WO2023111475A1 - Detection system suitable for use in the detection of chemical compounds comprising a detection strip - Google Patents

Detection system suitable for use in the detection of chemical compounds comprising a detection strip Download PDF

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Publication number
WO2023111475A1
WO2023111475A1 PCT/FR2022/052385 FR2022052385W WO2023111475A1 WO 2023111475 A1 WO2023111475 A1 WO 2023111475A1 FR 2022052385 W FR2022052385 W FR 2022052385W WO 2023111475 A1 WO2023111475 A1 WO 2023111475A1
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WO
WIPO (PCT)
Prior art keywords
support
detection
detection system
indicators
compounds
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PCT/FR2022/052385
Other languages
French (fr)
Inventor
Sébastien PENLOU
Jacqueline Bablet
Alexandre Carella
Jean-Pierre Simonato
Original Assignee
Commissariat A L'energie Atomique Et Aux Energies Alternatives
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Publication of WO2023111475A1 publication Critical patent/WO2023111475A1/en

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems 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
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84Systems specially adapted for particular applications
    • G01N21/8483Investigating reagent band
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems 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
    • G01N2021/7769Measurement method of reaction-produced change in sensor
    • G01N2021/7786Fluorescence
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems 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
    • G01N2021/7793Sensor comprising plural indicators
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems 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
    • G01N21/78Systems 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 producing a change of colour

Definitions

  • Detection system usable for the detection of chemical compounds comprising a detection strip
  • the present invention relates to a new detection system, for example colorimetric, usable for the detection of distinct chemical compounds and to a method for detecting one or more chemical compounds implementing this detection system.
  • the present invention can find application for the detection of toxic chemical compounds, such as toxic warfare compounds and, in particular, organophosphorus compounds; toxic industrial chemical compounds (known as TIC); vesicants; pesticides and arsenic compounds.
  • toxic chemical compounds such as toxic warfare compounds and, in particular, organophosphorus compounds; toxic industrial chemical compounds (known as TIC); vesicants; pesticides and arsenic compounds.
  • organophosphorus compounds are in the form of organic compounds with proven toxicity to the human body. Indeed, these compounds may be involved in the mechanism of inhibition of serine proteases and, in particular, of acetylcholinesterase, which intervenes in synaptic junctions and whose dysregulation of activity can prevent muscle relaxation and thus cause death. by asphyxiation.
  • These compounds can be included in the formulation of insecticides, pesticides or even chemical combatants (such as organophosphorus compounds of the G series, such as sarin or organophosphorus compounds of the V series, such as VX) and due to the high lethality of these compounds, their proliferation, it is important to be able to have detection and preliminary identification systems.
  • chemical combatants such as organophosphorus compounds of the G series, such as sarin or organophosphorus compounds of the V series, such as VX
  • Some detection systems used to date are based on technologies involving physical measurement means, such as ion mobility spectroscopy, flame photometry, IR spectroscopy and Raman with, for difficulties, that these systems require expensive complex equipment and not necessarily adapted to all intervention environments in terms of mass and size, to which is added the expertise of the operator to be considered.
  • the authors of the present invention have focused on the design of a detection system that can be used for the detection of one or more distinct chemical compounds, which system should allow the detection of said chemical compound(s) and , when there are several of them, preferably the discrimination of said compounds and meeting criteria of sensitivity, rapidity, portability, reliability and which can allow detection and, where appropriate, simple discrimination, such as discrimination visual to the naked eye, in particular when the detection is of a colorimetric nature.
  • the invention relates to a detection system usable for the detection of one or more chemical compounds comprising:
  • each of said detection indicators is distributed on the support in the form of one or more separate zones, the or said distinct areas of each of said detection indicators being arranged on the support without overlapping with the distinct area(s) of the other detection indicator(s);
  • a second support intended for depositing the medium, the presence or absence of said chemical compound(s) of which it is desired to determine, this second support being in contact with one of the faces of the first support.
  • detection indicators without there being any surface overlap between each of them, this can allow, by an appropriate choice of detection indicators, detection of one or more compounds and, ideally, when there are several chemical compounds, possibly a discrimination of distinct chemical compounds, without the detection properties (e.g., toning properties, when the detection indicators are colored indicators) of each indicators are not altered by a mixture of indicators, which could therefore interact with each other and bias the detection.
  • detection systems in accordance with the invention are particularly suitable for the detection of chemical compounds in liquid form, thanks to the second support.
  • the detection systems of the invention can allow, by the choice of appropriate colored indicators, the discrimination of distinct chemical compounds belonging to the same family, such as, by way of non-limiting example, organophosphorus compounds (such as those of the G-series, V-series or organophosphate nerve agents recently added to Schedule 1 of the Annex to the OPCW Convention for the Prohibition of Chemical Weapons S/1821/2019/Rev.l/Add. l (May 20, 2020)), vesicants (such as sulfur mustard, nitrogen mustard, lewisite), toxic industrial chemicals (such as ammonia, chloropicrin), pesticides.
  • organophosphorus compounds such as those of the G-series, V-series or organophosphate nerve agents recently added to Schedule 1 of the Annex to the OPCW Convention for the Prohibition of Chemical Weapons S/1821/2019/Rev.l/Add. l (May 20, 2020)
  • vesicants such as sulfur mustard, nitrogen mustard, lewisite
  • toxic industrial chemicals such as ammonia, chloropicri
  • the colored indicators could interact with each other, making the resulting color not necessarily predictable and reactivity to the chemical compounds to be detected not guaranteed;
  • detection indicator it is meant, conventionally, a chemical substance capable of being transformed on contact with at least one chemical compound that it is desired to detect, this transformation being the sign of the presence of said at least one chemical compound, this transformation materializing by a change of color, when the detection indicator is a colored indicator (also called colorimetric detection indicator). It may also be a fluorescence indicator (or fluorophore), depending on its nature.
  • the detection indicator is a colored indicator
  • this corresponds, conventionally, to a chemical substance which takes on at least one characteristic color in the presence of a chemical compound, i.e., in other words, a chemical substance which has at least two colored states, a colored state existing when the chemical substance is not in the presence of the chemical compound to be detected and at least one other colored state when the chemical substance is in the presence of the chemical compound or compounds to be detected.
  • the detection indicator can consist of one or more compounds allowing detection.
  • the distinct zone(s) of each of the detection indicators do not mix with the distinct zone(s) of the other detection indicators, which does not exclude that the the distinct zones of each detection indicator can be, in whole or in part, juxtaposed with the distinct zone(s) of the other detection indicator(s).
  • the detection system usable for the detection of one or more chemical compounds comprises a first support impregnated with separate detection indicators capable of detecting the presence of said chemical compound or of said chemical compounds, characterized in that each of said detection indicators is distributed on the support in the form of a or several distinct zones, the said distinct zone(s) of each of the said detection indicators being arranged on the support without overlapping with the distinct zone(s) of the other detection indicator(s).
  • each of said detection indicators is distributed on the support in the form of one or more distinct zones, the said distinct zone or zones possibly being in substantially circular, rectangular or square shapes, it being understood that other shapes can be envisaged, provided that there is no overlap between the distinct zones for distinct detection indicators.
  • the first constituent support of the detection system can be, in particular, a porous support and, more specifically, a paper support, it being understood that this support must be able to be impregnated by the various detection indicators to form the distinct zones.
  • the first constituent support conventionally comprises two faces, an upper face comprising the distinct zones comprising the detection indicators and a lower face opposite the upper face, the lower face being the face in contact with the second support.
  • the distinct zones can be partitioned by obstructing the porosity of the first support on the zones which are not the distinct zones, the porosity possibly being obstructed, more specifically, for example, by wax, paraffin, a polydimethylsiloxane or any other means to block the porosity.
  • the porosity thus obstructed makes it possible to limit the access to the analyte (namely, the medium, generally liquid, in which one wants to know the presence or the absence of compounds to be analyzed) to the zones thus obstructed and thus to create a fluidic circuit allowing privileged access of the analyte to the distinct zones comprising the detection indicators, which are not obstructed.
  • the first support may be in the form of a strip, as will be illustrated in particular embodiments illustrated in the appended figures.
  • the first support may comprise at one of its ends a recessed area, thus giving direct access to the second support, this recessed area thus allowing the direct deposition of the analyte on the second support on the area of the latter facing of the recessed area of the first support.
  • This hollowed out zone can constitute a “reservoir” for the analyte which will, in addition to the fact of being in contact with the second support, thus be retained in this zone without risk of flow to the outside.
  • the detection system can comprise, as detection indicators, colored indicators allowing colorimetric detection.
  • the person skilled in the art to design the detection system in accordance with the invention, will choose, when the detection indicators are colored indicators, preferably appropriate colored indicators by making a selection based in particular on the fact that the chosen colored indicators must obviously have at least one colorimetric shift in the presence of the chemical compound which it is desired to detect.
  • the colored indicators can be chosen from anthraquinone compounds, azo compounds, triarylmethane compounds, xanthenic compounds, indigo compounds, metal complexes, compounds comprising at least one stilbene group , coumarin compounds, compounds comprising at least one cyanine group, compounds comprising at least one phthalocyanine group, compounds comprising at least one porphyrin group, compounds comprising at least one hydrazone group.
  • anthraquinone compounds mention may be made of 1,4-dihydroxyanthraquinone, 1-aminoanthraquinone, carminic acid, 1,5-diaminoanthraquinone, 1,2-diaminoanthraquinone, 1,4 - diamino-5-nitroanthraquinone, 1,4,5,8-tetraaminoanthraquinone (Disperse Blue 1), l-methylamino-4-(2-hydroxyethyl)aminoanthraquinone (Disperse Blue 3), l-amino-2-methylanthraquinone (Disperse Orange 11), 1,4-h/s-(p-tolylamino)anthraquinone (Solvent Green 3).
  • azo compounds mention may be made of 10-(2',4'-dinitrophenylazo)-9-phenanthrol, 6-hydroxy-5-[(2-methoxy-5-methyl-4- disodium sulfophenyl)azo]-2-naphthalenesulfonate (also called Allura AC red), 4-dimethylaminoazobenzene (also called methyl yellow), 4-(2-carboxyphenylazo)-N,N-dipropylaniline (also called “Propyl red according to English terminology), 3-(diethylamino)-7- ⁇ (E)-[4-(dimethylamino)phenyl]diazenyl ⁇ -5-phenylphenazin-5-ium chloride (also called "Janus Green B”) , N,N-dimethyl-4,4'-azodianiline, N-ethyl-1-((4-phenyldiazenyl)phenyl)diazenyl)naphthal
  • triarylmethane compounds examples include aniline diammonium blue, bromophenol blue, m-cresol violet, cresol red, gentian violet (also called “Crystal Violet” in English terminology), chlorophenol red, (4-(a-(p-(diethylamino)phenyl)-2,4-disulfobenzylidene)-2,5-cyclohexadiene-l-ylidene hydroxide, sodium salt diethylammonium (also known as "Patent blue V sodium sait”), methyl blue, rosolic acid, pyrocatechol violet, brilliant green BS, pararosaniline base, fuchsin, thymol blue, 4- (dimethylamino )-a-[4-(dimethylamino)phenyl]-a-phenyl-benzenemethanol.
  • xanthene compounds mention may be made of [9-(2-carboxyphenyl)-6-diethylamino-3-xanthenylidene]-diethylammonium chloride (also called “Rhodamine 610”), rhodamine 6G optionally under perchlorate salt form, rhodamine B, sulforhodamine 101 hydrate, fluoresceinamine (especially Isomer I), rhodamine 110 chloride.
  • indigo compounds mention may be made of indigo.
  • metal complexes mention may be made of trisodium 5-nitroso-6-oxidonaphthalene-2-sulfonate complexed with iron (III) (also called “Naphthol Green B”).
  • coumarin compounds mention may be made of 7-amino-4-(trifluoromethyl)coumarin, 7-amino-4-methylcoumarin, 3-(2-N-Methylbenzimidazolyl)-7-N ,N-diethylaminocoumarin (also called “Coumarin 30”), 2,3,6,7-tetrahydro-10-(3-pyridyl)-1H,5H,11H-[l]benzopyrano[6,7,8-ij ]quinolizin-ll-one (also known as “Coumarin 510”), 3-(2-Benzothiazolyl)-7-(diethylamino)coumarin (also known as “Coumarin 6”).
  • indocyanine green 5,5'-dichloro-11-diphenylamino-3,3'-diethyl-10,12-ethylenethiatricarbocyanine perchlorate (also says IR140).
  • phthalocyanine iron (III) chloride phthalocyanine-4,4',4'',4'"-tetrasulfonic acid of iron (III ), 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine.
  • the detection system also comprises a second support intended for depositing the medium, of which it is desired to determine the presence or absence of at least one chemical compound and of which the colored indicator is present on the first support, this second support being in contact with one of the faces of the first support (conventionally, the lower face opposite the upper face, which is occupied by the distinct zones of the colored indicators).
  • This second support advantageously allows the diffusion or migration by capillarity of the medium deposited thereon, so that it can reach the various distinct zones mentioned above of the first support and allow, if necessary, the detection of one or more compounds possibly contained in this analyte and sensitive to the constituent colored indicators of the distinct zones.
  • This second support can be made of a material comprising (or consisting of) an entanglement of fibers, such as fibers chosen from cellulose fibers (in particular those used in filter papers for laboratories or in papers intended for use in the techniques chromatography), glass fibers, synthetic polymer fibers, such as polyester fibers, and mixtures thereof, this entanglement being able to form a non-woven material.
  • fibers such as fibers chosen from cellulose fibers (in particular those used in filter papers for laboratories or in papers intended for use in the techniques chromatography), glass fibers, synthetic polymer fibers, such as polyester fibers, and mixtures thereof, this entanglement being able to form a non-woven material.
  • This second support may be in the form of a strip, in particular when the first support is also in the form of a strip, and may in particular have the same dimensions as the first support, whereby it completely covers one of the faces of the first support (generally the lower face of the first support opposite the upper face, on which the aforementioned distinct zones are affixed).
  • This second support in particular when it is in the form of a strip, may comprise at the level of the face in contact with the first support, two opposite lateral strips located on the two largest sides of the strip, these two strips being sealed bands and providing a central zone devoid of these bands and constituting a space for the circulation of the medium, the presence or absence of said chemical compound or compounds of which it is desired to determine.
  • This circulation space advantageously constitutes a circulation space from the middle to the distinct zones of the first support and makes it possible to prevent the middle from coming out via the sides thanks to the presence of these bands.
  • the second support brought into contact with the first support may comprise a tab emerging from the stack of the first support and the second support, this tab serving as a deposit zone for the analyte and being conventionally made of a material identical to that constituting the rest of the medium.
  • the detection systems of the invention may further comprise an impermeable layer in contact with the second support via the face opposite to that which is in contact with the first support (this opposite face being able to be referred to as the lower face in opposition to the upper face which is in contact with the first support), which means, in other words, that the second support is sandwiched between the first support and the sealed layer, this arrangement being particularly favorable, in order to protect an operator who would manipulate the strip from any direct contact with the chemical compounds to be detected and in order to increase the capillary forces which will draw the analyte more quickly towards the interior of the second support.
  • This sealed layer advantageously has the same dimensions as the second support, whereby it entirely covers one of the faces of the second support (conventionally, the lower face of the second support).
  • the second support takes about 10 minutes to be impregnated with a colored solution based on dimethyl sulfoxide (DMSO) for a system where the second support is not sandwiched, against 4 minutes for a system where the second support is sandwiched.
  • DMSO dimethyl sulfoxide
  • the second support takes about 2 minutes to be impregnated with a system where the second support is sandwiched.
  • the detection systems of the invention may further comprise a transparent layer in contact with the first support via the face opposite to that which is in contact with the second support (this face being able to be called the upper face in opposition to the face lower which is in contact with the second support), this layer making it possible, in addition to isolating the analyte from the outside, to visualize, if necessary, the chromatic change at the level of the distinct zones present on the first support.
  • the impermeable layer and the transparent layer have in particular the function of completely encapsulating the detection system while allowing easier handling of the latter and limiting the risks of contamination linked to the handling of the system.
  • the systems of the invention can be defined otherwise as a multilayer stack comprising a first support and a second support in contact with each other, advantageously, an impermeable layer in contact with the lower face of the second support and a transparent layer in contact with the upper face of the first support, systems of this type being illustrated in the figures which are commented on below and which illustrate, in particular:
  • - detection systems intended for vertical use, namely, by dipping, vertically, said detection systems via one of the ends giving access to the second support in the analyte (such as the system shown in Figure 1 );
  • -detection systems intended for horizontal use, namely, by depositing, horizontally, on said detection systems via one of the ends giving access to the second support, one or more drops of the analyte (such as systems shown in Figures 2 and 3).
  • the first support 5 being in the form of a strip comprising 4 separate circular zones (respectively 7, 9, 11 and 13) each comprising a separate detection indicator, the first support extending at one of its ends 15 by a tab 17;
  • the second support 19 being in the form of a strip of dimensions similar to the strip of the first support, which strip is also extended at one of its ends 21 by a tongue 23, the contact with the analyte taking place at this tongue, which analyte then progresses in the direction of the arrow by capillarity;
  • a transparent plate 25 in the form of a strip of dimensions similar to that of the first support and of the second support, which strip also extends at one of its ends T1 by a tongue;
  • the first support 37 being in the form of a strip comprising 6 distinct rectangular zones (respectively 39, 41, 43, 45, 47 and 49) each comprising a distinct detection indicator;
  • the second support 51 being in the form of a strip of dimensions similar to the strip of the first support, which strip is extended at one of its ends 53 by a tab 55, the contact with the analyte taking place at the level of this tab by depositing one or more drops of said analyte, which analyte then progresses in the direction of the arrow by capillarity;
  • a transparent plate 57 in the form of a strip of dimensions similar to that of the first support
  • -a sealed plate 59 in the form of a strip of dimensions similar to that of the second support, which strip is extended at one of its ends 61 by a tongue 63, said strip having dimensions similar to the second support.
  • the first support 65 being in the form of a strip comprising 4 distinct rectangular zones (respectively 67, 69, 71, and 73) each comprising a distinct detection indicator and comprising at one end 75 a recessed zone 77;
  • the second support 79 being in the form of a strip of dimensions similar to the strip of the first support, the contact with the analyte being carried out through the recessed zone 77 of the first support, which is opposite the second support, which analyte then progresses in the direction of the arrow by capillarity;
  • a transparent plate 81 in the form of a strip of dimensions similar to that of the first support and also comprising a recessed area 82 facing the recessed area 77 of the first support;
  • -a sealed plate 83 in the form of a strip of similar dimensions to that of the first support, the second support and the transparent plate.
  • the detection systems in accordance with the invention can be prepared by a method comprising, for each of the detection indicators, a separate step of depositing on the first support by spraying an ink comprising the detection indicator concerned, which means in d in other words, that the method comprises as many deposition steps mentioned above as there are detection indicators, it being understood that each of the detection indicators is deposited so as not to mix with the other detection indicator(s) .
  • each of the detection indicators can be deposited according to a specific deposition mask, each of the deposition masks being designed so that the deposited points of each of the detection indicators do not overlap with those of the other(s). detection indicators.
  • the invention also relates to a method for detecting the presence or absence of one or more chemical compounds comprising the following steps:
  • This contacting step may consist of depositing one or more distinct drops of the analyte on the surface of the detection system, for example, via a pipette, in particular when the system is adapted for horizontal use, or may consist of immersing the one of the ends of the detection system so that the analyte comes into contact with the second support, this contacting mode being suitable for a system suitable for vertical use.
  • the detection system to be used in the context of the aforementioned method must be capable of detecting the chemical compound or compounds, the absence or presence of which is to be determined.
  • a waiting time may be provided so that, where appropriate, the migration of the chemical compound(s) to be detected can take place and the signal(s) (such color shifts) may also occur.
  • the operator can base himself on a colorimetric scale associated with the detection system, which will define, for all the chemical compounds capable of being detected by the system, the corresponding chromatic shift, this colorimetric scale being able to be determined, by preliminary tests, for each of the systems and the chemical compounds intended to be detected by said systems.
  • the deduction can be made with the naked eye or, if necessary, via opto-electronic means.
  • the compounds capable of being detected by the method of the invention can be toxic chemical compounds, such as toxic warfare compounds and, in particular, organophosphorus compounds; toxic industrial chemical compounds (known as TIC); vesicants; pesticides and arsenic compounds.
  • toxic chemical compounds such as toxic warfare compounds and, in particular, organophosphorus compounds
  • organophosphorus compounds toxic industrial chemical compounds (known as TIC)
  • TIC toxic industrial chemical compounds
  • vesicants pesticides and arsenic compounds.
  • the invention also relates to a colorimetric detection kit which can be used for the detection of one or more chemical compounds comprising the following elements:
  • the colorimetric scale can be located at the level of the first support, for example, on either side of distinct zones with at the level of each distinct zone, for example, on the left, the initial color of the colored indicator and on the right , the possible color(s) for the colored indicator.
  • FIG. 1 already commented upon, schematically illustrates an example of a detection system suitable for vertical use.
  • the first support 65 being in the form of a strip comprising 4 distinct rectangular zones (respectively 67, 69, 71, and 73) each comprising a distinct colored indicator (bromocresol green; 2.4-h/s[p- (dimethylamino)styryl]quinoline; Disperse Black 9 and Disperse Yellow 7) and comprising at one end 75 a recessed zone 77;
  • the second support 79 being in the form of a strip of dimensions similar to the strip of the first support, which strip, the contact with the analyte taking place through the recessed zone 77 of the first support, which is gaze of the second support, which analyte then progresses in the direction of the arrow by capillarity; a transparent layer 81 in the form of a strip of dimensions similar to those of the first support and of the second support but not going as far as the recessed deposition zone;
  • -a sealed layer 83 in the form of a strip of similar dimensions to that of the first support, of the second support.

Abstract

The invention relates to a detection system suitable for use in the detection of one or more chemical compounds, which comprises: - a first support (5) impregnated with discrete detection indicators capable of detecting the presence of said chemical compound or compounds, characterised in that each of said detection indicators is distributed on the support in the form of one or more discrete zones (7, 9, 11, 13), said discrete zone or zones (7, 9, 11, 13) of each of said detection indicators being arranged on the support (5) without overlapping the discrete zone or zones (7, 9, 11, 13) of the other detection indicator or indicators; and - a second support (19) intended for depositing the medium in which the presence or absence of said chemical compound or compounds is to be determined, this second support (19) being in contact with one of the faces of the first support (5).

Description

Système de détection utilisable pour la détection de composés chimiques comprenant une bandelette de détection Detection system usable for the detection of chemical compounds comprising a detection strip
DOMAINE TECHNIQUE TECHNICAL AREA
La présente invention a trait à un nouveau système de détection, par exemple, colorimétrique, utilisable pour la détection de composés chimiques distincts et à un procédé de détection d'un ou plusieurs composés chimiques mettant en œuvre ce système de détection. The present invention relates to a new detection system, for example colorimetric, usable for the detection of distinct chemical compounds and to a method for detecting one or more chemical compounds implementing this detection system.
En particulier, la présente invention peut trouver application pour la détection de composés chimiques toxiques, tels que les composés toxiques de guerre et, en particulier, les composés organophosphorés ; les composés toxiques industriels chimiques (connus sous la dénomination TIC) ; les vésicants ; les pesticides et les composés arséniés. In particular, the present invention can find application for the detection of toxic chemical compounds, such as toxic warfare compounds and, in particular, organophosphorus compounds; toxic industrial chemical compounds (known as TIC); vesicants; pesticides and arsenic compounds.
De manière générale, les composés organophosphorés se présentent sous la forme de composés organiques présentant une toxicité avérée pour l'organisme humain. En effet, ces composés peuvent être impliqués dans le mécanisme d'inhibition des sérineprotéases et, en particulier, de l'acétylcholinestérase, qui intervient dans les jonctions synaptiques et dont le dérèglement de l'activité peut empêcher le relâchement musculaire et ainsi provoquer la mort par asphyxie. In general, organophosphorus compounds are in the form of organic compounds with proven toxicity to the human body. Indeed, these compounds may be involved in the mechanism of inhibition of serine proteases and, in particular, of acetylcholinesterase, which intervenes in synaptic junctions and whose dysregulation of activity can prevent muscle relaxation and thus cause death. by asphyxiation.
Ces composés peuvent être compris dans la formulation d'insecticides, de pesticides ou encore d'agents chimiques de combat (tels que les composés organosphosphorés de la série G, comme le sarin ou les composés organophosphorés de la série V, comme le VX) et du fait de la létalité élevée de ces composés, de leur prolifération, il s'avère important de pouvoir disposer de systèmes de détection et d'identification préliminaire. These compounds can be included in the formulation of insecticides, pesticides or even chemical combatants (such as organophosphorus compounds of the G series, such as sarin or organophosphorus compounds of the V series, such as VX) and due to the high lethality of these compounds, their proliferation, it is important to be able to have detection and preliminary identification systems.
Certains systèmes de détection utilisés à ce jour sont basés sur des technologies impliquant des moyens de mesure physique, telles que la spectroscopie à mobilité ionique, la photométrie de flamme, les spectroscopies IR et Raman avec, pour difficultés, que ces systèmes nécessitent un appareillage complexe onéreux et pas forcément adaptés à tous les milieux d'intervention en termes de masse et d'encombrement, auxquelles s'ajoute l'expertise de l'opérateur à considérer. Some detection systems used to date are based on technologies involving physical measurement means, such as ion mobility spectroscopy, flame photometry, IR spectroscopy and Raman with, for difficulties, that these systems require expensive complex equipment and not necessarily adapted to all intervention environments in terms of mass and size, to which is added the expertise of the operator to be considered.
Au vu de ce qui existe, les auteurs de la présente invention se sont orientés vers la conception d'un système de détection utilisable pour la détection d'un ou plusieurs composés chimiques distincts, lequel système devant permettre la détection du ou desdits composés chimiques et, lorsqu'il y en a plusieurs, de préférence, la discrimination desdits composés et répondant à des critères de sensibilité, rapidité, portabilité, fiabilité et qui puissent permettre une détection et, le cas échéant, une discrimination simple, telle qu'une discrimination visuelle à l'œil nu, notamment lorsque la détection est de nature colorimétrique.In view of what exists, the authors of the present invention have focused on the design of a detection system that can be used for the detection of one or more distinct chemical compounds, which system should allow the detection of said chemical compound(s) and , when there are several of them, preferably the discrimination of said compounds and meeting criteria of sensitivity, rapidity, portability, reliability and which can allow detection and, where appropriate, simple discrimination, such as discrimination visual to the naked eye, in particular when the detection is of a colorimetric nature.
EXPOSÉ DE L' INVENTION DISCLOSURE OF THE INVENTION
Ainsi, l'invention a trait à un système de détection utilisable pour la détection d'un ou plusieurs composés chimiques comprenant : Thus, the invention relates to a detection system usable for the detection of one or more chemical compounds comprising:
-un premier support imprégné par des indicateurs de détection distincts aptes à détecter la présence dudit composé chimique ou desdits composés chimiques, caractérisé en ce que chacun desdits indicateurs de détection est réparti sur le support sous forme d'une ou plusieurs zones distinctes, la ou lesdites zones distinctes de chacun desdits indicateurs de détection étant disposée(s) sur le support sans recoupement avec la ou les zones distinctes du ou des autres indicateurs de détection ; et -a first support impregnated with separate detection indicators capable of detecting the presence of said chemical compound or said chemical compounds, characterized in that each of said detection indicators is distributed on the support in the form of one or more separate zones, the or said distinct areas of each of said detection indicators being arranged on the support without overlapping with the distinct area(s) of the other detection indicator(s); And
-un deuxième support destiné au dépôt du milieu, dont on veut déterminer la présence ou l'absence dudit ou desdits composés chimiques, ce deuxième support étant en contact avec l'une des faces du premier support. a second support intended for depositing the medium, the presence or absence of said chemical compound(s) of which it is desired to determine, this second support being in contact with one of the faces of the first support.
Grâce à la présence d'indicateurs de détection distincts sans qu'il n'y ait de recoupement de surface entre chacun d'entre eux, cela peut permettre, par un choix approprié d'indicateurs de détection, une détection d'un ou plusieurs composés et, idéalement, lorsqu'il y a plusieurs composés chimiques, éventuellement, une discrimination de composés chimiques distincts, sans que les propriétés de détection (par exemple, les propriétés de virage, lorsque les indicateurs de détection sont des indicateurs colorés) de chacun des indicateurs ne soient altérées par un mélange des indicateurs, qui pourrait de ce fait interagir entre eux et biaiser la détection. Par ailleurs, les systèmes de détection conformes à l'invention sont particulièrement adaptés pour la détection de composés chimiques sous forme liquide, grâce au deuxième support. Enfin, les systèmes de détection de l'invention peuvent permettre, par le choix d'indicateurs colorés appropriés, la discrimination de composés chimiques distincts appartenant à la même famille, tels que, à titre d'exemple non limitatif, les composés organophosphorés (comme ceux de la série G, de la série V ou des agents neurotoxiques organophosphorés récemment ajoutés au Tableau 1 de l'annexe de la convention de l'OIAC pour l'interdiction des armes chimiques S/1821/2019/Rev.l/Add.l (20 mai 2020)), les vésicants (tels que l'ypérite soufrée, l'ypérite azotée, la léwisite), les toxiques industriels chimiques (tels que l'ammoniac, la chloropicrine), les pesticides. Thanks to the presence of distinct detection indicators without there being any surface overlap between each of them, this can allow, by an appropriate choice of detection indicators, detection of one or more compounds and, ideally, when there are several chemical compounds, possibly a discrimination of distinct chemical compounds, without the detection properties (e.g., toning properties, when the detection indicators are colored indicators) of each indicators are not altered by a mixture of indicators, which could therefore interact with each other and bias the detection. Furthermore, the detection systems in accordance with the invention are particularly suitable for the detection of chemical compounds in liquid form, thanks to the second support. Finally, the detection systems of the invention can allow, by the choice of appropriate colored indicators, the discrimination of distinct chemical compounds belonging to the same family, such as, by way of non-limiting example, organophosphorus compounds (such as those of the G-series, V-series or organophosphate nerve agents recently added to Schedule 1 of the Annex to the OPCW Convention for the Prohibition of Chemical Weapons S/1821/2019/Rev.l/Add. l (May 20, 2020)), vesicants (such as sulfur mustard, nitrogen mustard, lewisite), toxic industrial chemicals (such as ammonia, chloropicrin), pesticides.
Autrement dit, dans le cas où les indicateurs de détection sont des indicateurs colorés, s'ils étaient mélangés, cela pourrait induire les inconvénients suivants : In other words, in the case where the detection indicators are colored indicators, if they were mixed, this could induce the following drawbacks:
-le mélange de plusieurs indicateurs colorés pourrait aboutir à une couleur terne ; - the mixing of several colored indicators could lead to a dull color;
-les indicateurs colorés pourraient interagir entre eux, rendant la couleur résultante pas forcément prévisible et une réactivité face aux composés chimiques à détecter non garantie ; - the colored indicators could interact with each other, making the resulting color not necessarily predictable and reactivity to the chemical compounds to be detected not guaranteed;
-l'identification des composés chimiques serait moins précise et moins aisée à l'œil nu. Avant d'entrer plus en détail dans l'exposé de l'invention, nous précisions les éléments suivants. -the identification of chemical compounds would be less precise and less easy with the naked eye. Before going into more detail in the description of the invention, we specify the following elements.
Par indicateur de détection, il s'entend, classiquement, une substance chimique capable de se transformer au contact d'au moins un composé chimique que l'on souhaite détecter, cette transformation étant le signe de la présence dudit au moins un composé chimique, cette transformation se matérialisant par un changement de couleur, lorsque l'indicateur de détection est un indicateur coloré (dit également indicateur de détection colorimétrique). Il peut s'agir également d'un indicateur de fluorescence (ou fluorophore), selon sa nature. Plus spécifiquement, lorsque l'indicateur de détection est un indicateur coloré, celui-ci correspond, classiquement, à une substance chimique qui prend au moins une couleur caractéristique en présence d'un composé chimique soit, en d'autres termes, une substance chimique qui présente au moins deux états colorés, un état coloré existant lorsque la substance chimique n'est pas en présence du composé chimique à détecter et au moins un autre état coloré lorsque la substance chimique est en présence du ou des composés chimiques à détecter. L'indicateur de détection peut être constitué d'un ou plusieurs composés permettant la détection. By detection indicator, it is meant, conventionally, a chemical substance capable of being transformed on contact with at least one chemical compound that it is desired to detect, this transformation being the sign of the presence of said at least one chemical compound, this transformation materializing by a change of color, when the detection indicator is a colored indicator (also called colorimetric detection indicator). It may also be a fluorescence indicator (or fluorophore), depending on its nature. More specifically, when the detection indicator is a colored indicator, this corresponds, conventionally, to a chemical substance which takes on at least one characteristic color in the presence of a chemical compound, i.e., in other words, a chemical substance which has at least two colored states, a colored state existing when the chemical substance is not in the presence of the chemical compound to be detected and at least one other colored state when the chemical substance is in the presence of the chemical compound or compounds to be detected. The detection indicator can consist of one or more compounds allowing detection.
Par « sans recoupement », il s'entend, classiquement, que la ou les zones distinctes de chacun des indicateurs de détection ne se mélangent pas avec la ou les zones distinctes des autres indicateurs de détection, ce qui n'exclut pas que la ou les zones distinctes de chaque indicateur de détection puissent être, en tout ou partie, juxtaposés avec la ou les zones distinctes du ou des autres indicateurs de détection. By “without overlapping”, it is meant, conventionally, that the distinct zone(s) of each of the detection indicators do not mix with the distinct zone(s) of the other detection indicators, which does not exclude that the the distinct zones of each detection indicator can be, in whole or in part, juxtaposed with the distinct zone(s) of the other detection indicator(s).
Comme défini ci-dessus, le système de détection utilisable pour la détection d'un ou plusieurs composés chimiques comprend un premier support imprégné par des indicateurs de détection distincts aptes à détecter la présence dudit composé chimique ou desdits composés chimiques, caractérisé en ce que chacun desdits indicateurs de détection est réparti sur le support sous forme d'une ou plusieurs zones distinctes, la ou lesdites zones distinctes de chacun desdits indicateurs de détection étant disposée(s) sur le support sans recoupement avec la ou le zones distinctes du ou des autres indicateurs de détection. As defined above, the detection system usable for the detection of one or more chemical compounds comprises a first support impregnated with separate detection indicators capable of detecting the presence of said chemical compound or of said chemical compounds, characterized in that each of said detection indicators is distributed on the support in the form of a or several distinct zones, the said distinct zone(s) of each of the said detection indicators being arranged on the support without overlapping with the distinct zone(s) of the other detection indicator(s).
Plus spécifiquement, chacun desdits indicateurs de détection est réparti sur le support sous forme d'une ou plusieurs zones distinctes, la ou lesdites zones distinctes pouvant se présenter sous des formes sensiblement circulaires, rectangulaires ou carrées, étant entendu que d'autres formes peuvent être envisagées, dès lors que qu'il n'y a pas de recoupement entre les zones distinctes pour des indicateurs de détection distincts. More specifically, each of said detection indicators is distributed on the support in the form of one or more distinct zones, the said distinct zone or zones possibly being in substantially circular, rectangular or square shapes, it being understood that other shapes can be envisaged, provided that there is no overlap between the distinct zones for distinct detection indicators.
Le premier support constitutif du système de détection peut être, en particulier, un support poreux et, plus spécifiquement, un support en papier, étant entendu que ce support doit être apte à être imprégné par les différents indicateurs de détection pour former les zones distinctes. The first constituent support of the detection system can be, in particular, a porous support and, more specifically, a paper support, it being understood that this support must be able to be impregnated by the various detection indicators to form the distinct zones.
Le premier support constitutif comporte classiquement deux faces, une face supérieure comprenant les zones distinctes comprenant les indicateurs de détection et une face inférieure opposée à la face supérieure, la face inférieure étant la face en contact avec le deuxième support. The first constituent support conventionally comprises two faces, an upper face comprising the distinct zones comprising the detection indicators and a lower face opposite the upper face, the lower face being the face in contact with the second support.
Avantageusement, les zones distinctes peuvent être cloisonnées en obstruant la porosité du premier support sur les zones qui ne sont pas les zones distinctes, la porosité pouvant être obstruée, plus spécifiquement, par exemple, par de la cire, de la paraffine, un polydiméthylsiloxane ou tous autres moyens pour obstruer la porosité. La porosité ainsi obstruée permet de limiter l'accès à l'analyte (à savoir, le milieu, généralement liquide, dans lequel on veut connaître la présence ou l'absence de composés à analyser) aux zones ainsi obstruées et créer ainsi un circuit fluidique permettant un accès privilégié de l'analyte aux zones distinctes comprenant les indicateurs de détection, lesquelles ne sont pas obstruées. Le premier support peut se présenter sous forme d'une bandelette, comme cela sera illustré dans des modes de réalisation particuliers illustrés sur des figures jointes. Advantageously, the distinct zones can be partitioned by obstructing the porosity of the first support on the zones which are not the distinct zones, the porosity possibly being obstructed, more specifically, for example, by wax, paraffin, a polydimethylsiloxane or any other means to block the porosity. The porosity thus obstructed makes it possible to limit the access to the analyte (namely, the medium, generally liquid, in which one wants to know the presence or the absence of compounds to be analyzed) to the zones thus obstructed and thus to create a fluidic circuit allowing privileged access of the analyte to the distinct zones comprising the detection indicators, which are not obstructed. The first support may be in the form of a strip, as will be illustrated in particular embodiments illustrated in the appended figures.
Le premier support peut comprendre à l'une de ses extrémités, une zone évidée, donnant ainsi accès directement au deuxième support, cette zone évidée permettant ainsi le dépôt direct de l'analyte sur le deuxième support sur la zone de celui-ci en regard de la zone évidée du premier support. Cette zone évidée peut constituer un « réservoir » pour l'analyte qui va, outre le fait d'être en contact avec le deuxième support, être ainsi retenue dans cette zone sans risque d'écoulement à l'extérieur. The first support may comprise at one of its ends a recessed area, thus giving direct access to the second support, this recessed area thus allowing the direct deposition of the analyte on the second support on the area of the latter facing of the recessed area of the first support. This hollowed out zone can constitute a “reservoir” for the analyte which will, in addition to the fact of being in contact with the second support, thus be retained in this zone without risk of flow to the outside.
Plus spécifiquement, le système de détection peut comprendre, comme indicateurs de détection, des indicateurs colorés permettant une détection colorimétrique. More specifically, the detection system can comprise, as detection indicators, colored indicators allowing colorimetric detection.
Selon les composés chimiques à détecter et à éventuellement discriminer, il s'entend que l'homme du métier, pour concevoir le système de détection conforme à l'invention, choisira, lorsque les indicateurs de détection sont des indicateurs colorés, de préférence, des indicateurs colorés appropriés en procédant à une sélection basée notamment sur le fait que les indicateurs colorés choisis doivent présenter, bien évidemment, au moins un virage colorimétrique en présence du composé chimique, que l'on souhaite détecter. Depending on the chemical compounds to be detected and possibly discriminated, it is understood that the person skilled in the art, to design the detection system in accordance with the invention, will choose, when the detection indicators are colored indicators, preferably appropriate colored indicators by making a selection based in particular on the fact that the chosen colored indicators must obviously have at least one colorimetric shift in the presence of the chemical compound which it is desired to detect.
Selon les composés chimiques que l'on souhaite détecter, les indicateurs colorés peuvent être choisis parmi les composés anthraquinoniques, les composés azoïques, les composés triarylméthanes, les composés xanthéniques, les composés indigoïques, les complexes métalliques, les composés comprenant au moins un groupe stilbène, les composés coumariniques, les composés comprenant au moins un groupe cyanine, les composés comprenant au moins un groupe phtalocyanine, les composés comprenant au moins un groupe porphyrine, les composés comprenant au moins un groupe hydrazone. A titre d'exemples de composés anthraquinoniques, il peut être fait mention de la 1,4-dihydroxyanthraquinone, la 1-aminoanthraquinone, l'acide carminique, la 1,5-diaminoanthraquinone, la 1,2-diaminoanthraquinone, la 1,4- diamino-5-nitroanthraquinone, la 1,4,5,8-tétraaminoanthraquinone (Disperse Blue 1), la l-méthylamino-4-(2-hydroxyéthyl)aminoanthraquinone (Disperse Blue 3), la l-amino-2-méthylanthraquinone (Disperse Orange 11), le l,4-h/s-(p- tolylamino)anthraquinone (Solvent Green 3). Depending on the chemical compounds that it is desired to detect, the colored indicators can be chosen from anthraquinone compounds, azo compounds, triarylmethane compounds, xanthenic compounds, indigo compounds, metal complexes, compounds comprising at least one stilbene group , coumarin compounds, compounds comprising at least one cyanine group, compounds comprising at least one phthalocyanine group, compounds comprising at least one porphyrin group, compounds comprising at least one hydrazone group. As examples of anthraquinone compounds, mention may be made of 1,4-dihydroxyanthraquinone, 1-aminoanthraquinone, carminic acid, 1,5-diaminoanthraquinone, 1,2-diaminoanthraquinone, 1,4 - diamino-5-nitroanthraquinone, 1,4,5,8-tetraaminoanthraquinone (Disperse Blue 1), l-methylamino-4-(2-hydroxyethyl)aminoanthraquinone (Disperse Blue 3), l-amino-2-methylanthraquinone (Disperse Orange 11), 1,4-h/s-(p-tolylamino)anthraquinone (Solvent Green 3).
A titre d'exemples de composés azoïques, il peut être fait mention du 10-(2',4'-dinitrophénylazo)-9-phénanthrol, le 6-hydroxy-5-[(2- méthoxy-5-méthyl-4-sulfophényl)azo]-2-naphtalènesulfonate de disodium (dit également rouge Allura AC), le 4-diméthylaminoazobenzène (dit également jaune de méthyle), le 4-(2-carboxyphénylazo)-N,N-dipropylaniline (dit également « Propyl red » selon la terminologie anglaise), le chlorure de 3-(diéthylamino)-7- {(E)-[4-(diméthylamino)phényl]diazényl}-5-phénylphénazin-5-ium (dit également « Vert Janus B »), le N,N-diméthyl-4,4'-azodianiline, le N-éthyl-l-((4- phényldiazényl)phényl)diazényl)naphtalèn-2-amine (dit également « Rouge Soudan 7B »), l'amarante, le dihydrochlorure de 4-[[3-[(2,4- diaminophényl)diazényl]phényl]diazényl]benzène-l,3-diamine (dit également « brun de Bismarck Y »), le 4-hydroxy-3-[(4-sulfo-l-naphtalényl)azo]-l- naphtalènesulfonate de disodium (dit également « Chromotrope FB »), l'acide benzidinediazo-bis-l-naphtylamine-4-sulfonique (dit également « Rouge Congo »), le 2,2'-[4-(4-Aminophénylazo)phénylimino]diéthanol (dit également « Disperse Black 9 » selon la terminologie anglaise), le 2,2'-[[4-[(4- nitrophényl)azo]phényl]imino]biséthanol (dit également « Disperse Red 19 » selon la terminologie anglaise), le (4Z)-4-[(l-hydroxynaphthalén-2-yl- hydrazinylidène]- 7-nitro-3-oxo Y-naphtalène-l-sulfonate de sodium (dit également « noir ériochrome T »), le 4'-(4-(diéthylamino)phénylazo)acétophénone, le 4-[(E)-(4- nitrophényl)diazényl]-N-phénylaniline (dit également « Disperse Orange 1 »), l'hélianthine (dit également méthylorange), la 4-(4-nitrophénylazo)aniline (dit également « Disperse Orange 3 »), le 4-[4-(phénylazo)-l-naphthylazo]phénol (dit également « Disperse Orange 13 »), le 3-[N-éthyl-4-(4- nitrophénylazo)phénylamino]propionitrile (dit également « Disperse Orange 25 »), le 4-amino-5-hydroxy-3-(4-nitrophénylazo)-6-(phénylazo)naphtalène-2,7- disulfonate de sodium (dit également « Bleu noir naphtol »), le (2,2-diméthyl-l,3- dihydropérimidin-6-yl)-(4-phénylazo-l-naphthyl)diazène (dit également « Sudan Black B » selon la terminologie anglaise), le 6-hydroxy-5-[(4- sulfonatophényl)azo]naphtalène-2-sulfonate de disodium (dit également «jaune orangé S ») , la tartrazine, le bleu Evans, le 4-[4-(phénylazo)phénylazo]-o-crésol (dit également «Disperse Yellow 7 » selon la terminologie anglaise), le 4'-nitro-4- diméthylaminoazobenzène. As examples of azo compounds, mention may be made of 10-(2',4'-dinitrophenylazo)-9-phenanthrol, 6-hydroxy-5-[(2-methoxy-5-methyl-4- disodium sulfophenyl)azo]-2-naphthalenesulfonate (also called Allura AC red), 4-dimethylaminoazobenzene (also called methyl yellow), 4-(2-carboxyphenylazo)-N,N-dipropylaniline (also called "Propyl red according to English terminology), 3-(diethylamino)-7-{(E)-[4-(dimethylamino)phenyl]diazenyl}-5-phenylphenazin-5-ium chloride (also called "Janus Green B") , N,N-dimethyl-4,4'-azodianiline, N-ethyl-1-((4-phenyldiazenyl)phenyl)diazenyl)naphthalen-2-amine (also known as "Sudan Red 7B"), amaranth , 4-[[3-[(2,4-diaminophenyl)diazenyl]phenyl]diazenyl]benzene-l,3-diamine dihydrochloride (also called “Bismarck brown Y”), 4-hydroxy-3-[ disodium (4-sulfo-l-naphthalenyl)azo]-l-naphthalenesulfonate (also called "Chromotrope FB"), benzidinediazo-bis-l-naphthylamine-4-sulfonic acid (also called "Congo Red"), 2,2'-[4-(4-Aminophenylazo)phenylimino]diethanol (also called "Disperse Black 9" according to English terminology), 2,2'-[[4-[(4-nitrophenyl)azo]phenyl] imino]bisethanol (also known as “Disperse Red 19” according to English terminology), (4Z)-4-[(l-hydroxynaphthalen-2-yl-hydrazinylidene]-7-nitro-3-oxo Y-naphthalene-l- sodium sulfonate (also called "eriochrome black T"), 4'-(4-(diethylamino)phenylazo)acetophenone, 4-[(E)-(4-nitrophenyl)diazenyl]-N-phenylaniline (also called " Disperse Orange 1"), helianthine (also known as methyl orange), 4-(4-nitrophenylazo)aniline (known as also “Disperse Orange 3”), 4-[4-(phenylazo)-l-naphthylazo]phenol (also known as “Disperse Orange 13”), 3-[N-ethyl-4-(4-nitrophenylazo)phenylamino] propionitrile (also known as "Disperse Orange 25"), sodium 4-amino-5-hydroxy-3-(4-nitrophenylazo)-6-(phenylazo)naphthalene-2,7-disulphonate (also known as "Black blue naphthol" ), (2,2-dimethyl-l,3-dihydroperimidin-6-yl)-(4-phenylazo-l-naphthyl)diazene (also called “Sudan Black B” according to English terminology), 6-hydroxy- disodium 5-[(4-sulfonatophenyl)azo]naphthalene-2-sulfonate (also known as "orange-yellow S"), tartrazine, Evans blue, 4-[4-(phenylazo)phenylazo]-o-cresol ( also called “Disperse Yellow 7” according to English terminology), 4'-nitro-4-dimethylaminoazobenzene.
A titre d'exemples de composés triarylméthanes, il peut être fait mention du bleu d'aniline diammonium, du bleu de bromophénol, le violet de m-crésol, le rouge de crésol, le violet de gentiane (dit également « Crystal Violet » en terminologie anglaise), le rouge de chlorophénol, le sel de sodium de l'hydroxyde de (4-(a-(p-(diéthylamino)phényl)-2,4-disulfobenzylidène)-2,5- cyclohexadiène-l-ylidène)diéthylammonium (dit également « Patent blue V sodium sait »), le bleu de méthyle, l'acide rosolique, le violet de pyrocatéchol, le vert brillant BS, la base pararosaniline, la fuchsine, le bleu de thymol, le 4- (diméthylamino)-a-[4-(diméthylamino)phényl]-a-phényl-benzèneméthanol. As examples of triarylmethane compounds, mention may be made of aniline diammonium blue, bromophenol blue, m-cresol violet, cresol red, gentian violet (also called "Crystal Violet" in English terminology), chlorophenol red, (4-(a-(p-(diethylamino)phenyl)-2,4-disulfobenzylidene)-2,5-cyclohexadiene-l-ylidene hydroxide, sodium salt diethylammonium (also known as "Patent blue V sodium sait"), methyl blue, rosolic acid, pyrocatechol violet, brilliant green BS, pararosaniline base, fuchsin, thymol blue, 4- (dimethylamino )-a-[4-(dimethylamino)phenyl]-a-phenyl-benzenemethanol.
A titre d'exemples de composés xanthéniques, il peut être fait mention du chlorure de [9-(2-carboxyphényl)-6-diéthylamino-3-xanthénylidène]- diéthylammonium (dit également « Rhodamine 610 »), la rhodamine 6G éventuellement sous forme de sel perchlorate, la rhodamine B, la sulforhodamine 101 hydratée, la fluorescéinamine (en particulier Isomère I), le chlorure de rhodamine 110. As examples of xanthene compounds, mention may be made of [9-(2-carboxyphenyl)-6-diethylamino-3-xanthenylidene]-diethylammonium chloride (also called "Rhodamine 610"), rhodamine 6G optionally under perchlorate salt form, rhodamine B, sulforhodamine 101 hydrate, fluoresceinamine (especially Isomer I), rhodamine 110 chloride.
A titre d'exemples de composés indigoïques, il peut être fait mention de l'indigo. A titre d'exemples de complexes métalliques, il peut être fait mention du 5-nitroso-6-oxidonaphthalene-2-sulfonate trisodique complexé par du fer (III) (dit également « Naphtol Green B »). As examples of indigo compounds, mention may be made of indigo. As examples of metal complexes, mention may be made of trisodium 5-nitroso-6-oxidonaphthalene-2-sulfonate complexed with iron (III) (also called “Naphthol Green B”).
A titre d'exemples de composés comprenant au moins un groupe stilbène, il peut être fait mention du colorant connu sous la terminologie anglaise « Fluorescent Brightener 28 ». As examples of compounds comprising at least one stilbene group, mention may be made of the dye known under the English terminology “Fluorescent Brightener 28”.
A titre d'exemples de composés coumariniques, il peut être fait mention de la 7-amino-4-(trifluorométhyl)coumarine, la 7-amino-4- méthylcoumarine, la 3-(2-N-Méthylbenzimidazolyl)-7-N,N-diéthylaminocoumarine (dit également « Coumarin 30 »), la 2,3,6,7-tétrahydro-10-(3-pyridyl)-lH,5H,llH- [l]benzopyrano[6,7,8-ij]quinolizin-ll-one (dit également « Coumarin 510 »), la 3- (2-Benzothiazolyl)-7-(diethylamino)coumarine (dit également « Coumarin 6 »). As examples of coumarin compounds, mention may be made of 7-amino-4-(trifluoromethyl)coumarin, 7-amino-4-methylcoumarin, 3-(2-N-Methylbenzimidazolyl)-7-N ,N-diethylaminocoumarin (also called “Coumarin 30”), 2,3,6,7-tetrahydro-10-(3-pyridyl)-1H,5H,11H-[l]benzopyrano[6,7,8-ij ]quinolizin-ll-one (also known as “Coumarin 510”), 3-(2-Benzothiazolyl)-7-(diethylamino)coumarin (also known as “Coumarin 6”).
A titre d'exemples de composés comprenant un groupe cyanine, il peut être fait mention du vert d'indocyanine, du perchlorate de 5,5'- dichloro-ll-diphénylamino-3,3'-diéthyl-10,12-éthylènethiatricarbocyanine (dit également IR140). As examples of compounds comprising a cyanine group, mention may be made of indocyanine green, 5,5'-dichloro-11-diphenylamino-3,3'-diethyl-10,12-ethylenethiatricarbocyanine perchlorate ( also says IR140).
A titre d'exemples de composés comprenant un groupe phtalocyanine, il peut être fait mention du chlorure de phtalocyanine de fer (III), d'acide phtalocyanine-4,4',4'',4'"-tétrasulfonique de fer (III), du l,2,3,4,8,9,10,ll,15,16,17,18,22,23,24,25-hexadécafluoro-29H,31H- phtalocyanine. As examples of compounds comprising a phthalocyanine group, mention may be made of phthalocyanine iron (III) chloride, phthalocyanine-4,4',4'',4'"-tetrasulfonic acid of iron (III ), 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine.
Le système de détection comprend, également, un deuxième support destiné au dépôt du milieu, dont on veut déterminer la présence ou l'absence d'au moins un composé chimique et dont l'indicateur coloré est présent sur le premier support, ce deuxième support étant en contact avec l'une des faces du premier support (classiquement, la face inférieure opposée à la face supérieure, laquelle est occupée par les zones distinctes des indicateurs colorés). Ce deuxième support permet, avantageusement, la diffusion ou migration par capillarité du milieu déposé sur celui-ci, de sorte à ce qu'il puisse atteindre les différentes zones distinctes susmentionnées du premier support et permettre le cas échéant la détection d'un ou des composés contenus éventuellement dans cet analyte et sensible aux indicateurs colorés constitutifs des zones distinctes. The detection system also comprises a second support intended for depositing the medium, of which it is desired to determine the presence or absence of at least one chemical compound and of which the colored indicator is present on the first support, this second support being in contact with one of the faces of the first support (conventionally, the lower face opposite the upper face, which is occupied by the distinct zones of the colored indicators). This second support advantageously allows the diffusion or migration by capillarity of the medium deposited thereon, so that it can reach the various distinct zones mentioned above of the first support and allow, if necessary, the detection of one or more compounds possibly contained in this analyte and sensitive to the constituent colored indicators of the distinct zones.
Ce deuxième support peut être en un matériau comprenant (ou constitué par) un enchevêtrement de fibres, telles que des fibres choisies parmi les fibres de celluloses (notamment celles utilisées dans des papiers filtres pour laboratoires ou dans des papiers destinés à être utilisés dans les techniques chromatographiques), les fibres de verres, des fibres polymériques synthétiques, comme des fibres de polyester, et les mélanges de celles-ci, cet enchevêtrement pouvant former un matériau intissé. This second support can be made of a material comprising (or consisting of) an entanglement of fibers, such as fibers chosen from cellulose fibers (in particular those used in filter papers for laboratories or in papers intended for use in the techniques chromatography), glass fibers, synthetic polymer fibers, such as polyester fibers, and mixtures thereof, this entanglement being able to form a non-woven material.
Ce deuxième support peut se présenter sous forme d'une bandelette, notamment lorsque le premier support est également sous forme d'une bandelette, et peut présenter notamment les mêmes dimensions que le premier support, moyennant quoi il recouvre entièrement l'une des faces du premier support (généralement la face inférieure du premier support opposée la face supérieure, sur laquelle sont apposées les zones distinctes susmentionnées). This second support may be in the form of a strip, in particular when the first support is also in the form of a strip, and may in particular have the same dimensions as the first support, whereby it completely covers one of the faces of the first support (generally the lower face of the first support opposite the upper face, on which the aforementioned distinct zones are affixed).
Ce deuxième support, notamment lorsqu'il se présente sous forme d'une bandelette, peut comprendre au niveau de la face en contact avec le premier support, deux bandes latérales opposées situées sur les deux plus grands côtés de la bandelette, ces deux bandes étant des bandes étanches et ménageant un zone centrale dénuée de ces bandes et constituant un espace de circulation du milieu, dont on veut déterminer la présence ou l'absence dudit ou desdits composés chimiques. Cet espace de circulation constitue avantageusement un espace de circulation du milieu vers les zones distinctes du premier support et permet d'éviter au milieu qu'il ne sorte pas par les côtés grâce à la présence de ces bandes. Ces bandes étanches peuvent résulter de l'obstruction de la porosité du deuxième support en ces endroits, par exemple, par application d'une cire, d'une paraffine, d'un polydiméthylsiloxane, d'une colle (qui permet par ailleurs de coller le premier support et le deuxième support l'un à l'autre) ou tous autres moyens pour obstruer la porosité. This second support, in particular when it is in the form of a strip, may comprise at the level of the face in contact with the first support, two opposite lateral strips located on the two largest sides of the strip, these two strips being sealed bands and providing a central zone devoid of these bands and constituting a space for the circulation of the medium, the presence or absence of said chemical compound or compounds of which it is desired to determine. This circulation space advantageously constitutes a circulation space from the middle to the distinct zones of the first support and makes it possible to prevent the middle from coming out via the sides thanks to the presence of these bands. These tight bands can result from the obstruction of the porosity of the second support in these places, for example, by application of a wax, a paraffin, a polydimethylsiloxane, an adhesive (which moreover makes it possible to stick the first support and the second support to each other) or any other means to obstruct the porosity.
Le deuxième support mis en contact avec le premier support peut comprendre une languette émergeant de l'empilement du premier support et du deuxième support, cette languette servant de zone de dépôt de l'analyte et étant classiquement en un matériau identique à celui constitutif du reste du support. The second support brought into contact with the first support may comprise a tab emerging from the stack of the first support and the second support, this tab serving as a deposit zone for the analyte and being conventionally made of a material identical to that constituting the rest of the medium.
Les systèmes de détection de l'invention peuvent comprendre, en outre, une couche étanche en contact avec le deuxième support via la face opposée à celle qui est en contact avec le premier support (cette face opposée pouvant être dénommée face inférieure en opposition à la face supérieure qui est en contact avec le premier support), ce qui signifie, autrement dit, que le deuxième support est pris en sandwich entre le premier support et la couche étanche, cette disposition étant particulièrement favorable, afin de protéger un opérateur qui manipulerait la bandelette de tout contact direct avec les composés chimiques à détecter et afin d'augmenter les forces capillaires qui entraîneront plus rapidement l'analyte vers l'intérieur du deuxième support. Cette couche étanche présente avantageusement les mêmes dimensions que le deuxième support, moyennant quoi il recouvre entièrement l'une des faces du deuxième support (classiquement, la face inférieure du deuxième support). The detection systems of the invention may further comprise an impermeable layer in contact with the second support via the face opposite to that which is in contact with the first support (this opposite face being able to be referred to as the lower face in opposition to the upper face which is in contact with the first support), which means, in other words, that the second support is sandwiched between the first support and the sealed layer, this arrangement being particularly favorable, in order to protect an operator who would manipulate the strip from any direct contact with the chemical compounds to be detected and in order to increase the capillary forces which will draw the analyte more quickly towards the interior of the second support. This sealed layer advantageously has the same dimensions as the second support, whereby it entirely covers one of the faces of the second support (conventionally, the lower face of the second support).
En effet, sans être lié par la théorie, pour un dépôt vertical de l'analyte (c'est-à-dire par immersion verticale d'une extrémité du système de détection dans l'analyte), le deuxième support met environ 10 minutes pour être imprégné par une solution colorée à base de diméthylsulfoxyde (DMSO) pour un système où le deuxième support n'est pas pris en sandwich, contre 4 minutes pour un système où le deuxième support est pris en sandwich. Pour un dépôt horizontal de l'analyte (notamment, pour les systèmes comportant un deuxième support avec une languette qui sert de zone de dépôt de l'analyte, par exemple, par dépôt de l'analyte au moyen d'une pipette), le deuxième support met environ 2 minutes pour être imprégné avec un système où le deuxième support est pris en sandwich. Indeed, without being bound by theory, for a vertical deposition of the analyte (that is to say by vertical immersion of one end of the detection system in the analyte), the second support takes about 10 minutes to be impregnated with a colored solution based on dimethyl sulfoxide (DMSO) for a system where the second support is not sandwiched, against 4 minutes for a system where the second support is sandwiched. For horizontal analyte deposition (especially for systems with a second support with a tab that serves as an analyte deposition area, for example, by deposition of the analyte by means of a pipette), the second support takes about 2 minutes to be impregnated with a system where the second support is sandwiched.
Les systèmes de détection de l'invention peuvent comprendre, en outre, une couche transparente en contact avec le premier support via la face opposée à celle qui est en contact avec le deuxième support (cette face pouvant être dénommée face supérieure en opposition avec la face inférieure qui est en contact avec le deuxième support), cette couche permettant, outre d'isoler l'analyte de l'extérieur, de visualiser, le cas échéant, le virage chromatique au niveau des zones distinctes présentes sur le premier support. The detection systems of the invention may further comprise a transparent layer in contact with the first support via the face opposite to that which is in contact with the second support (this face being able to be called the upper face in opposition to the face lower which is in contact with the second support), this layer making it possible, in addition to isolating the analyte from the outside, to visualize, if necessary, the chromatic change at the level of the distinct zones present on the first support.
La couche étanche et la couche transparente ont notamment pour fonction l'encapsulation complète du système de détection tout en permettant une manipulation plus aisée de celui-ci et en limitant les risques de contamination liés à la manipulation du système. The impermeable layer and the transparent layer have in particular the function of completely encapsulating the detection system while allowing easier handling of the latter and limiting the risks of contamination linked to the handling of the system.
En résumé, ainsi, les systèmes de l'invention peuvent être définis autrement comme un empilement multicouche comprenant un premier support et un deuxième support en contact l'un de l'autre, avantageusement, une couche étanche en contact avec la face inférieure du deuxième support et une couche transparente en contact avec la face supérieure du premier support, des systèmes de ce type étant illustrés sur les figures qui sont commentées ci-dessous et qui illustrent, en particulier : In summary, thus, the systems of the invention can be defined otherwise as a multilayer stack comprising a first support and a second support in contact with each other, advantageously, an impermeable layer in contact with the lower face of the second support and a transparent layer in contact with the upper face of the first support, systems of this type being illustrated in the figures which are commented on below and which illustrate, in particular:
-des systèmes de détection destinés à une utilisation verticale, à savoir, en trempant, de manière verticale, lesdits systèmes de détection via l'une des extrémités donnant accès au deuxième support dans l'analyte (tel que le système représenté sur la figure 1) ; -des systèmes de détection destinés à une utilisation horizontale, à savoir, en déposant, de manière horizontale, sur lesdits systèmes de détection via l'une des extrémités donnant accès au deuxième support, une ou plusieurs gouttes de l'analyte (tel que les systèmes représentés sur les figures 2 et 3). - detection systems intended for vertical use, namely, by dipping, vertically, said detection systems via one of the ends giving access to the second support in the analyte (such as the system shown in Figure 1 ); -detection systems intended for horizontal use, namely, by depositing, horizontally, on said detection systems via one of the ends giving access to the second support, one or more drops of the analyte (such as systems shown in Figures 2 and 3).
Plus spécifiquement, comme systèmes destinés à une utilisation verticale, il peut être fait mention du système représenté en vue éclatée et en vue compacte sur la figure 1 comprenant : More specifically, as systems intended for vertical use, mention may be made of the system shown in exploded view and in compact view in Figure 1 comprising:
-le premier support 5 se présentant sous forme d'une bandelette comportant 4 zones distinctes circulaires (respectivement 7, 9, 11 et 13) comportant chacune un indicateur de détection distinct, le premier support se prolongeant à l'une de ses extrémités 15 par une languette 17 ; the first support 5 being in the form of a strip comprising 4 separate circular zones (respectively 7, 9, 11 and 13) each comprising a separate detection indicator, the first support extending at one of its ends 15 by a tab 17;
-le deuxième support 19 se présentant sous forme d'une bandelette de dimensions similaires à la bandelette du premier support, laquelle bandelette se prolonge également à l'une de ses extrémités 21 par une languette 23, le contact avec l'analyte s'effectuant au niveau de cette languette, lequel analyte progressant ensuite dans la direction de la flèche par capillarité ; the second support 19 being in the form of a strip of dimensions similar to the strip of the first support, which strip is also extended at one of its ends 21 by a tongue 23, the contact with the analyte taking place at this tongue, which analyte then progresses in the direction of the arrow by capillarity;
-une plaque transparente 25 se présentant sous forme d'une bandelette de dimensions similaires à celle du premier support et du deuxième support, laquelle bandelette se prolonge également à l'une de ses extrémités Tl par une languette ; a transparent plate 25 in the form of a strip of dimensions similar to that of the first support and of the second support, which strip also extends at one of its ends T1 by a tongue;
-une plaque étanche 31 se présentant sous forme d'une bandelette de dimensions similaires à celle du premier support et du deuxième support, laquelle bandelette se prolonge également à l'une de ses extrémités 33 par une languette 35. Comme système destiné à une utilisation horizontale, il peut être fait mention du système représenté en vue éclatée et en vue compacte sur la figure 2 comprenant : -a sealed plate 31 in the form of a strip of dimensions similar to that of the first support and of the second support, which strip is also extended at one of its ends 33 by a tab 35. As a system intended for horizontal use, mention may be made of the system shown in exploded view and in compact view in Figure 2 comprising:
-le premier support 37 se présentant sous forme d'une bandelette comportant 6 zones distinctes rectangulaires (respectivement 39, 41, 43, 45, 47 et 49) comportant chacune un indicateur de détection distinct ; the first support 37 being in the form of a strip comprising 6 distinct rectangular zones (respectively 39, 41, 43, 45, 47 and 49) each comprising a distinct detection indicator;
-le deuxième support 51 se présentant sous forme d'une bandelette de dimensions similaires à la bandelette du premier support, laquelle bandelette se prolonge à l'une de ses extrémités 53 par une languette 55, le contact avec l'analyte s'effectuant au niveau de cette languette par dépôt d'une ou plusieurs gouttes dudit analyte, lequel analyte progressant ensuite dans la direction de la flèche par capillarité ; the second support 51 being in the form of a strip of dimensions similar to the strip of the first support, which strip is extended at one of its ends 53 by a tab 55, the contact with the analyte taking place at the level of this tab by depositing one or more drops of said analyte, which analyte then progresses in the direction of the arrow by capillarity;
-une plaque transparente 57 se présentant sous forme d'une bandelette de dimensions similaires à celle du premier support ; a transparent plate 57 in the form of a strip of dimensions similar to that of the first support;
-une plaque étanche 59 se présentant sous forme d'une bandelette de dimensions similaires à celle du deuxième support, laquelle bandelette se prolonge à l'une de ses extrémités 61 par une languette 63, ladite bandelette présentant des dimensions similaires au deuxième support. -a sealed plate 59 in the form of a strip of dimensions similar to that of the second support, which strip is extended at one of its ends 61 by a tongue 63, said strip having dimensions similar to the second support.
Enfin, comme système destiné à une utilisation horizontale, il peut être fait mention, également, du système représenté en vue éclatée et en vue compacte sur la figure 3 comprenant : Finally, as a system intended for horizontal use, mention may also be made of the system shown in exploded view and in compact view in Figure 3 comprising:
-le premier support 65 se présentant sous forme d'une bandelette comportant 4 zones distinctes rectangulaires (respectivement 67, 69, 71, et 73) comportant chacune un indicateur de détection distinct et comportant à une extrémité 75 une zone évidée 77 ; the first support 65 being in the form of a strip comprising 4 distinct rectangular zones (respectively 67, 69, 71, and 73) each comprising a distinct detection indicator and comprising at one end 75 a recessed zone 77;
-le deuxième support 79 se présentant sous forme d'une bandelette de dimensions similaires à la bandelette du premier support, le contact avec l'analyte s'effectuant par le biais de la zone évidée 77 du premier support, qui est en regard du deuxième support, lequel analyte progressant ensuite dans la direction de la flèche par capillarité ; -the second support 79 being in the form of a strip of dimensions similar to the strip of the first support, the contact with the analyte being carried out through the recessed zone 77 of the first support, which is opposite the second support, which analyte then progresses in the direction of the arrow by capillarity;
-une plaque transparente 81 se présentant sous forme d'une bandelette de dimensions similaires à celle du premier support et comprenant également une zone évidée 82 en regard de la zone évidée 77 du premier support; a transparent plate 81 in the form of a strip of dimensions similar to that of the first support and also comprising a recessed area 82 facing the recessed area 77 of the first support;
-une plaque étanche 83 se présentant sous forme d'une bandelette de dimensions similaires à celle du premier support, du deuxième support et de la plaque transparente. -a sealed plate 83 in the form of a strip of similar dimensions to that of the first support, the second support and the transparent plate.
Les systèmes de détection conformes à l'invention peuvent être préparés par un procédé comprenant, pour chacun des indicateurs de détection, une étape distincte de dépôt sur le premier support en projetant une encre comprenant l'indicateur de détection concerné, ce qui signifie en d'autres termes, que le procédé comprend autant d'étapes de dépôt mentionnées ci-dessus que d'indicateurs de détection, étant entendu que chacun des indicateurs de détection est déposé de sorte à ne pas se mélanger avec le ou les autres indicateurs de détection. The detection systems in accordance with the invention can be prepared by a method comprising, for each of the detection indicators, a separate step of depositing on the first support by spraying an ink comprising the detection indicator concerned, which means in d in other words, that the method comprises as many deposition steps mentioned above as there are detection indicators, it being understood that each of the detection indicators is deposited so as not to mix with the other detection indicator(s) .
Pour ce faire, chacun des indicateurs de détection peut être déposé selon un masque de dépôt spécifique, chacun des masques de dépôt étant conçu de sorte à ce que les points déposés de chacun des indicateurs de détection ne se recoupent pas avec ceux du ou des autres indicateurs de détection. To do this, each of the detection indicators can be deposited according to a specific deposition mask, each of the deposition masks being designed so that the deposited points of each of the detection indicators do not overlap with those of the other(s). detection indicators.
Concernant les techniques de dépôt envisageables, il peut s'agir de toutes techniques de dépôt permettant un dépôt localisé, telles que l'impression par jet d'encre, la sérigraphie, l'impression offset, l'héliographie, la flexographie. Enfin, l'invention a trait également à un procédé de détection de la présence ou de l'absence d'un ou plusieurs composés chimiques comprenant les étapes suivantes : As regards the deposition techniques that can be envisaged, these may be any deposition techniques allowing localized deposition, such as inkjet printing, screen printing, offset printing, heliography, flexography. Finally, the invention also relates to a method for detecting the presence or absence of one or more chemical compounds comprising the following steps:
-une étape de mise en contact du ou des milieux, dont on veut détecter la présence ou l'absence du ou desdits composés chimiques avec le système de détection tel que défini ci-dessus ; a step of bringing the medium(s) whose presence or absence of said chemical compound(s) is to be detected with the detection system as defined above;
-une étape de déduction, en fonction du ou des éventuels signaux de transformation de tout ou partie des indicateurs de détection (par exemple, des virages chromatiques, lorsque le ou indicateurs de détection sont des indicateurs colorés), de la présence ou de l'absence du ou desdits composés. a step of deduction, depending on the possible transformation signal(s) of all or part of the detection indicators (for example, chromatic changes, when the detection indicator(s) are colored indicators), the presence or the absence of said compound(s).
Cette étape de mise en contact peut consister à déposer en surface du système de détection une ou plusieurs gouttes distinctes de l'analyte, par exemple, via une pipette, notamment lorsque le système est adapté pour une utilisation horizontale ou peut consister à plonger l'une des extrémités du système de détection de sorte à ce que l'analyte entre en contact avec le deuxième support, ce mode de mise en contact étant adapté pour un système approprié pour une utilisation verticale. This contacting step may consist of depositing one or more distinct drops of the analyte on the surface of the detection system, for example, via a pipette, in particular when the system is adapted for horizontal use, or may consist of immersing the one of the ends of the detection system so that the analyte comes into contact with the second support, this contacting mode being suitable for a system suitable for vertical use.
Il s'entend que le système de détection devant être utilisé dans le cadre du procédé susmentionné doit être apte à détecter le ou les composés chimiques, dont on veut déterminer l'absence ou la présence. It is understood that the detection system to be used in the context of the aforementioned method must be capable of detecting the chemical compound or compounds, the absence or presence of which is to be determined.
Entre l'étape de mise en contact et l'étape de déduction, il peut être prévu un temps d'attente pour que, le cas échéant, la migration du ou des composés chimiques à détecter puisse avoir lieu et le ou les signaux (tels que des virages chromatiques) puissent également avoir lieu. Between the contacting step and the deduction step, a waiting time may be provided so that, where appropriate, the migration of the chemical compound(s) to be detected can take place and the signal(s) (such color shifts) may also occur.
Concernant l'étape de déduction, lorsque les indicateurs de détection sont des indicateurs colorés, l'opérateur pourra se baser sur une échelle colorimétrique associée au système de détection, qui définira, pour tous les composés chimiques susceptibles d'être détectés par le système, le virage chromatique correspondant, cette échelle colorimétrique pouvant être déterminée, par des essais préalables, pour chacun des systèmes et les composés chimiques destinés à être détectés par lesdits systèmes. La déduction pourra se faire à l'œil nu ou, si nécessaire, via des moyens opto-électroniques. Concerning the deduction step, when the detection indicators are colored indicators, the operator can base himself on a colorimetric scale associated with the detection system, which will define, for all the chemical compounds capable of being detected by the system, the corresponding chromatic shift, this colorimetric scale being able to be determined, by preliminary tests, for each of the systems and the chemical compounds intended to be detected by said systems. The deduction can be made with the naked eye or, if necessary, via opto-electronic means.
Les composés susceptibles d'être détectés par le procédé de l'invention peuvent être des composés chimiques toxiques, tels que les composés toxiques de guerre et, en particulier, les composés organophosphorés ; les composés toxiques industriels chimiques (connus sous la dénomination TIC) ; les vésicants ; les pesticides et les composés arséniés. The compounds capable of being detected by the method of the invention can be toxic chemical compounds, such as toxic warfare compounds and, in particular, organophosphorus compounds; toxic industrial chemical compounds (known as TIC); vesicants; pesticides and arsenic compounds.
L'invention a enfin également trait à un kit de détection colorimétrique utilisable pour la détection d'un ou plusieurs composés chimiques comprenant les éléments suivants : Finally, the invention also relates to a colorimetric detection kit which can be used for the detection of one or more chemical compounds comprising the following elements:
-un système de détection conforme à l'invention et tel que défini ci-dessus et dans lequel les indicateurs de détection sont des indicateurs colorés ; et a detection system in accordance with the invention and as defined above and in which the detection indicators are colored indicators; And
-une échelle colorimétrique permettant de faire la correspondance entre le virage chromatique observé et le ou les composés chimiques détectés. -a colorimetric scale making it possible to make the correspondence between the chromatic shift observed and the chemical compound(s) detected.
L'échelle colorimétrique peut être située au niveau du premier support, par exemple, de part et d'autres des zones distinctes avec au niveau de chaque zone distincte, par exemple, à gauche, la couleur initiale de l'indicateur coloré et à droite, la ou les couleurs possibles pour l'indicateur coloré. The colorimetric scale can be located at the level of the first support, for example, on either side of distinct zones with at the level of each distinct zone, for example, on the left, the initial color of the colored indicator and on the right , the possible color(s) for the colored indicator.
D'autres caractéristiques et avantages de l'invention apparaîtront mieux à la lecture du complément de description qui suit, lequel se rapporte à un exemple de préparation d'un système de détection conforme à l'invention. Bien entendu, l'exemple qui suit n'est donné qu'à titre d'illustration de l'objet de l'invention et ne constitue en aucun cas une limitation de cet objet. Other characteristics and advantages of the invention will appear better on reading the additional description which follows, which relates to an example of preparation of a detection system in accordance with the invention. Of course, the following example is given only by way of illustration of the object of the invention and in no way constitutes a limitation of this object.
BRÈVE DESCRIPTION DES DESSINS BRIEF DESCRIPTION OF DRAWINGS
La figure 1, déjà commentée, illustre schématiquement, un exemple de système de détection adapté à une utilisation verticale. FIG. 1, already commented upon, schematically illustrates an example of a detection system suitable for vertical use.
La figure 2, déjà commentée, illustre schématiquement, un exemple de système de détection adapté à une utilisation horizontale. Figure 2, already commented on, schematically illustrates an example of a detection system suitable for horizontal use.
La figure 3, déjà commentée, illustre schématiquement, un autre exemple de système de détection adapté à une utilisation horizontale. Figure 3, already commented on, schematically illustrates another example of a detection system suitable for horizontal use.
EXPOSÉ DÉTAILLÉ DE MODES DE RÉALISATION PARTICULIERS DETAILED DISCUSSION OF PARTICULAR EMBODIMENTS
EXEMPLE EXAMPLE
L'exemple ci-dessous illustre la mise en œuvre des systèmes de détection colorimétrique conformes à l'invention, ces systèmes de détection étant conformes à ce qui est déjà décrit ci-dessus pour la figure 3 avec les éléments suivants : The example below illustrates the implementation of the colorimetric detection systems in accordance with the invention, these detection systems being in accordance with what is already described above for FIG. 3 with the following elements:
-le premier support 65 se présentant sous forme d'une bandelette comportant 4 zones distinctes rectangulaires (respectivement 67, 69, 71, et 73) comportant chacune un indicateur coloré distinct (Vert de bromocrésol ; 2,4-h/s[p-(diméthylamino)styryl]quinoléine ; Disperse Black 9 et Disperse Yellow 7) et comportant à une extrémité 75 une zone évidée 77 ; the first support 65 being in the form of a strip comprising 4 distinct rectangular zones (respectively 67, 69, 71, and 73) each comprising a distinct colored indicator (bromocresol green; 2.4-h/s[p- (dimethylamino)styryl]quinoline; Disperse Black 9 and Disperse Yellow 7) and comprising at one end 75 a recessed zone 77;
-le deuxième support 79 se présentant sous forme d'une bandelette de dimensions similaires à la bandelette du premier support, laquelle bandelette, le contact avec l'analyte s'effectuant par le biais de la zone évidée 77 du premier support, qui est en regard du deuxième support, lequel analyte progressant ensuite dans la direction de la flèche par capillarité ; -une couche transparente 81 se présentant sous forme d'une bandelette de dimensions similaires à celle du premier support et du deuxième support mais n'allant pas jusqu'à la zone évidée de dépôt ; the second support 79 being in the form of a strip of dimensions similar to the strip of the first support, which strip, the contact with the analyte taking place through the recessed zone 77 of the first support, which is gaze of the second support, which analyte then progresses in the direction of the arrow by capillarity; a transparent layer 81 in the form of a strip of dimensions similar to those of the first support and of the second support but not going as far as the recessed deposition zone;
-une couche étanche 83 se présentant sous forme d'une bandelette de dimensions similaires à celle du premier support, du deuxième support. -a sealed layer 83 in the form of a strip of similar dimensions to that of the first support, of the second support.
Ces systèmes de détection sont préparés de la manière suivante : -une opération de dessin des trois couches (premier support, deuxième support, couche étanche) ; These detection systems are prepared as follows: an operation of drawing the three layers (first support, second support, sealed layer);
-une opération d'impression de ces trois couches sur un papier filtre (420*520 mm, épaisseur de 0,16 mm, masse surfacique de 65 g/m2, porosité de 7-10 pm, Référence de produit : VWR 115-2319) à l'aide d'une imprimante Xerox (ColorCube 8580) ; - a printing operation of these three layers on a filter paper (420*520 mm, thickness of 0.16 mm, basis weight of 65 g/m 2 , porosity of 7-10 μm, Product reference: VWR 115- 2319) using a Xerox printer (ColorCube 8580);
-une opération de création du cloisonnement par migration de l'encre de la cire imprimée en surface par l'imprimante dans les porosités du papier filtre lors d'un chauffage maîtrisé sur plaque chauffante ; an operation for creating the partitioning by migration of the ink from the wax printed on the surface by the printer into the porosities of the filter paper during controlled heating on a hot plate;
-une opération de dépôt à la pipette des 4 solutions d'indicateurs colorés dans les zones dédiées (respectivement, zones 67, 69, 71, et 73) sur la couche faisant office de premier support) ; an operation of deposition with a pipette of the 4 solutions of colored indicators in the dedicated zones (respectively, zones 67, 69, 71, and 73) on the layer acting as the first support);
-une opération d'encollage de la couche étanche uniquement sur la bords de la face où est destinée à être déposée la couche faisant office de deuxième support, la partie centrale de la couche étanche étant protégée pour ne pas être encollée et éviter que la colle utilisée (la colle spray 3M) ne soit en contact avec la zone de migration du deuxième support et engendre un virage chromogénique non désiré des indicateurs colorés présents sur le premier support ; -an operation of gluing the waterproof layer only on the edges of the face where the layer acting as a second support is intended to be deposited, the central part of the waterproof layer being protected so as not to be glued and to prevent the glue used (the 3M spray adhesive) is in contact with the migration zone of the second support and generates an undesired chromogenic change of the colored indicators present on the first support;
-une opération d'encollage de la couche faisant office de deuxième support au niveau des zones recouvertes préalablement de cire en excluant la zone centrale dite de migration, la colle étant déposée sur la face destinée à être en contact avec le premier support ; -an operation of gluing the layer acting as a second support at the level of the zones previously covered with wax in excluding the so-called central migration zone, the glue being deposited on the face intended to be in contact with the first support;
-une opération de dépôt sur le deuxième support de la couche faisant office de premier support et sur laquelle les indicateurs colorés ont été préalablement déposés ; -an operation of depositing on the second support the layer acting as the first support and on which the colored indicators have been previously deposited;
-une opération de dépôt de la couche transparente sous forme d'un film très collant (High Tack PE/barrier/PEN de chez Oike). -an operation of depositing the transparent layer in the form of a very sticky film (High Tack PE/barrier/PEN from Oike).
Quatre systèmes de détection de ce type sont préparés et sur lesquels sont déposés respectivement 5 pL de Sarin (dit GB, CAS n°107-44-8), 5 pL de VX (CAS N°50782-69-9), 5 pL d'ypérite soufrée (dite HD, CAS n°505-60-2) et 5 pL de léwisite (dite Ll, CAS n°541-25-3). Four detection systems of this type are prepared and on which are deposited respectively 5 pL of Sarin (known as GB, CAS No. 107-44-8), 5 pL of VX (CAS No. 50782-69-9), 5 pL of sulfur mustard (known as HD, CAS No. 505-60-2) and 5 μl of lewisite (known as Ll, CAS No. 541-25-3).
Il ressort que les indicateurs colorés virent différemment pour ces substances, le virage étant différent pour le Sarin, le VX, l'ypérite soufrée ou la léwisite Ll, avec toutefois une réponse similaire pour les deux vésicants, l'ypérite soufrée et la léwisite Ll. Les systèmes de détection conformes à cet exemple pourraient donc servir pour la discrimination entre le Sarin, le VX et les deux vésicants (l'ypérite soufrée et la léwisite Ll). It appears that the colored indicators turn differently for these substances, the turn being different for Sarin, VX, sulfur mustard or lewisite Ll, with however a similar response for the two vesicants, sulfur mustard and lewisite Ll . The detection systems in accordance with this example could therefore be used to discriminate between Sarin, VX and the two vesicants (sulfur mustard gas and lewisite L1).

Claims

REVENDICATIONS
1. Système de détection utilisable pour la détection d'un ou plusieurs composés chimiques comprenant : 1. Detection system usable for the detection of one or more chemical compounds comprising:
-un premier support imprégné par des indicateurs de détection distincts aptes à détecter la présence dudit composé chimique ou desdits composés chimiques, caractérisé en ce que chacun desdits indicateurs de détection est réparti sur le support sous forme d'une ou plusieurs zones distinctes, la ou lesdites zones distinctes de chacun desdits indicateurs de détection étant disposée(s) sur le support sans recoupement avec la ou les zones distinctes du ou des autres indicateurs de détection ; et -a first support impregnated with separate detection indicators capable of detecting the presence of said chemical compound or said chemical compounds, characterized in that each of said detection indicators is distributed on the support in the form of one or more separate zones, the or said distinct areas of each of said detection indicators being arranged on the support without overlapping with the distinct area(s) of the other detection indicator(s); And
-un deuxième support destiné au dépôt du milieu, dont on veut déterminer la présence ou l'absence dudit ou desdits composés chimiques, ce deuxième support étant en contact avec l'une des faces du premier support. a second support intended for depositing the medium, the presence or absence of said chemical compound(s) of which it is desired to determine, this second support being in contact with one of the faces of the first support.
2. Système de détection selon la revendication 1, dans lequel la ou lesdites zones distinctes se présente(nt) sous des formes sensiblement circulaires, rectangulaires ou carrées. 2. Detection system according to claim 1, wherein said distinct zone(s) is/are in substantially circular, rectangular or square shapes.
3. Système de détection selon la revendication 1 ou 2, dans lequel le premier support est un support poreux. 3. Detection system according to claim 1 or 2, wherein the first support is a porous support.
4. Système de détection selon l'une quelconque des revendications précédentes, dans lequel le premier support est un support en papier. 4. Detection system according to any one of the preceding claims, in which the first support is a paper support.
5. Système de détection selon l'une quelconque des revendications précédentes, dans lequel les zones distinctes sont cloisonnées en obstruant la porosité du premier support au niveau des zones qui ne sont pas les zones distinctes. 5. Detection system according to any one of the preceding claims, in which the distinct zones are partitioned by obstructing the porosity of the first support at the level of the zones which are not the distinct zones.
6. Système de détection selon l'une quelconque des revendications précédentes, dans lequel le premier support se présente sous forme d'une bandelette. 6. Detection system according to any one of the preceding claims, in which the first support is in the form of a strip.
7. Système de détection selon l'une quelconque des revendications précédentes, dans lequel le premier support comprend à l'une de ses extrémités, une zone évidée donnant ainsi accès directement au deuxième support. 7. Detection system according to any one of the preceding claims, wherein the first support comprises at one of its ends, a recessed area thus giving direct access to the second support.
8. Système de détection selon l'une quelconque des revendications précédentes, dans lequel le deuxième support est en un matériau comprenant un enchevêtrement de fibres choisies parmi les fibres de celluloses, les fibres de verres, les fibres polymériques synthétiques et les mélanges de celles- ci. 8. Detection system according to any one of the preceding claims, in which the second support is made of a material comprising an entanglement of fibers chosen from cellulose fibers, glass fibers, synthetic polymeric fibers and mixtures thereof. this.
9. Système de détection selon l'une quelconque des revendications précédentes, dans lequel le deuxième support se présente sous forme d'une bandelette. 9. Detection system according to any one of the preceding claims, in which the second support is in the form of a strip.
10. Système de détection selon l'une quelconque des revendications précédentes, dans lequel le deuxième support, lorsqu'il se présente sous forme d'une bandelette, comprend, au niveau de la face en contact avec le premier support, deux bandes latérales opposées situées sur les deux plus grands côtés de la bandelette, ces deux bandes étant des bandes étanches et ménageant un zone centrale dénuée de ces bandes et constituant un espace de circulation du milieu, dont on veut déterminer la présence ou l'absence dudit ou desdits composés chimiques. 10. Detection system according to any one of the preceding claims, in which the second support, when it is in the form of a strip, comprises, at the level of the face in contact with the first support, two opposite lateral strips located on the two longest sides of the strip, these two strips being impermeable strips and forming a central zone devoid of these strips and constituting a space for circulation of the medium, the presence or absence of said compound or compounds of which it is desired to determine chemicals.
11. Système de détection selon l'une quelconque des revendications précédentes, dans lequel le deuxième support comprend une languette émergeant de l'empilement du premier support et du deuxième support, cette languette servant de zone de dépôt de l'analyte. 11. Detection system according to any one of the preceding claims, in which the second support comprises a tab emerging from the stack of the first support and the second support, this tab serving as an analyte deposition zone.
12. Système de détection selon l'une quelconque des revendications précédentes, comprenant, en outre, une couche étanche en contact avec le deuxième support via la face opposée à celle qui est en contact avec le premier support. 12. Detection system according to any one of the preceding claims, further comprising an impermeable layer in contact with the second support via the face opposite to that which is in contact with the first support.
13. Système de détection selon l'une quelconque des revendications précédentes, comprenant, en outre, une couche transparente en contact avec le premier support via la face opposée à celle qui est en contact avec le deuxième support. 13. Detection system according to any one of the preceding claims, further comprising a transparent layer in contact with the first support via the face opposite to that which is in contact with the second support.
14. Système de détection selon l'une quelconque des revendications précédentes, dans lequel les indicateurs de détection sont des indicateurs colorés. 14. Detection system according to any one of the preceding claims, in which the detection indicators are colored indicators.
15. Procédé de préparation d'un système de détection tel que défini selon la revendication 1, comprenant, pour chacun des indicateurs de détection, une étape distincte de dépôt sur le premier support en projetant une encre comprenant l'indicateur de détection concerné. 15. A method of preparing a detection system as defined in claim 1, comprising, for each of the detection indicators, a separate step of depositing on the first support by spraying an ink comprising the detection indicator concerned.
16. Procédé de détection de la présence ou de l'absence d'un ou plusieurs composés chimiques comprenant les étapes suivantes : 16. Method for detecting the presence or absence of one or more chemical compounds comprising the following steps:
-une étape de mise en contact du ou des milieux, dont on veut détecter la présence ou l'absence du ou desdits composés chimiques, avec un système de détection tel que défini selon l'une quelconque des revendications 1 à 14 ; a step of bringing the medium(s) whose presence or absence of said chemical compound(s) is to be detected into contact with a detection system as defined according to any one of Claims 1 to 14;
-une étape de déduction, en fonction du ou des éventuels signaux de transformation de tout ou partie des indicateurs de détection, de la présence ou de l'absence du ou desdits composés. a deduction step, depending on the possible transformation signal(s) of all or part of the detection indicators, of the presence or absence of said compound(s).
17. Procédé selon la revendication 16, qui est un procédé de détection de la présence ou de l'absence d'au moins un composé chimique choisi parmi les composés chimiques toxiques ; les composés toxiques industriels chimiques ; les vésicants ; les pesticides et les composés arséniés. 17. A method according to claim 16, which is a method for detecting the presence or absence of at least one chemical compound chosen among toxic chemical compounds; chemical industrial toxic compounds; vesicants; pesticides and arsenic compounds.
18. Kit de détection colorimétrique utilisable pour la détection d'un ou plusieurs composés chimiques comprenant les éléments suivants : -un système de détection tel que défini selon l'une quelconque des revendications 1 à 14 et dans lequel les indicateurs de détection sont des indicateurs colorés ; et 18. Colorimetric detection kit usable for the detection of one or more chemical compounds comprising the following elements: a detection system as defined according to any one of claims 1 to 14 and in which the detection indicators are colored; And
-une échelle colorimétrique permettant de faire la correspondance entre le virage chromatique observé et le ou les composés chimiques détectés. -a colorimetric scale making it possible to make the correspondence between the chromatic shift observed and the chemical compound(s) detected.
PCT/FR2022/052385 2021-12-16 2022-12-15 Detection system suitable for use in the detection of chemical compounds comprising a detection strip WO2023111475A1 (en)

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