WO2025078687A1 - Composés ayant des groupes induisant une réticulation clivable et réseaux polymères dérivés de ceux-ci - Google Patents

Composés ayant des groupes induisant une réticulation clivable et réseaux polymères dérivés de ceux-ci Download PDF

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Publication number
WO2025078687A1
WO2025078687A1 PCT/EP2024/078873 EP2024078873W WO2025078687A1 WO 2025078687 A1 WO2025078687 A1 WO 2025078687A1 EP 2024078873 W EP2024078873 W EP 2024078873W WO 2025078687 A1 WO2025078687 A1 WO 2025078687A1
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group
oligomer
polymer
cleavable
synthetic compound
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Inventor
Sascha BERNARD
Jürgen Rühe
Thomas Brandstetter
Frank Daniel Scherag
Florian Tritz
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Albert Ludwigs Universitaet Freiburg
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Albert Ludwigs Universitaet Freiburg
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide

Definitions

  • the resulting structures can usually not be cleaved, dissolved and re-formed in a reversible manner.
  • the materials of such polymer networks are only recyclable to a very limited extent and can for example not be reused after damage.
  • particles or biological cells bound to such polymer networks can often only be released under harsh conditions. In many of these release processes, the cells are damaged.
  • it is also difficult to vary or change the crosslinking properties of these polymer networks e.g. to modify the mechanical properties of the network, to remodel the network or to release biological molecules or cells from the polymer network, while retaining the general properties of the polymer network.
  • a further disadvantage of such covalent polymer networks produced by in situ polymerization is that this type of polymerization and network formation is subject to several process-related restrictions with regard to general processing and applicability, as a monomeric liquid is polymerized.
  • monomers are generally categorized as hazardous substances and the processing of these substances is restricted to chemical laboratories.
  • EP1970400A1 , WO/2022/080408A1 , US20120232027, EP3808786A1 , US 8367051 and WO/2010/128007A1 disclose hydrophilic polymers, hydrogels, microbeads and polymer networks crosslinked by disulfide bonds synthesized by in situ polymerization or by subsequent crosslinking after polymer synthesis. These disulfide bonds can for example be cleaved in biological environment.
  • EP2111872A2 discloses a polymeric prodrug, wherein a therapeutic agent is covalently bound to a polymer backbone by a crosslinker, which is cleavable by biological stimuli.
  • US20060003900 discloses the use of boronic acids as crosslinking agents for the formation of a crosslinked gelling agent for increasing the viscosity of a fluid.
  • Polymers comprising crosslinkable groups which enable crosslinking via C-H insertion reactions (CHic reaction) allow polymer network formation with a variety of polymers comprising C-H groups.
  • These crosslinkable groups are usually photochemically or thermally activated.
  • Materials obtained by the CHic process are suitable for coatings, as the surface layer thickness is easily scalable, and the reaction allows the production of objects of arbitrary size and shape.
  • Synthetic compounds comprising such “cleavable CH-insertion groups” that crosslink via C-H insertion reactions (CHic reaction), allow effective and fast covalent network formation of the synthetic compound with a second synthetic compound, or oligomers and polymers in the solid state and glass state, thus not requiring specific reaction conditions or preprocessing of the synthetic compound, oligomers and polymers such as melting and dissolution.
  • crosslinkages formed within a covalent oligomer or polymer network can advantageously be cleaved in a timely and spatially controlled manner by using specific stimuli such as a change in pH, temperature, light exposure or oxidative state ( Figure 2).
  • the one or more crosslinkable groups are selected from the group consisting of an aromatic ketone such as benzophenone and anthraquinone, an azide such as sulfonyl azide, and a diazo ester group.
  • the at least one crosslinkable group forms a covalent bond with a C-H group of a second synthetic compound according to the present invention, an oligomer and/or a polymer. In one embodiment the at least one crosslinkable group forms a covalent bond with a C- H group of the oligomer backbone or polymer backbone of a second synthetic compound according to the present invention.
  • the external stimulation for cleaving a covalent bond of the one or more cleavable groups is a change in temperature, pH value, light exposure, oxidative state and/or the presence of competing exchange reactants.
  • Functional groups that can be cleaved by external stimuli such as in temperature, pH value, light exposure, oxidative state and/or the presence of competing exchange reactants are particularly advantageous, as cleavage by these stimuli can be easily and precisely controlled and carried out without special equipment or occurs in biological environment, thereby providing biologically responsive oligomer and polymer networks, such as networks releasing a therapeutic agent, protein, nucleic acid or antibody within a tissue of a subject upon a biological stimulus such as in inflamed or tumor tissue having a decreased pH value compared to other tissues.
  • the oligomer backbone is a homooligomer or a cooligomer. In one embodiment the oligomer backbone is a homooligomer backbone or a cooligomer backbone.
  • the invention relates to a composite comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to an oligomer and/or polymer.
  • the invention relates to an oligomer composite comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to an oligomer and/or polymer.
  • the invention relates to a polymer composite comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to an oligomer and/or polymer.
  • the invention relates to an oligomer or polymer composite comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to an oligomer and/or polymer.
  • the invention thus relates to an oligomer network or polymer network comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to an oligomer and/or polymer.
  • the invention relates to a covalent oligomer or polymer composite comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to an oligomer and/or polymer.
  • the invention relates to a covalent oligomer or polymer network comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to an oligomer and/or polymer.
  • the invention relates to a composite comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to an oligomer and/or polymer, wherein the oligomer and/or polymer is a second synthetic compound according to the present invention comprising an oligomer backbone or a polymer backbone and/or a different oligomer or polymer.
  • the invention relates to an oligomer composite comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to an oligomer, wherein the oligomer is a second synthetic compound according to the present invention comprising an oligomer backbone and/or a different oligomer.
  • the invention relates to a polymer composite comprising at least one synthetic compound according to the invention, wherein at least one crosslinkable group of the synthetic compound is covalently bound to a polymer, wherein the polymer is a second synthetic compound according to the present invention comprising a polymer backbone and/or a different polymer.
  • the oligomer composite comprises at least one oligomer compound according to the present invention, wherein at least one crosslinkable group of the oligomer compound is covalently bound to an oligomer.
  • the oligomer and/or polymer is selected from the group consisting of a thermoplastic oligomer or polymer, and a natural oligomer or polymer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the oligomer is selected from the group consisting of a thermoplastic oligomer and natural oligomer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the polymer is selected from the group consisting of a thermoplastic polymer and natural polymer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the oligomer is selected from the group consisting of a thermoplastic oligomer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Poly Acrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET), and natural oligomer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • a thermoplastic oligomer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Poly Acrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET), and natural oligomer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the polymer is selected from the group consisting of a polymer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Poly Acrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET), and natural polymer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • a polymer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Poly Acrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET)
  • natural polymer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the different oligomer or polymer is selected from the group consisting of a thermoplastic oligomer or polymer and a natural oligomer or polymer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the different oligomer is selected from the group consisting of a thermoplastic oligomer and a natural oligomer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the different polymer is selected from the group consisting of a thermoplastic polymer and a natural polymer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the different oligomer or polymer is selected from the group consisting of a thermoplastic oligomer or polymer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Polyacrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET), and natural oligomer or polymer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • a thermoplastic oligomer or polymer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Polyacrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET), and natural oligomer or polymer such as cellulose, lignin, alginate, collagen
  • the different oligomer is selected from the group consisting of a thermoplastic oligomer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Polyacrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET), and natural oligomer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • a thermoplastic oligomer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Polyacrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET), and natural oligomer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the different polymer is selected from the group consisting of a thermoplastic polymer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Polyacrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET), and natural polymer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • a thermoplastic polymer such as polyethylene (PE), polycarbonate (PC), polystyrene (PS), polyvinylchloride (PVC), polyamide (PA), Polyacrylonitrile butadiene styrene (ABS), polypropylene (PP) and polyethylene terephthalate (PET)
  • natural polymer such as cellulose, lignin, alginate, collagen, gelatin, silk fibroin and starch.
  • the invention relates to a composite comprising a synthetic compound according to the invention and a two or more oligomers and/or polymers, a. wherein the synthetic compound according to the invention comprises two crosslinkable groups covalently linked by a cleavable group, wherein the two crosslinkable groups are the same or different, and b. wherein each of the crosslinkable groups forms a covalent bond with a C-H group of one of the two oligomers and/or polymers upon an external stimulation.
  • the synthetic compound and (b.) the at least one oligomer and/or polymer are mixed prior to (c.) initiating a C,H insertion reaction. In one embodiment (a.) the synthetic compound and (b.) the at least one oligomer are mixed prior to (c.) initiating a C,H insertion reaction.
  • the invention relates to a method of producing an oligomer composite according to the present invention, comprising a. providing an oligomer compound according to the invention, the oligomer compound comprising one or more crosslinkable groups and one or more cleavable groups, b. providing at least one oligomer, and c. initiating a C,H insertion reaction of at least one crosslinkable group of the oligomer compound with the at least one oligomer, wherein a covalent bond between the oligomer compound and the at least one oligomer is formed.
  • the C,H insertion reaction is initiated by thermal, light and/or mechanic stimulation.
  • At least one crosslinkable group forms a covalent bond with a C-H group by a C,H insertion reaction upon an external stimulation, g. wherein at least one crosslinkable group is covalently bound to the oligomer backbone or polymer backbone by at least one cleavable group, and h. wherein a covalent bond of the cleavable group is cleavable upon an external stimulation.
  • the C,H-insertion crosslinker acts as a molecule that induces network formation and is selected from the group comprising (1) aromatic ketones, for example, benzophenone and anthraquinones, which upon activation form ketyl biradicals, (2) azides, for example, sulfonyl azides, which form nitrenes, and (3) diazo groups, which form carbenes.
  • aromatic ketones for example, benzophenone and anthraquinones, which upon activation form ketyl biradicals
  • azides for example, sulfonyl azides, which form nitrenes
  • diazo groups which form carbenes.
  • the invention relates to a polymer material or polymer composite or polymer network comprising at least one co-polymeric component according to at least one of the preceding embodiment, wherein the co-polymeric component is bound to at least one polymer chain of the polymer material or polymer composite or polymer network via the C,H-insertion crosslinker to crosslink the material or composite or network at least partially.
  • the at least partially crosslinked polymer material or polymer composite or polymer network can be at least partially broken up by cleaving the cleavable group.
  • the CH insertion is initiated via light and/or temperature and/or mechanical stimulation.
  • the invention relates to a method of cleaving a polymer material or polymer composite or polymer network, comprising a. Providing a polymer material or polymer composite or polymer network according to the invention, and b. Cleaving of the cleavable groups at least partially.
  • cleaving of the cleavable groups is activated by light, temperature, pH value and/or oxidative state, or by presenting competitive ex-change reactants.
  • the synthetic compound comprises one or more crosslinkable groups forming a covalent bond with a C-H group by a C,H insertion reaction upon an external stimulation.
  • crosslinkable groups and external stimuli in the context of C,H insertion reactions. Suitable non-limiting examples for such groups and external stimuli are disclosed herein.
  • the synthetic compound further comprises one or more cleavable groups, wherein a covalent bond of the cleavable group is cleavable upon an external stimulation.
  • cleavable groups and external stimuli. Suitable non-limiting examples for such groups and external stimuli are disclosed herein.
  • the mesh size or pore size of the network or composite may be reduced by increasing the degree of crosslinking.
  • the crosslinked network or composite such as an oligomer or polymer network or composite according to the present invention may without limitation have an altered swellability, hydrophobicity, mechanical strength, translucency, chemical resistance to specific chemical agents such as acids, oxidative agents and/or bases and/or flexibility compared to a non-crossliked molecule such as a synthetic compound according to the present invention, an oligomer or a polymer.
  • the “degree of crosslinking” in the context of the present invention refers to the extent to which the molecules of a network or composite such as oligomer or polymer chains are interconnected through covalent crosslinking bonds.
  • the degree of crosslinking quantifies the density or concentration of such bonds (crosslinks) within network or composite.
  • a higher degree of crosslinking indicates a greater number of crosslinks per unit volume or weight of the overall network or composite.
  • methods for determining the degree of crosslinking of an oligomer or polymer network or composite may include measurement of the degree of crosslinking by swelling tests.
  • the crosslinked sample such as the network or composite is placed into a good solvent at a specific temperature, and either the change in mass or the change in volume is measured.
  • crosslinkable group also termed “crosslinkable functional group” or “crosslinking group” according to the present invention refers to a functional group of a chemical compound or molecule such as the synthetic compound of the present invention, which may form a covalent bond with another molecule or with the molecule it is comprised in, thereby forming a covalent network or composite.
  • a crosslinkable group according to the present invention forms a covalent bond upon activation, preferably thermal, light or mechanic stimulation.
  • a crosslinkable group according to the present invention forms a covalent bond with another molecule or within the molecule it is comprised in by a C,H insertion reaction upon external stimulation, preferably upon thermal, light or mechanic stimulation.
  • C,H insertion reactions typically require reagents that possess specific functional groups capable of facilitating the insertion of a carbon atom into a C-H bond upon activation such as by external stimuli, for example thermal, light or mechanical stimuli.
  • cleavable C,H insertion group in the context of the present invention refers to C,H insertion group linked to a cleavable group by a covalent bond.
  • the term thus refers to a functional group comprising a crosslinkable group that forms a covalent bond with another molecule or within the molecule it is comprised in by a C,H insertion reaction upon external stimulation, which is covalently linked to a cleavable group.
  • oligomer or “oligomer “compound” refers to a molecule comprising at least two identical or similar substructures (also termed “subunits”) linked to each other, preferably by a covalent bond.
  • a substructure or subunit of an oligomer is termed monomer.
  • An oligomer comprising at least 50 subunits, such as 50, 55, 60, 70, 75, 80, 85, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 350, 300, 350, 400, 450 or 500, is termed a “polymer” or “polymer compound”.
  • Size Exclusion Chromatography is a technique used to determine the molecular weight distribution of polymers. By comparing the elution volume of the polymer with that of known standards, the average molecular weight and the DP can be calculated. NMR spectroscopy can provide detailed information about the chemical structure of the polymer. By analyzing the end groups of the polymer chain, it is possible to determine the DP. This method is especially useful for polymers with well-defined end groups. Osmometry measures the osmotic pressure of a polymer solution to determine the number average molecular weight (Mn). From Mn and the known molecular weight of the repeating unit, the DP can be calculated. Viscometry measures the viscosity of a polymer solution.
  • Mn number average molecular weight
  • thermoplastic oligomer or “thermoplastic polymer” is a class of oligomers or polymers that become soft and moldable upon heating and solidify upon cooling. This change in physical properties is reversible. The process of melting and solidifying can be repeated multiple times without significantly altering the polymer's chemical structure or properties, making thermoplastic polymers recyclable and versatile for various applications. Thermoplastic oligomers or polymers can be repeatedly heated to their melting point, shaped into desired forms, and then cooled to solidify. Further, thermoplastic oligomers or polymers can be processed using various techniques such as injection molding, extrusion, blow molding, and thermoforming, allowing for the production of a wide range of products including packaging material, automotive parts, consumer goods, medical devices, and construction materials.
  • a "receptor-like molecule” refers to a molecule that mimics the function or structure of a biological receptor.
  • Receptors are proteins on the surface of cells or within cells that bind to specific ligands (such as hormones, neurotransmitters, or other signaling molecules) and initiate a biological response.
  • Receptor-like molecules are designed to interact similarly with ligands or other molecules.
  • Types of receptor-like molecules include without limitation genetically engineered proteins such as chimeric receptors, peptides, small molecules, molecular imprinted polymers (PIPs), aptamers and nanobodies.
  • Single-chain Fv or “scFv” antibody fragments comprise the VH and VL domains of an antibody, wherein these domains are present in a single polypeptide chain and in either orientation ⁇ e.g., VL- VH orVH- VL).
  • the scFv polypeptide further comprises a polypeptide linker between the VH and VL domains which enables the scFv to form the desired structure for antigen binding.
  • the cleavage rate is influenced by using other cleavage reagents such as DTBA or GSH.
  • the numbers in the structure above refer to the relative amount (mol-%) of the respective monomers in the example compound.
  • oligomer composites can be created that comprise dissolvable and non- dissolvable domains.
  • functional magnetic, non-water-swellable polymers can be covalently linked to the compounds of the present invention such as example compound 2.
  • one or more layers can be released by cleaving the cleavable groups, such as the disulphide links of example compound 2.
  • aqueous solution of example compound 1 or example compound 2 (100 mg/ml) was microfluidically processed into particles.
  • the aqueous disperse flow was operated at 1 .3 pl/min and the oil flow as a continuous phase at 6.5 pl/min.
  • 365 nm By combining both streams in a T-junction and subsequent illumination with 365 nm for approx. 15 min (approx. 8 J), particles with low polydispersity were obtained.
  • These particles were treated with a solution of DTT (23.2 mg/15 ml, pH ⁇ 8, 10 mM). Complete cleavage was observed after 8 minutes.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un composé synthétique comprenant (a) un ou plusieurs groupes réticulables et un ou plusieurs groupes clivables, (b) au moins un groupe réticulable formant une liaison covalente avec un groupe C-H par une réaction d'insertion C, H lors d'une stimulation externe, (c) au moins un groupe réticulable étant lié de manière covalente à au moins un groupe clivable, et (d) une liaison covalente du groupe clivable étant clivable lors d'une stimulation externe. L'invention concerne en outre un composite oligomère comprenant le composé synthétique, un procédé de production dudit composite oligomère et un procédé de clivage dudit composite oligomère.
PCT/EP2024/078873 2023-10-13 2024-10-14 Composés ayant des groupes induisant une réticulation clivable et réseaux polymères dérivés de ceux-ci Pending WO2025078687A1 (fr)

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