# US 2014/0154770 A1 · Chemically Modified Graphene

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- Number: US 2014/0154770 A1
- Document ID: US20140154770A1
- Status: Published application
- Kind: A1
- Application number: 14/118,596
- Filed: 2012-05-18
- Published: 2014-06-05
- Earliest claimed: 2011-05-19
- Assignees: Rutgers, The State University of New Jersey
- Applicants: Rutgers, the State University of New Jersey; Research Foundation of the City University of New York
- Inventors: Michele Vittadello; Kamil Woronowicz; Manish Chhowalla; Paul G. Falkowski
- Web page: https://patentgrep.com/patent/US20140154770A1

## CPC

- G01N 33/551: the carrier being inorganic
- B01D 15/325: {Reversed phase}
- B01D 15/3809: {of the antigen-antibody type, e.g. protein A, G or L chromatography}
- B01D 15/3828: {Ligand exchange chromatography, e.g. complexation, chelation or metal interaction chromatography}
- B01J 20/205: {Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs (carbon nanotubes per se C01B32/15)}
- B01J 20/223: {containing metals, e.g. organo-metallic compounds, coordination complexes}
- B01J 20/289: bonded via a spacer
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- B01J 20/3204: {Inorganic carriers, supports or substrates}
- B01J 20/3206: {Organic carriers, supports or substrates}
- B01J 20/3219: {involving a particular spacer or linking group, e.g. for attaching an active group}
- B01J 20/3236: {containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts}
- B01J 20/3251: {comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur}
- B01J 20/3265: {with an organic functional group containing a metal, e.g. a metal affinity ligand}
- B01J 20/3274: {Proteins, nucleic acids, polysaccharides, antibodies or antigens}
- B01J 20/3289: {Coatings involving more than one layer of same or different nature}
- B01J 39/26: Cation exchangers for chromatographic processes
- B01J 45/00: Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties (ion-exchange chromatography processes B01D15/36)
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C01B 32/194: After-treatment
- C01B 32/23: Oxidation
- C07D 303/46: by amide or nitrile radicals
- C07K 1/20: Partition-, reverse-phase or hydrophobic interaction chromatography
- C07K 1/22: Affinity chromatography or related techniques based upon selective absorption processes
- C07K 14/31: from Staphylococcus (G)
- C07K 14/315: from Streptococcus (G), e.g. Enterococci
- C12N 11/02: Enzymes or microbial cells immobilised on or in an organic carrier
- C12N 11/14: Enzymes or microbial cells immobilised on or in an inorganic carrier
- C12P 3/00: Preparation of elements or inorganic compounds except carbon dioxide {(recovery of carbon dioxides as by-products C12F3/02)}
- C12P 7/06: Ethanol, i.e. non-beverage
- C25B 1/04: by electrolysis of water
- C25B 1/55: Photoelectrolysis
- C25B 9/40: Cells or assemblies of cells comprising electrodes made of particles; Assemblies of constructional parts thereof
- C25B 11/037: Electrodes made of particles
- C25B 11/051: Electrodes formed of electrocatalysts on a substrate or carrier
- C25B 11/057: consisting of a single element or compound
- C25B 11/069: consisting of at least one single element and at least one compound; consisting of two or more compounds
- C25B 11/073: characterised by the electrocatalyst material
- C25B 11/095: at least one of the compounds being organic
- B01J 2220/52: Sorbents specially adapted for preparative chromatography
- B01J 2220/58: Use in a single column
- B82Y 5/00: Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
- C07K 2319/20: containing a tag with affinity for a non-protein ligand
- C07K 2319/21: containing a His-tag
- Y02E 50/10: Biofuels, e.g. bio-diesel
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- Y10S 977/734: Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S 977/847: Surface modifications, e.g. functionalization, coating
- Y10S 977/914: Protein engineering
- 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)
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- 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)
- C12N: MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA (microbiological testing media C12Q1/00)
- C12P: FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE {(brewing of beer C12C; producing vinegar C12J; producing specific peptides or proteins C07K; producing enzymes C12N9/00; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; measuring or testing processes involving enzymes or microorganisms C12Q; measuring or testing processes involving nucleic acid amplification reactions C12Q1/6844; fermentation processes to form a food composition, A21 or A23; compounds in general, see the relevant compound class, e.g. C01, C07)}
- C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

This disclosure relates to graphene derivatives, as well as related devices including graphene derivatives and methods of using graphene derivatives.

## Claims

### Claim 1

A material, comprising:
a graphene derivative comprising a graphene core and a first pendant group, the first pendant group comprising a metal ion, a nanoparticle, a sulfonate group, an amine group, a quaternary ammonium group, or a chelating group.

### Claim 2 (depends on 1)

The material of claim 1, wherein the first pendant group comprises a metal ion.

### Claim 3 (depends on 2)

The material of claim 2, wherein the first pendant group comprising a linking group and the metal ion is complexed with the linking group.

### Claim 4 (depends on 3)

The material of claim 3, wherein the linking group comprises a nitrilotriacetic acid moiety, a tris-nitrilotriacetic acid moiety, or an iminodiacetic acid moiety.

### Claim 5 (depends on 3)

The material of claim 3, wherein the linking group is covalently bonded to the graphene core through an amide group.

### Claim 6 (depends on 3)

The material of claim 3, wherein the first pendant group further comprises a His-tagged protein binding to the metal ion.

### Claim 7 (depends on 6)

The material of claim 6, wherein the His-tagged protein is His-tagged Protein A or His-tagged Protein G.

### Claim 8 (depends on 2)

The material of claim 2, wherein the metal ion is Ni2+, Cu2+, Zn2+, Ag+, Fe3+, Ga3+, Zr3+, Ca2+, or Co2+.

### Claim 9 (depends on 1)

The material of claim 1, wherein the first pendant group comprises a nanoparticle.

### Claim 10 (depends on 9)

The material of claim 9, wherein the nanoparticle is a TiO2 nanoparticle or a SiO2 nanoparticle.

### Claim 11 (depends on 10)

The material of claim 10, wherein the nanoparticle is a SiO2 nanoparticle covalently bonded to the graphene core through an amide group.

### Claim 12 (depends on 11)

The material of claim 11, wherein the SiO2 nanoparticle is covalently bonded to the graphene core through a linkage —CO—NH—R—Si(—O—)3, in which R is C1-C20 alkylene.

### Claim 13 (depends on 10)

The material of claim 10, wherein the graphene derivative further comprises a second pendant group, the second pendant group comprising metal ion or a TiO2 nanoparticle.

### Claim 14 (depends on 1)

The material of claim 1, wherein the first pendant group comprises a sulfonate group, an amine group, a quaternary ammonium group, or a chelating group.

### Claim 15 (depends on 14)

The material of claim 14, wherein the first pendant group comprises —(CO)x—NH—R—SO3H, —(CO)x—NH—R—N(R′R″R′″)+, —(CO)x—NH—R—N(R′R″), —(CO)x—NH—R—SH, —(CO)x—NH—R—COOH, —(CO)x—NH—R—N(CH2COOH)2, —(CO)x—NH—R—NH—R—PO3H, or an EDTA derivative, wherein x is 0 or 1; each R, independently, is C1-C20 alkylene; and each of R′, R″, and R′″, independently, is H or C1-C20 alkyl.

### Claim 16 (depends on 1)

The material of claim 1, wherein the material is in the form of a powder, a liquid-based composition, or a film.

### Claim 17

A material, comprising:
a graphene derivative comprising a graphene core and a protein covalently bonded to the graphene core.

### Claim 18 (depends on 17)

The material of claim 17, wherein the protein is Protein A, Protein G, or an E72G3 protein.

### Claim 19 (depends on 17)

The material of claim 17, further comprising a linking group covalently bonded to the graphene core and the protein.

### Claim 20 (depends on 19)

The material of claim 19, wherein the linking group comprising an acetamide moiety, a succinimide moiety, a maleimide moiety, or a thiosulfate moiety.

### Claim 21 (depends on 1)

A chromatography column, comprising the material of claim 1.

### Claim 22 (depends on 21)

The column of claim 21, wherein the column further comprises a spacer mixed with the material.

### Claim 23 (depends on 22)

The column of claim 22, wherein the spacer is an oxide or a polymer.

### Claim 24 (depends on 21)

A chromatographic system, comprising the chromatography column of claim 21.

### Claim 25 (depends on 1)

A method of isolating a protein from a sample, comprising:
disposing the sample in a dispersion comprising the material of claim 1, thereby binding the protein to the material to form a protein-bound material;
isolating the protein-bound material; and
recovering the protein from the protein-bound material.

### Claim 26 (depends on 25)

The method of claim 25, wherein isolating the protein-bound material is carried out by centrifugation, filtration, or decantation.

### Claim 27 (depends on 25)

The method of claim 25, wherein the first pendant group comprises a metal ion.

### Claim 28 (depends on 27)

The method of claim 27, wherein the protein is a His-tagged protein, a FLAG-tagged protein, a HA-tagged protein, a myc-tagged protein, a GST-tagged protein, a MBP-tagged protein, or a lectin.

### Claim 29 (depends on 28)

The method of claim 28, wherein the His-tagged protein is a His-tagged photosystem I core complex, a His-tagged photosystem II core complex, or a His-tagged bacterial reaction center.

### Claim 30 (depends on 25)

The method of claim 25, wherein the first pendant group comprises a TiO2 nanoparticle.

### Claim 31 (depends on 30)

The method of claim 30, wherein the protein is a phosphoprotein.

### Claim 32 (depends on 31)

The method of claim 31, wherein the phosphoprotein is an Fe receptor, a Ulk antibody, a calcineurin, a K chromatin immunoprecipitate, or a urocotin.

### Claim 33 (depends on 25)

The method of claim 25, wherein the first pendant group comprises a protein.

### Claim 34 (depends on 33)

The method of claim 33, wherein the protein in the first pendant group comprises Protein A, Protein G, or an E72G3 protein.

### Claim 35 (depends on 34)

The method of claim 34, wherein the protein in the sample is an antibody having an Fe region.

### Claim 36

A method of preparing graphene oxide, comprising:
reacting graphite sequentially with an oxidizing acid and an oxidant to form an oxidized graphene;
washing the oxidized graphene with an aqueous solvent; and
treating the oxidized graphene with a solution containing an intercalant to form graphene oxide.

### Claim 37 (depends on 36)

The method of claim 36, wherein the oxidizing acid is nitric acid.

### Claim 38 (depends on 36)

The method of claim 36, wherein the oxidant is potassium chlorate.

### Claim 39 (depends on 36)

The method of claim 36, wherein the intercalant is tetrabutylammonium hydroxide.

### Claim 40 (depends on 36)

The method of claim 36, wherein the treating the oxidized graphene comprising heating the oxidized graphene in the solution containing the intercalant at a temperature of at least about 60° C.

### Claim 41

A device for producing hydrogen, comprising:
a graphene derivative suspended in an aqueous solution, the graphene derivative comprising a graphene core, a first pendant group, and a second pendant group,
wherein
the first pendant group comprises a first linking group attached to the graphene core and a photocathode nanoparticle; and
the second pendant group comprises a second linking group attached to the graphene core and a photoanode nanoparticle.

### Claim 42 (depends on 41)

The device of claim 41, wherein each of the first and second linking group comprises a nitrilotriacetic acid moiety.

### Claim 43 (depends on 42)

The device of claim 42, wherein the first pendant group further comprises a metal ion coordinated with the first linking group and the second pendant group further comprises a second metal ion coordinated with the second linking group.

### Claim 44 (depends on 43)

The device of claim 43, wherein each of the first and second metal ions is Ni2+.

### Claim 45 (depends on 44)

The device of claim 44, wherein the photocathode nanoparticle comprises a first His-tagged protein binding to the first metal ion and the photoanode nanoparticle comprises a second His-tagged protein binding to the second metal ion.

### Claim 46 (depends on 45)

The device of claim 45, wherein the first His-tagged protein comprises a His-tagged photosystem I core complex and the second His-tagged protein comprises a His-tagged photosystem II core complex.

### Claim 47 (depends on 46)

The device of claim 46, wherein the first pendant group further comprises a platinum nanoparticle or a hydrogenase.

### Claim 48 (depends on 47)

The device of claim 47, wherein the platinum nanoparticle is bonded to the His-tagged photosystem I core complex.

### Claim 49 (depends on 48)

The device of claim 48, wherein the platinum nanoparticle is bonded to the His-tagged photosystem I core complex through —S—(CH2)6—S—.

### Claim 50 (depends on 41)

The device of claim 41, wherein the photocathode comprises a first semiconductor and the photoanode comprises a second semiconductor.

### Claim 51 (depends on 50)

The device of claim 50, wherein the first semiconductor is coated with a catalyst for a hydrogen evolving reaction and the second semiconductor is coated with a catalyst for an oxygen evolving reaction.

### Claim 52

A device for producing hydrogen, comprising:
first and second transport layers;
a first graphene layer comprising a first graphene derivative, the first transport layer between the first graphene layer and the second transport layer; and
a second graphene layer comprising a second graphene derivative, the second transport layer between the first transport layer and the second graphene layer;
wherein
the first graphene derivative comprises a first graphene core and a first pendant group, the first pendant group comprising a first linking group covalently bonded to the first graphene core, a first metal ion coordinated with the first linking group, and a first His-tagged protein binding to the first metal ion;
the second graphene derivative comprises a second graphene core and a second pendant group, the second pendant group comprising a second linking group covalently bonded to the second graphene core, a second metal ion coordinated with the second linking group, and a second His-tagged protein binding to the second metal ion;
each of the first and second linking group comprises a nitrilotriacetic acid moiety;
each of the first and second metal ions is Ni2+;
the first His-tagged protein comprises a His-tagged photosystem I core complex; and
the second His-tagged protein comprises a His-tagged photosystem II core complex.

### Claim 53 (depends on 52)

The device of claim 52, where each of the first and second transport layers comprises a polyaniline or a sulfonated polyaniline.

### Claim 54 (depends on 52)

The device of claim 52, wherein the first pendant group further comprises a platinum nanoparticle or a hydrogenase.

### Claim 55 (depends on 54)

The device of claim 54, wherein the platinum nanoparticle is bonded to the His-tagged photosystem I core complex.

### Claim 56 (depends on 55)

The device of claim 55, wherein the platinum nanoparticle is bonded to the His-tagged photosystem I core complex through —S—(CH2)6—S—.

### Claim 57 (depends on 52)

The device of claim 52, further comprising first and second housings, wherein the first housing, together with the first transport layer, defines a first compartment and the second housing, together with the second transport layer, defines a second compartment.

### Claim 58 (depends on 57)

The device of claim 57, wherein the first graphene layer is disposed in the first compartment and the second graphene layer is disposed in the second compartment.