EP1746631B1 - Mikromechanisches Nano-Elektrodensystem - Google Patents
Mikromechanisches Nano-Elektrodensystem 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- capillary
- substrate
- electrode
- nanospray
- input
- 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.)
- Active
Links
- 239000000758 substrate Substances 0.000 claims description 41
- 150000002500 ions Chemical class 0.000 claims description 26
- 239000007921 spray Substances 0.000 claims description 19
- 239000012530 fluid Substances 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 238000004811 liquid chromatography Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- 238000000708 deep reactive-ion etching Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000005251 capillar electrophoresis Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003631 wet chemical etching Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 3
- 230000005684 electric field Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 25
- 235000012431 wafers Nutrition 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 210000001747 pupil Anatomy 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012491 analyte Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003491 array Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000132 electrospray ionisation Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000005459 micromachining Methods 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000006089 photosensitive glass Substances 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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.
Landscapes
- 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)
- Mikrotechnische Nanosprüh-Ionisationsvorrichtung, die auf einem einzelnen Chip (108) vorgesehen ist, der zur Kopplung zwischen einer Nano-Spray-Quelle und einem Massenspektrometer (106) konfiguriert ist, wobei die Vorrichtung ein erstes Ausrichtmittel (109) aufweist, das für ein Zusammenwirkten mit einem Kapillar-Eingang bestimmt ist, ein zweites Ausrichtmittel (110), dass zum Zusammenwirken mit einem Kapillar-Ausgang und einer öffnung bestimmt ist, die einen Ionenweg zwischen dem Kapillar-Eingang und dem Kapillar-Ausgang definiert, wobei die Vorrichtung weiters mindestens eine leilende Elektrode (111) aufweist, die in einer Orientierung von im Wesentlichen senkrechter Richtung zum Ionenweg vorgesehen ist, und wobei sowohl das erste Ausrichtmittel (109), das zweite Ausrichtmittel (110), die Öffnung und die mindestens eine Elektrode (111) in integral in dem Chip (108) gebildet sind.
- Vorrichtung nach Anspruch 1, wobei der Chip (208) aus zwei Substraten konstruiert ist, wobei die Substrate in einer Stapelkonfiguration kombiniert sind, um so den Chip (108) zu bilden.
- Vorrichtung nach Anspruch 2, wobei jedes der zwei Substrate mit einer Isolierbasis (201) versehen ist, wobei die Substrate relativ zueinander gestapelt sind, derart, dass der resultierende Chip (108) einen Isolationsabschnitt auf einer Außenfläche hiervon halt.
- Vorrichtung nach Anspruch 2 oder 3, wobei jedes der beiden Substrate mit individuellen Mitteln gebildet ist, welche Mitte derart konfiguriert sind, dass die resultierende Kombinatin der Mittel das Ausrichtmittel (109), das zweite Ausrichtmittel (110), die Öffnung und die mindestens eine Elektrode (111) definieren, wenn die zwei Substrate zusammengebracht werden.
- Vorrichtung nach Anspruch 4, wobei ein erstes Substrat ein erstes gerilltes Ausrichtmittel (204) für den Kapillar-Eingang und ein zweites gerilltes Ausrichtmittel (206) für den Kapillar-Ausgang definiert, wobei das Substrat zusätzlich hierauf die mindestens eine leitende Elektrode mit einem gerillten aufrechten Rand hat, der normal zum Substrat angeordnet ist.
- Vorrichtung nach Anspruch 5, wobei das zweite Substrat darauf mindestens eine leitende Elektrode (111) mit einem gerillten aufrechten Rand hat, der normal zum Substrat angeordnet ist.
- Vorrichtung nach Anspruch 6, wobei dem Stapeln des ersten und zweiten Substrates relativ zueinander die mindestens einen Elektroden (111), die auf dem ersten und zweiten Substrat vorgesehen sind, eine zusammenhängende Elektrode bilden, und die Elektrodenrillen sich zur Bildung von Öffnungen kombinieren.
- Vorrichtung nach einem der vorangehenden Ansprüche, wobei der Kapillar-Eingang eine Nano-Spray-Kapillare (106) ist.
- Vorrichtung Anspruch 8, wobei der Nano-Spray-Kapillar-Eingang ein Fluid bereitstellt, welches Fluid aus einem Flüssigkeitschromatographen-System entstammen kann.
- Vorrichtung nach Anspruch 8, wobei der Nano-Spray-Kapillar-Eingang ein Fluid bereitstellt, welches Fluid aus einem kapillaren elektrophoresichen System stammen kann.
- Vorrichtung nach einem der vorangehenden Anspruche, wobei die Elektrode (111) nächst zu der Eingangskapillare an erster Stelle dazu konfiguriert ist, einen Taylor-Kegel zu schaffen und dann Ionen von der in der Eingangskapillare enthaltendem Flüssigkeit zu extrahieren.
- Vorrichtung nach einem der vorangehenden Ansprüche, wobei der Kapillar-Ausgang den Eingang für einen Massenspektrometer (106) bildet.
- Vorrichtung nach einem der vorangehenden Ansprüche, aufweisend zumindest zwei Elektroden (111) und wobei mindestens eine zweite Elektrode konfiguriert list, um Ionen auf die Ausgangskapillare zu fokussieren.
- Vorrichtung nach einem der vorangehenden Ansprüche, wobei mindestens eine Elektrode elektrisch geheizt und konfiguriert ist, um vorzugsweise ein Lösungsmittel zu entfernen.
- Vorrichtung nach einem der Ansprüche, 1 - 13, wobei mindestens eine Elektrode segmentiert und konfiguriert ist, um ein ablenkendes laterales elektrisches Feld zu schaffen, um zur Separation von Ionen von Neutralen zu verhelfen.
- Vorrichtung nach Anspruch 15, wobei das ablenkende laterale Feld zeitlich variiert und konfiguriert ist, um eine Zerstäubung zu unterstützen.
- Vorrichtung nach einem der vorangehenden Ansprüche, wobei der Chip mindestens ein Entleerungsloch für Fluide enthält.
- Vorrichtung nach Anspruch 3, wobei zumindest eine erste Substratbasis mindestens ein Einlassloch für Gase und eine Plenumkammer (410) beinhaltet, die den Kapillar-Eingang umschließt.
- Vorrichtung nach Anspruch 18, wobei die Plenumkammer (410) angeordnet ist, um eine axiale Strömung von Gas zu schaffen, die als eine Umhüllung zum Spray angeordnet ist.
- Vorrichtung nach Anspruch 3, wobei die Isolationsbasis in einem fotomusterbaren Polymer gebildet ist.
- Vorrichtung nach Anspruch 18, wobei der Substrat-Basis-(201)-Außenumfang, die Entleerungslöcher und die Gaseinlässe durch Fotomusterung definiert sind.
- Vorrichtung nach einem der vorangehenden Ansprüche, wobei die Ausnchtmittel (109, 110) und Elektroden (111) in einem Halbleiter gebildet sind.
- Vorrichtung nach Anspruch 22, wobei der Halbleiter Silikon ist.
- Vorrichtung nach Anspruch 22, bei der der Halbleiter durch anisotrope Naßchemische Ätzung bis zu Kristallebenen verdrillt ist.
- Vorrichtung nach Anspruch 22, wobei der Halbleiter durch eine tiefenreaktive Ionenätzung (deep reactive ion etching) verrillt ist.
- Vorrichtung nach Anspruch 22, wobei entweder die Ausrichtmittel oder die Elektroden unter Anwendung einer tiefreaktiven Ionenätzung gebildet sind.
- Vorrichtung nach Anspruch 3, wobei die Elektroden, Rillen oder Substratbasen durch Sägen gebildet sind.
- Vorrichtung nach einem der vorangehenden Ansprüche, wobei die Ausrichtmittel (109, 110) und Elektroden (111) in einem Metall gebildet sind.
- Vorrichtung nach Anspruch 28, wobei das Metall durch Elektroplattierung abgesetzt ist.
- Vorrichtung nach Anspruch 3, wobei die Substratbasen in Glas geformt sind.
- Vorrichtung nach Anspruch 30, wobei das Glas fotomusterbar ist.
- Integrierte Systemeinheit mit einer Nano-Spray-Quelle mit einer Kapillar-Nadel an einem Ausgang hiervon, einem Massenspektrometer mit einer Kapillar-Nadel an einem Eingang hiervon und einer Nano-Spray-Ionisationsvorrichtung nach einem der vorangehenden Ansprüche, vorgesehen zwischen der Quelle und dem .Massenspektrometer (101), wobei die Ausrichtmittel (109, 110) der Vorrichtung Anschlussstellen für die Kapillar-Nadeln schaffen, um so ein von der Quelle abstammendes Fluid ionisieren und an dem Massenspektrometer (101) führen zu können.
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 (de) | 2007-01-24 |
| EP1746631A3 EP1746631A3 (de) | 2009-02-25 |
| EP1746631B1 true EP1746631B1 (de) | 2013-06-19 |
Family
ID=37305854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06117211.0A Active EP1746631B1 (de) | 2005-07-20 | 2006-07-14 | Mikromechanisches Nano-Elektrodensystem |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1746631B1 (de) |
| JP (1) | JP5265095B2 (de) |
| CA (1) | CA2552086C (de) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1959476A1 (de) * | 2007-02-19 | 2008-08-20 | Technische Universität Hamburg-Harburg | Massenspektrometer |
| 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 (en) * | 2003-08-26 | 2005-03-03 | Predicant Biosciences, Inc. | Microfluidic chip with enhanced tip for stable electrospray ionization |
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 |
| CN1312473C (zh) * | 1998-09-17 | 2007-04-25 | 阿德文生物科学公司 | 液相色谱*** |
| 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/de active Active
- 2006-07-14 CA CA2552086A patent/CA2552086C/en 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 (en) * | 2003-08-26 | 2005-03-03 | Predicant Biosciences, Inc. | Microfluidic chip with enhanced tip for stable electrospray ionization |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007027131A (ja) | 2007-02-01 |
| EP1746631A2 (de) | 2007-01-24 |
| CA2552086C (en) | 2014-09-09 |
| JP5265095B2 (ja) | 2013-08-14 |
| EP1746631A3 (de) | 2009-02-25 |
| CA2552086A1 (en) | 2007-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7973278B2 (en) | Microengineered ionisation device | |
| US7615744B1 (en) | Microengineered nanospray electrode system | |
| US8148681B2 (en) | Microengineered vacuum interface for an ionization system | |
| EP1540697B1 (de) | Monolitisches miniaturisiertes massenspektrometer | |
| EP1688985B1 (de) | Integriertes analytisches Gerät | |
| US8022361B2 (en) | Monolithic multinozzle emitters for nanoelectrospray mass spectrometry | |
| GB2471520A (en) | An electrospray pneumatic nebuliser ionisation source | |
| US6750076B2 (en) | Fabrication of a microchip-based electrospray device | |
| GB2479190A (en) | Microengineered multipole rod assembly | |
| CN105047520B (zh) | 一种微流控电喷雾芯片器件及制作方法 | |
| Wright et al. | MEMS-based nanospray-ionization mass spectrometer | |
| EP1746631B1 (de) | Mikromechanisches Nano-Elektrodensystem | |
| GB2455351A (en) | Planar air amplifier on substrate | |
| WO2003025982A1 (en) | Uniform patterning for deep reactive ion etching | |
| JP5785219B2 (ja) | インターフェース部品及びその作製方法 | |
| Yu et al. | Microfluidic self-aspiration sonic-spray ionization chip with single and dual ionization channels for mass spectrometry | |
| Syms et al. | A microengineered alignment bench for a nanospray ionization source | |
| CN204706538U (zh) | 一种电喷雾离子源器件 | |
| Syms | The development of MEMS mass spectrometers | |
| Wright et al. | MEMS-based Nanospray Ionisation Mass Spectrometer Steven Wright1, Richard RA Syms2, Richard Moseley1, Guodong Hong1, Shane O’Prey1, William E. Boxford1, Neil Dash1 and Peter Edwards1 | |
| Li | Leslie Yeo 2 Contact Information and James Friend 2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL BA HR MK YU |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
|
| 17P | Request for examination filed |
Effective date: 20090515 |
|
| AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: MICROSAIC SYSTEMS PLC |
|
| 17Q | First examination report despatched |
Effective date: 20120605 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 618067 Country of ref document: AT Kind code of ref document: T Effective date: 20130715 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: LEMAN CONSULTING S.A., CH Ref country code: IE Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602006036849 Country of ref document: DE Effective date: 20130814 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130920 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130930 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 618067 Country of ref document: AT Kind code of ref document: T Effective date: 20130619 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130919 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20130619 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130717 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131019 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131021 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 |
|
| 26N | No opposition filed |
Effective date: 20140320 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20130919 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602006036849 Country of ref document: DE Effective date: 20140320 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130714 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130919 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130619 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130714 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20060714 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: IP PARTNERS J. WENGER, CH |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20220726 Year of fee payment: 17 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20220728 Year of fee payment: 17 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20220802 Year of fee payment: 17 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602006036849 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20240201 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230731 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230731 |