DE3844796C2 - Chemical warfare agent detection with fluorescent reagent - Google Patents

Chemical warfare agent detection with fluorescent reagent

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Publication number
DE3844796C2
DE3844796C2 DE19883844796 DE3844796A DE3844796C2 DE 3844796 C2 DE3844796 C2 DE 3844796C2 DE 19883844796 DE19883844796 DE 19883844796 DE 3844796 A DE3844796 A DE 3844796A DE 3844796 C2 DE3844796 C2 DE 3844796C2
Authority
DE
Germany
Prior art keywords
detection
solvent
water
weapon
warfare agent
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.)
Expired - Fee Related
Application number
DE19883844796
Other languages
German (de)
Inventor
Wolfgang Dipl.-Ing. 6000 Frankfurt De Diehl
Monika Dr. 6108 Weiterstadt De Hepp
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.)
Antec Angewandte Neue Technologien 65779 Kel GmbH
Original Assignee
Battelle Institut eV
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 Battelle Institut eV filed Critical Battelle Institut eV
Priority to DE19883844796 priority Critical patent/DE3844796C2/en
Priority claimed from DE3803142A external-priority patent/DE3803142A1/en
Application granted granted Critical
Publication of DE3844796C2 publication Critical patent/DE3844796C2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/221—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating pH value
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence

Abstract

Detection of chemical warfare agent(s) (I) involves the use of a fluorescent reagent (II), the fluorescent emission of which changes in contact with (I). The novel features are that, for (II): a) the values of the log of the acid constant in the electronic ground state and in the excited state capable of emiss-ion differ by more than 2; b) the emission wavelength of the pro-tolytic form in an organic solvent is different from that in water; and c) (II) is dissolved or dispersed in a solvent with which (I) is immiscible.(II) is highly soluble in organic solvents and forms only a disp-ersion of undissolved solid in water. The solvent or dispersant used is a hardly flammable mixt. of water with max. 20% organic solvent, which is 1 x 10-3 to 1 x 10-2M in (II). (II) pref. is 6-aminoquinoline (IIA), 'Fluorol 086' (RTM; 2-butyl-6-butylamino-2,3- dihydro-1H-benz(de) isoaquinolin-1,3-dione, (IIB)) or Fluorol 088' (RTM; 2,8-dimethyl- naephtho(3,2,1-k1)xanthene)

Description

Die Erfindung betrifft ein Verfahren zum Nachweis eines Kampfstoffes, bei dem ein fluoreszieren­ des Nachweismittel mit dem Kampfstoff in Berührung gebracht wird, wobei sich das von ihm ausgesendete Fluoreszenzlicht ändert.The invention relates to a method for the detection of a warfare agent in which a fluoresce of the means of detection is brought into contact with the weapon, which is from him emitted fluorescent light changes.

Ein derartiges Verfahren beschreibt die DE-OS 33 44 700. Dort beruht der Nachweis auf der Adduktbildung eines Triphenyimethin-Farbstoffes mit dem betreffenden Kampfstoff. Dabei wird die Nachweisreaktion mit einer nukleophilen oder elektrophilen Reaktion des Kampfstoffes an einem reaktiven Zentrum des Farbstoffes oder mit einer Konformationsänderung des Farbstoffes durch adsorptive Anbindung des Kampfstoffes an das Farbstoffmolekül erklärt. Nach diesem bekannten Verfahren lassen sich aber als Kampfstoffe nur S-LOST oder N-LOST nachweisen [Bis-(2- chlorethyl)-sulfid und -iminj]. Ein Nachweis des ebenfalls wichtigen Kampfstoffes VX [O-Alkyl-S- N,N-dialkylaminoethyl)-alkylthiolphosphat] ist mit diesem bekannten Verfahren nicht möglich.Such a method is described in DE-OS 33 44 700. There, the detection is based on the Adduct formation of a triphenyimethine dye with the warfare agent in question. The Detection reaction with a nucleophilic or electrophilic reaction of the weapon on one reactive center of the dye or with a change in the conformation of the dye adsorptive binding of the warfare agent to the dye molecule explained. After this known However, methods can only be detected as S-LOST or N-LOST as warfare agents [Bis- (2- chloroethyl) sulfide and -iminj]. Evidence of the important warfare agent VX [O-alkyl-S- N, N-dialkylaminoethyl) alkylthiol phosphate] is not possible with this known method.

Die DE-PS 29 47 459 beschreibt ein Verfahren zum in-situ-Nachweis von Niederschlägen spezieller seßhafter Kampfstoffe aus der Gruppe der Phosphorsäureester. Diese Verbindungen zeigen eine Chemolumineszenz unter Einsatz von Indol, die berührungslos mittels eines optischen Detektors nachgewiesen werden kann. Finden Kampfstoff LOST versagt jedoch diese Reaktion. Für den Kampfstoff VX ist der Zusatz von Silberfluorid als Aktivator fast immer unabdingbar für den Nachweis mittels Indol. Einige Chargen lassen sich allerdings ohne Aktivator mit Indol nachweisen. Das hierbei verwendete Silberfluorid ist aber teuer und macht, insbesondere durch stark streuende Proben, bei der Anwendung Probleme.DE-PS 29 47 459 describes a method for the in-situ detection of precipitation special sedentary warfare agents from the group of phosphoric acid esters. These connections show chemiluminescence using indole, which is contactless by means of an optical Detector can be detected. Finding warfare agent LOST, however, fails this reaction. For the warfare agent VX, the addition of silver fluoride as an activator is almost always essential for detection using indole. However, some batches can be used with indole without an activator to prove. However, the silver fluoride used here is expensive and, in particular, goes through strongly scattering samples, problems when using.

Die der Erfindung zugrundeliegenden Idee besteht in einem Verfahren, mit dem in einwandfreier Art und Weise der Nachweis nicht nur von S-LOST, sondern auch von VX möglich ist.The idea on which the invention is based consists in a method with which, in a flawless manner, and Way the proof is possible not only from S-LOST, but also from VX.

Diese Aufgabe wird mit den Merkmalen des Anspruches 1 gelöst.This object is achieved with the features of claim 1.

Erfindungsgemäß wird also ein Nachweismittel verwendet, das in einem Lösungsmittel gelöst ist, das mit den Kampfstoffen S-LOST, N-LOST und oder VX nicht lösbar ist. Das Nachweismittel ist in der Phase des betreffenden Kampfstoffes löslich, so daß bei Kontaktieren des Nachweismittels mit dem Kampfstoff das Nachweismittel in die Phase des Kampfstoffes diffundiert, wo es das von ihm ausgesendete Fluoreszenzlicht ändert.According to the invention, a detection agent is therefore used which is dissolved in a solvent, that cannot be solved with the warfare agents S-LOST, N-LOST and or VX. The means of proof is soluble in the phase of the weapon in question, so that when the detection agent is contacted with the weapon, the detection agent diffuses into the phase of the weapon, where it is from fluorescent light emitted to him changes.

Die Änderung des Fluoreszenzlichtes ist also eine Wellenlängenänderung oder eine Änderung der Quantenausbeute. The change in fluorescent light is therefore a change in wavelength or a change in Quantum yield.  

Kern der Erfindung ist es somit, daß als Nachweismittel ein chemisch-physikalisches Reagens verwendet wird, das eine von Null verschiedene Löslichkeit in LOST oder VX bzw. in der Grenzschicht zwischen LOST bzw. VX und dem Lösungsmittel des Nachweismittels (im allgemeinen Wasser) hat und das in der LOST bzw. VX-Phase bei einer anderen Wellenlänge bzw. mit einer anderen Quantenausbeute, in der Regel mit einer sehr viel höheren Quanten­ ausbeute, fluoresziert als in der Lösungsmittelphase (Wasserphase).The essence of the invention is therefore that a chemical-physical reagent is used as the detection agent is used which has a non-zero solubility in LOST or VX or in the Boundary layer between LOST or VX and the solvent of the detection agent (in general water) in the LOST or VX phase at a different wavelength or with a different quantum yield, usually with a much higher quantum yield, fluoresces than in the solvent phase (water phase).

Vorzugsweise wird als Nachweismittel eine Substanz verwendet, deren Fluroeszenz nicht nur von der Lage der Säurekonstantwerte im Grundzustand zu den Säurekonstantwerten im angeregten Zustand, sondern auch von dem Aggregationsverhalten im wäßrigen und im organischen Solvens und von der Beeinflussung der nicht bindenden und der bindenden Molekülorbitale durch die Art des Solvens abhängt.A substance whose fluorescence is not only of the position of the constant acid values in the basic state to the constant acid values in the excited state State, but also of the aggregation behavior in the aqueous and in the organic solvent and of the influence of the non-binding and the binding molecular orbitals by Art of the solvent.

Die Lösungen der Nachweismittel sind vorzugsweise wäßrige oder wäßrig-organische 10-3 bis 10-2 molare Lösungen.The solutions of the detection means are preferably aqueous or aqueous-organic 10 -3 to 10 -2 molar solutions.

Erfindungsgemäß können alle Nachweismittel verwendet werden, die in der Grenzschicht von LOST oder VX zur Phase des Lösungsmittels des Nachweismittels (Wasserphase) gelöst werden bzw. sich dort anreichern und die in dieser Grenzschicht bzw. in der reinen LOST- und oder VX- Phase ein gegenüber der Lösungsmittelphase (Wasserphase) verändertes Fluoreszenzverhalten aufweisen. Eine Einschränkung bezüglich Anregungs- und Emissionswellenlänge besteht nicht. Die untersuchten Stoffe decken das gesamte Spektrum des sichtbaren Lichtes ab.According to the invention, all detection means that are in the boundary layer of LOST or VX to the solvent phase of the detection agent (water phase) can be solved or accumulate there and that in this boundary layer or in the pure LOST and or VX Phase a changed fluorescence behavior compared to the solvent phase (water phase) exhibit. There is no restriction regarding excitation and emission wavelength. The examined substances cover the entire spectrum of visible light.

Das Lösungsmittel ist zweckmäßig ein schwer entflammbares Gemisch aus Wasser mit maximal 20% organischem Lösungsmittel. Als Lösungsmittel für das Nachweismittel sind insbesondere Wasser und Wasser mit einem Alkoholzusatz bis zu 20% geeignet.The solvent is advantageously a flame retardant mixture of water with a maximum 20% organic solvent. In particular, as solvents for the detection means Water and water with an alcohol additive of up to 20% are suitable.

Claims (4)

1. Verfahren zum Nachweis eines Kampfstoffes, bei dem ein fluoreszenzfähiges Nachweis­ mittel mit dem Kampfstoff in Berührung gebracht wird, wobei sich das von ihm ausgesandte Fluoreszenzlicht ändert, dadurch gekennzeichnet, daß ein in einem wäßrigen Lösungsmittel, mit dem der Kampfstoff nicht mischbar ist, gelöstes Nachweis­ mittel verwendet wird, dessen Logarithmus der Säurekonstanten im elektronischen Grundzustand und dessen Logarithmus der Säurekonstanten im elektronisch angeregten, emissionsfähigen Zustand um mehr als zwei differieren und dessen protolytische Form in der Kampfstoffphase bei einer anderen Wellenlänge fluoresziert als dessen protolytische Form in Wasser.1. A method for the detection of a weapon, in which a fluorescent detection medium is brought into contact with the weapon, the fluorescent light emitted by it changing, characterized in that a solution in an aqueous solvent with which the weapon is not miscible Detection medium is used whose logarithm of the acid constant in the electronic ground state and whose logarithm of the acid constant in the electronically excited, emission-capable state differ by more than two and whose protolytic form in the warfare agent phase fluoresces at a different wavelength than its protolytic form in water. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Lösungsmittel für das Nachweismittel ein schwer entflammbares Gemisch aus Wasser mit maximal 20% organischem Lösungsmittel verwendet wird.2. The method according to claim 1, characterized in that as a solvent for the Detection means a flame-retardant mixture of water with a maximum of 20% organic solvent is used. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Lösungsmittel für das Nachweismittel ein Gemisch aus Wasser mit maximal 20% Alkohol verwendet wird.3. The method according to claim 1, characterized in that as a solvent for the Detection means a mixture of water with a maximum of 20% alcohol is used. 4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß 1×10-3 bis 1×10-2 molare Lösungen des Nachweismitteis in wäßriger oder wäßrig-organischer Lösung zum Nachweis verwendet werden.4. The method according to claim 1 or 2, characterized in that 1 × 10 -3 to 1 × 10 -2 molar solutions of the detection agent in aqueous or aqueous-organic solution are used for detection.
DE19883844796 1988-02-03 1988-02-03 Chemical warfare agent detection with fluorescent reagent Expired - Fee Related DE3844796C2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19883844796 DE3844796C2 (en) 1988-02-03 1988-02-03 Chemical warfare agent detection with fluorescent reagent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3803142A DE3803142A1 (en) 1988-02-03 1988-02-03 METHOD FOR DETECTING A COMBAT SUBSTANCE
DE19883844796 DE3844796C2 (en) 1988-02-03 1988-02-03 Chemical warfare agent detection with fluorescent reagent

Publications (1)

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DE3844796C2 true DE3844796C2 (en) 1993-01-21

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3344700A1 (en) * 1983-12-10 1985-06-20 Battelle-Institut E.V., 6000 Frankfurt METHOD FOR DETECTING BIS- (2-CHLORETHYL) -SULFIDE OR BIS- (2-CHLORETHYL) -IMINE

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3344700A1 (en) * 1983-12-10 1985-06-20 Battelle-Institut E.V., 6000 Frankfurt METHOD FOR DETECTING BIS- (2-CHLORETHYL) -SULFIDE OR BIS- (2-CHLORETHYL) -IMINE

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