CN104007168B - A kind of sample carrier for ionization massspectrum analysis and application thereof - Google Patents
A kind of sample carrier for ionization massspectrum analysis and application thereof Download PDFInfo
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- CN104007168B CN104007168B CN201410251333.1A CN201410251333A CN104007168B CN 104007168 B CN104007168 B CN 104007168B CN 201410251333 A CN201410251333 A CN 201410251333A CN 104007168 B CN104007168 B CN 104007168B
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Abstract
The present invention discloses a kind of sample carrier for ionization massspectrum analysis and application thereof. Described sample carrier is the eggshell that a kind of internal surface after treatment has loose and porous structure; Described process refers to that the eggshell by ripe birds, beasts and eggs takes off, and first inserts in the aqueous hydrochloric acid that concentration is 0.1��1mol/L and soaks 1��3 hour under room temperature, then takes out eggshell, clean the hydrochloric acid on clean eggshell with water, finally drying 3��6 hours at 30��40 DEG C. The present invention makes its internal surface have loose and porous structure by eggshell carries out process, thus increase this carrier and water, oily contact angle, can be used as the sample carrier that MALDI-MS and DESI-MS analyzes, not only solve during MALDI-MS and DESI-MS analyzes the some sample all existed and sprawl a difficult problem, and improve the sensitivity of analysis, and the change of discarded eggshell can be given up as " treasured ", there is practical value.
Description
Technical field
The present invention relates to a kind of sample carrier for ionization massspectrum analysis and application thereof, belong to analytical technique of mass spectrum field.
Background technology
The eighties in last century substance assistant laser desorpted ionization massspectrum (MALDI-MS) plough a kind of soft ionization ionization massspectrum analysis technology of a proposition by Japanese scholars Tanaka, the target plate of traditional MALDI-MS is stainless steel target plate, and traditional matrix is some protonic acids. When compound (such as organometallics) that analysis polarity is less, there is significant limitation in MALDI-MS, one is a sample problem, and these compounds often need to be dissolved in the very little organic solvent of surface tension (such as CH2Cl2), and this kind solvent can occur seriously to sprawl when some sample, this will certainly affect sensitivity and the accuracy of analysis; Another is substrate problem, and traditional proton type matrix can not make these compound ions, it is thus desirable to the electron transfer type matrix of development of new, the electron transfer type matrix reported is some condensed-nuclei aromaticss, this type of matrix toxicity is big, and specificity is strong, and the compound that can analyze is limited.
LC-MS spectrometry (ESI-MS) is when compound (such as organometallics) that analysis polarity is less, and ionization efficiency is very low, and there is serious crossed contamination.
Desorption electrospray ionization (DESI-MS) is that U.S. Cooks teaches a kind of soft ionization mass spectrum means proposed in 2004. DESI-MS is when analyzing some special compound (such as organometallicss), there is unique advantage, it avoid the serious crossed contamination existed when ESI-MS analyzes, therefore it does not need a large amount of organic solvent to go to clean sample pipe, not only saves analysis time but also substantially reduce environmental pollution. If but analyzed sample with DESI-MS, it is necessary to solving two problems, one would be a sample problem, because DESI-MS faces the some sample problem in MALDI-MS equally, two is the select permeability of spray solution, only selects suitable spray solution, just can make determinand ionization, thus be analyzed.
Summary of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of sample carrier for ionization massspectrum analysis and application thereof, to solve the difficult problem that the some sample existing for MALDI-MS and DESI-MS analysis means is sprawled.
For achieving the above object, the present invention adopts following technical scheme:
For the sample carrier that ionization massspectrum is analyzed, it it is the eggshell that a kind of internal surface after treatment has loose and porous structure; Described process refers to that the eggshell by ripe birds, beasts and eggs takes off, and first inserts in the aqueous hydrochloric acid that concentration is 0.1��1mol/L and soaks 1��3 hour under room temperature, then takes out eggshell, clean the hydrochloric acid on clean eggshell with water, finally drying 3��6 hours at 30��40 DEG C.
Sample carrier of the present invention can be used as the sample carrier that MALDI-MS and DESI-MS analyzes.
The application operating of sample carrier of the present invention in MALDI-MS analyzes is as follows: be fixed on by described sample carrier on stainless steel target plate, then by testing sample solution point on described sample carrier, after solvent volatilization is dry, operation carries out substance assistant laser desorpted ionization massspectrum (MALDI-MS) analysis routinely.
The application operating of sample carrier of the present invention in DESI-MS analyzes is as follows: be fixed on DESI ion source device by described sample carrier, and make the spray pin 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 carries out desorption electrospray ionization mass spectrum (DESI-MS) analysis routinely.
The area of sample carrier of the present invention used in MALDI-MS or DESI-MS analyzes is 4��10mm2��
Compared with prior art, the present invention has the useful effect of following significance:
1, the present invention makes its internal surface have loose and porous structure by eggshell carries out process, thus increase this carrier and water, oily contact angle, thus solve MALDI-MS and DESI-MS analyze in the some sample that all exists sprawl a difficult problem, it is to increase the sensitivity analyzed.
2, by the process of the present invention and application, being become by discarded eggshell gives up as " treasured ", can be used as the sample carrier of disposable consumption is used in the analysis of MALDI-MS and DESI-MS, it is finished and directly abandons, avoid the operation of a large amount of solvent cleaning sample carrier, not only increase analysis efficiency, it is important to avoid the cross interference problem caused because not washing clean clearly, further ensure that the precision of analysis and accuracy.
3, sample carrier of the present invention has source and enriches, processes the advantages such as simple, easy to use, has practical value.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope comparison diagram that eggshell processes the internal surface shape of front and back through the present invention;
Fig. 2-a is that eggshell is through the present invention photoelectron spectrum figure before treatment;
Fig. 2-b is the photoelectron spectrum 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, atomizer; 2, sample carrier; 3, sample; 12, spray solution entrance; 13, auxiliary gas entrance; 14, sheath gas entrance; 15, pin is sprayed;
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 mixture 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.
Mass spectrograph used in embodiment is the ThermoTSQQuantum mass spectrograph of ThermoFisherScientific company.
Embodiment 1
The eggshell of ripe birds, beasts and eggs is taken off, insert in the aqueous hydrochloric acid that concentration is 0.5mol/L and to soak 2 hours under room temperature, then take out eggshell, with washed with de-ionized water eggshell surface 3 times, then freeze-day with constant temperature 5 hours at 37 DEG C, namely obtain the eggshell that internal surface has loose and porous structure.
Fig. 1 show the internal surface shape figure that eggshell carries out processing front and back, a figure wherein is the internal surface shape figure of the front eggshell of process 100 ��m of levels, b figure is the internal surface shape figure of the rear eggshell of process 100 ��m of levels, c figure is that before process, eggshell is at the internal surface shape figure of 5 ��m of levels, and d figure is the internal surface shape figure of the rear eggshell of process 5 ��m of levels.
As seen from Figure 1: through process, the fibrous texture of eggshell surface disappears, and turns into loose coarse vesicular structure, and this kind of change makes eggshell after treatment, increase with the contact angle of water, oil.
Fig. 2-a show eggshell photoelectron spectrum figure before treatment, Fig. 2-b show eggshell photoelectron spectrum figure after treatment, by Fig. 2-a and Fig. 2-b it can be seen that through process, the element sulphur of eggshell surface disappears, this disappears corresponding with the fibrous texture of eggshell surface in Fig. 1.
Application examples 1
Compound 1-3, as the sample carrier in MALDI-MS analysis, is carried out MALDI-MS analysis by eggshell after processing using embodiment 1 respectively, and concrete operation comprises:
1, cut and get 5mm2Eggshell after embodiment 1 processes, is fixed on stainless steel target plate on as sample carrier with two-sided glue using this eggshell;
2, pipetting the dichloromethane solution that 1 �� L concentration is the testing compound of 0.1 ��M, point is on this sample carrier;
3, not adding matrix, operation carries out MALDI-MS analysis routinely.
Fig. 3 is the MALDI-MS spectrogram of the compound 1 obtained, as seen from Figure 3: the molecular ion peak M having occurred m/z=248 in spectrogram+.;
Fig. 4 is the MALDI-MS spectrogram of the compound 2 obtained, as seen from Figure 4: the molecular ion peak M having occurred m/z=427 in spectrogram+.;
Fig. 5 is the MALDI-MS spectrogram of the compound 3 obtained, as seen from Figure 5: the molecular ion peak M having occurred m/z=571 in spectrogram+.��
Application examples 2
Compound 4-11, as the sample carrier in DESI-MS analysis, is carried out DESI-MS analysis by eggshell after processing using embodiment 1 respectively, and concrete operation comprises:
1, cut and get 5mm2Eggshell after embodiment 1 processes, is fixed on this eggshell on DESI ion source device with two-sided glue as sample carrier, and makes the spray pin of DESI ion source device and the horizontal plane angle at described sample carrier place be 30��80 ��; Fig. 6 show the structural representation of the DESI ion source device being fixed with described sample carrier, comprise atomizer 1 and sample carrier 2, atomizer 1 is provided with spray solution entrance 12, auxiliary gas entrance 13, sheath gas entrance 14 and spray pin 15, angle �� between spray pin 15 and sample carrier 2 place horizontal plane is 50 ��, and the distance between sample carrier 2 and spray pin 15 is 2mm;
2,1 �� L testing sample solution point is pipetted respectively on described sample carrier 2, adjust auxiliary entraining air stream and sheath entraining air stream is respectively 5arb, 15psi, spray solution flow velocity 10 �� L/s, spray voltage are 3800V, desolventizing pipe temperature is 270 DEG C, carries out desorption electrospray ionization mass spectrum (DESI-MS) and analyzes.
The testing sample solution that compound 4��8 is mixed with 0.1 ��M respectively with methylene dichloride, is mixed with the testing sample solution of 0.1 ��M respectively by compound 9��11 with water; During the mixture of analysis of compounds 9 and compound 10, the preparation of testing sample solution is mixed by the aqueous solution of the aqueous solution of the compound 9 of 3 �� L0.1 ��M with the compound 10 of 2 �� L0.1 ��M.
The DESI-MS carrying 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 obtained, and as seen from Figure 7: the positively charged ion peak having occurred m/z=745 in spectrogram, the isotopic distribution theoretical with compound of the isotopic distribution in spectrogram is consistent.
Fig. 8 is the DESI-MS spectrogram of the compound 5 obtained, and as seen from Figure 8: the positively charged ion peak having occurred m/z=773 in spectrogram, the isotopic distribution theoretical with compound of the isotopic distribution in spectrogram is consistent.
Fig. 9 is the DESI-MS spectrogram of the compound 6 obtained, as seen from Figure 9: [6-H] having occurred m/z=791 in spectrogram+Ion peak.
Figure 10 is the DESI-MS spectrogram of the compound 7 obtained, as seen from Figure 10: [7-H] having occurred m/z=847 in spectrogram+Ion peak.
Figure 11 is the DESI-MS spectrogram of the compound 8 obtained, as seen from Figure 11: [M-H] having occurred compound 8 m/z=413 in the negative ion mode in spectrogram-Ion peak.
Figure 12 is the DESI-MS spectrogram of the compound 9 obtained, as seen from Figure 12: [9-Na] having occurred m/z=178 in spectrogram-Ion peak.
Figure 13 is the DESI-MS spectrogram of the compound 9 and mixture of compound 10 obtained, as seen from Figure 13: that occurred m/z=182 in spectrogram is [10-Na]-Ion peak.
Figure 14 is the DESI-MS spectrogram of the compound 11 obtained, as seen from Figure 14: [M+H] having occurred m/z=127 in spectrogram+Ion peak.
To sum up application experiment proves, sample carrier of the present invention can be applicable in the analysis of MALDI-MS and DESI-MS, not only solves a sample and sprawls a difficult problem, also improves the sensitivity of analysis, has significance progress and useful effect.
Finally it is necessary described herein: above embodiment is only for being described in more detail the technical scheme of the present invention; can not being interpreted as limiting the scope of the invention, improvement and the adjustment of some non-intrinsically safes that the technician of this area makes according to the foregoing of the present invention all belong to protection scope of the present invention.
Claims (5)
1. the sample carrier analyzed for ionization massspectrum, it is characterised in that: described sample carrier is the eggshell that a kind of internal surface after treatment has loose and porous structure; Described process refers to that the eggshell by ripe birds, beasts and eggs takes off, and first inserts in the aqueous hydrochloric acid that concentration is 0.1��1mol/L and soaks 1��3 hour under room temperature, then takes out eggshell, clean the hydrochloric acid on clean eggshell with water, finally drying 3��6 hours at 30��40 DEG C.
2. the application of sample carrier according to claim 1 in substance assistant laser desorpted ionization massspectrum (MALDI-MS) or desorption electrospray ionization mass spectrum (DESI-MS) are analyzed.
3. apply as claimed in claim 2, it is characterized in that: on the stainless steel target plate that described sample carrier is fixed in MALDI-MS analyser, then, by testing sample solution point on described sample carrier, after solvent volatilization is dry, operation carries out MALDI-MS analysis routinely.
4. apply as claimed in claim 2, it is characterized in that: described sample carrier is fixed on DESI ion source device, and make the spray pin 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 carries out DESI-MS analysis routinely.
5. application as described in claim 3 or 4, it is characterised in that: the area every time analyzing sample carrier used is 4��10mm2��
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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 |
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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 |
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