Chemically sensitive sensor comprising arylene alkenylene oligomers

Abstract

The invention concerns the use of semi-conductive coatings, based on doped π-conjugated arylene alkenylene oligomers, in the active layer of sensors, and in arrays of such sensors applicable for the analytical characterization of gases and liquids, applicable in detecting systems for chromatography as well as in the context of an “electronic nose” or “electronic tongue”.

1 . A chemically sensitive sensor for the detection of an analyte in a fluid comprising: 
 a chemically sensitive probe comprising at least one arylene alkenylene oligomer, wherein at least one response signal being determined by said oligomer; and    means for converting said response signal to a sensor response.    
     
     
         2 . The sensor as recited in  claim 1 , wherein said response signal is determined by the interaction of said oligomer with said analyte.  
     
     
         3 . The sensor as recited in  claim 1 , wherein said response signal is determined by the interaction of said oligomer with said fluid.  
     
     
         4 . A chemically sensitive sensor as recited in  claim 1 , wherein said fluid is a liquid.  
     
     
         5 . A chemically sensitive sensor as recited in  claim 1 , wherein said fluid is a gas.  
     
     
         6 . A chemically sensitive sensor as recited in  claim 1 , wherein said fluid is a vapour.  
     
     
         7 . A chemically sensitive sensor as recited in  claim 1 , wherein said probe further comprises a carrier, said probe being a coating on the carrier surface.  
     
     
         8 . A chemically sensitive sensor as recited in  claim 7 , wherein said probe forms a film, said film having a thickness being in the range of 1 nm to 0,5 mm.  
     
     
         9 . A chemically sensitive sensor as recited in  claim 1 , wherein said sensor further comprises electrodes able to put a voltage over said chemically sensitive probe.  
     
     
         10 . A chemically sensitive sensor as recited in the  claim 1 , wherein said arylene alkenylene oligomers comprise a number of aromatic and/or heteroaromatic residus, said number being in the range of 2 to 20.  
     
     
         11 . A chemically sensitive sensor as recited in  claim 10 , wherein said aromatic and/or heteroaromatic residus are chosen from the group comprising benzene, pyrrole, thiophene, naphtalene, anthracene, bithienyl, aniline and indole.  
     
     
         12 . A chemically sensitive sensor as recited in  claim 10 , wherein said aromatic and/or heteroaromatic residus are connected by one or more alkenyl segments.  
     
     
         13 . A chemically sensitive sensor as recited in  claim 10 , wherein said aromatic and/or heteroaromatic residus and/or said alkenyl segments are substituted with one or more substituents chosen from the group comprising all alkyl groups, all alkoxy groups, —CHO, —CN, —COOH 2 ,—C 6 H 5 , anthracene, naphtalene and —CH 2 X and —X with X chosen from the group comprising F, Cl, Br and I.  
     
     
         14 . A chemically sensitive sensor as recited in  claim 1 , wherein said arylene alkenylene oligomers are doped with one or several dopants, thereby changing the resistance of said oligomers.  
     
     
         15 . A chemically sensitive sensor as recited in  claim 14 , wherein the doping is oxidative or reductive.  
     
     
         16 . A chemically sensitive sensor as recited in  claim 14 , wherein the doping is chemical or electrochemical.  
     
     
         17 . A chemically sensitive sensor as recited in  claim 14 , wherein said dopant is advantageously chosen from the group comprising I 2 , AsF 5 , AlCl 3 , MoOCl 4 , MoCl 5 , NO + en NO 2   +  salts (e.g. NOBF 4 , NOPF 6 , NOSbF 6 , NOAsF 6 , NOCuCl 3 , NOCH 3 SO 3 , NO 2 BF 4 , NO 2 PF 6 , NO 2 AsF 6 , NO 2 SbF 6 , NO 2 CF 3 SO 3 ), O 2   + AsF 6   − , HClO 4 , HNO 3 , H 2 SO 4 , p-toluenesulfonicacid, benzoylperoxide, CF 3 SO 3 H, SO 3 Br 2 , (FSO 3 ) 2 , FSO 3 H, Fe(ClO 4 ) 3 , FeCl 3 , Fe(OTs) 3 , Fe(CF 3 SO 3 ) 3 , Ag salts (e.g. AgSbF 6 , AgCF 3 SO 3 , AgOTs) leading to doped oligomers with incorporated counterions of the form chosen from the group comprising I − , I 3   − , I 5   − , NO 3   − , NO 2   − , BF 4   − , AsF 5   − , PF 6   − , Cl − , Br − , SbF 6   − , MoOCl 4   − , MoCl 6   − , FeCl 4   − , FeCl 2   − , FSO 3   − , SO 3   − , C 6 H 5 CO 2   − , OTs − , AsF 6   − , Br 3   − , Br 5   − , CF 3 SO 3   − , CF 3 CO 2   − , and HSO 4   − , electrolytes giving the anionic counterions chosen from the group comprising BF 4   − , NO 3   − , NO 2   − , F − , Cl − , Br − , I − , ClO 4   − , ClO 3   − , BrO 3   − , FeCl 4   − , FeCl 2   − , CF 3 CO 2   − , MoOCl 4   − , MoCl 6   − , AlCl 4   − , KS 2   − , PF 6   − , SbF 6   − , HSO 4   −  CF 3 SO 3   − , CH 3 SO 3   − , and CH 3 CO 2   − , CH 3 C 6 H 4 SO 3   − , and electrolytes giving the cationic counterions NO + , or NO 2   + .  
     
     
         18 . A chemically sensitive sensor as recited in  claim 1 , wherein said arylene alkylene oligomers are blended with one or several polymers.  
     
     
         19 . A chemically sensitive sensor as recited in  claim 18 , wherein said polymers are chosen from the group comprising: polyacrylonitril, polyvinylchloride, polymethylmethacrylate, polyvinyl idenechloride, polyethyleneoxide, polystyrene, polycarbonate, nylon, celullose-acetate-butyrate, polypropylene, polyethylene, celullose-acetate, polyphenyleneoxide, polyisobutylene, phenylmethyl-diphenylsiloxane copolymers, polybis (cyanopropyl), siloxane, polyethyleneimine, polyethylenemaleate, fluoropolyol.  
     
     
         20 . A method of constructing the chemically sensitive sensor as recited in  claim 7 , comprising the step of coating said arylene alkylene oligomers on said carrier surface by a coating technique chosen from the group comprising: spin-coating, spray-coating, dip-coating, vacuum deposition and electro-deposition.  
     
     
         21 . Array of chemically sensitive sensors, comprising two or more chemically sensitive sensors as recited in  claim 1 .  
     
     
         22 . Electronic nose for the detection and/or identification of an analyte in gaseous phase solution, wherein it comprises an array of chemically sensitive sensors such as recited in  claim 21  and a sensor response pattern recognition system.  
     
     
         23 . Electronic tongue for the detection and/or identification of an analyte in liquid phase solution, wherein it comprises an array of chemically sensitive sensors such as recited in  claim 21  and a sensor response pattern recognition system.