CN102262121A - Method for coupling porous electrode electrochemical cell with desorption electrospray ionization mass spectrometry of liquid samples - Google Patents
Method for coupling porous electrode electrochemical cell with desorption electrospray ionization mass spectrometry of liquid samples Download PDFInfo
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- CN102262121A CN102262121A CN2010101831644A CN201010183164A CN102262121A CN 102262121 A CN102262121 A CN 102262121A CN 2010101831644 A CN2010101831644 A CN 2010101831644A CN 201010183164 A CN201010183164 A CN 201010183164A CN 102262121 A CN102262121 A CN 102262121A
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Abstract
The invention relates to a method for coupling a porous electrode electrochemical cell with the desorption electrospray ionization mass spectrometry of liquid samples. By the method, the problems of difficulty in matching high and low voltage, background oxidization, non-free selection of solvents and low oxidization/reduction efficiency of cells in the conventional process of coupling the electrochemical cell with the electrospray ionization mass spectrometry are mainly solved. In the method for coupling the porous electrode electrochemical cell with the desorption electrospray ionization mass spectrometry of the liquid samples, the problems are better solved by the technical scheme that products oxidized or reduced by the porous electrode electrochemical cell (2) are desorbed or ionized directly by a spray solvent which is generated by a high-speed electrospray ionization (ESSI) probe (1) and carries charges at a high speed and enter a mass spectrometry detector (3) to be detected, so the method can be used for the industrial production of the electrochemical cells and mass spectrum analysis.
Description
Technical field
The present invention relates to a kind of porous electrode electrochemical cell and fluid sample and resolve the electrospray ionization mass spectrum coupling method.
Background technology
The combination of galvanochemistry Electrochemistry and mass spectrum Mass spectrometry is a kind of effective tool of studying electrochemical reaction product and intermediate, can be used for the mechanism research of redox reaction.Adopt mass spectrum as electrochemical detecting device, it is advantageous that mass spectrum can provide the information of molecular weight, tandem mass spectrum can also provide structure analysis.Traditional have thermal spray TS, fast atom bombardment FAB and electron spray ESI with mass spectrum ionization mode galvanochemistry EC coupling.Electrospray ionization mass spectrum ESI-MS is that ionization is non-volatile, the effective means of polarity, thermal stability compound and biomacromolecule, but the redox reaction of galvanochemistry EC and electrospray ionization mass spectrum ESI-MS coupling modeling effort biosome.
Atmospheric pressure mass spectrum ionization technique is the new ionization technique of a class that grew up in recent years, its allows under atmospheric pressure ionized sample and sample pretreatment simple, comprise and resolve electron spray ionisation DESI, directly real-time ionization DART, analyzing atmospheric pressure chemical ionization DAPCI etc., resolving electron spray ionisation DESI is wherein a kind of representational ionization method, resolves electrospray ionization mass spectrum DESI-MS usually and is used for analysing solid sample.
Document Electrochemistry Combined Online with Electrospray Mass Spectrometry (FeimengZhou and Gary J.Van Berkel, Anal.Chem.1995,67 (20), 3643-3649) reported the online coupling of different electrochemical cell (stainless-steel tube battery, thin layer electrode battery and porous electrode battery) and electrospray ionization mass spectrum.Because the voltage that electron spray ionisation uses is 3000～5000V, and the voltage that electrochemical cell uses is 0.5～2.0V normally, adopt galvanochemistry and the direct coupling of electrospray ionization mass spectrum, electrochemical cell need be connected with quartz capillary with the electron spray ionisation source and at middle ground or allow and float on the high voltage of voltage at electron spray ionisation of electrochemical cell, this galvanochemistry and electrospray ionization mass spectrum coupling devices still exist high low-voltage to be difficult to coupling, background oxidation, solvent to select comfortless problem.
Document Direct Analysis of Liquid Samples by Desorption Electrospray Ionization-MassSpectrometry (DESI-MS) (Zhixin Miao and Hao Chen, Journal of the America Society for MassSpectrometry 2009,20,10-19) reported that parsing electrospray ionization mass spectrum DESI-MS is used for analyzing liquid sample and with the stainless-steel tube battery with resolve the direct coupling of electrospray ionization mass spectrum DESI-MS.This stainless-steel tube battery and parsing electrospray ionization mass spectrum coupling devices exist electrochemical redox and the low problem of ionizing efficiency.
Document Online Coupling of Electrochemical Reactions with Liquid Samples DesorptionElectrospray Ionization-Mass Spectrometry (Jiwen Li, Howard D.Dewald, and Hao Chen, Anal.Chem.2009,81,9716-9722) reported that a kind of thin layer electrode electrochemical cell and fluid sample resolve the electrospray ionization mass spectrum coupling method and studied the application of this method in bio-oxidation/reduction, the oxidation/reduction efficiency of this method still awaits further raising.
Summary of the invention
Technical matters to be solved by this invention exists high low-voltage to be difficult to coupling, background oxidation, solvent to select not freedom and the inefficient problem of battery redox, provide a kind of new porous electrode electrochemical cell and fluid sample to resolve the electrospray ionization mass spectrum coupling method when being electrochemical cell and electrospray ionization mass spectrum coupling in the past.This method has that device is simple, easy to operate, the response time is short, battery oxidation/reduction and the high advantage of ionizing efficiency.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of porous electrode electrochemical cell and fluid sample are resolved the electrospray ionization mass spectrum coupling method, the spraying solvent that carries electric charge by the high speed of high speed electron spray ionisation ESSI probe (1) product of (2) oxidation of porous electrode electrochemical cell or reduction is directly resolved or ionization after enter mass detector (3) and detect.
In the technique scheme, high-voltage power supply (6) voltage of high speed electron spray ionisation ESSI probe is ± (3000～5000) volt, and high velocity fog gas is nitrogen, pressure is 110～200Psi.The power supply of porous electrode electrochemical cell (17) voltage is ± (0.5～2.0) volt.Kapillary (10) sample export of the solvent outlet of probe rod (9) and conveying electrochemical cell oxidation/reduzate and the injection port (12) of mass detector (11) are located along the same line.
Porous electrode battery Porous electrode flow cell and fluid sample are resolved the redox product that the direct coupling of electrospray ionization mass spectrum DESI-MS can utilize parsing of high speed electron spray ESSI probe or ionization porous electrode battery, the molecular structure and the valence state information of research redox product.Because resolving the ionization principle of electrospray ionization mass spectrum DESI-MS and be the high speed of utilizing high speed electron spray ESSI probe to produce carries the ion in the sample of carrying on another road of vaporific drop extraction/ionization of electric charge and it is transferred to gas phase formation gas phase dry ion, import the mass detector analysis then, so high speed electron spray ESSI probe and porous electrode battery be direct coupling but physics separately, the low-voltage of the high voltage of high speed electron spray ESSI ionization and electrochemical cell is not disturbed and both sides can adopt different dicyandiamide solutions to strengthen the efficient of ionization mutually like this, high speed electron spray ESSI probe also can adopt different polarity with the porous electrode cell voltage, high speed electron spray ESSI probe use positive voltage (+3000～+ 5000V) analyze positive ion, use negative voltage (3000～-5000V) analyze negative ion; Porous electrode battery use positive voltage (+05～+ 2.0V) oxidation, the use negative voltage (0.5～-2.0V) reduction, can widen the scope of analysis greatly like this.Because porous electrode battery Porous electrode flow cell has higher redox efficient than other electrochemical cells such as sheet cell etc., and resolve electrospray ionization mass spectrum DESI-MS and better anti-salt depression effect is arranged than electrospray ionization mass spectrum ESI-MS, and electrochemical cell need add electrolyte usually, so porous electrode battery Porous electrode flow cell and resolve electrospray ionization mass spectrum DESI-MS coupling and have higher battery oxidation/reduction efficiency, have better adaptability and anti-salt depression effect.
Use porous electrode electrochemical cell of the present invention and fluid sample to resolve the analysis that the electrospray ionization mass spectrum coupling method is used for dopamine D opamine oxidation product, when the porous electrode electrochemical cell is closed, Mass Spectrometer Method to ion be the protonated quasi-molecular ion [Dopamine+H] of Dopamine (molecular weight MW 153Da)
+(m/z 154) and take off [NH
3] fragment ion peak [154-NH
3] (m/z137); During the work of porous electrode electrochemical cell, Mass Spectrometer Method is to the protonated ion of oxidation product [DQ] [DQ+H] of dopamine (Dopamine)
+(m/z 152) and oxidation product thereof are taken off [CH
2=NH] fragmention [152-CH that produces
2=NH] (m/z 123), oxidation product ion [DQ+H]
+(m/z 152) are extracted mass spectrogram and are shown that this ion controlled by cell voltage, and when cell voltage was closed, this ion disappeared, and when battery was opened, this ion produced, oxidation product ion [DQ+H]
+(m/z152) cell voltage is had good response, the response time be cell voltage when opening the time to Mass Spectrometer Method to this ion be about 3.6S.Use porous electrode electrochemical cell of the present invention and fluid sample to resolve the electrospray ionization mass spectrum coupling method and be used for 3, the analysis of 4-dihydrophenylacetic acid (molecular weight MW 168Da) oxidation product, when the porous electrode electrochemical cell is closed, Mass Spectrometer Method to ion be 3, the quasi-molecular ion [M-H] of 4-dihydrophenylacetic acid (molecular weight MW 168Da) deprotonation
+(m/z 167) and take off [CO
2] fragmention [167-CO
2] (m/z 137); During the work of porous electrode electrochemical cell, Mass Spectrometer Method to 3, the product ion [165-2H-2e] (m/z 163) of the oxidation product deprotonation ion [167-2H-2e] (m/z 165) of 4-dihydrophenylacetic acid and further oxidation thereof.The inventive method and thin layer electrode electrochemical cell and fluid sample are resolved the comparison of electrospray ionization mass spectrum coupling method, adopt the protonated ion of porous electrode electrochemical cell dopamine D opamine oxidation product [DQ] [DQ+H]
+(m/z 152) and oxidation product thereof are taken off [CH
2=NH] fragmention [152-CH that produces
2=NH] peak height of (m/z 123) is apparently higher than sheet cell, with dopamine D opamine oxidation product ion m/z152,123 peak height sum accounts for the ratio of whole ion peak heights and calculates the oxidation productive rate, the oxidation productive rate of thin layer electrode electrochemical cell is 25.1%, and the oxidation productive rate of porous electrode electrochemical cell is 61.2%.The inventive method can freely be selected the polarity (oxidation or reduction) and the mass spectral negative ions pattern (detection of positive ions or negative ion respectively) of battery, and the thinner layer electrochemical cell has higher oxidation efficiency.Adopt that porous electrode electrochemical cell of the present invention and fluid sample resolve that electrospray ionization mass spectrum coupling method equipment is simple, easy to operate, the response time short, battery oxidation/reduction and ionizing efficiency height, obtained better technical effect.
Description of drawings
Fig. 1 resolves the schematic flow sheet of electrospray ionization mass spectrum coupling devices for porous electrode electrochemical cell of the present invention and fluid sample.
Fig. 2 analyzes the mass spectrogram that obtains when the porous electrode electrochemical cell is closed for adopting the inventive method to be used for dopamine D opamine oxidation product.
Mass spectrogram when Fig. 3 analyzes the work of porous electrode electrochemical cell for adopting the inventive method to be used for dopamine D opamine oxidation product.
Fig. 4 is used for the oxidation product ion m/z152 mass spectrogram that the analysis of dopamine D opamine oxidation product is extracted for adopting the inventive method.
Fig. 5 is used for 3 for adopting the inventive method, and 4-dihydrophenylacetic acid oxidation product is analyzed the mass spectrogram that obtains when the porous electrode electrochemical cell is closed.
Fig. 6 is used for 3 for adopting the inventive method, the mass spectrogram that 4-dihydrophenylacetic acid oxidation product obtains when analyzing the work of porous electrode electrochemical cell.
Mass spectrogram when Fig. 7 analyzes the work of porous electrode electrochemical cell for adopting the inventive method to be used for dopamine D opamine oxidation product.
Fig. 8 resolves the electrospray ionization mass spectrum coupling method for thin layer electrode electrochemical cell and fluid sample and is used for dopamine D opamine oxidation product and analyzes mass spectrogram when battery operated.
1 is high speed electron spray ionisation ESSI probe among Fig. 1,2 is the porous electrode electrochemical cell, 3 is mass detector, 4 is the sample inlet of high speed electron spray ionisation ESSI probe, 5 is the kapillary that high speed electron spray ionisation ESSI probe is carried sample, 6 is the high-voltage power supply of high speed electron spray ionisation ESSI probe, 7 is high voltage ground connection, 8 is high velocity fog gas (nitrogen), 9 is the probe rod of delivery solvent, 10 for carrying the chuck of gases at high pressure, 11 is the sample inlet of porous electrode electrochemical cell oxidation/reduction, and 12 for carrying the kapillary of sample, and 13 is the porous electrode electrochemical cell, 14 is the auxiliary electrode of porous electrode electrochemical cell, 15 is the contrast electrode of porous electrode electrochemical cell, and 16 is the working electrode of porous electrode electrochemical cell, and 17 is the power supply of porous electrode electrochemical cell, 18 for carrying the kapillary of electrochemical cell oxidation/reduzate, and 19 is the inlet of mass detector.
Workflow among Fig. 1 is: adopt the sample inlet 4 input solvents of infusion pump from high speed electron spray ionisation ESSI probe 1, flow out from the electron spray outlet of probe rod 9, high-voltage power supply 6 applies high voltage, high velocity fog gas 8 input gases at high pressure, the outlet of the probe rod 9 of delivery solvent produces the vaporific drop that carries electric charge at a high speed; The fluid sample for the treatment of oxidation/reduction enters porous electrode electrochemical cell 13 by infusion pump from the sample inlet 11 of porous electrode electrochemical cell oxidation/reduction, after the working electrode 16 oxidation/reduction of porous electrode electrochemical cell, flow out from kapillary 18 outlets of the conveying electrochemical cell oxidation/reduzate of electrochemical cell, probe rod 9 exports the high speed that produces and carries the sample that the vaporific drop of electric charge is resolved or the kapillary 18 of the conveying electrochemical cell oxidation/reduzate of ionization electrochemical cell exports, and it is transferred to gas phase form the gas phase dry ion, the inlet 19 that enters mass detector 3 then detects.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Adopt porous electrode electrochemical cell of the present invention and fluid sample to resolve the analysis that the electrospray ionization mass spectrum coupling method is used for dopamine D opamine (molecular weight MW 153Da) oxidation.Instrument condition sees the following form 1, and the mass spectrogram when the porous electrode electrochemical cell is closed is seen Fig. 2, and the mass spectrogram the during work of porous electrode electrochemical cell is seen Fig. 3, the oxidation product ion [DQ+H] of extraction
+(m/z 152) mass spectrogram is seen Fig. 4.
Table 1 is analyzed the porous electrode electrochemical cell and the fluid sample of dopamine and is resolved the electrospray ionization mass spectrum condition
From Fig. 2～4 as can be seen, when the porous electrode electrochemical cell is closed, Mass Spectrometer Method to ion be the protonated quasi-molecular ion [Dopamine+H] of Dopamine (molecular weight MW 153Da)
+(m/z 154) and take off [NH
3] fragment ion peak [154-NH
3] (m/z137); During the work of porous electrode electrochemical cell, Mass Spectrometer Method is to the protonated ion of oxidation product [DQ] [DQ+H] of dopamine (Dopamine)
+(m/z 152) and oxidation product thereof are taken off [CH
2=NH] fragmention [152-CH that produces
2=NH] (m/z 123), oxidation product ion [DQ+H]
+(m/z 152) are extracted mass spectrogram and are shown that this ion controlled by cell voltage, and when cell voltage was closed, this ion disappeared, and when battery was opened, this ion produced, oxidation product ion [DQ+H]
+(m/z152) cell voltage is had good response, the response time be cell voltage when opening the time to Mass Spectrometer Method to this ion be about 3.6S.
[embodiment 2]
Adopt porous electrode electrochemical cell of the present invention and fluid sample to resolve the electrospray ionization mass spectrum coupling method and under negative ion mode, be used for 3, the analysis of 4-dihydrophenylacetic acid (molecular weight MW 168Da) oxidation.Instrument condition sees the following form 2, and the mass spectrogram when the porous electrode electrochemical cell is closed is seen Fig. 5, and the mass spectrogram the during work of porous electrode electrochemical cell is seen Fig. 6.
Table 2 analyzes 3, the porous electrode electrochemical cell of 4-dihydrophenylacetic acid and mass spectrum condition
From Fig. 5～6 as can be seen, when the porous electrode electrochemical cell is closed, Mass Spectrometer Method to ion be 3, the quasi-molecular ion [M-H] of 4-dihydrophenylacetic acid (molecular weight MW 168Da) deprotonation
+(m/z 167) and take off [CO
2] fragmention [167-CO
2] (m/z 137); During the work of porous electrode electrochemical cell, Mass Spectrometer Method to 3, the oxidation product deprotonation ion [167-2H-2e] (m/z 165) of 4-dihydrophenylacetic acid and the further product ion [165-2H-2e] (m/z 163) of oxidation thereof illustrates that the inventive method can freely select polarity of battery (oxidation or reduction) and mass spectral negative ions pattern (distinguishing detection of positive ions or negative ion).
[comparative example 1]
The instrument condition that adopts porous electrode electrochemical cell of the present invention and fluid sample to resolve electrospray ionization mass spectrum coupling method oxidation dopamine D opamine (molecular weight MW 153Da) sees Table 1, and the mass spectrogram the during work of porous electrode electrochemical cell is seen Fig. 7.Under the high speed electron spray ionisation probe situation identical with the mass spectrum condition, the thin layer electrode electrochemical cell is resolved the electrospray ionization mass spectrum coupling employing coupling method identical with the present invention with fluid sample, instrument condition sees Table 3, mass spectrogram during the work of thin layer electrode electrochemical cell is seen Fig. 8, relatively the oxidation efficiency of 2 kinds of electrochemical cells.
Table 3 is analyzed the thin layer electrode electrochemical cell and the fluid sample of dopamine and is resolved the electrospray ionization mass spectrum condition
From Fig. 7 and Fig. 8 more as can be seen, adopt the protonated ion of porous electrode electrochemical cell dopamine D opamine oxidation product [DQ] [DQ+H]
+(m/z 152) and oxidation product thereof are taken off [CH
2=NH] fragmention [152-CH that produces
2=NH] peak height of (m/z 123) is apparently higher than sheet cell, illustrates that the porous electrode electrochemical cell has higher oxidation efficiency.With dopamine D opamine oxidation product ion m/z152,123 peak height sum accounts for the ratio of whole ion peak heights and calculates the oxidation productive rate, and the oxidation productive rate of thin layer electrode electrochemical cell is 25.1%, and the oxidation productive rate of porous electrode electrochemical cell is 61.2%.
Can illustrate by top embodiment and comparative example, the present invention is a kind of high electrochemical cell and mass spectrum coupling method of oxidation efficiency that installs short, electrochemical cell of simple, easy to operate, response time, is applicable to the Mass Spectrometer Method of the electrochemical oxidation/reduzate of polarity and biological sample.
Claims (4)
1. porous electrode electrochemical cell and fluid sample are resolved the electrospray ionization mass spectrum coupling method, the spraying solvent that the high speed that is produced by high speed electron spray ionisation ESSI probe (1) is carried electric charge the product of (2) oxidation of porous electrode electrochemical cell or reduction is directly resolved or ionization after enter mass detector (3) and detect.
2. porous electrode electrochemical cell according to claim 1 and fluid sample are resolved the electrospray ionization mass spectrum coupling method, high-voltage power supply (6) voltage that it is characterized in that high speed electron spray ionisation ESSI probe is ± (3000～5000) volt, high velocity fog gas is nitrogen, and pressure is 110～200Psi.
3. porous electrode electrochemical cell according to claim 1 and fluid sample are resolved the electrospray ionization mass spectrum coupling method, and power supply (17) voltage that it is characterized in that the porous electrode electrochemical cell is ± (0.5～2.0) volt.
4. porous electrode electrochemical cell according to claim 1 and fluid sample are resolved the electrospray ionization mass spectrum coupling method, it is characterized in that the solvent outlet of probe rod (9) and carry kapillary (18) sample export of electrochemical cell oxidation/reduzate and the injection port (19) of mass detector (3) to be located along the same line.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105259230A (en) * | 2015-11-14 | 2016-01-20 | 哈尔滨工业大学 | Integrated electrolytic tank system and method for in-situ electrochemical mass spectrum detection system |
| WO2019192037A1 (en) * | 2018-04-03 | 2019-10-10 | 哈尔滨工业大学（威海） | Electrochemistry-mass spectrometry hybrid device, and use method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100044560A1 (en) * | 2006-07-06 | 2010-02-25 | Franco Basile | Method and Apparatus for Pyrolysis-Induced Cleavage in Peptides and Proteins |
| US20100059674A1 (en) * | 2008-09-05 | 2010-03-11 | Ohio University | Method and apparatus of liquid sample-desorption electrospray ionization-mass specrometry (ls-desi-ms) |
-
2010
- 2010-05-26 CN CN2010101831644A patent/CN102262121A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100044560A1 (en) * | 2006-07-06 | 2010-02-25 | Franco Basile | Method and Apparatus for Pyrolysis-Induced Cleavage in Peptides and Proteins |
| US20100059674A1 (en) * | 2008-09-05 | 2010-03-11 | Ohio University | Method and apparatus of liquid sample-desorption electrospray ionization-mass specrometry (ls-desi-ms) |
Non-Patent Citations (4)
| Title |
|---|
| DEMIAN R. IFA等: "Desorption electrospray ionization and other ambient ionization methods: current progress and preview", 《ANALYST》 * |
| FEIMENG ZHOU 等: "Electrochemistry Combined On-Line with Electrospray Mass Spectrometry", 《ANALYTICAL CHEMISTRY》 * |
| JIWEN LI等: "Online Coupling of Electrochemical Reactions with Liquid Sample Desorption Electrospray Ionization-Mass Spectrometry", 《ANAL. CHEM.》 * |
| ZHIXIN MIAO等: "Direct Analysis of Liquid Samples by Desorption Electrospray Ionization-Mass Spectrometry (DESI-MS)", 《J AM SOC MASS SPECTROM》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105259230A (en) * | 2015-11-14 | 2016-01-20 | 哈尔滨工业大学 | Integrated electrolytic tank system and method for in-situ electrochemical mass spectrum detection system |
| WO2019192037A1 (en) * | 2018-04-03 | 2019-10-10 | 哈尔滨工业大学（威海） | Electrochemistry-mass spectrometry hybrid device, and use method thereof |
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Application publication date: 20111130 |