Patent US5576424A successfully refreshed from Google Patents.
← Back to Patent Explorer
US5576424A Expired / Lapsed US ⏱️ 0.0 years remaining

Haloalkyl derivatives of reporter molecules used to analyze metabolic activity in cells

Assignee: Molecular Probes Inc
•
Filing: 1994-11-08
•
Granted: 1996-11-19
•
Expires: 2014-11-08
📄 Original PDF 🌐 Google Patents 🔄 Sync Now

Abstract

Abstract The subject invention provides substrates useful for analyzing the metabolic activity in cells by improving the retention of a detectable reporter molecule only in intact cells where a particular enzyme is present. In particular, improved retention results from a two part process involving conjugation of haloalkyl-substituted derivatives of a reporter molecule with intracellular cysteine-containing peptides while unblocking the reporter molecule. The substrates have the form XR-SPACER-REPORTER-BLOCK wherein -BLOCK is a group selected to be removable by action of a specific analyte, to give REPORTER spectral properties different from those of the substrate, -REPORTER- is a molecule that, when no longer bound to BLOCK by a BLOCK-REPORTER bond, has spectral properties different from those of the substrate, -SPACER- is a covalent linkage, and XR- is a haloalkyl moiety that can covalently react with an intracellular thiol (Z-S-H) to form a thioether conjugate (Z-S-R-). After the substrate enters the cells, the analyte removes BLOCK to make REPORTER detectable by the change in spectral properties, and the haloalkyl XR reacts with the intracellular thiol to form the thioether conjugate inside the cells, which is well-retained in the cells.

Inventors

  • 👤 Fei Mao
  • 👤 Ram Sabnis
  • 👤 John Naleway
  • 👤 Nels Olson
  • 👤 Richard P. Haugland

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-02 16:36
CPC Classifications
G; G01; G01N; G01N33/00; G01N33/48; G01N33/50; G01N33/53; G01N33/531; G01N33/532; G01N33/535; C; C12; C12Q; C12Q1/00; C12Q1/02; C12Q1/04; C12Q1/34; C12Q2334/00; C12Q2334/20; C12Q2334/40; C12Q2337/00; C12Q2337/20; G01N2333/00; G01N2333/90; G01N2333/914; G01N2333/924

Claims Analysis

Total Claims: 26
Claim 1
Independent Claim 197 words
A substrate having the formula: XR-SPACER-REPORTER-BLOCK wherein BLOCK is a monovalent moiety derived by removal of a hydroxy group from phosphate or from sulfate, or a biologically compatible salt thereof; or a monovalent moiety derived by removal of a hydroxy group from a carboxy group of an aromatic carboxylic acid or of an amino acid, protected amino acid, peptide, or protected peptide; or a monovalent moiety derived by removal of a hydroxy group from an alcohol or from a mono- or polysaccharide, where said BLOCK is selected to be removable from -REPORTER by action of an enzyme; -REPORTER- is an anthracene, a benzphenalenone, an acridinone, a coumarin, a fluorescein, a naphthalene, a phenalenone, a pyrene, a resorufin, a rhodol, or a rhodamine, that when no longer bound to BLOCK by a BLOCK-REPORTER bond, is fluorescent; -SPACER- is a single covalent bond, or a covalent linkage having 0-8 carbon atoms and 1-4 heteroatoms, wherein said heteroatoms, which may be the same or different, are selected from the group consisting of O, N and S; and XR-- is a haloalkyl moiety, where X is a single Cl, I, or Br, and R is an alkyl linkage having 1-4 carbons.
Claim 2
Dependent Claim 197 words
A substrate having the formula: XR-SPACER-REPORTER-BLOCK wherein BLOCK is a monovalent moiety derived by removal of a hydroxy group from phosphate or from sulfate, or a biologically compatible salt thereof; or a monovalent moiety derived by removal of a hydroxy group from a carboxy group of an aromatic carboxylic acid or of an amino acid, protected amino acid, peptide, or protected peptide; or a monovalent moiety derived by removal of a hydroxy group from an alcohol or from a mono- or polysaccharide, where said BLOCK is selected to be removable from -REPORTER by action of an enzyme; -REPORTER- is an anthracene, a benzphenalenone, an acridinone, a coumarin, a fluorescein, a naphthalene, a phenalenone, a pyrene, a resorufin, a rhodol, or a rhodamine, that when no longer bound to BLOCK by a BLOCK-REPORTER bond, is fluorescent; -SPACER- is a single covalent bond, or a covalent linkage having 0-8 carbon atoms and 1-4 heteroatoms, wherein said heteroatoms, which may be the same or different, are selected from the group consisting of O, N and S; and XR-- is a haloalkyl moiety, where X is a single Cl, I, or Br, and R is an alkyl linkage having 1-4 carbons.
Claim 3
Dependent Claim 29 words
A substrate, as claimed in claim 1, wherein -SPACER-XR is one of --(C═O)--XR, --(SO 2 )--XR, XR--C 6 H 4 --(C═O)--, or XR--C 6 H 4 --(SO 2 )--.
Claim 4
Dependent Claim 43 words
A substrate, as claimed in claim 1, wherein the BLOCK-REPORTER bond is an amide bond that results from removal of a hydroxy group from a carboxylic acid of an amino acid or peptide and a hydrogen atom from an amino moiety on REPORTER.
Claim 5
Dependent Claim 50 words
A substrate, as claimed in claim 1, wherein the BLOCK-REPORTER bond is an ether bond formed by removal of a hydroxy group from a lower alcohol having 6 or less carbon atoms or of hydroxy from a mono- or polysaccharide and a hydrogen atom from a phenolic moiety on REPORTER.
Claim 6
Dependent Claim 34 words
A substrate, as claimed in claim 1, wherein the BLOCK-REPORTER bond is an ester bond, wherein the ester is an ester of a guanidinobenzoic, phosphoric, or sulfuric acid, or a biologically compatible salt thereof.
Claim 7
Dependent Claim 44 words
A substrate, as claimed in claim 1, that is an ether of either a fluorescein or a rhodol and a lower alcohol having 6 or fewer carbon atoms, or a steriodal alcohol, or of a mono- or polysaccharide, and XR-- is XCH 2 --.
Claim 8
Dependent Claim 22 words
A substrate, as claimed in claim 6, where the monosaccharide is β-D-galactose, β-D-glucose or β-D-glucuronic acid and XR-- is ClCH 2 --.
Claim 9
Dependent Claim 39 words
A substrate, as claimed in claim 1, that is an ether of a 7-hydroxycoumarin and a mono- or polysaccharide, or a lower alcohol having 6 or fewer carbon atoms, or a steroidal alcohol, and XR-- is XCH 2 --.
Claim 10
Dependent Claim 22 words
A substrate, as claimed in claim 8, where the monosaccharide is β-D-galactose, β-D-glucose or β-D-glucuronic acid and XR-- is ClCH 2 --.
Claim 11
Dependent Claim 35 words
A substrate, as claimed in claim 1, that is an ether of a fluorescein and a mono- or polysaccharide, or a lower alcohol having 6 or fewer carbon atoms, and XR-- is XCH 2 --.
Claim 12
Dependent Claim 22 words
A substrate, as claimed in claim 10, where the monosaccharide is β-D-galactose, β-D-glucose or β-D-glucuronic acid and XR-- is ClCH 2 --.
Claim 13
Dependent Claim 37 words
A substrate, as claimed in claim 1, that is an amide of a 7-aminocoumarin and an amino acid or peptide or a biologically compatible salt of an amino acid or peptide and XR-- is XCH 2 --.
Claim 14
Dependent Claim 40 words
A substrate, as claimed in claim 1, that is an amide of rhodamine 110 and an amino acid, protected amino acid, or peptide, or a biologically compatible salt of an amino acid or peptide, and XR-- is XCH 2 --.
Claim 15
Dependent Claim 49 words
A substrate, as claimed in claim 1, that is an amide of rhodamine 110 and an amino acid, protected ammo acid or peptide or biologically compatible salt of an amino acid, protected amino acid or peptide, and -SPACER- is a carboxamide or sulfonamide bound to the second rhodamine nitrogen.
Claim 16
Dependent Claim 11 words
A substrate, as claimed in claim 1, having the formula ##STR28##
Claim 17
Dependent Claim 11 words
A substrate, as claimed in claim 1, having the formula ##STR29##
Claim 18
Dependent Claim 29 words
A substrate, as claimed in claim 16, wherein XR-SPACER- is one of XR--(C═O)--, XR--(SO 2 )--, XR--C 6 H 4 --(C═O)--, or XR--C 6 H 4 --(SO 2 )--.
Claim 19
Dependent Claim 11 words
A substrate, as claimed in claim 1, having the formula ##STR30##
Claim 20
Dependent Claim 11 words
A substrate, as claimed in claim 1, having the formula ##STR31##
Claim 21
Dependent Claim 11 words
A substrate, as claimed in claim 1, having the formula ##STR32##
Claim 22
Dependent Claim 11 words
A substrate, as claimed in claim 1, having the formula ##STR33##
Claim 23
Dependent Claim 204 words
A fluorescent enzymatic reaction producing the formula ##STR34## where REPORTER is an anthracene a benzphenalenone, an acridinone, a coumarin, a fluorescein, a naphthalene, phenalenone, a pyrene, a resorufin a rhodol, or a rhodamine; -SPACER- is a single covalent bond, or a covalent linkage having 0-8 carbon atoms and 1-4 heteroatoms, wherein said heteroatoms, which may be the same or different, are selected from the group consisting of O, N and S; and R is an alkyl linker having 1-4 carbon atoms; wherein, in the presence of reduced glutathione, said enzymatic reaction product is the result of the action of an analyte enzyme on the substrate XR-SPACER-REPORTER-BLOCK wherein BLOCK is a monovalent moiety derived by removal of a hydroxy group from phosphate or from sulfate, or a biologically compatible salt thereof; or a monovalent moiety derived by removal of a hydroxy group from a carboxy group of an aromatic carboxylic acid or of an amino acid or of a peptide; or a monovalent moiety derived by removal of a hydroxy group from an alcohol or from a mono- or polysaccharide, where said BLOCK is selected to be removable from -REPORTER by action of an analyte enzyme; and X is a single Cl, I, or Br.
Claim 24
Dependent Claim 204 words
A fluorescent enzymatic reaction producing the formula ##STR34## where REPORTER is an anthracene a benzphenalenone, an acridinone, a coumarin, a fluorescein, a naphthalene, phenalenone, a pyrene, a resorufin a rhodol, or a rhodamine; -SPACER- is a single covalent bond, or a covalent linkage having 0-8 carbon atoms and 1-4 heteroatoms, wherein said heteroatoms, which may be the same or different, are selected from the group consisting of O, N and S; and R is an alkyl linker having 1-4 carbon atoms; wherein, in the presence of reduced glutathione, said enzymatic reaction product is the result of the action of an analyte enzyme on the substrate XR-SPACER-REPORTER-BLOCK wherein BLOCK is a monovalent moiety derived by removal of a hydroxy group from phosphate or from sulfate, or a biologically compatible salt thereof; or a monovalent moiety derived by removal of a hydroxy group from a carboxy group of an aromatic carboxylic acid or of an amino acid or of a peptide; or a monovalent moiety derived by removal of a hydroxy group from an alcohol or from a mono- or polysaccharide, where said BLOCK is selected to be removable from -REPORTER by action of an analyte enzyme; and X is a single Cl, I, or Br.
Claim 25
Dependent Claim 17 words
A fluorescent enzymatic reaction product, as claimed in claim 22, wherein said analyte enzyme is present intracellularly.
Claim 26
Dependent Claim 24 words
A fluorescent enzymatic reaction product, as claimed in claim 22, where REPORTER is a coumarin, a fluorescein, a resorufin, a rhodol, or a rhodamine.

References Cited (Backward Citations)

US4557862A Cited
US4640893A Cited
US4812409A Cited
US4777269A Cited
US4810636A Cited
US5070012A Cited
US5208148A Cited
US5110725A Cited
US5242805A Cited
US5362628A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1999-11-19 2000-05-20 2000-11-19 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 2003-11-19 2004-05-20 2004-11-19 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2007-11-19 2008-05-20 2008-11-19 $7700.00 Window Closed / Lapsed

Assigned Categories & Tags

No categories assigned to this patent yet.

Assign Category Tag