-COF as MALDI-TOF MS matrix to detection of cytidine in example 1
Respectively adding 5mg of Au-COF with the mass fraction of each gold nanoparticle prepared in example 1 into 1mL of acetonitrile, and performing ultrasonic dispersion uniformly to form a suspension; and quickly dripping 1 mu L of the suspension onto a MALDI-TOF MS sample target, naturally airing at room temperature, dripping 1 mu L of 0.05mg/mL cytidine aqueous solution, naturally airing at room temperature, and carrying out MALDI-TOF MS analysis. As can be seen from FIG. 6, the peak intensity of cytidine was best detected at 16.45% Au-COF. As can be seen from FIG. 7, the molecular ion peaks of cytidine sodium and cytidine potassium at m/z 266.0 and m/z 282.0 appeared with TTB-COF and 16.45% Au-COF as MALDI-TOF MS matrices, indicating that TTB-COF as MALDI-TOF MS matrix can recognize cytidine. Meanwhile, it can be seen that the mass spectrum signal obtained by detecting adenosine using 16.45-percent Au-COF as MALDI-TOF MS matrix is much stronger than that obtained by detecting adenosine using TTB-COF as MALDI-TOF MS matrix, and that the cytidine molecular signal detected by 16.45-percent Au-COF after intensity normalization is as much as ten times that of TTB-COF, demonstrating that 16.45-percent Au-COF as MALDI-TOF MS matrix can enhance the small molecule mass spectrum signal.
Example 3
Example 1 use of 16.45% Au-COF as MALDI-TOF MS matrix for adenosine detection
Dispersing 5mg of 16.45% Au-COF in 1mL of acetonitrile, and uniformly dispersing by ultrasonic waves to form a suspension; and quickly dripping 1 mu L of the suspension onto a MALDI-TOF MS sample target, naturally airing at room temperature, dripping 1 mu L of 0.05mg/mL adenosine aqueous solution, naturally airing at room temperature, and carrying out MALDI-TOF MS analysis, wherein the analysis result is shown in figure 8. As can be seen from FIG. 8, taking 16.45% of Au-COF and TTB-COF as MALDI-TOF MS matrices, adenosine plus sodium molecular ion peaks appeared at 290.1 m/z and adenosine plus potassium molecular ion peaks appeared at 306.1 m/z, indicating that 16.45% of Au-COF and TTB-COF as MALDI-TOF MS matrices were able to recognize adenosine. Also, it was observed that under the same conditions, the mass spectrum signal obtained by detecting adenosine using 16.45% Au-COF as MALDI-TOF MS matrix was much stronger than that obtained by using TTB-COF as MALDI-TOF MS matrix, demonstrating that 16.45% Au-COF as MALDI-TOF MS matrix can enhance the small molecule mass spectrum signal.
Example 4
Example 1 use of 16.45% Au-COF as MALDI-TOF MS matrix for detection of adenine
Dispersing 5mg of 16.45% Au-COF in 1mL of acetonitrile, and uniformly dispersing by ultrasonic waves to form a suspension; and quickly dripping 1 mu L of the suspension onto a MALDI-TOF MS sample target, naturally airing at room temperature, dripping 1 mu L of 0.05mg/mL adenine aqueous solution, naturally airing at room temperature, and carrying out MALDI-TOF MS analysis, wherein the analysis result is shown in figure 9. As can be seen from FIG. 9, the 16.45% Au-COF as the MALDI-TOF MS matrix exhibited a molecular ion peak of adenine at 135.8 m/z and a molecular ion peak of adenine plus potassium at 173.8 m/z, indicating that 16.45% Au-COF as the MALDI-TOF MS matrix was able to recognize adenine and enhance the mass spectrum signal for adenine.
Example 5
Example 1 use of 16.45% Au-COF as MALDI-TOF MS matrix for detection of thiabendazole
Dispersing 5mg of 16.45% Au-COF in 1mL of acetonitrile, and uniformly dispersing by ultrasonic waves to form a suspension; and quickly dripping 1 mu L of the suspension onto a MALDI-TOF MS sample target, naturally airing at room temperature, dripping 1 mu L of 0.05mg/mL thiabendazole aqueous solution, naturally airing at room temperature, and carrying out MALDI-TOF MS analysis, wherein the analysis result is shown in figure 10. As can be seen from FIG. 10, 16.45% Au-COF as MALDI-TOF MS matrix showed the appearance of the molecular ion peak of thiabendazole at m/z of 201.9, the appearance of the molecular ion peak of thiabendazole plus sodium at m/z of 223.9, and the appearance of the molecular ion peak of thiabendazole plus potassium at m/z of 239.9, indicating that 16.45% Au-COF as MALDI-TOF MS matrix was able to recognize thiabendazole and enhance the mass spectrum signal of thiabendazole.
Example 6
Example 1 use of 16.45% Au-COF as MALDI-TOF MS matrix for detection of Melamine
Dispersing 5mg of 16.45% Au-COF in 1mL of acetonitrile, and uniformly dispersing by ultrasonic waves to form a suspension; and quickly dripping 1 mu L of the suspension onto a MALDI-TOF MS sample target, naturally airing at room temperature, dripping 1 mu L of 0.05mg/mL melamine aqueous solution, naturally airing at room temperature, and carrying out MALDI-TOF MS analysis, wherein the analysis result is shown in figure 11. As can be seen from FIG. 11, 16.45% Au-COF as MALDI-TOF MS matrix showed melamine molecular ion peak at m/z 126.9, melamine plus sodium molecular ion peak at m/z 149.0, and melamine plus potassium molecular ion peak at m/z 165.0, indicating that 16.45% Au-COF as MALDI-TOF MS matrix was able to identify melamine and enhance the melamine mass spectrum signal.
Example 7
Example 1 use of 16.45% Au-COF as MALDI-TOF MS matrix for detection of Diethylstilbestrol
Dispersing 5mg of 16.45% Au-COF in 1mL of acetonitrile, and dispersing the solution uniformly by sonication to form a suspension; and quickly dripping 1 mu L of the suspension onto a MALDI-TOF MS sample target, naturally airing at room temperature, dripping 1 mu L of 0.05mg/mL diethylstilbestrol aqueous solution, naturally airing at room temperature, and carrying out MALDI-TOF MS analysis, wherein the analysis result is shown in figure 12. As can be seen from FIG. 12, 16.45% Au-COF as MALDI-TOF MS matrix showed the appearance of the molecular ion peak of diethylstilbestrol at m/z 268.2, the appearance of the molecular ion peak of diethylstilbestrol plus sodium at m/z 290.1, and the appearance of the molecular ion peak of diethylstilbestrol plus potassium at m/z 307.1, indicating that 16.45% Au-COF as MALDI-TOF MS matrix was able to recognize diethylstilbestrol and enhance the diethylstilbestrol mass spectrum signal.
Claims (9)
1. A MALDI-TOF MS matrix for small molecule detection, wherein: the substrate is a gold nanoparticle-covalent organic framework composite material formed by incubating a covalent organic framework material with a thioether cantilever and a chloroauric acid aqueous solution at room temperature and reducing gold ions on the covalent organic framework material into gold nanoparticles through the interaction of Au-S bonds, wherein the mass fraction of the gold nanoparticles is 6-24%;
the structural units of the covalent organic framework material with thioether cantilevers are shown as follows:
the small molecule is any one of nucleoside, nucleic acid, environmental organic pollutant, drug small molecule, estrogen and amino acid.
2. The MALDI-TOF MS matrix for small molecule detection according to claim 1, characterized by: the mass fraction of the gold nanoparticles in the matrix is 14-20%.
3. The MALDI-TOF MS matrix for small molecule detection according to claim 1, characterized by: the incubation time at room temperature is 10-15 hours.
4. The MALDI-TOF MS matrix for small molecule detection according to claim 1, characterized by: the nucleoside is any one of cytidine, adenosine, guanosine and uridine.
5. The MALDI-TOF MS matrix for small molecule detection according to claim 1, characterized by: the nucleic acid is any one of adenine, guanine and urine.
6. The MALDI-TOF MS matrix for small molecule detection according to claim 1, characterized by: the environmental organic pollutant is any one of thiabendazole, triazine nitrogen-containing heterocyclic compounds and pyrene derivatives.
7. The MALDI-TOF MS matrix for small molecule detection according to claim 1, characterized by: the drug micromolecules are any one of norfloxacin, folic acid and artemisinin.
8. The MALDI-TOF MS matrix for small molecule detection according to claim 1, characterized by: the estrogen is any one of diethylstilbestrol, estradiol, estriol and estrone.
9. The MALDI-TOF MS matrix for small molecule detection according to any one of claims 4 to 8, wherein: the mass ratio of the matrix to the small molecules is 1-1:1, wherein the matrix is dissolved by acetonitrile, and the small molecules are dissolved by any one of water, methanol, ethanol and acetonitrile.
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