EP1746631B1 - Système de nano-électrodes micro-mécanique - Google Patents
Système de nano-électrodes micro-mécanique Download PDFInfo
- Publication number
- EP1746631B1 EP1746631B1 EP06117211.0A EP06117211A EP1746631B1 EP 1746631 B1 EP1746631 B1 EP 1746631B1 EP 06117211 A EP06117211 A EP 06117211A EP 1746631 B1 EP1746631 B1 EP 1746631B1
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- EP
- European Patent Office
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- capillary
- substrate
- electrode
- nanospray
- input
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/165—Electrospray ionisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0013—Miniaturised spectrometers, e.g. having smaller than usual scale, integrated conventional components
- H01J49/0018—Microminiaturised spectrometers, e.g. chip-integrated devices, Micro-Electro-Mechanical Systems [MEMS]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/06—Electron- or ion-optical arrangements
- H01J49/067—Ion lenses, apertures, skimmers
Definitions
- This invention relates to mass spectrometry, and in particular to the use of mass spectrometry in conjunction with liquid chromatography or capillary electrophoresis.
- the invention particularly relates to a system and method that is implemented in a microengineered configuration.
- the spray is passed from atmospheric pressure via a chamber held at an intermediate pressure.
- Several vacuum interfaces that use differential pumping to match flow rates to achievable pressures have been developed [Duffin 1992].
- the ion optics normally consist of input and output orifices such as capillaries, capillary arrays and skimmer electrodes, and occasionally also a quadrupole lens operating as an ion guide in all-pass mode. These components are used to maximise the ratio of coupled ions to neutrals, which would otherwise swamp the chamber.
- US 5,386,115 discloses a solid state mass spectrograph that includes an inlet, a gas ionizer, a mass filter and a detector array all formed within a cavity in a semiconductor substrate.
- WO 2005/019804 A2 discloses a microfluidic chip formed with multiple fluid channels terminating at a tapered electrospray ionization tip for mass spectrometric analysis.
- the fluid channels may be formed onto a channel plate that are in fluid communication with corresponding reservoirs.
- the electrospray tip can be formed along a defined distal portion of the channel plate that can include a single or multiple tapered surfaces.
- the fluid channels may terminate at an open-tip region of the electrospray tip.
- a covering plate may substantially enclose most portions of the fluid channels formed on the channel plate except for the open-tip region.
- Another aspect of the invention provides methods for conducting mass spectrometric analysis of multiple samples flowing through individual fluid channels in a single micro fluidic chip that is formed with a tapered electrospray tip having an open-tip region.
- MEMS technology could be used to provide nanospray devices.
- the device must typically operate with high voltages, in a wet environment, so that electrical isolation and drainage are both required.
- the substrate material most commonly used in MEMS, silicon is therefore not appropriate; however, other insulating materials such as glasses are difficult to micromachine.
- an electrode containing an axially aligned orifice is typically required.
- electrostatic deflection or focusing is required.
- further electrodes containing aligned orifices are needed. If the ion path is itself in the plane of a substrate, such orifices are extremely difficult to form by in plane patterning alone.
- FIG. 1 illustrates the concept of a microengineered nanospray electrode system.
- a mass spectrometer 101 is provided in a high-vacuum enclosure 102 pumped (for example) by a turbomolecular pump 103. Ions are channelled into this chamber via a further chamber 104 held at an intermediate pressure and pumped (again, for example) by a rotary pump 105.
- the inlet to the vacuum system is assumed to be a capillary 106.
- the filter element of the mass spectrometer could be an ion trap, a quadrupole, a magnetic sector, a crossed-field or a time of flight device.
- the intermediate vacuum chamber could contain a range of components including further capillaries and skimmer electrodes.
- the overall input to the system is provided by a nanospray capillary 107.
- Alignment between the nanospray capillary 107 and the capillary input to the mass spectrometer 106 is provided by a microengineered chip 108.
- the chip contains a first set of mechanical alignment features 109 for the nanospray capillary and a second set of alignment features 110 for the capillary input to the mass spectrometer.
- the chip also contains a set of electrodes 111 set up perpendicular to the ion path, which may (for example, but not exclusively) consist of diaphragm electrodes. Other features may be integrated on the chip, including holes for drainage and gas inlet.
- the second substrate again consists of a base 208 formed in insulating material, and carrying a further set of electrodes corresponding to a further part of the features 111 in Figure 1 and consisting of grooves 209 etched into upright plates of conducting or semiconducting material 210.
- the partial electrode sets combine to form complete diaphragm electrodes with closed pupils 211.
- Figure 8 shows a mode of thermal operation.
- a current I is passed through one or more of the electrodes 801 to provide local heating, which may preferentially evaporate more volatile components in the spray such as a carrier solvent, thus enriching the analyte ion stream.
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Claims (32)
- Dispositif d'ionisation nanopulvérisation micro-usiné disposé sur une puce unique (108) configuré pour réaliser un couplage entre une source de nanopulvérisation et un spectromètre de masse (106), le dispositif comprenant un premier élément d'alignement (109) conçu pour coopérer avec une entrée capillaire, un second élément d'alignement (110) conçu pour coopérer avec une sortie capillaire et un orifice définissant une trajectoire ionique entre l'entrée capillaire et la sortie capillaire, le dispositif comprenant en outre au moins une électrode conductrice (111) disposée dans une orientation sensiblement perpendiculaire à la trajectoire ionique, et où chacun du premier élément d'alignement (109), du second élément d'alignement (110), de l'orifice et de la au moins une électrode (111) sont intégralement formés dans la puce (108).
- Dispositif selon la revendication 1, dans lequel la puce (208) est construite à partir de deux substrats, les substrats étant combinés dans une configuration empilée de manière à former la puce (108).
- Dispositif selon la revendication 2, dans lequel chacun des deux substrats sont pourvus d'une base isolante (201), les substrats étant empilés l'un par rapport à l'autre de sorte que la puce résultante (108) ait une partie isolante sur une surface extérieure de celle-ci.
- Dispositif selon la revendication 2 ou 3, dans lequel chacun des deux substrats sont formés avec des éléments individuels, les éléments étant configurés de sorte que lorsque les deux substrats sont assemblés conjointement, la combinaison résultante d'éléments définit le premier élément d'alignement (109), le second élément d'alignement (110), l'orifice et la au moins une électrode (111).
- Dispositif selon la revendication 4, dans lequel un premier substrat définit un premier élément d'alignement rainuré (204) pour l'entrée capillaire et un second élément d'alignement rainuré (206) pour la sortie capillaire, le substrat comprenant en outre sur celui-ci la au moins une électrode conductrice avec un bord vertical rainuré agencé de façon normale par rapport au substrat.
- Dispositif selon la revendication 5, dans lequel le second substrat comprend sur celui-ci au moins une électrode conductrice (111) avec un bord vertical agencé de façon normale par rapport au substrat.
- Dispositif selon la revendication 6, dans lequel, par empilement des premier et second substrats l'un par rapport à l'autre, les au moins une électrodes (111) disposées sur les premier et second substrats forment une électrode contiguë et les rainures d'électrode sont combinées pour former des orifices.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel l'entrée capillaire est un capillaire de nanopulvérisation (106).
- Dispositif selon la revendication 8, dans lequel l'entrée capillaire de nanopulvérisation fournit un fluide, le fluide étant dérivé depuis un système de chromatographie en phase liquide.
- Dispositif selon la revendication 8, dans lequel l'entrée capillaire de nanopulvérisation fournit un fluide, le fluide étant dérivé depuis un système d'électrophorèse capillaire.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel l'électrode (111) la plus proche du capillaire d'entrée est configurée dans un premier temps pour créer un cône de Taylor et ensuite pour extraire des ions depuis le liquide contenu dans le capillaire d'entrée.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel la sortie capillaire forme l'entrée d'un spectromètre de masse (106).
- Dispositif selon l'une quelconque des revendications précédentes, comprenant au moins deux électrodes (111) et dans lequel au moins une deuxième électrode est configurée pour focaliser des ions sur le capillaire de sortie.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel au moins une électrode est électriquement chauffée et configurée pour éliminer un solvant de façon préférentielle.
- Dispositif selon l'une quelconque des revendications 1 à 13, dans lequel au moins une électrode est segmentée et configurée pour produire un champ électrique latéral de déviation afin de faciliter la séparation des ions par rapport aux particules neutres.
- Dispositif selon la revendication 15, dans lequel le champ latéral de déviation est variable dans le temps et configuré pour favoriser la nébulisation.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel la puce contient au moins un trou de vidange pour les fluides.
- Dispositif selon la revendication 3, dans lequel au moins une première base de substrat contient au moins un trou d'entrée pour des gaz et une chambre de détente (410) entourant l'entrée capillaire.
- Dispositif selon la revendication 18, dans lequel la chambre de détente (410) est agencée pour créer un flux axial de gaz agencé sous la forme d'une gaine par rapport à la pulvérisation.
- Dispositif selon la revendication 3, dans lequel la base isolante est formée en polymère photomodelable.
- Dispositif selon la revendication 18, dans lequel le périmètre de la base de substrat (201), les trous de vidange et les entrées de gaz sont définis par photomodelage.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel les éléments d'alignement (109, 110) et les électrodes (111) sont formés dans un semi-conducteur.
- Dispositif selon la revendication 22, dans lequel le semi-conducteur est le silicium.
- Dispositif selon la revendication 22, dans lequel le semi-conducteur est rainuré par gravure chimique humide anisotrope descendante des plans cristallins.
- Dispositif selon la revendication 22, dans lequel le semi-conducteur est rainuré par gravure ionique réactive profonde.
- Dispositif selon la revendication 22, dans lequel les éléments d'alignement ou les électrodes sont formées en utilisant la gravure ionique réactive profonde.
- Dispositif selon la revendication 3, dans lequel les électrodes, les rainures ou les bases de substrat sont formées par sciage.
- Dispositif selon l'une quelconque des revendications précédentes, dans lequel les éléments d'alignement (109, 110) et les électrodes (111) sont formés dans un métal.
- Dispositif selon la revendication 28, dans lequel le métal est déposé par placage électrolytique.
- Dispositif selon la revendication 3, dans lequel les bases de substrat sont formées en verre.
- Dispositif selon la revendication 30, dans lequel le verre est photomodelable.
- Module intégré comprenant une source de nanopulvérisation ayant une aiguille capillaire à une sortie de celui-ci, un spectromètre de masse ayant une aiguille capillaire à une entrée de celui-ci et un dispositif d'ionisation nanopulvérisation selon l'une quelconque des revendications précédentes disposé entre la source et le spectromètre de masse (101), les éléments d'alignement (109, 110) du dispositif formant des orifices de connexion pour les aiguilles capillaires de manière à permettre qu'un fluide provenant de la source soit ionisé et transféré vers le spectromètre de masse (101).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0514843.2A GB0514843D0 (en) | 2005-07-20 | 2005-07-20 | Microengineered nanospray electrode system |
| GB0519439A GB2428514B (en) | 2005-07-20 | 2005-09-23 | Microengineered nanospray electrode system |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1746631A2 EP1746631A2 (fr) | 2007-01-24 |
| EP1746631A3 EP1746631A3 (fr) | 2009-02-25 |
| EP1746631B1 true EP1746631B1 (fr) | 2013-06-19 |
Family
ID=37305854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06117211.0A Active EP1746631B1 (fr) | 2005-07-20 | 2006-07-14 | Système de nano-électrodes micro-mécanique |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1746631B1 (fr) |
| JP (1) | JP5265095B2 (fr) |
| CA (1) | CA2552086C (fr) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1959476A1 (fr) * | 2007-02-19 | 2008-08-20 | Technische Universität Hamburg-Harburg | Spectromètre de masse |
| US8242441B2 (en) * | 2009-12-18 | 2012-08-14 | Thermo Finnigan Llc | Apparatus and methods for pneumatically-assisted electrospray emitter array |
| GB2527803B (en) * | 2014-07-02 | 2018-02-07 | Microsaic Systems Plc | A method and system for monitoring biomolecule separations by mass spectrometry |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005019804A2 (fr) * | 2003-08-26 | 2005-03-03 | Predicant Biosciences, Inc. | Puce microfluidique presentant une pointe amelioree pour une ionisation par electonebulisation stable |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5386115A (en) * | 1993-09-22 | 1995-01-31 | Westinghouse Electric Corporation | Solid state micro-machined mass spectrograph universal gas detection sensor |
| EP1876442A3 (fr) * | 1998-09-17 | 2008-03-05 | Advion BioSciences, Inc. | Système chromatographique liquidemicrofabriquée en monolithique intégré et procédé |
| US6633031B1 (en) * | 1999-03-02 | 2003-10-14 | Advion Biosciences, Inc. | Integrated monolithic microfabricated dispensing nozzle and liquid chromatography-electrospray system and method |
| US6396057B1 (en) * | 2000-04-18 | 2002-05-28 | Waters Investments Limited | Electrospray and other LC/MS interfaces |
| JP2002190272A (ja) * | 2000-12-21 | 2002-07-05 | Jeol Ltd | エレクトロスプレー・イオン源 |
| GB2391694B (en) * | 2002-08-01 | 2006-03-01 | Microsaic Systems Ltd | Monolithic micro-engineered mass spectrometer |
| GB2422951B (en) * | 2005-02-07 | 2010-07-28 | Microsaic Systems Ltd | Integrated analytical device |
-
2006
- 2006-07-14 EP EP06117211.0A patent/EP1746631B1/fr active Active
- 2006-07-14 CA CA2552086A patent/CA2552086C/fr active Active
- 2006-07-20 JP JP2006197964A patent/JP5265095B2/ja not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005019804A2 (fr) * | 2003-08-26 | 2005-03-03 | Predicant Biosciences, Inc. | Puce microfluidique presentant une pointe amelioree pour une ionisation par electonebulisation stable |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2552086C (fr) | 2014-09-09 |
| EP1746631A2 (fr) | 2007-01-24 |
| EP1746631A3 (fr) | 2009-02-25 |
| JP5265095B2 (ja) | 2013-08-14 |
| JP2007027131A (ja) | 2007-02-01 |
| CA2552086A1 (fr) | 2007-01-20 |
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