# US 10,245,355 B2 · Modification of surfaces for fluid and solid repellency

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- Number: US 10,245,355 B2
- Document ID: US10245355B2
- Status: Granted
- Kind: B2
- Application number: 14/904,399
- Filed: 2014-07-10
- Published: 2016-05-26
- Granted: 2019-04-02
- Earliest claimed: 2013-07-10
- Assignees: President and Fellows of Harvard College
- Applicants: President and Fellows of Harvard College
- Inventors: Donald Ingber; Daniel C. Leslie; Michael Super; Alexander L. Watters; Anna Waterhouse
- Web page: https://patentgrep.com/patent/US10245355B2

## CPC

- A61L 31/08: Materials for coatings
- A61L 27/34: Macromolecular materials
- A61L 29/08: Materials for coatings
- A61L 29/085: {Macromolecular materials}
- C09D 5/16: Antifouling paints; Underwater paints
- A61L 31/14: Materials characterised by their function or physical properties {, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials}
- A61L 2400/10: Materials for lubricating medical devices
- A61L 2420/02: Methods for coating medical devices
- B05D 5/08: to obtain an anti-friction or anti-adhesive surface (rendering particulate materials free-flowing in general, e.g. making them hydrophobic B01J2/30)
- B05D 5/086: {having an anchoring layer}
- 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)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)

## Abstract

Articles, methods of making, and uses for modifying surfaces for liquid repellency are disclosed. The liquid repellant surfaces comprise a surface comprising an anchoring layer. The anchoring layer, which forms an immobilized molecular anchoring layer on the surface, has anchoring molecules, where each anchoring molecule has a head group that is covalently linked to the surface and a functional tail group. The anchoring molecules are crosslinked to each other to form a crosslinked network. The functional tail group has an affinity for a lubricating liquid, which is applied to the treated surface to form a lubricating layer. The anchoring layer and replenishable lubricating liquid are held together by non-covalent attractive forces. Together, these layers form an ultra-repellant slippery surface that repels certain immiscible liquids and prevents adsorption, coagulation, and surface fouling by components contained within.

## Claims

### Claim 1

An article having a slippery surface, comprising:
a substrate comprising an anchoring layer, the anchoring layer comprising:
anchoring molecules comprising a head group attached to the substrate and a functional tail group directly or indirectly attached to the head group; and
a crosslinking agent that crosslinks the anchoring molecules to one another;
a lubricating layer comprising a lubricating liquid having an affinity for the functional tail group and disposed over the anchoring layer, wherein the anchoring layer and the lubricating layer are held together by non-covalent attractive forces,
wherein the anchoring layer and the lubricating layer form a slippery surface configured and arranged for contact with a material that is substantially immiscible with the lubricating liquid,
wherein the slippery surface is omniphobic, and
wherein the article is substantially free of anchoring molecules not bound to the substrate, unreacted crosslinking agent, and reaction byproducts between the anchoring molecules and the crosslinking agent.

### Claim 2 (depends on 1)

The article of claim 1, wherein the immiscible material is selected from the group consisting of a liquid, complex fluid, solution, suspension, a gas and a solid.

### Claim 3 (depends on 1)

The article of claim 1, wherein said head group of the anchoring molecules include ethers, silyl ethers, siloxanes, esters of carboxylic acids, esters of sulfonic acids, esters of sulfinic acids, esters of sulfuric acids, esters of phosphonic acids, esters of phosphinic acids, esters of phosphoric acids, silyl esters of carboxylic acids, silyl esters of sulfonic acids, silyl esters of sulfinic acids, silyl esters of sulfuric acids, silyl esters of phosphonic acids, silyl esters of phosphinic acids, silyl esters of phosphoric acids, oxides, sulfides, carbocycles, heterocycles with at least one oxygen atom, heterocycles with at least one nitrogen atom, heterocycles with at least one sulfur atom, heterocycles with at least one silicon atom, ‘click’ reactions-derived heterocycles, Diels-Alder reactions-derived carbocycles, Diels-Alder reactions-derived heterocycles, amides, imides, sulfides, thiolates, metal thiolates, urethanes, oximes, hydrazides, hydrazones, or combinations thereof.

### Claim 4 (depends on 1)

The article of claim 1, wherein the functional tail group of the anchoring molecules comprise a fluorocarbons or perfluorocarbons, and the lubricating layer comprises hydrocarbon liquid, fluorinated organic liquid, or perfluorinated organic liquid.

### Claim 5 (depends on 1)

The article of claim 1, wherein the functional tail group of the anchoring molecules includes perfluorocarbons, perfluorooligoethers or perfluoropolyethers.

### Claim 6 (depends on 1)

The article of claim 1, wherein, the anchoring molecules comprise a silyl group covalently attached to a perfluorocarbon tail, and the lubricating layer comprises fluorinated organic liquid, or perfluorinated organic liquid.

### Claim 7 (depends on 1)

The article of claim 1, wherein, the anchoring molecules comprise a phosphonate or carboxylate group covalently attached to a perfluorocarbon tail, and the lubricating layer comprises fluorinated organic liquid, or perfluorinated organic liquid.

### Claim 8 (depends on 1)

The article of claim 1, wherein the slippery surface is slippery to water-based and hydrocarbon-based liquids.

### Claim 9 (depends on 1)

The article of claim 1, wherein the slippery surface is slippery to biological fluids.

### Claim 10 (depends on 1)

The article of claim 1, wherein the slippery surface is slippery to non-heparinized blood.

### Claim 11 (depends on 1)

The article of claim 1, wherein the slippery surface comprises beads, hollow fibers, membranes, thin films, tubing, fluidized bed, filters, mixers, impellers, connectors, cannula, flow cells, or needles.

### Claim 12 (depends on 1)

The article of claim 1, wherein the surface comprises medical grade materials or medical devices.

### Claim 13

A method of preventing adhesion, adsorption, surface-mediated clot formation, or coagulation of a material onto a substrate, comprising
providing a slippery surface comprising an anchoring layer, the anchoring layer comprising anchoring molecules having a head group attached to a substrate and a functional tail group directly or indirectly attached to the head group and crosslinking agents that crosslink the anchoring molecules to one another; and a lubricating layer comprising a lubricating liquid having an affinity for the functional tail group and disposed over the anchoring layer, wherein the slippery surface is omniphobic and substantially free of anchoring molecules not bound to the substrate, unreacted crosslinking agent, and reaction byproducts between the anchoring molecules and the crosslinking agent, and wherein the anchoring layer and the lubricating layer are held together by non-covalent attractive forces; and
contacting a material that is immiscible with the lubricating layer to the slippery surface.

### Claim 14 (depends on 13)

The method of claim 13, wherein the head group is covalently attached to the surface.

### Claim 15 (depends on 13)

The method of claim 13, wherein the anchoring layer forms a monomolecular layer on the surface.

### Claim 16 (depends on 13)

The method of claim 13, wherein the surface is selected from the group consisting of acrylic, glass, polymers, metals, carbon, plastics, paper, ceramics, and combinations thereof.

### Claim 17 (depends on 13)

The method of claim 13, wherein the surface is treated to activate the surface prior to exposure to the anchoring layer.

### Claim 18 (depends on 17)

The method of claim 17, wherein activation comprises acid treatment, base treatment, oxidization, ammonization, heat, peroxide, photon, electron, ion, plasma, or microwave treatment.

### Claim 19 (depends on 13)

The method of claim 13, wherein the functional tail group is a perfluorocarbon.

### Claim 20 (depends on 13)

The method of claim 13, wherein the functional tail group is a fluorocarbon.

### Claim 21 (depends on 13)

The method of claim 13, wherein the immiscible material is selected from the group consisting of non-viscous and viscous liquids, complex fluids, semi-solids, tacky liquids, solids and combinations thereof.

### Claim 22 (depends on 13)

The method of claim 13, wherein the surface reduces coagulation of blood.

### Claim 23 (depends on 13)

The method of claim 13, wherein the surface reduces adhesion of fibrin, fibrinogen, blood proteins, platelets, leukocytes, red blood cells and/or coagulation factors.

### Claim 24 (depends on 13)

The method of claim 13, wherein the immiscible material contains an additive, the additive being selected from the group consisting of a solute, a particulate, an emulsion, a liposome, a bubble, a droplet, or a combination thereof.

### Claim 25 (depends on 24)

The method of claim 24, wherein the immiscible material is repelled by the surface and the additive is attracted to the surface.

### Claim 26 (depends on 24)

The method of claim 24, wherein the immiscible material and the additive are repelled by the surface.

### Claim 27 (depends on 13)

The method of claim 13, wherein the lubricating layer, the anchoring layer, the substrate or combinations thereof contains an additive selected from the group consisting of a solute, a particulate, an emulsion, a liposome, a bubble, a droplet, or a combination thereof.

### Claim 28 (depends on 27)

The method of claim 27, wherein the additive is eluted from the lubricating layer, the anchoring layer, the substrate, or combination thereof into the immiscible material.

### Claim 29 (depends on 13)

The method of claim 13, wherein the immiscible material is selected from the group consisting of whole blood, plasma, serum, buffy coat, sweat, feces, urine, saliva, tears, vaginal fluid, prostatic fluid, gingival fluid, amniotic fluid, intraocular fluid, cerebrospinal fluid, seminal fluid, sputum, ascites fluid, pus, nasopharengal fluid, wound exudate fluid, aqueous humour, vitreous humour, bile, cerumen, endolymph, perilymph, gastric juice, mucus, peritoneal fluid, pleural fluid, sebum, vomit, and combinations thereof.

### Claim 30 (depends on 13)

The method of claim 13, wherein the immiscible material is a solution or suspension containing bacteria selected from the group consisting of Actinobacillus, Acinetobacter (e.g., Acinetobacter baumannii), Aeromonas, Bordetella, Brevibacillus, Brucella, Bacteroides, Burkholderia, Borelia, Bacillus, Campylobacter, Capnocytophaga, Cardiobacterium, Citrobacter, Clostridium, Chlamydia, Eikenella, Enterobacter, Escherichia, Francisella, Fusobacterium, Flavobacterium, Haemophilus, Helicobacter, Kingella, Klebsiella, Legionella, Listeria, Leptospirae, Moraxella, Morganella, Mycoplasma, Mycobacterium, Neisseria, Pasteurella, Proteus, Prevotella, Plesiomonas, Pseudomonas, Providencia, Rickettsia , Stenotrophomonas, Staphylococcus, Streptococcus (group A), Streptococcus agalactiae (group B), Streptococcus bovis, Streptococcus pneumoniae, Streptomyces, Salmonella, Serratia, Shigella, Spirillum, Treponema, Veillonella, Vibrio, Yersinia, Xanthomonas, and combinations thereof.

### Claim 31 (depends on 13)

The method of claim 13, wherein the immiscible material is a solution or suspension containing fungi selected from the group consisting of a member of the genus Aspergillus, Blastomyces dermatitidis, Candida, Coccidioides immitis, Cryptococcus, Histoplasma capsulatum var. capsulatum, Histoplasma capsulatum var. duboisii, Paracoccidioides brasiliensis, Sporothrix schenckii, Absidia corymbifera; Rhizomucor pusillus, Rhizopus arrhizous, and combinations thereof.

### Claim 32 (depends on 13)

The method of claim 13, wherein the material is a solution or suspension containing viruses selected from the group consisting of cytomegalovirus (CMV), dengue, Epstein-Barr, Hantavirus, human T-cell lymphotropic virus (HTLV I/II), Parvovirus, hepatitides, human papillomavirus (HPV), human immunodeficiency virus (HIV), acquired immunodeficiency syndrome (AIDS), respiratory syncytial virus (RSV), Varicella zoster, West Nile, herpes, polio, smallpox, yellow fever, rhinovirus, coronavirus, Orthomyxoviridae (influenza viruses), and combinations thereof.

### Claim 33 (depends on 13)

The method of claim 13, wherein the material is a solution or suspension containing particles selected from the group consisting of normal cells, diseased cells, parasitized cells, cancer cells, foreign cells, stem cells, and infected cells, microorganisms, viruses, virus-like particles, bacteria, bacteriophages, proteins, cellular components, biofilm, biofilm components, cell organelles, cell fragments, cell membranes, cell membrane fragments, cytosolic proteins, secreted proteins, signaling molecules, embedded proteins, nucleic acid/protein complexes, nucleic acid precipitants, chromosomes, nuclei, mitochondria, liposomes, vesicles, chloroplasts, flagella, biominerals, protein complexes, and minicells.

### Claim 34

A method of making an article having a slippery surface, comprising:
contacting a substrate with anchoring molecules having a head group that is reactive with the substrate and a functional tail group directly or indirectly attached to the head group to form an anchoring layer on the substrate;
crosslinking the anchoring molecules to one another using a crosslinking agent;
washing away anchoring molecules not bound to the substrate, unreacted crosslinking agent, and reaction byproducts between the anchoring molecules and the crosslinking agent; and
contacting the anchoring layer with a lubricating liquid having an affinity for the functional tail group to form a lubricating layer disposed over the anchoring layer, wherein the anchoring layer and the lubricating layer are held together by non-covalent attractive forces,
wherein the anchoring layer and the lubricating layer form a slippery surface configured and arranged for contact with a material that is immiscible with the lubricating liquid, and wherein the slippery surface is omniphobic.

### Claim 35 (depends on 34)

The method of claim 34, wherein contacting the anchoring layer with lubricating liquid comprises passing lubricating liquid through micropassages or nanopassages in the substrate.

### Claim 36 (depends on 34)

The method of claim 34, wherein the substrate comprises a reservoir through which lubricating liquid is replenished.

### Claim 37 (depends on 34)

The method of claim 34, wherein the substrate comprises tubing and wherein contacting the anchoring layer with lubricating liquid comprises passing boluses of lubricating liquid through the tube.

### Claim 38 (depends on 34)

The method of claim 34, wherein the lubricating liquid is replenished on the anchoring layer.

### Claim 39 (depends on 1)

The article of claim 1, wherein the article is selected from the group consisting of: cannula, catheter, central line, peripherally inserted central catheter (PICC) line, urinary cathether, vascular cathether, peritoneal dialysis catheter, central venous catheters, catheter connector, shunt, capillary tube, endotracheal tube, tubing connector, defibrillator, biosensor, endoscope, extracorporeal membrane oxygenation machines, heart-lung machines, suture and vascular grafts, vascular shunts, and combinations thereof.

### Claim 40 (depends on 13)

The method of claim 13, wherein the surface is a surface of an article selected from the group consisting of: cannula, catheter, central line, peripherally inserted central catheter (PICC) line, urinary cathether, vascular cathether, peritoneal dialysis catheter, central venous catheters, catheter connector, shunt, capillary tube, endotracheal tube, tubing connector, defibrillator, biosensor, endoscope, extracorporeal membrane oxygenation machines, heart-lung machines, suture and vascular grafts, vascular shunts, and combinations thereof.

### Claim 41 (depends on 1)

The article of claim 1, the lubricating layer comprises a fluorinated hydrocarbon liquid or a perfluorocarbon liquid.