# US 8,772,197 B2 · Compositions for chemical and biological defense

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- Number: US 8,772,197 B2
- Document ID: US8772197B2
- Status: Granted
- Kind: B2
- Application number: 12/672,611
- Filed: 2008-08-18
- Published: 2011-02-03
- Granted: 2014-07-08
- Earliest claimed: 2007-08-17
- Assignees: Massachusetts Institute of Technology
- Applicants: Trevor Alan Hatton; Lev E. Bromberg; Huan Zhang
- Inventors: Trevor Alan Hatton; Lev E. Bromberg; Huan Zhang
- Web page: https://patentgrep.com/patent/US8772197B2

## CPC

- A01N 43/92: having rings with one or more halogen atoms as ring hetero atoms
- A01N 25/24: containing ingredients to enhance the sticking of the active ingredients
- A01N 25/34: Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
- A62D 3/35: by hydrolysis
- D06M 15/29: containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
- D06M 16/00: Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- A62D 2101/02: Chemical warfare substances, e.g. cholinesterase inhibitors
- A62D 2101/04: Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
- A62D 2101/26: containing nitrogen or phosphorus
- D06M 2400/01: Creating covalent bondings between the treating agent and the fibre
- 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
- A62D: CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- D06M: TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS

## Abstract

One aspect of the present invention relates to reactive compositions and methods of use thereof, wherein a metal oxide cluster is used to connect a reactive group (or groups) to the surface of a substrate. In certain embodiments, the reactive group in the compositions decomposes organophosphate agents through nucleophilic hydrolysis. In certain embodiments, the reactive group in the compositions is bactericidal. Remarkably, the use of metal oxide clusters in the disclosed compositions and methods permits incorporation of higher quantities of nucleophilic and bactericidal groups without the difficulties associated with having to pretreat the substrate prior to its association with the reactive groups.

## Claims

### Claim 1

A composition, comprising a substrate, a cluster, and a reactive group, wherein
the cluster comprises ceria, silica, titania, or an iron oxide;
the reactive group comprises an oximate, an iodosobenzoate, an iodoxybenzoate, an amidooxime, a hydroxamate, an imidazole, an amine, a peroxide, a guanidine, a nucleophile, an oxidant, or a bactericide;
a bond connects the cluster to the substrate; and
a linker connects the cluster to the reactive group or a second bond connects the cluster to the reactive group.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the substrate is a polymer having pendant hydroxyl, carboxylate, or amino groups.

### Claim 3 (depends on 1)

The composition of claim 1, wherein the substrate is a polysaccharide, cellulose or poly(vinyl alcohol).

### Claim 4 (depends on 1)

The composition of claim 1, wherein the bond is a coordination bond metal-organic, a covalent bond, a hydrogen bond or an ionic bond.

### Claim 5 (depends on 1)

The composition of claim 1, wherein the second bond is a coordination bond metal-organic, a covalent bond, a hydrogen bond or an ionic bond.

### Claim 6 (depends on 1)

The composition of claim 1, wherein the cluster is ceria, silica, titania or an iron oxide.

### Claim 7 (depends on 1)

The composition of claim 1, wherein the substrate is a polymer having pendant hydroxyl, carboxylate, or amino groups; and the bond is a bond from the oxygen of the pendant hydroxyl, an oxygen of the pendant carboxylate, or the nitrogen of the pendant amino, to a cerium atom, a silicon atom, a titanium atom, or an iron atom in the cluster.

### Claim 8 (depends on 1)

The composition of claim 1, wherein the linker is a bond or is represented by B1—Y—Z—B2; wherein B1 is a bond to the cluster; Y is alkylene; Z is absent, —O—, —N(H)—, —S—, —C(═O)O—, —C(═O)N(H)—, —OC(═O)O—, —OC(═O)N(H)—, —N(H)C(═O)O—, —N(H)C(═O)N(H)—, —C(═O)S—, —S(═O)—, —S(═O)2—, —C(═O)—, —C(═NH)—, —C(═S)—, or —C(═O) N(H) N(H)—; and B2 is a bond to the reactive group.

### Claim 9 (depends on 1)

The composition of claim 1, wherein the reactive group is chlorhexidine; and said chlorhexidine is bonded to the linker through one of its amines.

### Claim 10 (depends on 1)

The composition of claim 1, wherein the cluster is silica; and the tether-reactive group is
and B1 is a bond to a silicon atom in the cluster.

### Claim 11

A composition, comprising a substrate, a cluster, and a reactive group, wherein
the cluster comprises ceria, silica, titania, or an iron oxide;
the reactive group comprises an oximate, an iodosobenzoate, an iodoxybenzoate, an amidooxime, a hydroxamate, an imidazole, an amine, a peroxide, a guanidine, a nucleophile, an oxidant, or a bactericide;
a bond connects the cluster to the substrate; and
a linker connects the substrate to the reactive group.

### Claim 12 (depends on 11)

The composition of claim 11, wherein the substrate is a polymer having pendant hydroxyl, carboxylate, or amino groups.

### Claim 13 (depends on 11)

The composition of claim 11, wherein the substrate is an acrylic acid-vinylsulfonic acid, 4-styrenesulfonic acid copolymer.

### Claim 14 (depends on 13)

The composition of claim 13, wherein the substrate further comprises 10-undecenoic acid.

### Claim 15 (depends on 11)

The composition of claim 11, wherein the cluster is ceria, silica, titania, or an iron oxide.

### Claim 16 (depends on 11)

The composition of claim 11, wherein the substrate is a polymer having pendant hydroxyl, carboxylate, or amino groups; and the bond is a bond from the oxygen of the pendant hydroxyl, an oxygen of the pendant carboxylate, or the nitrogen of the pendant amino, to a cerium atom, a silicon atom, a titanium atom, or an iron atom in the cluster.

### Claim 17 (depends on 11)

The composition of claim 11, wherein the linker is a bond or is represented by B1—Y—Z—B2; wherein B1 is a bond to the reactive group; Y is alkylene; Z is absent, —O—, —N(H)—, —S—, —C(═O)O—, —C(═O)N(H)—, —OC(═O)O—, —OC(═O)N(H)—, —N(H)C(═O)O—, —N(H)C(═O)N(H)—, —C(═O)S—, —S(═O)—, —S(═O)2—, —C(═O)—, —C(═NH)—, —C(═S)—, or —C(═O)N(H)N(H)—; and B2 is a bond to the substrate.

### Claim 18 (depends on 11)

The composition of claim 11, wherein the reactive group is chlorhexidine; and said chlorhexidine is bonded to the linker through one of its amines.

### Claim 19

A method of making a modified substrate,
comprising the step of reacting under sol-gel conditions a substrate with pendant hydroxyl or amino groups with a compound comprising a cluster tethered via a tether to a reactive group; or
comprising the step of reacting a substrate with pendant hydroxyl or amino groups with a ceria, silica, titania, or an iron oxide, thereby forming a cluster bonded to said substrate;
and reacting said cluster with a compound having a reactive group, thereby tethering the reactive group to the cluster via a tether,
wherein
the cluster comprises ceria, silica, titania, or an iron oxide;
the reactive group comprises an oximate, an iodosobenzoate, an iodoxybenzoate, an amidooxime, a hydroxamate, an imidazole, an amine, a peroxide, a guanidine, a nucleophile, an oxidant, or a bactericide.

### Claim 20

A method for the hydrolysis of a compound which contains at least one oxidized phosphorus group or killing a bacterium, comprising the step of contacting said compound or said bacterium with a composition for sufficient time to hydrolyze at least some of the oxidized phosphorus groups in said compound or to kill the bacterium,
wherein
said composition comprises a substrate, a cluster, and a reactive group;
the cluster comprises ceria, silica, titania, or an iron oxide;
the reactive group comprises an oximate, an iodosobenzoate, an iodoxybenzoate, an amidooxime, a hydroxamate, an imidazole, an amine, a peroxide, a guanidine, a nucleophile, an oxidant, or a bactericide;
a bond connects the cluster to the substrate; and
a linker connects the cluster to the reactive group, a second bond connects the cluster to the reactive group, or a linker connects the substrate to the reactive group.