CN106680360A - Preparation method and application of mercury ion charge carrier-based gas-phase polypeptide cations - Google Patents

Preparation method and application of mercury ion charge carrier-based gas-phase polypeptide cations Download PDF

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Publication number
CN106680360A
CN106680360A CN201710055082.3A CN201710055082A CN106680360A CN 106680360 A CN106680360 A CN 106680360A CN 201710055082 A CN201710055082 A CN 201710055082A CN 106680360 A CN106680360 A CN 106680360A
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polypeptide
gas phase
ion
cation
preparation
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陈相峰
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Shandong Analysis and Test Center
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Shandong Analysis and Test Center
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/68Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving proteins, peptides or amino acids
    • G01N33/6803General methods of protein analysis not limited to specific proteins or families of proteins
    • G01N33/6848Methods of protein analysis involving mass spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q

Abstract

The invention discloses a preparation method and application of mercury ion charge carrier-based gas-phase polypeptide cations. The gas-phase polypeptide cations can be quickly and stably prepared. A research result shows that the prepared polypeptide cations can generate more structural information fragment ions than traditional collision dissociation and electron capture dissociation. According to the technical scheme, a mixed solution is prepared by mixing polypeptide and mercury salt; electro-spray ionization is carried out on the mixed solution to obtain gas-phase polypeptide parent ions; and the gas-phase polypeptide parent ions are treated by adopting electron capture dissociation/collision dissociation to obtain fragment ions, namely the mercury ion charge carrier-based gas-phase polypeptide cations.

Description

The preparation method and application of the gas phase polypeptide cation based on mercury ion charge carrier
Technical field
Preparation method and application the present invention relates to be based on the gas phase polypeptide cation of mercury ion charge carrier.
Background technology
Development based on mass spectrographic molecular ion activating technology has favorably promoted biomolecular structure confirmation.Biomolecule string The structural information that connection mass spectrum is obtained depends on the selection of parent ion and cracking technique.For same unknown structure, polymorphic type Parent ion be selected to provide abundant chemical groups information for structural confirmation process, effectively ensure structural confirmation result Accuracy.Under normal circumstances, parent ion is using single or many protonations, or deprotonation negative molecular ion.Secondly level Mass-spectrometric technique uses Collision-induced dissociation technology.Traditional Collision-induced dissociation technology can only often make molecule build passage cracking along low energy, Obtain structural information limited;Additionally, due to there is moveable proton in Collision-induced dissociation reaction, molecule can not occur free radical and lure Lead cracking, making it difficult to obtain the specific finger-print of molecule.
Gas phase polypeptide radical cation and poor hydrogen cation, intramolecule do not exist removable proton, can avoid Effect ground is due to the limitation of molecular cleavage passage.However, because such ion has very strong reactivity, being often difficult capture Its signal.If the stabilization signal of gas phase polypeptide radical cation can be realized, it becomes possible to further obtain its fragment from Son, can provide abundant fragment ion information for the structure determination of peptide and protein molecule, promote unknown exact sequence knot The measure of structure.The homolysis that the acquisition of traditional poor hydrogen polypeptide cation drives by the reaction of laser and chromophore or free radical Reaction.The former relies on laser, and requires that biomolecule can introduce group of adding lustre in itself;The latter is complicated due to course of reaction, Often be difficult to live the poor hydrogen polypeptide radical cation that must stablize.Therefore, a kind of gas phase polypeptide cation of fast and stable is set up Production method be highly desirable to.
The content of the invention
To overcome the defect of prior art, the invention provides the gas phase polypeptide cation based on mercury ion charge carrier Preparation method, is capable of the preparation gas phase polypeptide cation of fast and stable, and result of study shows that the polypeptide cation of preparation can compare Traditional Collision-induced dissociation and electronics capture cracking can produce more structural information fragment ions.
To achieve the above object, the technical scheme is that:
The preparation method of the gas phase polypeptide cation based on mercury ion charge carrier, polypeptide and mercury salt is prepared by mixing into mixed Close solution, by the mixed solution carry out electro-spray ionization obtain gas phase polypeptide parent ion, using electronics capture cracking and/or Collision is split and gas phase polypeptide parent ion is carried out treatment acquisition fragment ion, the gas phase polypeptide sun as based on mercury ion charge carrier Ion.
The present invention is introducing mercury ion as charge carrier, shields the cracking passage that proton is produced as charge carrier, Obtain stabilization gas phase polypeptide cation signal, the method produce polypeptide cation ratio by laser, chromophore label with And the cationic stabilized that the method for metal complex-polypeptide ternary complex is produced, can realize polypeptide structure using the method Confirm, the binding site of synchronization gain polypeptide and mercury ion, reduce cost required for traditional gas phase polypeptide cation generation, It is easy to operate, signal stabilization.
The invention aims to obtain monovalence gas phase polypeptide cation, divalence gas phase polypeptide cation, or simultaneously Obtain monovalence gas phase polypeptide cation and divalence gas phase polypeptide cation.So, the present invention captures cracking and obtains one by electronics Valency gas phase polypeptide cation, divalence gas phase polypeptide cation is obtained by Collision-induced dissociation, and by the divalence of Collision-induced dissociation acquisition Gas phase polypeptide cation can further obtain monovalence gas phase polypeptide cation by electronics capture cracking again.
Polypeptide and mercury salt solubility in a solvent are simultaneously differed, in order that polypeptide can be well mixed with mercury salt, this hair The bright a kind of method mixed with mercury salt there is provided polypeptide, polypeptide solution is configured to by polypeptide, then by mercury salt add to methyl alcohol with go Metal ion solution is configured in the mixed solvent of ionized water, mixing is obtained after polypeptide solution is mixed with metal ion solution molten Liquid.Polypeptide can be made to be well mixed with mercury salt.
In order that obtaining more qualified gas phase polypeptide parent ion, the present invention provides a kind of electro-spray ionization method, The mixed solution is processed using Nanoliter electrospray, parent ion selection is then carried out using level Four bar.
The second object of the present invention is there is provided the gas phase polypeptide cation based on mercury ion charge carrier.The gas phase polypeptide Cation has more structural informations.
In order to confirm the structure of polypeptide, the invention provides above-mentioned gas phase polypeptide cation in analysis polypeptide structure Using.Because the gas phase polypeptide cation for preparing is more stable, structural information more comprehensively, thus is divided using the gas phase polypeptide cation Analyse corresponding polypeptide structure more accurate.
The third object of the present invention is the method for providing above-mentioned gas phase polypeptide cation analysis polypeptide, using Fourier transform ICR carries out information gathering acquisition Collision-induced dissociation spectrogram to above-mentioned gas phase polypeptide cation and/or electronics is caught Cracking pattern is obtained, the type of gas phase polypeptide cation is analyzed according to Collision-induced dissociation spectrogram and/or electronics capture cracking pattern and is returned Category, so as to confirm polypeptide structure.The binding site of mercury ion and polypeptide can also be obtained, so as to be mercury ion to the toxicity of polypeptide Analysis provides foundation.
Compared with prior art, the beneficial effects of the invention are as follows:
Preparation method of the invention introduces mercury ion as charge carrier, shields proton as splitting that charge carrier is produced Solution passage, obtains the gas phase polypeptide cation signal of stabilization, and the polypeptide cation ratio that the method is produced relies on laser, chromophore The cationic stabilized that the method for mark and metal complex-polypeptide ternary complex is produced, can be realized many using the method Peptide structural confirmation, synchronization gain polypeptide and the binding site of mercury ion, reduce traditional gas phase polypeptide cation generation required Cost is wanted, easy to operate, signal stabilization.
The method that mixes with mercury salt of polypeptide that the present invention is used, can be such that polypeptide is well mixed with mercury salt, make mercury ion and The binding site of polypeptide increases, so as to obtain more more stable gas phase polypeptide cations.
Gas phase polypeptide cation prepared by the present invention has more structural informations, using the gas phase polypeptide cation to many The structural analysis of peptide is more accurate.
Gas phase polypeptide cation prepared by the present invention can not only analyze the structure for obtaining polypeptide, additionally it is possible to obtain mercury ion With the binding site of polypeptide so that for mercury ion provides foundation to the oxicity analysis of polypeptide.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing further understanding of the present application, and the application's shows Meaning property embodiment and its illustrated for explaining the application, does not constitute the improper restriction to the application.
Fig. 1 is the electronics capture Pyrolysis Mass Spectrometry figure of model peptide fragment 1 (RGGGWGGGR) and mercury ion compound;
Fig. 2 is the Collision-induced dissociation mass spectrogram of model peptide fragment 2 (RPPGFSPFR) and mercury ion compound;
Fig. 3 is the Collision-induced dissociation mass spectrogram of model peptide fragment 2 (RPPGFSPFR) bivalent cation;
Fig. 4 is the electro transfer Pyrolysis Mass Spectrometry figure of model peptide fragment 2 (RPPGFSPFR) bivalent cation;
Fig. 5 is the Collision-induced dissociation mass spectrogram of model peptide fragment 3 (RAAAWAAAR) monovalent radical cation.
Specific embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative Be also intended to include plural form, additionally, it should be understood that, when in this manual use term "comprising" and/or " bag Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Heretofore described polypeptide is the compound that a-amino acid is formed so that peptide chain links together, and it is also albumen The intermediate product of matter hydrolysis.Such as model peptide fragment 1 (RGGGWGGGR, such as SEQ ID NO:1), model peptide fragment 2 (RPPGFSPFR, Such as SEQ ID NO:2), model peptide fragment 3 (RAAAWAAAR, such as SEQ ID NO:3) or other protein hydrolysis intermediate product.
Heretofore described mercury salt is that cation is the compound of mercury ion.Such as mercuric nitrate (Hg (NO3)2), mercuric sulfate (HgSO4), mercuric bromide (HgBr2) etc..
Heretofore described gas phase polypeptide parent ion is to process polypeptide with mixing that mercury salt is prepared by mixing into by electron spray Close the parent ion that solution is obtained.Heretofore described parent ion, also referred to as precursor ion (precursor ion), can enter one Step is decomposed and reacts the ion of generation fragment ion.
Heretofore described deionized water for nature water eliminate the elements such as sodium, calcium, iron, copper cation and Water after the anion of the elements such as chlorine, bromine.
As background technology is introduced, the poor hydrogen polypeptide radical cation course of reaction complexity of prior art preparation, Less stable, in order to solve the above technical problems, the invention provides the gas phase polypeptide cation based on mercury ion charge carrier Preparation method.
In a kind of typical implementation method of the invention, polypeptide and mercury salt are prepared by mixing into mixed solution, will be described mixed Closing solution carries out electro-spray ionization acquisition gas phase polypeptide parent ion, is split using electronics capture cracking and/or collision many to gas phase Peptide parent ion carries out treatment and obtains fragment ion, the gas phase polypeptide cation as based on mercury ion charge carrier.
In order to ensure that polypeptide can be well mixed with mercury salt, enable mercury ion that multidigit point combination is carried out on polypeptide, preferably Polypeptide be with the hybrid mode of mercury salt:Polypeptide is configured to polypeptide solution, then mercury salt is added to methyl alcohol and deionized water Metal ion solution is configured in mixed solvent, mixed solution is obtained after polypeptide solution is mixed with metal ion solution.Methyl alcohol It is a kind of polar solvent, can be miscible with water, methyl alcohol forms azeotropic mixture with water, and its boiling point reduces solvent less than the boiling point of water The temperature of evaporation.First prepare polypeptide solution, can be dispersed into solvent by polypeptide, then again with metal ion solution Mixing, can be such that more mercury ions are combined with polypeptide macromolecule, so that mercury ion can carry out multidigit point combination on polypeptide.
It is further preferred that the resistance of the deionized water for using is more than 18.2 megaohms.It is more beneficial for using the deionized water The dissolving of polypeptide, so as to will improve polypeptide solubility.
In order to be further ensured that mercury salt preferably dissolves, methyl alcohol is 1 with the volume ratio of deionized water:1.
It is further preferred that the volume ratio of polypeptide solution and metal ion solution is 1:1.
It is further preferred that polypeptide and the mol ratio of mercury ion are 1 in mixed solution:5.
In order that obtaining more qualified gas phase polypeptide parent ion, the present invention provides a kind of electro-spray ionization method, The mixed solution is processed using Nanoliter electrospray, parent ion selection is then carried out using level Four bar.
Used in a kind of embodiment of the invention the condition of Nanoliter electrospray for:Flow rate set is 10 μ L/hr, capillary Voltage is set to 1kV, and the temperature of transfer capillary is 275 DEG C.
Sextupole bar ion assemble index is set to 5s in a kind of embodiment of the invention.Mass spectrum collection molecular weight is set as 100-1500。
Collision-induced dissociation is carried out in collision cell in a kind of embodiment of the invention, electronics capture cracking Fourier transform from Carried out in the ion pond (cell) of sub- synchrometer.
In order to increase Collision-induced dissociation, the impact energy of Collision-induced dissociation is set as 10-25V.
In order to increase electronics capture cracking, electron radiation set of time is 1s.
The invention provides a kind of preparation method of the gas phase polypeptide cation for being preferably based on mercury ion charge carrier, step It is rapid as follows:
(1) sample pre-treatments:Weigh appropriate polypeptide (about 0.5mg), configuration concentration be 0.1 μM (μM be μm ol/L) it is many Peptide solution, weighs appropriate mercuric nitrate, is 1 with volume ratio:1 methyl alcohol and deionized water (>18.2 megaohms) be configured to mercury from Sub- concentration is 0.5 μM of metal ion solution, is 1 according to volume ratio by polypeptide solution and metal ion solution:1 mixing.
(2) electro-spray ionization condition:Using Fourier's series ICR.Using Nanoliter electrospray, Flow rate set is 10 μ L/hr, and capillary voltage is set to 1kV, and the temperature of transfer capillary is 275 DEG C.Using mass spectrometric four Pole bar carries out parent ion selection, and selection parent ion mass number is polypeptide and dimercurion adduct, i.e. ([M+Hg]2+), sextupole Bar ion assemble index is set to 5s.Mass spectrum gathers molecular weight ranges and is changed according to polypeptide molecular weight, is set to 100-1500.
(3) tandem mass spectrum cleavage method:For the compound parent ion for selecting, Collision-induced dissociation and electronics can be respectively adopted Inducing lysis obtain polypeptide (free radical) cation of monovalence and divalence.Collision-induced dissociation is carried out in collision cell, and condition is use Impact energy is set to 10-25V, and electronics capture cracking is entered in the mass spectrometric ion pond (cell) of Fourier Transform Ion cyclotron Resonance OK, in order to increase electronics capture cracking, electron radiation set of time be 1s, for Collision-induced dissociation produce divalence polypeptide sun from Son, can further carry out electronics capture cracking in ion pond.
The second object of the present invention is there is provided the gas phase polypeptide cation based on mercury ion charge carrier.The gas phase polypeptide Cation has more structural informations.
In order to confirm the structure of polypeptide, the invention provides above-mentioned gas phase polypeptide cation in analysis polypeptide structure Using.Because the gas phase polypeptide cation for preparing is more stable, structural information more comprehensively, thus is divided using the gas phase polypeptide cation Analyse corresponding polypeptide structure more accurate.
The third object of the present invention is the method for providing above-mentioned gas phase polypeptide cation analysis polypeptide, using Fourier transform ICR carries out information gathering acquisition Collision-induced dissociation spectrogram to above-mentioned gas phase polypeptide cation and/or electronics is caught Cracking pattern is obtained, the type of gas phase polypeptide cation is analyzed according to Collision-induced dissociation spectrogram and/or electronics capture cracking pattern and is returned Category, so as to confirm polypeptide structure.The binding site of mercury ion and polypeptide can also be obtained, so as to be mercury ion to the toxicity of polypeptide Analysis provides foundation.
The mass spectrometric accuracy of Fourier Transform Ion cyclotron Resonance is set as 5ppm, energy by a kind of embodiment of the invention Enough more accurate types and ownership for determining fragment ion.
Embodiment 1
The polypeptide that the present embodiment is used is model peptide fragment 1 (RGGGWGGGR), such as SEQ ID NO:1.
(1) sample pre-treatments:The polypeptide of 0.5mg is weighed, is 1 with volume ratio:1 methyl alcohol and deionized water configuration concentration is 0.1 μM of polypeptide solution, weighs appropriate mercuric nitrate, is 1 with volume ratio:1 methyl alcohol and deionized water (>18.2 megaohms) match somebody with somebody The metal ion solution that ion concentration of mercury is 0.5 μM is set to, is 1 according to volume ratio by polypeptide solution and metal ion solution:1 mixes Close.
(2) electro-spray ionization condition:Using Fourier's series ICR.Using Nanoliter electrospray, Flow rate set is 10 μ L/hr, and capillary voltage is set to 1kV, and the temperature of transfer capillary is 275 DEG C.Using mass spectrometric four Pole bar carries out parent ion selection, and selection parent ion mass number is polypeptide and dimercurion adduct, i.e. ([M+Hg]2+), sextupole Bar ion assemble index is set to 5s.Mass spectrum gathers molecular weight ranges and is changed according to polypeptide molecular weight, is typically set to 800.
(3) tandem mass spectrum cleavage method:For the compound parent ion for selecting, Collision-induced dissociation and electronics can be respectively adopted Inducing lysis obtain polypeptide (free radical) cation of monovalence and divalence.Collision-induced dissociation is carried out in collision cell, and condition is use Impact energy is set to 15V, and electronics capture cracking is carried out in the mass spectrometric ion pond (cell) of Fourier Transform Ion cyclotron Resonance, It is 1s to increase electronics capture cracking electron radiation set of time, for the divalence polypeptide cation that Collision-induced dissociation is produced, can Further to carry out electronics capture cracking in ion pond.
(4) fragment ion type analysis:According to the mass spectrometric high-resolution feature of Fourier Transform Ion cyclotron Resonance, knot Possible fragment type is closed, accuracy is set as 5ppm.Respectively for Collision-induced dissociation and electronics capture cracking pattern in fragment from Son is analyzed, and determines the type and ownership of the fragment ion of electronic induction cracking.
Embodiment 2
The present embodiment is same as Example 1, and difference is to employ model peptide fragment 2 (RPPGFSPFR), such as SEQ ID NO:2。
Embodiment 3
The present embodiment is same as Example 1, and difference is to employ model peptide fragment 3 (RAAAWAAAR), such as SEQ ID NO:3。
The fragment ion that embodiment 1~3 is obtained is analyzed as follows:
Visible by Fig. 1, for model peptide fragment 1 (RGGGWGGGR) and the compound of mercury ion, the capture cracking of its electronics is removed Produce outside without the c-/z- type fragment ions of metal ion, can also produce the monovalence polypeptide free radical sun of signal stabilization from Son;Visible by Fig. 2, for model peptide fragment 2 (RPPGFSPFR) and mercury ion compound, its Collision-induced dissociation mass spectrogram has bright The signal of aobvious divalence polypeptide cation, it can be seen that, by using metal mercury ion as charge carrier, polypeptide can be obtained Monovalent radical cation and bivalent cation;It is visible by Fig. 3, it is multiple for model peptide fragment 2 (RPPGFSPFR) and mercury ion Divalence polypeptide cation produced by compound, its Collision-induced dissociation can generate continuous b-/y- types fragment ion;It is visible by Fig. 4, For the divalence polypeptide cation produced by model peptide fragment 2 (RPPGFSPFR) and mercury ion compound, electronics capture can be carried out Cracking, and continuous c-/z- types fragment ion can be generated;It is visible by Fig. 5, for model peptide fragment 3 (RAAAWAAAR) monovalence The Collision-induced dissociation of radical cation, it is seen that the peptide fragment can produce continuous a-/z- types fragment ion.From use above, Gas phase polypeptide cation generation method based on mercury ion charge carrier can generate monovalence and divalence the polypeptide sun of signal stabilization Ion, and can meet continuous series connection cracking, obtains polytype fragment ion, can apply to polypeptide and other The structural analysis of biomolecule.
Although above-mentioned be described with reference to accompanying drawing to specific embodiment of the invention, not to invention protection domain Limitation, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to The various modifications or deformation made by paying creative work are still within the scope of the present invention.
SEQUENCE LISTING
<110>Shandong Forecasting and Analysis Center
<120>The preparation method and application of the gas phase polypeptide cation based on mercury ion charge carrier
<130> 2017
<160> 3
<170> PatentIn version 3.5
<210> 1
<211> 9
<212> PRT
<213>Simulation peptide fragment
<400> 1
Arg Gly Gly Gly Trp Gly Gly Gly Arg
1 5
<210> 2
<211> 9
<212> PRT
<213>Simulation peptide fragment
<400> 2
Arg Pro Pro Gly Phe Ser Pro Phe Arg
1 5
<210> 3
<211> 9
<212> PRT
<213>Simulation peptide fragment
<400> 3
Arg Ala Ala Ala Trp Ala Ala Ala Arg
1 5

Claims (10)

1. the preparation method of the gas phase polypeptide cation of mercury ion charge carrier is based on, it is characterized in that, polypeptide is mixed with mercury salt Mixed solution is prepared into, the mixed solution is carried out into electro-spray ionization obtains gas phase polypeptide parent ion, is captured using electronics Cracking and/or collision are split and gas phase polypeptide parent ion is carried out treatment acquisition fragment ion, as based on mercury ion charge carrier Gas phase polypeptide cation.
2. preparation method as claimed in claim 1, it is characterized in that, polypeptide is configured to polypeptide solution, then by mercury salt add to Metal ion solution is configured in methyl alcohol and the mixed solvent of deionized water, is obtained after polypeptide solution is mixed with metal ion solution Obtain mixed solution.
3. preparation method as claimed in claim 2, it is characterized in that, the resistance of the deionized water of use is more than 18.2 megaohms.
4. preparation method as claimed in claim 2, it is characterized in that, methyl alcohol is 1 with the volume ratio of deionized water:1.
5. preparation method as claimed in claim 1, it is characterized in that, using Nanoliter electrospray to the mixed solution at Reason, then carries out parent ion selection using level Four bar.
6. preparation method as claimed in claim 5, it is characterized in that, use the condition of Nanoliter electrospray for:Flow rate set is 10 μ L/hr's, capillary voltage is set to 1kV, and the temperature of transfer capillary is 275 DEG C.
7. preparation method as claimed in claim 1, it is characterized in that, the impact energy of Collision-induced dissociation is set as 10-25V;
Or, the electron radiation set of time of electronics capture cracking is 1s.
8. the gas phase polypeptide cation of mercury ion charge carrier is based on, it is characterized in that, using any described systems of claim 1-7 Preparation Method is prepared.
9. application of the gas phase polypeptide cation described in claim 8 in analysis polypeptide structure.
10. the method for the gas phase polypeptide cation analysis polypeptide described in claim 8, using Fourier Transform Ion cyclotron Resonance Mass spectrograph carries out information gathering to above-mentioned gas phase polypeptide cation and obtains Collision-induced dissociation spectrogram and/or electronics capture cracking pattern, The type and ownership of gas phase polypeptide cation are analyzed according to Collision-induced dissociation spectrogram and/or electronics capture cracking pattern, so as to confirm Polypeptide structure.
CN201710055082.3A 2017-01-24 2017-01-24 Preparation method and application of mercury ion charge carrier-based gas-phase polypeptide cations Pending CN106680360A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101936948A (en) * 2010-08-06 2011-01-05 浙江省肿瘤医院 Mass spectrum detection method of serum polypeptide
CN105572273A (en) * 2016-01-20 2016-05-11 山东省分析测试中心 Ginsenoside isomerism monomer recognition method based on electron induced pyrolysis mass spectrometry
CN106198713A (en) * 2016-09-09 2016-12-07 山东省分析测试中心 A kind of Electrospray Ionization Mass Spectrometry system based on micro-solid phase extraction pond and its preparation method and application

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CN101936948A (en) * 2010-08-06 2011-01-05 浙江省肿瘤医院 Mass spectrum detection method of serum polypeptide
CN105572273A (en) * 2016-01-20 2016-05-11 山东省分析测试中心 Ginsenoside isomerism monomer recognition method based on electron induced pyrolysis mass spectrometry
CN106198713A (en) * 2016-09-09 2016-12-07 山东省分析测试中心 A kind of Electrospray Ionization Mass Spectrometry system based on micro-solid phase extraction pond and its preparation method and application

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CHIH-WEI LIU等: "Effects of Electron-Transfer Coupled with Collision-Induced Dissociation (ET/CID) on Doubly Charged Peptides and Phosphopeptides", 《JOURNAL OF AMERICAN SOCIETY FOR MASS SPECTROMETRY》 *
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Application publication date: 20170517