# US 10,770,197 B2 · Polymer-silica hybrid Pdots and methods of use thereof

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- Number: US 10,770,197 B2
- Document ID: US10770197B2
- Status: Granted
- Kind: B2
- Application number: 16/309,795
- Filed: 2017-06-13
- Published: 2020-01-02
- Granted: 2020-09-08
- Earliest claimed: 2016-06-14
- Assignees: University of Washington
- Applicants: University of Washington
- Inventors: Daniel T. Chiu; Jiangbo Yu; Yu Rong; Changfeng Wu
- Web page: https://patentgrep.com/patent/US10770197B2

## CPC

- C09K 11/06: containing organic luminescent materials
- H01B 1/18: the conductive material comprising carbon-silicon compounds, carbon or silicon
- C07K 14/00: Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K 16/00: Immunoglobulins [IG], e.g. monoclonal or polyclonal antibodies
- C08K 3/36: Silica
- C08L 83/04: Polysiloxanes
- C09K 11/02: Use of particular materials as binders, particle coatings or suspension media therefor
- G01N 33/582: {with fluorescent label}
- G01N 33/587: {Nanoparticles}
- G01N 33/588: {with semiconductor nanocrystal label, e.g. quantum dots}
- G02F 1/015: based on semiconductor elements having potential barriers, e.g. having a PN or PIN junction (G02F1/03 takes precedence)
- C08K 2201/001: Conductive additives
- C08L 2203/20: use in electrical or conductive gadgets
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- C07K: PEPTIDES (peptides in foodstuffs A23; obtaining protein compositions for foodstuffs, working-up proteins for foodstuffs A23J; preparations for medicinal purposes A61K; peptides containing beta-lactam rings C07D; cyclic dipeptides not having in their molecule any other peptide link than those which form their ring, e.g. piperazine-2,5-diones, C07D; ergot alkaloids of the cyclic peptide type C07D519/02; macromolecular compounds having statistically distributed amino acid units in their molecules, i.e. when the preparation does not provide for a specific; but for a random sequence of the amino acid units, homopolyamides and block copolyamides derived from amino acids C08G69/00; macromolecular products derived from proteins C08H1/00; preparation of glue or gelatine C09H; single cell proteins, enzymes C12N; genetic engineering processes for obtaining peptides C12N15/00; compositions for measuring or testing processes involving enzymes C12Q; investigation or analysis of biological material G01N33/00)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS

## Abstract

The present disclosure provides organic-inorganic hybrid polymer particles, which have desirable surface chemistry and optical properties that make them particularly suitable for biological and optical applications. The present disclosure also provides methods of making organic-inorganic hybrid polymer particles. The present disclosure also provides methods of using the organic-inorganic hybrid polymer particles for biological and optical applications.

## Claims

### Claim 1

An organic-inorganic hybrid polymer dot comprising:
a semiconducting chromophoric polymer; and
an inorganic network,
wherein the semiconducting chromophoric polymer and the inorganic network form an organic-inorganic interpenetrated network through physical association of the semiconducting chromophoric polymer and the inorganic network, and
wherein the physical association of the semiconducting chromophoric polymer and the inorganic network does not include covalent bonding between the semiconducting chromophoric polymer and the inorganic network.

### Claim 2 (depends on 1)

The polymer dot of claim 1, wherein the inorganic network comprises a siloxane network, an alumino-siloxane network, a titanium-siloxane network, a titanium oxide network, or a combination thereof.

### Claim 3 (depends on 2)

The polymer dot of claim 2, wherein the inorganic network comprises a siloxane network.

### Claim 4 (depends on 3)

The polymer dot of claim 3, wherein the siloxane network comprises a plurality of interconnected units, and wherein each interconnected unit is selected from the group consisting of:
wherein:
A0, A1, A2, A3, A4, A5, A6, A7, A8, A9 are each independently CnH2n+1, CnH2nX, CnF2n+1, or CnF2nX;
X is a functional group suitable for bioconjugation;
D0, D1, D2, D3, D4, D5, D6, D7, D8, D9 are each independently LX, wherein L is a linker moiety; and
n is not less than 1.

### Claim 5 (depends on 4)

The polymer dot of claim 4, wherein X comprises an amine, a carboxylate, a carboxyl, a maleimide, a thiol, a maleic anhydride, an N-hydroxysuccinimide ester, a mercapto, an azido, an alkyne, an aldehyde, a hydroxyl, a carbonyl, a sulfate, a sulfonate, a phosphate, a cyanate, a succinimidyl ester, a strained alkyne, an azide, a diene, an alkene, a tetrazine, a strained alkene, a cyclooctyne, or a phosphine.

### Claim 6 (depends on 4)

The polymer dot of claim 4, wherein at least one D is positioned on the surface of the polymer dot.

### Claim 7 (depends on 4)

The polymer dot of claim 4, further comprising a biological molecule conjugated to D.

### Claim 8 (depends on 7)

The polymer dot of claim 7, wherein the biological molecule comprises a protein or a nucleic acid.

### Claim 9 (depends on 7)

The polymer dot of claim 7, wherein the biological molecule comprises an antibody.

### Claim 10 (depends on 3)

The polymer dot of claim 3, wherein the siloxane network is fully or partially hydrolyzed from an alkyl silane, an alkoxy silane, a chloro silane, an orthosilicate, a siloxane, an alpha silane, an acetoxy silane, an amino silane, a bis silane, an epoxy silane, a halo silane, a hydrogen silane, a hydrogen siloxane, a hydroxyl silane, an ester silane, an aryl silane, an acryl silane, a methacryl silane, a styryl silane, a vinyl silane, an olefin silane, a sulfur silane, a phosphine silane, a phosphate silane, an isocyanate silane, an azide silane, an anhydride silane, or a combination thereof.

### Claim 11 (depends on 3)

The polymer dot of claim 3, wherein the siloxane network is fully or partially hydrolyzed from octodecyltrimethoxysilane, octodecyltrichlorosilane, tetraethylorthosilicate, trifluoropropyltrimethoxysilane, phenyltrimethoxysilane, chloropropyltrimethoxysilane, heptadecafluorodecyltrichlorosilane, glycidoxypropyltrimethoxysilane, epoxyhexyltriethoxysilane, hydroxymethyltriethoxysilane, iodopropyltrimethoxysilane, isocyantopropyltrimethoxysilane, methacryloxymethyltriethoxysilane, vinyltrimethoxysilane, styrylethyltrimethoxysilane, or a combination thereof.

### Claim 12 (depends on 3)

The polymer dot of claim 3, wherein a weight percent of silicon from the siloxane network in the polymer dot is within a range from about 1% to about 47%.

### Claim 13 (depends on 3)

The polymer dot of claim 3, wherein the siloxane network comprises an alkyl chain and wherein the semiconducting chromophoric polymer is physically associated with an alkyl chain of the siloxane network, thereby forming the organic-inorganic interpenetrated network.

### Claim 14 (depends on 3)

The polymer dot of claim 3, wherein the siloxane network comprises orthogonally cross-linked units.

### Claim 15 (depends on 3)

The polymer dot of claim 3, wherein the siloxane network is not covalently bonded to the semiconducting chromophoric polymer.

### Claim 16 (depends on 1)

The polymer dot of claim 1, wherein the semiconducting chromophoric polymer comprises a fluorene polymer, a fluorene-based polymer or copolymer, a phenylene vinylene-based polymer or copolymer, a phenylene ethynylene-based polymer or copolymer, a BODIPY-based polymer or copolymer, or a combination thereof.

### Claim 17 (depends on 1)

The polymer dot of claim 1, further comprising a functional group attached to the polymer dot.

### Claim 18 (depends on 17)

The polymer dot of claim 17, wherein the functional group comprises a hydrophobic functional group, a hydrophilic functional group, or a combination thereof.

### Claim 19 (depends on 17)

The polymer dot of claim 17, wherein the functional group is suitable for bioconjugation.

### Claim 20 (depends on 19)

The polymer dot of claim 19, further comprising a biological molecule attached to the polymer dot, wherein the biological molecule is attached to the polymer dot directly or indirectly by a functional group.

### Claim 21

A method of making an organic-inorganic hybrid polymer dot, the method comprising:
providing a solution, wherein the solution comprises a solvent, a semiconducting chromophoric polymer, and an organo-silane; and
mixing the solution with an aqueous solution thereby forming an inorganic network,
wherein at least one of the solution or the aqueous solution comprises an organo-silane comprising X, and wherein X is a functional group suitable for bioconjugation,
wherein the semiconducting chromophoric polymer and the inorganic network form an organic-inorganic interpenetrated network through physical association of the semiconducting chromophoric polymer and the inorganic network, and
wherein the physical association of the semiconducting chromophoric polymer and the inorganic network does not include covalent bonding between the semiconducting chromophoric polymer and the inorganic network.

### Claim 22 (depends on 21)

The method of claim 21, wherein the solution comprises the organo-silane comprising X.

### Claim 23 (depends on 21)

The method of claim 21, wherein the aqueous solution comprises the organo-silane comprising X.

### Claim 24 (depends on 21)

The method of claim 21, wherein X comprises an amine, a carboxylate, a carboxyl, a maleimide, a thiol, a maleic anhydride, an N- hydroxysuccinimide ester, a mercapto, an azido, an alkyne, an aldehyde, a hydroxyl, a carbonyl, a sulfate, a sulfonate, a phosphate, a cyanate, a succinimidyl ester, a strained alkyne, an azide, a diene, an alkene, a tetrazine, a strained alkene, a cyclooctyne, or a phosphine.

### Claim 25 (depends on 21)

The method of claim 21, wherein the organo-silane is selected from:
wherein:
A1, A2, A3, A6, A7, A11, A16, A17, A18, A19, A20, and A21 are each independently CnH2n+1, CnH2nX, CnF2n+1, or CnF2nX;
A0, A4, A5, A8, A9, A10, A12, A13, A14, and A15 are each independently CmH2m+1, CmH2mX, CmF2m+1, or CmF2mX.

### Claim 26 (depends on 21)

The method of claim 21, wherein the organo-silane comprising X is selected from:
wherein:
A0, A1, A2, A3, A4, and A5, are each independently CmH2m+1, CmF2m+1, CmH2mX, or CmF2mX;
D is LX, wherein L is a linker moiety; and
m is not less than 1.

### Claim 27 (depends on 26)

The method of claim 26, wherein L is selected from a chemical bond, an amino acid, an ester, an amide, a carbamate, an ether, an alkylene, an alkenylene, an alkynylene, an arylene, a polyether, a polyester, a polyamide, a polycarbamate, a polyaryl, a polystyrene, or a polyolefin, or a fluorinated or partially fluorinated derivative thereof, or a combination thereof.

### Claim 28 (depends on 21)

The method of claim 21, further comprising providing a first and a second organo-silane.