EP0068443A2 - Méthode d'analyse sélective de composés individuels présents sous forme de traces dans les gaz et les liquides - Google Patents

Méthode d'analyse sélective de composés individuels présents sous forme de traces dans les gaz et les liquides Download PDF

Info

Publication number
EP0068443A2
EP0068443A2 EP82105550A EP82105550A EP0068443A2 EP 0068443 A2 EP0068443 A2 EP 0068443A2 EP 82105550 A EP82105550 A EP 82105550A EP 82105550 A EP82105550 A EP 82105550A EP 0068443 A2 EP0068443 A2 EP 0068443A2
Authority
EP
European Patent Office
Prior art keywords
component
mass spectrometer
solid
components
carrier film
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.)
Granted
Application number
EP82105550A
Other languages
German (de)
English (en)
Other versions
EP0068443B1 (fr
EP0068443A3 (en
Inventor
Alfred Prof. Dr. Benninghoven
Günther Prof. Dr. Kämpf
Reimer Dr. Holm
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Priority to AT82105550T priority Critical patent/ATE22368T1/de
Publication of EP0068443A2 publication Critical patent/EP0068443A2/fr
Publication of EP0068443A3 publication Critical patent/EP0068443A3/de
Application granted granted Critical
Publication of EP0068443B1 publication Critical patent/EP0068443B1/fr
Expired legal-status Critical Current

Links

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
    • H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
    • H01J49/164—Laser desorption/ionisation, e.g. matrix-assisted laser desorption/ionisation [MALDI]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/24—Nuclear magnetic resonance, electron spin resonance or other spin effects or mass spectrometry
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
    • Y10T436/25375—Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.]
    • Y10T436/255—Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.] including use of a solid sorbent, semipermeable membrane, or liquid extraction

Definitions

  • the known method of paper strip chromatography has also been combined with a mass spectrometer.
  • the substance mixture is pre-separated in the paper strip.
  • the paper strip was then placed in a mass spectrometer and the spots associated with the individual substances were analyzed with SIMS (see R. J. Day et al, Anal. Chem. 52 No. 4 (1980) pp. 557a-572a).
  • SIMS see R. J. Day et al, Anal. Chem. 52 No. 4 (1980) pp. 557a-572a.
  • a disadvantage of these methods is that the pre-separation is carried out chromatographically, with long analysis times having to be accepted. In many cases, the pre-separation is difficult or even impossible, especially if the individual components differ little in terms of their migration speed.
  • Common to all chromatographic separation methods is that it is a volume process, i.e. that the separation effect is based on transport phenomena that take place in a porous carrier layer many thousands of
  • a pre-separation with the aid of a porous sintered body in combination with a mass spectrometric detection is also described in GB-OS 2 008 434.
  • the method described here is limited to substances that can evaporate out of the sintered body in the mass spectrometer.
  • the substance enriched in the sintered body is namely converted into the gas phase by heating and then, for. B. ionized by electron impact or field ionization. Direct ionization on the solid is not possible.
  • the pre-separation is either based on a chromatographic separation effect or is due to a kind of fractional distillation within the sintered body.
  • the main disadvantage of this method is that thermally labile substances can partially or completely decompose during thermal expulsion from the sintered body and thus result in incorrect or non-evaluable mass spectra. This applies in particular to high molecular weight organic compounds.
  • first monolayer is understood to mean the molecular layer which has direct contact with the (original) solid surface (substrate).
  • the "monolayer area” is to be understood to mean a layer thickness of at most a few monolayers in such a way that the adsorption behavior of the adsorbing molecules in this thickness range is still largely determined by the original substrate surface. This definition is in line with the literature (e.g. Adsorption on Solids by V.
  • the solid surfaces to be used must meet the requirements for a defined phase boundary between solid-liquid or solid-gaseous; this is only possible if there is a continuous, continuous surface, such as metal or plastic foils. In contrast, this requirement would not be met with a porous body, since the gas or liquid can be distributed in the entire volume. However, essentially only the uppermost molecular layers are accessible to mass spectrometric detection by means of surface-sensitive methods, such as, for example, secondary ion mass spectrometry. When using a porous body for pre-separation, most of the substance to be detected is contained in deeper pockets and channels and can therefore not be detected by the mass spectrometer.
  • An important step in achieving effective pre-separation is the preparation of the solid surface with a reagent that binds the desired component directly or selectively as a secondary product.
  • the component sought is first precipitated together with other components on the solid surface and then the other components are extracted by a solvent.
  • the solid surface is therefore subjected to a systematic pretreatment in order to deposit the sought-after component or a subsequent product characteristic of it at high density on the solid surface.
  • the deposited component or the subsequent product delivers a characteristic peak in the mass spectrum.
  • a laser-excited micro mass analyzer with a time-of-flight spectrometer can also be used in the method according to the invention.
  • this variant is not a surface-specific detection method.
  • this method is also suitable for detecting the component enriched on the surface of a carrier film.
  • test strip method for examining body fluids is modified in such a way that the test strip is used as a solid in the above sense and is evaluated by mass spectrometry.
  • Test strip technology is understood to mean the method of selective optical detection of individual substances by means of a targeted chemical reaction with a chemical compound applied to the test strip, combined with a color change.
  • Such test strips are known for example for the determination of sugar in human urine.
  • test strips and optical detection devices are on the market.
  • the modification of the known optical test strip technology consists in the fact that the special chemical compounds which selectively select individual substances from the given substance mixture by adsorption or chemical reaction (e.g. complex formation with chemical substances or enzymatic reactions with biochemical substances or antibody-antigen Remove the binding from biological substances), are firmly attached to the surface of the mass spectrometric slide.
  • the special chemical compounds which selectively select individual substances from the given substance mixture by adsorption or chemical reaction e.g. complex formation with chemical substances or enzymatic reactions with biochemical substances or antibody-antigen Remove the binding from biological substances
  • the speed with which the pre-separation or enrichment takes place on the solid depends only on the kinetics of the absorption process, which causes the component sought to bind to the solid surface.
  • this process takes place at times which are orders of magnitude less than the times required for the chromatographic separation.
  • the method according to the invention can always be used successfully if the task is to detect one or more components known per se in a solution "or a mixture (gaseous or liquid). In particular, this includes solutions of non-evaporable organic substances that used to be used were analyzed with a liquid chromatograph.
  • the enrichment in a monolayer on the surface of the solid allows the use of all surface analysis methods that are suitable for the detection of elements and, to a limited extent, of connections.
  • Next SIMS and laser excitation can also be used for bombardment with fast neutral particles (fast atom bombardment, FAB).
  • the first step of the process i.e. H. the selective enrichment of the sought component on the upper body. surface
  • H. the selective enrichment of the sought component on the upper body. surface is based on a precipitation of the substance sought on the surface of the solid.
  • a gas component can be precipitated from a gas that forms a non-volatile bond with the surface.
  • a liquid component or a dissolved component is precipitated, which is bound to the surface.
  • the solution component In order to detect or quantify a certain substance in a solution, it is brought into contact with a solid surface. Because of its chemical composition, it reacts with the solution component to be detected in such a way that the surface of the solid is chemically changed in a way that is specific to the substance. In the simplest case, this substance can be bound directly to the surface. But it can also be derived products of The reaction between the solid surface and the substance from the solution remains on the surface.
  • the detection of the substance-specific surface reaction products is preferably carried out in a SIMS or a laser-excited micro mass analyzer.
  • a simple example is the detection of Cl in a solution.
  • a cleaned Ag foil is sufficient as the reaction surface.
  • Insoluble AgCl forms in the C1-containing solution, which is detected with SIMS as Cl - or AgCl 2 - .
  • Electrical direct or alternating fields can be used to initiate, reinforce or generally control the component-specific surface reaction when the dissolved substances are present as ions or have a dipole moment. Their effect can be enhanced by a micro-roughness of the surface.
  • Suitable chemical or physical post-preparation can additionally increase the sensitivity of the detection or simplify the detection of the change in the surface caused by the detection reaction by means of SIMS.
  • laser desorption can also be used to record substance-specific surface changes.
  • a monolayer process is particularly favorable because it proves the connection as such, an extreme sensation and only covers the uppermost monolayer.
  • other mass spectrometric detection methods can also be used, such as the 252 California technique and ionization by bombardment with neutral atoms. Those methods are preferred in which the component sought or its secondary product is detected in undestroyed form.
  • This route which is labeled III in FIG. 3, is based on the collective precipitation of all components present on the solid surface and the subsequent preservation of the sought component Ai by treating the optionally prepared surface with a solvent which removes the other bound components ( Extraction).
  • Fig. 3 designated II.
  • the mass spectrometric detection of A i takes place either directly or after activation of an intermediate step in which all components except A i are extracted in the manner described.
  • As indicated under III it is also conceivable that only a part of the other, not wanted components is washed out by the solvent and the searched component A i remains on the surface together with a few other components. In such cases, it must be ensured that the subsequent mass spectrometric detection of A i is not disturbed by the other components.
  • activation it is known that the probability of ionization on the solid surface by doping with certain substances, e.g. Alkali compounds can increase.
  • the component activated in this way can then be detected with increased sensitivity.
  • this step inserted immediately before the mass spectrometric detection is referred to as "activation".
  • the precipitated component reacts with the surface reagent in such a way that a characteristic secondary product is formed, which is then identified either directly or after further modification (if extraction and / or activation is provided) by mass spectrometry. With the exception of physical adsorption, there is a structural change in the surface reagent and the absorbed component in all cases.
  • the secondary ion mass spectrometer shown schematically in FIG. 4 essentially consists of the mass spectrometer room 1 with the primary ion source 2, ion optics 3 and Quadr u pol- Mass filter 4 with detector 5.
  • the ion source 2 is connected to an argon bottle 6.
  • the solid surface used as target 7 with the enriched component located thereon is introduced into mass spectrometer room 1 via a lock device 8.
  • the vacuum supply for the mass spectrometer consists of the titanium sublimation pump 9, the cryopump 10, the turbomolecular pump 11 and the rotary pump 12. Ionization manometers 13 are used to control the vacuum.
  • the ion source 2 allows the generation of primary ions (argon ions) with an energy of several keV and one Current density from 10 -9 to 10 -8 A / cm 2 .
  • the measurements take place in a high vacuum at approx. 10 torr.
  • the second apparatus which was used in combination with the planar separation technology, is a laser-excited micromass analyzer.
  • the apparatus shown schematically in FIG. 5 essentially consists of a time-of-flight mass spectrometer 14 with detector 15 and a pulsed high-power laser 16 for vaporization and ionization of the sample 17.
  • the laser beam is focused on the sample 17 with the aid of an objective 18.
  • the aid of a mirror 19 and an eyepiece 20 With the aid of a mirror 19 and an eyepiece 20, the position of the sample in the mass spectrometer space with respect to the laser beam can be checked visually and readjusted if necessary.
  • the laser 16 generates a very short light pulse (laser flash), which evaporates the sample located on a suitable object holder very quickly and largely ionizes it.
  • the ions formed are detected by the time-of-flight mass spectrometer 14 and separated on the principle of the transit time measurement.
  • the ions arriving at the multiplier 15 generate an electrical signal which, after amplification (21), is fed to a transient recorder 22 and is subsequently displayed on a recorder 23 and an oscillograph 24.
  • the transient recorder 22 is triggered by the laser.
  • the time-of-flight mass spectrometer 14 is connected to corresponding vacuum pumps.
  • the sample 17 is arranged on a thin polymeric carrier film and is in the high vacuum of the mass spectrometer.
  • the laser beam is focused on the sample through a glass pane attached to the mass spectrometer 14, which creates the vacuum-tight separation between the mass spectrometer (high vacuum) and the laser (air).
  • the thin polymeric backing film thickness about 0.1 / um
  • these support film does not rupture even after several interleaf with the laser, the vacuum required to operate the mass spectrometer itself is not impaired even by several such holes (diameter approx. 2 / um).
  • the sample 17 lies on the sample holder 25, which is arranged via the sealing ring 26 centrally via a recess 27 in the outer wall 28 of the mass spectrometer 14 '.
  • Apertures can be used as the sample holder 25, as used, for example, in electron microscopy.
  • These are massive metal flakes, for example made of platinum, silver, steel and others with a thickness of approximately 1 mm, which have one or more bores 29 with diameters between 10 and 100 / um.
  • Metal flakes are also known which have a larger bore centrally, which in turn is closed with a metal net with mesh sizes between 20 and 100 / um.
  • Thin polymer foils are stretched onto these metal screens, which on the one hand serve as a vacuum seal and on the other hand represent non-porous supports for the substances to be examined.
  • the carrier films are coated with chemically or biochemically selective reagents, as described on pages 14-17. It is also conceivable that these reagents are contained in the film itself.
  • the material of the carrier film can consist, for example, of collodion varnish or of zapon varnish or of form var. these materials are also used as carrier foils in electron microscopy.
  • the carrier film is applied to the sample holder 25 by lowering one by spreading collodion lacquer or Zapon lacquer or Formvar or the like. '' very thin film created on a water surface, for example in a separating funnel or by producing the carrier film by spreading the lacquer on a smooth carrier, for example a glass plate, detaching the film, for example by slowly immersing it in water and transferring the carrier film to the sample holder 25.
  • a 0.1 mm thick silver plate measuring 10 x 20 mm serves as the separation and detection area.
  • the plate was immersed in HNO 3 (20%) for 3 minutes before cleaning in the solution to be analyzed for cleaning and roughening, then rinsed 3 times with distilled water in an ultrasonic bath.
  • the selective extraction was carried out using water as solvent.
  • the target loaded with the components of the solution was immersed 3 times in a row in distilled water in an ultrasonic bath for about 1 minute.
  • the target was then dried in air and in this form represented the sample in the "exposed and then rinsed" state.
  • the SIMS spectra of the individual connections used are known on the basis of corresponding preliminary tests.
  • the "parent ions” (M + Ag) + or (MH) - (cf. table) were used to detect the compounds present on the respective surfaces.
  • the spectra sections shown in the figures were obtained in measuring times of about 2 minutes.
  • the introduced target was treated with Ar ions with an energy of 3 keV and a current strength of. Bombard 2 ⁇ 10 -10 A at 0.1 cm 2 .
  • the mass analysis of the positive and negative secondary ions was carried out with a quadrupole mass spectrometer and subsequent single ion detection.
  • the known total cross section for the damage caused by ion bombardment is present in all compounds of this B eispiel marina some 10 -14 cm 2. With a scan speed of about 1 amu / s, it is therefore ensured that there was no disturbing change in the surface concentration of the examined compounds during the analysis time.
  • the time constant of the recorder was 1/4 s.
EP82105550A 1981-06-27 1982-06-24 Méthode d'analyse sélective de composés individuels présents sous forme de traces dans les gaz et les liquides Expired EP0068443B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82105550T ATE22368T1 (de) 1981-06-27 1982-06-24 Verfahren zur selektiven analyse einzelner spurenfoermiger komponenten in gasen und fluessigkeiten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813125335 DE3125335A1 (de) 1981-06-27 1981-06-27 Verfahren zur analyse von gasen und fluessigkeiten
DE3125335 1981-06-27

Publications (3)

Publication Number Publication Date
EP0068443A2 true EP0068443A2 (fr) 1983-01-05
EP0068443A3 EP0068443A3 (en) 1984-07-04
EP0068443B1 EP0068443B1 (fr) 1986-09-17

Family

ID=6135517

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82105550A Expired EP0068443B1 (fr) 1981-06-27 1982-06-24 Méthode d'analyse sélective de composés individuels présents sous forme de traces dans les gaz et les liquides

Country Status (6)

Country Link
US (2) US4468468A (fr)
EP (1) EP0068443B1 (fr)
JP (1) JPS589040A (fr)
AT (1) ATE22368T1 (fr)
CA (1) CA1195013A (fr)
DE (2) DE3125335A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4017805A1 (de) * 1989-08-22 1991-03-07 Finnigan Mat Gmbh Verfahren, praeparat und vorrichtung zur bereitstellung eines analytes fuer eine untersuchung
WO1998016948A1 (fr) * 1996-10-11 1998-04-23 Alfred Benninghoven Procede de determination de profils de profondeur dans une zone a couche mince

Families Citing this family (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3125335A1 (de) * 1981-06-27 1983-01-13 Alfred Prof. Dr. 4400 Münster Benninghoven Verfahren zur analyse von gasen und fluessigkeiten
GB8513687D0 (en) * 1985-05-30 1985-07-03 Analytical Instr Ltd Detection of airborne low volatility vapours
GB2177507B (en) * 1985-06-13 1989-02-15 Mitsubishi Electric Corp Laser mass spectroscopic analyzer
US4728796A (en) * 1986-04-10 1988-03-01 Medical College Of Wisconsin Method for ionization of polymers
US4777363A (en) * 1986-08-29 1988-10-11 Research Corporation Technologies, Inc. Ion mobility spectrometer
US4988879A (en) * 1987-02-24 1991-01-29 The Board Of Trustees Of The Leland Stanford Junior College Apparatus and method for laser desorption of molecules for quantitation
US4988628A (en) * 1989-02-28 1991-01-29 New England Deaconess Hospital Corporation Method of drug detection
US5118937A (en) * 1989-08-22 1992-06-02 Finnigan Mat Gmbh Process and device for the laser desorption of an analyte molecular ions, especially of biomolecules
US5045694A (en) * 1989-09-27 1991-09-03 The Rockefeller University Instrument and method for the laser desorption of ions in mass spectrometry
GB2269934B (en) * 1992-08-19 1996-03-27 Toshiba Cambridge Res Center Spectrometer
ATE242485T1 (de) * 1993-05-28 2003-06-15 Baylor College Medicine Verfahren und massenspektrometer zur desorption und ionisierung von analyten
US20020037517A1 (en) * 1993-05-28 2002-03-28 Hutchens T. William Methods for sequencing biopolymers
US6071610A (en) 1993-11-12 2000-06-06 Waters Investments Limited Enhanced resolution matrix-laser desorption and ionization TOF-MS sample surface
US5498545A (en) * 1994-07-21 1996-03-12 Vestal; Marvin L. Mass spectrometer system and method for matrix-assisted laser desorption measurements
USRE39353E1 (en) 1994-07-21 2006-10-17 Applera Corporation Mass spectrometer system and method for matrix-assisted laser desorption measurements
DE19608963C2 (de) * 1995-03-28 2001-03-22 Bruker Daltonik Gmbh Verfahren zur Ionisierung schwerer Moleküle bei Atmosphärendruck
WO1996037777A1 (fr) * 1995-05-23 1996-11-28 Nelson Randall W Immuno-dosage spectrometrique de masse
DE19617011C2 (de) * 1996-04-27 2000-11-02 Bruker Daltonik Gmbh Matrixkomponentengemisch für die matrixunterstützte Laserdesorption und Ionisierung sowie Verfahren zur Zubereitung eines Matrixkomponentengemisches
DE19642261A1 (de) * 1996-10-11 1998-04-16 Hoechst Ag Verfahren und Vorrichtung zum Erkennen der katalytischen Aktivität von Feststoffen
NZ516848A (en) 1997-06-20 2004-03-26 Ciphergen Biosystems Inc Retentate chromatography apparatus with applications in biology and medicine
EP1387390B1 (fr) 1997-06-20 2009-02-18 Bio - Rad Laboratories, Inc. Chromatographie par retentat et ensembles de détection de protéines ayant des applications biologiques et médicales
US6265715B1 (en) * 1998-02-02 2001-07-24 Helene Perreault Non-porous membrane for MALDI-TOFMS
US6849847B1 (en) 1998-06-12 2005-02-01 Agilent Technologies, Inc. Ambient pressure matrix-assisted laser desorption ionization (MALDI) apparatus and method of analysis
DE19934242A1 (de) * 1999-07-21 2001-01-25 Clariant Gmbh Verfahren zum Nachweis von organischen Verbindungen auf Oberflächen beim Menschen
JP2001132638A (ja) * 1999-11-10 2001-05-18 Ebara Corp トラップ装置
CA2301451A1 (fr) * 2000-03-20 2001-09-21 Thang T. Pham Methode d'analyse par spectrometrie de masse
US7375319B1 (en) 2000-06-09 2008-05-20 Willoughby Ross C Laser desorption ion source
US7087898B2 (en) * 2000-06-09 2006-08-08 Willoughby Ross C Laser desorption ion source
US20020150509A1 (en) * 2001-04-17 2002-10-17 Houge Erik C. Laboratory specimen sampler with integrated specimen mount
JP4194370B2 (ja) * 2001-05-25 2008-12-10 ウォーターズ・インヴェストメンツ・リミテッド Ｍａｌｄｉ質量分析用脱塩プレート
AU2002305710A1 (en) * 2001-05-25 2002-12-09 Waters Investments Limited Sample concentration maldi plates for maldi mass spectrometry
US7728048B2 (en) 2002-12-20 2010-06-01 L-1 Secure Credentialing, Inc. Increasing thermal conductivity of host polymer used with laser engraving methods and compositions
US7793846B2 (en) 2001-12-24 2010-09-14 L-1 Secure Credentialing, Inc. Systems, compositions, and methods for full color laser engraving of ID documents
US7694887B2 (en) 2001-12-24 2010-04-13 L-1 Secure Credentialing, Inc. Optically variable personalized indicia for identification documents
AU2002353174A1 (en) * 2001-12-24 2003-07-15 Digimarc Id Systems, Llc Laser engraving methods and compositions
AU2002364036A1 (en) * 2001-12-24 2003-07-15 Digimarc Id Systems, Llc Laser etched security features for identification documents and methods of making same
CA2471457C (fr) 2001-12-24 2011-08-02 Digimarc Id Systems, Llc Documents d'identification comprenant des informations invisibles variables et leurs procedes de production
WO2003088144A2 (fr) 2002-04-09 2003-10-23 Digimarc Id Systems, Llc Techniques de traitement d'images pour imprimer des cartes et des documents d'identification
US7824029B2 (en) 2002-05-10 2010-11-02 L-1 Secure Credentialing, Inc. Identification card printer-assembler for over the counter card issuing
US7687276B2 (en) * 2002-05-30 2010-03-30 Massachusetts Institute Of Technology Method of detecting analyte vaporized from sample with low-power UV radiation
US7095019B1 (en) 2003-05-30 2006-08-22 Chem-Space Associates, Inc. Remote reagent chemical ionization source
US7109038B2 (en) * 2002-06-13 2006-09-19 The Johns Hopkins University Occult blood detection in biological samples by laser desorption and matrix-assisted laser desorption/ionization mass spectrometry for biomedical applications
JP4241006B2 (ja) * 2002-11-11 2009-03-18 株式会社島津製作所 レーザー脱離イオン化質量分析方法とそれに用いるサンプルプレート
US7105809B2 (en) * 2002-11-18 2006-09-12 3M Innovative Properties Company Microstructured polymeric substrate
US7804982B2 (en) 2002-11-26 2010-09-28 L-1 Secure Credentialing, Inc. Systems and methods for managing and detecting fraud in image databases used with identification documents
US6639217B1 (en) * 2002-12-20 2003-10-28 Agilent Technologies, Inc. In-line matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) systems and methods of use
US7763179B2 (en) 2003-03-21 2010-07-27 Digimarc Corporation Color laser engraving and digital watermarking
DE602004030434D1 (de) 2003-04-16 2011-01-20 L 1 Secure Credentialing Inc Dreidimensionale datenspeicherung
US7113277B2 (en) * 2003-05-14 2006-09-26 Lockheed Martin Corporation System and method of aerosolized agent capture and detection
WO2004112074A2 (fr) * 2003-06-07 2004-12-23 Willoughby Ross C Source d'ions de desorption laser
CA2480549A1 (fr) * 2004-09-15 2006-03-15 Phytronix Technologies Inc. Source d'ionisation pour spectrometre de masse
US7138626B1 (en) 2005-05-05 2006-11-21 Eai Corporation Method and device for non-contact sampling and detection
US20060266941A1 (en) * 2005-05-26 2006-11-30 Vestal Marvin L Method and apparatus for interfacing separations techniques to MALDI-TOF mass spectrometry
US7568401B1 (en) 2005-06-20 2009-08-04 Science Applications International Corporation Sample tube holder
US20070095726A1 (en) * 2005-10-28 2007-05-03 Tihiro Ohkawa Chafftron
US7576322B2 (en) * 2005-11-08 2009-08-18 Science Applications International Corporation Non-contact detector system with plasma ion source
US8123396B1 (en) 2007-05-16 2012-02-28 Science Applications International Corporation Method and means for precision mixing
US8008617B1 (en) 2007-12-28 2011-08-30 Science Applications International Corporation Ion transfer device
US8071957B1 (en) 2009-03-10 2011-12-06 Science Applications International Corporation Soft chemical ionization source
CN105762055B (zh) * 2014-12-17 2018-06-26 中国科学院大连化学物理研究所 一种用于研究等离子体-小分子体系反应的质谱装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1450511A (fr) * 1965-04-29 1966-06-24 Séparation chromatographique sélective
US3567927A (en) * 1969-04-11 1971-03-02 Nasa Ion microprobe mass spectrometer for analyzing fluid materials
FR2406823A1 (fr) * 1977-10-20 1979-05-18 Shionogi & Co Element support d'echantillon pour spectrometre de masse

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2211032C3 (de) * 1972-03-08 1975-05-28 Varian Mat Gmbh, 2800 Bremen Verfahren und Vorrichtung zur Bestimmung der Partialdrucke oder Konzentrationen von in einer Flüssigkeit, insbesondere Im Blut, gelösten Gasen
CA1039649A (fr) * 1973-08-30 1978-10-03 General Electric Company Methode pour former des films d'un complexe immunologique en plusieurs couches
DE2442346C3 (de) * 1974-09-04 1978-09-21 Bayer Ag, 5090 Leverkusen Verfahren und Vorrichtung zur Bestimmung von Quecksilber-Spuren in Flüssigkeiten
GB1574812A (en) * 1976-05-06 1980-09-10 Barringer Research Ltd Spectrochemical analysis
US4080170A (en) * 1976-09-20 1978-03-21 Borkenstein Robert F Alcohol retainer cartridge and method for using same
DE2739829C2 (de) * 1977-09-03 1986-04-10 Gesellschaft für Strahlen- und Umweltforschung mbH, 8000 München Anordnung zur Analyse einer Probenschicht durch Beschuß mit elektromagnetischer Strahlung
FR2454635A1 (fr) * 1979-04-18 1980-11-14 Commissariat Energie Atomique Procede et dispositif de reglage de l'impact sur une cible d'un faisceau de lumiere monochromatique emis par une source laser
US4378499A (en) * 1981-03-31 1983-03-29 The Bendix Corporation Chemical conversion for ion mobility detectors using surface interactions
DE3125335A1 (de) * 1981-06-27 1983-01-13 Alfred Prof. Dr. 4400 Münster Benninghoven Verfahren zur analyse von gasen und fluessigkeiten

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1450511A (fr) * 1965-04-29 1966-06-24 Séparation chromatographique sélective
US3567927A (en) * 1969-04-11 1971-03-02 Nasa Ion microprobe mass spectrometer for analyzing fluid materials
FR2406823A1 (fr) * 1977-10-20 1979-05-18 Shionogi & Co Element support d'echantillon pour spectrometre de masse

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANALYTICAL CHEMISTRY, Band 52, Nr. 4, April 1980, Seiten 557a-572a, Columbus, Ohio, US *
APPLIED PHYSICS, Band 8, Nr. 4, Dezember 1975, Seiten 341-348, Springer-Verlag, Heidelberg, DE *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4017805A1 (de) * 1989-08-22 1991-03-07 Finnigan Mat Gmbh Verfahren, praeparat und vorrichtung zur bereitstellung eines analytes fuer eine untersuchung
DE4017805C2 (de) * 1989-08-22 1998-03-26 Finnigan Mat Gmbh Verfahren, Präparat und Vorrichtung zur Bereitstellung eines Analytes für eine Untersuchung
WO1998016948A1 (fr) * 1996-10-11 1998-04-23 Alfred Benninghoven Procede de determination de profils de profondeur dans une zone a couche mince

Also Published As

Publication number Publication date
DE3273325D1 (en) 1986-10-23
JPS589040A (ja) 1983-01-19
EP0068443B1 (fr) 1986-09-17
EP0068443A3 (en) 1984-07-04
ATE22368T1 (de) 1986-10-15
DE3125335A1 (de) 1983-01-13
US4468468A (en) 1984-08-28
CA1195013A (fr) 1985-10-08
US4527059A (en) 1985-07-02

Similar Documents

Publication Publication Date Title
EP0068443B1 (fr) Méthode d'analyse sélective de composés individuels présents sous forme de traces dans les gaz et les liquides
Pitarch et al. Analytical strategy based on the use of liquid chromatography and gas chromatography with triple-quadrupole and time-of-flight MS analyzers for investigating organic contaminants in wastewater
EP1481416B1 (fr) Procede de spectrometrie de masse pour analyser des melanges de substances
DE4408034C1 (de) Verfahren zur massenspektrometrischen Analyse von Proben aus 2D-Gel-Elektrophoreseplatten mit matrixunterstützter ionisierender Laser-Desorption
DE19618032C2 (de) Lagerfähig vorpräparierte Maldi-Probenträger
DE102008041813B4 (de) Verfahren zur Tiefenanalyse einer organischen Probe
DE102012224172B4 (de) Nachgewiesene Uringeruchszusammensetzung aus einer Kilmaanlage, Verfahren zum Analysieren der Verbindungen, die zu Uringeruch aus einer Klimaanlage beitragen und Verfahren zum Herstellen einer nachgewiesenen Uringeruchszusammensetzung
DE19617011A1 (de) Verfahren zur matrixunterstützten ionisierenden Laserdesorption
DE102007043456A1 (de) Matrixunterstützte Laserdesorption hoher Ionisierungsausbeute
EP0795749A2 (fr) Spectrométrie à mobilité d'ions par photoionisation
DE102007035827A1 (de) Präparative Ionenmobilitätsspektrometrie
DE3221681A1 (de) Massenspektrometer mit externer probenhalterung
DE102016008230A1 (de) Elementaranalyse von organischen Proben
DE2819711C2 (de) Verfahren und Vorrichtung zur Analyse einer Probe mit Hilfe gepulster Laserstrahlung
DE10322701B4 (de) Probenträger unter Verwendung eines porösen, Metalloxidpartikel umfassenden Films, Verfahren zur Herstellung eines Probenträgers, Verwendung des Probenträgers sowie Verfahren zum selektiven Nachweis von phosphorylierten/sulfatierten Biopolymeren, insbesondere Peptiden/Proteinen
DE19637480A1 (de) Massenspektrometrische Analyse von Oberflächen
DE102004025841A1 (de) Verfahren und Vorrichtung zur massenspektroskopischen Untersuchung von Analyten
WO2009062652A1 (fr) Procédé et dispositif pour analyser les rapports isotopiques
EP1573776B1 (fr) Procédé de production d'un support d'échantillons pour spectromètrie de masse de type maldi
DE10292304B4 (de) Separation von Komponenten einer Analysenprobe in einem Ionenmobilitätsspektrometer durch Zuführung selektiv wechselwirkender gasförmiger Partikel
DE19820626A1 (de) Verfahren und Vorrichtung zum Nachweis von Probenmolekülen
DE4017805C2 (de) Verfahren, Präparat und Vorrichtung zur Bereitstellung eines Analytes für eine Untersuchung
DE102010054581A1 (de) Probenpräparation für die Ionisierung mit matrixunterstützter Laserdesorption
DE2346422A1 (de) Verfahren und system zur feststellung von explosivstoffen
DE1957311A1 (de) Verfahren zur massenspektrometrischen Analyse von Festkoerperoberflaechen

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

17P Request for examination filed

Effective date: 19820624

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

RHK1 Main classification (correction)

Ipc: H01J 49/10

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL SE

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 22368

Country of ref document: AT

Date of ref document: 19861015

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3273325

Country of ref document: DE

Date of ref document: 19861023

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

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

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19890531

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19890601

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19890621

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19890622

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19890626

Year of fee payment: 8

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19890630

Year of fee payment: 8

Ref country code: FR

Payment date: 19890630

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19900624

Ref country code: AT

Effective date: 19900624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19900625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19900630

Ref country code: CH

Effective date: 19900630

Ref country code: BE

Effective date: 19900630

BERE Be: lapsed

Owner name: BAYER A.G.

Effective date: 19900630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19910101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19910227

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19910228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19920401

EUG Se: european patent has lapsed

Ref document number: 82105550.6

Effective date: 19910206