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US5565552A
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Method of expanded porphyrin-oligonucleotide conjugate synthesis
Assignee: Pharmacyclics LLC
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Filing: 1995-06-07
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Granted: 1996-10-15
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Expires: 2015-06-07
Abstract
Abstract The invention is directed to a method of incorporating expanded porphyrins, and particularly of incorporating a sapphyrin or a texaphyrin, before, during, or after chemical synthesis of an oligomer to form an expanded porphyrin-oligonucleotide conjugate, and particularly a sapphyrin- or texaphyrin-oligonucleotide conjugate. This method includes reacting derivatized nucleotides and a sapphyrin or a texaphyrin in a desired order in an automated or manual DNA synthesizer having a solid support to form a sapphyrin- or a texaphyrin-oligonucleotide conjugate.
Inventors
- 👤 Darren Magda
- 👤 Jonathan L. Sessler
- 👤 Brent L. Iverson
- 👤 Petra I. Sansom
- 👤 Shaun P. Crofts
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 03:59
CPC Classifications
A; A61; A61K; A61K41/00; A61K41/0038; A61K41/0042; A61K41/0057; A61K41/0076; A61K47/00; A61K47/50; A61K47/51; A61K47/54; A61K47/545; A61K47/546; A61K49/00; A61K49/001; A61K49/0013; A61K49/0017; A61K49/0019; A61K49/0021; A61K49/005; A61K49/0052; A61K49/0054; A61K49/06; A61K49/08; A61K49/085; A61K49/10; A61K49/101; A61K49/106; A61K49/12; A61K49/126; A61K51/00; A61K51/02; A61K51/04; A61K51/0474; A61K51/0485; A61L; A61L2/00; A61L2/02; B; B01; B01J; B01J31/00; B01J31/16; B01J31/165; B01J31/1658; B01J31/18; B01J31/1805; B01J31/181; B01J31/1815; C; C07; C07D; C07D487/00; C07D487/22; C07H; C07H21/00; C12; C12N; C12N15/00; C12N15/09; C12N15/11; C12N15/113; A61L2103/00; A61L2103/05; B01J2531/00; B01J2531/02; B01J2531/0238; B01J2531/0241; B01J2531/025; B01J2531/20; B01J2531/26; B01J2531/27; B01J2531/30; B01J2531/33; B01J2531/37; B01J2531/38; B01J31/02; B01J31/0201; B01J31/06; B01J31/061; C12N2310/00; C12N2310/10; C12N2310/15; C12N2310/30; C12N2310/32; C12N2310/321; C12N2310/35; C12N2310/351; C12N2310/3511
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
32 words
A method of synthesizing an expanded porphyrin-nucleotide conjugate in a DNA synthesizer, the method comprising reacting an expanded porphyrin with a nucleotide using the DNA synthesizer, to form an expanded porphyrin-nucleotide conjugate.
Claim 2
Independent Claim
32 words
A method of synthesizing an expanded porphyrin-nucleotide conjugate in a DNA synthesizer, the method comprising reacting an expanded porphyrin with a nucleotide using the DNA synthesizer, to form an expanded porphyrin-nucleotide conjugate.
Claim 3
Dependent Claim
12 words
The method of claim 1 wherein the expanded porphyrin is a rubyrin.
Claim 4
Dependent Claim
12 words
The method of claim 1 wherein the expanded porphyrin is a sapphyrin.
Claim 5
Dependent Claim
12 words
The method of claim 1 wherein the expanded porphyrin is a texaphyrin.
Claim 6
Dependent Claim
12 words
The method of claim 4 wherein the texaphyrin is a phosphoramidite derivative.
Claim 7
Dependent Claim
12 words
The method of claim 1 wherein the synthesizer is an automated synthesizer.
Claim 8
Dependent Claim
11 words
The method of claim 1 wherein the nucleotide is an oligonucleotide.
Claim 9
Dependent Claim
12 words
The method of claim 7 wherein the oligonucleotide is an oligonucleotide derivative.
Claim 10
Dependent Claim
21 words
The method of claim 8 wherein the oligonucleotide derivative is selected from the group consisting of phosphorothioates, phosphoramidates, methylphosphonates and phosphotriesters.
Claim 11
Dependent Claim
13 words
The method of claim 8 wherein the oligonucleotide derivative is a 2'-O-methyl ribonucleotide.
Claim 12
Independent Claim
71 words
A method of obtaining a 3'-linked expanded porphyrin-nucleotide conjugate, the method comprising the steps of: attaching an expanded porphyrin to a solid support of a DNA synthesizer; attaching a nucleic acid residue to the expanded porphyrin, followed by the attachment of one or more additional nucleic acid residues in stepwise synthesis to obtain a desired oligonucleotide; cleaving the resulting 3'-linked expanded porphyrin-nucleotide conjugate from the solid support; and deprotecting the oligonucleotide.
Claim 13
Independent Claim
71 words
A method of obtaining a 3'-linked expanded porphyrin-nucleotide conjugate, the method comprising the steps of: attaching an expanded porphyrin to a solid support of a DNA synthesizer; attaching a nucleic acid residue to the expanded porphyrin, followed by the attachment of one or more additional nucleic acid residues in stepwise synthesis to obtain a desired oligonucleotide; cleaving the resulting 3'-linked expanded porphyrin-nucleotide conjugate from the solid support; and deprotecting the oligonucleotide.
Claim 14
Dependent Claim
12 words
The method of claim 11 wherein the expanded porphyrin is a sapphyrin.
Claim 15
Dependent Claim
12 words
The method of claim 11 wherein the expanded porphyrin is a texaphyrin.
Claim 16
Dependent Claim
12 words
The method of claim 13 wherein the texaphyrin is a phosphoramidite derivative.
Claim 17
Dependent Claim
12 words
The method of claim 11 wherein the synthesizer is an automated synthesizer.
Claim 18
Independent Claim
64 words
A method of obtaining a 5'-linked expanded porphyrin-nucleotide conjugate, the method comprising the steps of: attaching one or more nucleic acid residues to a solid support of a DNA synthesizer in stepwise synthesis to obtain a desired oligonucleotide; attaching an expanded porphyrin to the oligonucleotide as the final residue; cleaving the resulting 5'-linked expanded porphyrin-nucleotide conjugate from the solid support; and deprotecting the oligonucleotide.
Claim 19
Independent Claim
64 words
A method of obtaining a 5'-linked expanded porphyrin-nucleotide conjugate, the method comprising the steps of: attaching one or more nucleic acid residues to a solid support of a DNA synthesizer in stepwise synthesis to obtain a desired oligonucleotide; attaching an expanded porphyrin to the oligonucleotide as the final residue; cleaving the resulting 5'-linked expanded porphyrin-nucleotide conjugate from the solid support; and deprotecting the oligonucleotide.
Claim 20
Dependent Claim
12 words
The method of claim 16 wherein the expanded porphyrin is a sapphyrin.
Claim 21
Dependent Claim
12 words
The method of claim 16 wherein the expanded porphyrin is a texaphyrin.
Claim 22
Dependent Claim
12 words
The method of claim 18 wherein the texaphyrin is a phosphoramidite derivative.
Claim 23
Dependent Claim
12 words
The method of claim 16 wherein the synthesizer is an automated synthesizer.
Claim 24
Independent Claim
29 words
A method of synthesizing a texaphyrin-nucleotide conjugate in a DNA synthesizer, the method comprising reacting a texaphyrin with a nucleotide using the DNA synthesizer, to form a texaphyrin-nucleotide conjugate.
Claim 25
Independent Claim
29 words
A method of synthesizing a texaphyrin-nucleotide conjugate in a DNA synthesizer, the method comprising reacting a texaphyrin with a nucleotide using the DNA synthesizer, to form a texaphyrin-nucleotide conjugate.
Claim 26
Dependent Claim
143 words
The method of claim 21 wherein the texaphyrin is a phosphoramidite derivative of a texaphyrin metal complex where the texaphyrin metal complex has the following formula: ##STR5## wherein, M is H, a divalent metal cation or a trivalent metal cation; R 1 -R 4 , R 7 and R 8 are independently hydrogen, halide, hydroxyl, alkyl, aryl, haloalkyl, nitro, formyl, acyl, hydroxyalkyl, oxyalkyl, oxyhydroxyalkyl, saccharide, carboxy, carboxyalkyl, carboxyamide, carboxyamidealkyl, aminoalkyl, sulfonatoalkyl, amidealkyl, or aryl; R 6 and R 9 are independently selected from the groups of R 1 -R 4 , R 7 and R 8 , with the proviso that the halide is other than iodide and the haloalkyl is other than iodoalkyl; R 5 and R 10 -R 12 are independently hydrogen, alkyl, aryl, hydroxyalkyl, oxyalkyl, oxyhydroxyalkyl, carboxyalkyl, or carboxyamidealkyl; and Z is an integer less than or equal to 5.
Claim 27
Dependent Claim
13 words
The method of claim 21 wherein the DNA synthesizer is an automated synthesizer.
Claim 28
Dependent Claim
11 words
The method of claim 21 wherein the nucleotide is an oligonucleotide.
Claim 29
Dependent Claim
12 words
The method of claim 24 wherein the oligonucleotide is an oligonucleotide derivative.
Claim 30
Dependent Claim
12 words
The method of claim 11 wherein the oligonucleotide is an oligonucleotide derivative.
Claim 31
Dependent Claim
144 words
The method of claim 11 wherein the expanded porphyrin is a phosphoramidite derivative of a texaphyrin metal complex where the texaphyrin metal complex has the following formula: ##STR6## wherein, M is H, a divalent metal cation or a trivalent metal cation; R 1 -R 4 , R 7 and R 8 are independently hydrogen, halide, hydroxyl, alkyl, aryl, haloalkyl, nitro, formyl, acyl, hydroxyalkyl, oxyalkyl, oxyhydroxyalkyl, saccharide, carboxy, carboxyalkyl, carboxyamide, carboxyamidealkyl, aminoalkyl, sulfonatoalkyl, amidealkyl, or aryl; R 6 and R 9 are independently selected from the groups of R 1 -R 4 , R 7 and R 8 , with the proviso that the halide is other than iodide and the haloalkyl is other than iodoalkyl; R 5 and R 10 -R 12 are independently hydrogen, alkyl, aryl, hydroxyalkyl, oxyalkyl, oxyhydroxyalkyl, carboxyalkyl, or carboxyamidealkyl; and Z is an integer less than or equal to 5.
Claim 32
Dependent Claim
12 words
The method of claim 16 wherein the oligonucleotide is an oligonucleotide derivative.
Claim 33
Dependent Claim
144 words
The method of claim 16 wherein the expanded porphyrin is a phosphoramidite derivative of a texaphyrin metal complex where the texaphyrin metal complex has the following formula: ##STR7## wherein, M is H, a divalent metal cation or a trivalent metal cation; R 1 -R 4 , R 7 and R 8 are independently hydrogen, halide, hydroxyl, alkyl, aryl, haloalkyl, nitro, formyl, acyl, hydroxyalkyl, oxyalkyl, oxyhydroxyalkyl, saccharide, carboxy, carboxyalkyl, carboxyamide, carboxyamidealkyl, aminoalkyl, sulfonatoalkyl, amidealkyl, or aryl; R 6 and R 9 are independently selected from the groups of R 1 -R 4 , R 7 and R 8 , with the proviso that the halide is other than iodide and the haloalkyl is other than iodoalkyl; R 5 and R 10 -R 12 are independently hydrogen, alkyl, aryl, hydroxyalkyl, oxyalkyl, oxyhydroxyalkyl, carboxyalkyl, or carboxyamidealkyl; and Z is an integer less than or equal to 5.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1999-10-15 | 2000-04-15 | 2000-10-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2003-10-15 | 2004-04-15 | 2004-10-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2007-10-15 | 2008-04-15 | 2008-10-15 | $7700.00 | Window Closed / Lapsed |