CN104007168A - Sample carrier for ionization mass spectrometric analysis and application thereof - Google Patents
Sample carrier for ionization mass spectrometric analysis and application thereof Download PDFInfo
- Publication number
- CN104007168A CN104007168A CN201410251333.1A CN201410251333A CN104007168A CN 104007168 A CN104007168 A CN 104007168A CN 201410251333 A CN201410251333 A CN 201410251333A CN 104007168 A CN104007168 A CN 104007168A
- Authority
- CN
- China
- Prior art keywords
- sample carrier
- desi
- analysis
- eggshell
- maldi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a sample carrier for ionization mass spectrometric analysis and an application thereof. The sample carrier is an egg shell which is treated to enable the inner surface to have a loose and porous structure. The treatment comprises the following steps: taking down the egg shell of a cooked poultry egg, firstly putting the egg shell into a 0.1-1mol/L hydrochloric acid aqueous solution, soaking at room temperature for 1-3 hours, then taking out the egg shell, cleaning hydrochloric acid on the egg shell by using water, and finally drying at the temperature of 30-40 DEG C for 3-6 hours. The sample carrier disclosed by the invention has the advantages that the egg shell is treated to enable the inner surface to have the loose and porous structure, so that the contact angle of the carrier with water and oil is enlarged; the sample carrier can be used as a sample carrier for MALDI-MS (Matrix-Assisted Laser Desorption Ionization Mass Spectrometry) and DESI-MS (Desorption Electrospray Ionisation-Mass Spectrometry) analysis, not only can the difficulty of spreading in sample application of the MALDI-MS and DESI-MS analysis be solved, but also the sensitivity of the analysis is improved, and the wasted egg shell can be turned into valuables, so that the sample carrier has practical value.
Description
Technical field
The present invention relates to a kind of sample carrier and application thereof of analyzing for ionization massspectrum, belong to analytical technique of mass spectrum field.
Background technology
Substance assistant laser desorpted ionization massspectrum (MALDI-MS) is by Japanese scholars Tanaka, to plough an a kind of soft ionization ionization massspectrum analytical technology proposing the eighties in last century, the target plate of traditional MALDI-MS is stainless steel target plate, and traditional matrix is some Bronsted acids.When analyzing the less compound (such as metal organic compound) of polarity, there is significant limitation in MALDI-MS, and the one, point sample problem, these compounds often need to be dissolved in the organic solvent that surface tension is very little (as CH
2cl
2), and this kind solvent can occur seriously to sprawl when point sample, sensitivity and accuracy that this will certainly impact analysis; Another is substrate problem, and traditional proton type matrix can not make these compound ions, therefore needs the electron transfer type matrix of development of new, the electron transfer type matrix of having reported is some condensed-nuclei aromaticss, this type of matrix toxicity is large, and specificity is strong, and the compound that can analyze is limited.
Electro-spray ionization mass spectrum (ESI-MS) is when analyzing the less compound (such as metal organic compound) of polarity, and Ionization Efficiency is very low, and has serious cross pollution.
Desorption electrospray ionization (DESI-MS) is that U.S. Cooks teaches a kind of soft ionization mass spectrum means that proposed in 2004.DESI-MS is when analyzing some special compounds (as metal organic compound), there is unique advantage, the serious cross pollution that it has existed while having avoided ESI-MS to analyze, therefore it does not need a large amount of organic solvents to remove to clean sample pipe, has not only saved analysis time but also greatly reduced environmental pollution.If but use DESI-MS analytic sample, and need to solve two problems, the one, point sample problem, because DESI-MS faces the point sample problem in MALDI-MS equally, the 2nd, the selection problem of spray solution, only has and selects suitable spray solution, just can make determinand ionization, thereby be analyzed.
Summary of the invention
For the above-mentioned problems in the prior art, the object of this invention is to provide a kind of sample carrier and application thereof of analyzing for ionization massspectrum, a difficult problem of sprawling to solve MALDI-MS and the existing point sample of DESI-MS analysis means.
For achieving the above object, the present invention adopts following technical scheme:
A sample carrier of analyzing for ionization massspectrum is the eggshell that a kind of inside surface after treatment has loose and porous structure; Described processing refers to takes off the eggshell of ripe birds, beasts and eggs, first inserts in the aqueous hydrochloric acid solution that concentration is 0.1～1mol/L and under room temperature, soaks 1～3 hour, then takes out eggshell, and water cleans the hydrochloric acid on clean eggshell, finally at 30～40 ℃, is dried 3～6 hours.
Sample carrier of the present invention can be used as the sample carrier of MALDI-MS and DESI-MS analysis use.
The application operating of sample carrier of the present invention in MALDI-MS analyzes is as follows: described sample carrier is fixed on stainless steel target plate, then by testing sample solution point on described sample carrier, after solvent evaporates is dry, substance assistant laser desorpted ionization massspectrum (MALDI-MS) analysis is carried out in operation routinely.
The application operating of sample carrier of the present invention in DESI-MS analyzes is as follows: described sample carrier is fixed on DESI ion source device, and to make the nozzle needle of DESI ion source device and the horizontal plane angle at described sample carrier place be 30～80 °, then by testing sample solution point on described sample carrier, operation is carried out desorption electrospray ionization mass spectrum (DESI-MS) and is analyzed routinely.
In MALDI-MS or DESI-MS analysis, the area of sample carrier of the present invention used is 4～10mm
2.
Compared with prior art, the present invention has following conspicuousness beneficial effect:
1, the present invention makes its inside surface have loose and porous structure by eggshell is processed, thereby increased the contact angle of this carrier and water, oil, thereby solved the point sample that MALDI-MS and DESI-MS exist in analyzing and sprawl a difficult problem, improved the sensitivity of analysis.
2, by processing of the present invention and application, discarded eggshell is become and given up as " treasured ", the sample carrier that can be used as disposable consumption is used in the analysis of MALDI-MS and DESI-MS, be finished directly and abandon, avoided the operation of a large amount of solvent cleaning sample carriers, not only improved analysis efficiency, key is to have avoided the intersection interference problem that causes because not washing clean clearly, has further guaranteed precision and the accuracy analyzed.
3, sample carrier of the present invention have source enrich, process the advantages such as simple, easy to use, there is practical value.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope comparison diagram of the internal surface shape of eggshell before and after the present invention processes;
Fig. 2-a is the photoelectron spectroscopy figure of eggshell before the present invention processes;
Fig. 2-b is the photoelectron spectroscopy figure of eggshell after the present invention processes;
Fig. 3 is the MALDI-MS figure of compound 1 in application examples 1;
Fig. 4 is the MALDI-MS figure of compound 2 in application examples 1;
Fig. 5 is the MALDI-MS figure of compound 3 in application examples 1;
Fig. 6 is the structural representation of DESI ion source device in application examples 2, number in the figure schematically as follows: 1, sprayer; 2, sample carrier; 3, sample; 12, spray solution entrance; 13, auxiliary gas entrance; 14, sheath gas entrance; 15, nozzle needle;
Fig. 7 is the DESI-MS spectrogram of compound 4 in application examples 2;
Fig. 8 is the DESI-MS spectrogram of compound 5 in application examples 2;
Fig. 9 is the DESI-MS spectrogram of compound 6 in application examples 2;
Figure 10 is the DESI-MS spectrogram of compound 7 in application examples 2;
Figure 11 is the DESI-MS spectrogram of compound 8 in application examples 2;
Figure 12 is the DESI-MS spectrogram of compound 9 in application examples 2;
Figure 13 is the DESI-MS spectrogram of compound 9 and 10 potpourris in application examples 2;
Figure 14 is the DESI-MS spectrogram of compound 11 in application examples 2.
Embodiment
Below in conjunction with embodiment, technical solution of the present invention is described in further detail and completely.
In embodiment, mass spectrometer used is the Thermo TSQ Quantum mass spectrometer of Thermo Fisher Scientific company.
Embodiment 1
The eggshell of ripe birds, beasts and eggs is taken off, insert in the aqueous hydrochloric acid solution that concentration is 0.5mol/L and under room temperature, soak 2 hours, then take out eggshell, use washed with de-ionized water eggshell surface 3 times, then freeze-day with constant temperature 5 hours at 37 ℃, obtains the eggshell that inside surface has loose and porous structure.
Figure 1 shows that the internal surface shape figure of eggshell before and after processing, a figure wherein processes front eggshell at the internal surface shape figure of 100 μ m levels, b figure processes rear eggshell at the internal surface shape figure of 100 μ m levels, c figure is that before processing, eggshell is at the internal surface shape figure of 5 μ m levels, and d figure processes rear eggshell at the internal surface shape figure of 5 μ m levels.
As seen from Figure 1: through processing, the fibre structure of eggshell surface disappears, become loose coarse porous structure, this variation makes eggshell after treatment, increases with the contact angle of water, oil.
Fig. 2-a is depicted as the photoelectron spectroscopy figure of eggshell before processing, Fig. 2-b is depicted as the photoelectron spectroscopy figure of eggshell after processing, by Fig. 2-a and Fig. 2-b, can be found out: through processing, the element sulphur of eggshell surface disappears, this disappears corresponding with the fibre structure of eggshell surface in Fig. 1.
Application examples 1
Eggshell after the embodiment 1 of usining processes, as the sample carrier in MALDI-MS analysis, carries out MALDI-MS analysis to compound 1-3 respectively, and concrete operations comprise:
1, clip 5mm
2eggshell after embodiment 1 processes, is fixed on stainless steel target plate with double faced adhesive tape this eggshell as sample carrier;
2, pipetting 1 μ L concentration is the dichloromethane solution of the testing compound of 0.1 μ M, and point is on this sample carrier;
3, do not add matrix, MALDI-MS analysis is carried out in operation routinely.
Fig. 3 is the MALDI-MS spectrogram of the compound 1 that obtains, as seen from Figure 3: the molecular ion peak M that has occurred m/z=248 in spectrogram
+.;
Fig. 4 is the MALDI-MS spectrogram of the compound 2 that obtains, as seen from Figure 4: the molecular ion peak M that has occurred m/z=427 in spectrogram
+.;
Fig. 5 is the MALDI-MS spectrogram of the compound 3 that obtains, as seen from Figure 5: the molecular ion peak M that has occurred m/z=571 in spectrogram
+..
Application examples 2
Eggshell after the embodiment 1 of usining processes, as the sample carrier in DESI-MS analysis, carries out DESI-MS analysis to compound 4-11 respectively, and concrete operations comprise:
1, clip 5mm
2eggshell after embodiment 1 processes, is fixed on DESI ion source device with double faced adhesive tape this eggshell as sample carrier, and to make the nozzle needle of DESI ion source device and the horizontal plane angle at described sample carrier place be 30～80 °; Figure 6 shows that the structural representation of the DESI ion source device that is fixed with described sample carrier, comprise sprayer 1 and sample carrier 2, sprayer 1 is provided with spray solution entrance 12, auxiliary gas entrance 13, sheath gas entrance 14 and nozzle needle 15, angle α between nozzle needle 15 and sample carrier 2 place surface levels is 50 °, and the distance between sample carrier 2 and nozzle needle 15 is 2mm;
2, pipette respectively 1 μ L testing sample solution point on described sample carrier 2, adjust auxiliary entraining air stream and sheath entraining air stream is respectively 5arb, 15psi, spray solution flow velocity 10 μ L/s, spray voltage are that 3800V, desolventizing pipe temperature are 270 ℃, carry out desorption electrospray ionization mass spectrum (DESI-MS) analysis.
Compound 4～8 is mixed with respectively to the testing sample solution of 0.1 μ M with methylene chloride, by compound 9～11 respectively water be mixed with the testing sample solution of 0.1 μ M; During the potpourri of analysis of compounds 9 and compound 10, the preparation of testing sample solution is that the aqueous solution of the compound 9 of 3 μ L0.1 μ M is mixed with the aqueous solution of the compound 10 of 2 μ L0.1 μ M.
The DESI-MS that carries out each testing sample analyzes, and spray solution used is as shown in Table 1 below.
The spray solution that table 1 is used
Fig. 7 is the DESI-MS spectrogram of the compound 4 that obtains, as seen from Figure 7: in spectrogram, occurred the kation peak of m/z=745, the isotope in spectrogram distributes consistent with the theoretical isotope distribution of compound.
Fig. 8 is the DESI-MS spectrogram of the compound 5 that obtains, as seen from Figure 8: in spectrogram, occurred the kation peak of m/z=773, the isotope in spectrogram distributes consistent with the theoretical isotope distribution of compound.
Fig. 9 is the DESI-MS spectrogram of the compound 6 that obtains, as seen from Figure 9: [6-H] that has occurred m/z=791 in spectrogram
+quasi-molecular ions.
Figure 10 is the DESI-MS spectrogram of the compound 7 that obtains, as seen from Figure 10: [7-H] that has occurred m/z=847 in spectrogram
+quasi-molecular ions.
Figure 11 is the DESI-MS spectrogram of the compound 8 that obtains, as seen from Figure 11: [M-H] that has occurred the m/z=413 of compound 8 under negative ion mode in spectrogram
-quasi-molecular ions.
Figure 12 is the DESI-MS spectrogram of the compound 9 that obtains, as seen from Figure 12: [9-Na] that has occurred m/z=178 in spectrogram
-quasi-molecular ions.
Figure 13 is the compound 9 that obtains and the DESI-MS spectrogram of the potpourri of compound 10, as seen from Figure 13: that in spectrogram, occurred m/z=182 is [10-Na]
-quasi-molecular ions.
Figure 14 is the DESI-MS spectrogram of the compound 11 that obtains, as seen from Figure 14: [M+H] that has occurred m/z=127 in spectrogram
+quasi-molecular ions.
To sum up application experiment proves, sample carrier of the present invention can be applicable in the analysis of MALDI-MS and DESI-MS, has not only solved point sample and has sprawled a difficult problem, has also improved the sensitivity of analyzing, and has conspicuousness progress and beneficial effect.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (5)
1. a sample carrier of analyzing for ionization massspectrum, is characterized in that: described sample carrier is the eggshell that a kind of inside surface after treatment has loose and porous structure; Described processing refers to takes off the eggshell of ripe birds, beasts and eggs, first inserts in the aqueous hydrochloric acid solution that concentration is 0.1～1mol/L and under room temperature, soaks 1～3 hour, then takes out eggshell, and water cleans the hydrochloric acid on clean eggshell, finally at 30～40 ℃, is dried 3～6 hours.
2. the application of sample carrier claimed in claim 1 in substance assistant laser desorpted ionization massspectrum (MALDI-MS) and desorption electrospray ionization mass spectrum (DESI-MS) analysis.
3. application as claimed in claim 2, it is characterized in that: described sample carrier is fixed on the stainless steel target plate in MALDI-MS analyser, then by testing sample solution point on described sample carrier, after solvent evaporates is dry, MALDI-MS analysis is carried out in operation routinely.
4. application as claimed in claim 2, it is characterized in that: described sample carrier is fixed on DESI ion source device, and to make the nozzle needle of DESI ion source device and the horizontal plane angle at described sample carrier place be 30～80 °, then by testing sample solution point on described sample carrier, DESI-MS analysis is carried out in operation routinely.
5. the application as described in claim 3 or 4, is characterized in that: the area of at every turn analyzing sample carrier used is 4～10mm
2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410251333.1A CN104007168B (en) | 2014-06-09 | 2014-06-09 | A kind of sample carrier for ionization massspectrum analysis and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410251333.1A CN104007168B (en) | 2014-06-09 | 2014-06-09 | A kind of sample carrier for ionization massspectrum analysis and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104007168A true CN104007168A (en) | 2014-08-27 |
| CN104007168B CN104007168B (en) | 2016-06-01 |
Family
ID=51367922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410251333.1A Active CN104007168B (en) | 2014-06-09 | 2014-06-09 | A kind of sample carrier for ionization massspectrum analysis and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104007168B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114460213A (en) * | 2020-11-10 | 2022-05-10 | 中国科学院化学研究所 | Real-time online analysis system and method for complex sample |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01255147A (en) * | 1988-04-02 | 1989-10-12 | Kokuritsu Kogai Kenkyusho | Ionizing method for high pressure mass analysis |
| DE10054906A1 (en) * | 2000-11-03 | 2002-05-08 | Univ Schiller Jena | Sample carrier used in MALDI mass spectrometry has receiving surfaces lying in a common upper plane separated by intermediate chambers with base surfaces arranged in a lower deeper lying plane of a base body |
| CN101829545A (en) * | 2010-05-12 | 2010-09-15 | 北京航空航天大学 | Heavy metal biological adsorbent using eggshell membrane as matrix and preparation method thereof |
| CN103063730A (en) * | 2012-12-13 | 2013-04-24 | 中国科学院化学研究所 | Application of naphthylhydrazine inorganic acid salt or Naphthylhydrazine organic acid salt as matrix in MALDI MS (matrix-assisted laser desorption/ionization mass spectrometry) |
| CN103111278A (en) * | 2013-01-18 | 2013-05-22 | 昆明理工大学 | Egg-shell oxygen carrier and preparation method thereof |
-
2014
- 2014-06-09 CN CN201410251333.1A patent/CN104007168B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01255147A (en) * | 1988-04-02 | 1989-10-12 | Kokuritsu Kogai Kenkyusho | Ionizing method for high pressure mass analysis |
| DE10054906A1 (en) * | 2000-11-03 | 2002-05-08 | Univ Schiller Jena | Sample carrier used in MALDI mass spectrometry has receiving surfaces lying in a common upper plane separated by intermediate chambers with base surfaces arranged in a lower deeper lying plane of a base body |
| CN101829545A (en) * | 2010-05-12 | 2010-09-15 | 北京航空航天大学 | Heavy metal biological adsorbent using eggshell membrane as matrix and preparation method thereof |
| CN103063730A (en) * | 2012-12-13 | 2013-04-24 | 中国科学院化学研究所 | Application of naphthylhydrazine inorganic acid salt or Naphthylhydrazine organic acid salt as matrix in MALDI MS (matrix-assisted laser desorption/ionization mass spectrometry) |
| CN103111278A (en) * | 2013-01-18 | 2013-05-22 | 昆明理工大学 | Egg-shell oxygen carrier and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| HPS MAKKAR 等: ""Egg Shell as a Carrier for Enzyme Immobilization"", 《BIOTECHNOLOGY AND BIOENGINEERING》 * |
| W ZHU 等: ""Processed eggshell as sample carrier for rapid analysis of organometallic compounds by desorption electrospray ionization mass spectrometry"", 《JOURNAL OF MASS SPECTROMETRY》 * |
| 刘新喜 等: ""蛋壳作载体固定化脂肪酶"", 《固原师专学报(自然科学版)》 * |
| 田耀伟 等: ""基质辅助激光解吸离子化技术研究进展"", 《烟草科技》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114460213A (en) * | 2020-11-10 | 2022-05-10 | 中国科学院化学研究所 | Real-time online analysis system and method for complex sample |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104007168B (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Piezoelectric inkjet assisted rapid electrospray ionization mass spectrometric analysis of metabolites in plant single cells via a direct sampling probe | |
| CN105929017B (en) | Application of the molybdenum disulfide/nano-ag composite as matrix in Matrix-assisted laser desorption ionization detection | |
| Zhang et al. | In situ metabolic analysis of single plant cells by capillary microsampling and electrospray ionization mass spectrometry with ion mobility separation | |
| CN105021758B (en) | Chemical derivatization-based phosphatide classification detection and quantification method | |
| CN103258711B (en) | Solvent auxiliary electrospray ionization device and method for achieving electrospray ionization by utilizing same | |
| Mandal et al. | Biomolecular analysis and cancer diagnostics by negative mode probe electrospray ionization | |
| CN102645481A (en) | Application for analyzing micromolecules with irradiating nanometer carbon spots serving as matrix assisted laser desorption ionization (MALDI) matrix | |
| WO2009042328A2 (en) | Low pressure electrospray ionization system and process for effective transmission of ions | |
| Kondrat et al. | Native mass spectrometry: towards high-throughput structural proteomics | |
| CN102297791A (en) | Method for processing sampling slice specially used for ion mobility spectrometry | |
| CN103063730A (en) | Application of naphthylhydrazine inorganic acid salt or Naphthylhydrazine organic acid salt as matrix in MALDI MS (matrix-assisted laser desorption/ionization mass spectrometry) | |
| CN104007168A (en) | Sample carrier for ionization mass spectrometric analysis and application thereof | |
| CN103969325B (en) | The synthetic method of the MALDI target plate that a kind of poly-dopamine is modified and application thereof | |
| CN104599935A (en) | Carbon fiber electric atomizing ionization device and method for realizing electric atomizing ionization by using device | |
| US11754572B2 (en) | Mass spectrophotometric detection of microbes | |
| CN111413395A (en) | Application of porous silicon nanowire combined with MA L DI-TOF MS in metabolic small molecule detection | |
| CN103901139A (en) | Pretreatment method for analyzing tetrabromobisphenol A in biologic urine | |
| JP2008292422A (en) | Preparation method of mass spectrometry sample, ionization method of ribonucleic acid, mass spectrometry method of ribonucleic acid, and this mass spectrometry method of low molecule ribonucleic acid of cell provenance | |
| CN105572273A (en) | Ginsenoside isomerism monomer recognition method based on electron induced pyrolysis mass spectrometry | |
| Xiong et al. | The study of bismuth ions in drinking water at ultratrace levels by a microwave plasma torch coupled with linear ion trap mass spectrometry | |
| CN114887605A (en) | Perfluoro cotton solid phase extraction material and application thereof in enrichment and detection of organic fluoride | |
| CN204348680U (en) | A kind of carbon fiber electrically electrospray ionization device | |
| CN104237343A (en) | Preparation method and application of zirconium dioxide/porous polyaniline modified electrode | |
| Jia-Jun et al. | Development and characterization of a linear matrix-assisted laser desorption ionization mass spectrometer | |
| Li et al. | Molecular ion yield enhancement in static secondary ion mass spectrometry by soft landing of protonated water clusters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230524 Address after: Room 196-8, Building 3, No. 1999 Beixing Road, Sanxing Town, Chongming District, Shanghai, 202152 Patentee after: Guoke Xinyan international technology transfer Co.,Ltd. Address before: 200032 No. 345, Lingling Road, Shanghai, Xuhui District Patentee before: SHANGHAI INSTITUTE OF ORGANIC CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |