CN105987964A - High-efficiency separation and identification method for analyte by liquid chromatography-mass spectrometry - Google Patents
High-efficiency separation and identification method for analyte by liquid chromatography-mass spectrometry Download PDFInfo
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- CN105987964A CN105987964A CN201510064869.7A CN201510064869A CN105987964A CN 105987964 A CN105987964 A CN 105987964A CN 201510064869 A CN201510064869 A CN 201510064869A CN 105987964 A CN105987964 A CN 105987964A
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Abstract
The invention relates to a high-efficiency separation and identification method for an analyte by liquid chromatography-mass spectrometry. According to the method, trifluoroacetic acid is used as a liquid chromatogram mobile phase additive, volatile acid gas is introduced at an enclosed electro-spray ion source position, introduction of the volatile acid gas in an ionizationoun area can reduce or eliminate inhibition of trifluoroacetic acid to an electro-spray ionization mass spectrometry detection signal, and resolution and sensitivity of mass spectrum detection are increased. The separation and identification method is simple, the volatile acid introduced at the electro-spray ion source position can reduce or eliminate inhibition of trifluoroacetic acid to the electro-spray ionization mass spectrometry detection signal, and resolution and sensitivity of mass spectrum detection are increased.
Description
Technical field
The invention belongs to the studying technological domain of liquid chromatograph mass spectrography, be specifically related to one
Improve analyte chromatographic isolation resolution and Mass Spectrometer Method sensitivity, thus realize analyte
The method that high efficiency separation is identified.
Background technology
Liquid chromatograph mass spectrography is common isolation identification technology.Flowing mutually in add from
Son is to reagent, such as trifluoroacetic acid (TFA), formic acid etc., contributes to obtaining and preferably separates effect
Rate.Although trifluoroacetic acid in terms of separation on show the separating effect more superior than formic acid
(document 1.Garcia, M.C.；Hogenboom,A.C.；Zappey,H.；Irth,H.,Effect of
the mobile phase composition on the separation and detection of intact
proteins by reversed-phase liquid chromatography-electrospray mass
Spectrometry.Journal of chromatography.A 2002,957 (2), 187-99.), but by
Ionization Efficiency can be suppressed, with the mass spectrum of current high throughput identification protein not in trifluoroacetic acid
Compatible (document 2.Apffel, A.；Fischer,S.；Goldberg,G.et al.Enhanced
Sensitivity for Peptide-Mapping with Electrospray Liquid-Chromatography
Mass-Spectrometry in the Presence of Signal Suppression Due to
Trifluoroacetic Acid-Containing Mobile Phases.Journal of Chromatography A
1995,712 (1), 177-190.), therefore, many research work personnel are dropped by various methods
The ion depression effect of low trifluoroacetic acid.
Kuhlman etc. add the aqueous isopropanol containing propanoic acid, failure analysis thing and TFA after post
The ion pair formed, discharges analyte thus reduces ion inhibitory action, and the method has aobvious
Writing shortcoming is to cause the dilution of sample (document 3.Kuhlmann, F.E.；Apffel,A.；Fischer,
S.M.et al.Signal enhancement for gradient reverse-phase high-performance
liquid chromatography-electrospray ionization mass spectrometry analysis
with trifluoroacetic and other strong acid modifiers by postcolumn addition of
propionic acid and isopropanol.J Am Soc Mass Spectrom 1995,6(12),1221-
5.)；Corradini etc. reduce the concentration of the trifluoroacetic acid in flowing mutually, in chromatographic isolation and matter
Spectrum detection needs to find suitable concentration identification of analytes (document 4.Corradini, D.；
Huber,C.G.；Timperio,A.M.；Zolla,L.,Resolution and identification of the
protein components of the photosystem II antenna system of higher plants by
reversed-phase liquid chromatography with electrospray-mass spectrometric
detection.Journal of chromatography.A 2000,886(1-2),111-21.)；Also grind
Study carefully personnel and additionally add the volatile acids such as formic acid (document 5.You, J. in flowing mutually；Wang,L.；
Saji,M.et al.High-sensitivity TFA-free LC-MS for profiling histones.
Proteomics 2011,11 (16), 3326-34.), other additives of the method are still in flowing
It is unfavorable in mutually efficiently separating；Liu Huwei etc. use Bipolar Membrane electricity in the interface of application of gas chromatorgraphy/mass
The method of dialysis remove flowing phase TFA (document 6. Peking University. a kind of trifluoroacetic acid is removed
Device and application thereof: China, CN201110345371.X [P] .2012-6-20.), but build device
Complexity, needs suitable flow velocity voltage, changes the shortcomings such as liquid.
The acid that the present invention utilizes above-mentioned document to mention just can effectively reduce the depression effect of TFA,
Volatile high concentrated acid gas is introduced directly at airtight electric spray ion source, is analyzing
During the drop explosion of thing, the sour competitive binding trifluoroacetic acid root anion of high concentration
And realize protonation, destroy the effect of trifluoroacetic acid and analyte, discharge analyte, thus
Eliminate the trifluoroacetic acid inhibitory action to mass spectrum ion signal as much as possible, and then effectively dividing
The efficient qualification of analyte is realized on the basis of from.
Summary of the invention
The present invention is introducing volatility in the liquid chromatograph that Mobile Phase Additives is trifluoroacetic acid
Acid, eliminates the trifluoroacetic acid inhibitory action to mass spectrum ion signal, reaches liquid chromatograph-matter
Spectrum combination carries out the purpose of high efficiency separation qualification to analyte.
The technical scheme is that
Liquid chromatograph mass spectrography system of the present invention isolation identification efficient to analyte
Method is: use trifluoroacetic acid as liquid chromatogram mobile phase additive, and at airtight electricity
Introduce volatile acid gas at esi ion source and eliminate trifluoroacetic acid to Electrospray Mass Spectrometry detection letter
Number suppression.
Described volatile acid is that formic acid, acetic acid, propanoic acid, butanoic acid etc. can be used for mass spectrographic waving
One or more mixing in the property sent out acid, the purity of volatile acid is 98%-100%,
The introducing total amount of volatile acid be 7000 times of the quality of trifluoroacetic acid in ionisation region extremely
90 000 times.Volatile acid is to the pump that the method that liquid chromatograph introduces is by mass spectrum evacuation
Make the electric spray ion source closed be in the even lower negative pressure of 0.08Torr, force air
Collaborative volatile acid gas enters at airtight electric spray ion source, and described volatile acid uses
Liquid chromatograph separated flow be water and acetonitrile, wherein additive trifluoroacetic acid concentration range mutually
For 0.001%-20.000%.
The mechanism of action of trifluoroacetic acid is by volatile acid:
What the present invention proposed introduces at airtight electric spray ion source by volatile acid gas so that
The volatile acid gas of high concentration present in analyte ions region, competitive binding is also
Protonation trifluoroacetic acid root anion, destroys the effect of trifluoroacetic acid and analyte, release point
Analysis thing, thus eliminate the trifluoroacetic acid inhibitory action to mass spectrum ion signal as much as possible, have
Effect ground improves the ion signal intensity of analyte, and then improves the isolation identification efficiency of analyte.
The invention have the benefit that
This isolation and identification method is simple, it is only necessary to introduce volatilization at airtight electric spray ion source
Property acid i.e. can reduce or eliminate trifluoroacetic acid to Electrospray Mass Spectrometry detection signal suppression, carry
High mass signal, and then improve resolution and the sensitivity of detection.
Accompanying drawing explanation
Fig. 1 is the schematic drawing of instrument, uses and closes the combination of ionogenic liquid chromatography mass,
Wherein, volatile acid gas enters airtight electron spray by the pump of mass spectrum evacuation under negative pressure
At ion source.
Fig. 2 be formic acid and trifluoroacetic acid as Mobile Phase Additives time, ribonuclease, thin
Born of the same parents pigment c, lysozyme, the chromatograph base peak figure of Myoglobin；Wherein, during A figure is flowing mutually
Adding the formic acid of 0.1% volume fraction, B figure is to add 0.05% volume fraction in flowing mutually
Trifluoroacetic acid.
Fig. 3 be trifluoroacetic acid as additive in the case of, draw in analyte ions region
Entering the chromatograph base peak figure of different volatile acid, wherein, Fig. 3 A is for being not introduced into acid, and Fig. 3 B is
Introducing formic acid, Fig. 3 C is for introducing acetic acid, and Fig. 3 D is for introducing propanoic acid.
Fig. 4 be trifluoroacetic acid as additive in the case of, draw in analyte ions region
The chromatograph base peak figure entering propanoic acid and be not introduced into propanoic acid, wherein, solid line represents and is not introduced into propanoic acid,
Dotted line represents and introduces propanoic acid (PA).
Detailed description of the invention
Further illustrate the present invention below by embodiment, but the most therefore limit the invention to
Among described scope of embodiments, the equipment that the present invention uses is more preferable to the present invention
Open, it is not intended to the range of application of the present invention.
Liquid chromatograph uses the Accela 600HPLC system of Thermo company, and mass spectrum uses
The LTQ Orbitrap of Thermo company, the ion source of closing uses by thing exploitation of creating well
Coanda effect ion source CEESI, implements following experiment.
Embodiment 1 Mobile Phase Additives is formic acid or the trifluoroacetic acid impact on liquid chromatography mass
Selection standard pyrenoids ribonuclease T. (RNase), cytochrome c (Cyt c), bacteriolyze
Enzyme (Lysozyme), Myoglobin (Myoglobin) biased sample as analyte,
Liquid-phase chromatographic column uses C5 reversed phase chromatographic column (column length 130mm, internal diameter 75 μm, filler
Aperture), flowing selects formic acid or 0.05% volume fraction of 0.1% volume fraction mutually
Trifluoroacetic acid, flow velocity is about 200nL/min.Separation gradient is: after 5min, acetonitrile arrives mutually
Reach 20%, rise to 50% at 45min, reach 90% at 46min and continue 8min,
Aqueous phase balance 10min during 55min.Not blasting acid at ion source, other parameters of mass spectrum are as follows:
Voltage 1.9kV, mass ranges 500-2000m/z, resolution 60 000 is (at m/z 400
Place), use data dependence pattern that the parent ion of 5 before intensity is entered collision-induced cracking
(CID) obtaining the data of second order ms, collision energy is set to 35%.Sample introduction albumen is total
Measuring 0.6 μ g, each condition in triplicate, observes the change of its intensity.
As shown in Figure 2 A, when the formic acid that Mobile Phase Additives is 0.1% volume fraction, four
Plant albumen can not well be separated, as shown in Figure 2 B, when Mobile Phase Additives is
The trifluoroacetic acid of 0.05%, four kinds of albumen is well separated and peak shape is preferable, but its letter
Number intensity significantly weakens.Therefore, although trifluoroacetic acid can realize the high efficiency separation of liquid chromatograph,
But reduce mass signal, be unfavorable for the efficient qualification of analyte.
The effect of disinthibiting to trifluoroacetic acid of embodiment 2 volatile acid
Selection standard pyrenoids ribonuclease T. (RNase), cytochrome c (Cyt c), molten
Bacterium enzyme (Lysozyme), Myoglobin (Myoglobin) biased sample as analyte,
Liquid-phase chromatographic column uses C5 reversed phase chromatographic column (column length 130mm, internal diameter 75 μm, filler
Aperture), flow velocity is about 200nL/min.Separation gradient is: acetonitrile phase after 5min
Arrive 20%, rise to 50% at 45min, reach 90% at 46min and continue 8min,
The aqueous phase balance 10min when 55min.Air is blasted respectively at ion source, formic acid, acetic acid,
Propanoic acid, three kinds of sour consumptions are 4.6mL/min respectively, 2.64mL/min, 0.92mL/min.
Mass spectrometry parameters is as follows: voltage 1.9kV, mass ranges 500-2000m/z, resolution 60
000 (at m/z 400), uses data dependence pattern to be entered by the parent ion of 5 before intensity and touches
Hitting inducing lysis (CID) and obtain the data of second order ms, collision energy is set to 35%.
Sample introduction Tot Prot 0.6 μ g, each condition in triplicate, observes the change of its intensity.
From figure 3, it can be seen that in the case of trifluoroacetic acid is as Mobile Phase Additives, drum
Enter formic acid (Fig. 3 B), acetic acid (Fig. 3 C), propanoic acid (Fig. 3 D) and do not blasted acid (figure
Chromatograph base peak figure 3A) compares, and along with blasting of acid, the inhibitory action of trifluoroacetic acid subtracts
Weak, intensity is effectively improved.Wherein, the chromatograph base peak figure intensity that propanoic acid is corresponding is blasted
That improves is most, and acetic acid takes second place, and formic acid is the most weak, and reason is blasting due to acid, competitive
Combine trifluoroacetic acid root anion, destroy the combination of trifluoroacetic acid and analyte, release point
Analysis thing, so that signal improves.The ratio that the signal of overall albumen is improved by three kinds of acid is such as
Shown in table 1, sour blasts the intensity that improve each albumen, formic acid, acetic acid, and propanoic acid divides
The intensity level not making albumen averagely improves 3 times, 8 times, 10 times.
The ratio that the signal of overall albumen is improved by 1 three kinds of acid of table
Embodiment 3,4 is on the basis of Mobile Phase Additives is trifluoroacetic acid, after introducing acid
Explanation on the impact of analyte qualification result, but the most therefore limit the present invention to described
Among scope of embodiments.
Embodiment 3
Analyte is escherichia coli (K12 class) protein mixture, uses 20mM DTT,
After disulfide bond is opened by the method for 40mM IAA, desalination lyophilizing is redissolved.Liquid-phase chromatographic column is adopted
With C5 reversed phase chromatographic column (column length 130mm, internal diameter 75 μm, filler aperture),
Containing the TFA of 0.05% volume fraction in flowing mutually, flow velocity is about 200nL/min.During analysis
Between 120min, separate gradient be: after 5min, acetonitrile arrives 20% mutually, 95min rise
To 50%, reach 80% at 97min and continue 10min, the aqueous phase balance 12 when 108min
min.Air, propanoic acid (consumption is 0.92mL/min) is blasted respectively at ion source.Mass spectrum
Parameter is as follows: voltage 1.9kV, mass ranges 500-2000m/z, resolution 60 000
(at m/z 400), uses data dependence pattern that the parent ion of 5 before intensity is entered collision
Inducing lysis (CID) obtains the data of second order ms, and collision energy is set to 35%.7μg
Sample introduction, searches storehouse by ProSightPC, searches lab setting cysteine through IAA process, broken
Sheet tolerance is 20ppm, and quality is more than 5000Da.Data base uses people in Uniprot
Storehouse.The result obtained selects E value less than 1E-4.
The blasting of propanoic acid as can be seen from Figure 4, makes the signal of overall albumen the most significantly be carried
Height, meanwhile, searches storehouse by ProSightPC, and the result of three repetitive identified is as shown in table 2,
Do not blast propanoic acid identifies 58 albumen, and brings up to 79 albumen after blasting propanoic acid,
The qualification number of albumen improves 36%.Therefore, this method is keeping trifluoroacetic acid flowing phase
System reduces while the high separating efficiency to overall albumen or eliminates it to Electrospray Mass Spectrometry
The suppression of detection signal, is advantageously implemented the analysis of extensive overall albumen.
Embodiment 4
Analyte is the trypsin digestion sample of the BT474 cell protein after desalination, uses
The TFA of 0.05% volume fraction uses C18 reversed phase chromatographic column as additive, liquid chromatograph
(column length 130mm, internal diameter 75 μm, packing material size 5 μm), flow velocity is about 200
nL/min.Analysis time 120min, separate gradient be: after 2min, B acetonitrile arrives mutually
10%, rise to 35% at 92min, reach 100% at 98min and continue 7min,
A aqueous phase balance 14min during 106min.Blasting air at ion source respectively, acetic acid (disappears
Consumption is 2.64mL/min).Mass spectrometry parameters is as follows: voltage 1.9kV, mass ranges 400-
2000m/z, resolution 60 000 (at m/z 400), use data dependence pattern by strong
Spend the parent ion of front 6 to enter collision-induced cracking (CID) and obtain the data of second order ms,
Collision energy is set to 35%.2 μ g sample introductions, search storehouse by Mascot software, arrange alkyl
Turn to fixing modification, be oxidized to variable modification, mass deviation 20ppm, second order ms quality
Tolerance 0.8Da.Data base uses the storehouse of people in Uniprot.The result obtained selects score
Value is more than 20, and confidence interval is less than 0.01.
Searching storehouse by Mascot, the result of three repetitive identified is as shown in table 2, does not blasts second
Identify 343 albumen, 1360 peptide fragments during acid, and when blasting acetic acid, identify 616
Albumen, 2511 peptide fragments, the number increase of albumen and peptide fragment connects by about one time.To sum up, trifluoro
Acetic acid achieves the high efficiency separation of peptide hydrolysis, and blasting of acetic acid, reduce or eliminate three
The Fluoroethanoic acid suppression to Mass Spectrometer Method signal, is advantageously implemented the analysis of extensive peptide hydrolysis.
Qualification result contrast in table 2 complex sample
Claims (5)
1. a liquid chromatograph mass spectrography system isolation and identification method to analyte, it is special
Levy and be: use trifluoroacetic acid is as liquid chromatogram mobile phase additive, at airtight electron spray
Volatile acid gas is introduced, by introducing volatile acid gas in ionisation region at ion source
Reduce or eliminate the trifluoroacetic acid suppression to Electrospray Mass Spectrometry detection signal, improving mass signal,
And then improve resolution and the sensitivity of detection.
Isolation and identification method the most according to claim 1, it is characterised in that:
Described volatile acid is that formic acid, acetic acid, propanoic acid, butanoic acid etc. can be used for mass spectrographic volatilization
Property acid in one or more mixing, the purity of volatile acid is 98%-100%, volatilization
Property acid introducing total amount be 7000 times to 90000 times of trifluoroacetic acid quality in ionisation region.
Isolation and identification method the most according to claim 1, it is characterised in that:
Volatile acid is to make to close by the pump of mass spectrum evacuation to the method that liquid chromatograph introduces
Electric spray ion source be in the even lower negative pressure of 0.08Torr, force air to work in coordination with volatility
Acid gas enters at airtight electric spray ion source.
Isolation and identification method the most according to claim 1, it is characterised in that:
The liquid chromatograph separated flow that described volatile acid uses is water and acetonitrile mutually, Qi Zhongtian
Adding agent trifluoroacetic acid concentration range is 0.001%-20.000%.
Isolation and identification method the most according to claim 1, it is characterised in that:
Described analyte is the biological sample such as peptide hydrolysis or overall protein example.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111655349A (en) * | 2018-01-29 | 2020-09-11 | 沃特世科技公司 | Difluoroacetic acid ion pairing reagents for high sensitivity, high resolution LC-MS of biomolecules |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000070335A2 (en) * | 1999-05-17 | 2000-11-23 | Advanced Research & Technology Institute | Ion mobility and mass spectrometer |
| CN101363779A (en) * | 2008-06-26 | 2009-02-11 | 复旦大学 | Method for enhancing ionization efficiency of peptide segment |
| CN102507296A (en) * | 2011-11-04 | 2012-06-20 | 北京大学 | Trifluoroacetic acid removing device and application thereof |
-
2015
- 2015-02-06 CN CN201510064869.7A patent/CN105987964B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000070335A2 (en) * | 1999-05-17 | 2000-11-23 | Advanced Research & Technology Institute | Ion mobility and mass spectrometer |
| CN101363779A (en) * | 2008-06-26 | 2009-02-11 | 复旦大学 | Method for enhancing ionization efficiency of peptide segment |
| CN102507296A (en) * | 2011-11-04 | 2012-06-20 | 北京大学 | Trifluoroacetic acid removing device and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| ANASTASIA KHARLAMOVA等: "Electrospray droplet exposure to gaseous acids for reduction of metal counter-ions in nucleic acid ions", 《INTERNATIONAL JOURNAL OF MASS SPECTROMETRY》 * |
| ANASTASIA KHARLAMOVA等: "Electrospray Droplet Exposure to Gaseous Acids for the Manipulation of Protein Charge State Distributions", 《ANAL CHEM.》 * |
| YAN LIU等: "Signal and charge enhancement for protein analysis by liquid chromatography–mass spectrometry with desorption electrospray ionization", 《INTERNATIONAL JOURNAL OF MASS SPECTROMETRY》 * |
| ZENGRU WU等: "Favorable Effects of Weak Acids on Negative-Ion Electrospray Ionization Mass Spectrometry", 《ANAL CHEM.》 * |
| 张婷婷等: "采用柱后抑制器技术降低流动相中三氟乙酸（TFA）对多肽质谱信号抑制作用", 《第十届全国生物医药色谱及相关技术学术交流会论文集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111655349A (en) * | 2018-01-29 | 2020-09-11 | 沃特世科技公司 | Difluoroacetic acid ion pairing reagents for high sensitivity, high resolution LC-MS of biomolecules |
| CN111655349B (en) * | 2018-01-29 | 2022-04-19 | 沃特世科技公司 | Difluoroacetic acid ion pairing reagents for high sensitivity, high resolution LC-MS of biomolecules |
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