CN109752447B - Application of graphdiyne in detection of small molecular substance as MALDI matrix - Google Patents
Application of graphdiyne in detection of small molecular substance as MALDI matrix Download PDFInfo
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Abstract
The invention discloses application of graphdiyne as a MALDI matrix to detection of small molecular substances. The application is specifically the application of the graphdiyne in detecting micromolecular substances with the mass-to-charge ratio of 0-1000 by taking the graphdiyne as a matrix-assisted laser desorption ionization mass spectrometry matrix. The small molecule substance can be amino acid, oligopeptide, small molecule medicine, uric acid, rutin, bisphenol A or tetrabromobisphenol A. The sample to be detected of the matrix-assisted laser desorption ionization mass spectrometry can be a small molecular solution, human serum, human urine, a plant extract or a material extract. The invention overcomes the defect that the common organic micromolecule matrix is easy to generate matrix background interference phenomenon in a low molecular weight region, thereby causing the failure of effectively analyzing micromolecule samples. The matrix adopted by the invention does not need to be added with an ionizing reagent, so that the requirement on sample treatment is reduced; the background interference is small in the test range (m/z 0-1000), and various complex mixed systems can be analyzed; stable property, convenient storage and use, and easy synthesis.
Description
Technical Field
The invention belongs to the field of mass spectrometry, and particularly relates to application of graphdiyne as a MALDI matrix to detection of small molecular substances.
Background
Matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS) has the advantages of sensitivity, rapidness, high flux, salt tolerance, accuracy and the like, and is an important scientific research tool for researchers in various countries. The matrix-assisted laser desorption ionization mass spectrometry can detect proteins, nucleic acids, high molecular materials and the like, and plays an important role in the fields of proteomics, disease diagnosis, environmental science and the like. The matrix-assisted laser desorption ionization method is a soft ionization method, can be used for analyzing polar or non-polar molecules, and can be used for effectively analyzing biological macromolecules, and the obtained analyte generates a small amount of fragment ions or does not generate fragment ions. When the sample is a mixture, matrix-assisted laser desorption ionization time-of-flight mass spectrometry can also be analyzed.
Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) works on the principle that a sample to be detected is mixed with a matrix, so that the sample is uniformly dispersed in the matrix, when the mixture of the dried sample and the matrix is irradiated by laser, the matrix absorbs the energy of the laser and transfers the energy to sample molecules, so that the sample molecules are ionized and enter a time-of-flight mass detector, and detection is carried out according to the difference of the time when the ions reach the detector. The matrix in the experiment has the functions of dispersing sample molecules, protecting analysis molecules, absorbing laser energy and transmitting the laser energy to the sample molecules. The matrix must have the ability to absorb energy over a range of laser energies, and to have good energy transfer to the analyte; the matrix has stable chemical properties, is easy to store and use, and does not react with the analyte to cause oxidative decomposition of the analyte and the like; has better compatibility with the analyte and can disperse analyte molecules.
In matrix-assisted laser desorption ionization time-of-flight mass spectrometry, a matrix can cause important influence on an experimental result, so that the selection of the matrix is very important. Organic small molecule compounds including 2, 5-dihydroxybenzoic acid (DHB), alpha-cyano-4-hydroxycinnamic acid (CCA), 3-hydroxy-2-picolinic acid (3-HPA), Sinapinic Acid (SA), 3-aminoquinoline (3-AQ), anthratriphenol (DI), etc. are commonly used matrices. The above-mentioned matrix molecules are likely to be fragmented or associated with each other in a low mass range during the analysis process, thereby causing serious background interference to complicate the spectrum and causing inconvenience in the analysis of the spectrum. However, in some scientific research fields, the detection of small molecular substances is also very important, and many small molecular substances exist in biological metabolism, natural products and environmental pollutants, and in addition, some medicines such as huperzine A and the like are small molecular medicines.
Some improved methods have been proposed to overcome background interference phenomena with the matrix, including methods that incorporate nanomaterials as matrices or that fabricate and modify porous silicon surfaces to achieve desorption ionization without matrices. However, the synthesis and surface modification processes of some nanomaterials are complicated. Therefore, the matrix has stable property, simple and convenient synthesis, low cost, simple operation, wide application and wide practical significance in low-quality areas with small interference.
Disclosure of Invention
The invention aims to provide application of graphdiyne in detection of small molecular substances as a MALDI matrix, and overcomes the defect that a small molecular sample cannot be effectively analyzed due to the fact that a matrix background interference phenomenon is easily generated in a low molecular weight region by a common organic small molecular matrix.
The invention provides application of graphdiyne in detection of micromolecule substances with a mass-to-charge ratio of 0-1000 as a matrix-assisted laser desorption ionization mass spectrometry matrix.
In the above application, the mass spectrometer mass analyzer used in the matrix-assisted laser desorption ionization mass spectrometry is not limited, and in the embodiment of the present invention, the matrix-assisted laser desorption ionization mass spectrometry is a matrix-assisted laser desorption ionization time-of-flight mass spectrometry, that is, the mass analyzer used is a time-of-flight mass analyzer.
In the above application, the small molecule substance may be any substance detectable by matrix-assisted laser desorption ionization mass spectrometry, including but not limited to amino acids, oligopeptides, small molecule drugs, uric acid, rutin, bisphenol a or tetrabromobisphenol a. Specifically, the small molecule drug can be an anticancer drug, a hormone drug or a drug for treating dementia. More specifically, the anticancer drug may be doxorubicin hydrochloride; the hormone drug can be estradiol or ethinyl estradiol; the dementia treating drug may be huperzine A.
In the application, the sample to be detected of the matrix-assisted laser desorption ionization mass spectrometry can be a micromolecular solution, human serum, human urine, a plant extract or a material extract.
In the application, the sample to be detected is a small molecule solution or human serum; the ratio of the graphdiyne to the small molecular substance may be (0.05-0.2) g: (0.005-1) mmol, preferably 0.1 g: (0.005-1) mmol. Specifically, the ratio of the graphdiyne to the small molecule species may be 0.1 g: (0.01-1) mmol, 0.1 g: 1mmol, 0.1 g: 0.5 mmol.
The graphdiyne can be mixed with a sample to be detected in the form of graphdiyne dispersion liquid; the mass volume concentration of the graphite alkyne dispersion liquid can be 0.05-0.2 mg/mL, and preferably 0.1 mg/mL. The solvent of the graphite alkyne dispersion liquid can be any solvent capable of dispersing graphite alkyne; specifically, the solvent of the graphdine dispersion may be an aqueous solution of PEG 2000; more specifically, the PEG2000 aqueous solution may have a mass volume concentration of 0.1 mg/mL. The concentration of the small molecule substance may be 0.005-1 mM, such as 0.5mM, 1 mM. The volume ratio of the matrix solution to the sample to be tested may be 1: 1.
when the matrix-assisted laser desorption ionization time-of-flight mass spectrometer is used for detecting small molecular substances, the invention selects an anion mode, and the operating conditions are as follows: the acceleration voltage is 20kv, the delay extraction voltage is 17.7kv, the reflector voltage is 21.10kv, the lens voltage is 6.4kv, the frequency is 1000Hz, the laser energy is 20%, and the accumulation times are 500 times.
The invention has the following beneficial effects:
the invention overcomes the defect that the common organic micromolecule matrix is easy to generate matrix background interference phenomenon in a low molecular weight region, thereby causing the failure of effectively analyzing micromolecule samples. The matrix adopted by the invention does not need to be added with an ionizing reagent, so that the requirement on sample treatment is reduced; the background interference is small in the test range (m/z 0-1000), and various complex mixed systems can be analyzed; stable property, convenient storage and use, and easy synthesis.
Drawings
FIG. 1 is a flow chart of the detection of a sample according to an embodiment of the present invention.
Fig. 2 is a background image of a graphdine matrix.
FIG. 3 is a mass spectrometric detection of a mixture of four oligopeptides using graphdiyne as a matrix.
FIG. 4 is a mass spectrometric detection of serum using graphdine as a matrix.
Figure 5 is a mass spectrometric image of urine using graphdine as a matrix.
FIG. 6 is a mass spectrometric and magnified view of a portion of the area of a test image of a plant extract using graphdine as a matrix.
FIG. 7 is a mass spectrometric detection of a paper extract using graphdiyne as a matrix.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The graphtylene used in the following examples is a carbon material having a two-dimensional planar network structure similar to graphene, which is formed by conjugating benzene rings by acetylene bonds, has the characteristics of a planar two-dimensional material, has the characteristics of a three-dimensional porous material, and has a high specific surface area, and is synthesized by the preparation method disclosed in Li, g.x., et al, Architecture of graphene nanoscales chemical Communications,2010.46(19): p.3256-3258. The synthetic process is simply expressed as follows: the graphyne is synthesized on the surface of copper through coupling of monomer hexaalkynyl benzene; the copper foil not only serves as a catalyst in the formation process of the graphdiyne, but also serves as a growth substrate for the graphdiyne.
The matrix-assisted laser desorption ionization mass spectrometry using the graphdine as the matrix is generally analyzed by a time-of-flight mass analyzer, but is compatible with other mass spectrometers in practical application. The matrix assisted laser desorption ionization time-of-flight mass spectrometer used in the examples described below was of the type UltraFlexTreme (Bruker).
Example 1 detection of Small molecule substance oligopeptide by graphite alkyne as MALDI-TOF MS matrix
The oligopeptide was detected according to the scheme shown in FIG. 1, and the specific steps were as follows:
(1) mixing the graphdiyne with a PEG2000 aqueous solution to obtain a matrix solution. The concentration of graphdine in the matrix solution was 0.1mg/ml and the PEG2000 concentration was 0.1 mg/ml.
(2) Oligopeptide mixed liquor is prepared as an analyte, the mixed liquor contains 4 oligopeptides which are respectively Gly-Ala, Gly-Asp, Gly-Glu and Gly-Leu-Tyr, and the concentration of each peptide is 1 mM.
(3) After mixing 1 μ L of analyte with 1 μ L of graphite alkyne matrix solution, 1 μ L of point target is taken, dried in the air and sent into a matrix-assisted laser desorption ionization time-of-flight mass spectrometer for detection. Selecting a negative ion mode, wherein the mass spectrum running conditions are as follows: the acceleration voltage is 20kv, the delay extraction voltage is 17.7kv, the reflector voltage is 21.10kv, the lens voltage is 6.4kv, the frequency is 1000Hz, the laser energy is 20%, and the accumulation times are 500 times.
The spectra obtained are shown in FIG. 2 (background) and FIG. 3. From the spectra, it can be seen that the matrix can be detected for the deprotonated peaks of the four peptides, and a higher intensity, signal-to-noise ratio and clean background are obtained. The method can avoid the interference of matrix to low-quality area.
Example 2 identification of doxorubicin hydrochloride in serum by graphdine as MALDI-TOF MS matrix
The method for detecting the doxorubicin hydrochloride in the serum according to the flow chart shown in fig. 1 comprises the following specific steps:
(1) mixing the graphdiyne with a PEG2000 aqueous solution to obtain a matrix solution. The concentration of graphdine in the matrix solution was 0.1mg/ml and the PEG2000 concentration was 0.1 mg/ml.
(2) A certain volume of normal human serum is taken and added with acetonitrile solution, and the volume ratio of the serum to the acetonitrile is 1: 2. Placing into a centrifuge for centrifugation (rotating speed of 3600rpm, time of 10 min). After centrifugation, the supernatant was collected and the precipitate was removed. Doxorubicin hydrochloride was added to the supernatant so that the concentration of doxorubicin hydrochloride in the finally obtained serum supernatant was 0.5 mM.
(3) And mixing 1 mu L of serum supernatant containing the doxorubicin hydrochloride with 1 mu L of the graphdine matrix solution, taking 1 mu L of mixed solution as a target, drying in the air, and detecting in a matrix-assisted laser desorption ionization time-of-flight mass spectrometer. Selecting a negative ion mode, wherein the mass spectrum running conditions are as follows: the acceleration voltage is 20kv, the delay extraction voltage is 17.7kv, the reflector voltage is 21.10kv, the lens voltage is 6.4kv, the frequency is 1000Hz, the laser energy is 20%, and the accumulation times are 500%. This method can avoid the interference of the substrate with the low-quality region.
The obtained spectrum is shown in FIG. 4, and it can be seen that the matrix can obtain higher intensity and signal-to-noise ratio and clean background for detecting doxorubicin hydrochloride in blood. The method can avoid the interference of matrix to low-quality area.
Example 3 identification of metabolites in urine by graphdiyne as MALDI-TOF MS matrix
The method for detecting metabolites in urine according to the flow chart shown in FIG. 1 comprises the following steps:
(1) mixing the graphdiyne with a PEG2000 aqueous solution to obtain a matrix solution. The concentration of graphdine in the matrix solution was 0.1mg/ml and the PEG2000 concentration was 0.1 mg/ml.
(2) Mixing 1 mu L of healthy adult urine with 1 mu L of graphite alkyne matrix solution, taking 1 mu L of point target from the mixture, and after the sample point is dried, entering a matrix-assisted laser desorption ionization time-of-flight mass spectrometer for detection. Selecting a negative ion mode, wherein the mass spectrum running conditions are as follows: the acceleration voltage is 20kv, the delay extraction voltage is 17.7kv, the reflector voltage is 21.10kv, the lens voltage is 6.4kv, the frequency is 1000Hz, the laser energy is 20%, and the accumulation times are 500 times.
The obtained spectrum is shown in FIG. 5. From the spectrum, the matrix can be easily detected for the deprotonation peak 167 of uric acid in urine, and higher intensity and signal-to-noise ratio are obtained. This method can avoid the interference of the substrate with the low-quality region. The method eliminates complicated pretreatment by simple operation.
Example 4 identification of Natural products in Clausena lansium leaves by use of graphdiyne as MALDI-TOF MS matrix
The method for detecting the doxorubicin hydrochloride in the serum according to the flow chart shown in fig. 1 comprises the following specific steps:
(1) mixing the graphdiyne with a PEG2000 aqueous solution to obtain a matrix solution. The concentration of graphdine in the matrix solution was 0.1mg/ml and the PEG2000 concentration was 0.1 mg/ml.
(2) Adding 519 μ L ethanol into 10.38mg Chinese wampee leaf, and performing ultrasonic treatment for 30min (power of 110W and frequency of 40KHz) to obtain green solution.
(3) mu.L of the green solution was mixed with 1. mu.L of the matrix, and 1. mu.L of the mixture was added to the MALDI target plate and sufficiently dried. And (3) sending the mixture into a matrix-assisted laser desorption ionization time-of-flight mass spectrometer for detection. Selecting a negative ion mode, wherein the mass spectrum running conditions are as follows: the acceleration voltage is 20kv, the delay extraction voltage is 17.7kv, the reflector voltage is 21.10kv, the lens voltage is 6.4kv, the frequency is 1000Hz, the laser energy is 20%, and the accumulation times are 500 times.
The obtained spectrum is shown in FIG. 6. The matrix can detect natural products in plant extract, and obtain high intensity, signal-to-noise ratio and clean background. The mass spectrum peak of mass-to-charge ratio at 609, 301 is the characteristic peak of rutin which is a common product in clausena lansium. The mass spectrum peak of the mass-to-charge ratio 201 in the spectrogram may be derived from the deprotonated peak of xanthotoxol which is a natural product in rutaceae plants. This method can avoid the interference of the substrate with the low-quality region. And the method is simple to operate, and avoids complex pretreatment.
Example 5 identification of bisphenol A in paper with graphdine as MALDI-TOF MS matrix
Detecting bisphenol A in paper according to a flow chart shown in figure 1, which comprises the following steps:
(1) mixing the graphdiyne with a PEG2000 aqueous solution to obtain a matrix solution. The concentration of graphdine in the matrix solution was 0.1mg/ml and the PEG2000 concentration was 0.1 mg/ml.
(2) Adding 3.24mg of thermal sensitive paper into a centrifuge tube, adding 648 μ L of methanol, performing ultrasonic treatment for 20min (power of 110W and frequency of 40KHz), and collecting the extractive solution.
(3) And mixing 1 mu L of extracting solution with 1 mu L of graphite alkyne matrix solution, drying the mixed solution of the analyte and the matrix in the air, and then, introducing the dried mixed solution into a matrix-assisted laser desorption ionization time-of-flight mass spectrometer for detection. Selecting a negative ion mode, wherein the mass spectrum running conditions are as follows: the acceleration voltage is 20kv, the delay extraction voltage is 17.7kv, the reflector voltage is 21.10kv, the lens voltage is 6.4kv, the frequency is 1000Hz, the laser energy is 20%, and the accumulation times are 500 times.
The resulting spectrum is shown in FIG. 7, from which it can be seen that the deprotonated peak 227 of bisphenol A can be detected with high intensity and high signal-to-noise ratio. And the method avoids complex pretreatment by simple operation.
Claims (8)
1. The application of the graphdiyne in detecting micromolecular substances with the mass-to-charge ratio of 0-1000 by using the graphdiyne as a matrix-assisted laser desorption ionization mass spectrum matrix;
the graphdiyne is synthesized on the copper surface by coupling of monomer hexaalkynyl benzene.
2. Use according to claim 1, characterized in that: the matrix-assisted laser desorption ionization mass spectrum is a matrix-assisted laser desorption ionization time-of-flight mass spectrum.
3. Use according to claim 1 or 2, characterized in that: the micromolecule substance is amino acid, oligopeptide, micromolecule medicine, uric acid, rutin, bisphenol A or tetrabromobisphenol A;
the small molecule drug is an anticancer drug, a hormone drug or a drug for treating dementia.
4. Use according to claim 3, characterized in that: the anti-cancer drug is doxorubicin hydrochloride; the hormone medicine is estradiol or ethinyl estradiol; the medicine for treating dementia is huperzine A.
5. Use according to claim 1 or 2, characterized in that: the sample to be detected of the matrix-assisted laser desorption ionization mass spectrometry is a small molecular solution, human serum, human urine or a material extracting solution.
6. Use according to claim 1 or 2, characterized in that: the sample to be detected of the matrix-assisted laser desorption ionization mass spectrum is plant extract.
7. Use according to claim 5, characterized in that: the sample to be detected is a small molecule solution or human serum; the ratio of the graphdiyne to the small molecular substance is (0.05-0.2) g: (0.005-1) mmol.
8. Use according to claim 1 or 2, characterized in that: mixing the graphdiyne with a sample to be detected in the form of graphdiyne dispersion liquid; the mass volume concentration of the graphite alkyne dispersion liquid is 0.05-0.2 mg/mL; the volume ratio of the graphite alkyne dispersion liquid to the sample to be detected is 1: 1.
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| CN101846650B (en) * | 2009-03-25 | 2012-12-05 | 中国科学院大连化学物理研究所 | Application of diamond-like carbon film used as matrix in laser desorption ionization mass spectra |
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| CN102426187A (en) * | 2011-11-21 | 2012-04-25 | 程金生 | Graphene matrix and application of graphene matrix in matrix-assisted laser desorption/ionization-time of flight-mass spectrometry detection |
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| CN103776892B (en) * | 2014-01-16 | 2014-12-17 | 陕西师范大学 | Matrix with selectivity for micromolecule MALDI-TOF MS (Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry) detection and application thereof |
| CN106814129A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院化学研究所 | Purposes and Mass Spectrometry detection method of the hexagonal boron nitride nanosheet in matrix solution is prepared |
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