# US 9,433,698 B2 · High strength chitin composite material and method of making

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- Number: US 9,433,698 B2
- Document ID: US9433698B2
- Status: Granted
- Kind: B2
- Application number: 13/819,391
- Filed: 2011-08-30
- Published: 2013-10-31
- Granted: 2016-09-06
- Earliest claimed: 2010-08-30
- Assignees: President and Fellows of Harvard College
- Applicants: Donald E. Ingber; Javier Gomez Fernandez
- Inventors: Donald E. Ingber; Javier Gomez Fernandez
- Web page: https://patentgrep.com/patent/US9433698B2

## CPC

- A61L 27/24: Collagen
- A61L 15/225: {Mixtures of macromolecular compounds}
- A61L 15/28: Polysaccharides or their derivatives {(A61L15/225 takes precedence)}
- A61L 15/325: {Collagen}
- A61L 15/38: containing enzymes
- A61L 15/425: {Porous materials, e.g. foams or sponges}
- A61L 15/44: Medicaments
- A61L 15/52: Water-repellants
- A61L 27/20: Polysaccharides
- A61L 27/227: {Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24}
- A61L 27/34: Macromolecular materials
- A61L 27/48: with macromolecular fillers
- A61L 27/54: Biologically active materials, e.g. therapeutic substances {(A61L27/227 takes precedence)}
- A61L 27/56: Porous materials, {e.g. foams or sponges}
- A61P 1/02: Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
- A61P 1/04: for ulcers, gastritis or reflux esophagitis, e.g. antacids, inhibitors of acid secretion, mucosal protectants
- A61P 17/02: for treating wounds, ulcers, burns, scars, keloids, or the like
- A61P 19/08: for bone diseases, e.g. rachitism, Paget's disease
- A61P 25/04: Centrally acting analgesics, e.g. opioids
- A61P 27/02: Ophthalmic agents
- A61P 29/00: Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
- A61P 31/00: Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P 31/04: Antibacterial agents
- A61P 37/06: Immunosuppressants, e.g. drugs for graft rejection
- A61P 43/00: Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
- B05D 3/104: {Pretreatment of other substrates}
- C08L 1/02: Cellulose; Modified cellulose
- C08L 3/02: Starch; Degradation products thereof, e.g. dextrin
- C08L 5/00: Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L 5/08: Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
- C08L 5/10: Heparin; Derivatives thereof
- C08L 89/00: Compositions of proteins; Compositions of derivatives thereof
- A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K)
- A61P: SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The present invention is directed to a composite laminar material with high mechanical strength and methods of fabricating the material. The invention also provides a method of attaching a medical implant device to tissue.

## Claims

### Claim 1

A composite laminate material comprising a carbohydrate based layer and a protein based layer, wherein carbohydrate to protein are present in a ratio in the range of 1:1.5 to 1:2.5, where the ratio is based on dry weight or moles of carbohydrate and protein, and wherein chitosan is the carbohydrate in the carbohydrate based layer and silk fibroin is the protein in the protein based layer.

### Claim 2 (depends on 1)

The composite laminate material of claim 1 wherein the carbohydrate based layer comprises a film, a fiber, a sponge, a mesh, a foam, or a nanoscale structure.

### Claim 3 (depends on 1)

The composite laminate material of claim 1, wherein the ratio of carbohydrate to protein is 1:2, where the ratio is based on dry weight or moles of carbohydrate and protein.

### Claim 4 (depends on 1)

The composite laminate material of claim 1, wherein the carbohydrate based layer includes at least one surface having a predefined microtopography and the protein is applied to the surface.

### Claim 5 (depends on 1)

The composite laminate material of claim 1, wherein the composite material further comprises a molecule selected from the group consisting of carbon fibers, carbon nanotubes, fiberglass, small molecules, polymers, proteins, peptides, peptidomimimetics, nucleic acids, organic compounds, inorganic compounds, crystalline compounds, biological compounds, and biologically active compounds, and any combinations thereof, in at least one of the carbohydrate layer or the protein layer.

### Claim 6 (depends on 1)

The composite laminate material of claim 1 further comprising a water repelling coating on at least a portion of the composite material.

### Claim 7 (depends on 6)

The composite laminate material of claim 6, wherein the water repelling coating comprises parylene.

### Claim 8

A method of forming a composite laminate material comprising:
providing a carbohydrate based layer and neutralizing the carbohydrate based layer with a base solution;
optionally dehydrating the carbohydrate based layer; and
contacting the carbohydrate based layer with a protein solution to produce a composite material; and optionally treating the composite material with an alcohol based solution, and wherein carbohydrate to protein are present in a ratio in the range of 1:1.5 to 1:2.5 and wherein chitosan is the carbohydrate in the carbohydrate based layer and silk fibroin is the protein.

### Claim 9

A composition of matter formed by a method comprising:
providing a carbohydrate based layer and neutralizing the carbohydrate based layer with a base solution;
optionally dehydrating the carbohydrate based layer; and
contacting the carbohydrate based layer with a protein solution to produce a composite material; and
optionally treating the composite material with an alcohol based solution,
wherein carbohydrate to protein are present in a ratio in the range of 1:1.5 to 1:2.5, and wherein chitosan is the carbohydrate in the carbohydrate based layer and silk fibroin is the protein.

### Claim 10

A multi-laminate material having the structure [(protein-layer)x:[(carbohydrate-layer)y:(protein-layer)z]m]n, wherein m, n, y, and z are independently an integer equal to or greater than 1; and x is 0 or an integer equal to or greater than 1, and wherein ratio of carbohydrate to protein are present in a ratio in the range of 1:1.5 to 1:2.5, and wherein chitosan is the carbohydrate in the carbohydrate based layer and silk fibroin is the protein in the protein based layer.

### Claim 11

A method of forming a composite laminate material comprising:
dissolving a chitin based material in an acidic solution;
forming a chitin based structure of the chitin based material by evaporating the solvent;
treating the chitin based structure with a base solution to neutralize protonated amino groups;
washing the chitin based structure;
optionally dehydrating the chitin based structure;
applying a protein solution to the chitin based structure to produce a composite material having at least one layer of protein on the chitin based structure;
drying the protein-layer on the chitin based structure; and
treating the composite material with an alcohol based solution to induce a beta transition of the protein,
wherein a ratio of chitin to protein is 1:1.5 to 1:2.5, where the ratio is based on dry weight or moles of chitin and protein, and wherein chitosan is the chitin in the chitin based layer and silk fibroin is the protein.

### Claim 12 (depends on 10)

The composite laminate material of claim 10, wherein the ratio of chitosan to silk fibroin is 1:2.

### Claim 13 (depends on 1)

The composite laminate material of claim 1, wherein the ratio of chitosan to silk fibroin is 1:2.