IP Library Granted Patent US 8,076,072
Granted Patent B2
US 8,076,072 · App. 12/892,531 · Granted Dec 13, 2011

Nucleic acid labeling compounds

View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 8,076,072
App. No.
12/892,531
Granted
Dec 13, 2011
Kind
B2
Abstract

Nucleic acid labeling compounds including the following are disclosed: These compounds are useful for attaching a detectable label to a nucleic acid.

Claims (184)

1. A nucleic acid labeling compound having the formula:

wherein A is hydrogen, monophosphate, diphosphate, triphosphate, α-thiotriphosphate, phosphoramidite, or H-phosphonate;

L is a linker moiety selected from the group consisting of —CH═CH—R 11 , or C≡C—R 11 wherein R 11 comprises a moiety selected from the group consisting of alkyl, functionalized alkyl, alkenyl alkyl, alkynyl alkly, amido alkyl, amino alkyl, alkoxy, amino, aryl, and thio;

Q is a detectable moiety selected from the group consisting of a raiolabel, a magnetic particle, colloidal gold, fluorescein, texas red, rhodamine, green fluorescent protein, luminal lophine, acridine salts, luciferin, vanadium spin labels, copper spin labels, iron spin labels, manganese spine labels, nitroxide free radicals, quinoline dyes, triarlmethane dyes, acridine dyes, colored glass beads, polystyrene beads, polypropylene beads, latex beads, biotin, horseradish peroxidase, alkaline phosphatase, 1-aminonapthalene, 2-aminonapthalene, p,p′-diaminostilbenes, pyrenes, quaternary phenanthridine salts, 9-aminoacridines, p,p′-diaminobenzophenone imines, anthracenes, oxacarbocyanines, marocyanine, 3-amino aminoequilenin, perylene, bisbenzoxazole, bis-p-oxazolyl benzene, 1,2-benzophenazin, retinol, bis-3-aminopridinium salts, hellebrigenin, tetracyline, sterophenol, benzimidazolyl phenylamine, 2-oxo-3-chromen, indole, xanthen, 7-hydroxycoumarin, phenoxazine, salycilate, strophanthidin, porphyrins, triarylmethanes, flavin, xanthene dyes, rhodamine dyes, cyanine dyes, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene dyes, phycobiliprotein, dansyl chloride, 3,6-dihydroxy-9-phenylxanthhydrol; rhodamineisothiocyanate; N-phenyl-1-amino-8-sulfonatonaphthalene; N-phenyl-2-amino-6-sulfonatonaphthanlene; 4-acetamido-4-isothiocyanatostilbene-2,2′-disulfonic acid; pyrene-3-sulfonic acid; 2-toluidinonapththalene-6-sulfonate; N-phenyl, N-methyl 2-aminonaphthalene-6-sulfonate; ethidium bromide; stebrine; auromine-0,2-(9′-anthroyl)palmitate; dansyl phosphatidylethanolamin; N,N′-dioctadecyl oxacarbocycanine; N,N′-dihexyl oxacarbocyanine; merocyanine, 4-(3′-pyrenyl)butryate; d-3-aminodesoxy-equilenin; 12-(9′-anthroyl)stearate; 2-methylanthracene; 9-vinylanthracene; 2,2′-(vinylene-p-phenylene)bisbenzoxazole; p-bis[2-(4-methyl-5-phenyl oxazolyl)]benzene; 6-dimethylamino-1,2-benzophenzin; retinol; bis(3′-aminopyridinium)-1,10-decandiyl diiodide; sulfonaphthylhydrazone of hellibrienin; chlorotetracycline; N-(7-dimethylamino-4-methyl-2-oxo-3-chromenyl)maleimide; N-[p-(2-benzimidazolyl)phenyl]maleimide; N-(4-fluoranthyl)maleimide; bis(homovanillic acid); resazarin; 4-chloro-7-nitro-2,1,3-benzooxadizole; merocyanine 540; resorufin; rose bengal and 2,4-diphenyl-3(2H)-furanone; and

M is a connecting group selected from the group consisting of amino alkyl, —CO(CH 2 ) 5 NH—, —CO—, —CO(O)—, CO(NH)—, —CO(CH 2 ) 5 NHCO(CH 2 ) 5 NH—, —NH(CH 2 CH 2 O) k NH—, —NH(CH 2 CH 2 O) k CH 2 CH 2 NH— and —CO(CH 2 ) 5 —, wherein k is an integer from 1 to 5, wherein m is an integer ranging from 0 to about 3.

2. The nucleic acid labeling compound of claim 1 , wherein A is H or H 4 O 9 P 3 —;

L is alkanoyl; and

Q is biotin or a carboxyfluorescein;

M is —NR 3 — where R 3 is hydrogen or alkyl, and wherein m is 1 or 0.

3. The nucleic acid labeling compound of claim 2 , wherein L is —C(O)(CH 2 ) n —

wherein n is an integer ranging from about 1 to about 10;

M is —NH—;

Q is biotin or a carboxyfluorescein.

4. The nucleic acid labeling compound of claim 3 , wherein -L-(M) m - is

—C(O)(CH 2 ) 6 —NH—; and

Q is biotin.

5. The nucleic acid labeling compound of claim 3 , wherein -L-(M) m - is

—C(O)(CH 2 ) 6 —NH—; and

Q is carboxyfluorescein.

6. A nucleic acid labeling compound having the formula:

wherein A is hydrogen or, monophosphate, diphosphate, triphosphate, α-thiotriphosphate, phosphoramidite, or H-phosphonate;

X 1 is O, S, NR 1 or CHR 2 ,

wherein R 1 and R 2 are, independently, hydrogen, alkyl or aryl;

R 15 is hydrogen, alkyl or aryl;

Y 1 is hydrogen, N 3 , F, OR 9 , SR 9 or NHR 9 , wherein R 9 is hydrogen, alkyl or aryl;

Z 1 is hydrogen, N 3 , F, OR 9 , SR 9 or NHR 10 , wherein R 10 is hydrogen, alkyl or aryl;

wherein one of Y, or Z, is a group having the formula —X 2 L-(M), -Q;

X 2 is O, S, or NR 16 , and R 16 is hydrogen, alkyl or aryl;

L is a linker moiety selected from the group consisting of —CH═CH—R 11 , or C≡C—R 11 wherein

R 1 comprises a moiety selected from the group consisting of alkyl, functionalized alkyl, alkenyl alkyl, alkynyl alkly, amido alkyl, amino alkyl, alkoxy, amino, aryl, and thio;

Q is a detectable moiety selected from the group consisting of a raiolabel, a magnetic particle, colloidal gold, fluorescein, texas red, rhodamine, green fluorescent protein, luminal lophine, acridine salts, luciferin, vanadium spin labels, copper spin labels, iron spin labels, manganese spine labels, nitroxide free radicals, quinoline dyes, triarlmethane dyes, acridine dyes, colored glass beads, polystyrene beads, polypropylene beads, latex beads, biotin, horseradish peroxidase, alkaline phosphatase, 1-aminonapthalene, 2-aminonapthalene, p,p′-diaminostilbenes, pyrenes, quaternary phenanthridine salts, 9-aminoacridines, p,p′-diaminobenzophenone imines, anthracenes, oxacarbocyanines, marocyanine, 3-amino aminoequilenin, perylene, bisbenzoxazole, bis-p-oxazolyl benzene, 1,2-benzophenazin, retinol, bis-3-aminopridinium salts, hellebrigenin, tetracyline, sterophenol, benzimidazolyl phenylamine, 2-oxo-3-chromen, indole, xanthen, 7-hydroxycoumarin, phenoxazine, salycilate, strophanthidin, porphyrins, triarylmethanes, flavin, xanthene dyes, rhodamine dyes, cyanine dyes, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene dyes, phycobiliprotein, dansyl chloride, 3,6-dihydroxy-9-phenylxanthhydrol; rhodamineisothiocyanate; N-phenyl-1-amino-8-sulfonatonaphthalene; N-phenyl-2-amino-6-sulfonatonaphthanlene; 4-acetamido-4-isothiocyanatostilbene-2,2′-disulfonic acid; pyrene-3-sulfonic acid; 2-toluidinonapththalene-6-sulfonate; N-phenyl, N-methyl 2-aminonaphthalene-6-sulfonate; ethidium bromide; stebrine; auromine-0,2-(9′-anthroyl)palmitate; dansyl phosphatidylethanolamin; N,N′-dioctadecyl oxacarbocycanine; N,N′-dihexyl oxacarbocyanine; merocyanine, 4-(3′-pyrenyl)butryate; d-3-aminodesoxy-equilenin; 12-(9′-anthroyl)stearate; 2-methylanthracene; 9-vinylanthracene; 2,2′-(vinylene-p-phenylene)bisbenzoxazole; p-bis[2-(4-methyl-5-phenyl oxazolyl)]benzene; 6-dimethylamino-1,2-benzophenzin; retinol; bis(3′-aminopyridinium)-1,10-decandiyl diiodide; sulfonaphthylhydrazone of hellibrienin; chlorotetracycline; N-(7-dimethylamino-4-methyl-2-oxo-3-chromenyl)maleimide; resazarin; 4-chloro-7-nitro-2,1,3-benzooxadizole; merocyanine 540; resorufin; rose bengal and 2,4-diphenyl-3(2H)-furanone; and

M is a connecting group selected from the group consisting of amino alkyl, —CO(CH 2 ) 5 NH—, —CO—, —CO(O)—, CO(NH)—, —CO(CH 2 ) 5 NHCO(CH 2 ) 5 NH—, —NH(CH 2 CH 2 O) k NH—, NH(CH 2 CH 2 O) k CH 2 CH 2 NH— and —CO(CH 2 ) 5 —, wherein m is an integer ranging from 0 to about 20.

7. The nucleic acid labeling compound of claim 6 , wherein A is H or H 4 O 9 P 3 —;

X 1 is 0;

Y 1 is hydrogen, or OR 9 , wherein R 9 is hydrogen, alkyl, or —NR 16 -L-(M) m -Q;

wherein R 16 is hydrogen, alkyl or aryl;

Z 1 is hydrogen or OR 10 , wherein R 10 is hydrogen, alkyl, or —NR 16 -L-(M) m -Q,

wherein R 16 is hydrogen, or alkyl;

L is N-alkyl amido;

R 15 is hydrogen or alkyl;

M is —(CH 2 )—NR 3 — wherein R 3 is hydrogen or alkyl, and m is from 1 to about 15.

8. The nucleic acid labeling compound of claim 7 , wherein Y 1 is hydrogen or OH;

Z 1 is —NH-L-(M) m -Q;

L is —(CH 2 ) n NHC(O)— where n is an integer from 1 to about 10;

M is —NH(CH 2 ) p — where p is an integer from 1 to about 10;

R 15 is hydrogen or methyl; and

Q is biotin or a carboxyfluorescein.

9. The nucleic acid labeling compound of claim 8 , wherein Y 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —(CH 2 ) 4 NH—C(O)(CH 2 ) 5 NH—; and

Q is biotin.

10. The nucleic acid labeling compound of claim 9 , wherein Y 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —(CH 2 ) 4 NH—C(O)(CH 2 ) 5 NH—; and

Q is a carboxyfluorescein.

11. The nucleic acid labeling compound of claim 9 , wherein Y 1 is OH;

R 15 is methyl;

-L-(M) m - is —(CH 2 ) 4 NH—C(O)(CH 2 ) 5 NH—; and

Q is biotin.

12. The nucleic acid labeling compound of claim 9 , wherein Y 1 is OH;

R 15 is methyl;

-L-(M) m is —(CH 2 ) 4 NH—C(O)(CH 2 ) 5 NH—; and

Q is a carboxyfluorescein.

13. The nucleic acid labeling compound of claim 7 , wherein Y 1 is —NH-L-(M) m -Q;

Z 1 is hydrogen or OH;

L is —(CH 2 ) n NHC(O)— where n is an integer from 1 to about 10;

M is —NH(CH 2 ) n — where n is an integer from 1 to about 10;

R 15 is hydrogen or methyl; and

Q is biotin or a carboxyfluorescein.

14. The nucleic acid labeling compound of claim 13 , wherein Z 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —(CH 2 ) 4 NH—C(O)(CH 2 ) 5 NH—; and

Q is biotin.

15. The nucleic acid labeling compound of claim 13 , wherein Z 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —(CH 2 ) 4 NH—C(O)(CH 2 ) 5 NH—; and

Q is a carboxyfluorescein.

16. The nucleic acid labeling compound of claim 13 , wherein Z 1 is OH;

R 15 is methyl;

-L-(M) m - is —(CH 2 ) 4 NH—C(O)(CH 2 ) 5 NH—; and

Q is biotin.

17. The nucleic acid labeling compound of claim 13 , wherein Z 1 is OH;

R 15 is methyl;

-L-(M) m - is —(CH 2 ) 4 NH—C(O)(CH 2 ) 5 NH—; and

Q is a carboxyfluorescein.

18. The nucleic acid labeling compound of claim 7 , wherein A is H or H 4 O 9 P 3 —;

X 1 is O;

Y 1 is hydrogen, OR 9 , wherein R 9 is hydrogen, alkyl, or —O-L-(M) m -Q;

Z, is hydrogen OR 10 , wherein R 10 is hydrogen, alkyl, or —O-L-(M) m -Q,

L is alkylene; and

m is from 1 to about 10.

19. The nucleic acid labeling compound of claim 18 , wherein Y 1 is hydrogen or OH;

Z 1 is —O-L-(M) m -Q;

L is —(CH 2 ) n — where n is an integer from 1 to about 12;

M is —NH—;

R 15 is hydrogen or methyl; and

Q is biotin or a carboxyfluorescein.

20. The nucleic acid labeling compound of claim 19 , wherein Y 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —(CH 2 ) 6 —NH—; and

Q is biotin.

21. The nucleic acid labeling compound of claim 19 , wherein Y 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —(CH 2 ) 6 —NH—; and

Q is a carboxyfluorescein.

22. The nucleic acid labeling compound of claim 19 , wherein Y 1 is OH;

R 15 is methyl;

-L-(M) m - is —(CH 2 ) 6 —NH—; and

Q is biotin.

23. The nucleic acid labeling compound of claim 19 , wherein Y 1 is OH;

R 15 is methyl;

-L-(M) m - is —(CH 2 ) 6 —NH—; and

Q is a carboxyfluorescein.

24. The nucleic acid labeling compound of claim 7 , wherein Y 1 is —O-L-(M) m -Q;

Z 1 is hydrogen or OH;

L is —(CH 2 ) n — where n is an integer from 1 to about 12;

M is —NH—;

R 15 is hydrogen or methyl; and

Q is biotin or a carboxyfluorescein.

25. The nucleic acid labeling compound of claim 24 , wherein Z 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —(CH 2 ) 6 —NH—; and

Q is biotin.

26. The nucleic acid labeling compound of claim 24 , wherein Z 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —(CH 2 ) 6 —NH—; and

Q is a carboxyfluorescein.

27. The nucleic acid labeling compound of claim 24 , wherein Z 1 is OH;

R 15 is methyl;

-L-(M) m - is —(CH 2 ) 6 —NH—; and

Q is biotin.

28. The nucleic acid labeling compound of claim 24 , wherein Z 1 is OH;

R 15 is methyl;

-L-(M) m - is —(CH 2 ) 6 —NH—; and

Q is a carboxyfluorescein.

29. The nucleic acid labeling compound of claim 7 , wherein A is H or H 4 O 9 P 3 —;

X 1 is O;

Y 1 is hydrogen, OR 9 , wherein R 9 is hydrogen, alkyl, or —S-L-(M) m -Q;

Z 1 is hydrogen OR 10 , wherein R 10 is hydrogen, alkyl, or —S-L-(M) m -Q;

L is alkyl thio; and m is from 1 to about 10.

30. The nucleic acid labeling compound of claim 29 , wherein Y 1 is hydrogen or OH;

Z 1 is —S-L-(M) m -Q;

L is —S—(CH 2 ) n — where n is an integer from 1 to about 10;

M is —NH—;

R 15 is hydrogen or methyl; and

Q is biotin or a carboxyfluorescein.

31. The nucleic acid labeling compound of claim 30 , wherein Y 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —S—(CH 2 ) 2 —NH—; and

Q is biotin.

32. The nucleic acid labeling compound of claim 30 , wherein Y 1 is OH;

R 15 is hydrogen;

-L-(M) m - is —S—(CH 2 ) 2 —NH—; and

Q is a carboxyfluorescein.

33. The nucleic acid labeling compound of claim 30 , wherein Y 1 is OH;

R 15 is methyl;

-L-(M) m -is —S—(CH 2 ) 2 —NH—; and

Q is biotin.

34. The nucleic acid labeling compound of claim 30 , wherein Y 1 is OH;

R 15 is methyl;

-L-(M) m - is —S—(CH 2 ) 2 —NH—; and

Q is a carboxyfluorescein.

35. The nucleic acid labeling compound of claim 7 , wherein Y 1 is —S-L-(M) m -Q;

Z 1 is hydrogen or OH;

L is —S—(CH 2 ) n — where n is an integer from 1 to about 10;

M is —NH—;

R 15 is hydrogen or methyl; and

Q is biotin or a carboxyfluorescein.

36. The nucleic acid labeling compound of claim 35 , wherein Z 1 is OH;

R 15 is hydrogen;

-L-(M) m is —S—(CH 2 ) 2 —NH—; and

Q is biotin.

37. The nucleic acid labeling compound of claim 35 , wherein Z 1 is OH;

R 15 is hydrogen;

-L-(M) m -is —S—(CH 2 ) 2 —NH—; and

Q is a carboxyfluorescein.

38. The nucleic acid labeling compound of claim 35 , wherein Z 1 is OH;

R 15 is methyl;

-L-(M) m -is —S—(CH 2 ) 2 —NH—; and

Q is biotin.

39. The nucleic acid labeling compound of claim 35 , wherein Z 1 is OH;

R 15 is methyl;

-L-(M) m -is —S—(CH 2 ) 2 —NH—; and

Q is a carboxyfluorescein.

Assignments (4)
NOTICE OF RELEASE Recorded Apr 5, 2016
From: BANK OF AMERICA, N.A.
To: AFFYMETRIX, INC.
Reel/Frame 038361/0891 →
RELEASE OF SECURITY INTEREST Recorded Nov 13, 2015
From: GENERAL ELECTRIC CAPITAL CORPORATION, AS AGENT
To: AFFYMETRIX, INC.
Reel/Frame 037109/0132 →
SECURITY INTEREST Recorded Oct 28, 2015
From: AFFYMETRIX, INC.
To: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 036988/0166 →
SECURITY AGREEMENT Recorded Jun 27, 2012
From: AFFYMETRIX, INC.
To: GENERAL ELECTRIC CAPITAL CORPORATION, AS AGENT
Reel/Frame 028465/0541 →