Compositions comprising macrocyclic hosting moieties

Patent metadata

Field	Value
Publication number	US-2023234865-A1
Application number	US-202318101092-A
Country	US
Kind code	A1
Filing date	Jan 24, 2023
Priority date	Jan 25, 2022
Publication date	Jul 27, 2023
Grant date	—

Abstract

A method of sequestering anions from a liquid including the anions includes contacting a composition comprising at least one macrocyclic moiety with the liquid. The macrocyclic moiety includes groups including an electropositive E-H bond donor extending into a cavity of the macrocyclic moiety wherein E is selected from the group consisting of C, N, and O, wherein two or more groups including an electropositive E-H donor interact with an anion to form a chelate with the anion.

First claim

What is claimed is:

1 . A method of sequestering anions from a liquid including the anions, comprising:
contacting a composition comprising at least one macrocyclic moiety with the liquid, the macrocyclic moiety comprising groups including an electropositive E-H bond donor extending into a cavity of the macrocyclic moiety wherein E is selected from the group consisting of C, N, and O, wherein two or more groups include an electropositive E-H bond donor interacting with an anion to form a chelate with the anion.

2 . The method of claim 1 wherein the groups including the electropositive E-H bond donor extending into the cavity of the macrocyclic moiety are aromatic groups, amine groups, amide groups, urea groups, or thiourea groups.

3 . The method of claim 1 wherein the groups including the electropositive E-H bond donor extending into the cavity of the macrocyclic moiety are aromatic groups or heterocyclic aromatic groups.

4 . The method of claim 1 wherein the macrocyclic moiety exhibits an affinity toward anions that are non-spherical anions.

5 . The method of claim 4 wherein the macrocyclic moiety exhibits an affinity for anions that are large anions.

6 . The method of claim 5 wherein the macrocyclic moiety has an affinity for at least one of sulfonates and carboxylates.

7 . The method claim 1 wherein a plurality of the macrocyclic moieties are immobilized upon a surface of a solid or covalently incorporated within a polymer.

8 . The method of claim 1 wherein the groups including the electropositive E-H bond donor extending into the cavity of the macrocyclic moiety are conformationally constrained.

9 . The method of claim 1 wherein the macrocyclic moiety is synthesized by providing an end group including a macrocyclic compound that is sufficiently rigid that it presents a plurality of functional groups extending from a first axial side of the end group and reacting a plurality of reactive compounds with the plurality of functional groups extending from the first axial side of the end group, wherein each of the plurality of reactive compounds is a precursor for one of the groups including the electropositive E-H bond donor and includes a functional group reactive with at least one of the plurality of functional groups extending from the first axial side of the end group, each of the reactive compounds comprising at least one electron withdrawing substituent and one of the electropositive E-H donors.

10 . The method of claim 9 wherein the macrocyclic compound is a resorcin[n]arene wherein n is an integer between 4 and 8, a bridged resorcin[n′]arene wherein n′ is an integer between 4 and 8, a calix[n″ ]pyrrole-resorcinarene wherein n″ is 4, and a calix[n″′]arene wherein n″′ is an integer between 4 and 6.

11 . The method of claim 1 wherein each of the groups including the electropositive E-H bond donor has the formula:

wherein R n is an electron withdrawing group.

12 . The method of claim 11 wherein R n is selected from the group of F, —CN, —NO 2 , SO 2 CF 3 , NR 3 + , SO 3 H, SO 2 R, —COR, CO 2 H, —CO 2 R, —CONH 2 , —CONHR, and —CONR 2 , wherein R is an alkyl group having one and up to 20 carbon atoms, or an aryl group with or without substituents, where substituents may include any one or combinations of the following groups F, —CN, —NO 2 , SO 2 CF 3

13 . The method of claim 11 wherein R n is selected from the group of F, —CN, and —NO 2 .

14 . The method of claim 1 I wherein each of the groups including the electropositive E-H bond donor has the formula:

15 . The method of claim 14 wherein the macrocyclic moiety is a resorcin[n]arene wherein n is 4.

16 . The method of claim 9 wherein the macrocyclic compound is generally cylindrical or ellipsoidal.

17 . The method of claim 9 wherein the macrocyclic compound comprise arene groups.

18 . The method of claim 9 wherein the plurality of functional groups extending from the first axial side of the end group are selected from the group consisting of halide groups, boronate esters, and acetylenic groups.

19 . The method of claim 9 wherein the macrocyclic compound further comprises a plurality of functional groups on a second axial side of the macrocyclic compound.

20 . The method of claim 19 wherein the plurality of functional groups on the second axial side of the macrocyclic compound are selected from the group consisting of alkyl group, an aryl group, an aldehyde group, an alkyl halide, an alcohol group, an ether group, an alkyl epoxide group, an olefinic group, an acetylenic group, carboxylic group, or a polymeric group.

21 . The method of claim 19 wherein at least a portion of the plurality of functional groups on the second axial side of the macrocyclic compound are selected to react in a polymerization reaction.

22 . The method of claim 9 wherein the macrocyclic compound is:

wherein R′ is a hydroxyl group or an alkoxy, R″ is a halide, a boronate ester group, an acetylenic group, an amine group, an amide group, a urea group, a thiourea group, an aldehyde group, or a carboxylic group, R″′ is a halide group, a hydroxyl group, an alkoxy group, an amine group, an aldehyde group, an imine group, or a carboxylic group, and R is an alkyl group, an aryl group, an aldehyde group, an alkyl halide, an alcohol group, an ether group, an alkyl epoxide group, an olefinic group, an acetylenic group, a carboxylic group, or a polymeric group.

23 . The method of claim 1 wherein the anions are perfluorinated compounds and polyfluorinated compounds.

24 . The method of claim 1 wherein the macrocyclic moieties also interact with neutral compounds to sequester a neutral compound.

25 . The method of claim 1 wherein a plurality of the macrocyclic moieties of different ring size are immobilized upon a surface of a solid or covalently incorporated within a polymer to sequester anions of different size.

26 . A composition, comprising at least one macrocyclic moiety, the macrocyclic moiety comprising groups including an electropositive E-H bond donor extending into a cavity of the macrocyclic moiety, wherein E is selected from the group consisting of C, N, and O, wherein two or more groups include an electropositive E-H donor to interact with an entity to be hosted by the macrocyclic moiety.

27 . A composition, having the formula:

wherein R n is an electron withdrawing group, and wherein R is an alkyl group, an aryl group, an aldehyde, an alkyl halide group, an alcohol group, an ether group, an alkyl epoxide, an olefinic group, or a carboxylic group.

Assignees

• Univ Pittsburgh Commonwealth Sys Higher Education

Inventors

• Hernandez Sanchez Raul
• Mirzaei Saber
• Arora Swati
• Espinoza Castro Victor Manuel

Classifications

• C02F1/683 Primary

  by addition of complex-forming compounds · CPC title

• C02F2101/14

  Fluorine or fluorine-containing compounds · CPC title

• C02F1/44

  by dialysis, osmosis or reverse osmosis {(general membrane separation processes B01D61/00, membrane modules B01D63/00, electrodialysis C02F1/4693, combination of membrane modules and bioreactors C02F3/1268)} · CPC title

• C02F2101/36

  containing halogen · CPC title