Dyes undergoing changes in color and fluorescence upon binding of organic oxo compounds

1 . A dye comprising an electron donor-electron acceptor-electron donor motif, wherein the electron donor-electron acceptor-electron donor motif comprises a structure according to formula 1:

wherein, independently from each other,

R 1 =H, C n F 2n+1 , C 5 NH 4 , C 4 N 2 H 3 ,

(CH 2 ) n Q, (C 6 H 5-m )Q m or (OCH 2 CH 2 ) n Q, wherein m=1,2, 3 or 4, and Q is selected from:

H,

C(H)═CH 2 ,

OC(O)C(H)═CH 2 , OC(O)C(CH 3 )═CH 2 ,

N(H)CC(H)═CH 2 , N(H)CC(CH 3 )═CH 2 ,

Si(OH) 3 , Si(OCH 3 ) 3 , Si(OC 2 H 5 ) 3 ,

OH, SH, NH 2 , NO 2 , CN, CF 3 , C≡CH, N═N + ═N − , F, Cl, Br, I, C 2 H 3 O, C 6 H 5 ,

C(O)F, C(O)Cl, C(O)Br, C(O)I, CF 3 SO 3 ,

B(OZ) 2 , OZ, C(O)Z, C(O)OZ, C(O)NHZ, C(O)NZ 2 , and SSZ, wherein

 Z═H, C n H 2n+1 , C n F 2n+1 , C n H 2n C(H)═CH 2 , C n H 2n C≡CH,

C 6 H 4 C(H)═CH 2 , C 6 H 5 , CH 2 C 6 H 5 , C 5 NH 4 or C 4 N 2 H 3 ,

wherein n=1 to 20;

R 2 ═H, C n F 2n+1 , C 5 NH 4 , C 4 N 2 H 3 ,

(CH 2 ) n Q or (C 6 H 5-m )Q m , wherein m=1, 2, 3 or 4, and Q is selected from:

H,

C(H)═CH 2 ,

OC(O)C(H)═CH 2 , OC(O)C(CH 3 )═CH 2 ,

N(H)CC(H)═CH 2 , N(H)CC(CH 3 )═CH 2 ,

Si(OH) 3 , Si(OCH 3 ) 3 , Si(OC 2 H 5 ) 3 ,

OH, SH, NH 2 , NO 2 , CN, CF 3 , C≡CH, N═N + ═N − , F, Cl, Br, I, C 2 H 30 , C 6 H 5 ,

C(O)F, C(O)Cl, C(O)Br, C(O)I, CF 3 SO 3 ,

B(OZ) 2 , OZ, C(O)Z, C(O)OZ, C(O)NHZ, C(O)NZ 2 , and SSZ, wherein

 Z═H, C n H 2n+1 , C n F 2n+1 , C n H 2n C(H)═CH 2 , C n H 2n C≡CH,

 C 6 H 4 C(H)═CH 2 , C 6 H 5 , CH 2 C 6 H 5 , C 5 NH 4 or C 4 N 2 H 3 ,

wherein n=1 to 20;

R 3 ═H, C n F 2n+1 , C 5 NH 4 , C 4 N 2 H 3 , C(O)C 6 H 5 , C(S)C 6 H 5 ,

(CH 2 ) n Q or (C 6 H 5-m )Q m , wherein m=1, 2, 3 or 4, and Q is selected from:

H,

C(H)═CH 2 ,

OC(O)C(H)═CH 2 , OC(O)C(CH 3 )═CH 2 ,

N(H)CC(H)═CH 2 , N(H)CC(CH 3 )═CH 2 ,

Si(OH) 3 , Si(OCH 3 ) 3 , Si(OC 2 H 5 ) 3 ,

OH, SH, NH 2 , NO 2 , CN, CF 3 , C≡CH, N═N + ═N − , F, Cl, Br, I, C 2 H 3 O, C 6 H 5 ,

C(O)F, C(O)Cl, C(O)Br, C(O)I, CF 3 SO 3 ,

B(OZ) 2 , OZ, C(O)Z, C(O)OZ, C(O)NHZ, C(O)NZ 2 , and SSZ, wherein

 Z═H, C n H 2n+1 , C n F 2n+1 , C n H 2n C(H)═CH 2 , C n H 2n C≡CH,

 C 6 H 4 C(H)═CH 2 , C 6 H 5 , CH 2 C 6 H 5 , C 5 NH 4 or C 4 N 2 H 3 ,

wherein n=1 to 20;

X 1 ═N, C(CN), C(COOEt) or C(NO 2 );

X 2 =C(CH 3 ) 2 , Si (CH 3 ) 2 , O, S, Se or Te; and

X 3 =O, S, NH or NH 2 + X − , wherein X − is selected from:

F − , Cl − , Br − , I − , NO 3 − , PF 6 − , ClO 4 , BF 4 − , B 4 − , B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 − , B(C 6 H 5 ) 4 − , Al[OC(CF 3 ) 3 ] 4 − , H 2 BO 3 − , BrO 3 − , HCO 3 − , H 2 NCO 2 − , C 6 H 5 CO 2 − , C 6 H 5 CH 2 − , and RCOO − , wherein R=saturated alkyl or unsaturated alkyl or aryl.

2 . The dye according to claim 1 , wherein the donor-acceptor-donor motif is selected according to:

formula (1), comprising a polymerizable monomer when R 1 is (CH 2 ) n Q, (C 6 H 5-m )Q m or (OCH 2 CH 2 ) n Q with m=1, 2, 3 or 4, and wherein Q is selected from: C(H)═CH 2 , OC(O)C(H)═CH 2 , OC(O)C(CH 3 )═CH 2 , N(H)CC(H)═CH 2 , N(H)CC(CH 3 )═CH 2 and C 2 H 3 O, wherein n=1 to 20;

or,

formula (1), comprising a polymerizable monomer when R 3 is (CH 2 ) n Q or (C 6 H 5-m )Q m with m=1, 2, 3 or 4, and wherein Q is selected from: C(H)═CH 2 , OC(O)C(H)═CH 2 , OC(O)C(CH 3 )═CH 2 , N(H)CC(H)═CH 2 , N(H)CC(CH 3 )═CH 2 and C 2 H 3 O, wherein n=1 to 20.

3 . The dye according to claim 1 , wherein the donor-acceptor-donor motif is selected according to:

formula (1), comprising a polymerizable crosslinker when both substituents R 1 and R 2 or R 1 and R 3 are (CH 2 ) n Q or (C 6 H 5-m )Q m with m=1, 2, 3 or 4, and wherein Q is selected from: C(H)═CH 2 , OC(O)C(H)═CH 2 , OC(O)C(CH 3 )═CH 2 , N(H)CC(H)═CH 2 , N(H)CC(CH 3 )═CH 2 and C 2 H 3 O, wherein n=1 to 20.

4 . The dye according to claim 1 , wherein the donor-acceptor-donor motif is selected according to:

formula (1), comprising a silane derivative when one of the substituents R 1 or R 3 or R 1 and R 3 is or are (CH 2 ) n Q or (C 6 H 5-m )Q m , wherein m=1, 2, 3 or 4, and Q is selected from: Si(OH) 3 , Si(OCH 3 ) 3 or Si(OC 2 H 5 ) 3 wherein n=1 to 20.

5 . The dye according to claim 1 , wherein

R 1 =CH 3 , CH 2 CH 2 OH, CH 2 CH 2 OC(O)C(H)═CH 2 or CH 2 CH 2 OC(O)C(CH 3 )═CH 2 ;

R 2 =H, CH 3 or C 2 H 5 ;

R 3 =C 6 H 4 NO 2 , C(O)C 6 H 5 , CH 2 CH 2 OC(O)C(H)═CH 2 or CH 2 CH 2 OC(O)C(CH 3 )═CH 2 ;

X 2 =O;

X 3 =S, NH, NH 2 + X − , wherein X − is selected from: Cl − and PF 6 − , resulting, accordingly, in [~NH 2 + /Cl − ] or [~NH 2 + /PF 6 − ], respectively.

6 . A molecular probe for detection of an analyte comprising an organic oxo compound, an organic oxo acid and/or an anion thereof,

wherein the molecular probe comprises a dye according to claim 1 ,

wherein the molecular probe is able to indicate the presence of the analyte by changing a fluorescence property selected from: a fluorescence intensity, a Stokes shift of a fluorescence, a fluorescence lifetime, and/or a fluorescence yield.

7 . The molecular probe according to claim 6 , wherein the analyte is selected from:

a perfluoroalkyl acid (PFAA) or perfluoroalkyl carboxylic acid (PFCA), a perfluoroalkyl sulfonic acid (PFSA), a perfluoroalkyl phosphonic acid (PFPA), a perfluoroalkyl phosphinic acid (PFPiA), a N-Alkyl perfluoroalkane sulphonamido acetic acid (FASAA), a perfluoroether sulphonic acid (PFESA), a perfluoroether carboxylic acid (PFECA), a fluorotelomer sulphonic acid (FTSA), a fluorotelomer carboxylic acid (FRCA), a fluorotelomer unsaturated carboxylic acid (FTUCA); a herbicide or its degradation product selected from: a glyphosate analyte selected from Glyphosate (GPS); Methylphosphonic acid (MPA); Aminomethylphosphonic acid (AMPA), 3-Methylphosphinicopropionic acid (MPPA), and Butylphosphonic acid (BPA);

an auxin mimic selected from: dicamba, MCPA, 2,4-D, aminopyralid, tridopyr, 2,4-DP, MCPB, 2,4-DB, quinclorac, naptalam, MCPP/CMPP, clopyralid, picloram and diflufenzopyr and their alkali, alkaline earth, transition, post-transition and metalloid metal salts; enoxacine, ampicillin, amoxicillin, sialic acid, ciprofloxacin, cetirizine, atorvastatin, flurbiprofen, ragaglitazar, γ-aminobutyric acid, (S)glutamic acid, ibotenic acid, thioibotenic acid, baclofen, phaclofen, saclofen, oseltamivir active principle, lovastatin active principle, losartan active principle, clopidogrel active principle and their alkali, alkaline earth, transition, post-transition and metalloid metal salts.

8 . An analyte-sensitive layer for detection of an organic oxo compound, an organic oxo acid and/or an anion thereof,

wherein the analyte-sensitive layer comprises a dye according to claim 1 ,

wherein the dye is adsorbed at, covalently bound to and/or sterically entrapped within a matrix,

wherein the matrix comprises a glass, a semiconductor, a ceramic, or a polymer.

9 . The analyte-sensitive layer according to claim 8 , wherein the matrix is a polymer and the polymer is a molecularly imprinted polymer.

10 . The analyte-sensitive layer according to claim 9 , wherein the molecularly imprinted polymer is disposed on a solid substrate selected from: a polymer, a silica, or a polymer core/silica shell particle.

11 . A sensor arrangement for detection of an analyte in a liquid sample, the liquid sample comprising an organic oxo compound, an organic oxo acid and/or an anion thereof,

wherein the sensor arrangement comprises an analyte-sensitive layer according to claim 8 .

12 . The sensor arrangement according to claim 11 , further comprising:

a light source, adapted for emitting light in a wavelength range from 400-500 nm;

a measuring device for detecting and/or quantifying a fluorescence light in a wavelength range from 500-700 nm and outputting an output signal; and

a control and processing unit (CPU) adapted to calculate an amount of the analyte corresponding to the output signal and/or to quantitatively evaluate a concentration of the analyte in the sample.

13 . A molecularly imprinted polymer for detection of an analyte comprising an organic oxo compound, an organic oxo acid and/or an anion thereof, wherein the molecularly imprinted polymer comprises a dye according to claim 1 .

14 . A method of a quantitative or qualitative detection of an analyte selected from an organic oxo compound, an organic oxo acid or an anion thereof in a liquid sample or in an organic extract of the liquid sample,

wherein the sample presumably contains the analyte,

wherein the detection is based on an optical measurement of a fluorescence property of a dye according to claim 1 , the method comprising the steps:

providing the sample,

contacting the dye with the sample,

exposing the sample to an excitation light,

measuring a fluorescence property of the sample selected from the list consisting of: a fluorescence intensity at an emission wavelength peak, a shift or change of a fluorescence related peak, and

detecting the analyte quantitatively or qualitatively.