# US 11,026,419 B2 · Silver- and copper-chelating ionic liquids, polymers, and gels, and uses thereof

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- Number: US 11,026,419 B2
- Document ID: US11026419B2
- Status: Granted
- Kind: B2
- Application number: 16/349,800
- Filed: 2017-11-20
- Published: 2019-10-31
- Granted: 2021-06-08
- Earliest claimed: 2016-11-21
- Assignees: Massachusetts Institute of Technology
- Applicants: Massachusetts Institute of Technology
- Inventors: T. Alan Hatton; Timothy Kuan-Ta Lu; Paul Brown; Cesar de la Fuente Nunez; Sahag Voskian
- Web page: https://patentgrep.com/patent/US11026419B2

## CPC

- A01N 33/04: Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
- A01N 25/02: containing liquids as carriers, diluents or solvents
- A01N 37/18: containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N 43/00: Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds (containing cyclic anhydrides, cyclic imides A01N37/00; containing compounds of the formula [IMAGE cpc-sch-A01N-0942.gif] containing only one heterocyclic ring, wherein m>=1 and n>=0 and [IMAGE cpc-sch-A01N-0943.gif]is unsubstituted or alkylsubstituted pyrrolidine, piperidine, morpholine, thiomorpholine, piperazine or a polymethyleneimine with four or more CH2 groups, A01N33/00 - A01N41/12; containing cyclopropane carboxylic acids or derivatives thereof, e.g. esters having heterocyclic rings, A01N53/00)
- A01N 59/20: Copper
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS

## Abstract

Disclosed are methods of antimicrobial treatment using ionic liquids (ILs), IL complexes, polymers comprising ILs, and polymers comprising neutral ethylene diamine compounds. Also disclosed are novel IL complexes, polymers comprising ILs, and polymers comprising neutral ethylene diamine compounds.

## Claims

### Claim 1

A method of antimicrobial treatment, comprising:
providing a sample comprising a plurality of microorganisms;
adding to the sample an ionic liquid mixture comprising an ionic liquid complex comprising an ionic liquid chelated to a metal cation;
thereby killing or inhibiting the growth of at least a portion of the plurality of microorganisms in the sample,
wherein the ionic liquid comprises a cation and an anion; and
the cation is represented by the following structural formula I:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy, or
the cation is represented by the following structural formula II:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 2

A method of antimicrobial treatment, comprising:
providing a sample comprising a plurality of microorganisms, wherein said microorganisms comprise a metal cation;
adding to the sample an ionic liquid, thereby killing or inhibiting the growth of at least a portion of the plurality of microorganisms in the sample,
wherein the ionic liquid comprises a cation and an anion; and
the cation is represented by the following structural formula I:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy, or
the cation is represented by the following structural formula II:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 3

A method of preventing or suppressing microbial growth on a surface, comprising:
applying to the surface an ionic liquid mixture comprising an ionic liquid complex comprising an ionic liquid chelated to a metal cation;
thereby preventing or suppressing microbial growth on the surface,
wherein the ionic liquid comprises a cation and an anion; and
the cation is represented by the following structural formula I:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy, or
the cation is represented by the following structural formula II:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 4

A method of preventing or suppressing microbial growth on a surface, comprising:
applying to the surface an ionic liquid, thereby preventing or suppressing microbial growth on the surface,
wherein the ionic liquid comprises a cation and an anion; and
the cation is represented by the following structural formula I:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy, or
the cation is represented by the following structural formula II:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 5 (depends on 1)

The method of claim 1, wherein the cation is represented by the following structural formula I:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 6 (depends on 1)

The method of claim 1, wherein the cation is represented by the following structural formula II:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 7 (depends on 2)

The method of claim 2, wherein the cation is represented by the following structural formula I:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 8 (depends on 2)

The method of claim 2, wherein the cation is represented by the following structural formula II:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 9 (depends on 3)

The method of claim 3, wherein the cation is represented by the following structural formula I:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 10 (depends on 3)

The method of claim 3, wherein the cation is represented by the following structural formula II:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 11 (depends on 4)

The method of claim 4, wherein the cation is represented by the following structural formula I:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 12 (depends on 4)

The method of claim 4, wherein the cation is represented by the following structural formula II:
wherein, independently for each occurrence:
R1 is —(C(R)2)n—;
n is 2, or 3;
R2 is —(C(R′)2)m—R″;
m is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and
R is H, F, C1-C3 alkyl, or C1-C3 fluoroalkyl;
R′ is H, F, C1-C8 alkyl, or C1-C8 fluoroalkyl; and
R″ is H, F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, C1-C3 fluoroalkyloxy, C6-C10 aryl, C2-C8 alkenyl or C2-C8 fluoroalkenyl; wherein each instance of C6-C10 aryl is optionally substituted with one, two, three, four or five substituents independently selected from the group consisting of F, C1-C3 alkyl, C1-C3 fluoroalkyl, C1-C3 alkyloxy, and C1-C3 fluoroalkyloxy.

### Claim 13 (depends on 1)

The method of claim 1, wherein the metal cation is a cation of Ag, Ca, Cu, or Zn.

### Claim 14 (depends on 1)

The method of claim 1, wherein the anion is boron tetrafluoride, phosphorus hexafluoride, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, p-toluenesulfonate, bis(methanesulfonyl)amide, bis(trifluoromethanesulfonyl)amide, bis(benzenesulfonyl)amide, or bis(p-toluenesulfonyl)amide.

### Claim 15 (depends on 2)

The method of claim 2, wherein the metal cation is a cation of Mg, Fe, Hg, Sr, Sn, Ca, Cd, Zn, Co, Cu, Pb, Ni, Sc, V, Cr, Mn, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu.

### Claim 16 (depends on 2)

The method of claim 2, wherein the anion is boron tetrafluoride, phosphorus hexafluoride, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, p-toluenesulfonate, bis(methanesulfonyl)amide, bis(trifluoromethanesulfonyl)amide, bis(benzenesulfonyl)amide, or bis(p-toluenesulfonyl)amide.

### Claim 17 (depends on 3)

The method of claim 3, wherein the metal cation is a cation of Ag, Ca, Cu, or Zn.

### Claim 18 (depends on 3)

The method of claim 3, wherein the anion is boron tetrafluoride, phosphorus hexafluoride, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, p-toluenesulfonate, bis(methanesulfonyl)amide, bis(trifluoromethanesulfonyl)amide, bis(benzenesulfonyl)amide, or bis(p-toluenesulfonyl)amide.

### Claim 19 (depends on 4)

The method of claim 4, wherein the anion is boron tetrafluoride, phosphorus hexafluoride, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, p-toluenesulfonate, bis(methanesulfonyl)amide, bis(trifluoromethanesulfonyl)amide, bis(benzenesulfonyl)amide, or bis(p-toluenesulfonyl)amide.