EP0571622B1 - Procede d'observation sequentielle des etats successifs d'une reaction chimique - Google Patents

Procede d'observation sequentielle des etats successifs d'une reaction chimique Download PDF

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Publication number
EP0571622B1
EP0571622B1 EP93902336A EP93902336A EP0571622B1 EP 0571622 B1 EP0571622 B1 EP 0571622B1 EP 93902336 A EP93902336 A EP 93902336A EP 93902336 A EP93902336 A EP 93902336A EP 0571622 B1 EP0571622 B1 EP 0571622B1
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EP
European Patent Office
Prior art keywords
molecules
target
jet
dissociation
molecular
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EP93902336A
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German (de)
English (en)
French (fr)
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EP0571622A1 (fr
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Fernand Marcel Devienne
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    • 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
    • H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • H01J49/142—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using a solid target which is not previously vapourised
    • 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

Definitions

  • the main object of the present invention is a method of sequential observation of the successive states of a chemical reaction during the course of vacuum or at low pressure and also the analysis of solids, liquids, gases (under certain conditions) and aerosols.
  • the present invention specifically relates to a method for observing the successive states of a chemical reaction during a vacuum which meets the stated needs.
  • the process which is the subject of the invention uses known techniques for dissociation of molecular ions by impact on neutral gas molecules and for subsequent identification of the secondary dissociation ions formed during the reaction. As such, it is largely inspired by the methods described in documents FR-A-2, 622, 699 and FR-A-2, 655,149, at least as regards the analytical phase of the process using a dissociation box filled with a neutral gas, from which secondary ions filtered into energy emerge in an electrostatic analyzer whose filtration level is adjustable.
  • the originality of the process, object of the invention lies in the simultaneous use of two high-energy neutral molecular jets and in the fact that the axes of these jets are located during the implementation of the process in the same plane vertical.
  • This latter arrangement which is preferable although not compulsory, allows in particular to work on liquids or powders contained in a small horizontal container. The first brings continuously, into the vacuum enclosure in which the target provided for this purpose is placed, the atoms and molecules of which we want to study precisely the chemical reaction in vacuum.
  • the second intermittent molecular jet is a jet of neutral gas molecules, for example: argon, krypton, xenon whose energy is such that it causes the molecules in situ and immediate ionization as soon as they are formed and which, by spraying ( sputtering), forms a beam of secondary ions.
  • the dissociation occurs only later in the dissociation box provided for this purpose, at the exit of which the secondary ionic fragments formed are identified by their energy using the electrostatic analyzer.
  • the second jet is intermittent and c is it which allows, in a way, to photograph the instantaneous state of evolution of the chemical reaction in progress. Indeed, with each intervention of this second intermittent jet, chemical molecules which have just been formed are ionized then immediately extracted from the reaction chamber, dissociated in the dissociation chamber and analyzed by the detector analyzer system.
  • This second molecular jet can moreover intervene according to any temporal program desired in advance, namely, for example, an intervention at a chosen time t or several successive interventions at times also chosen, either even in pulsed form at a frequency constant.
  • the method can operate with a second pulsed jet, the period of which can vary from 10 ⁇ 9 seconds to a few hundred seconds when necessary.
  • the implementation of the process requires very precise programming and control by computer of the times of intervention of this second molecular jet.
  • the molecular jets commonly have an energy of 0.5 to 15 keV and the vacuum enclosure is brought to a potential of a few thousand volts, for example from 1000 to 15 000 V.
  • the vacuum enclosure is placed at the pressure desired by the experimenter for the precise study of a determined reaction, but, more often than not, when one wants to simulate reactions likely to take place, for example in the interstellar space, this enclosure is brought to a very high vacuum, of the order of 133.10 ⁇ 6 to 133.10 ⁇ 9 Pa (10 ⁇ 6 to 10 ⁇ 9 torr). It is also possible to have a higher limit vacuum by using two turbo-molecular pumps in series.
  • FIG 1 there is shown the vacuum enclosure 2 inside which is implemented the method, object of the invention.
  • This is a simple diagram because the enclosure is much more complicated so that the molecular canons in particular can have the desired inclination relative to the vertical axis of the body of the device so as to be able to have the same impact zone of the two molecular jets on the target.
  • a high vacuum is maintained, using a primary pump and a turbo-molecular pump, possibly up to at 133.10 ⁇ 9 Pa (10 ⁇ 9 torr) (this, without the molecular canons working) and, in principle, between 133.10 ⁇ 7 and 133.10 ⁇ 8 Pa (10 ⁇ 7 and 10 ⁇ 8 torr) when everything is working.
  • the target holder (4) which can be a small bin whose largest dimension does not exceed 20 mm- which can contain either a liquid, a solid powder or en bloc (the target carrier being different in the case of gases or aerosols).
  • the target carrier being different in the case of gases or aerosols.
  • target the body actually affected by the simultaneous imprint of the two beams.
  • the target holder is included in a conductive enclosure (6) -in principle a vertical cylinder portion pierced with holes- carried at high voltage V0, this enclosure comprising in particular five orifices, namely: the orifices 8 and 10 for the introduction of molecular jets, 8bis for a direct vision system of the target thanks to a system of optical lenses, 10bis for the introduction of a laser beam and the orifice 12 for the extraction of the molecular ions formed on the target 4.
  • This extraction is carried out thanks to a lens system (14, 14a, 14b, 14c, 14d) brought to different potentials, the last 14d being at zero potential.
  • the source (16), or first jet sends to the target (4), through the orifice 8, atoms and molecules of compounds whose reaction in vacuum is to be studied.
  • the second molecular jet (18) introduced by the orifice (10), into the enclosure (6), on the target (4), a jet of neutral molecules obtained by charge exchange, of an inert gas such as, for example, argon, krypton or xenon.
  • an inert gas such as, for example, argon, krypton or xenon.
  • the target (4) in fact, can be either foreign to the chemical reaction studied, or, on the contrary, participate in it as it is the case, for example, when it is made of carbon which can react with atoms and molecules of the molecular stream (16).
  • the molecules formed on the target (4) by chemical reaction are extracted by sputtering and thanks to the lenses electrostatic (14) along the path shown schematically by the arrow "F" and they enter a dissociation box (20) filled with a neutral gas where they partially explode into different fragments of secondary ions.
  • each of the secondary ions thus formed takes with it a share of the total energy of the incident ion M, equal at eV0.m1 / M, and eV0.m2 / M and eV0.m k / M, values which we will designate by eV ".
  • these secondary ions arrive in the electrostatic analyzer (22) whose filtration energy is eV ".
  • the secondary ions leaving the electrostatic analyzer (22) enter a detector (24) which allows, possibly, their identification.
  • This body is formed by bombarding pure graphite with a mixture of molecular jets of nitrogen, hydrogen and oxygen.
  • the molecular peak 83 corresponding to the formula: and different mass peaks 69, 68, 67, 66, 56, 55, 52, 40, 29 and 27.
  • the detection, using the apparatus of FIG. 1, of a significant number of these secondary peaks confirms that the cytosine molecule was present in the enclosure (6) at the time of the intervention of the molecular jet (18).
  • the molecular masses indicated sometimes differ by one or a few units from the mass corresponding to the chemical formula, this due to the departure of a proton or even a group of atoms.
  • Figure 3 shows a diagram of breakdown into secondary fragments of the same nature, but relating to the phosphocytosine of general formula C4H6O4N3P and of structural formula:
  • This body was obtained under the same conditions as above but with approximately 1 microgram of pure phosphoric acid PO4H3 which was added to the graphite tablet before the experiment using a special device.
  • Another example of implementation of the process which is the subject of the invention relates, for example, to the study of the oxidation of a metal.
  • a molecular jet of oxygen is sent using the jet (16) to a metal target whose oxidation is to be studied.
  • the compounds formed, including the metal clusters, can thus be analyzed by dissociation.
  • X a bivalent metal whose primary ions in oxidized form can be, for example: XO, X2O, X2O2, X3O3, etc ...
  • X3O3, etc. we study the formation secondary compounds for example in X3 and we will look for masses m whose ratio m / M is equal to the values X3 / X3O, X3O / X3O2, etc.
  • Ta4O5 with an oxygen pressure 199.5.10 ⁇ 6 Pa (1.5.10 ⁇ 6 torr) which dissociates as follows: Ta404, Ta4O3, Ta4O2, Ta4O, which gives the mass ratios, that is to say of filtered energies: 0.979; 0.959; 0.939 and 0.919.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP93902336A 1991-12-17 1992-12-16 Procede d'observation sequentielle des etats successifs d'une reaction chimique Expired - Lifetime EP0571622B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9115648 1991-12-17
FR9115648A FR2685086A1 (fr) 1991-12-17 1991-12-17 Procede d'observation sequentielle des etats successifs d'une reaction chimique.
PCT/FR1992/001190 WO1993012535A1 (fr) 1991-12-17 1992-12-16 Procede d'observation sequentielle des etats successifs d'une reaction chimique

Publications (2)

Publication Number Publication Date
EP0571622A1 EP0571622A1 (fr) 1993-12-01
EP0571622B1 true EP0571622B1 (fr) 1996-04-17

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Application Number Title Priority Date Filing Date
EP93902336A Expired - Lifetime EP0571622B1 (fr) 1991-12-17 1992-12-16 Procede d'observation sequentielle des etats successifs d'une reaction chimique

Country Status (5)

Country Link
US (1) US5374559A (enrdf_load_stackoverflow)
EP (1) EP0571622B1 (enrdf_load_stackoverflow)
DE (1) DE69210015T2 (enrdf_load_stackoverflow)
FR (1) FR2685086A1 (enrdf_load_stackoverflow)
WO (1) WO1993012535A1 (enrdf_load_stackoverflow)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436635B1 (en) 1992-11-06 2002-08-20 Boston University Solid phase sequencing of double-stranded nucleic acids
US5795714A (en) 1992-11-06 1998-08-18 Trustees Of Boston University Method for replicating an array of nucleic acid probes
US7803529B1 (en) 1995-04-11 2010-09-28 Sequenom, Inc. Solid phase sequencing of biopolymers
FR2745382B1 (fr) * 1996-02-27 1998-05-07 Devienne Fernand Marcel Appareil de detection et d'analyse de molecules de natures diverses

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2195349A5 (en) * 1972-08-04 1974-03-01 Anvar Molecular beam study of gas-phase reactions - esp. to analyse for very short life inters in non-photochemical reactions
AU557816B2 (en) * 1981-09-18 1987-01-08 Prutec Ltd. Method for the determination of species in solution with an optical wave-guide
JPS6044A (ja) * 1983-06-16 1985-01-05 Hitachi Ltd 二次イオン化質量分析装置
FR2655149B1 (fr) * 1989-11-24 1994-03-18 Devienne Fernand Appareil et procede de detection dans une atmosphere a surveiller d'un corps chimique de masse m connue et dont on connait les fragments de dissociation.

Also Published As

Publication number Publication date
FR2685086B1 (enrdf_load_stackoverflow) 1994-07-13
DE69210015T2 (de) 1997-01-23
EP0571622A1 (fr) 1993-12-01
WO1993012535A1 (fr) 1993-06-24
US5374559A (en) 1994-12-20
DE69210015D1 (de) 1996-05-23
FR2685086A1 (fr) 1993-06-18

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