METHOD AND SENSOR FOR DETECTION OF TRIACETONE TRIPEROXIDE (TATP), DIACETONE DIPEROXIDE (DADP), HEXAMETHYLENE TRIPEROXIDE DIAMINE (HMTD) AND HYDROGEN PEROXIDE

Abstract

A sensor is suggested, comprising a substrate and a first mixed layer arranged on the substrate, the first mixed layer comprising: a molecular probe; a sulfonic acid; and a hydrophilic compound; wherein the molecular probe is selected from: a triarylamine; a biphenyl diamine, a benzene diamine, a diaryl benzamide, and/or a triarylborane.

Claims

1-42. (canceled).

43. A sensor comprising a substrate and a first mixed layer arranged on the substrate, the first mixed layer comprising: a molecular probe; a sulfonic acid; and a hydrophilic compound; wherein the molecular probe is selected from: a triarylamine; a biphenyl diamine, a benzene diamine, a diaryl benzamide, and/or a triarylborane.

44. The sensor according to claim 43, wherein the sulfonic acid/sulfonamide is selected from a substance according to structure (1), (2), (3), (4) and (5): ##STR00025## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are independently from each other =H, Me, Et, alkyl, vinyl, Ph, aryl, I, IO, IOH, IO.sub.2, I(OH).sub.2, I(OH)OTs, I(OH)SO.sub.3(aryl), I(OH)Ph, I(OH)aryl, I(aryl).sub.2, I(OAc).sub.2, IO.sub.3, I(OH).sub.3, CH.sub.2I, Br, Cl, F, NO.sub.2, NH.sub.2, CH.sub.2OH, OH, CF.sub.3, CN, CO.sub.2H, PO.sub.3H.sub.2, OMe, O(alkyl), OPh, O(aryl) or SO.sub.3R.sup.6; R.sup.6=H, Na, K, Me, Et, alkyl, vinyl, aryl, tetrabutylammonium, tetraoctylammonium, tetraalkylammonium, and n>8, particularly n=8-500 or 100-500; preferably n=150-400; R.sup.7=H, Me, Et, alkyl, vinyl, I, CH.sub.2I, Br, Cl, F, NO.sub.2, NH.sub.2, NHMe, NHEt, NMe.sub.2, NEt.sub.2, NH(alkyl), N(alkyl).sub.2, NHPh, NPh.sub.2, NH(aryl), CH.sub.2OH, OH, CF.sub.3, CN, CO.sub.2H, OMe, SO.sub.3H; and R.sup.8=H, Me, Et, alkyl, Ph, aryl or any combination thereof, or wherein the sulfonic acid is selected from a perfluorosulfonic acid and/or any salt thereof, particularly a sodium or a potassium salt, wherein the perfluorosulfonic acid is selected from a substance according to structure (6) and (7): ##STR00026## with R.sup.6=H, Na, K, tetrabutylammonium, tetraoctylammonium, tetraalkylammonium, n≥8, x=y=50-150, especially 75-125, and z=0, 1, 2, 3; wherein substances according to structure (7) are known as Nafion™, Hyflon™ Aquivion™, and/or 3M™-ionomer; or wherein the sulfonic acid is the naphthalenedisulfonic acid/naphthalenedisulfonamide according to structure (4) or (5) or an ester thereof, or an amide thereof or a salt thereof, wherein the cation of the salt is selected from: sodium, potassium, ammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium and/or tetraoctylammonium, wherein R.sup.7=H, Me, Et, alkyl, vinyl, I, CH.sub.2I, Br, Cl, F, NO.sub.2, NH.sub.2, NHMe, NHEt, NMe.sub.2, NEt.sub.2, NH(alkyl), N(alkyl).sub.2, NHPh, NPh.sub.2, NH(aryl), CH.sub.2OH, OH, CF.sub.3, CN, CO.sub.2H, OMe, SO.sub.3H; R.sup.8=H, Me, Et, alkyl, Ph, aryl or any combination thereof; or wherein the sulfonic acid is selected from a substance according to structure (1) and: R.sup.1 and/or R.sup.5=H, I, Br, Cl, F, Me, OMe, NO.sub.2 or CN; R.sup.2 and/or R.sup.4=H, I, Br, Cl, F, Me, OMe, NO.sub.2 or CN; and R.sup.3=H, I, Br, F, Cl, Me, NO.sub.2 or CN; independently from each other; preferably R.sup.1 and/or R.sup.5=H or I; R.sup.2 and/or R.sup.4=H or I; and R.sup.3=H or I; independently from each other.

45. The sensor according to claim 43, wherein the hydrophilic compound comprises a hydrophilic polymer selected from: a block copolymer comprising at least a hydrophilic block, a hydrophilic polyurethane, and an aliphatic polyether-based polyurethane; wherein the block copolymer comprising at least a hydrophilic block is a nonionic triblock copolymer comprising units of poly(propylene oxide) and poly(ethylene oxide); and wherein the hydrophilic polyurethane is selected from: ether-based hydrophilic polyurethanes, e.g. Hydromed™-D1, Hydromed™-D2, Hydromed™-D3, Hydromed™-D4, Hydromed™-D6, Hydromed™-D640, Hydromed™-D7, and HydroSlip C; a hydrophilic thermoplastic polyurethane elastomer, e.g. HydroThane™, Nanosan®; and aliphatic polyether-based thermoplastic polyurethanes, e.g. Tecoflex™ and Tecophilic™.

46. The sensor according to claim 43, wherein the hydrophilic compound comprises: a poly(ethylene glycol), a poly(ethylene glycol) diacrylate, a poly(ethylene glycol) dialkyl ether, a poly(ethylene glycol) dimethacrylate, a poly(ethylene glycol) dimethyl ether, a poly(ethylene glycol) methyl ether, a polyvinyl alcohol, a polyvinyl pyrrolidone, and/or a poly(diallyldimethylammonium chloride), each having a molecular weight M.sub.a≤35.000; and/or a (co)-polymer of at least two of them, the (co)-polymer having a molecular weight M.sub.n≤35.000; and/or a mixture of one of the above with either a porous material or a solid foam, the porous material and the solid foam being selected from: a fumed silica, a mesoporous silica, and a polyHIPE.

47. The sensor according to claims 43, wherein the substrate is selected from: a glass, a metal, a polymer, a mineral, a ceramic, or a composite comprising at least one of them; wherein the polymer comprises a cyclic olefin polymer (COP), a cyclic olefin copolymer (COC), a polyethylene (PE), a polypropylene (PP), a polyvinyl chloride (PVC), a polystyrene (PS), a polytetrafluoroethylene (PTFE), a polymethylmethacrylate (PMMA), a polyacrylonitrile (PAN), a polyamide, an aramide i.e. aromatic polyamide, a polyetherketone (PEK), a polycarbonate (PC), a polyethylene terephthalate (PET), preferably a cyclic olefin polymer, a cyclic olefin copolymer and/or a polycarbonate; wherein the substrate in a wavelength range between 300 nm and at least 800 nm has a transparency of at least 50%.

48. The sensor according to claim 43, further comprising an excitation light and an optical detector, wherein main optical axes of the excitation light and of the optical detector are arranged with respect to each other within an angle of less than 45°.

49. The sensor according to claim 43, wherein the molecular probe is selected from: a triarylamine; a biphenyl diamine, a benzene diamine, and/or a diaryl benzamide, and the first mixed layer comprises: a iodinated sulfonic acid and/or a mixture of a sulfonic acid with an organoiodine compound; wherein the organoiodine compound is selected from a substance according to structure (8) and (9) indicated below: ##STR00027## wherein R.sup.9, R.sup.10, R.sup.11, R.sup.12, and R.sup.13 are independently from each other =H, Me, Et, alkyl, vinyl, alkynyl, Ph, aryl, I, IO, IOH, IO.sub.2, I(OH).sub.2, I(OH)OTs, I(OH)SO.sub.3aryl, I(OH)Ph, I(OH)aryl, I(aryl).sub.2, I(OAc).sub.2, IO.sub.3, I(OH).sub.3, CH.sub.2I, Br, Cl, NO.sub.2, NH.sub.2, CH.sub.2OH, OH, CF.sub.3, CN, CO.sub.2H, PO.sub.3H.sub.2, O(alkyl), OPh, O(aryl) or OMe, and R.sup.14=alkyl, alkenyl, alkynyl; preferably R.sup.10 and/or R.sup.12=H, I; R.sup.9 and/or R.sup.13=H, I; and R.sup.11=H, I; independently from each other; wherein the sensor further comprises: a fluorescent dye, which is either homogenously distributed within the first mixed layer or which constitutes a first separate layer on top or beneath the first mixed layer, wherein the fluorescent dye comprises an absorption maximum within a range of 340-550 nm; and wherein the fluorescent dye is selected from a list comprising: a naphthalenedisulfonic acid, a salt of the naphthalenedisulfonic acid, an ester of the naphthalenedisulfonic acid, and an amide of the naphthalenedisulfonic acid; wherein the molecular probe is optionally selected from a triarylamine according to structure (10) indicated below: ##STR00028## wherein R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, and R.sup.29 are independently from each other =H, Me, Et, alkyl, I, Br, Cl, F, OH, CH.sub.2OH, Ph, aryl, vinyl, CF.sub.3, CN, NO.sub.2, NH.sub.2, NMe.sub.2, alkynyl, CO.sub.2H, CHO, ##STR00029## wherein R.sup.3 and R.sup.31 are independently from each other =H, Me, Et, alkyl, I, Br, Cl, F, OH, CH.sub.2OH, Ph, aryl, vinyl, CF.sub.3, CN, NO.sub.2, NH.sub.2, NMe.sub.2, alkynyl, CO.sub.2H, CHO, resulting—in accordance with IUPAC rules—in a biphenyl dye, e.g., in N.sup.4, N.sup.4, N.sup.4′, N.sup.4′-tetraphenylbiphenyl-4,4′-diamine dye for the molecular probe if R.sup.22 is ##STR00030## and R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 and R.sup.31 are H; and resulting—in accordance with IUPAC rules—in a diamine, e.g., in N,N,N′,N′-tetraphenyl-p-phenylenediamine if R.sup.22 is ##STR00031## and R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30 and R.sup.31 are H.

50. The sensor according to claim 43, wherein the molecular probe is selected from a substance according to structures (11) and (12) indicated below: ##STR00032## wherein R.sup.32, R.sup.33, R.sup.34, R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50 and R.sup.51 are independently from each other =H, Me, Et, alkyl, I, Br, Cl, F, OH, CH.sub.2OH, Ph, aryl, vinyl, CH.sub.2I, CF.sub.3, CN, NO.sub.2, NH.sub.2, NMe.sub.2, alkynyl, CO.sub.2H, or CHO; wherein, optionally, in structure (11) and in structure (12) the residues R.sup.32, R.sup.33, R.sup.34, R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50 and R.sup.51 are identical =H, resulting in substances (11′) and (12′) as indicated below: ##STR00033## and wherein the substance (11′) according to IUPAC may be regarded as a biphenyl diamine, particularly as N.sup.4, N.sup.4, N.sup.4′, N.sup.4′-tetraphenylbiphenyl-4,4′-diamine; and the substance (12′) according to IUPAC may be regarded as a benzene diamine, particularly N,N,N′,N′-tetraphenyl-p-phenylenediamine.

51. The sensor according to claim 43, wherein the molecular probe is selected from a diaryl benzamide and the diaryl benzamide is a substance according to structure (13) indicated below: ##STR00034## or wherein the molecular probe is selected from a triarylborane, the sensor further comprising a second separate layer adjacent to the first mixed layer, the second separate layer comprising: a sulfonic acid, or a sulfonic acid and a salt of the sulfonic acid, or a sulfonic acid and the hydrophilic compound, or a sulfonic acid, a salt of the sulfonic acid and the hydrophilic compound; wherein a cation of the salt of the sulfonic acid is selected from: a sodium, a potassium, an ammonium, a methylammonium, a dimethylammonium, a trimethylammonium, a tetramethylammonium, a tetraethylammonium, a tetrapropylammonium, tetrabutylammonium and/or tetraoctylammonium cation; and wherein the second separate layer does not overlap with the first mixed layer; and, optionally, the first mixed layer further comprising a fluorescence attenuating compound is selected from: 3,5-dinitrosalicylic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrosalicylic acid, 2,4-dinitrobenzoic acid, 2,4,6-trinitrobenzoic acid, 2,4-dinitro-6-amino-benzoic acid and their esters, in particular from a methylester, an ethylester, a phenylester and their amides, in particular from N-methylamide, N-ethylamide, N,N-dimethylamide, N,N-diethylamide, N-phenylamide, N,N-diphenylamide. and wherein, optionally, the sensor further comprises another first mixed layer adjacent to the second separate layer such as to be located downstream of a layer arrangement comprising the first mixed layer and the separate layer, if these layers are in contact with a fluid stream potentially carrying an analyte; and, optionally, the triarylborane is a substance according to structure (14): ##STR00035## wherein a bond between the residue R.sup.52 and the adjacent phenyl group is selected from: a single sigma bond as shown, a phenylene group, a double bond, and a triple bond; and R.sup.52=B(O).sub.2.sup.2−, B(OH)(O).sup.−, B(OH).sub.2, B(OH).sub.3B(OMe).sub.2, B(OEt).sub.2, B(OPr).sub.2, B(Oalkyl).sub.2, B(OPh).sub.2, B(Oaryl).sub.2 or B(OCH.sub.2CH.sub.2).sub.xOR.sup.2).sub.2 wherein R.sup.2=H, Me or alkyl with x=1, 2, 3; n, m=0, 1, 2, 3, 4; wherein n+m≥1; R.sup.53, R.sup.56, R.sup.57=H, Me, alkyl, F, Cl, Br, I, CH.sub.2OH, CH.sub.2O(alkyl), CH.sub.2NMe.sub.2, CH.sub.2N(alkyl).sub.2, CH.sub.2P(t-Bu).sub.2, CH.sub.2P(alkyl).sub.2, OMe, OiPr, O(alkyl), O(poly)ethylene oxide; R.sup.54, R.sup.55, R.sup.58=H, Me, alkyl, Ph, aryl,F, Cl, Br, I, NMe.sub.2N(alkyl).sub.2; and R.sup.59, R.sup.60=H, Me, alkyl, Ph, aryl, F, Cl, Br, I, CF.sub.3, NMe.sub.2, N(alkyl).sub.2, ##STR00036## wherein n =1, 2, 3, 4; or R.sup.52=a boronic ester, respectively a cyclic boron compound, of glycol, pinacol, 1,4-butanediol, 1,5-pentanediol, tartaric acid, 2,2-dimethyl-1,3-propanediol, a cyclic boronate of methyliminodiacetic acid (MIDA), a cyclic boronamide of brenzcatechine, 1,8-diaminonaphthalene, o-phenylenediamine, or a derivative of them; wherein n, m=0, 1, 2, 3, 4, wherein (n+m)≥1; R.sup.53, R.sup.56, R.sup.57=H, Me, alkyl, F, Cl, Br, I, CH2OH, CH.sub.2O(alkyl), CH.sub.2NMe.sub.2CH.sub.2N(alkyl).sub.2, CH.sub.2P(t-Bu).sub.2, CH.sub.2P(alkyl).sub.2, OMe, OiPr, O(alkyl), O(poly)ethylene oxide; R.sup.54, R.sup.55, R.sup.58=H, Me, alkyl, Ph, aryl, F, Cl, Br, I, NMe.sub.2, N(alkyl).sub.2; and R.sup.59, R.sup.60=H, I, Me, NMe.sub.2, N(alkyl).sub.2, NPh.sub.2, N(aryl).sub.2, ethynyl, trimethylsilylethynyl, 1-propynyl, alkynyl, phenylethynyl; wherein a triple in substance according to structure (14) and in one of the optional residues R.sup.59 and R.sup.60 is optionally replaced by one of: a double bond, a phenylene group or a simple sigma bond.

52. The sensor according to claim 43, wherein the molecular probe is selected from a triarylborane, and the triarylborane is selected among a substance according to structure (14′), (14″) and (14″′): ##STR00037## with R.sup.61=H, F, Cl, Br, I, Me, alkyl, aryl, vinyl, ethynyl, alkynyl, CF.sub.3, NMe.sub.2, NPh.sub.2, Mes.sub.2.

53. The sensor according to claim 43, wherein the molecular probe is selected from a triarylborane, wherein the triarylborane is selected from a substance according to structure (14*): ##STR00038## wherein R.sup.52=B(O).sub.2.sup.2−, B(OH)(O).sup.−, B(OH).sub.2, B(OH).sub.3, B(OMe).sub.2B(OEt).sub.2B(OPr).sub.2, B(Oalkyl).sub.2, B(OPh).sub.2, B(Oaryl).sub.2, or B(OCH.sub.2CH.sub.2).sub.nOR.sup.2).sub.2, wherein R.sup.2=H, Me, or alkyl with x=1, 2, 3; or R.sup.52=boronic ester respectively cyclic boron compounds of glycol, pinacol, 1,4-butanediol, 1,5-pentanediol, tartaric acid, 2,2-dimethyl-1,3-propanediol, a cyclic boronate of methyliminodiacetic acid (MIDA) i.e. at least one of the cyclic boronates of MIDA, a cyclic boronamide of brenzcatechine, 1,8-diaminonaphthalene, o-phenylenediamine, or derivatives thereof.

54. The sensor according to claim 43, wherein the molecular probe is selected from a triarylborane, wherein the triarylborane is a substance according to structure (15) as indicated below: ##STR00039##

55. The sensor according to claim 43, wherein the molecular probe is selected from a triarylborane, and wherein the sulfonic acid is selected from a substance according to structure (1), (2) and (3): ##STR00040## or their mixture, wherein R.sup.1, R.sup.5=H, Me, Et, Pr, alkyl, vinyl, Ph, aryl, F, Cl, Br, I, CF.sub.3, CH.sub.2OH, CO.sub.2H, PO.sub.3H.sub.2, O(alkyl), OPh, O(aryl), OH, OMe, CN, NO.sub.2, NH.sub.2, SO3H, SO.sub.3.sup.−; R.sup.2, R.sup.4=H, Me, Et, Pr, alkyl, vinyl, Ph, aryl, F, Cl, Br, I, CF.sub.3, CH.sub.2OH, CO.sub.2H, PO.sub.3H.sub.2, O(alkyl), OPh, O(aryl), OH, OMe, CN, NO.sub.2, NH.sub.2, SO.sub.3H, SO.sub.3.sup.−; R.sup.3=H, Me, Et, Pr, alkyl, vinyl, Ph, aryl, F, Cl, Br, I, CF.sub.3, CH.sub.2OH, CO.sub.2H, PO3H2, O(alkyl), OPh, O(aryl), OH, OMe, CN, NO.sub.2, NH.sub.2, SO.sub.3H, SO.sub.3.sup.−, (poly)ethylene oxide, wherein n≥8, or wherein the sulfonic acid is selected from a perfluorosulfonic acid according to structure (6) and (7), or their mixture: ##STR00041## with R.sup.6=H, Na, K; n≥8, =y=50-150, especially 75-125, and z=0, 1, 2, 3; wherein substances according to structure (7) are known as Nafion.sup.198, Hyflon™, Aquivion™, and/or 3M™-ionomer.

56. The sensor according to claim 43, wherein the sulfonic acid is selected from a substance according to structure (1), wherein, independently from each other, R.sup.1, R.sup.5=H, Me, Et, CF.sub.3, SO.sub.3H, CO.sub.2H, PO.sub.3H.sub.2, F, Cl, Br, or I; R.sup.2, R.sup.4=H, Me, Et, CF.sub.3, SO.sub.3H, CO.sub.2H, PO.sub.3H.sub.2, F, Cl, Br, or I; and R.sup.3=H, Me, Et, CF.sub.3, SO.sub.3H, CO.sub.2H, PO.sub.3H.sub.2, F, Cl, Br, or I.

57. The sensor according to claim 51, wherein the second separate layer is arranged adjacent to the first mixed layer and downstream with respect to a fluid stream, the fluid stream potentially containing the analyte, wherein the second separate layer and the first mixed layer are arranged on the same substrate.

58. The sensor according to claim 43, wherein a second mixed layer is arranged downstream of the first mixed layer with respect to an applicable fluid stream which carries the analyte.

59. A method of fabricating a sensor comprising: mixing a molecular probe, a sulfonic acid, and a hydrophilic compound; and forming a first mixed layer comprising the mixed molecular probe, the sulfonic acid, and the hydrophilic compound on a substrate; wherein the molecular probe is selected from: a triarylamine; a biphenyl diamine, a benzene diamine, a diaryl benzamide, and/or a triarylborane.

60. The method according to claim 59, wherein the hydrophilic compound and/or a mixing ratio of the molecular probe, the sulfonic acid, and the hydrophilic compound is/are selected such as to form, optionally upon drying, a free standing film; wherein the molecular probe is selected from: a triarylamine, a biphenyl diamine, a benzene diamine, and/or a diaryl benzamide, and the mixing comprises: adding a organoiodine compound if the selected sulfonic acid is not iodinated.

61. The method according to claim 59, wherein the molecular probe is selected from a triarylborane, the method further comprising: forming a second separate layer adjacent to the first mixed layer, wherein the second separate layer comprises: a sulfonic acid, or a sulfonic acid and a salt of the sulfonic acid, or a sulfonic acid and the hydrophilic compound, or a sulfonic acid, a salt of the sulfonic acid and a hydrophilic compound; wherein the salt of the sulfonic acid comprises a cation selected from: a sodium, a potassium, an ammonium, a methylammonium, a dimethylammonium, a trimethylammonium, a tetramethylammonium, a tetraethylammonium, a tetrapropylammonium, tetrabutylammonium and/or a tetraoctylammonium cation; and wherein the second separate layer does not overlap with the first mixed layer; wherein the second separate layer in the second depositing step optionally further comprises a fluorescence attenuating compound selected from: 3,5-dinitrosalicylic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrosalicylic acid, 2,4-dinitrobenzoic acid, 2,4,6-trinitrobenzoic acid, 2,4-dinitro-6-amino-benzoic acid and their esters, in particular from methylester, ethylester, phenylester and their amides, in particular from N-methylamide, N-ethylamide, N,N-dimethylamide, N,N-diethylamide, N-phenylamide, N,N-diphenylamide.

62. A method of detecting an analyte selected from: triacetone triperoxide, diacetone diperoxide, hexamethylene triperoxide diamine, and hydrogen peroxide; the method comprising: providing at least one sensor according to claim 43; directing a fluid stream comprising the vaporized or gaseous analyte on at least one layer of the sensor, wherein the fluid is preferably air or an inert gas of a temperature within a range from 15-200° C.; exposing the at least one layer to an excitation light, thus exciting a fluorescent compound which is formed within or at the at least one layer upon interaction with the analyte; detecting an intensity of a fluorescence; and detecting at least one of the analytes qualitatively and/or quantitatively by measuring an enhancement or a decline of a ratio of the intensity.

63. The method according to claim 62, wherein detecting the intensity comprises measuring an attenuation by absorption of at least a part of an excitation light and/or by absorption of at least a part of an emission light, i.e. a fluorescence within or by at least one layer of the sensor.

64. The method according to claim 62, wherein the provided sensor comprises a first mixed layer comprising: a molecular probe; a sulfonic acid; and a hydrophilic compound; wherein the molecular probe is selected from: a triarylamine; a biphenyl diamine, a benzene diamine, a diaryl benzamide, and/or a triarylborane; and a fluorescent dye which is either homogenously distributed within the first mixed layer or which constitutes a first separate layer on top or beneath the first mixed layer.

65. The method according to claim 62, wherein the sensor further comprises a second separate layer which is arranged downstream of the first mixed layer, wherein triacetone triperoxide is detected by a fluorescence attenuation at the first mixed layer and/or a fluorescence enhancement at the second separate layer.

66. A molecular probe for detecting an analyte selected from triacetone triperoxide, diacetone diperoxide, hexamethylene triperoxide diamine, and hydrogen peroxide by means of a fluorescence signal generated in response to an excitation in the wavelength range between 330-390 nm, wherein the molecular probe is a triaryl borane dye according to formula (14*): ##STR00042## wherein R.sup.52=B(O).sub.2.sup.2−, B(OH)(O).sup.−, B(OH).sub.2, B(OH).sub.3, B(OMe).sub.2, B(OEt).sub.2, B(OPr).sub.2, B(Oalkyl).sub.2, B(OPh).sub.2, B(Oaryl).sub.2, or B(OCH.sub.2CH.sub.2).sub.nOR.sup.2).sub.2, wherein R.sup.2=H, Me, or alkyl with x=1, 2, 3; or R.sup.52=boronic ester respectively cyclic boron compounds of glycol, pinacol, 1,4-butanediol, 1,5-pentanediol, tartaric acid, 2,2-dimethyl-1,3-propanediol, a cyclic boronate of methyliminodiacetic acid (MIDA) i.e. at least one of the cyclic boronates of MIDA, a cyclic boronamide of brenzcatechine, 1,8-diaminonaphthalene, o-phenylenediamine, or derivatives thereof.

67. The molecular probe according to claim 66, wherein the triarylborane is a substance according to structure (15): ##STR00043##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0193] A full and enabling disclosure of the present invention, including the best mode thereof, to one of ordinary skill in the art, is set forth more particularly in the remainder of the description, including reference to the accompanying figures.

[0194] FIGS. 1-6 and 6A-6C belong to the first aspect; FIGS. 7, 7A and 10-18 belong to the second aspect of the invention. FIGS. 8 and 9 show the combination of the first aspect and the second aspect.

[0195] FIG. 1 shows the absorption spectra of a sensor, comprising a first mixed layer with triphenylamine, 1,5-naphthalenedisulfonic acid, 4-iodobenzenesulfonic acid in HD1 after exposure to hydrogen peroxide.

[0196] FIG. 2 shows results of the fluorescence intensity measurement of sensors, comprising each a first mixed layer which were prepared according to the description of example 1. On two fluorescence indicators were applied: twice 10 μg TATP, 1 μL water and 1 μg hydrogen peroxide in 1 μL water. For the measurement of TATP 10 mg TATP were dissolved in 10 mL acetone. 10 μL of the samples were applied every 30 s on the sensor layer and were measured each after 2 min waiting time.

[0197] FIG. 3 shows results of the fluorescence intensity measurement of first mixed layers on glass which were prepared according to the description of example 2. With two fluorescence indicators were detected: twice 10 μg TATP, 1 μL water, and 1 μg hydrogen peroxide in 1 μL water. The samples were applied every 30 s on the sensor layers and were measured each after 2 min waiting time.

[0198] FIG. 4 shows results of the fluorescence intensity measurement of first mixed layers on a Teflon foil which were prepared according to the description of example 3. With two separate fluorescence indicators were detected: twice 10 μg TATP, 1 μL water, and 1 μg hydrogen peroxide in 1 μL water. The samples were applied every 30 s on the sensor layer and were measured each after 2 min waiting time.

[0199] FIG. 5 shows results of the fluorescence intensity measurement of first mixed layers on a Teflon foil which were prepared according to the description of example 4. With two separate fluorescence indicators were detected: twice 10 μg TATP, 1 μL water, and 1 μg hydrogen peroxide in 1 μL water. The samples were applied every 30 s on the respective sensor and were measured each after 2 min waiting time.

[0200] FIG. 6 shows corresponding results of the fluorescence intensity measurement of first mixed layers on a Teflon foil which were prepared according to the description of example 5. In this measurement, the metal surface of the sensor head with sensors 1 and 2 was coated with a dye in polystyrene.

[0201] FIGS. 6A-6C show the corresponding results of the fluorescence intensity measurements of first mixed layers on glass which were prepared according to the description of example 6. As apparent from FIG. 6A, signal regeneration takes some time for a high quantity of analyte (10 μg TATP), whereas return to a stable signal is much faster for clearly lower quantities of analytes (cf. FIG. 6B and FIG. 6C for TATP and HMTD in ng-range, respectively).

[0202] FIG. 7 shows a sequence of adjacent layers which is suitable to discriminate between hydrogen peroxide and the organic peroxides TATP if the analyte carrying fluid (gas/air) stream is flowing from the left to the right. The positions 1 and 3 comprise each a first mixed layer and the layer at position 2 is a second separate layer, i.e. an acidic catalyst layer. The scheme marked (A) shows the sensor chip before reaction with peroxides, the scheme marked (B) shows the chip after reaction with TATP and (C) illustrates the fluorescence picture after reaction with hydrogen peroxide. Strong fluorescence enhancement (from white to black); weak fluorescence enhancement (from white to hashed); no fluorescence enhancement (white). The (peroxide containing) fluid (e.g. airflow) is directed at first to position 1, than to position 2 and to position 3.

[0203] FIG. 7A shows a sequence of adjacent layers which is suitable to discriminate between hydrogen peroxide and the organic peroxide TATP if the analyte carrying fluid (gas) stream is flowing from left to right. The positions 1 and 2 comprise each a first mixed layer. Sensor before reaction with peroxides (D), after reaction with TATP (E) and after reaction with hydrogen peroxide (F). Strong fluorescence enhancement (from white to black); fluorescence enhancement (from white to hashed); no fluorescence enhancement (white). The (peroxide containing) airflow is directed at first to position 1 and then to position 2.

[0204] FIG. 8 shows a combination of different layers: At position 1 is a first mixed layer as described according to the first aspect and at position 2 is a first mixed layer according to the second aspect (i.e. with a triarylborane instead of a triarylamine as the molecular probe) with low acid concentration (m.sub.carrier material/m.sub.acid>1) described above, before and after contact with TATP and hydrogen peroxide. Position 1 contains the first mixed layer according to aspect 1. Position 2 contains the first mixed layer according to aspect 2. Sensor chip before reaction with peroxides (G), after reaction with TATP (H). Position 1 shows a fluorescence quenching and position 2 a fluorescence enhancement. Fluorescence enhancement (from white to black); fluorescence quenching (from black to white). The (peroxide containing) airflow is directed at first to position 1 and then to position 2.

[0205] FIG. 9 shows the reversal of the arrangement of FIG. 8, i.e. a first mixed layer combination according to the second aspect at position 1 with low acid concentration (m.sub.carrier material/m.sub.acid>>1) and a sensor/catalyst layer according to the first aspect at position 2. The sensor chip before reaction with peroxides (I), after reaction with TATP (J) and after reaction with hydrogen peroxide (K). Strong fluorescence enhancement (from white to black); fluorescence quenching (from black to white).

[0206] FIG. 10 and FIG. 11 show on two different charts measurement signals (fluorescence light intensity—FI) for different quantities of TATP (10 ng TATP—FIGS. 10 and 100 ng—FIG. 11) on Teflon as measured with a combination of two “first mixed layers” on position 1 and 3 and a “second separate layer” (i.e. a catalyst layer) on position 2 of a COC-type lab-on-chip according to FIG. 7. The analyte sensitive layers (“first mixed layers”) and the catalyst layer (“second separate layer”) are prepared according to example 7 and, respectively.

[0207] FIG. 12 shows measurement signals (fluorescence light intensity—FI) for 1 μL water and 8 ng hydrogen peroxide in 1 μL water as measured with two “first mixed layers” on position 1 and 3 and a “second separate layer” on position 2 of a COC-type lab-on-chip according to FIG. 7. The analyte sensitive layers (“first mixed layers”) and the catalyst layer (“second separate layer”) are prepared according to example 7 and 9b.

[0208] FIG. 12A shows measurement signals (fluorescence light intensity—FI) for 200 ng HMTD on Teflon as measured with two “first mixed layers” on position 1 and 3 and a “second separate layer” on position 2 of a COC-type lab-on-chip according to FIG. 7. The analyte sensitive layers (“first mixed layers”) and the catalyst layer (“second separate layer”) are prepared according to example 7 and 9b.

[0209] FIG. 13 shows measurement signals (fluorescence light intensity—FI) of 10 μg TATP and 1 μg hydrogen peroxide in 1 μL water on Teflon as measured with two “first mixed layers” on position 1 and 2 on glass according to FIG. 7A. The analyte sensitive layers (“first mixed layers”) are prepared according to example 10.

[0210] FIG. 14 shows measurement signals (fluorescence light intensity—FI) of 10 μg TATP and 1 μg hydrogen peroxide in 1 μL water as measured with two “first mixed layers” on position 1 and 3 and a “second separate layer” on position 2 on glass according to FIG. 7. The analyte sensitive layers (“first mixed layers”) and the catalyst layer (“second separate layer”) are prepared according to example 10 and 8.

[0211] FIG. 15 shows measurement signals (fluorescence light intensity—FI) of 10 μg TATP and 1 μg hydrogen peroxide in 1 μL water as measured with two “first mixed layers” on position 1 and 3 and a “second separate layer” on position 2 on glass according to FIG. 7. The analyte sensitive layers (“first mixed layers”) and the catalyst layer (“second separate layer”) are prepared according to example 11 and 9a.

[0212] FIG. 16 shows fluorescence excitation spectra of an analyte sensitive layer with a triarylborane dye according to structure (14′) with R.sup.61=Me (or according to structure (14*) with R.sup.52=B(OH).sub.2) before (dashed) and after (solid line) the presence of hydrogen peroxide in the carrier gas. The peroxide sensitive layer was prepared according to the following procedure: Solution 1=576 mg Hydromed™-D7 (referred to as HD7 hereinafter)+6404 mg ethanol+754 mg water; solution 2=7 mg 4-bromobenzenesulfonic acid monohydrate+107 mg solution 1+152 mg ethanol+17 mg water+0.7 mg the triarylborane dye according to structure (14′) with R.sup.61=Me; solution 3=28 mg solution 2+17.6 μg 3,5-dinitrosalicylic acid; 5 μL of the solution 3 is drop-coated onto the COC-substrate.

[0213] FIG. 17 shows the emission spectra of the analyte sensitive layer with a triarylborane dye according to structure (14′) with R.sup.61=Me before (dashed) and after (solid line) the presence of hydrogen peroxide in the carrier gas; background (dotted). The analyte sensitive layer (“first mixed layer”) was prepared as described above with respect to FIG. 16.

[0214] FIG. 18 shows the absorption spectra of the analyte sensitive layer (“first mixed layer”) with a triarylborane dye according to structure (14′) with R.sup.61=Me (dashed) and after (solid line) the presence of hydrogen peroxide in the carrier gas. The analyte sensitive layer was prepared as described above with respect to FIG. 16.

[0215] In the following detailed description, reference is made to the accompanying figures, which form a part hereof, and in which are shown by way of illustration specific embodiments and features of the invention. It is to be understood that other embodiments may be utilized and structural or logical changes may be made without departing from the scope of the present invention. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope of the present invention is defined by the appended claims.

DETAILED DESCRIPTION

[0216] The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0217] The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.”

[0218] As used in this specification (above and below) and claims, the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0219] As used in this specification (above and below) and claims, the word “substantially” when used with a numerical value is to be understood as encompassing a deviation from the indicated value within a range which is typical for the method or apparatus used for measuring the value. In particular, the word “substantially” indicates including a deviation from the indicated value by as much as ±5%, i.e. a range. When used with an adjective or adverb the word “substantially” is intended to enhance the scope of the particular characteristic; e.g., substantially planar is intended to mean planar, nearly planar and/or exhibiting characteristics associated with a planar element.

[0220] As used in this specification (above and below) and claims, the terms “fluorescence measurement”, “fluorescent dye”, and any related thereto term is to be understood as comprising an optical property, in particular a luminescence or its detection, e.g., an excitation wavelength, an emission wavelength, a fluorescence intensity, a fluorescence quantum yield, a fluorescence life time or decay, a fluorescence ratio, or the like and/or its detection.

[0221] The technical object of the described embodiments is to provide necessary elements of a device, the device itself, and its use, i.e. a method of analysis, for detecting minute amounts of peroxide explosives and products of their decomposition wherever they may occur: from soil samples, from wipe samples and from fluid extracts of different matrices. Therein, the detection is accomplished in fluid streams comprising gaseous or vaporized residues of the peroxide explosives. The method and device allow discriminating between residues of hydrogen peroxide and peroxidic explosives such as TATP (triacetone triperoxide), DADP (diacetone diperoxide), and HMTD (hexamethylene triperoxide diamine) Accordingly, the device and method shall allow detection of these substances in nano- and picogram quantities.

EXAMPLES

Example 1

[0222] A first mixed layer was prepared on a glass substrate by using the ether-based hydrophilic polyurethane Hydromed™-D4, designated as HD4 thereinafter, the sulfonic acid 4-iodobenzenesulfonic acid and the arylamine N,N,N′,N′-tetraphenylbenzidine according to the earlier mentioned structure (11) where R.sup.32, R.sup.33, R.sup.34, R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50 and R.sup.51=H as follows:

[0223] 1. 2 g HD4 were dissolved in 22 g EtOH and 2.5 g H.sub.2O (solution A).

[0224] 2. 3.0 mg of the arylamine were dissolved in 75 μL EtOH and 75 μL ethyl acetate (solution B).

[0225] 3. 22.3 mg 4-iodobenzenesulfonic acid was dissolved in 50 μL EtOH and 50 μL ethyl acetate (solution C).

[0226] 4. A mixture of 1 μL of solution A, 11 μL of solution B and 5 μL of solution C were put for 30 min at 60° C. in an ultrasonic bath.

[0227] 5. 0.5 μL of the resulting mixture were applied onto the chosen substrate by drop-coating. After drying under reduced pressure, the first mixed layer was stored in the dark excluding any moisture.

[0228] Other names of the mentioned substance N,N,N′,N′-tetraphenylbenzidine are: Benzidine, N,N,N′,N′-tetraphenyl-(6CI,7CI,8CI); [1,1′-Biphenyl]-4,4′-diamine, N,N,N′,N′-tetraphenyl-(9CI); N,N,N′,N′-Tetraphenyl-[1,1′-biphenyl]-4,4′-diamine; N,N,N′,N′-Tetraphenylbenzidine; N,N,N′,N′-Tetraphenylbiphenyl-4,4′-diamine

[0229] For the detection of TATP 10 μg of TATP were dissolved in 10 mL acetone. 10 μL samples of this solution were placed at intervals of 30 s on a Teflon foil each and measured after 2 min waiting time.

Example 2

[0230] Further, another first mixed layer was prepared on a glass substrate by using the ether-based hydrophilic polyurethane Hydromed™-D7, designated as HD7 thereinafter, the sulfonic acid 4-iodobenzenesulfonic acid and the arylamine N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine according to the earlier mentioned structure (11) with R.sup.32, R.sup.33, R.sup.34, R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, and R.sup.51 are identical =H; and the residues R.sup.33 and R.sup.50 are identical =Me as described below.

[0231] Particularly, the first mixed layer , i.e. the fluorescence indicator according to example 2 was prepared as follows:

[0232] 1. 2 g HD7 were dissolved in 22 g EtOH and 2.5 g H.sub.2O (solution A).

[0233] 2. 3.0 mg of the arylamine according to structure (11) mentioned above were dissolved in 75 μL EtOH and 75 μL ethyl acetate (solution B).

[0234] 3. 22.3 mg 4-iodobenzenesulfonic acid were dissolved in 50 μL EtOH and 50 μL ethyl acetate (solution C).

[0235] 4. A mixture of 1 μL of solution A, 11 μL of solution B and 5 μL of solution C were put for 30 min at 60° C. in an ultrasonic bath.

[0236] 5. 0.5 μL of the resulting mixture were applied onto the chosen substrate by drop-coating.

[0237] 6. After drying under reduced pressure, the first mixed layer was stored in the dark excluding any moisture. Detection of TATP was tested as described above.

Example 3

[0238] Further, another first mixed layer was prepared on a glass substrate by using the ether-based hydrophilic polyurethane Hydromed™-D4, designated as HD4 thereinafter, the sulfonic acids, 4-iodobenzenesulfonic acid and 1,5-naphthalenedisulfonic acid, and triphenylamine as described below:

[0239] 1. 2 g HD4 were dissolved in 22 g EtOH and 2.5 g H.sub.2O (solution A).

[0240] 2. 5.6 mg triphenylamine were dissolved in 75 μL EtOH and 75 μL ethyl acetate (solution B).

[0241] 3. 6.9 mg 1,5-naphthalenedisulfonic acid were dissolved in 50 μL EtOH and 50 μL ethyl acetate (solution C).

[0242] 4. 22.3 mg 4-iodobenzenesulfonic acid were dissolved in 50 μL EtOH and 50 μL ethyl acetate (solution D).

[0243] 5. A mixture of 2 μL solution A, 3 μL solution B, 15 μL solution C and 5 μL solution D were ultrasonicated for 30 min at 60° C.

[0244] 6. 0.5 μL of the mixture were applied to the substrate by drop-coating.

[0245] 7. After drying under reduced pressure, the sensor was stored under exclusion of light and moisture.

Example 4

[0246] Further, another first mixed layer was prepared on a glass substrate by using the ether-based hydrophilic polyurethane Hydromed™-D7, designated as HD7 thereinafter, the sulfonic acids, 4-iodobenzenesulfonic acid and 1,5-naphthalenedisulfonic acid, and triphenylamine as described below:

[0247] 1. 2 g HD7 were dissolved in 22 g EtOH and 2.5 g H.sub.2O (solution A).

[0248] 2. 5.6 mg triphenylamine were dissolved in 75 μL EtOH and 75 μL ethyl acetate (solution B).

[0249] 3. 6.9 mg 1,5-naphthalenedisulfonic acid were dissolved in 50 μL EtOH and 50 μL ethyl acetate (solution C).

[0250] 4. 22.3 mg 4-iodobenzenesulfonic acid were dissolved in 50 μL EtOH and 50 μL ethyl acetate (solution D).

[0251] 5. A mixture of 2 μL of solution A, 3 μL solution B, 15 μL solution C and 5 μL solution D were ultrasonicated for 30 min at 60° C.

[0252] 6. 0.5 μL of the mixture were applied to the substrate by drop-coating.

[0253] 7. After drying under reduced pressure, the sensor was stored under exclusion of light and moisture.

Example 5

[0254] Further, another first mixed layer was prepared on glass as substrate by using the ether-based hydrophilic polyurethane Hydromed™-D4, designated as HD4 thereinafter, the sulfonic acids, 4-iodobenzenesulfonic acid and 4-toluenesulfonic acid and triphenylamine as described below:

[0255] 1. 2 g HD4 were dissolved in 22 g EtOH and 2.5 g H.sub.2O.

[0256] 2. 8 μL HD4-solution, 5.0 mg 4-iodobenzenesulfonic acid, 5.0 mg 4-toluenesulfonic acid and 0.8 mg triphenylamine were mixed with 15 μL EtOH and 15 μL ethylene acetate and ultrasonicated for 30 min at 60° C.

[0257] 3. 0.5 μL of the resulting mixture were applied to the substrate by drop-coating.

[0258] 4. After drying under reduced pressure, the sensor was stored under exclusion of light and moisture.

Example 6

[0259] Further, another first mixed layer was prepared on glass as substrate by using the ether-based hydrophilic polyurethane Hydromed™-D7, designated as HD7 thereinafter, the sulfonic acids, 4-iodobenzenesulfonic acid and 1,5-naphthalenedisulfonic acid, triphenylamine as well as the fluorescent dye rhodamine 6G as described below:

[0260] 1. 2 g HD7 were dissolved in 22 g EtOH and 2.5 g H.sub.2O(solution A).

[0261] 2. 5.6 mg triphenylamine were dissolved in 75 μL EtOH and 75 μL ethyl acetate (solution B).

[0262] 3. 6.9 mg 1,5-naphthalenedisulfonic acid were dissolved in 50 μL EtOH and 50 μL ethyl acetate (solution C).

[0263] 4. 22.3 mg 4-iodobenzenesulfonic acid were dissolved in 50 μL EtOH and 50 μL ethyl acetate (solution D).

[0264] 5. 3.1 mg rhodamine 6G were dissolved in 2.1 mL MeOH (solution E).

[0265] 6. A mixture of 3 μL solution A, 3.4 μL solution B, 15 μL solution C, 30 μL solution D, 20 μL solution E were ultrasonicated for 30 min at 60° C.

[0266] 7. 0.3 μL of the mixture were applied to the substrate by drop-coating.

[0267] 8. After drying under reduced pressure, the sensor was stored under exclusion of light and moisture.

[0268] Corresponding graphs of the observed fluorescence intensity are shown in FIGS. 2 through 6C (corresponding to examples 1 through 6).

[0269] FIG. 2 shows the temporal fluorescence responses of the sensor of example 1. Twice 10 μg TATP were detected, exemplified by a decrease in fluorescence. Also 1 μL water shows a small modulation in fluorescence. 1 μg Hydrogen peroxide shows a drastic decrease in fluorescence. FIG. 3 shows the temporal fluorescence responses of the sensor of example 2. Again twice 10 μg TATP were measured, which induce a strong decrease in fluorescence. 1 μL water also shows a slight decrease, whereas hydrogen peroxide shows a drastic decrease in fluorescence. FIG. 4 shows the temporal fluorescence responses of the sensor of example 3. The first 10 μg TATP already induce a drastic decrease in fluorescence, whereas the second 10 μg TATP show just a slight decrease. 1 μL water shows a brief modulation, while hydrogen peroxide shows a drastic decrease. FIG. 5 shows the temporal fluorescence responses of example 4. FIG. 6 shows the temporal fluorescence responses of example 5. Twice 10 μg TATP cause both a decrease in fluorescence. 1 μL water increases the fluorescence transiently. 1 μg hydrogen peroxide decreases the fluorescence drastically. FIGS. 6A and 6B show the temporal fluorescence responses of example 6. FIG. 6B shows the fluorescence decrease on detection of 25, 50 and 100 ng TATP. FIG. 6C shows the slow, but drastic decrease of fluorescence on detection of 230 and 460 ng of HMTD.

[0270] The following examples correspond to the second aspect:

Example 7—Preparation of the Analyte Sensitive Layer According to Method 1

[0271] Solution 1=789 mg Hydromed198-D7 (referred to as HD7 hereinafter)+8781 mg ethanol+1043 mg water; solution 2=567 mg 4-bromobenzenesulfonic acid monohydrate+8683 mg solution 1+12329 mg ethanol+1374 mg water+58.5 mg the triarylborane dye according to structure (14′) with R.sup.61=Me; solution 3=11807 mg solution 2+7.3 mg 3,5-dinitrosalicylic acid; 0.25-0.5 μL of the solution 3 is drop-coated onto the substrate. Herein the ratio m.sub.carrier material/m.sub.acid was 1.13.

Example 8—Preparation of the Catalyst Layer According to Method 2

[0272] Solution 1=397 mg Hydromed™-D640 (referred to as HD640 hereinafter)+4396 mg ethanol +495 mg water; solution 2=24 mg 4-bromobenzenesulfonic acid monohydrate+56 mg solution 1. 0.25-0.5 μL of the solution 2 were applied to the substrate by drop-coating.

Example 9a—Preparation of the Catalyst Layer According to Method 3

[0273] Solution 1 =2690 mg 4-bromobenzenesulfonic acid monohydrate+1459 mg tetrabutylammonium hydroxide solution (40%) in water; suspension 1=206 mg fumed silica (0.2-0.3 μm)+504 mg solution 1+3249 mg ethanol+4117 mg water. 2-3 μL of the homogenized suspension were applied to the substrate by drop-coating. In their mixture the components of solution 1 are forming 4-bromobenzenesulfonic acid.

Example 9b—Preparation of the Catalyst Layer According to Method 4

[0274] 2-3 μL of the perfluorinated resin Nafion (5% in lower aliphatic alcohols and water, contains 15-20% water) were applied to the substrate by drop-coating. 2-3 μL of the homogenized suspension/solution were applied to the substrate by drop-coating.

Example 9—Detection of TATP With Explosive Trace

[0275] The peroxide sensor was introduced in an explosive trace detector (prototype) and connected with the analyte/sample admission (heated from 70-160° C.) and with a pump. The peroxides were directed at first to the first mixed layer on position 1 then to the acidic catalyst on position 2 and then to the first mixed layer on position 3. The positions 1 and 3 excited by LEDs at 355-365 nm and the fluorescence intensity changes of the mixed layers were detected.

[0276] Quantities of 10 ng-10 μg TATP on wipe sample material teflon were heated up with a hot carrier gas stream (air) to 50-150° C. The maximal fluorescence intensity is obtained within 6 seconds (cf. FIGS. 10 and 11, 13, 14 and 15). First mixed layers were prepared according to examples 7, 10 and 11 as described above.

[0277] The current detection limit for TATP is <10 ng, <100 ng for HMTD, and <8 ng for hydrogen peroxide. When measuring pure water (>1 μL), the analyte sensitive layers show fluorescence quenching. When measuring pure acetone (1 μL), the first mixed layers show no reaction.

Example 10—Preparation of First Mixed Layers Comprising HD6 According to Above Method 1 for Detection of Peroxides, Wherein the Ratio m.SUB.carrier material./m.SUB.acid.=2.12.

[0278] Solution 1=204 mg HD6+2254 mg ethanol+254 mg water; solution 2=6.6 mg 4-bromobenzenesulfonic acid monohydrate+186 mg solution 1; solution 3=0.1 mg of triarylborane dye according to structure (14′) with R.sup.61=Me+20 μL solution 2. Finally, 0.25-0.5 μL of the solution 3 has been drop-coated on the substrate.

Example 11—Preparation of First Mixed Layers Comprising HD7 According to Above Method 1, Wherein the Ratio m.SUB.carrier material./m.SUB.acid.=0.7.

[0279] Solution 1=194 mg HD7+2139 mg ethanol+245 mg water; solution 2=7.6 mg 4-bromobenzenesulfonic acid monohydrate+72 mg solution 1; solution 3=0.1 mg of triarylborane dye according to structure (14′) with R.sup.61=Me+20 μL solution 2. Finally, 0.25-0.5 μL of the solution 3 has been drop-coated on the substrate.

[0280] Thus, according to the first aspect the sensor (fluorescence indicator) for detecting an organic peroxide or its disintegration product comprises a first mixed layer comprising: a molecular probe selected from: triphenylamine, N,N,N′,N′-tetraphenylbenzidine, a substance according to formula (11), where R.sup.32, R.sup.33, R.sup.34, R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50 and R.sup.51=H, .sub.a substance according to formula (11) with R.sup.32, R.sup.33, R.sup.34, R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49, and R.sup.51 are identical =H and the residues R.sup.33 and R.sup.50 are identical =Me/i.e. N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine; a sulfonic acid, selected from: 4-iodobenzenesulfonic acid, 1,5-naphthalenedisulfonic acid, 4-toluenesulfonic acid, and a Nafion™; and a hydrophilic substance selected from: Hydromed™-D4, Hydromed™-D6, Hydromed™-D7, Hydromed™-D640 and/or a tetrabutylammonium, a tetraoctylammonium, or a tetraalkylammonium hydroxide or salt of the indicated sulfonic acid; wherein the first mixed layer is deposited on a substrate, selected from a glass and a COC comprising TOPAS. Instead of the non-iodinated sulfonic acid another fluorescent dye which absorbs at the emission wavelength of the reaction product formed and thus attenuates its fluorescence may be used in order to enhance detection sensitivity.

[0281] According to the second aspect the sensor (fluorescence indicator) for detecting an organic peroxide or its disintegration product comprises at least a first mixed layer containing a molecular probe selected from: a triarylborane dye according to formula (14′) with R.sup.61=Me; a sulfonic acid, selected from: 4-iodobenzenesulfonic acid and 4-bromobenzenesulfonic acid monohydrate, 1,5-naphthalenedisulfonic acid, 4-toluenesulfonic acid, and a Nafion™; a hydrophilic substance selected from: Hydromed™-D4, Hydromed™-D6, Hydromed™-D7, Hydromed™-D640 and/or a tetrabutylammonium, a tetraoctylammonium, or a tetraalkylammonium hydroxide or salt of the indicated sulfonic acid and, optionally, 3,5-dinitrosalicylic acid. Further, the sensor according to the second aspect may comprise a separate layer which acts as a catalytic layer and comprises at least a sulfonic acid, selected from: a Nafion™ and 4-bromobenzenesulfonic acid monohydrate either alone or with one of the hydrophilic substances indicated or together with a tetrabutylammonium, a tetraoctylammonium, or a tetraalkylammonium hydroxide or a a tetrabutylammonium, a tetraoctylammonium, or a tetraalkylammonium salt of the indicated sulfonic acid. If the sulfonic acid is used together with the hydroxide, a thickener such as fumed silica may be added. According to preferred embodiments, the sensor comprises a first mixed layer as indicated, a catalytic layer and yet another first mixed layer which are arranged sequentially after each other such as to allow when used a stream of hot air carrying the analyte(s) to establish fluidic contact with these layers. The layers are arranged on either glass or on a COC, e.g. TOPAS.

[0282] In typical embodiments according to both, first and second aspects, light sources and optical detectors are suitably arranged to detect at the first mixed layers a fluorescent light. In an epi-fluorescence set-up backscattered fluorescent light is detected or, optionally by using a suitable edge filter, the fluorescent light is acquired in a trans-illumination mode.

[0283] The synthesis of the molecular probe according to structure (14*) starts from 4-iodophenylboronic acid and 4-[di(nesityl)boronyl]phenylacetylene (acquired as described in J. Phys. Chem. A 2009, 113, 5585-5593) according to the following scheme.

##STR00024##

[0284] In particular, 4-iodophenylhoronic acid (45.5 mg, 0.188 mmol) and 4-{di(mesityl)boronyl}phenylacetylene (70 mg, 0.200 mmol) were solved in dry tetrahydrofuran (THF) (2 mL) and dry triethylamine (TEA) (1 mL). After adding tetrakis(triphenylphosphine)palladium(O) (Pd(Ph.sub.3).sub.4) (17.2 mg, 0.015 mmol) and copper iodide (CuI) (15.8 mg, 0.083 mmoll the mixture was vigorously stirred at room temperature for 18 hours under a argon atmosphere. When the reaction was completed, the mixture was poured on water (50 mL) containing concentrated hydrochloric acid (2 mL). The crude product was extracted with dichloromethane (3×50 mL), dried over sodium sulfate, concentrated under reduced pressure and purified by flash silica gel column chromatography (dichloromethane/methanol 5:0.1) to obtain the corresponding product as pale green solid (72.1 mg, yield: 81%). .sup.1H NMR (600 MHz, CDCl.sub.3, ppm): δ 8.24 (d, J=12Hz, 2H), 7.73 (d, J=12.6Hz, 2H), 7.56 (m, 4H), 6.86 and 6.87 (s, 4H), 2.34 and 2.35 (s, 6H), 2.04 and 2.05 (s, 12H). .sup.13C NMR (150 MHz, CDCl.sub.3, ppm): δ 146.3, 141.5, 140.8, 138.9, 136.1, 135.5, 133.2, 131.2, 131.1, 128.3, 127.4, 126.2, 91.9, 91.4, 23.4, 21.2. .sup.11B NMR (192 MHz, CDCl.sub.3, ppm): δ 27.9, 74.5.

[0285] Some aspects of the embodiments described herein can briefly be summarized as follows.

[0286] 1. simple preparation of the sensors respective of the analyte sensitive layers;

[0287] 2. reaction of peroxides with specially selected molecular probes;

[0288] 3. detection of peroxides by fluorescence amplification;

[0289] 4. selective detection of relevant peroxides;

[0290] 5. quantitative detection of these peroxides;

[0291] 6. sensitive detection of relevant peroxides;

[0292] 7. selective detection of important peroxides in a complex mixture;

[0293] 8. detection of these peroxides in air, in solution and as wipe samples, i.e. from solid surfaces;

[0294] 9. multiple measurement/simultaneous detection;

[0295] 10. internal referencing.

[0296] The present invention has been explained with reference to various illustrative embodiments and examples. These embodiments and examples are not intended to restrict the scope of the invention, which is defined by the claims and their equivalents. As is apparent to one skilled in the art, the embodiments described herein can be implemented in various ways without departing from the scope of what is invented. Various features, aspects, and functions described in the embodiments can be combined with other embodiments.