US5696157A
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US
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Sulfonated derivatives of 7-aminocoumarin
Assignee: Molecular Probes Inc
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Filing: 1996-11-15
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Granted: 1997-12-09
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Expires: 2016-11-15
Abstract
Abstract The present invention describes 7-aminocoumarin dyes that are substituted one or more times at the 3-, 6- and/or 8-positions by a sulfonic acid or a salt of a sulfonic acid, said dyes being useful as fluorescent probes or in the preparation of enzyme substrates, caged probes, or adducts with reducing sugars. The dyes of the invention optionally possess a reactive group useful for preparing fluorescent conjugates, which conjugates and methods for their preparation are described herein.
Inventors
- 👤 Hui-Ying Wang
- 👤 Wai-Yee Leung
- 👤 Fei Mao
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 04:22
CPC Classifications
C; C07; C07D; C07D405/00; C07D405/02; C07D405/12; C07D311/00; C07D311/02; C07D311/04; C07D311/06; C07D311/08; C07D311/16
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
370 words
A compound of the formula ##STR44## wherein R 5 is H; R 6 is H, methyl, halogen, or SO 3 X; R 7 is NR 1 R 2 ; wherein R 1 and R 2 are independently H, C 1 -C 18 alkyl, C 6 -C 18 aryl, C 1 -C 18 alkanoyl, C 7 -C 18 arylalkanoyl; or R 1 in combination with R 2 forms a saturated 5- or 6-membered heterocycle that is a piperidine, a morpholine, a pyrrolidine or a piperazine; or R 2 is H and R 1 is a radical formed by a removal of the hydroxyl group from the carboxylic acid of an amino acid or from the carboxylic acid of the carboxy-terminal amino acid of a linear peptide consisting of 2-6 amino acids; or R 1 is a 2-nitrobenzyloxycarbonyl of the formula ##STR45## wherein R 9 and R 10 are H, C 1 -C 6 alkoxy, or R 9 and R 10 taken in combination are --O--CH 2 --O--; and R 11 is H, CH 3 , a carboxylic acid or a biologically compatible salt of a carboxylic acid; or R 7 is a nitrogen atom that is linked by a single or double covalent bond to the anomeric carbon of a mono- or polysaccharide and formally replaces the anomeric oxygen atom of the mono- or polysaccharide; R 8 is H, halogen or SO 3 X; X is H, or a biologically compatible cation; R 3 is H, SO 3 X, halogen, CN, NO 2 , or --L--R X or --L--S C ; R 4 is H, CN, C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, CH 2 SO 3 X; or --L--R X or --L--S C ; wherein each L is a single covalent bond, or L is a covalent linkage having 1-24 nonhydrogen atoms selected from the group consisting of C, N, O and S and is composed of any combination of single, double, triple or aromatic carbon-carbon bonds, carbon-nitrogen bonds, nitrogen-nitrogen bonds, carbon-oxygen bonds and carbon-sulfur bonds; R X is a reactive group; and S C is a conjugated substance; provided that at least one of R 3 , R 6 or R 8 is SO 3 X.
Claim 2
Dependent Claim
370 words
A compound of the formula ##STR44## wherein R 5 is H; R 6 is H, methyl, halogen, or SO 3 X; R 7 is NR 1 R 2 ; wherein R 1 and R 2 are independently H, C 1 -C 18 alkyl, C 6 -C 18 aryl, C 1 -C 18 alkanoyl, C 7 -C 18 arylalkanoyl; or R 1 in combination with R 2 forms a saturated 5- or 6-membered heterocycle that is a piperidine, a morpholine, a pyrrolidine or a piperazine; or R 2 is H and R 1 is a radical formed by a removal of the hydroxyl group from the carboxylic acid of an amino acid or from the carboxylic acid of the carboxy-terminal amino acid of a linear peptide consisting of 2-6 amino acids; or R 1 is a 2-nitrobenzyloxycarbonyl of the formula ##STR45## wherein R 9 and R 10 are H, C 1 -C 6 alkoxy, or R 9 and R 10 taken in combination are --O--CH 2 --O--; and R 11 is H, CH 3 , a carboxylic acid or a biologically compatible salt of a carboxylic acid; or R 7 is a nitrogen atom that is linked by a single or double covalent bond to the anomeric carbon of a mono- or polysaccharide and formally replaces the anomeric oxygen atom of the mono- or polysaccharide; R 8 is H, halogen or SO 3 X; X is H, or a biologically compatible cation; R 3 is H, SO 3 X, halogen, CN, NO 2 , or --L--R X or --L--S C ; R 4 is H, CN, C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, CH 2 SO 3 X; or --L--R X or --L--S C ; wherein each L is a single covalent bond, or L is a covalent linkage having 1-24 nonhydrogen atoms selected from the group consisting of C, N, O and S and is composed of any combination of single, double, triple or aromatic carbon-carbon bonds, carbon-nitrogen bonds, nitrogen-nitrogen bonds, carbon-oxygen bonds and carbon-sulfur bonds; R X is a reactive group; and S C is a conjugated substance; provided that at least one of R 3 , R 6 or R 8 is SO 3 X.
Claim 3
Dependent Claim
19 words
A compound, as claimed in claim 1, wherein one of R 3 and R 4 is --L--R X .
Claim 4
Dependent Claim
74 words
A compound, as claimed in claim 2, wherein R X is an acrylamide, a carboxylic acid, an activated ester of a carboxylic acid, a hydroxy, an aldehyde, an alkyl halide, a sulfonate, an amine, an anhydride, an aniline, an aryl halide, an azide, an aziridine, a boronate, a carbodiimide, an epoxide, a glycol, a haloacetamide, a halotriazine, a hydrazine, a hydroxylamine, an isothiocyanate, a ketone, a maleimide, a sulfonyl halide, or a thiol group.
Claim 5
Dependent Claim
43 words
A compound, as claimed in claim 1, wherein R X is a carboxylic acid, an activated ester of a carboxylic acid, an alcohol, an aldehyde, an alkyl halide, an amine, a haloacetamide, a halotriazine, a hydrazine, an isothiocyanate, a maleimide or a thiol.
Claim 6
Dependent Claim
20 words
A compound, as claimed in claim 2, wherein R 3 is --L--R X and R X is a succinimidyl ester.
Claim 7
Dependent Claim
24 words
A compound, as claimed in claim 1, wherein R 4 is sulfomethyl, halomethyl, C 1 -C 18 alkyl or C 1 -C 18 perfluoroalkyl.
Claim 8
Dependent Claim
19 words
A compound, as claimed in claim 1, wherein one of R 3 and R 4 is --L--S C .
Claim 9
Dependent Claim
69 words
A compound, as claimed in claim 7, wherein S C is an amino acid, a tyramine, a peptide, a protein, a monosaccharide, a polysaccharide, an ion-complexing moiety, a nucleoside, a nucleotide, an oligonucleotide, a nucleic acid, a hapten, a drug, a lipid, a phospholipid, a lipoprotein, a lipopolysaccharide, a liposome, a lipophilic polymer, a polymeric microparticle, an animal cell, a plant cell, a bacterium, a yeast, or a virus.
Claim 10
Dependent Claim
32 words
A compound, as claimed in claim 8, wherein S C is an amino acid, a peptide, a protein, a nucleotide, an oligonucleotide, a nucleic acid, a monosaccharide, a polysaccharide, or a drug.
Claim 11
Dependent Claim
16 words
A compound, as claimed in claim 9, wherein S C is a peptide or a protein.
Claim 12
Dependent Claim
27 words
A compound, as claimed in claim 7, wherein S C is further substituted by one or more additional dye compounds, which may be the same or different.
Claim 13
Dependent Claim
30 words
A compound, as claimed in claim 1, wherein R 7 is NR 1 R 2 and R 1 and R 2 are independently H or C 1 -C 18 alkyl.
Claim 14
Dependent Claim
62 words
A compound, as claimed in claim 1, wherein R 7 is NR 1 R 2 , where R 2 is H and R 1 is a radical formed by a removal of the hydroxyl group from the carboxylic acid of an amino acid or from the carboxylic acid of the carboxy-terminal amino acid of a linear peptide consisting of 2-6 amino acids.
Claim 15
Dependent Claim
75 words
A compound, as claimed in claim 1, wherein R 7 is NR1R 2 , where R 2 is H and R 1 is a 2-nitrobenzyloxycarbonyl of the formula ##STR46## wherein R 9 and R 10 are H, C 1 -C 6 alkoxy, or R 9 and R 10 taken in combination are --O--CH 2 --O--; and R 11 is H, CH 3 , a carboxylic acid or a biologically compatible salt of a carboxylic acid.
Claim 16
Dependent Claim
45 words
A compound, as claimed in claim 1, wherein R 7 is a nitrogen atom that is linked by a single or double covalent bond to the anomeric carbon of a mono- or polysaccharide and formally replaces the anomeric oxygen atom of the mono- or polysaccharide.
Claim 17
Dependent Claim
59 words
A compound, as claimed in claim 1, wherein R 3 is H, --L--R X , or --L--S C ; R 4 is CH 3 , --L--R X or --L--S C R 7 is NH 2 ; and R 8 is H; provided that at least one of R 3 , R 6 and R 8 is SO 3 X.
Claim 18
Independent Claim
376 words
A method of detecting a complementary member of a specific binding pair in a sample, comprising: a) adding to said sample a dye-conjugate of a first member of a specific binding pair for which there is a complementary member, where said first member of a specific binding pair is attached to one or more dye molecules, which may be the same or different, having the formula ##STR47## wherein R 5 is H; R 6 is H, methyl, halogen, or SO 3 X; R 7 is NR 1 R 2 ; wherein R 1 and R 2 are independently H, C 1 -C 18 alkyl; or R 1 in combination with R 2 forms a saturated 5- or 6-membered heterocycle that is a piperidine, a morpholine, a pyrrolidine or a piperazine; or R 1 is a 2-nitrobenzyloxycarbonyl of the formula ##STR48## wherein R 9 and R 10 are H, C 1 -C 6 alkoxy, or R 9 and R 10 taken in combination are --O--CH 2 --O--; and R 11 is H, CH 3 , a carboxylic acid or a biologically compatible salt of a carboxylic acid; R 8 is H, halogen or SO 3 X; X is H, or a biologically compatible cation; R 3 is H, SO 3 X, halogen, CN, NO 2 , or --L--S C ; R 4 is H, CN, C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, CH 2 SO 3 X; or --L--S C ; wherein each L is a single covalent bond, or L is a covalent linkage having 1-24 nonhydrogen atoms selected from the group consisting of C, N, O and S and is composed of any combination of single, double, triple or aromatic carbon-carbon bonds, carbon-nitrogen bonds, nitrogen-nitrogen bonds, carbon-oxygen bonds and carbon-sulfur bonds; and S C is a conjugated substance that is said first member of a specific binding pair; provided that at least one of R 3 , R 6 or R 8 is SO 3 X; and provided that one of R 3 and R 4 is --L--S C ; b) allowing sufficient time for the dye-conjugate to form a complex with the complementary member, said complex exhibiting a detectable optical response; and c) detecting said complex to locate the complementary member.
Claim 19
Independent Claim
376 words
A method of detecting a complementary member of a specific binding pair in a sample, comprising: a) adding to said sample a dye-conjugate of a first member of a specific binding pair for which there is a complementary member, where said first member of a specific binding pair is attached to one or more dye molecules, which may be the same or different, having the formula ##STR47## wherein R 5 is H; R 6 is H, methyl, halogen, or SO 3 X; R 7 is NR 1 R 2 ; wherein R 1 and R 2 are independently H, C 1 -C 18 alkyl; or R 1 in combination with R 2 forms a saturated 5- or 6-membered heterocycle that is a piperidine, a morpholine, a pyrrolidine or a piperazine; or R 1 is a 2-nitrobenzyloxycarbonyl of the formula ##STR48## wherein R 9 and R 10 are H, C 1 -C 6 alkoxy, or R 9 and R 10 taken in combination are --O--CH 2 --O--; and R 11 is H, CH 3 , a carboxylic acid or a biologically compatible salt of a carboxylic acid; R 8 is H, halogen or SO 3 X; X is H, or a biologically compatible cation; R 3 is H, SO 3 X, halogen, CN, NO 2 , or --L--S C ; R 4 is H, CN, C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, CH 2 SO 3 X; or --L--S C ; wherein each L is a single covalent bond, or L is a covalent linkage having 1-24 nonhydrogen atoms selected from the group consisting of C, N, O and S and is composed of any combination of single, double, triple or aromatic carbon-carbon bonds, carbon-nitrogen bonds, nitrogen-nitrogen bonds, carbon-oxygen bonds and carbon-sulfur bonds; and S C is a conjugated substance that is said first member of a specific binding pair; provided that at least one of R 3 , R 6 or R 8 is SO 3 X; and provided that one of R 3 and R 4 is --L--S C ; b) allowing sufficient time for the dye-conjugate to form a complex with the complementary member, said complex exhibiting a detectable optical response; and c) detecting said complex to locate the complementary member.
Claim 20
Dependent Claim
36 words
A method, as claimed in claim 17, wherein the first member of the specific binding pair is a peptide, a protein, a nucleotide, an oligonucleotide, a nucleic acid polymer, a drug, a toxin, or a polysaccharide.
Claim 21
Dependent Claim
15 words
A method, as claimed in claim 17, wherein the optical response is a fluorescence response.
Claim 22
Dependent Claim
55 words
A method, as claimed in claim 17, wherein the first member of the specific binding pair is an antibody, an antibody fragment, avidin, streptavidin, or a conjugate of an antibody, an antibody fragment, avidin, or streptavidin and the complementary member is a hapten having a molecular weight less than 1,000, an antigen or a biotin.
Claim 23
Dependent Claim
31 words
A method, as claimed in claim 17, wherein the complementary member is present in a cell, bacteria, virus, yeast cell or is immobilized on a polymer, polymeric membrane or polymeric particle.
Claim 24
Dependent Claim
24 words
A method, as claimed in claim 19, further comprising distinguishing said fluorescence response from that of a second fluorophore having detectably different optical properties.
Claim 25
Independent Claim
335 words
A method of staining a sample, comprising: a) adding to said sample a compound of the formula ##STR49## wherein R 5 is H; R 6 is H, methyl, halogen, or SO 3 X; R 7 is NR 1 R 2 ; wherein R 1 and R 2 are independently H, C 1 -C 18 alkyl; or R 1 in combination with R 2 forms a saturated 5- or 6-membered heterocycle that is a piperidine, a morpholine, a pyrrolidine or a piperazine; or R 2 is H and R 1 is a radical formed by a removal of the hydroxyl group from the carboxylic acid of an amino acid or from the carboxylic acid of the carboxy-terminal amino acid of a linear peptide consisting of 2-6 amino acids; or R 1 is a 2-nitrobenzyloxycarbonyl of the formula ##STR50## wherein R 9 and R 10 are H, C 1 -C 6 alkoxy, or R 9 and R 10 taken in combination are --O--CH 2 --O--; and R 11 is H, CH 3 , a carboxylic acid or a biologically compatible salt of a carboxylic acid; R 8 is H, halogen or SO 3 X; X is H, or a biologically compatible cation; R 3 is H, SO 3 X, halogen, CN, NO 2 , or --L--S C ; R 4 is H, CN, C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, CH 2 SO 3 X; or --L--S C ; wherein each L is a single covalent bond, or L is a covalent linkage having 1-24 nonhydrogen atoms selected from the group consisting of C, N, O and S and is composed of any combination of single, double, triple or aromatic carbon-carbon bonds, carbon-nitrogen bonds, nitrogen-nitrogen bonds, carbon-oxygen bonds and carbon-sulfur bonds; and S C is a conjugated substance; provided that at least one of R 3 , R 6 or R 8 is SO 3 X; in an amount sufficient to produce an optical response when said sample is illuminated at an appropriate wavelength.
Claim 26
Independent Claim
335 words
A method of staining a sample, comprising: a) adding to said sample a compound of the formula ##STR49## wherein R 5 is H; R 6 is H, methyl, halogen, or SO 3 X; R 7 is NR 1 R 2 ; wherein R 1 and R 2 are independently H, C 1 -C 18 alkyl; or R 1 in combination with R 2 forms a saturated 5- or 6-membered heterocycle that is a piperidine, a morpholine, a pyrrolidine or a piperazine; or R 2 is H and R 1 is a radical formed by a removal of the hydroxyl group from the carboxylic acid of an amino acid or from the carboxylic acid of the carboxy-terminal amino acid of a linear peptide consisting of 2-6 amino acids; or R 1 is a 2-nitrobenzyloxycarbonyl of the formula ##STR50## wherein R 9 and R 10 are H, C 1 -C 6 alkoxy, or R 9 and R 10 taken in combination are --O--CH 2 --O--; and R 11 is H, CH 3 , a carboxylic acid or a biologically compatible salt of a carboxylic acid; R 8 is H, halogen or SO 3 X; X is H, or a biologically compatible cation; R 3 is H, SO 3 X, halogen, CN, NO 2 , or --L--S C ; R 4 is H, CN, C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, CH 2 SO 3 X; or --L--S C ; wherein each L is a single covalent bond, or L is a covalent linkage having 1-24 nonhydrogen atoms selected from the group consisting of C, N, O and S and is composed of any combination of single, double, triple or aromatic carbon-carbon bonds, carbon-nitrogen bonds, nitrogen-nitrogen bonds, carbon-oxygen bonds and carbon-sulfur bonds; and S C is a conjugated substance; provided that at least one of R 3 , R 6 or R 8 is SO 3 X; in an amount sufficient to produce an optical response when said sample is illuminated at an appropriate wavelength.
Claim 27
Dependent Claim
15 words
A method, as claimed in claim 23, wherein said optical response is a fluorescence response.
Claim 28
Dependent Claim
12 words
A method, as claimed in claim 23, wherein said sample comprises cells.
Claim 29
Dependent Claim
15 words
A method, as claimed in claim 25, further comprising observing said cells using flow cytometry.
Claim 30
Dependent Claim
24 words
A method, as claimed in claim 24, further comprising distinguishing the fluorescence response from that of a second fluorophore having detectably different optical properties.
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