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WO2025043025A2 - Procédés de synthèse de membranes de nanofeuilles - Google Patents

Procédés de synthèse de membranes de nanofeuilles Download PDF

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Publication number
WO2025043025A2
WO2025043025A2 PCT/US2024/043300 US2024043300W WO2025043025A2 WO 2025043025 A2 WO2025043025 A2 WO 2025043025A2 US 2024043300 W US2024043300 W US 2024043300W WO 2025043025 A2 WO2025043025 A2 WO 2025043025A2
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WIPO (PCT)
Prior art keywords
membrane
nanosheets
crosslinker
membrane support
polymer
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WO2025043025A3 (fr
Inventor
Manish Kumar
Ronald Justin VOGLER
Dominic Diego BUJANOS
Katherine Elizabeth KIMBALL
Fnu RAMAN
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University of Texas System
University of Texas at Austin
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University of Texas System
University of Texas at Austin
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Publication of WO2025043025A2 publication Critical patent/WO2025043025A2/fr
Publication of WO2025043025A3 publication Critical patent/WO2025043025A3/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
    • B01D69/144—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers" containing embedded or bound biomolecules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • B01D71/601—Polyethylenimine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/218—Additive materials
    • B01D2323/2181—Inorganic additives
    • B01D2323/21819—Carbon, carbon nanotubes, graphene or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/218—Additive materials
    • B01D2323/2182—Organic additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones

Definitions

  • Synthetic polymeric membranes which are widely used in water purification, gas separations, chemical processing, and bioprocessing, suffer from a ubiquitous trade-off trend: high permeability leads to low selectivity and vice versa.
  • This trade-off manifests due to the structural variations in state-of-the-art membranes, which typically use differences in molecular sizes to affect a separation.
  • angstrom-scale separations such as water desalination and gas separations, where nonporous polymeric membranes operate via the solution-diffusion mechanism, the variable size of the free volume elements through which diffusion occurs hampers membrane performance.
  • porous membranes such as ultrafiltration and microfiltration, this trade-off is primarily due to the broad pore size distribution seen in commercial membranes.
  • Biological membranes exhibit high permeability' and high selectivity combinations because, in addition to possessing various transmembrane proteins with well-defined channel pore sizes, they synergistically combine size, charge, van der Waals, and specific binding interactions within the channels to enhance the transport of target species.
  • size exclusion is the major mechanism for water-over-solute selectivity of biological water channel proteins, aquaporins. Water dipole reorientation through a series of specific hydrogen bonding steps is another selectivity mechanism that prevents protons
  • Biological membrane protein channels, synthetic channels, and carbon nanotubes have emerged as promising platforms for the development of separation membranes with precise molecular selectivity.
  • Artificial channels can be synthesized using simple chemistry, and are solvent compatible, thus allowing manufacturing techniques common in polymer processing to be applied. More importantly, flexibility in design of the chemical structures of artificial channels further allows for specific functionalization to tailor their permeability and selectivity. These precisely designed pore structures are ideal for membranes that can overcome the aforementioned permeability-selectivity trade-off of current commercial membranes.
  • biomimetic membranes incorporating these pore structures are expected to exhibit high permeability and selectivity because they possess a high density of channels with a well-defined pore geometry and functionality designed to exclude or pass specific components from complicated mixtures.
  • Membrane protein-based biomimetic membranes studied thus far have been limited to small improvements in performance that are much lower than the orders of magnitude enhancement anticipated from early experiments.
  • Current membrane protein-based biomimetic membranes show 2-3 times increases in permeability over commercial membranes with similar or worse selectivity. This has been attributed to the use of vesicular morphologies of channel-reconstituted liposomes and the low protein content in biomimetic matrices used for membrane fabrication.
  • membrane compositions as well as methods of making membrane compositions.
  • single-step methods of forming membrane compositions can comprise contacting a membrane support with a solution comprising a matrix polymer and a plurality of nanosheets, thereby depositing the matrix polymer and the plurality of nanosheets on a surface of the membrane support; and crosslinking the matrix polymer and the plurality of nanosheets.
  • these methods can comprise a single contacting step.
  • the method can further comprise crosslinking the matrix polymer, the plurality of nanosheets, or a combination thereof to the membrane support.
  • contacting the membrane support with the solution comprising the matrix polymer and the plurality of nanosheets can comprise positioning the membrane support within a filtration cell, such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode; introducing the solution comprising the matrix polymer and the plurality of nanosheets into the filtration cell so as to contact a surface of the membrane support; applying pressure to filtration cell to drive solvent across the membrane support, thereby depositing the matrix polymer and the plurality of nanosheets on the surface of the membrane support; and introducing a solution comprising one or more crosslinking reagents into the filtration cell under conditions effective to covalently crosslink the plurality of nanosheets to the matrix polymer.
  • a filtration cell such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode
  • introducing the solution comprising the matrix polymer and the plurality of nanosheets into the filtration cell so as to contact a surface of the membrane
  • the matrix polymer and the nanosheets can exhibit opposite charges.
  • the matrix polymer can comprise a positively- charged polymer and the nanosheets are negatively charged.
  • the matrix polymer comprises a negatively charged polymer and the nanosheets are positively charged.
  • the matrix polymer and the nanosheets can both be uncharged.
  • the matrix polymer can comprise a negatively charged polymer or a positively charged polymer and the nanosheets are uncharged.
  • the matrix polymer comprises an uncharged polymer and the nanosheets are positively charged or negatively charged.
  • the membrane support can comprises a porous membrane.
  • the membrane support can comprise a polymeric substrate or an inorganic substrate.
  • the membrane support comprises an ultrafiltration membrane (e.g., a polymeric ultrafiltration membrane).
  • the membrane support can comprise a non-porous membrane (e.g., a non-porous polymeric membrane).
  • the membrane support can comprise a reverse osmosis (RO) membrane.
  • the membrane support can comprise a nanofiltration membrane.
  • the membrane support exhibits a negatively charged surface.
  • the negatively charged surface can be applied by UV-ozone treatment of the membrane surface.
  • each of the nanosheets comprise one or more channels.
  • the channels can comprise a membrane protein, a carbon nanotube, or an artificial channel.
  • each of the plurality of nanosheets can comprise a polymer and a membrane protein.
  • each of the plurality of nanosheets can comprise a polymer, lipid, or a combination thereof, and a membrane protein.
  • the polymer can comprise a block copolymer (e.g., an amphiphilic block copolymer).
  • the block copolymer can comprise one or more hydrophobic blocks of polybutadiene (PB) and one or more hydrophilic blocks of polyethylene oxide (PEO).
  • the block copolymer can comprise one or more hydrophobic blocks of poly caprolactone (PC) and one or more hydrophilic blocks of polyethylene oxide (PEO).
  • the amphiphilic block copolymer comprises a negatively charged moiety, such as a carboxylate.
  • the polymer and membrane protein are present at a mass ratio of from 1000:1 to 1: 1000 (e.g., from 100: 1 to 1: 100 or from 10: 1 to 1 :10).
  • membrane compositions prepared using molecular crosslinkers as well as methods of making membrane compositions using molecular crosslinkers.
  • membrane compositions that comprise a membrane support; and a plurality of nanosheets covalently crosslinked to the membrane support via a molecular crosslinker.
  • the plurality of nanosheets can also be covalently crosslinked to one another via the molecular crosslinker.
  • SUBSTITUTE SHEET (RULE 26) ferrichrome outer membrane transporter (FhuA), AquaporinO, or aquaporin Z (AqpZ) such as Rs AqpZ).
  • the molecular crosslinker comprises a bifunctional crosslinker.
  • the molecular crosslinker comprises a diamine crosslinker, a diester crosslinker, a dithiol crosslinker, a diazide crosslinker, a dialkyne crosslinker, a divinyl crosslinker, a di(meth)acrylate crosslinker, or a combination thereof.
  • contacting a membrane support with a molecular crosslinker and a plurality of nanosheets can comprise depositing the plurality of nanosheets on a surface of the membrane support; and contacting the surface with a solution comprising the molecular crosslinker under conditions effective to covalently crosslink the plurality of nanosheets to the membrane support.
  • contacting a membrane support with a molecular crosslinker and a plurality of nanosheets can comprise positioning the membrane support within a filtration cell, such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode; introducing a solution comprising the plurality of nanosheets dissolved or dispersed in a solvent into the filtration cell so as to contact a surface of the membrane support; applying pressure to the filtration cell to drive the solvent across the membrane support, thereby depositing the plurality of nanosheets on the surface of the membrane support; and introducing a solution comprising the molecular crosslinker into the filtration cell so as to contact a surface of the membrane support under conditions effective to covalently crosslink the plurality of nanosheets to the membrane support.
  • a filtration cell such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode
  • Figure 2A is a plot showing the water permeance of a poly(acrylonitrile) (PAN) ultrafiltration membrane and a PAN membrane after deposition of OmpF nanosheets using the single-step method described herein.
  • PAN poly(acrylonitrile)
  • Figure 3A is a plot showing the percent of solute rejection for solutes of varying molecular weight from a PAN membrane after deposition of OmpF nanosheets using the single-step method described herein.
  • Figure 3B is a plot showing the percent of solute rejection for solutes of varying molecular weight from membrane compositions prepared by depositing 1, 2, and 3 layers OmpF nanosheets on a membrane support using the layer-by-layer deposition methods described in U.S. Patent No. 2022/0080364.
  • Figure 4 is a schematic illustration of example methods of fabricating membrane compositions described herein.
  • Figure 5 is a plot showing the water permeance of a PAN ultrafiltration membrane and a PAN membrane after deposition of polyethyleneimine (PEI)/OmpF nanosheets using the single-step method with EDC/NHS crosslinking.
  • PEI polyethyleneimine
  • FIG. 6 is a plot showing the water permeance of a polyethersulfone (PES) ultrafiltration membrane and a PES membrane after deposition of polyethyleneimine (PEI)/ OmpF nanosheets using the single-step method with gultaraldehyde crosslinking.
  • PES polyethersulfone
  • PEI polyethyleneimine
  • Figure 7 is a plot showing the water permeance of a cellulose ultrafiltration membrane and a cellulose membrane after deposition of OmpF nanosheets using the single- step method with dopamine crosslinking/coating. The permeance of a membrane prepared using dopamine only is also included as a control.
  • Figure 8 is a schematic illustration of the methods of fabricating membrane compositions described herein.
  • Figure 9 is a plot showing the water permeance of a poly(acrylomtrile) (PAN) ultrafiltration membrane and a PAN membrane after deposition of 2D OmpF sheets and 2D RsAqpZ sheets (PAN-OmpF-RsAqpZ).
  • PAN poly(acrylomtrile)
  • Figure 10A is a micrograph of a PAN support membrane (10 pm scale, 10,000X mag).
  • Figure 1 OB is a micrograph of a PAN membrane after deposition of 2D OmpF sheets and 2D RsAqpZ sheets (PAN-OmpF-RsAqpZ) (10 pm scale, 10,000X mag).
  • Figure 11 A is a micrograph of a PAN support membrane (4 pm scale, 30,000X mag).
  • Figure 1 IB is a micrograph of a PAN membrane after deposition of 2D OmpF sheets and 2D RsAqpZ sheets (PAN-OmpF-RsAqpZ) (4 pm scale, 30,000X mag).
  • Figures 12A-12B are micrographs of a PAN membrane after deposition of 2D OmpF sheets and 2D RsAqpZ sheets (PAN-OmpF-RsAqpZ).
  • Figure 12A includes a 4 pm scale, (30,000X mag) and
  • Figure 12B includes a 1 pm scale, (10,000X mag).
  • Figures 13A-13B are micrographs of a PAN membrane after deposition of 2D OmpF sheets and 2D RsAqpZ sheets (PAN-OmpF-RsAqpZ).
  • Figure 13A includes a 10 pm scale, (10,000X mag) and
  • Figure 13B includes a 4 pm scale, (30,000X mag).
  • Figure 14 is a plot showing the water permeance of a poly(acrylonitrile) (PAN) ultrafiltration membrane and a PAN membrane after deposition of 2D RsAqpZ sheets (PAN-RsAqpZ).
  • PAN poly(acrylonitrile)
  • PAN-RsAqpZ 2D RsAqpZ sheets
  • Described herein are membrane compositions and methods for preparing membrane compositions.
  • the methods described herein can provide a simplified route to
  • SUBSTITUTE SHEET (RULE 26) prepare membrane compositions, including biomimetic-membrane filters, from proteincontaining 2D sheets.
  • the membrane compositions described herein can be prepared by mixing 2D sheets containing membrane proteins, carbon nanotubes, or their artificial mimics optionally with a cationic polymer (e.g., a polymeric amine such as poly(ethyleneimine) (PEI)).
  • a cationic polymer e.g., a polymeric amine such as poly(ethyleneimine) (PEI)
  • PEI poly(ethyleneimine)
  • the mixture can then be applied to a membrane support and crosslinked (e.g., using 1 -Ethyl-3-(3- dimethylaminopropyl)carbodiimide (EDC), glutaraldehyde, and/or N-hydroxysuccinimide (NHS)).
  • EDC 1 -Ethyl-3-(3- dimethylaminopropyl)carbodiimide
  • NHS N-hydroxysuccinimide
  • the methods described herein may offer advantages over existing methods for fabricating membrane compositions.
  • the methods described herein can provide for the preparation of highly porous biological or biomimetic channel -based membrane fabrications in a scalable membrane structure prepared using simple processing steps. Further, these membranes are covalently crosslinked, resulting in membranes with improved stability.
  • range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6, and decimals and fractions, for example, 1.2, 3.8, 1 'A, and 4% This applies regardless of the breadth of the range.
  • the term “about,” as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring techniques and equipment, with respect to any quantifiable variable, including, but not limited to mass, volume, time, temperature, distance, molecular weight, and water permeability. Further, given solid and liquid handling procedures used in the real world, there is certain inadvertent error and variation that is likely through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods and the like. The term “about” also encompasses these variations. Whether or not modified by the term “about,” the claims include equivalents to the quantities.
  • analog means a molecular derivative of a molecule.
  • structural analog or “chemical analog.”
  • compositions described herein may comprise, consist essentially of, or consist of the components and ingredients of the present invention as well as other ingredients described herein.
  • “consisting essentially of’ means that the methods, systems, apparatuses and compositions may include additional steps, components
  • oligo-'' refers to a molecular complex comprised of between two and ten monomeric units.
  • oligosaccharides are comprised of between two and ten monosaccharides.
  • oligo- shall include all possible isomeric configurations of the molecule, including, but are not limited to isotactic, syndiotactic and random symmetries, and combinations thereof.
  • oligo- shall include all possible geometrical configurations of the molecule.
  • polypeptide “peptide,” and “protein” are used interchangeably to refer to a polymer of amino acid residues.
  • the term also applies to amino acid polymers in which one or more amino acids are chemical analogues or modified derivatives of a corresponding naturally-occurring amino acids.
  • amino acid residue or “amino acid residue” or “amino acid” are used interchangeably herein to refer to an amino acid that is incorporated into a protein, polypeptide, or peptide (collectively “protein”).
  • the amino acid may be a naturally occurring amino acid and, unless otherwise limited, may encompass non-natural analogs of natural amino acids that can function in a similar manner as naturally occurring amino acids.
  • water soluble and “water miscible” as used herein, means that the component is soluble or miscible in water at 25° C. preferably at a concentration of 0.01 wt. %, more preferably at 0. 1 wt. %, and most preferably at 1 wt. %.
  • channel refers to a pathway formed in or through a medium that allows for movement of fluids, such as liquids and gases.
  • nanosheet refers to a material with a thickness on the nanometer scale or less, and lateral dimensions (e.g., a length and a width) that are each larger than the thickness of the material.
  • Described herein are methods of forming membrane compositions. These methods can comprise contacting a membrane support with a solution comprising a matrix polymer
  • these methods can comprise a single contacting step (i.e., a single step in which a solution comprising both the matrix polymer and the plurality of nanosheets is applied to the membrane support).
  • the matrix polymer and/or the nanosheets can also be crosslinked to the membrane support.
  • the method can further comprise crosslinking the matrix polymer, the plurality of nanosheets, or a combination thereof to the membrane support.
  • contacting the membrane support with the solution comprising the matrix polymer and the plurality of nanosheets can comprise positioning the membrane support within a filtration cell, such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode; introducing the solution comprising the matrix polymer and the plurality of nanosheets into the filtration cell so as to contact a surface of the membrane support; applying pressure to filtration cell to drive solvent across the membrane support, thereby depositing the matrix polymer and the plurality of nanosheets on the surface of the membrane support; and introducing a solution comprising one or more crosslinking reagents into the filtration cell under conditions effective to covalently crosslink the plurality of nanosheets to the matrix polymer.
  • a filtration cell such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode
  • introducing the solution comprising the matrix polymer and the plurality of nanosheets into the filtration cell so as to contact a surface of the membrane
  • filtration cells can be used, if desired, provided these cells are operated in a "‘deadend” mode where the only path for liquid is through the membrane.
  • the membrane compositions can similarly be formed by performing these contacting steps using a membrane support formed as a membrane module (e.g., in a flat sheet, a spiral-wound, a hollow fiber, or a plate-and-frame configuration).
  • Also described herein are method of forming membrane compositions that comprise contacting a membrane support with a solution comprising a plurality of nanosheets, thereby depositing the plurality of nanosheets on a surface of the membrane support; and contacting a membrane support with a solution comprising a matrix polymer, thereby physically immobilizing the plurality of nanosheets on a surface of the membrane support within the matrix polymer; wherein each of the nanosheets comprise one or more channels.
  • the matrix polymer and the plurality of nanosheets are present in the same solution, and the method comprises a single contacting step.
  • contacting the membrane support with the solution comprising the matrix polymer and the solution comprising the plurality of nanosheets comprises positioning the membrane support within a filtration cell, such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode; introducing the solution comprising the plurality of nanosheets into the filtration cell so as to contact a surface of the membrane support; applying pressure to filtration cell to drive solvent across the membrane support, thereby depositing the plurality of nanosheets on the surface of the membrane support; introducing a solution comprising a matrix polymer into the filtration cell so as to contact a surface of the membrane support; and applying pressure to filtration cell to drive solvent across the membrane support, thereby depositing the matrix polymer on the surface of the membrane support so that the plurality of nanosheets are physically immobilized on the surface of the membrane support within the matrix polymer.
  • a filtration cell such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode
  • contacting the membrane support with the solution comprising the matrix polymer and the solution comprising the plurality of nanosheets comprises positioning the membrane support within a filtration cell, such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode; introducing the solution comprising the plurality of nanosheets and the matnx polymer into the filtration cell so as to contact a surface of the membrane support; applying pressure to filtration cell to drive solvent across the membrane support, thereby depositing the plurality of nanosheets and the matrix polymer on the surface of the membrane support, wherein the plurality of nanosheets are physically immobilized on the surface of the membrane support within the matrix polymer.
  • the membrane compositions can similarly be formed by performing these contacting steps using a membrane support formed as a membrane module (e.g., in a flat sheet, a spiral-wound, a hollow fiber, or a plate-and-frame configuration).
  • the matrix polymer and the nanosheets can exhibit opposite charges.
  • the matrix polymer can comprise a positively charged polymer and the nanosheets are negatively charged.
  • the matrix polymer comprises a negatively charged polymer and the nanosheets are positively charged.
  • the matrix polymer and the nanosheets can both be uncharged.
  • the matrix polymer can comprise a negatively charged polymer or a positively charged polymer and the nanosheets are uncharged.
  • the matrix polymer comprises an uncharged polymer and the nanosheets are positively charged or negatively charged.
  • the membrane support can comprise a porous membrane. In some embodiments, the membrane support can comprise a polymeric substrate or an inorganic substrate. In certain embodiments, the membrane support comprises an ultrafiltration membrane (e.g., a polymeric ultrafiltration membrane).
  • the membrane support can comprise a non-porous membrane (e.g., a non-porous polymeric membrane).
  • the membrane support can comprise a reverse osmosis (RO) membrane.
  • the membrane support can comprise a nanofiltration membrane.
  • the membrane support exhibits a negatively charged surface.
  • the negatively charged surface can be applied by UV-ozone treatment. Examples of suitable membrane supports are discussed in more detail below.
  • Each of the nanosheets comprise one or more channels.
  • the channels can comprise a membrane protein, a carbon nanotube, or an artificial channel.
  • each of the plurality of nanosheets can comprise a polymer, a lipid, or a combination thereof, and a membrane protein. Examples of suitable nanosheets, as well as methods of forming nanosheets, are discussed in more detail below.
  • the polymer can comprise a block copolymer (e.g., an amphiphilic block copolymer).
  • the block copolymer can comprise one or more hydrophobic blocks of polybutadiene (PB) and one or more hydrophilic blocks of polyethylene oxide (PEO), or one or more hydrophobic blocks of poly caprolactone (PC) and one or more hydrophilic blocks of polyethylene oxide (PEO).
  • the amphiphilic block copolymer comprises a negatively charged moiety, such as a carboxylate.
  • the polymer and membrane protein are present at mass ratio of from 1000: 1 to 1: 1000 (e.g., from 100: 1 to 1 : 100 or from 10:1 to 1: 10). Examples of suitable polymers are discussed in more detail below.
  • the membrane protein can comprise a beta barrel membrane protein. In some embodiments, the membrane protein can comprise an alpha helical membrane protein. In some embodiments, the membrane protein can comprise a porin, a pore-forming toxin, or an aquaporin. In certain embodiments, the membrane protein can comprise outer membrane protein F (OmpF), outer membrane protein X (OmpX), a- hemolysin toxin (aHL), ferrichrome outer membrane transporter (FhuA), AquaporinO, or
  • the matrix polymer can comprise a positively charged polymer.
  • the matrix poly mer comprises an amine group, an amide group, an imide group, an imine group, an azide group, a nitrate group, a nitrite group, a cyanate group, a nitrile group, or a combination thereof.
  • the matrix polymer comprises a polyamine.
  • the matrix polymer comprises polyethylenimine.
  • the membrane compositions described herein can have specific solute selectivity, high permeabilities, or a combination thereof.
  • the improved solute selectivity and high permeabilities can be an improvement over existing commercial membranes.
  • the membrane compositions provide enhanced permeability.
  • the water permeability of the membrane compositions can be, for example, at least about 10 LMH bar 1 , at least about 25 LMH bar at least about 50 LMH bar 1 , at least about 75 LMH bar 1 , at least about 100 LMH bar at least about 150 LMH bar 1 , at least about 200 LMH bar 1 , at least about 250 LMH bar 1 , at least about 300 LMH bar '. at least about 500 LMH bar 1 , at least about 750 LMH bar 1 , at least about 1000 LMH bar 1 , at least about 1500 LMH bar 1 , at least about 2000 LMH bar or more.
  • the membrane compositions provide high selectivity.
  • the membrane compositions can exclude molecules larger than 25 Da, 50 Da, 75 Da, 100 Da, 150 Da, 200 Da, 250 Da, 300 Da, 350 Da, 400 Da, 450 Da, 500 Da, 550 Da, 600 Da, 650 Da, 700 Da, 750 Da, 800 Da, 850 Da, 900 Da, 950 Da, or 1000 Da.
  • the membranes can be suitable for use in precision separations.
  • the membrane compositions can be used in a variety of separations, biomimetic devices, sensors, drug delivery devices, etc. Precision separations can be performed with the use of the membrane compositions in filtration devices, including, but not limited to, masks, air purifiers, water filters, desalination devices, and biomimetic devices.
  • the compositions described herein can provide substantial energy savings in applications ranging from water treatment to small molecule bioseparations.
  • membrane compositions described herein examples include water vapor transport, water-borne pollutant rejection, resource recovery, and ion-ion separations.
  • the membrane compositions described herein are utilized to perform solute-water separations in the
  • SUBSTITUTE SHEET (RULE 26) angstrom to nanometer size range (e.g., ion-ion separations or the separation of small molecule in solution).
  • membrane compositions that comprise a membrane support; and a plurality of nanosheets covalently crosslinked to the membrane support via a molecular crosslinker.
  • the plurality of nanosheets can also be covalently crosslinked to one another via the molecular crosslinker.
  • the membrane support can comprise a porous membrane. In some embodiments, the membrane support can comprise a polymeric substrate or an inorganic substrate. In certain embodiments, the membrane support comprises an ultrafiltration membrane (e.g., a polymeric ultrafiltration membrane).
  • the membrane support can comprise a non-porous membrane (e.g., a non-porous polymeric membrane).
  • the membrane support can comprise a reverse osmosis (RO) membrane.
  • the membrane support can comprise a nanofiltration membrane. Examples of suitable membranes are discussed in more detail below.
  • Each of the nanosheets comprise one or more channels.
  • the channels can comprise a membrane protein, a carbon nanotube, or an artificial channel.
  • each of the plurality of nanosheets can comprise a polymer, a lipid, or a combination thereof, and a membrane protein. Examples of suitable nanosheets, as well as methods of forming nanosheets, are discussed in more detail below.
  • the polymer can comprise a block copolymer.
  • the block copolymer can comprise one or more hydrophobic blocks of polybutadiene (PB) and one or more hydrophilic blocks of polyethylene oxide (PEG), one or more hydrophobic blocks of poly caprolactone (PC) and one or more hydrophilic blocks of polyethylene oxide (PEG).
  • the polymer and membrane protein are present at mass ratio of from 1000: 1 to 1: 1000 (e.g., from 100: 1 to 1: 100 or from 10:1 to 1: 10). Examples of suitable polymers are discussed in more detail below.
  • the membrane protein can comprise a beta barrel membrane protein. In some embodiments, the membrane protein can comprise an alpha helical membrane protein. In some embodiments, the membrane protein can comprise a porin, a pore-forming toxin, or an aquaporin. In certain embodiments, the membrane protein can comprise outer membrane protein F (OmpF), outer membrane protein X (OmpX), a-
  • SUBSTITUTE SHEET (RULE 26) hemolysin toxin (otHL), ferrichrome outer membrane transporter (FhuA), AquaporinO, or aquaporin Z (AqpZ) such as RsAqpZ. Examples of suitable proteins are discussed in more detail below.
  • the molecular crosslinker comprises a small molecule crosslinker.
  • the small molecule crosslinker can have a molecular weight of 1000 g/mol or less, such as a molecular weight of 800 g/mol or less, a molecular weight of 600 g/mol or less, or a molecular weight of 500 g/mol or less.
  • the molecular crosslinker comprises a bifunctional crosslinker.
  • the molecular crosslinker comprises a diamine crosslinker, a diester crosslinker, a dithiol crosslinker, a diazide crosslinker, a dialkyne crosslinker, a divinyl crosslinker, a di(meth)acrylate crosslinker, a dialdehyde crosslinker (e.g., glutaraldehyde), or a combination thereof.
  • the molecular crosslinker can comprise a polyfunctional crosslinker (e.g., a tnfunctional crosslinker or a tetrafunctional crosslinker).
  • methods can further comprise activating the membrane support to introduce chemical moieties that can react with the molecular crosslinker to form covalent bonds.
  • contacting a membrane support with a molecular crosslinker and a plurality of nanosheets can comprise depositing the plurality of nanosheets on a surface of the membrane support; and contacting the surface with a solution comprising the molecular crosslinker under conditions effective to covalently crosslink the plurality of nanosheets to the membrane support.
  • contacting a membrane support with a molecular crosslinker and a plurality of nanosheets can comprise positioning the membrane support within a filtration cell, such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode; introducing a solution comprising the plurality of nanosheets dissolved or dispersed in a solvent into the filtration cell so as to contact a surface of the membrane support; applying pressure to filtration cell to drive the solvent across the membrane support, thereby depositing the plurality of nanosheets on the surface of the a filtration cell, such as a dead-end filtration cell or other filtration cell operating in a normal flow (dead-end) mode; introducing a solution comprising the plurality of nanosheets dissolved or dispersed in a solvent into the filtration cell so as to contact a surface of the membrane support; applying pressure to filtration cell to drive the solvent across the membrane support, thereby depositing the plurality of nanosheets on the surface of the
  • SUBSTITUTE SHEET (RULE 26) membrane support; and introducing a solution comprising the molecular crosslinker into the filtration cell so as to contact a surface of the membrane support under conditions effective to covalently crosslink the plurality of nanosheets to the membrane support.
  • the membrane compositions can similarly be formed by performing these contacting steps using a membrane support formed as a membrane module (e.g., in a flat sheet, a spiral-wound, a hollow fiber, or a plate-and-frame configuration).
  • the molecular crosslinker comprises a small molecule crosslinker.
  • the small molecule crosslinker can have a molecular weight of 1000 g/mol or less, such as a molecular weight of 800 g/mol or less, a molecular weight of 600 g/mol or less, or a molecular weight of 500 g/mol or less.
  • the molecular crosslinker comprises a bifunctional crosslinker.
  • the molecular crosslinker comprises a diamine crosslinker, a diester crosslinker, a dithiol crosslinker, a diazide crosslinker, a dialkyne crosslinker, a divinyl crosslinker, a di(meth)acrylate crosslinker, a dialdehyde crosslinker (e.g., glutaraldehyde), or a combination thereof.
  • the molecular crosslinker can comprise a polyfunctional crosslinker (e.g., a trifunctional crosslinker or a tetrafunctional crosslinker).
  • the membrane compositions described herein can have specific solute selectivity, high permeabilities, or a combination thereof.
  • the improved solute selectivity and high permeabilities can be an improvement over existing commercial membranes.
  • the membrane compositions provide enhanced permeability.
  • the water permeability of the membrane compositions can be, for example, at least about 10 LMH bar 1 , at least about 25 LMH bar at least about 50 LMH bar 1 , at least about 75 LMH bar 1 , at least about 100 LMH bar at least about 150 LMH bar 1 , at least about 200 LMH bar 1 , at least about 250 LMH bar 1 , at least about 300 LMH bar '. at least about 500 LMH bar 1 , at least about 750 LMH bar 1 , at least about 1000 LMH bar 1 , at least about 1500 LMH bar 1 , at least about 2000 LMH bar h or more.
  • the membrane compositions provide high selectivity.
  • the membrane compositions can exclude molecules larger than 25 Da, 50 Da, 75 Da, 100 Da, 150 Da, 200 Da, 250 Da, 300 Da, 350 Da, 400 Da, 450 Da, 500 Da, 550 Da, 600 Da, 650 Da, 700 Da, 750 Da, 800 Da, 850 Da, 900 Da, 950 Da, or 1000 Da.
  • the membranes can be suitable for use in precision separations.
  • the membrane compositions can be used in a variety of separations, biomimetic devices, sensors, drug
  • SUBSTITUTE SHEET (RULE 26) delivery devices etc. Precision separations can be performed with the use of the membrane compositions in filtration devices, including, but not limited to, masks, air purifiers, water filters, desalination devices, and biomimetic devices.
  • the compositions described herein can provide substantial energy savings in applications ranging from water treatment to small molecule bioseparations.
  • the membrane compositions described herein may be utilized include water vapor transport, water-borne pollutant rejection, resource recovery, and ion-ion separations.
  • the membrane compositions described herein are utilized to perform solute-water separations in the angstrom to nanometer size range (e.g., ion-ion separations or the separation of small molecule in solution).
  • compositions and methods described herein can comprise a membrane support.
  • the membrane support can comprise a porous support.
  • the porous structure can have a plurality of pores.
  • the plurality of pores can have an average pore diameter from about 10 nm and about 500 pm, such as from about 15 nm and about 100 pm, or from about 20 nm and about 1 pm.
  • the membrane support can comprise a non-porous membrane (e.g., a non-porous polymeric membrane).
  • the membrane support can comprise a reverse osmosis (RO) membrane.
  • the membrane support can comprise a nanofiltration membrane.
  • the membrane support can comprise a polymeric substrate and/or an inorganic substrate.
  • Example polymeric substrates include, but are not limited to, a thermoplastic, a thermoset, or a combination thereof.
  • the membrane support can comprise a synthetic polymer.
  • synthetic polymers include polysulfones, poly ethersulfones, poly vinylidene difluoride (PVDF), polypropylene, acrylic polymers; poly(methyl methacrylate), polyamide (Nylon), polyimide polytetrafluoroethylene (PTFE), polyetherimide, polyacrylonitrile, polyethylene, polycarbonate, polytetrafluoroethylene, poly(dimethylsiloxane), polystyrene, and polyphenylene oxide.
  • the polymeric substrate can comprise poly ethersulfone or polycarbonate.
  • the membrane support may comprise a natural polymer or modified natural polymer.
  • natural polymer and modified natural polymer are examples of natural poly mer and modified natural polymer
  • SUBSTITUTE SHEET (RULE 26) polymers include cellulose, cellulose esters, cellulose nitrate, cellulose acetate, and regenerated cellulose.
  • the membrane support may comprise an inorganic material.
  • suitable inorganic materials include, but are not limited to, aluminum oxide (AI2O3), metal oxide/ceramic; silicon carbide (SiC), zirconium oxide, silicon dioxide, and titanium dioxide.
  • the inorganic substrate is aluminum oxide.
  • a surface of the membrane support can be negatively charged.
  • the methods and compositions comprise a matrix polymer.
  • the matrix polymer can comprise a positively charged polymer.
  • Example matrix polymers include those with a functional group such as an amine group, an amide group, an imide group, an imine group, an azide group, a nitrate group, a nitrite group, a cyanate group, a nitrile group, or a combination thereof.
  • a functional group such as an amine group, an amide group, an imide group, an imine group, an azide group, a nitrate group, a nitrite group, a cyanate group, a nitrile group, or a combination thereof.
  • matrix polymers that have an amino group include polyethyleneimine, polyallylamine, and polyvinylamine.
  • the matrix polymer can comprise polyethyleneimine or polyallylamine. In certain embodiments, the matrix polymer can comprise polyethyleneimine.
  • compositions and methods described herein can comprise nanosheets comprise one or more channels.
  • the channels can comprise a membrane protein, a carbon nanotube, or an artificial channel.
  • each of the channels can comprise a membrane protein, a carbon nanotube, or an artificial channel.
  • the combined solution is mixed. In certain embodiments, the combined solution is mixed homogeneously. Any suitable method of mixing can be performed. Preferred methods of mixing include, but are not limited to, sonicating, manual mixing, automatic mixing, stirring, or a combination thereof.
  • the combined solution can be applied to a substrate.
  • the substrate can be of any suitable size for preparation of the desired membrane size.
  • the substrate can be of a suitable for preparation of a membrane.
  • the substrates can comprise glass, plastic, composite, metal, or a mixture or combination thereof.
  • the combined solution can be applied to a substrate by any suitable method, including, but not limited to, spraying, pouring, extruding, squirting, or otherwise applying.
  • the combined solution can be spread on the substrate.
  • Porins are beta barrel membrane proteins present in the outer membrane of gramnegative bacteria and some gram-positive Mycobacteria, the outer membrane of mitochondria, and the outer chloroplast membrane.
  • the porin is outer membrane protein F (OmpF) from E. coli.
  • the porin is outer membrane protein F (OmpF) from E. coli.
  • Pore-forming toxins are produced by bacteria as well as other organisms including earthworms, which produce the pore-forming toxin lysenin.
  • Pore-forming toxins may be beta barrel pore-forming toxins (including a- hemolysin, Panton-Valentine leucocidin, Clostridial Epsilon-toxin) or alpha helical poreforming toxins (including haemolysin E, actinoporins, Corynebactenal porin B).
  • the pore-forming toxin is a-hemolysin (o.HL). a self-assembled structure created by Staphylococcus aureus to porate cell membranes.
  • the membrane protein comprises between about 0. 1 wt. % and about 60 wt. % of the combined solution, more preferably between about 0.5 wt. % and about 55 wt. % of the combined solution, most preferably between about 1 wt. % and about 50 wt. % of the combined solution.
  • the nanosheets used in the compositions and methods described herein can comprise a polymer.
  • Example polymers include, but are not limited to, a thermoplastic, a thermoset, or a combination thereof.
  • the polymer can be a block copolymer.
  • the copolymer is an ABA copolymer, where A is hydrophilic and B is hydrophobic where A is the same or different hydrophilic segments and B is a hydrophobic segment.
  • ABA copolymer includes an ABC copolymer, where the hydrophilic segments A and C are different. AB copolymers can also be used.
  • the block copolymer includes at least one segment B that includes a hydrophobic polymer.
  • a hydrophobic polymer such as, but not limited to, polysiloxane such as poly dimethylsiloxane and poly diphenylsiloxane, perfluoropolyether, polystyrene, polyoxypropylene, polyvinylacetate, polyoxybutylene, polyisoprene, polybutadiene, polyvinylchloride, polyalkylacrylate (PAA), polyalkylmethacrylate, polyacrylonitrile, polypropylene, PTHF, polymethacrylates, polyacrylates, polysulfones, polyvinylethers, and polypropylene oxide), and copolymers thereof.
  • PAA polyalkylacrylate
  • PAA polyalkylmethacrylate
  • polyacrylonitrile polypropylene
  • PTHF polymethacrylates
  • polyacrylates polysulfones, polyvinylethers
  • the hydrophobic segment contains a predominant amount of hydrophobic monomers.
  • a hydrophobic monomer is a monomer that typically gives a homopolymer that is insoluble in water and can absorb less than 10% by weight of water.
  • Suitable hydrophobic monomers are C1-C18 alkyl and C3-C18 cycloalkyl acrylates and methacrylates.
  • the hydrophobic polymer includes a perfluoroalkyl-polyether block.
  • the hydrophobic polymer includes an unsaturated polymer, such as a polymer of a conjugated aliphatic or alicyclic diene, which may be substituted by halogen or lower alkyl, a polymer of an alkyne or dialkyne, which may be substituted by
  • SUBSTITUTE SHEET (RULE 26) lower alkyl or trimethyl silyl a copolymer of a conjugated diene and a hydrophilic or hydrophobic vinylic monomer, and also partially hydrated derivatives of these compounds.
  • polymers of conjugated dienes are cis-, trans-, iso- or syndiotactic poly-l,2-butadiene, poly-1, 4-butadiene or polyisoprene, poly-pentenamer, poly chloroprene and polypiperylen.
  • copolymers are butadiene- or isoprene-copolymers with hydrophilic or hydrophobic vinylic monomers, such as acrylonitrile, styrene, acrylic acid or hydroxy ethylmethacrylate.
  • An example of a poly alkyne is poly-1 -trimethylsilyl-propyne.
  • examples of polymers included unsaturated polymers are syndiotactic poly-1, 2-butadiene, poly- 1, 4-butadiene and polyisoprene.
  • An especially preferred unsaturated polymer is poly-1 -trimethylsilyl-propyne.
  • Another especially preferred unsaturated polymer is poly- 1, 4-butadiene.
  • the hydrophobic polymer may include a single type of polymer or more than one type of polymer, such as two or more of those discussed above.
  • the mean molecular weight of one segment B is in the range from about 500 to about 50,000, preferably in the range from about 800 to about 15,000, more preferably in the range of about 1,000 to 12,000, particularly preferably in the range from about 5,000 to about 12,000. In certain embodiments, the mean molecular weight of one segment B is in the range of abut 1,000 to about 2,000.
  • the amphiphilic segmented copolymer includes at least one segment A which includes at least one hydrophilic polymer, such as, but not limited to, polyoxazoline, polyethylene glycol, polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly(meth)acrylic acid, polyethylene oxide-co-polypropyleneoxide block copolymers, poly(vinylether), poly(N,N-dimethylacrylamide), polyacrylic acid, polyacyl alkylene imine, polyhydroxyalkylacrylates such as hydroxyethyl methacrylate (HEMA), hydroxy ethyl acrylate, and hydroxypropyl acrylate, polyols, and copolymeric mixtures of two or more of the above mentioned polymers, natural polymers such as polysaccharides and polypeptides, and copolymers thereof, and polyionic molecules such as polyallylammonium, polyethyleneimine
  • hydrophilic polymer such as, but not limited
  • the hydrophilic segment preferably contains a predominant amount of hydrophilic monomers.
  • a hydrophilic comonomer is a monomer that typically gives a homopolymer that is soluble in water or can absorb at least 10% by weight of water.
  • Suitable hydrophilic monomers are hydroxyl-substituted lower alkyl acrylates and methacr lates, acrylamide, methacrylamide, (lower alkyl) acrylamides and methacrylamides, N,N-dialkyl-acrylamides, ethoxylated acrylates and methacrylates, polyethyleneglycol-mono methacrylates and polyethyleneglycolmonomethylether methacrylates, hydroxyl-substituted (lower alkyl)acrylamides and methacrylamides, hydroxyl-substituted lower alkyl vinyl ethers, sodium vinylsulfonate, sodium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2- pyrrolidone, 2-vinyloxazoline, 2-vinyl-4,4'-dialkyloxazolin-5-one,
  • the segment A includes a polymer displaying a relatively high water or ion diffusion rate there through.
  • hydrophilic monomers from which such polymers can be made are cyclic imino ethers, vinyl ethers, cyclic ethers including epoxides, cyclic unsaturated ethers, N-substituted aziridines, beta-lactones and beta-lactams. Further suitable monomers include ketene acetals, vinyl acetals and phosphoranes. Suitable cyclic imino ethers include 2-oxazoline.
  • a 2-oxazoline having an alkenyl group in 2 position is used as hydrophilic monomer
  • a polymerizable unsaturated group is provided within segment A (in a side chain) of the amphiphilic segmented copolymer to serve as the polymerizable unsaturated group necessary for the final polymerization to obtain a polymeric product or as an additional polymerizable unsaturated group which offers the possibility of direct crosslinking in the preparation of the polymer.
  • the cyclic imino ether is 2-methyloxazoline.
  • the most preferred vinyl ethers are methyl vinyl ether, ethyl vinyl ether and methoxy ethyl vinyl ether.
  • the mean molecular weight of one segment A is in the range from about 200 to about 50,000, from about 500 to about 50,000, from about 800 to about 15,000, from about 1,000 to 12,000, particularly from about 5,000 to about 12,000.
  • Preferred block copolymers include, but are not limited to, an amphiphilic diblock or triblock block copolymer comprising one or more hydrophobic blocks selected from the group consisting of polybutadiene (PB), poly dimethylsiloxane (PDMS), polypropylene
  • PB polybutadiene
  • PDMS poly dimethylsiloxane
  • Preferred block copolymers include, but are not limited to, an amphiphilic diblock or triblock block copolymer comprising one or more hydrophobic blocks selected from the group consisting of polybutadiene (PB), poly dimethylsiloxane (PDMS), polypropylene
  • PB polybutadiene
  • PDMS poly dimethylsiloxane
  • polypropylene polypropylene
  • the block copolymer comprises one or more hydrophobic blocks of polybutadiene (PB) and one or more hydrophilic blocks of polyethylene oxide (PEO).
  • the block copolymer comprises one or more hydrophobic blocks of poly caprolactone (PC) and one or more hydrophilic blocks of polyethylene oxide (PEO).
  • the polymer comprises between about 10 wt. % and about 90 wt. % of the nanosheet or two-dimensional crystal, more preferably between about 15 wt. % and about 85 wt. % of the nanosheet or two-dimensional crystal, most preferably between about 20 wt. % and about 80 wt. % of the nanosheet or two-dimensional crystal.
  • the polymer comprises between about 0.1 wt. % and about 60 wt. % of the combined solution, more preferably between about 0.5 wt. % and about 55 wt. % of the combined solution, most preferably between about 1 wt. % and about 50 wt. % of the combined solution.
  • the polymer comprises between about 0.01 wt. % and about 20 wt. % of the combined solution, more preferably between about 0.1 wt. % and about 15 wt. % of the combined solution, most preferably between about 0.5 wt. % and about 10 wt. % of the combined solution.
  • the polymer comprises between about 0.001 wt. % and about 20 wt. % of the combined solution, more preferably about 0.005 wt. % and about 20 wt. % of the combined solution, more preferably between about 0.01 wt. % and about 15 wt. % of the combined solution, most preferably between about 0.05 wt. % and about 10 wt. % of the combined solution.
  • the nanosheets used in the compositions and methods described herein can comprise a lipid.
  • suitable lipids include cationic lipids, neutral lipids, PEGylated lipids, and ionizable lipids.
  • cationic lipids include, but are not limited to, DOTMA: [ 1 -(2,3- sioleyloxy)propyl)]-N,N,N-trimethylammonium chloride, DMRIE, di-C14-amidine, DOTIM, SAINT, DC-Chol, BGTC, CTAP, DOPC, DODAP, DOPE: Dioleyl phosphatidylethanol-amine, DOSPA (2,3-dioleyloxy-N-[2-(spermine carboxamido)ethyl]-
  • SUBSTITUTE SHEET (RULE 26) N.N-dimethyl-l -propanaminium trifluoroacetate), DORIE (N-[l-(2,3-dioleyloxypropyl)]- N,N-dimethyl-N-hydroxy ethylammonium bromide), DODAB, DOIC, DMEPC, DOGS: Dioctadecylamidoglicylspermin, DIMRI: Dimyristooxypropyl dimethyl hydroxyethyl ammonium bromide, DOTAP: dioleoyloxy-3-(trimethylammonio)propane, DC-6-14: 0,0- ditetradecanoyl-N-. alpha.
  • CLIP 1 rac- [(2,3-dioctadecyloxypropyl)(2-hydroxyethyl)]-dimethylammonium chloride
  • CLIP6 rac- [2(2,3 -dihexadecyloxypropyloxy methyloxy )ethy 1 ] -trimethylammonium
  • CLIP9 rac- [2(2,3- dihexadecyloxy propyloxy succinyloxy)ethyl] -trimethylammonium, oligofectamine, lipids described in U.S. Patent No.
  • neutral lipids include, but are not limited to, dipalmitoylphosphatidylcholine (DPPC), dioleoylphosphatidylethanolamine (DOPE), palmitoyloleoylphosphatidylcholine (POPC), egg phosphatidylcholine (EPC), distearoylphosphatidylcholine (DSPC), cholesterol, or any combination thereof.
  • DPPC dipalmitoylphosphatidylcholine
  • DOPE dioleoylphosphatidylethanolamine
  • POPC palmitoyloleoylphosphatidylcholine
  • EPC egg phosphatidylcholine
  • DSPC distearoylphosphatidylcholine
  • cholesterol or any combination thereof.
  • the one or more neutral lipids can include cholesterol.

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Abstract

L'invention concerne des compositions de membrane et des procédés de préparation de compositions de membrane.
PCT/US2024/043300 2023-08-21 2024-08-21 Procédés de synthèse de membranes de nanofeuilles Pending WO2025043025A2 (fr)

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