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A method for measuring the difference in internal energy of monovalent positive ions obtained by electrospray ionization and electrospray extraction ionization

An electrospray ionization and electrospray technology, which is applied in the fields of analytical chemistry and mass spectrometry, can solve the problems of not calculating the internal energy difference of different ion sources, lack of parent ion selection, enrichment process, extension of fragmentation time scale, etc. Simple, short timescale, accurate results

Active Publication Date: 2021-11-12
EAST CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage of using in-source CID technology is that it lacks the selection and enrichment process of parent ions. All ions generated during the ionization process will be activated by collisions, and because the energy of CID in the source is lower than that of CID, resulting in fragmentation. The longer the time scale, the smaller the rate of direct fragmentation and dissociation, so rearrangement reactions are prone to occur, and finally the average internal energy value measured is often lower than that measured by high-energy CID technology
At present, there is no method to use CID technology to calculate the difference in internal energy of different ion sources

Method used

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  • A method for measuring the difference in internal energy of monovalent positive ions obtained by electrospray ionization and electrospray extraction ionization
  • A method for measuring the difference in internal energy of monovalent positive ions obtained by electrospray ionization and electrospray extraction ionization
  • A method for measuring the difference in internal energy of monovalent positive ions obtained by electrospray ionization and electrospray extraction ionization

Examples

Experimental program
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Effect test

Embodiment 1

[0076] The EESI-MS and ESI-MS device platforms were respectively set up, and rhodamine B was analyzed by tandem mass spectrometry by adjusting the energy of CID. The parent ion mass-to-charge ratio formed in positive ion mode was m / z 443, and the rhodamine B EESI-MS 2 Graph and ESI-MS 2 picture. image 3 (a) is the EESI-MS of Rhodamine B 2 Figure, when the collision energy is 30%, the parent ion m / z 443 mainly loses C respectively 2 h 4 、C 2 h 6 and CO 2 Neutral molecule, producing fragment ions at m / z 415, m / z 413 and m / z 399. Under the same collision energy conditions, ESI-MS 2 Rhodamine B was tested and the results were as follows image 3 As shown in (b), m / z 415, m / z 413 and m / z 399 fragment ions are also available, these fragment ions are compatible with EESI-MS 2 The results are consistent. However, compared to image 3 (a) and image 3 (b) It can be found that in ESI-MS, the relative abundance of fragment ions is significantly higher than that in EESI-MS, ...

Embodiment 2

[0083] Taking the fragment ion m / z 415 as an example, the method of the present invention is used to calculate the internal energy difference of the two ion sources. Image 6 Under the condition of low collision energy (1%~22%), ESI-MS 2 and EESI-MS 2 Trend diagram of the absolute intensity of the middle fragment ion m / z 415 peak. in ESI-MS 2 Medium, slowly increasing ESI-MS 2 The collision energy in %, the parent ion begins to form fragment ions, and the intensity of the fragment ion m / z 415 is In EESI-MS 2 In , the peak intensity of the fragment ion m / z 415 is to be Corresponding collision energy It can be known from formula (3) that the difference between the collision energies in the tandem mass spectrometers of the two is:

[0084] Combining with formula (4), it can be known that 13% of the collision energy is the internal energy difference between the two ion sources. The difference in internal energy of monovalent positive ions obtained by the two ionizat...

Embodiment 3

[0087] Taking the fragment ion m / z 399 as an example, the method of the present invention is used to calculate the internal energy difference of the two ion sources. Figure 7 Under the condition of low collision energy (1%~22%), ESI-MS 2 and EESI-MS 2 Trend diagram of the absolute intensity of the middle fragment ion m / z 399 peak. in ESI-MS 2 , when the collision energy is , the parent ion begins to form fragment ions, and the intensity of the fragment ion m / z 399 is In EESI-MS 2 In , the peak intensity of the fragment ion m / z 399 is to be Corresponding collision energy It can be known from formula (3) that the difference between the collision energies in the tandem mass spectrometers of the two is:

[0088]

[0089] Combining with formula (4), it can be known that 13% of the collision energy is the internal energy difference between the two ion sources. From the formula (6) can get:

[0090] ΔE ion =(NCE 2 -NCE 1 )×(isolation center)×(charge factor)÷500=(1...

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Abstract

The invention provides a method for measuring the difference in the internal energy of monovalent positive ions obtained by electrospray ionization and electrospray extraction ionization: using tandem mass spectrometry, the two ion sources of electrospray ionization and electrospray extraction ionization are respectively used to make the ions in the sample solution The target molecule is ionized to form a monovalent positive ion parent ion, which enters the ion trap under the action of capillary transport, and fragment ions are obtained by collision-induced dissociation technology; in the above process, the ionization conditions are kept consistent with the transmission conditions, and the collision energy is changed to make the parent ions collide Induced dissociation, when the intensity of the same kind of fragment ions obtained by the two methods is equal, the energy difference during the collision-induced dissociation process is the internal energy difference of the obtained monovalent positive ions. The present invention adopts collision-induced dissociation technology, which can select, activate, and collide parent ions, effectively avoiding interference from other ions; the calculation method is simple in principle and easy to operate; the difference in internal energy calculated by this method is 11.5±0.2eV, and the result Accurate, high stability, strong reliability.

Description

technical field [0001] The invention belongs to the field of analytical chemistry and relates to the technical field of mass spectrometry, in particular to a method for measuring the difference in internal energy of monovalent positive ions obtained by electrospray ionization and electrospray extraction ionization. Background technique [0002] Electrospray ionization mass spectrometry (ESI-MS) technology and electrospray extraction ionization mass spectrometry (EESI-MS) technology can be used for the detection of small molecules, peptides, proteins, nucleic acids and other macromolecules, in chemistry, biology, pharmacy, medicine, environment, etc. fields have important uses. Both ESI and EESI are soft ionization techniques, but their working principles and analytical performance are both different and related. In ESI, a high-voltage electric field is directly applied to the analytical sample solution flowing through a narrow capillary (inner diameter 100 μm), and the anal...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): G01N27/64
CPCG01N27/64
Inventor 张小平钟达财刘建川陈焕文
Owner EAST CHINA UNIV OF TECH
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