Method for separating molecules

• US 5,744,302 A
• Filed: 05/11/1995
• Issued: 04/28/1998
• 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: Shreder, Kevin, Kral, Vladimir, Thomas, Richard E., Furuta, Hiroyuki, Sessler, Jonathan L., Iverson, Brent L.
• Primary Examiner(s): Jones, W. Gary
• Assistant Examiner(s): REES, DIANE
• Application Number:
  US08/438,948
• Time in Patent Office: 1,083 Days
• Field of Search: 435/6, 435/5, 435/91.1, 435/91.2, 422/48, 423/129, 540/472, 540/145, 536/24.3-24.33
• US Class Current: 435/6.12
• 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 various novel covalently modified sapphyrin derivatives and conjugates; polymers including sapphyrin or derivatives thereof; and chromatographic supports including sapphyrins and other expanded porphyrins and derivatives thereof. Disclosed are water soluble sapphyrins, including polyhydroxysapphyrins and sapphyrin-sugar derivatives; sapphyrin-metal chelating conjugates; sapphyrin nucleobase conjugates; oligosapphyrins and polysapphyrins, including sapphyrin dimers, trimers, oligomers and higher polymers; and polymer supported expanded porphyrin compositions, including advantageous rubyrin- and sapphyrin-based chromatography columns and electrophoretic supports. Sapphyrin oligomers and polymers and polymer supported expanded porphyrins, such as, e.g., glass and silica expanded porphyrin constructs, are disclosed which include both repeating units of sapphyrin derivatives alone and which include other units, for example, nucleobases, sapphyrin-nucleobase conjugates and long chain alkyl groups.

Claims

1. A method for separating a first molecule from a mixture of at least two molecules, the method comprising contacting said mixture with a matrix-supported expanded porphyrin to separate said first molecule from said mixture, wherein the matrix-supported expanded porphyrin further comprises a nucleobase-containing group.

2. The method of claim 1 wherein the nucleobase-containing group is attached to the matrix support of the matrix-supported expanded porphyrin.

3. The method of claim 1 wherein the nucleobase-containing group is attached to the expanded porphyrin of the matrix-supported expanded porphyrin.

4. The method of claim 1 wherein the nucleobase-containing group comprises a nucleoside or a nucleotide or a derivative thereof.

5. The method of claim 1 wherein the nucleobase-containing group comprises from 1 to 10 nucleobase units.

20. The method of claim 1 wherein the matrix support of the matrix-supported expanded porphyrin is silica gel, silica, Merrifield resin, glass, controlled pore glass, polystyrene, sepharose, agarose, clay, zeolite or polyacrylamide.

6. A method for separating a first molecule from a mixture of at least two molecules, the method comprising contacting said mixture with a matrix-supported sapphyrin to separate said first molecule from said mixture, wherein the matrix-supported sapphyrin has the structure:

##STR4## wherein, each of R¹ -R¹⁰ is independently H, alkyl, alkene, alkyne, halide, alkyl halide, hydroxyalkyl, glycol, polyglycol, thiol, alkyl thiol, aminoalkyl, carboxyalkyl, alkoxyalkyl, aryloxyalkyl, alkyloxycarbonyl, aryloxycarbonyl, aldehyde, ether, ketone, carboxylic acid, phosphate, phosphonate, sulfate, phosphate substituted alkyl, phosphonate substituted alkyl, or sulfate substituted alkyl, such that the total number of carbon atoms in each substituent R is less than or equal to 10; and

wherein at least one of R¹ -R¹⁰ is of the formula (CH₂)_n --A--(CH₂)_m --B, wherein A is CH₂, O, S, NH or NR¹¹, wherein R¹¹ is alkyl, alkene, alkyne, halide, alkyl halide, hydroxyalkyl, glycol, polyglycol, thiol, alkyl thiol, substituted alkyl, phosphate, phosphonate, sulfate, phosphate substituted alkyl, phosphonate substituted alkyl, sulfate substituted alkyl, COO, CONH, CSNH, CONR¹¹ ;

B is a polymeric or solid support matrix; and

n and m are integers of less than or equal to 10 or zero.

7. The method of claim 6 wherein B further comprises an aryl, silyl, siloxy, aminoaryl, amino, amidoaryl or silyloxy group as a linking agent to the support matrix.

8. The method of claim 6 wherein the support matrix is selected from the group consisting of silica gel, silica, Merrifield resin, glass, controlled pore glass, polystyrene, sepharose, agarose, clay, zeolite and polyacrylamide.

9. The method of claim 6 wherein the matrix-supported sapphyrin further comprises a long chain alkyl group of one to twenty carbon atoms attached to the support matrix.

10. The method of claim 6 wherein the matrix-supported sapphyrin further comprises a long chain alkyl group of one to twenty carbon atoms attached to the sapphyrin.

11. The method of claim 6 wherein said first molecule is a molecule having a negatively charged chloride, bromide, fluoride, phosphate, phosphonate, phosphate ester, arsenate, arsenate ester, sulfate, or sulfonate moiety.

12. The method of claim 6 wherein said first molecule is a molecule having a negatively-charged phosphate moiety.

13. The method of claim 6 wherein said first molecule comprises a nucleobase-containing group.

14. The method of claim 13 wherein said first molecule comprises a nucleoside or a nucleotide or a derivative thereof.

15. The method of claim 13 wherein said first molecule comprises an oligonucleotide.

16. The method of claim 6 wherein said first molecule comprises DNA or RNA.

17. The method of claim 6 wherein said first molecule is an organophosphorus compound.

18. The method of claim 17 wherein said first molecule is a pesticide, a herbicide, or a fungicide.

19. The method of claim 6 wherein the matrix-supported sapphyrin has a structure as shown in any one of structures 31-38 of FIG. 5D.