CN109187713B - Loaded paper base, preparation method thereof, ion source and application thereof - Google Patents
Loaded paper base, preparation method thereof, ion source and application thereof Download PDFInfo
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- CN109187713B CN109187713B CN201811206822.XA CN201811206822A CN109187713B CN 109187713 B CN109187713 B CN 109187713B CN 201811206822 A CN201811206822 A CN 201811206822A CN 109187713 B CN109187713 B CN 109187713B
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Abstract
The application relates to a loaded paper base, a preparation method thereof, an ion source and application thereof. Wherein, the load paper base comprises a blank paper base and the alkali metal salt loaded on the blank paper base. The ion source takes the loaded paper base as a carrier, when the ion source is used for detecting carbohydrate compounds by paper spray mass spectrometry, alkali metal adduct ions with high selectivity and high abundance can be formed, ionization of other background components is also obviously inhibited, and the ion source has higher selectivity and anti-interference capability compared with electrospray ionization.
Description
Technical Field
The invention relates to the technical field of sugar chemistry and mass spectrometry, in particular to a loaded paper base, a preparation method thereof, an ion source and application thereof.
Background
Carbohydrate compounds, one of the most important biological macromolecules (proteins, nucleic acids, polysaccharides, lipids), have important biological significance and complex structural diversity, and their analysis has been very challenging. At present, there are many qualitative and quantitative analysis methods for carbohydrate compounds, such as: nuclear Magnetic Resonance (NMR), High Performance Liquid Chromatography (HPLC), infrared spectroscopy (IR), Mass Spectroscopy (MS), and the like. Among them, mass spectrometry is the most commonly used method. By using tandem mass spectrometry, high resolution mass spectrometry, particle mobility mass spectrometry, and the like, carbohydrate compounds of different configurations can be characterized. Ionization, which is the most fundamental part of sugar mass spectrometry, determines the success or failure of the overall analysis process. With respect to ionization, the most commonly used mass spectrometry ion sources include: electrospray, fast atom bombardment, matrix-assisted laser desorption, and the like. The ionizing action of carbohydrate compounds in such ion sources is typically manifested as proton addition, alkali metal addition, and the like. However, the specificity of alkali metal ion addition is not high, because such ion sources cannot introduce high-concentration salt, the formation of high-selectivity and high-abundance alkali metal addition is inhibited, and the analysis of the carbohydrate cannot embody the specificity of alkali metal addition despite the alkali metal addition characteristics. Because, mass spectrometry of multiple ions such as [ M + H ]]+，[M+Na]+And [ M + K]+) And the existence of the method causes the spectrogram to be more complex and the qualitative and quantitative effects to be influenced.
However, in many ion sources, particularly electrospray ion sources, the salt tolerance is low. Because the electrospray ion source has low tolerance to salt and the ionization is easily affected by solution ions such as inorganic salt and buffer, the ionization of the saccharide compound is inhibited under the condition of high-concentration salt, and salt cluster ions and a plurality of alkali metal adduct ions appear, so that single high-selectivity metal adduct ions cannot be formed.
Disclosure of Invention
Based on this, this application provides a load paper base, this load paper base through load the alkali metal salt and be used for paper spraying mass spectrum in the blank paper base to analyze carbohydrate, can form high selectivity, high abundant alkali metal adduct ion, specific technical scheme is as follows:
a loaded paper base comprises a blank paper base and an alkali metal salt loaded on the blank paper base.
In one embodiment, the mass content of the alkali metal salt in the supporting paper base is 0.01-30%.
In one embodiment, the alkali metal in the alkali metal salt is selected from at least one of lithium, sodium, potassium, rubidium, and cesium.
In one embodiment, the alkali metal salt is at least one selected from lithium sulfate, sodium sulfate, potassium sulfate, cesium nitrate, and rubidium nitrate.
The application also provides a preparation method of the load paper base, and the specific technical scheme is as follows:
a preparation method of a loaded paper base comprises the following steps:
providing a blank paper substrate and an alkali metal salt solution;
and immersing the blank paper base into the alkali metal salt solution, performing ultrasonic impregnation, and drying to obtain the load paper base.
In one embodiment, the drying method comprises the following steps: drying at 100-110 deg.c.
In one embodiment, the ultrasonic immersion time is 30-60 minutes.
The application also provides an ion source, and the specific technical scheme is as follows:
an ion source, the carrying paper base of any one of the above is used as a carrier.
The application also provides an application of the ion source, and the specific technical scheme is as follows:
the ion source is applied to the detection of paper spray mass spectrum samples.
In one embodiment, the sample is a carbohydrate.
The paper spray ionization technology is a novel normal-pressure ionization source developed in recent years, a triangular paper base is used as a carrier, a sample is loaded on the paper base, target molecules reach a paper tip under the driving of an electric field by applying high voltage, electrospray is formed by instant gasification, the sample is ionized and then enters a mass spectrum for analysis, real-time online detection is realized, the process is simple and efficient, and the analysis cost is low. The inventor of the present application has made a great deal of attempts to solve the problems of possible ionization behaviors of saccharides (usually expressed as proton addition, alkali metal addition, etc.) and poor salt tolerance of electrospray mass spectrometry, and the like, and based on the ionization mode of paper spraying, the results are not satisfactory, and until the discovery is discovered by chance, when the ion source using the supported paper base as the carrier is used for detecting saccharides by paper spraying mass spectrometry, alkali metal addition ions with high selectivity and high abundance can be formed, and ionization of other background components is also significantly inhibited, so that compared with electrospray ionization, the ionization has higher selectivity and anti-interference capability.
Drawings
FIG. 1 is a spectrum of a paper-loaded substrate prepared in example 1 for analyzing three sugar mixtures of ribose, fructose and maltose by paper spray mass spectrometry;
FIG. 2 is a graph of the loaded paper substrate prepared in example 2 used for paper spray mass spectrometry analysis of fructose;
FIG. 3 is a graph of the loaded paper substrate prepared in example 2 used for paper spray mass spectrometry for verbascoside;
FIG. 4 the paper base loaded with the preparation of example 1 is used for the paper spray mass spectrometry of the spectrum of the Codonopsis pilosula extract;
FIG. 5 is a graph of the loaded paper substrate prepared in example 1 used for paper spray mass spectrometry of ginseng extract;
FIG. 6 is a graph of the loaded paper substrate prepared in example 1 used for paper spray mass spectrometry of honey (crown garden);
FIG. 7 is a spectrum of the loaded paper substrate prepared in example 1 for paper spray mass spectrometry of blood samples (whole blood of pregnant women);
FIG. 8 is a chart of three sugar mixtures for analyzing ribose, fructose and maltose by paper spray mass spectrometry, wherein the alkali metal salt solution is directly mixed with a sample.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The ion source of one embodiment takes a supported paper base as a carrier, and the supported paper base comprises a blank paper base and an alkali metal salt supported on the blank paper base.
Wherein the blank paper base is chromatographic paper. Further, the blank paper base is chromatographic paper after methanol ultrasonic treatment.
It is understood that the sonication with methanol is mainly for the purpose of removing impurities.
Further, the alkali metal in the alkali metal salt is at least one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs).
Further, the alkali metal salt is at least one selected from the group consisting of lithium sulfate, sodium sulfate, potassium sulfate, rubidium nitrate and cesium nitrate.
Furthermore, the mass content of the alkali metal salt in the loaded paper base is 0.01-30%. Furthermore, the mass content of the alkali metal salt in the loaded paper base is 1-5%.
The ion source is used for detecting the saccharide compounds by paper spray mass spectrometry, and alkali metal adduct ions with high selectivity and high abundance can be formed.
Specifically, the saccharide compounds include monosaccharide, polysaccharide, oligosaccharide, glycoside, glycopeptide, etc., and their derivatives and glycoconjugates.
The ion source is used for detecting the saccharide compounds by paper spray mass spectrometry, has high structure selectivity and high sensitivity, and can effectively inhibit the ionization of non-saccharide components, thereby further improving the sensitivity of the ion source.
The application also provides a preparation method of the load paper base, which comprises the following steps of S110-S120:
s110, providing a blank paper base and an alkali metal salt solution.
The preparation method of the alkali metal salt solution comprises the following steps: and (3) putting the alkali metal salt into a centrifuge tube, adding deionized water, and fully oscillating by using a vortex oscillator to obtain an alkali metal salt solution.
And S120, immersing the blank paper base into an alkali metal salt solution, and carrying out ultrasonic impregnation and drying to obtain the loaded paper base.
Furthermore, the ultrasonic immersion time is 30-60 minutes.
Further, the drying method comprises the following steps: drying at 100-110 deg.c.
Drying at 100-110 ℃ can ensure that free water and bound water can be completely removed, thereby ensuring the accuracy of an analysis result.
It should be noted that the supporting paper base can be cut into an isosceles triangle for paper spray mass spectrometry. Wherein the ratio of the bottom edge to the height of the isosceles triangle is 1: 2.
Or the paper base to be modified can be firstly cut into an isosceles triangle, then the isosceles triangle is immersed in the alkali metal salt solution, and finally the prepared load paper base is used for paper spray mass spectrometry.
According to the preparation method of the load paper base, the blank paper base is immersed into the alkali metal solution, and then ultrasonic impregnation and drying are carried out, so that the alkali metal salt can be effectively loaded on the blank paper base.
In addition, because the blank paper base is directly immersed into the alkali metal salt solution, the mass content of the alkali metal salt in the paper base can be flexibly and accurately controlled.
In addition, the alkali metal salt is loaded on the blank paper base by the method, so that the equipment can be prevented from being blocked by the salt, and the service life of the equipment can be prolonged.
The following are specific examples.
Example 1
Putting the alkali metal salt into a centrifuge tube, adding deionized water, and fully oscillating by a vortex oscillator to obtain about 0.01mol/L alkali metal salt aqueous solution.
And (3) immersing the blank paper base into the alkali metal salt aqueous solution, ultrasonically immersing for 50 minutes, and drying at 100 ℃ to obtain a loaded paper base with a uniform surface, wherein the mass content of the alkali metal salt in the loaded paper base is 1-5%.
Respectively preparing a sodium sulfate loaded paper base, a lithium sulfate loaded paper base, a potassium sulfate loaded paper base, a rubidium nitrate loaded paper base and a cesium nitrate loaded paper base according to the method, respectively cutting the loaded paper bases into isosceles triangles with the bottom side length of 5mm and the height of 10mm, and using the isosceles triangles for paper spray mass spectrometry.
Wherein, three kinds of sugar of ribose, fructose and maltose are mixed and labeled, and the detection conditions are as follows:
in the positive scanning mode, the extractor voltage is 3V, the RF lens voltage is 0.5V, the source temperature is 105 ℃, the full scanning mode is adopted, the mass scanning range is 100-800Da, the taper hole voltage is respectively set to 30V and the spray voltage is respectively set to 3.5 kV.
The results of the detection are shown in FIG. 1.
The detection conditions of the codonopsis pilosula medicinal material extract are as follows:
in the positive scanning mode, the extractor voltage is 3V, the RF lens voltage is 0.5V, the source temperature is 105 ℃, the full scanning mode is adopted, the mass scanning range is 100-800Da, the taper hole voltage is respectively set to 50V and the spray voltage is respectively set to 3.5 kV.
The results of the detection are shown in FIG. 4.
The detection conditions of the ginseng medicinal material extract are as follows:
in the positive scanning mode, the extractor voltage is 3V, the RF lens voltage is 0.5V, the source temperature is 105 ℃, the full scanning mode, the mass scanning range is 400-1500Da, the taper hole voltage is 50V and the spray voltage is 3.5kV respectively.
The results of the detection are shown in FIG. 5.
The detection conditions of honey (Guanshengyuan) are as follows:
in the positive scanning mode, the extractor voltage is 3V, the RF lens voltage is 0.5V, the source temperature is 105 ℃, the full scanning mode, the mass scanning range is 150-.
The results of the detection are shown in FIG. 6.
The test conditions of the blood sample (whole blood of pregnant woman) were as follows:
in the positive scanning mode, the extractor voltage is 3V, the RF lens voltage is 0.5V, the source temperature is 105 ℃, the full scanning mode, the mass scanning range is 150-.
Dropwise adding 2-3 mu L of frozen whole blood onto blank paper/alkali metal loaded paper, then placing a sample prepared from the blood in a room-temperature ventilated place for drying for 3h, and after the blood sheet is fully dried, carrying out ZQ2000 analysis.
The results of the detection are shown in FIG. 7.
Example 2
The paper base modified by the sodium sulfate, the lithium sulfate, the potassium sulfate, the rubidium nitrate and the cesium nitrate together is prepared according to the method of the embodiment 1, and the loaded paper base is cut into isosceles triangles with the bottom side length of 5mm and the height of 10mm, and the isosceles triangles are respectively used for paper spray mass spectrometry.
Wherein, the fructose detection conditions are as follows:
in the positive scanning mode, the extractor voltage is 3V, the RF lens voltage is 0.5V, the source temperature is 105 ℃, the full scanning mode, the mass scanning range is 150-.
The results of the detection are shown in FIG. 2.
The detection conditions for verbascoside are as follows:
in the positive scanning mode, the extractor voltage is 3V, the RF lens voltage is 0.5V, the source temperature is 105 ℃, the full scanning mode, the mass scanning range is 600- & ltSUB & gt 1000Da, & ltSUB & gt, the taper hole voltage is respectively set to 30V and the spray voltage is respectively set to 3.5 kV.
The results of the detection are shown in FIG. 3.
Comparative example 1
Putting the alkali metal salt into a centrifuge tube, adding deionized water, and fully oscillating by a vortex oscillator to obtain about 0.01mol/L alkali metal salt aqueous solution. The alkali metal salt solution was directly mixed with the sample and used as a standard for paper spray mass spectrometry analysis of three kinds of sugars, ribose, fructose, and maltose, and the results are shown in fig. 8.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A supporting paper base, which is characterized by comprising a blank paper base and an alkali metal salt supported on the blank paper base; the blank paper base is chromatographic paper subjected to methanol ultrasonic treatment;
the supported paper base is used as a carrier of an ion source for detecting carbohydrate compounds by paper spray mass spectrometry.
2. The loaded paper base according to claim 1, wherein the mass content of the alkali metal salt in the loaded paper base is 0.01-30%.
3. The loaded paper substrate of claim 1 or 2, wherein the alkali metal of the alkali metal salt is selected from at least one of lithium, sodium, potassium, rubidium, and cesium.
4. The loaded paper substrate according to claim 3, wherein the alkali metal salt is at least one selected from the group consisting of lithium sulfate, sodium sulfate, potassium sulfate, rubidium nitrate, and cesium nitrate.
5. The preparation method of the loaded paper base according to any one of claims 1 to 4, characterized by comprising the following steps:
providing a blank paper substrate and an alkali metal salt solution;
and immersing the blank paper base into the alkali metal salt solution, performing ultrasonic impregnation, and drying to obtain the load paper base.
6. The method for preparing the loaded paper substrate according to claim 5, wherein the drying method comprises the following steps: drying at 100-110 deg.c.
7. The preparation method of the loaded paper base according to claim 5, wherein the ultrasonic impregnation time is 30-60 minutes.
8. An ion source, which is characterized in that the supported paper base of any one of claims 1-2 is used as a carrier, and the ion source is used for detecting carbohydrate compounds by paper spray mass spectrometry.
9. Use of the ion source of claim 8 in paper spray mass spectrometry sample detection.
10. Use of an ion source according to claim 9 in the detection of a sample, wherein the sample is a carbohydrate.
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| CN1226619C (en) * | 2003-03-20 | 2005-11-09 | 华中科技大学同济医学院附属同济医院 | Method for detecting organic acid/amino acid metabolic product by filter paper shect gas chromatography-mass spectrum analysis |
| CN101015391A (en) * | 2007-03-08 | 2007-08-15 | 云南烟草科学研究院 | Composite additive for reducing harmful constituents in cigarette smoke gas and use thereof |
| CN102414778B (en) * | 2009-04-30 | 2016-03-16 | 普度研究基金会 | Moist porous material is used to produce ion |
| CN101614673A (en) * | 2009-07-21 | 2009-12-30 | 北京智云达科技有限公司 | Test paper of nitrite and preparation method thereof in a kind of fast detecting food |
| CN102236005B (en) * | 2011-04-18 | 2014-06-18 | 林维宣 | Method for detecting residual quantity of multiple polypeptidepolypeptide veterinary drugs in animal-derived food |
| CN103018450B (en) * | 2011-09-20 | 2016-03-30 | 北京勤邦生物技术有限公司 | A kind of preparation method of chemical luminescence ELISA detection kit of chloromycetin |
| CN103499632A (en) * | 2013-09-17 | 2014-01-08 | 中国广州分析测试中心 | Paper-based electrospray ionization mass spectrometry fingerprint technology and construction method thereof |
| US10395913B2 (en) * | 2013-12-30 | 2019-08-27 | Purdue Research Foundation | Mass spectrometry probes and systems for ionizing a sample transport |
| EP3090252A4 (en) * | 2014-01-05 | 2017-08-30 | Board of Regents, The University of Texas System | Methods and systems for the electrochemical detection of analytes |
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| CN104502333A (en) * | 2014-12-05 | 2015-04-08 | 苏州国环环境检测有限公司 | Method for rapidly detecting chloride ion concentration in water |
| US20160313311A1 (en) * | 2015-04-24 | 2016-10-27 | The Regents Of The University Of California | Label-free detection of macromolecules binding to compound libraries |
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Application publication date: 20190111 Assignee: Hunan Hanmiao Technology Co.,Ltd. Assignor: HUNAN NORMAL University Contract record no.: X2023980033665 Denomination of invention: Loaded paper base, preparation method, ion source, and application thereof Granted publication date: 20201222 License type: Common License Record date: 20230316 |