# US 9,517,357 B2 · Plasmonic nanoparticle-doped silk materials

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- Number: US 9,517,357 B2
- Document ID: US9517357B2
- Status: Granted
- Kind: B2
- Application number: 13/819,419
- Filed: 2011-09-03
- Published: 2013-11-21
- Granted: 2016-12-13
- Earliest claimed: 2010-09-03
- Assignees: Tufts University
- Applicants: Fiorenzo Omenetto; David L. Kaplan; Hu Tao
- Inventors: Fiorenzo Omenetto; David L. Kaplan; Hu Tao
- Web page: https://patentgrep.com/patent/US9517357B2

## CPC

- A61N 5/0625: {Warming the body, e.g. hyperthermia treatment}
- A61F 7/03: thermophore, i.e. self-heating, {e.g. using a chemical reaction}
- A61K 41/0052: {Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy}
- A61L 31/005: {Ingredients of undetermined constitution or reaction products thereof}
- A61L 31/125: {having a macromolecular matrix}
- A61L 31/14: Materials characterised by their function or physical properties {, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials}
- A61N 5/062: {Photodynamic therapy, i.e. excitation of an agent}
- A61P 29/00: Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
- A61P 35/00: Antineoplastic agents
- H10N 10/13: characterised by the heat-exchanging means at the junction
- A61L 2400/12: Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
- Y10T 428/268: Monolayer with structurally defined element
- Y10T 428/2927: including structurally defined particulate matter
- A61N: ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY (measurement of bioelectric currents A61B; surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body A61B18/00; anaesthetic apparatus in general A61M; incandescent lamps H01K; infrared radiators for heating H05B)
- A61F: FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS (dental prosthetics A61C)
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- 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
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Provided herein are silk fibroin-based photothermal elements and uses thereof. The silk fibroin-based photothermal elements comprise a plurality of plasmonic nanoparticle distributed in a silk fibroin matrix, and can generate heat when the plasmonic nanoparticles are exposed to electromagnetic radiation. The silk fibroin-based photothermal elements can be adapted to be conformable and biodegradable, and can further be integrated with various electronic components, such as a thermo-electric device for conversion of heat into electricity. The invention is useful for various in vivo applications, such as photothermal therapy, controlled drug-delivery devices or wireless powering of implanted micro-devices.

## Claims

### Claim 1

A photothermal element comprising:
a plurality of plasmonic nanoparticles that generate heat when exposed to electromagnetic radiation; and
a silk fibroin matrix,
wherein the plurality of plasmonic nanoparticles is distributed within the silk fibroin matrix; and,
wherein the average diameter of the plurality of plasmonic nanoparticles is between about 5 nm and 100 nm.

### Claim 2 (depends on 1)

The photothermal element of claim 1, wherein the silk fibroin matrix is in a form of:
a wire, an optical fiber, a film, an ultrathin film, a gel, an injectable matrix, a coating, a vesicle, a sponge, a block, a porous structure or any combination thereof.

### Claim 3 (depends on 1)

The photothermal element of claim 1 wherein the silk fibroin matrix has a thickness of 30 nm to 500 μm.

### Claim 4 (depends on 1)

The photothermal element of claim 1, wherein the photothermal element is adapted to conform to a surface upon contact with the surface.

### Claim 5 (depends on 1)

The photothermal element of claim 1, wherein the plurality of plasmonic nanoparticles are evenly dispersed within the silk fibroin matrix.

### Claim 6 (depends on 1)

The photothermal element of claim 1, wherein the plurality of plasmonic nanoparticles are distributed in a gradient within the silk fibroin matrix.

### Claim 7 (depends on 1)

The photothermal element of claim 1, wherein the plurality of plasmonic nanoparticles are distributed in a pattern, said pattern comprises an optical pattern, a micropattern, or a nanopattern.

### Claim 8 (depends on 1)

The photothermal element of claim 1, wherein the at least one plasmonic nanoparticle is selected from the group consisting of a nanosphere, a nanoshell, a nanorod, a nanocage, a nanocrystal, nanopowder, and any combinations thereof.

### Claim 9 (depends on 1)

The photothermal element of claim 1, wherein the plurality of plasmonic nanoparticles comprise at least one metal.

### Claim 10 (depends on 9)

The photothermal element of claim 9, wherein the metal is selected from the group consisting of a noble metal, a non-noble metal, an oxide thereof, an alloy thereof, and any combinations thereof.

### Claim 11 (depends on 10)

The photothermal element of claim 10, wherein the noble metal is gold.

### Claim 12 (depends on 1)

The photothermal element of claim 1, further comprising a thermo-electric device.

### Claim 13 (depends on 1)

The photothermal element of claim 1, wherein the plurality of plasmonic nanoparticles and/or the silk fibroin matrix further comprises at least one active agent.

### Claim 14 (depends on 1)

The photothermal element of claim 1, further comprising at least one contrast-enhancing agent.

### Claim 15 (depends on 1)

The photothermal element of claim 1, wherein the silk fibroin matrix further comprises at least one optical pattern to modulate the electromagnetic radiation.

### Claim 16 (depends on 1)

An implantable device comprising the photothermal element of claim 1, wherein the implantable device is configured for in vivo photothermal therapy.

### Claim 17 (depends on 1)

A photothermal-electric device comprising:
a photothermal element of claim 1; and
a thermoelectric device in contact with the photothermal element, wherein the thermoelectric device converts at least a portion of heat transferred from the photothermal element into electricity.

### Claim 18 (depends on 17)

The photothermal-electric device of claim 17, further comprising an electric circuit connected to the thermoelectric device to transmit the converted electricity as an output energy.

### Claim 19 (depends on 17)

The photothermal-electric device of claim 17, wherein the thermoelectric device comprises a thin-film thermoelectric material.

### Claim 20 (depends on 17)

The photothermal-electric device of claim 17, wherein the thermoelectric device is adapted to conform to a surface upon contact with the surface.

### Claim 21 (depends on 17)

A wireless powering device comprising the photothermal-electric device of claim 17.

### Claim 22 (depends on 21)

The wireless powering device of claim 21 wherein the wireless powering device is adapted to conform to a surface upon contact with the surface.

### Claim 23 (depends on 21)

The wireless powering device of claim 21, wherein the wireless powering device is adapted to be implantable.

### Claim 24

A method of photothermal therapy comprising:
(a) contacting an internal or external tissue with a silk fibroin-based photothermal element comprising a silk fibroin matrix and a plurality of plasmonic nanoparticles dispersed therein, wherein the silk fibroin-based photothermal element is adapted to conform to the tissue upon contact; and
(b) exposing the at least one plasmonic nanoparticle to electromagnetic radiation, wherein the at least one plasmonic nanoparticle generates heat upon irradiation, and wherein at least a portion of the generated heat is transferred to at least a portion of the tissue.

### Claim 25 (depends on 24)

The method of claim 24, wherein the silk fibroin-based photothermal element comprises at least one active agent.

### Claim 26 (depends on 24)

The method of claim 24, further comprising modulating the electromagnetic radiation,
wherein the modulation of the electromagnetic radiation is selected from the group consisting of:
modulating the intensity of a source of the electromagnetic radiation;
modulating the distribution of the source of the electromagnetic radiation;
applying at least one optical grating to the source of the electromagnetic radiation;
varying the wavelength of the electromagnetic radiation; and
any combinations thereof.

### Claim 27 (depends on 26)

The method of claim 26, wherein the at least one optical grating is adapted to localize the heat generation.

### Claim 28

A method of generating electricity comprising:
(a) providing a photothermal element comprising a silk fibroin matrix, the silk fibroin matrix comprising at least one plasmonic nanoparticle that absorbs radiation to generate heat when irradiated with electromagnetic radiation, and a thermoelectric device in contact with the photothermal element;
(b) irradiating the photothermal element with electromagnetic radiation, wherein the thermoelectric device converts at least a portion of the heat transferred from the photothermal element into electricity.

### Claim 29 (depends on 28)

The method of claim 28, further comprising modulating the electromagnetic radiation,
wherein the modulation of the electromagnetic radiation is selected from the group consisting of:
modulating the intensity of a source of the electromagnetic radiation;
modulating the distribution of the source of the electromagnetic radiation;
applying at least one optical grating to the source of the electromagnetic radiation;
varying the wavelength of the electromagnetic radiation; and
any combinations thereof.

### Claim 30 (depends on 28)

The method of claim 28, wherein the method is adapted for an in vivo application.

### Claim 31 (depends on 28)

The method of claim 28, further comprising connecting the thermoelectric device with an electric circuit to transmit at least a portion of the generated electricity as an output energy.