WO2001060526A1 - Dispositif d'electronebulisation - Google Patents

Dispositif d'electronebulisation Download PDF

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Publication number
WO2001060526A1
WO2001060526A1 PCT/EP2000/011022 EP0011022W WO0160526A1 WO 2001060526 A1 WO2001060526 A1 WO 2001060526A1 EP 0011022 W EP0011022 W EP 0011022W WO 0160526 A1 WO0160526 A1 WO 0160526A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid
atomizing
conical
threads
fibers
Prior art date
Application number
PCT/EP2000/011022
Other languages
German (de)
English (en)
Inventor
Günter KLESPER
Gregor FUSSHÖLLER
Original Assignee
CARBOTEC Gesellschaft für instrumentelle Analytik mbH
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 CARBOTEC Gesellschaft für instrumentelle Analytik mbH filed Critical CARBOTEC Gesellschaft für instrumentelle Analytik mbH
Priority to AU2001215196A priority Critical patent/AU2001215196A1/en
Publication of WO2001060526A1 publication Critical patent/WO2001060526A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/0255—Discharge apparatus, e.g. electrostatic spray guns spraying and depositing by electrostatic forces only

Definitions

  • the invention relates to a device for atomizing electrically charged liquids.
  • sample solution that is to say a liquid
  • metal capillary which is at a high electrical potential with respect to a counter electrode.
  • the sample solution is electrochemically charged and atomized at the end of the capillary at atmospheric pressure into an aerosol of small charged drops.
  • Such a device is used for example in electrospray mass spectroscopy. Subsequent decays of the charged, atomized drops, with constant evaporation of the solvent, finally lead to the release of ions. These ions are fed to a mass analyzer via a pump system.
  • the inner diameter of the capillaries is normally around 100 ⁇ m, the applied potential difference is 3-6 kV and the flow rates are 1-10 ⁇ l / min.
  • capillaries with an inner diameter of approx. 1 ⁇ m are used in the method called nano-electrospray mass spectroscopy.
  • the applied voltage is below 1 kV and the flow rates are below approx. 20 nl / in.
  • Electrospray mass spectroscopy is used today in both research and analytical applications. fertilizer, one of the most widespread mass spectrometric techniques.
  • Electrospray mass spectroscopy is of particular importance for the detection of thermally labile and high molecular substances such as e.g. of biomolecules (peptides, proteins, nucleic acids, carbohydrates and lipids - Richard B. Cole; "Electrospray Ionization Mass Spectrometry: Fundamentals, Instrumentation &Applications”; John iley & Sons Inc., New York, 1997).
  • the mass spectrometric detection of substances is essentially only determined by the solubility in a polar solvent and a sufficient analyte concentration corresponding to the efficiency of the atomization and the sensitivity of the mass spectrometer.
  • the mass range of the spectrometer can have a limiting effect.
  • the mass range of a spectrometer is automatically expanded by desolvating the analyte ions in an uploaded state. N-times charged molecules appear on their 1 / nth mass. For example, albumin with a molecular weight of 66,430 Da can still be detected with a quadrupole mass spectrometer. In the case of nano-electrospray mass spectroscopy, the flow rates and, consequently, the amount of sample required are much lower. It can be seen that the ionization efficiency is higher with these small diameters.
  • Electrospray mass spectroscopy has gained particular importance in recent years as a detector for liquid chromatography (LC) and capillary electrophoresis (CE), since the separated sample solution is passed on to the electrospray capillary immediately after leaving the separation medium, and so on can be detected by mass spectrometry. This method is also expected to become increasingly widespread in the future. This coupling assumes that the flow rate through the electrospray capillary is adapted to the flow rate of the separation column. At present, however, electrospray mass spectroscopy is subject to some restrictions that prevent an even wider range of applications and performance from this analysis method.
  • LC liquid chromatography
  • CE capillary electrophoresis
  • the electrospray only achieves approximately the same ion intensity at high flow rates (1000 ⁇ l / min) as at low flow rates (5 ⁇ l / min).
  • a loss of sensitivity by a factor of 100 has to be accepted for electrospray mass spectroscopy.
  • electrospray mass spectroscopy In general, only relatively polar analyte solutions are accessible for measurement using electrospray mass spectroscopy.
  • electrolyte-free analyte solutions in electrospray mass spectroscopy eg non-polar analytes in non-polar solvents
  • the requirements for generating a sufficient amount of excess charges are no longer met, since the ion formation in the electro spray mass spectroscopy begins with the electrochemical charging of the analyte solution.
  • the APCI atmospheric pressure chemical ionization
  • this does not allow ionization as mild as electrospray mass spectroscopy.
  • Nano-electrospray mass spectroscopy can also be operated with the smallest sample quantities.
  • nano-electrospray mass spectroscopy With the aid of nano-electrospray mass spectroscopy, the same ion intensities are achieved at flow rates of approx. 20 nl / min as with electrospray mass spectroscopy at flow rates of approx. 5 ⁇ l / min and the ion spray with flow rates of about 1000 ⁇ l / min.
  • the sensitivity of nano-electrospray mass spectroscopy is therefore approximately four decades higher than that of ion spray. This higher sensitivity in nano-electrospray mass spectroscopy is attributed to the fact that, on the one hand, smaller droplets form (droplet diameters in the micrometer range for ion spray, for nano electrospray mass spectroscopy one order of magnitude smaller) and, on the other hand, these arise
  • Droplets have a relatively high surface charge. Both factors support efficient ion release. • Compared to the IonSpray, nano-electrospray mass spectroscopy can be carried out at an electrolyte concentration that is an order of magnitude higher (e.g. salt contamination, buffer) in the analyte solution without problems caused by suppression effects. In order to get from the initially larger drops to the point of ion release with the IonSpray, more solvent must evaporate than is necessary with the smaller, uploaded drops in nano electrospray mass spectroscopy. This leads to a concentration of the electrolytes in the
  • the spraying of finely atomized liquids is also always of economic importance if thin layers are to be applied evenly.
  • Such layers can be, for example, lacquers.
  • the means for changing the electrical potential of the liquid in the aforementioned manner is, for example, an electrode that the liquid is directed past. A strong electric field is then generated by this electrode and by a counter electrode by applying a voltage. Depending on the geometry, a voltage of 800 V can be sufficient his. Typically, the voltage applied is at least 3 kV.
  • the liquid is charged electrochemically by the aforementioned means. This is at least always the case when a polar liquid has been used.
  • Non-polar liquids such as benzene, hexane or toluene are less suitable.
  • Aqueous or methanolic solutions are suitable, for example salt or sugar solutions.
  • An aqueous solution with proteins dissolved in it is another example of a polar and therefore well-suited solution.
  • a metal tube through which the liquid is conducted can be provided as the electrode.
  • the electrode is in the liquid. For example, it is washed around by it.
  • the device according to the claim further comprises a large number of means with which the liquid brought to potential is mechanically finely divided or atomized. This can involve a large number of capillaries with very thin diameters of a few ⁇ m.
  • the surface of these mechanical dividing or atomizing means consist in particular of a material in which there are only slight adhesive forces between the liquid and the material. Examples of suitable materials are fluorine compounds such as PTFE (Teflon ® ) and FEP, Polyethylene or polypropylene. Materials with high adhesive forces are Si0 2 , glasses or metals.
  • the adhesive forces that occur between the liquid and the mechanical disintegrating or atomizing agent are preferably low in order to prevent the liquid droplets from reuniting after exiting from the mechanical atomizing agents.
  • the mechanical atomizing means are designed in such a way that the outlet area of the liquid from the mechanical atomizing means is formed by a plurality of conical, tubular or thread-like elements.
  • the liquid is passed through or along the aforementioned elements.
  • the conical, tubular or thread-like elements finally have open ends from which the liquid emerges from the mechanical atomizing agent.
  • An example of a plurality of tubular elements is a plurality of capillaries. These are arranged essentially parallel to one another or in the form of a brush. The liquid brought to potential is passed through the capillary for atomization.
  • This variant is not only particularly easy to manufacture, but also enables particularly good atomization of the liquid.
  • FIG. 1 shows in section the basic structure of a particularly suitable device of the type mentioned at the beginning.
  • a methanolic sugar solution is passed through a thin tube 1.
  • the tube is made of metal and serves as an electrode.
  • the inside of the tube is filled with a large number of threads 2, which consist of polytetrafluoroethylene.
  • the threads 2 run essentially parallel in the tube and emerge in a pin-shaped manner at one end of the tube. The threads are pointed at the end of the "brush".
  • a counter electrode 3 is provided. This is placed in such a way that the liquid, which is passed through the tube 1, exits the atomizing device at the pin-shaped ends in the direction of the counter electrode.
  • the threads can consist of metal wires which are coated in the area of the open ends with fluoropolymer such as polytetrafluoroethylene (PTFE) or with graphite fluoride.
  • fluoropolymer such as polytetrafluoroethylene (PTFE) or with graphite fluoride.
  • the voltage is then applied to the wires to bring the liquid to potential.
  • the wires then serve as an electrode.
  • the open ends are the ends from which the liquid leaves the disintegrating or atomizing agent.
  • the metal capillary according to FIG. 1 has an inner diameter of 600 ⁇ m, for example.
  • the outside diameter is e.g. 900 ⁇ m.
  • 600 threads or fibers each with a diameter of 21 ⁇ m and made of Teflon. The threads protrude from the capillary from one end by approx. 1-2 mm and have open ends here
  • At least 5 of the aforementioned threads should be in one Capillary can be provided to achieve noticeable desired results.
  • 2000 threads are also possible without any problems.
  • a stable spray is also possible at higher flow rates. With conventional capillaries, the spray breaks down at higher flows.
  • the behavior resembles a large number of nano-electrosprays without having to accept the disadvantages of the difficult handling, the clogging of the nano-capillaries and the low flow rates.
  • Field-strengthening structures (thin fiber ends according to FIG. 1): At high field strengths, which are very limited in space (on pointed needles), spraying sprykoni can form particularly effectively. In addition, the conditions for the formation of a corona discharge are limited to such a spatially so small area that disadvantageous corona discharges can hardly occur.
  • Non-polar and non-wetting surface of the Teflon fibers The liquid emerging from the capillary is split up by the individual fibers. Normally, the liquid would contract again into a single liquid cone due to cohesive forces
  • Fluoropolymers such as PTFE are resistant to all common solvents.
  • Fluoropolymers such as PTFE do not have a memory effect even when measuring different samples in succession. • Long durability even under heavy use: The PTFE fibers are inert to electrochemical corrosion processes with the analyte solution and under atmospheric pressure and thus allow long measuring times. • Gas discharges occur, if at all, only between the counter electrode and the metal capillary (or contact point) so that the Teflon fibers are not changed.
  • the invention is used inter alia for efficient ion formation, for uniform coating of surfaces or for effective atomization. puts. Effective atomization is of interest, for example, when injecting fuel into engines.
  • the invention can also be used in combination with "sheat gas”.
  • FIG. 3 shows results which, according to the prior art, are achieved with a normal electrospray capillary and with the device according to the invention were.
  • the signal intensities I as a measure of the desired effects could be increased significantly by the invention.
  • 10-4 mol / 1 raffinose in methanol was used as the solution.

Landscapes

  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

L'invention concerne un dispositif pour la pulvérisation de liquides, pourvu de moyens permettant d'amener un liquide à un potentiel électrique. Le dispositif selon l'invention comprend une multitude de moyens servant à pulvériser ou à décomposer mécaniquement le liquide mis au potentiel, les moyens mécaniques de décomposition ou de pulvérisation étant réalisés de façon que la zone de sortie du liquide hors du moyen de pulvérisation mécanique est formée par une pluralité d'éléments filiformes, tubulaires ou coniques. Les surfaces des éléments filiformes, tubulaires ou coniques sont constituées, au moins dans la zone de leurs extrémités ouvertes, de préférence d'un matériau où n'apparaissent que des forces d'adhésion faibles entre le liquide et le matériau. Des fils saillant hors d'un tube métallique servent notamment de moyens de pulvérisation. Grâce au dispositif selon l'invention, on obtient une pulvérisation particulièrement fine d'un liquide avec un grand débit.
PCT/EP2000/011022 2000-02-18 2000-11-08 Dispositif d'electronebulisation WO2001060526A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001215196A AU2001215196A1 (en) 2000-02-18 2000-11-08 Electrospray device

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10007498.7 2000-02-18
DE2000107498 DE10007498B4 (de) 2000-02-18 2000-02-18 Elektrosprühvorrichtung

Publications (1)

Publication Number Publication Date
WO2001060526A1 true WO2001060526A1 (fr) 2001-08-23

Family

ID=7631473

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/011022 WO2001060526A1 (fr) 2000-02-18 2000-11-08 Dispositif d'electronebulisation

Country Status (3)

Country Link
AU (1) AU2001215196A1 (fr)
DE (1) DE10007498B4 (fr)
WO (1) WO2001060526A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7798420B2 (en) 2005-02-11 2010-09-21 Battelle Memorial Institute Aerosol dispensing device and method

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE20210784U1 (de) 2001-11-14 2003-11-27 CARBOTEC Gesellschaft für instrumentelle Analytik mbH Fokussierte Elektrosprayvorrichtung
DE10155775B4 (de) * 2001-11-14 2006-04-06 CARBOTEC Gesellschaft für instrumentelle Analytik mbH Fokussierte Elektrosprayvorrichtung
DE102005016829A1 (de) * 2005-04-12 2006-11-02 Iff International Flavors & Fragrances Verfahren, Düse und Vorrichtung zur Zerstäubung von in einer Flüssigkeit enthaltenen Wirkstoffen

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB729842A (en) * 1952-01-30 1955-05-11 Licentia Gmbh Devices for an electrostatic application of liquid coating materials
US3897905A (en) * 1973-10-19 1975-08-05 Universal Oil Prod Co Electrostatic spraying nozzle
GB2018627A (en) * 1978-04-17 1979-10-24 Ici Ltd Process and apparatus for spraying liquid
WO1992015339A1 (fr) * 1991-03-11 1992-09-17 Peltier Mark E Generateur de vapeurs et/ou d'aerosols electrostatique
US5697555A (en) * 1995-07-18 1997-12-16 Robinson; Arthur Apparatus for dispersing liquid in droplets
US5975426A (en) 1998-05-14 1999-11-02 Waters Investments Limited Use of porous beads as a tip for nano-electrospray
EP1010468A1 (fr) * 1998-12-14 2000-06-21 FENN, John B. Procédé et dispositif d'ionisation électrospray

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9416581D0 (en) * 1993-09-02 1994-10-12 Ici Plc Electrostatic spraying device
GB9406171D0 (en) * 1994-03-29 1994-05-18 Electrosols Ltd Dispensing device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB729842A (en) * 1952-01-30 1955-05-11 Licentia Gmbh Devices for an electrostatic application of liquid coating materials
US3897905A (en) * 1973-10-19 1975-08-05 Universal Oil Prod Co Electrostatic spraying nozzle
GB2018627A (en) * 1978-04-17 1979-10-24 Ici Ltd Process and apparatus for spraying liquid
WO1992015339A1 (fr) * 1991-03-11 1992-09-17 Peltier Mark E Generateur de vapeurs et/ou d'aerosols electrostatique
US5697555A (en) * 1995-07-18 1997-12-16 Robinson; Arthur Apparatus for dispersing liquid in droplets
US5975426A (en) 1998-05-14 1999-11-02 Waters Investments Limited Use of porous beads as a tip for nano-electrospray
EP1010468A1 (fr) * 1998-12-14 2000-06-21 FENN, John B. Procédé et dispositif d'ionisation électrospray

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7798420B2 (en) 2005-02-11 2010-09-21 Battelle Memorial Institute Aerosol dispensing device and method
US8141795B2 (en) 2005-02-11 2012-03-27 Battelle Memorial Institute Aerosol dispensing device and method

Also Published As

Publication number Publication date
DE10007498B4 (de) 2006-06-14
DE10007498A1 (de) 2001-08-30
AU2001215196A1 (en) 2001-08-27

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