Cyclophane-sustained high performance porphyrins

Patent metadata

Field	Value
Publication number	US-12084579-B2
Application number	US-202117445057-A
Country	US
Kind code	B2
Filing date	Aug 13, 2021
Priority date	Aug 13, 2020
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

Disclosed herein are receptor-substrate complexes comprising an octacationic tricyclic cyclophane and a pyrrole dye complexed therein and methods of using and making the same.

First claim

We claim:

1. A receptor-substrate complex, or a salt thereof, the complex comprising a tricyclic octacationic cyclophane and a pyrrole dye complexed therein, wherein the cyclophane is

2. The complex of claim 1 , wherein the pyrrole dye is a porphyrin dye.

3. The complex of claim 1 , wherein the pyrrole dye is a metalloporphyrin dye.

4. The complex of claim 1 , wherein the pyrrole dye has a formula

wherein R 1 and R 2 are independently selected from hydrogen, —OH, —NRR′, —NO 2 , —SH, —SR, —R, —OR, —COOR, —OCH 2 CH 2 (OCH 2 CH 2 ) n —OR, or —OCH 2 -(triazole)-CH 2 CH 2 —(OCH 2 CH 2 ) n —OR, wherein each R and R′ are independently selected from a substituted or unsubstituted, branched or unbranched, saturated or unsaturated C 1 -C 6 alkyl, and wherein n is an integer greater than or equal to zero.

5. The complex of claim 1 , wherein the pyrrole dye has a formula

wherein R 1 and R 2 are independently selected from hydrogen, —OH, —NRR′, —NO 2 , —SH, —SR, —R, —OR, —COOR, —OCH 2 CH 2 (OCH 2 CH 2 ) n —OR, or —OCH 2 -(triazole)-CH 2 CH 2 —(OCH 2 CH 2 ) n —OR, wherein each R and R′ are independently selected from a substituted or unsubstituted, branched or unbranched, saturated or unsaturated C 1 -C 6 alkyl, wherein n is an integer greater than or equal to zero, and wherein M is a transition metal or an alkaline earth metal.

6. A salt comprising the complex according to claim 1 and a counter anion.

7. The salt of claim 6 , wherein the counter anion is CF 3 CO 2 31 , PF 6 − , or Cl − .

8. A crystalline composition comprising the complex of claim 1 .

9. The crystalline composition of claim 8 , wherein the crystalline composition has a triclinic, space group P-1 (no. 2) crystal parameter and wherein the crystalline composition has unit cell parameters: a=14.7±0.1 Å, b=17.5±0.1 Å, c=19.1±0.1 Å, α=109.0±0.1°, β=106.7±0.1°, and γ=102.3±0.1°.

10. The crystalline composition of claim 8 , wherein the crystalline composition has a triclinic, space group P-1 (no. 2) crystal parameter and wherein the crystalline composition has unit cell parameters: a=14.7±0.1 Å, b=17.5±0.1 Å, c=19.0±0.1 Å, α=108.9±0.1°, β=106.7±0.1°, and γ=102.1±0.1°.

11. A method for fluorescence spectroscopy, comprising providing the complex according to claim 1 , irradiating the complex with an irradiation source, and detecting an emission signal from the complex.

12. The method of claim 11 further comprising providing a dye and detecting an emission signal from the dye.

13. The method of claim 12 , wherein the complex and the dye are irradiated by the same irradiation source and wherein the emission signal of the complex and the emission signal of the dye are detectably distinct.

14. The method of claim 11 , wherein the complex is localized in an aqueous environment.

15. A method for stabilizing a pyrrole dye, the method comprising providing a tricyclic octacationic cyclophane and complexing the cyclophane with the pyrrole dye to prepare the receptor-substrate complex according to claim 1 .

16. The method of claim 15 , wherein the pyrrole dye resists protonation in an aqueous environment.

17. The method of claim 15 , wherein the pyrrole dye resists NH proton exchange with a pyrrole core in an aqueous environment.

18. The method of claim 15 , wherein the pyrrole dye resists solvolysis in an aqueous environment.

19. A method for preparing the receptor-substrate complex of claim 1 , the method comprising providing the tricyclic octacationic cyclophane, providing a pyrrole dye, and contacting the tricyclic octacationic cyclophane and the pyrrole dye.

20. The complex of claim 1 , wherein the pyrrole dye is a chlorin, a bacteriochlorin, a phthalocyanine, a naphthalocyanine, or a subphthalocyanine.

21. The complex of claim 5 , wherein M is Au, Pd, Pt, Cu, Ni, Mg, Fe, Mn, or Co.

Assignees

• Univ Northwestern

Inventors

• Stoddart James Fraser
• Liu Wenqi

Classifications

• G01N33/582

  with fluorescent label · CPC title

• G01N21/6428

  Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" (in vivo A61B5/00; immunoassay G01N33/53) · CPC title

• G01N2021/6439

  with indicators, stains, dyes, tags, labels, marks · CPC title

• C09B67/0025

  Crystal modifications; Special X-ray patterns · CPC title

• C09B67/0097

  Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes · CPC title