CN112540118B - Method for rapidly detecting metal ions based on mercaptobenzoic acid-assisted laser desorption ionization mass spectrum - Google Patents
Method for rapidly detecting metal ions based on mercaptobenzoic acid-assisted laser desorption ionization mass spectrum Download PDFInfo
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Abstract
The invention belongs to the technical field of metal ion detection methods, and particularly relates to a method for rapidly detecting metal ions based on mercaptobenzoic acid-assisted laser desorption ionization mass spectrometry. The method develops a method for rapidly detecting metal ions based on an organic mass spectrometry technology by taking mercaptobenzoic acid as a matrix. The method can be successfully applied to the detection of more than 40 metal ions, and overcomes the problem that the laser desorption ionization mass spectrometry cannot be well applied to the high-sensitivity and high-flux detection of the metal ions due to the serious ionization inhibition and the serious matrix interference. The method has the advantages of simple sample preparation, no need of complex pretreatment, small sample consumption (1 mu L), low time consumption, good reproducibility and the like, is favorable for rapid detection of metal ions in complex samples, and has good application prospects in the safety fields of environment, food, medicines and the like.
Description
Technical Field
The invention belongs to the technical field of metal ion detection methods, and particularly relates to a method for rapidly detecting metal ions based on mercaptobenzoic acid-assisted laser desorption ionization mass spectrometry.
Background
In recent years, the modern industry has been rapidly developed, and a large amount of metal ions are discharged into the environment, which causes a sharp increase in the content of metal ions in soil, atmosphere and food, however, since metal ions can enter the human body through various routes and accumulate in the human body, which will seriously harm the health of human beings, it is of great importance to develop a method for rapidly detecting metal ions.
At present, the traditional metal ion detection methods mainly include Atomic Absorption Spectrometry (AAS), inductively coupled plasma emission spectrometry (ICP-OES), Atomic Fluorescence Spectrometry (AFS), inductively coupled plasma mass spectrometry (ICP-MS), and the like. However, these techniques suffer from the disadvantages of large sample consumption, time consuming, complex pre-processing and good instrument handling skills. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS) is a fast and high throughput ionization technique that can analyze hundreds of samples in a short time with minimal sample consumption and without the need for complex sample and instrument preparation procedures. In recent years, the technology is widely applied to the field of medicine, but because of the problems of serious ionization inhibition, high background interference related to the matrix and the like, the direct identification of metal ions by using MALDI-TOF-MS is still a great challenge.
To further extend the ability of MALDI-TOF-MS for rapid detection of metal ions, the development of new matrices is a very critical aspect. In order to generate higher signal intensity and lower background, some nanomaterials are applied as matrices for MALDI-TOF-MS for detection of metal ions. However, most materials are not commercially available and need to be self-synthesized and characterized. In addition, since the nanomaterial has high electrical conductivity and chemical stability, it will easily cause malfunction or damage of the instrument. Thus, conventional, commercially available and used organic substrates would be a good substrate choice compared to those new materials.
Disclosure of Invention
The invention aims to provide a method for rapidly detecting metal ions based on mercaptobenzoic acid assisted laser desorption ionization mass spectrometry. Meanwhile, the method has high detection speed, does not need a complex sample pretreatment step, and requires a very small amount of samples (1 mu L), so the method has high application value for the actual detection of metal ions in complex samples.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for rapidly detecting metal ions based on mercaptobenzoic acid assisted laser desorption ionization mass spectrometry is characterized in that a mercaptobenzoic acid matrix and a sample to be detected are mixed and placed on a target plate, and a laser desorption ionization mass spectrometer is used for performing mass spectrometry detection and rapidly detecting the metal ions in the sample.
Further, the suitable concentration of the substrate is 1 mg/mL or more.
Further, the method specifically comprises the following steps:
step 1: preparation of reagents and instruments: matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS, model: Bruker Autoflex speed II, Bruker Daltonics Inc., USA), vortex apparatus, metal ion standard, mercaptobenzoic acid, sample;
step 2: preparation of matrix solution: weighing 6 mg of mercaptobenzoic acid, dissolving the mercaptobenzoic acid in 3 mL of mixed solvent of ethanol/water (1: 1), carrying out vortex, uniformly mixing, and preparing a matrix solution with the mass concentration of 2 mg/mL;
and step 3: preparing a metal ion standard solution and a standard curve: gradually diluting a metal ion (1 mg/mL) solution with deionized water, and uniformly mixing for 5 min on a vortex instrument to prepare the metal ion solution with the respective preparation concentrations; 20, 50, 100, 200, 500, 800, 1000 ng/mL of metal ion standard solution.
And 4, step 4: uniformly mixing a mercaptobenzoic acid matrix solution with the mass concentration of 2 mg/mL with a metal ion standard solution or an actual sample (the volume ratio is 1: 1), moving 1 mu L of the mixture to a target plate, and naturally drying at room temperature;
and 5: and (3) directly putting the dried target plate into a MALDI-TOF-MS instrument, calling a detection method and parameters, and directly striking the target object. Detecting parameters: a linear positive ion mode and a linear negative ion mode are adopted, the ion source voltage is 19 kV, the pulse delay time is 130 ns, the laser irradiation is set to be 500 times, and spectrograms are continuously adopted. Experimental data were processed using flexAnalysis (Bruker Daltonics inc., usa) software.
Further, the sample includes atmospheric fine Particulate Matter (PM)2.5) Or urine.
The invention has the following advantages:
1) the prepared substrate has low cost and can be obtained commercially;
2) the matrix reproducibility is good and no obvious matrix interference exists;
3) the dosage of the detected actual sample is very small (1 mu L), and the detection process is simple;
4) the analysis speed is high (< 1 min/sample);
5) the method can be used for detecting more than 40 types of heavy metal ions, and has high sensitivity, wherein the detection limits of mercury ions and cadmium ions can reach 150 pg/mL and 50 pg/mL respectively.
Drawings
FIG. 1 is a MALDI detection mass spectrum of 9 metal ion standards with mercaptobenzoic acid as a matrix;
FIG. 2 is a diagram of the optimization of the suitable concentration of matrix for detecting metal ions with mercaptobenzoic acid as the matrix;
FIG. 3 is a graph of PM with mercaptobenzoic acid as a base pair2.5Mass spectrogram of metal ion detection in (1);
FIG. 4 is a mass spectrum diagram of mercaptobenzoic acid as matrix for detecting metal ions in urine.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and specific embodiments, but the present invention is not limited thereto.
Example 1: standard solution for detecting metal ions by using mercaptobenzoic acid as matrix
(1) Preparing an instrument: matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS, model: Bruker Autoflex speed II, Bruker Daltonics Inc., USA), vortex apparatus;
(2) mixing 2 mg/mL mercaptobenzoic acid matrix solution with standard metal ion of silver, lithium, barium, rhenium, bismuth, europium, strontium, indium and manganese (volume ratio is 1: 1), placing 1 μ L on a target plate, and drying at room temperature;
(3) and (3) directly putting the dried target plate into a MALDI-TOF-MS instrument, calling a detection method and parameters, and directly striking the target object. Detecting parameters: a linear positive ion mode and a linear negative ion mode are adopted, the ion source voltage is 19 kV, the pulse delay time is 130 ns, the laser irradiation is set to be 500 times, and spectrograms are continuously adopted. Experimental data were processed using flexAnalysis (Bruker Daltonics inc., usa) software. .
The mass spectrum results are shown in fig. 1, and obvious metal ion characteristic peaks are detected without obvious background interference.
Example 2: optimization of suitable concentration using mercaptobenzoic acid as substrate
(1) Preparing an instrument: matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS, model: Bruker Autoflex speed II, Bruker Daltonics Inc., USA), vortex apparatus;
(2) mixing the mercaptobenzoic acid matrix solutions with the concentrations of 0.5 mg/mL, 1 mg/mL, 2 mg/mL and 4 mg/mL respectively with the mercury standard substance (volume ratio of 1: 1), spotting 1 μ L on a target plate, and drying at room temperature;
(3) and (3) directly putting the dried target plate into a MALDI-TOF-MS instrument, calling a detection method and parameters, and directly striking the target object. Detecting parameters: a linear positive ion mode and a linear negative ion mode are adopted, the ion source voltage is 19 kV, the pulse delay time is 130 ns, the laser irradiation is set to be 500 times, and spectrograms are continuously adopted. Experimental data were processed using flexAnalysis (Bruker Daltonics inc., usa) software. .
The mass spectrum results are shown in FIG. 2, when the substrate concentration is more than or equal to 1 mg/mL, obvious mercury ion characteristic peaks are detected and the signal intensity is not greatly changed.
Example 3: PM detection by using mercaptobenzoic acid as matrix2.5Metal ion element of (1)
(1) Preparing an instrument: matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS, model: Bruker Autoflex speed II, Bruker Daltonics Inc., USA), vortex apparatus;
(2) mixing the mercaptobenzoic acid substrate solution with the mass concentration of 2 mg/mL and PM2.5Mixing the sample uniformly (volume ratio is 1: 1), transferring 1 mu L of the sample on a target plate, and drying at room temperature;
(3) and (3) directly putting the dried target plate into a MALDI-TOF-MS instrument, calling a detection method and parameters, and directly striking the target object. Detecting parameters: a linear positive ion mode and a linear negative ion mode are adopted, the ion source voltage is 19 kV, the pulse delay time is 130 ns, the laser irradiation is set to be 500 times, and spectrograms are continuously adopted. Experimental data were processed using flexAnalysis (Bruker Daltonics inc., usa) software.
The results of mass spectrometry, PM measured, are shown in FIG. 32.5The mercury ion-containing cadmium ion-containing mercury ion-containing cadmium ion-containing mercury ion-containing cadmium ion-containing mercury ion-containing cadmium ion-containing mercury ion-containing cadmium ion-containing characteristic peaks.
Example 4: method for detecting metal ion elements in urine by taking mercaptobenzoic acid as matrix
(1) Preparing an instrument: matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS, model: Bruker Autoflex speed II, Bruker Daltonics Inc., USA), vortex apparatus;
(2) uniformly mixing a mercaptobenzoic acid matrix solution with the mass concentration of 2 mg/mL and a urine sample (the volume ratio is 1: 1), transferring 1 mu L of spot on a target plate, and drying at room temperature;
(3) and (3) directly putting the dried target plate into a MALDI-TOF-MS instrument, calling a detection method and parameters, and directly striking the target object. Detecting parameters: a linear positive ion mode and a linear negative ion mode are adopted, the ion source voltage is 19 kV, the pulse delay time is 130 ns, the laser irradiation is set to be 500 times, and spectrograms are continuously adopted. Experimental data were processed using flexAnalysis (Bruker Daltonics inc., usa) software.
The mass spectrum results are shown in fig. 4, and the urine containing characteristic peaks of sodium ion, potassium ion, iron ion and strontium ion is measured.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (2)
1. A method for rapidly detecting metal ions based on mercaptobenzoic acid assisted laser desorption ionization mass spectrometry is characterized in that a mercaptobenzoic acid matrix and a sample to be detected are mixed and put on a target plate, and a laser desorption ionization mass spectrometer is used for performing mass spectrometry detection and rapidly detecting the metal ions in the sample; the appropriate concentration of the mercaptobenzoic acid substrate solution is more than or equal to 1 mg/mL; the volume ratio of the mercaptobenzoic acid matrix solution to the sample to be detected is 1: 1; the method specifically comprises the following steps:
step 1: preparation of reagents and instruments: matrix assisted laser desorption ionization time of flight mass spectrometer MALDI-TOF-MS, vortex instrument, metal ion standard, mercaptobenzoic acid, sample;
step 2: preparation of matrix solution: weighing mercaptobenzoic acid, dissolving the mercaptobenzoic acid in a mixed solvent of ethanol and water, carrying out vortex, uniformly mixing, and preparing a mercaptobenzoic acid substrate solution;
and step 3: preparing a metal ion standard solution and a standard curve: gradually diluting the metal ion solution by using deionized water, and uniformly mixing the metal ion solution on a vortex instrument to prepare a series of metal ion standard solutions with concentration;
and 4, step 4: uniformly mixing the mercaptobenzoic acid matrix solution with a metal ion standard solution or an actual sample, moving 1 mu L of the mixture to a target plate, and naturally drying at room temperature;
and 5: and (3) directly putting the dried target plate into a MALDI-TOF-MS instrument, calling a detection method and parameters, and directly striking the target object.
2. The method for rapidly detecting metal ions based on the mercaptobenzoic acid-assisted laser desorption ionization mass spectrometry as claimed in claim 1, wherein the detection parameters of step 5 are as follows: a linear positive ion mode and a linear negative ion mode are adopted, the ion source voltage is 19 kV, the pulse delay time is 130 ns, the laser irradiation is set to be 500 times, and spectrograms are continuously adopted.
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| EP3464463A4 (en) * | 2016-06-06 | 2020-07-29 | The Administrators of The Tulane Educational Fund | Iodo-functionalized polymers as mass spectrometry calibrants with a mass-defect offset |
| DK3706802T3 (en) * | 2017-11-07 | 2024-09-09 | Sellergren Boerje | LIDPID BILAYER MIMIC |
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