CN108666201A - Incude Nanoliter electrospray ion source and its working method - Google Patents

Incude Nanoliter electrospray ion source and its working method Download PDF

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Publication number
CN108666201A
CN108666201A CN201711494145.1A CN201711494145A CN108666201A CN 108666201 A CN108666201 A CN 108666201A CN 201711494145 A CN201711494145 A CN 201711494145A CN 108666201 A CN108666201 A CN 108666201A
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CN
China
Prior art keywords
nozzle
ion source
induction
electrospray ion
nanoliter electrospray
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711494145.1A
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Chinese (zh)
Inventor
赵鹏
闻路红
洪欢欢
章文天
毕磊
宁录胜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Huayi Ningchuang Intelligent Science & Technology Co Ltd
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Ningbo Huayi Ningchuang Intelligent Science & Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Huayi Ningchuang Intelligent Science & Technology Co Ltd filed Critical Ningbo Huayi Ningchuang Intelligent Science & Technology Co Ltd
Priority to CN201711494145.1A priority Critical patent/CN108666201A/en
Publication of CN108666201A publication Critical patent/CN108666201A/en
Priority to PCT/CN2018/125563 priority patent/WO2019129276A1/en
Pending legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/10Ion sources; Ion guns
    • H01J49/16Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/165Electrospray ionisation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/10Ion sources; Ion guns

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

The present invention provides a kind of induction Nanoliter electrospray ion source and its working method, the induction Nanoliter electrospray ion source includes nozzle, electrode;Further comprise:Coating, the coating use hydrophobicity or hydrophilic material, the coating that the inner wall in the nozzle is arranged.The present invention has many advantages, such as that Ionization Efficiency height, high sensitivity, signal-to-noise ratio are high.

Description

Incude Nanoliter electrospray ion source and its working method
Technical field
The present invention relates to ion sources, more particularly to incude Nanoliter electrospray ion source and its working method.
Background technology
Cell is the basic unit of vital movement, is carried out to vital movement on unicellular and subcellsular level real-time, former The problem of position, dynamic detection are the challenges that life science proposes analytical chemistry.Open type mass ions source technology because High sensitivity, can analyze the features such as ultra-small volume sample, selectivity good, fast response time obtained in single cell analysis it is wide General application.
Single cell metabolite and trace samplings may be implemented under open type environment in induction Nanoliter electrospray technology of ion source Sampling and efficient analysis, amount of samples can be reduced to pL ranks, and have higher sensitivity and accuracy, can solve slender The problem of being difficult to detect below born of the same parents or other biological sample nL ranks provides science, efficient for environment measuring, bioanalysis etc. Technical support.The deficiency of above-mentioned induction Nanoliter electrospray technology of ion source is:
Sample spray flow velocity it is unstable, the spray time of different samples can not be adjusted, cause different sample ionization efficiency, The problems such as sensitivity for analysis is low with signal-to-noise ratio.
Invention content
For the deficiency for solving in above-mentioned prior art, the present invention provides a kind of high sensitivity, signal-to-noise ratio is high, can weigh The induction Nanoliter electrospray ion source utilized again, realizes the efficient analysis of unicellular metabolin and content polarity sample.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of induction Nanoliter electrospray ion source, the induction Nanoliter electrospray ion source includes nozzle, electrode;The sense Nanoliter electrospray ion source is answered to further comprise:
Coating, the coating use hydrophobicity or hydrophilic material, the coating that the inner wall in the nozzle is arranged.
The present invention also aims to provide the working method of above-mentioned induction Nanoliter electrospray ion source, the goal of the invention Technical scheme is that:
According to the working method of above-mentioned induction Nanoliter electrospray ion source, the working method includes the following steps:
(A1) above-mentioned nozzle is immersed in sample solution, the sample solution enters nozzle;
The distance of the electrode and solution is 0.3-1cm;
(A2) apply voltage on the electrode, the sample in nozzle is ionized, and is projected from nozzle inside, and enter matter Spectrometer injection port.
Compared with prior art, the device have the advantages that being:
1. the Ionization Efficiency of sample can be improved, higher sensitivity and signal-to-noise ratio are obtained;
2. the coating that different samples are bonded different chemical property can be directed to, make induction Nanoliter electrospray ion source application model It encloses more extensively;
3. the spraying flow velocity of sample can be changed, keep spray time adjustable, realizes corpusculum enthusiasm sample and unicellular generation Thank to the efficient analysis of object;
4. can ensure that sample forms lasting, stable, lasting electron spray;
5. method is simple, easy to operate, nozzle is repeatable to be utilized.
Description of the drawings
With reference to attached drawing, the disclosure will be easier to understand.Skilled addressee readily understands that be:This A little attached drawings are used only for the technical solution illustrated the present invention, and are not intended to and are construed as limiting to protection scope of the present invention. In figure:
Fig. 1 is the structure diagram of induction Nanoliter electrospray ion source according to the ... of the embodiment of the present invention;
Fig. 2 is the diphenylamines mass spectrogram measured according to the prior art;
Fig. 3 is the according to embodiments of the present invention 2 diphenylamines mass spectrograms measured;
Fig. 4 is the caffeine mass spectrogram measured according to the prior art;
Fig. 5 is the according to embodiments of the present invention 2 caffeine mass spectrograms measured;.
Specific implementation mode
Fig. 1-5 and following description describe the present invention optional embodiment to instruct how those skilled in the art implement It is of the invention with reproducing.In order to instruct technical solution of the present invention, some conventional aspects are simplified or have been omitted.Those skilled in the art It should be appreciated that modification or replacement from these embodiments will within the scope of the invention.Those skilled in the art should understand that Following characteristics can be combined in various ways to form multiple modifications of the present invention.As a result, the invention is not limited in it is following can Embodiment is selected, and is only limited by the claims and their equivalents.
Embodiment 1:
Fig. 1 schematically illustrates the structure diagram of the induction Nanoliter electrospray ion source of the embodiment of the present invention 1, such as Fig. 1 Shown, the induction Nanoliter electrospray ion source includes:
Nozzle 2, the nozzle both ends open lead directly to section and internal diametric reduction from the first opening to the second opening direction It is sequentially distributed;It is maximum in the internal diameter of the first opening, it is minimum in the internal diameter of the second opening;
Coating 4, the coating use hydrophobicity or hydrophilic material, are determined with specific reference to sample to be tested, e.g., described hydrophobic Property material use polyvinyl alcohol, the hydrophilic material use hydroxyl or amino ionic coating;The coating is arranged in the spray The inner wall of head, such as internal diametric reduction;The hydrophobicity or hydrophilic material are arranged by PB-DS-PB methods in the nozzle Inner wall;
Electrode 3, the electrode enter from the first opening and are deep into the internal diametric reduction;The central shaft of the electrode Line is conllinear with the central axis of internal diametric reduction;
Power supply 1, the power supply are that the electrode applies high-voltage dc voltage.
The working method according to above-mentioned induction Nanoliter electrospray ion source of the embodiment of the present invention, the working method packet Include following steps:
(A1) the second open end of above-mentioned nozzle is immersed in sample solution, if Immersion time is 10-15s, the sample Product solution enters in nozzle;
The distance of the electrode 3 and solution 5 is 0.3-1cm;
(A2) apply voltage on the electrode, the sample in nozzle is ionized, and is projected from nozzle inside, and enter matter Spectrometer injection port;The distance of the nozzle 1 to the mass spectrograph injection port 5 is 0.3-1.5cm.
Embodiment 2:
According to embodiments of the present invention 1 induction Nanoliter electrospray ion source and its working method answering in diphenylamines detection Use-case.
In the application examples, in order to be adapted to the detection of diphenylamines, coating is using the hydrophobic material to match, such as poly- second Enol polymer;The inner wall in the internal diametric reduction of the nozzle is arranged by PB-DS-PB methods for hydrophobic material.
In the working method of ion source, namely during detection diphenylamines:
Above-mentioned nozzle is soaked in 10~15s in sample solution, you can sample solution is introduced to the point of nozzle, sample Spacing between solution and electrode is 0.3~1cm.Nozzle is between electrode and mass spectrum injection port, the point of nozzle and institute It can be 0.3~1.5cm to state the distance between mass spectrometric injection port.High-voltage dc voltage is set as 1.0kV, and sheath gas is set as 0L/min, Mass Spectrometer Method m/z ranges are set as 50~1000, and detection sample is that diphenylamines standard sample (is dissolved in methanol, concentration 50ppb), as shown in figure 3, Mass Spectrometer Method sensitivity improves 9 times, as shown in Figure 2,3.
Embodiment 3:
According to embodiments of the present invention 1 induction Nanoliter electrospray ion source and its working method answering in caffeine detection Use-case.
In the application examples, in order to be adapted to the detection of caffeine, coating is using the hydrophilic material to match, such as band hydroxyl The ionic coating of base or amino;Hydrophilic material is arranged by PB-DS-PB methods in the internal diametric reduction of the nozzle Wall.
In the working method of ion source, namely during detection caffeine:
Above-mentioned nozzle is soaked in 10~15s in sample solution, you can sample solution is introduced to the point of nozzle, sample Spacing between solution and electrode is 0.3~1cm.The distance between the point of nozzle and the mass spectrometric injection port can be 0.3~1.5cm.High-voltage dc voltage is set as 2.0kV, and sheath gas is set as 0L/min, and Mass Spectrometer Method m/z ranges are set as 50~ 1000, detection sample is caffeine standards sample (being dissolved in methanol, concentration 50ppb), as shown in figure 5, Mass Spectrometer Method sensitivity carries It is 12 times high, as shown in Figure 4,5.

Claims (10)

1. a kind of induction Nanoliter electrospray ion source, the induction Nanoliter electrospray ion source includes nozzle, electrode;Its feature exists In:The induction Nanoliter electrospray ion source further comprises:
Coating, the coating use hydrophobicity or hydrophilic material, the coating that the inner wall in the nozzle is arranged.
2. induction Nanoliter electrospray ion source according to claim 1, it is characterised in that:The hydrophobicity or hydrophily material The inner wall in the nozzle is arranged by PB-DS-PB methods for material.
3. induction Nanoliter electrospray ion source according to claim 1, it is characterised in that:
The both ends open of the nozzle, inside have internal diametric reduction, are open onto the second opening direction along from first, described The internal diameter of nozzle gradually tapers up, minimum in the internal diameter of the second opening;
The electrode enters from the first opening and is deep into the internal diametric reduction.
4. induction Nanoliter electrospray ion source according to claim 3, it is characterised in that:The coating is arranged in the spray The internal diametric reduction of head.
5. induction Nanoliter electrospray ion source according to claim 1, it is characterised in that:The central axis of the electrode with The central axis of internal diametric reduction is conllinear.
6. induction Nanoliter electrospray ion source according to claim 1, it is characterised in that:The hydrophobic material is using poly- Vinyl alcohol.
7. induction Nanoliter electrospray ion source according to claim 1, it is characterised in that:The hydrophilic material uses hydroxyl Base or amino ionic coating.
8. according to the working method of any induction Nanoliter electrospray ion sources of claim 1-7, the working method packet Include following steps:
(A1) above-mentioned nozzle is immersed in sample solution, the sample solution enters nozzle;
The distance of the electrode and solution is 0.3-1cm;
(A2) apply voltage on the electrode, the sample in nozzle is ionized, and is projected from nozzle inside, and enter mass spectrograph Injection port.
9. working method according to claim 8, it is characterised in that:Distance of the nozzle to the mass spectrograph injection port For 0.3-1.5cm.
10. working method according to claim 8, it is characterised in that:Nozzle is immersed in the time in sample solution as 10- 15s。
CN201711494145.1A 2017-12-31 2017-12-31 Incude Nanoliter electrospray ion source and its working method Pending CN108666201A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201711494145.1A CN108666201A (en) 2017-12-31 2017-12-31 Incude Nanoliter electrospray ion source and its working method
PCT/CN2018/125563 WO2019129276A1 (en) 2017-12-31 2018-12-29 Induction nanoliter electrospray ion source and method of operation thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109270157A (en) * 2018-11-03 2019-01-25 广州市华粤行仪器有限公司 Sampling device and mass spectrometric analysis method based on induction electron spray
WO2019129276A1 (en) * 2017-12-31 2019-07-04 宁波华仪宁创智能科技有限公司 Induction nanoliter electrospray ion source and method of operation thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030168591A1 (en) * 2002-03-05 2003-09-11 Smith Richard D. Method and apparatus for multispray emitter for mass spectrometry
WO2005019804A2 (en) * 2003-08-26 2005-03-03 Predicant Biosciences, Inc. Microfluidic chip with enhanced tip for stable electrospray ionization
CA2609840A1 (en) * 2007-11-02 2009-05-02 Licentia Oy Micropillar array electrospray chip
US20090189952A1 (en) * 2008-01-28 2009-07-30 Konkuk University Industrial Cooperation Corp. Apparatus for jetting droplets using super-hydrophobic nozzle
CN101598706A (en) * 2009-07-23 2009-12-09 上海华质生物技术有限公司 The device of online concentrating sample when liquid chromatography and mass spectrometry
CN101620974A (en) * 2009-07-21 2010-01-06 上海华质生物技术有限公司 Device for eliminating bubbles in mass spectrum electron-spray ion source
CN106783511A (en) * 2017-02-27 2017-05-31 中国计量科学研究院 Esi ion source and its operating method are received based on polarity inversion voltage strategy

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108666201A (en) * 2017-12-31 2018-10-16 宁波华仪宁创智能科技有限公司 Incude Nanoliter electrospray ion source and its working method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030168591A1 (en) * 2002-03-05 2003-09-11 Smith Richard D. Method and apparatus for multispray emitter for mass spectrometry
WO2005019804A2 (en) * 2003-08-26 2005-03-03 Predicant Biosciences, Inc. Microfluidic chip with enhanced tip for stable electrospray ionization
CA2609840A1 (en) * 2007-11-02 2009-05-02 Licentia Oy Micropillar array electrospray chip
US20090189952A1 (en) * 2008-01-28 2009-07-30 Konkuk University Industrial Cooperation Corp. Apparatus for jetting droplets using super-hydrophobic nozzle
CN101620974A (en) * 2009-07-21 2010-01-06 上海华质生物技术有限公司 Device for eliminating bubbles in mass spectrum electron-spray ion source
CN101598706A (en) * 2009-07-23 2009-12-09 上海华质生物技术有限公司 The device of online concentrating sample when liquid chromatography and mass spectrometry
CN106783511A (en) * 2017-02-27 2017-05-31 中国计量科学研究院 Esi ion source and its operating method are received based on polarity inversion voltage strategy

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019129276A1 (en) * 2017-12-31 2019-07-04 宁波华仪宁创智能科技有限公司 Induction nanoliter electrospray ion source and method of operation thereof
CN109270157A (en) * 2018-11-03 2019-01-25 广州市华粤行仪器有限公司 Sampling device and mass spectrometric analysis method based on induction electron spray
CN109270157B (en) * 2018-11-03 2024-04-09 广州市华粤行仪器有限公司 Sampling device based on induction electric spray and mass spectrometry method

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