EP0970507A1 - Procede et dispositif pour identifier des specimens complexes de gaz, de substances odorantes ou d'aromes d'une substance, par spectroscopie de masse - Google Patents

Procede et dispositif pour identifier des specimens complexes de gaz, de substances odorantes ou d'aromes d'une substance, par spectroscopie de masse

Info

Publication number
EP0970507A1
EP0970507A1 EP98922603A EP98922603A EP0970507A1 EP 0970507 A1 EP0970507 A1 EP 0970507A1 EP 98922603 A EP98922603 A EP 98922603A EP 98922603 A EP98922603 A EP 98922603A EP 0970507 A1 EP0970507 A1 EP 0970507A1
Authority
EP
European Patent Office
Prior art keywords
sample
reference sample
mass
line
determined
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.)
Withdrawn
Application number
EP98922603A
Other languages
German (de)
English (en)
Inventor
Gerhard Horner
Siegfried Nitz
Brigitte Dittmann
Harun Parlar
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.)
HKR Sensorsysteme GmbH
Original Assignee
HKR Sensorsysteme GmbH
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 HKR Sensorsysteme GmbH filed Critical HKR Sensorsysteme GmbH
Publication of EP0970507A1 publication Critical patent/EP0970507A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/0027—Methods for using particle spectrometers
    • H01J49/0036—Step by step routines describing the handling of the data generated during a measurement
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G01N30/7206—Mass spectrometers interfaced to gas chromatograph

Definitions

  • the present invention relates to a method for identifying properties of interest of a substance on the basis of the volatile and / or vaporizable fractions of this substance.
  • the invention serves, in particular, to be able to make comparisons of substances / substances which are considered to be the same / similar per se, in order to recognize whether there are actually differences of these compared substances with respect to the properties concerned.
  • a special area of application is e.g. the food sector in order to be able to classify batches of the same.
  • the combination of mass spectrometric detection with static headspace gas chromatography is an established routine analytical method for the qualitative and quantitative determination of the volatile constituents of an unknown sample.
  • This analytical method is based on the fact that the light and medium-volatile constituents of a sample are distributed between the sample matrix and the gas phase over this matrix in a closed vessel.
  • the sample matrix itself can be liquid or solid.
  • the gas phase contains a qualitatively and quantitatively representative equivalent of all volatile ingredients. Therefore, the Identification of the volatile constituents of an unknown sample of the gas phase, a defined gas volume, the so-called aliquot, taken and sent to the gas chromatographic separation with subsequent mass spectrometric detection.
  • sample is an aliquot of the gas phase, which is located above the actual liquid or solid sample matrix
  • the task is often to identify substances, for example batches, goods deliveries and the like. to be carried out, for example, in order to be able to classify the same or to enable evaluative comparisons of substances of the same / similar appearance to one another, for which this supposed equality does not actually apply.
  • substances for example batches, goods deliveries and the like.
  • Different batches of parsley, for example are supposed to be of uniform quality. For example, these batches are visually indistinguishable, but still have differences in smell.
  • the recognition to be carried out with the invention is intended to enable objective differentiation of the individual batches, for example for the purpose of classification into product classes. It is an object of the present invention to provide a method which makes such recognition or differentiation possible with as little effort and, in particular, as little time-consuming.
  • the invention is based on a known recording and evaluation of mass spectra of complex substance mixtures, but with the inclusion according to the invention of measures which allow the principle known mass spectrometry to be simplified in such a way that a respective reference
  • the method according to the invention has the advantage that in the (goods) classification not every single sample is time-consuming to examine in detail. Rather, as can also be seen from the detailed description below, a one-off conditioning measure is carried out with a reference (stitch) sample for this product, preferably with an arrangement which can also be used to carry out the subsequent series tests, as described, for example, for FIG. 2.
  • a pattern relevant here comprises a number n pattern values which, taken together, are to be regarded as an n-dimensional vector in n-dimensional space and form the pattern.
  • Matching two patterns means that the vector of one pattern and the vector of the other pattern match in magnitude and orientation.
  • a single sample with n sample values is obtained if one determines the number n of given property values from a (first) reference sample. If one examines an apparently identical second reference sample, which, as is customary in practice, is only almost identical to the first reference sample, a second, almost identical sample is obtained.
  • a second variant is to have such a tolerance range for the reference samples, for example from experience (values) Requirements of the task derived and the like to determine or specify. All that is required here is a reference sample for the pattern vector as such, that for the property to serve as a reference sample, the predetermined tolerance is thus (subjectively) assigned.
  • a conditioning measure belonging to the invention is carried out in two stages, in order for this reference sample with its tolerance space of its pattern vector for the series examinations of the example, which are then to be carried out subsequently
  • a conditioning measure belonging to the invention is carried out in two stages, in order for this reference sample with its tolerance space of its pattern vector for the series examinations of the example, which are then to be carried out subsequently
  • the mass spectra of the (interesting) individual substance constituents are determined by gas chromatography separated from (at least) one reference sample.
  • Each such single mass line spectrogram of substance components contained in the reference sample consists of e.g. 50 to 250 fragment ions.
  • this first stage it is sufficient in this first stage to record the single mass-line spectrograms from only a single selected reference sample in a time-saving manner.
  • the subsequent comparison of the reduced total mass line spectrograms determined on the individual unseparated samples of the batches of the series examination with the pattern of the reference sample is carried out by means of a pattern analysis based on the weighted, selected fragment ions, e.g. such 20 weighted fragment ions are evaluated.
  • a further simplification for a further development of the invention results from the fact that, for example, catalogs of the samples, consisting of the weighted, reduced mass spectra of the reference samples for different substances, for example different types of vegetables, fruits and the like, are created, which always come with the delivery of new goods can be used for the comparison to be made according to the invention. Then, as described above, the respective reduced overall mass spectrum of this product sample only needs to be recorded and evaluated for the samples of the series examinations, and specifically without gas-chromatographic division of the product samples.
  • the procedure according to the invention is also explained in more detail below with reference to an exemplary embodiment and the apparatus used.
  • FIG. 1 shows a diagram of the sequence of a method carried out according to the invention.
  • Figure 2 shows a possible schematic structure of an arrangement for performing this method.
  • FIG. 1 shows the process according to the invention as a flow diagram.
  • the first four lines 1, 2, 3 and 4 relate to the measures described above for conditioning the arrangement likewise according to the invention with the aid of the (at least) one reference sample (lines 1 and 2) and the reference sample
  • the fifth line of FIG. 1 relates to these mass spectrometric examinations of series samples to be evaluated (assigned) which are to be examined according to the order.
  • the sixth line of FIG. 1 relates to the comparison of the respectively examined sample of the step of the fifth line with the conditioning result of the fourth line of FIG. 1, namely with the pattern of the reference sample.
  • the arrangement according to FIG. 2 comprises a headspace sampling device 1 as described in principle above and known per se, a gas chromatograph 2 known per se with a first 6-way valve 3 and a second 6-way valve 4 which are arranged in the furnace space of the gas chromatograph. a mass spectrometer 5 and a personal computer 6.
  • Port c and port f of the first 6-way valve 3 are connected to one another by means of a sample loop 8.
  • Port a is with the headspace sampling device 1 connected, this connection being, for example, a fused silica capillary or a steel capillary.
  • the respective one of the two ends of a gas chromatography column 7 is connected to port i and port 1 of the second 6-way valve 4.
  • the first 6-way valve 3 and the second 6-way valve 4 are connected to one another via a first capillary 11.
  • one end of this connection is connected to the port e of the first 6-way valve 3 and the other end of this connection is connected to the port g of the second 6-way valve 4.
  • a supply for inert gas is connected to port j of the second 6-way valve 4.
  • Ports b and k of the respective 6-way valve are provided as gas connections for flushing purposes.
  • the second 6-way valve 4 and the mass spectrometer 5 are connected to one another, this connection containing a second capillary 10, a restriction capillary.
  • Both the gas chromatograph 2 and the mass spectrometer 5 can be controlled with signals from a personal computer 6.
  • the data to be obtained is evaluated e.g. also with this personal computer.
  • a predetermined reference sample is brought to an optionally preset sample pressure for a period of time that can be freely selected by the user and incubated at a constant, likewise optionally predetermined temperature.
  • the state of thermodynamic equilibrium is reached at the end of the equilibration phase.
  • the gas phase which is then above the sample matrix, there is a representative equivalent of all volatile and medium volatile compounds originally contained in the (reference) sample. These compounds are both odor-relevant compounds and compounds that do not contribute to the smell of the sample.
  • a volume of the gas phase to be measured in the sample loop 8, which has a defined volume, is relaxed.
  • This sample loop connected to the first 6-way valve 3 is located in the furnace chamber of the gas chromatograph 2. By switching over the first 6-way valve 3, the gas phase to be measured is then passed on to the second 6-way valve 4.
  • the gas phase to be measured can either be directly or via the gas chromatography column 7, e.g. is executed in the same way as the loop 8, into the mass spectrometer 5.
  • the control of the first ⁇ -way valve 3 and the second 6-way valve 4 for metering or forwarding the sample is controlled by the gas chromatograph 2.
  • the supply of the (reference) sample to be measured via the gas chromatography column 7 into the mass spectrometer 5 thus creates the conditions for the quantitative and qualitative determination of all odor-relevant ingredients of this substance based on their mass spectra.
  • a direct supply of a sample (past the gas chromatography column 7) into the mass spectrometer 5 results in the recording of a total spectrum of the respective now unseparated, now gaseous sample described below.
  • this recording of the entire spectrum takes place for the reference sample.
  • the two stages of conditioning the reference sample thus supply the above-mentioned individual spectra of the individual volatile fractions of the reference sample and the total spectrum of the same.
  • the difference in the complex composition of the individual sample compared to the reference can be determined in a time-saving manner for in particular a large number of samples to be examined.
  • the performance of a sensor array is heavily dependent on the optimal sensor combination.
  • the pattern recognition can only be optimized to a very limited extent. As a rule, this can only be achieved by exchanging or changing the Arrays can be achieved.
  • the method according to the invention is characterized in that the adaptation to the sample to be evaluated does not require a change in the array hardware.
  • the optimal adjustment takes place by taking into account the information determined in the conditioning about the qualitative and quantitative composition (at least) of a representative reference sample with regard to the property / quality to be recognized.
  • the fragment ions necessary for optimal discrimination of the sample are determined from the individual spectra of these ingredients. The type and number of fragment ions that are necessary for optimal discrimination of the sample are therefore flexibly adapted to the given classification problem.
  • the method according to the invention can be standardized and transferred to similar arrangements, consisting of a headspace sample inlet system, gas chromatograph and mass spectrometer, such as the described arrangement according to the invention.
  • a headspace sample inlet system gas chromatograph and mass spectrometer, such as the described arrangement according to the invention.
  • the comparability of the classification results when measuring with the aid of different arrangements is ensured, since in all cases the same measured variables, namely fragment ions and their intensity, are used as the basis for the pattern recognition analysis.
  • Such a transferability of the results is only possible to a limited extent in the case of chemosensor arrays, since most “electronic noses” differ in the type of measurement signal evaluated in the pattern recognition analysis.
  • the arrangement according to the invention has over chemical sensor arrays is the better reproducibility of the results.
  • the Arrangement according to the invention no such signs of aging.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

Selon le procédé de l'invention, le conditionnement au moyen d'un échantillon de référence et la formation d'un spécimen présentant un nombre réduit d'ions-fragment, ces derniers étant choisis parmi des spectres de masse individuels séparés par chromatographie en phase gazeuse, et la formation d'un spécimen d'un échantillon de référence pris au hasard, à partir des spectrogrammes de pics de masse globaux, réduits de façon appropriée, de plusieurs échantillons de référence, permet d'évaluer par spectrographie de masse comparative, de façon rapide, des échantillons de série affectée à la référence, par ex. une marchandise.
EP98922603A 1997-03-27 1998-03-16 Procede et dispositif pour identifier des specimens complexes de gaz, de substances odorantes ou d'aromes d'une substance, par spectroscopie de masse Withdrawn EP0970507A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19713194A DE19713194C2 (de) 1997-03-27 1997-03-27 Verfahren und Anordnung zum Erkennen von Eigenschaften einer Probe auf der Basis der Massenspektroskopie
DE19713194 1997-03-27
PCT/DE1998/000762 WO1998044536A1 (fr) 1997-03-27 1998-03-16 Procede et dispositif pour identifier des specimens complexes de gaz, de substances odorantes ou d'aromes d'une substance, par spectroscopie de masse

Publications (1)

Publication Number Publication Date
EP0970507A1 true EP0970507A1 (fr) 2000-01-12

Family

ID=7824979

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98922603A Withdrawn EP0970507A1 (fr) 1997-03-27 1998-03-16 Procede et dispositif pour identifier des specimens complexes de gaz, de substances odorantes ou d'aromes d'une substance, par spectroscopie de masse

Country Status (4)

Country Link
US (1) US6492639B1 (fr)
EP (1) EP0970507A1 (fr)
DE (1) DE19713194C2 (fr)
WO (1) WO1998044536A1 (fr)

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US6647343B1 (en) 1999-04-29 2003-11-11 Agilent Technologies, Inc. Temporal profile analysis of mass data in a mass sensor system
DE10123711A1 (de) * 2001-05-15 2003-02-27 Wolfgang Altmeyer Verfahren zur Bestimmung der Herkunft biologischer Materialien
US20060089253A1 (en) * 2002-08-13 2006-04-27 Shahram Mihan Monocyclopentadienyl complexes
DE10358366B4 (de) * 2003-12-10 2008-04-03 Bruker Daltonik Gmbh Massenspektrometrische Substanzidentifizierung
JP2005291715A (ja) * 2004-03-31 2005-10-20 Shimadzu Corp におい測定装置
CA2501003C (fr) 2004-04-23 2009-05-19 F. Hoffmann-La Roche Ag Analyse d'echantillons pour obtenir des donnees de caracterisation
JP5764433B2 (ja) * 2011-08-26 2015-08-19 株式会社日立ハイテクノロジーズ 質量分析装置及び質量分析方法
MX2011009486A (es) 2011-09-09 2013-03-15 Ct Investig Y Estudios Del Ipn Metodo combinado de espectroscopias de masas de iones secundarios y de rayos x de energia dispersada, para analisis quimico cuantitativo de diversos materiales solidos y peliculas delgadas.
DE102013100693B4 (de) * 2012-01-24 2014-07-31 Step Sensortechnik Und Elektronik Pockau Gmbh Verfahren zur Identifizierung und Klassifizierung von Geruchsmustern und anderen Multikomponentengemischen aus Ionenmobilitätsspektren

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US4507555A (en) * 1983-03-04 1985-03-26 Cherng Chang Parallel mass spectrometer
WO1990007326A1 (fr) 1988-12-30 1990-07-12 Edko Trading And Representation Company Limited Compositions pharmaceutiques
US5119315A (en) * 1989-04-28 1992-06-02 Amoco Corporation Method of correlating a record of sample data with a record of reference data
MY107650A (en) * 1990-10-12 1996-05-30 Exxon Res & Engineering Company Method of estimating property and / or composition data of a test sample
FR2672141B1 (fr) 1991-01-25 1993-04-09 Commissariat Energie Atomique Procede de reconnaissance d'objets codes par des vecteurs.
US5247175A (en) * 1992-05-27 1993-09-21 Finnigan Corporation Method and apparatus for the deconvolution of unresolved data
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Also Published As

Publication number Publication date
US6492639B1 (en) 2002-12-10
DE19713194C2 (de) 1999-04-01
WO1998044536A1 (fr) 1998-10-08
DE19713194A1 (de) 1998-10-01

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