Sapphyrin multimers

• US 5,587,478 A
• Filed: 03/15/1995
• Issued: 12/24/1996
• Est. Priority Date: 10/21/1992
• Status: Expired due to Fees

• Current Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Original Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Inventors: Andrievsky, Andrei, Sessler, Jonathan L., Kr al, Vladimir
• Primary Examiner(s): Shah, Mukund J.
• Assistant Examiner(s): Sripada, Pavanaram K.
• Application Number:
  US08/405,275
• Time in Patent Office: 650 Days
• Field of Search: 528/230, 540/145, 540/472, 540/474, 536/28.1
• US Class Current: 540/474
• CPC Class Codes: A61K 41/0076 PDT with expanded (metallo)porphyrins, i.e. having more than 20 ring atoms, e.g. texaphyrins, sapphyrins, hexaphyrins, pentaphyrins, porphocyanines
• CPC Class Codes: A61K 47/54 the modifying agent being an organic compound
• CPC Class Codes: A61K 47/546 Porphyrines; Porphyrine with an expanded ring system, e.g. texaphyrine
• CPC Class Codes: A61K 47/558 the modifying agent being a chemiluminescent acceptor
• CPC Class Codes: C07D 487/22 in which the condensed system contains four or more hetero rings
• CPC Class Codes: C07H 15/26 Acyclic or carbocyclic radicals, substituted by hetero rings
• CPC Class Codes: C07H 21/00 Compounds containing two or more mononucleotide units having separate phosphate or polyphosphate groups linked by saccharide radicals of nucleoside groups, e.g. nucleic acids
• CPC Class Codes: C12N 15/101 by chromatography, e.g. electrophoresis, ion-exchange, reverse phase

Abstract

The present invention provides novel sapphyrin dimers, trimers, oligomers and polymers, which multimers may include repeating units of sapphyrin or sapphyrin derivatives alone, or may further incorporate other units such as nucleobases.

Claims

1. A sapphyrin multimer having structure I:

##STR14## wherein each of R¹ --R¹⁰ are independently hydrogen, alkyl, alkene, alkyne, halide, alkylhalide, hydroxyalkyl, hydroxyalkylamido, glycol, polyglycol, thiol, thioalkyl, aminoalkyl, carboxyalkyl, carboxyamidealkyl, oxyalkyl, alkoxyalkyl, aryloxyalkyl, oxyhydroxyalkyl, alkyloxycarbonyl, aryloxycarbonyl, aldehyde, ether, ketone, carboxylic acid, phosphate, phosphonate, saccharide, nucleobase, sulfate, phosphate substituted alkyl, phosphonate substituted alkyl or sulfate substituted alkyl;

wherein at least one of R¹ -R¹⁰ is of the formula (CH₂)_n --A--(CH₂)_m --B, where

A is alkyl, oxy, sulfide, amide, carbonyl, alkenyl, alkynyl, aryl, alkylhalide, hydroxyalkyl, glycol, polyglycol, alkylthiol, substituted alkyl, phosphate, phosphonate, sulfate, phosphate substituted alkyl, phosphonate substituted alkyl, sulfate substituted alkyl, carbonate, carbamate, bis(aminoguanidinium), carboxy, carboxyamide, carboxyamidealkyl, carboxyamidearyl, thiol-substituted carboxyamide, or derivatized carboxyamide;

B is a sapphyrin, or a sapphyrin derivative, or an oligomer or polymer of sapphyrin or of a sapphyrin derivative having up to about 200 sapphyrin units; and

n and m are independently an integer from 0 to 10.

2. The sapphyrin multimer of claim 1 wherein A is carboxyamidearyl;

B is a sapphyrin or a sapphyrin derivative; and

n and m are independently 1, 2 or 3.

3. The sapphyrin multimer of claim 1 wherein A is carboxyamidealkyl;

B is a sapphyrin or a sapphyrin derivative; and

n and m are independently 1, 2 or 3.

4. The sapphyrin multimer of claim 3 wherein B is a sapphyrin derivative and the sapphyrin derivative is hydroxyalkyl, saccharide or aminosaccharide derivative.

5. The sapphyrin multimer of claim 1 wherein A is carboxyamidealkyl bound to a further amide;

and the further amide is covalently bound to two molecules of B to form a tethered sapphyrin trimer.

6. The sapphyrin multimer of claim 1 wherein B is a sapphyrin or sapphyrin derivative and B is further bound to a third sapphyrin or sapphyrin derivative to form a linear sapphyrin trimer.

7. The sapphyrin multimer of claim 6 wherein the linear sapphyrin trimer is covalently bound to form a cyclic trimer.

8. The sapphyrin multimer of claim 1 wherein A is carboxyamidealkyl bound to a further amide;

the further amide being covalently bound to a second sapphyrin and a linker, the linker being bound to a third and a fourth sapphyrin to form a tethered sapphyrin tetramer.

9. The sapphyrin multimer of claim 8 wherein the linker is a tertiary amine.

10. The sapphyrin multimer of claim 1 wherein B is an oligomer or polymer of sapphyrin or sapphyrin derivative.

11. The sapphyrin multimer of claim 10 where B is a polymer of sapphyrin or sapphyrin derivative having from 4 to about 200 sapphyrin units.

12. The sapphyrin multimer of claim 9 wherein A is phosphate.

15. The sapphyrin multimer of claim 11 wherein B is a polymer of sapphyrin derivative and the derivative is a nucleobase.

16. The sapphyrin multimer of claim 15 further comprising a noncovalently bound oligonucleotide.

13. The sapphyrin multimer of claim t wherein at least one of R¹ -R¹⁰ is a nucleobase.

14. The sapphyrin multimer of claim 13 where B is a sapphyrin derivative and the derivative is a nucleobase.

17. A sapphyrin multimer having structure 14, 15, 15b, 15c, 19, 21, 22, 23, 24, 25, 26, 27, 34, 35, or 36.

18. A method of making a sapphyrin multimer comprising the steps of

obtaining a sapphyrin or sapphyrin derivative, and

reacting the sapphyrin or sapphyrin derivative with a further sapphyrin or sapphyrin derivative to form a sapphyrin multimer.

19. A method of binding an anion comprising the step of contacting the anion with a multimeric sapphyrin or sapphyrin derivative.

20. The method of claim 19 where the anion is a phosphate anion or a dicarboxylate anion.