CN102980796A - Sample preparation method for mass spectrometry - Google Patents
Sample preparation method for mass spectrometry Download PDFInfo
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Abstract
The invention provides a sample preparation method for mass spectrometry, aiming to solve the problems of non-ideal detection sensitivity and poor resistance to interference in the field of environmental mass spectrometry. The method comprises the following steps of placing a mixed solution of a sample or specimen and a solvent on chromatography paper, wherein the chromatography paper has an end portion with the width shrunk gradually; performing paper chromatography operation, placing the chromatography paper in a developing solvent to make the sample move toward the end portion of the chromatography paper along with the developing solvent and enrich at the end portion of the chromatography paper; and placing the end portion of the chromatography paper at a detection point of a desorption ionization ion source in a mass spectrometer so as to be desorbed and ionized.
Description
Technical field
The present invention relates to paper chromatography and mass spectrometry combination method, especially relate to a kind of sample preparation methods of mass spectrophotometry.
Background technology
Environment ionization (Ambient Ionization), in recent years development rapidly, wherein with desorption electrospray ionization (DESI " Science ", the 306th volume, 471 pages (2004)) and direct real-time analysis (DART, " Analytical Chemistry " magazine, the 77th volume, 2297 pages (2005)) the most representative.Environment for use MALDI-MS coupling technique is analyzed micro-object, does not need or the only simple sample preparation of need, shows good application potential in sample express-analysis field.So far, multiple kinds of energy carrier such as charged drop, plasma, ultraviolet ray, sharp light and heat have been used on the environment ionization technique.Wherein, desorb corona beam technology of ion source (DCBI " Analyst " magazine, the 135th volume, 688 pages (2010)) is simple and efficient and convenient characteristics of locating with it, become under the application that the certain space resolution requirement is arranged and well select.
Environment MALDI-MS technology can realize the express-analysis to urine, saliva, blood plasma, skin and hair usually, but still has in actual applications following several problem: be difficult to get rid of the interference that impurity brings in the complex matrices; Sample concentration is crossed detection difficult when hanging down, and sensitivity is low; Desorption efficiency is low in part matrix.
(Paper Spray in the paper spray technique of the people such as R.G.Cooks report, " Angewandte Chemie " magazine, the 122nd volume, 889 pages (2010)), dc high voltage directly is added on the triangle filter paper, when analyte solution dropped on the filter paper, electron spray will occur at the tip of filter paper under the applying high voltage effect, thereby realized the ionization to the molecule that contains polar functional group.This utilization triangle filter paper is most advanced and sophisticated promotes electron spray, and can remove to a certain extent the indissoluble thing to the interference of electron spray process, its method is simple, sample need not pre-treatment.This technology has been used to do the analysis and research of blood sample, characteristics with dynamic outflow sample, but it is relatively poor that sample and the separating power of impurity are compared with methods such as conventional thin layer chromatographies, and for example the trace medicine in the sample generally can not well separate with blood sample matrix with metabolic product; When it sprayed from the paper spraying is most advanced and sophisticated simultaneously, the Ionization Efficiency of medicine can be produced strong depression effect by substrate competition.Simultaneously, similar to other technology based on electron spray, the paper spraying is relatively difficult to the ionization of low pole and nonpolar medicine and metabolic product.
In order further to improve sensitivity and the selectivity of environment ionization source, people have attempted using thin-layered chromatography (TLC) and paper chromatography (PC) and its coupling.For example, electron spray assisted laser desorption ionisation (ELDI at Xie Jiantai, " Analytical Chemistry " impurity, the 79th volume, 8789 pages (2007)) in the technology, they have used the pre-separation means of thin-layer chromatography (TLC) as sample, and sample separates at the TLC plate, and the correspondence position after separation is by laser desorption.Under normal conditions, what traditional TLC or PC adopted is rectangular slab, by regulating the polarity of developping agent, makes sample band after the expansion between upper sampling point and solvent front, R
fValue is between 0.1 and 0.8.Yet eddy current and molecular diffusion make analyte district band broadening, and this causes target analytes to be diluted and affects quantitative test.Another shortcoming is, when analyte lacked chromophore, analyte district band was that naked eyes are sightless, and this is so that be difficult to position when carrying out desorb.Although can take dyeing to wait the processing means that as seen analyte district band is become, this will make prolong analysis time; In addition, the structure of analyte may make the Mass Spectrometer Method difficult processed middle destruction.
Therefore, the sample preparation technology of developing a kind of simple and easy effective collection sample separation, enrichment and being easy to advantages such as locating will be expanded environment ionization effectively in the application in express-analysis field.
Summary of the invention
For the problems referred to above, the invention provides a kind of sample preparation methods that the environment MALDI-MS is analyzed that is adapted to, the method can be used for the Direct Analysis of microanalysis thing in the complex matrices, solves the problem that environment mass spectrophotometry field detection sensitivity is undesirable, antijamming capability is weak.
The present invention proposes a kind of sample preparation methods of mass spectrophotometry, comprises following steps: the mixed liquor of sample or sample and solution is placed on the chromatographic paper, and this chromatographic paper has the end that a width shrinks gradually; Carry out the paper chromatography operation, chromatographic paper is placed developping agent, sample is moved to the end of chromatographic paper with developping agent, and in the enrichment of the end of chromatographic paper; And the end of chromatographic paper placed the ionogenic check point of desorption ionization of mass spectrometer, to be desorbed ionization.
In one embodiment of this invention, described chromatographic paper is triangle, and described end is a leg-of-mutton angle.In one embodiment, the subtended angle scope of described end is between 15～45 degree.
In another embodiment of the present invention, described chromatographic paper is trapezoidal, described end be trapezoidal upper base institute at one end.In one embodiment, the width of described upper base is less than 5mm.
In one embodiment of this invention, described chromatographic paper is qualitative filter paper.In another embodiment of the present invention, described chromatographic paper is chromatography filter paper.
In one embodiment of this invention, described desorption ionization ion gun uses the desorption electrospray method.
In one embodiment of this invention, the ionogenic desorption method of described desorption ionization has comprised one or more in thermal desorption means, laser desorption means, the sound wave desorb means.
In one embodiment of this invention, described desorption ionization ion gun makes the alpha bombardment method.
In one embodiment of this invention, the ionogenic ionization method of described desorption ionization has comprised ionization means that photoionization means, chemi-ionization means, electron spray droplet and desorbing neutral molecule merge, in the thermal ionization means one or more.
In one embodiment of this invention, said method carries out the drying processing to described chromatographic paper before also being included in desorption ionization.
In one embodiment of this invention, said method comprises that also the disengaging time of controlling paper chromatography shifts at least a sample to be analyzed and is enriched near the check point.
In one embodiment of this invention, before said method also was included in desorption ionization, the part that will be positioned at the outer chromatographic paper of described check point was removed, and adsorbed impurity on this part chromatographic paper to mass spectrum result's negative effect to reduce.
In one embodiment of this invention, said method also comprises according to analyte to be adjusted the composition of employed developping agent, so that described sample is with the developping agent Front movement.
Method proposed by the invention is compared advantage with known the whole bag of tricks and is, sample is after simple the extraction, directly gained fluid sample or the mixed liquor that comprises sample are used for paper chromatographic analysis, analyte separates with main chaff interference and in the enrichment of chromatographic paper end behind chromatography.To the evidence of this end, this method can Realization analysis the enrichment of matter sample and the purpose of removing main chaff interference, improve the sensitivity of determinand more than 30 times.
Description of drawings
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, below in conjunction with accompanying drawing the specific embodiment of the present invention is elaborated, wherein:
Fig. 1 is the method flow diagram of one embodiment of the invention.
Fig. 2 A-2D is the operation chart of the flow process of one embodiment of the invention.
Fig. 3 A is in one embodiment of the invention, the contained chlorpheniramine of cold drug tablet behind the triangle filter paper chromatography, the mass spectrogram that after the ionization of DCBI ion gun, obtains at the filter paper tip.
Fig. 3 B and Fig. 3 C are the reference examples mass spectrogram of Fig. 3 A.
Fig. 4 is in one embodiment of the invention, the contained melamine of milk powder behind the triangle filter paper chromatography, the mass spectrogram that after the ionization of DCBI ion gun, obtains at the filter paper tip.
Fig. 5 is in one embodiment of the invention, the alkaloid that urine sample is added behind the triangle filter paper chromatography, the mass spectrogram that after the ionization of DCBI ion gun, obtains at the filter paper tip.
Embodiment
Summarily say, the invention provides a kind of sample preparation methods that the environment MALDI-MS is analyzed that is applicable to.The method combines the steps such as sample extraction, impurity separation and enrichment of analytes, can be used for the Direct Analysis of microanalysis thing in the complex matrices, solves the difficult problem that environment mass spectrophotometry field detection sensitivity is undesirable and antijamming capability is weak.
Fig. 1 is the method flow diagram of one embodiment of the invention.Fig. 2 A-2D is the operation chart of the flow process of one embodiment of the invention.
With reference to shown in Figure 1, the method according to this invention at first in step S11, provides sample to be detected.This sample can be solid sample or fluid sample.
For solid sample, sample can be become mixed liquor with solvent, mixed liquor can be solution or suspension.A kind of method of making the mixed liquor of solid sample is, takes by weighing a small amount of solid sample to be analyzed in the disposable plastic centrifuge tube, adds two steel balls and an amount of solvent, behind the cover lid, in shaking on the bowl mill sample carried out fragmentation.For fluid sample, sample can be become mixed liquor with solvent, also can directly use fluid sample and not with solvent.A kind of method of making the mixed liquor of fluid sample is, takes by weighing a small amount of fluid sample to be analyzed in the disposable plastic centrifuge tube, adds an amount of solvent, mixes.
Then, at step S12, draw sample, perhaps the mixed liquor of sample and solvent places on the chromatographic paper.At this, chromatographic paper has an end at least, and this end has the shape that width shrinks gradually.The typical shape of chromatographic paper is triangle, gets an one angle as the end, and the scope at this angle is 15～45 degree.Other examples of chromatographic paper also can be trapezoidal, get its upper base institute at one end as the end, and upper base length is less than 5mm.In general, the antijamming capability of triangle or trapezoidal chromatographic paper is similar, but the former will be higher than the latter to the enrichment times of analyte.
In an embodiment of the present invention, chromatographic paper 21 can be qualitative filter paper, its exemplary aperture 5-20 μ m, exemplary thickness 80-200 μ m.Chromatographic paper 21 can also be chromatography filter paper, its exemplary aperture 5-20 μ m, exemplary thickness 80-200 μ m.Both do not have significant difference in performance.
Fig. 2 A illustrates leg-of-mutton chromatographic paper 21, and this chromatographic paper 21 is isosceles triangle, bottom width 1-2cm, and high 3-4cm gets its drift angle 22 and is aforesaid end.Fig. 2 B illustrates the operation chart of step S12, in Fig. 2 B, gets 10 to 20 microlitre fluid samples or comprises solid or the mixed liquor of fluid sample 23, along evenly dripping apart from chromatographic paper 21 bases 1 centimeters.
Then, at step S13, carry out the paper chromatography operation.Chromatographic paper is placed developping agent, analyte is moved towards chromatographic paper 21 ends with developping agent, and in end that the width of chromatographic paper 21 zooms in and enrichment.
In step S13, the composition of employed developping agent can be adjusted according to analyte is different, so that analyte can be with the developping agent Front movement.Analyte finally is compressed in solvent front along with solvent front moves, and the analyte that has been caused by molecular diffusion or target analytes hangover when having avoided the conventional paper chromatography is diluted at paper.
Fig. 2 C illustrates the exemplary operation of step S13.Shown in Fig. 2 C, chromatographic paper 21 inserted in chromatography cylinder 24, carry out chromatography, used developping agent is the mixed solution of multi-solvents, usually be comprised of one or more intensive polar solvents (such as acetic acid esters, ethanol, methyl alcohol etc.) and one or more weak polar solvents (such as normal hexane, methylene chloride, chloroform, sherwood oil etc.), the polarity of solvent can be by changing the ratio adjustment of intensive polar solvent and weak polar solvent.The purpose of adjusting the polarity of developping agent is to make analyte with the developping agent Front movement, for achieving this end, to the partial analysis thing, also need in developping agent, to add an amount of alkali (such as triethylamine, ammoniacal liquor etc.) or acid (such as formic acid, hydrochloric acid, acetic acid, trifluoroacetic acid etc.).
At last, at step S14, the chromatographic paper end is placed the ionogenic check point of desorption ionization of mass spectrometer.At this, the sample that is enriched in this end will be desorbed attached and ionization generation ion, and obtain its mass spectrum.Compare with more traditional paper chromatography, the method is enriched in the chromatographic paper end with target analytes, is easy to desorption ionization ion gun check point to the location of analyte.
In another embodiment of the present invention, before the mass spectrophotometry step, can also carry out drying to chromatographic paper 21 and process.
In preferred embodiment of the present invention, can control the disengaging time of paper chromatography, at least a sample to be analyzed is shifted be enriched near the check point.And, in a preferred embodiment, can be before mass spectrophotometry, the part that will be positioned at the outer chromatographic paper of check point is removed, to reduce the impurity that adsorbs on this part chromatographic paper to mass spectrum result's negative effect.
In an embodiment of the present invention, desorption method in the desorption ionization ion gun can be one or more of desorption electrospray method, thermal desorption means, laser desorption means, sound wave desorb means kind, and ionization method can be for particle bombardment method, photoionization means, chemi-ionization means, use electron spray droplet and the ionization means of desorbing neutral molecule fusion, in the thermal ionization means one or more.
Fig. 2 D illustrates the exemplary operation of step S14.Shown in Fig. 2 D, exemplary desorption ionization ion gun can have helium entrance 25, heating tube 26, helium hollow needle point outlet 27, high-voltage power supply 28, to electrode 29 etc.
The advantage of method proposed by the invention is, sample is after simple the extraction, need not centrifugal, directly with the gained fluid sample or the mixed liquor that comprises (solid or liquid) sample be used for paper chromatographic analysis, analyte separates with main chaff interference (such as matrix) and in the enrichment of chromatographic paper end behind chromatography.And this has will be placed in after end of enrichment of analyte and carries out desorption ionization in the environment ionization source, and the ion of generation will be admitted to mass spectrometer analysis.Evidence, this method can Realization analysis the enrichment of matter sample and the purpose of removing main chaff interference, improve the sensitivity of determinand more than 30 times.In sum, this method has fast, cheap, antijamming capability reaches by force highly sensitive advantage.
The below illustrates sample preparation methods of the present invention more in conjunction with specific embodiments.
Embodiment 1
Take by weighing 10 milligrams of cold drug tablets (volume 1.5ml) in the disposable plastic centrifuge tube, add two steel balls and 1.0 milliliters of ethanol, behind the cover lid, on the vibrations bowl mill, sample is carried out fragmentation, extract the target analytes chlorpheniramine.Getting 10 microlitre gained suspensions evenly drips along distance isosceles triangle filter paper (shown in Fig. 2 A) base 1.0 centimeters.
Carry out paper chromatography.Used developping agent is the water saturated ethyl acetate of ammonia, and developping agent is climbed to the tip by isosceles triangle filter paper bottom and approximately needed 3 minutes.After developping agent launches, the chlorpheniramine that is added in the cold drug tablet is enriched in triangle filter paper tip, this tip is placed under the ionogenic plasma probe of DCBI, target analytes desorb and ionization from the filter paper, the ion that produces is analyzed by single quadrupole mass spectrometer (2010EV), and the gained spectrogram is shown in Fig. 3 A.
In contrast, directly on cold drug tablet surface the target analytes chlorpheniramine is carried out desorb and ionization with the DCBI ion gun, the gained spectrogram is shown in Fig. 3 B.Extract is dropped on the filter paper, do not carry out paper chromatography, with the DCBI ion gun extract spot on the filter paper is carried out desorb and ionization, the gained spectrogram is shown in Fig. 3 C.
Because impurity brings in the tablet interference and desorption efficiency are low, target analytes is not detected (shown in Fig. 3 B) when directly the tablet surface desorption being ionized; And drop on the filter paper through solvent extraction and with extract, carry out again desorption ionization, then can detect target analytes, but corresponding mass spectrogram peak by force a little less than, and impurity disturbs obviously (shown in Fig. 3 C); Behind the triangle filter paper chromatography, the powerful large enhancing in target analytes peak, and impurity disturbs obviously minimizing (shown in Fig. 3 A).Be the analysis showed that by above experiment acquired results the method that present embodiment provides has improved sensitivity for analysis and reduced the impurity interference when the microcomponent in the complex matrices is analyzed.
Embodiment 2
In order to measure the content of Melamine in the milk powder, claim 10mg Sanlu milk powder (1.5mL) in the disposable plastic centrifuge tube, sample preparation and analytical procedure are with embodiment 1.The gained spectrogram is shown in Fig. 4.
Embodiment 3
In order to measure alkaloidal content in the urine sample, get 100 μ L urines in the disposable plastic centrifuge tube, add 2 μ L standard solution (ketamine, 10 μ g/mL; Amphetamine, 10 μ g/mL; Crystal methamphetamine, 10 μ g/mL; The methylene-dioxy amphetamine, 10 μ g/mL), mixing.Getting 10 μ L mentioned solutions evenly drips along 1.0cm place, distance isosceles triangle filter paper base.The expansion of filter paper and mass spectrophotometry are with embodiment 1.The gained spectrogram is shown in Fig. 5.
Although the present invention discloses as above with preferred embodiment; so it is not to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when can doing a little modification and perfect, so protection scope of the present invention is when with being as the criterion that claims were defined.For example, specimen in use might not be solid form, also can directly be added in for liquid sample and separate on the chromatographic paper and analyze.And for example, used chromatographic paper two ends also can add certain voltage, so that the auxiliary of electrophoretic effect be finished or be obtained to the process of separating can by electrophoretic effect.
Claims (16)
1. the sample preparation methods of a mass spectrophotometry comprises following steps:
The mixed liquor of sample or sample and solvent is placed on the chromatographic paper, and this chromatographic paper has the end that a width shrinks gradually;
Carry out the paper chromatography operation, chromatographic paper is placed developping agent, sample is moved to the end of chromatographic paper with developping agent, and in the enrichment of the end of chromatographic paper;
The end of chromatographic paper is placed the ionogenic check point of desorption ionization of mass spectrometer, to be desorbed ionization.
2. the method for claim 1 is characterized in that, described chromatographic paper is triangle, and described end is a leg-of-mutton angle.
3. method as claimed in claim 2 is characterized in that, the subtended angle scope of described end is between 15～45 degree.
4. the method for claim 1 is characterized in that, described chromatographic paper is trapezoidal, described end be trapezoidal upper base institute at one end.
5. the method for claim 1 is characterized in that, the width of described upper base is less than 5mm.
6. the method for claim 1 is characterized in that, described chromatographic paper is qualitative filter paper.
7. the method for claim 1 is characterized in that, described chromatographic paper is chromatography filter paper.
8. the method for claim 1 is characterized in that, described desorption ionization ion gun uses the desorption electrospray method.
9. the method for claim 1 is characterized in that, the ionogenic desorption method of described desorption ionization has comprised one or more in thermal desorption means, laser desorption means, the sound wave desorb means.
10. the method for claim 1 is characterized in that, described desorption ionization ion gun makes the alpha bombardment method.
11. the method for claim 1, it is characterized in that the ionogenic ionization method of described desorption ionization has comprised ionization means that photoionization means, chemi-ionization means, electron spray droplet and desorbing neutral molecule merge, in the thermal ionization means one or more.
12. the method for claim 1 is characterized in that, also is included in before the desorption ionization described chromatographic paper is carried out drying processing.
13. the method for claim 1 is characterized in that, comprises that also the disengaging time of controlling paper chromatography shifts at least a sample to be analyzed and is enriched near the check point.
14. the method for claim 1 is characterized in that, also be included in desorption ionization before, the part that will be positioned at the outer chromatographic paper of described check point is removed, to reduce on this part chromatographic paper absorption impurity to mass spectrum result's negative effect.
15. the method for claim 1 is characterized in that, also comprises according to analyte the composition of employed developping agent is adjusted, so that described sample is with the developping agent Front movement.
16. the method for claim 1 is characterized in that, the two ends that also are included in chromatographic paper apply certain voltage, separate or the separation of auxiliary sample by electrophoretic effect.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103558076A (en) * | 2013-11-08 | 2014-02-05 | 东华理工大学 | Device for extracting inner substances of ionized condensed state sample |
| CN105571918A (en) * | 2016-01-18 | 2016-05-11 | 中国农业科学院茶叶研究所 | Sample pre-treatment method for precise quantification detection of bioactive substances |
| CN106483186A (en) * | 2016-10-11 | 2017-03-08 | 清华大学 | A kind of ionization massspectrum detection means and its application |
| CN106932524A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院化学研究所 | Thin layer of liquid chromatograph-mass spectrometer coupling device, purposes and detection method |
| CN109799223A (en) * | 2019-03-09 | 2019-05-24 | 湖北工业大学 | For detecting the Raman substrate and detection method of Acrylamide in Foods and bisphenol-A |
| CN111103388A (en) * | 2018-10-29 | 2020-05-05 | 中山大学 | Method for integrating thin layer chromatography and mass spectrometry detection |
| CN111569840A (en) * | 2020-05-12 | 2020-08-25 | 山东师范大学 | Adsorption material for organic pollutants, paper spray mass spectrometry detection device and detection method |
| CN112525980A (en) * | 2020-11-26 | 2021-03-19 | 厦门大学 | Mass spectrum detection method for melamine in dairy products |
| CN112540070A (en) * | 2020-09-27 | 2021-03-23 | 西安电子科技大学 | Test paper box for detecting anti-cancer drugs in body fluid and preparation and use methods thereof |
| CN114078687A (en) * | 2020-08-20 | 2022-02-22 | 中国科学院化学研究所 | Capillary paper spray ion source device and ion generation method |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103558076A (en) * | 2013-11-08 | 2014-02-05 | 东华理工大学 | Device for extracting inner substances of ionized condensed state sample |
| CN106932524A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院化学研究所 | Thin layer of liquid chromatograph-mass spectrometer coupling device, purposes and detection method |
| CN106932524B (en) * | 2015-12-30 | 2018-11-27 | 中国科学院化学研究所 | Thin layer of liquid chromatograph-mass spectrometer coupling device, purposes and detection method |
| CN105571918A (en) * | 2016-01-18 | 2016-05-11 | 中国农业科学院茶叶研究所 | Sample pre-treatment method for precise quantification detection of bioactive substances |
| CN105571918B (en) * | 2016-01-18 | 2018-04-10 | 中国农业科学院茶叶研究所 | A kind of sample-pretreating method for the detection of bioactive substance accurate quantification |
| CN106483186A (en) * | 2016-10-11 | 2017-03-08 | 清华大学 | A kind of ionization massspectrum detection means and its application |
| CN111103388A (en) * | 2018-10-29 | 2020-05-05 | 中山大学 | Method for integrating thin layer chromatography and mass spectrometry detection |
| CN109799223A (en) * | 2019-03-09 | 2019-05-24 | 湖北工业大学 | For detecting the Raman substrate and detection method of Acrylamide in Foods and bisphenol-A |
| CN111569840A (en) * | 2020-05-12 | 2020-08-25 | 山东师范大学 | Adsorption material for organic pollutants, paper spray mass spectrometry detection device and detection method |
| CN114078687A (en) * | 2020-08-20 | 2022-02-22 | 中国科学院化学研究所 | Capillary paper spray ion source device and ion generation method |
| CN114078687B (en) * | 2020-08-20 | 2023-03-21 | 中国科学院化学研究所 | Capillary paper spray ion source device and ion generation method |
| CN112540070A (en) * | 2020-09-27 | 2021-03-23 | 西安电子科技大学 | Test paper box for detecting anti-cancer drugs in body fluid and preparation and use methods thereof |
| CN112525980A (en) * | 2020-11-26 | 2021-03-19 | 厦门大学 | Mass spectrum detection method for melamine in dairy products |
| CN112525980B (en) * | 2020-11-26 | 2022-09-06 | 厦门大学 | Mass spectrometry detection method for melamine in dairy products |
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