Molecule functionalisation

Abstract

There is provided a method of producing a functionalised molecule. The method comprises: providing a first aqueous precursor composition comprising a molecule in aqueous solution or suspension, wherein the molecule has a reactive group; providing a second precursor composition comprising a surface modifying agent in solution or suspension, wherein the surface modifying agent has a linker group and a functionalising group; forming a reaction mixture comprising the first aqueous precursor composition, the second precursor composition, and a mixed metal catalyst that comprises a first transition metal and a second metal which is a transition metal or Group 13 or 14 metal; and allowing the linker group of the surface modifying agent to react with the reactive group of the molecule in the presence of the catalyst, to thereby provide a functionalised molecule. The reactive group of the molecule comprises a carboxylic acid or salt thereof or derivative thereof and the linker group of the surface modifying agent is an amine or salt thereof. The reactive group of the molecule comprises an amine or salt thereof and the linker group of the surface modifying agent is a carboxylic acid or salt thereof or derivative thereof; such that the functionalising group is attached to the surface of the molecule via the formation of an amide bond.

Description

[0001] MOLECULE FUNCTIONALISATION

[0002] Field of the invention

[0003] The present invention relates to methods of functionalising molecules, including macromolecules and biomolecules. It enables the surface modification of molecules such as biopolymers and other biomolecules (including carbohydrates, proteins and amino acids).

[0004] Background of the invention

[0005] It is often desirable to alter the surface properties of molecules, such as biopolymers. It is known in that art that the surface properties of molecules may be altered via a process known as surface modification. Surface modification of molecules involves altering their surface characteristics, usually with the aim of providing or enhancing certain properties, such as hydrophilicity, hydrophobicity, biocompatibility, and adhesion.

[0006] Polysaccharides are long chains of sugar molecules (monosaccharides) linked together by glycosidic bonds. Their properties, including solubility, mechanical strength, and biodegradability, are influenced by factors such as monosaccharide composition, chain length, and branching. Polysaccharides such as cellulose, chitosan, alginate and pollul an have attracted significant attention for surface modification due to their unique properties and widespread availability.

[0007] There are a range of surface modification techniques to modify molecule surfaces, each tailored to achieve distinct enhancements. These surface modification techniques can be broadly categorized into physical, biological, and chemical methods.

[0008] Physical methods of surface modification involve physical alterations of the surface without altering the chemical structure of the molecule. Techniques such as plasma treatment, ion beam irradiation, and ultraviolet (UV) irradiation are employed to introduce functional groups or induce structural changes on the surface.

[0009] Biological methods of surface modification include enzymatic modification, which leverages enzymes to catalyse specific reactions on the molecule surface. This approach offers a more selective and environmentally friendly option for surface modification.

[0010] Chemical methods of surface modification include the covalent attachment of various molecules to the molecule surface. This may be achieved through reactions such as grafting, crosslinking, and chemical derivatization. Commonly used strategies include the use of reagents like glutaraldehyde, epichlorohydrin, and various coupling agents.

[0011] Several factors influence the choice of surface modification technique, including the intended end application for the functionalised material, the desired properties, and compatibility with the starting material. Additionally, considerations such as cost, scalability, and environmental impact are relevant in selecting the most suitable method.

[0012] Using chemical surface modification of molecules, it is possible to alter the properties of the molecule by selecting the functionalising group to be covalently attached to the molecule surface. For example, this may be through selection of chain length and branching of the functionalising group to be attached.

[0013] The chemical surface modification of molecules offers a wealth of opportunities for synthesising novel molecules with tailored properties to address diverse industrial and medical challenges. For example, such modified molecules can find utility in biomedical applications, cosmetic applications, and food and environmental remediation, including water purification and the like.

[0014] Typically, chemical surface modification involves the use of a catalyst, which may be homogeneous or heterogeneous.

[0015] The disadvantages of utilising a homogeneous catalyst are the chance of catalyst contamination with the product, and the difficulty of recovering and reusing the homogeneous catalyst for subsequent reactions.

[0016] Existing heterogeneous catalysts often heavy metal based. This brings associated disadvantages such as low yield of surface modified molecules, lack of selectivity, lengthy reaction procedures, high cost of catalyst materials, the use of hazardous organic solvents, use of elevated reaction temperatures and the production of toxic byproducts.

[0017] There remains the need for further options for surface modification of molecules, such as macromolecules and biomolecules, especially routes for surface modification that are sustainable and environmentally friendly, and which are applicable to a range of different molecules, such as macromolecules and biomolecules. Summary of the invention

[0018] In a first aspect of the present invention, there is provided a method of producing a functionalised molecule. The method comprises : a) providing a first aqueous precursor composition comprising a molecule in aqueous solution or suspension, wherein the molecule has a reactive group; b) providing a second precursor composition comprising a surface modifying agent in solution or suspension, wherein the surface modifying agent has a linker group and a functionalising group; and c) forming a reaction mixture comprising the first aqueous precursor composition, the second aqueous precursor composition, and a mixed metal oxide catalyst that comprises a first transition metal and a second metal that is a transition metal or a Group 13 or 14 metal (e.g. tin or germanium); and allowing the linker group of the surface modifying agent to react with the reactive group of the molecule in the presence of the catalyst, such that the functionalising group is attached to the surface of the molecule via the formation of an amide bond, to thereby provide a functionalised molecule.

[0019] The method according to the first aspect permits functionalisation of a wide range of molecules, including macromolecules and biomolecules. The method provides a route to functionalising molecules, in particular including macromolecules and biomolecules, for a wide range of end uses.

[0020] The method according to the first aspect enables an environmentally friendly (“green”) synthesis of functionalised molecules .

[0021] The method may be carried out without formation of any toxic by-products. The products as made by the method may also be biodegradable and considered environmentally friendly.

[0022] The method can, if desired, be carried out under fully aqueous conditions or can be caried out under fully anhydrous solvent-free conditions. There is therefore the benefit that the skilled person can completely avoid the use of hazardous organic solvents. However, the skilled person may choose to use organic solvents, such as alcohols (e.g. methanol and ethanol) and THF (and / or 2-Methyltetrahydrofuran, meTHF), for the second precursor composition if desired. The method also involves a short reaction time, e.g. less than 12 hours, and even as short as 1 to 6 hours, such as about 1 hour. This enables the method to be very cost effective. In addition, there may be environmental benefits, such as a reduction in the amount of energy required.

[0023] The method can be carried out as a “one -pot” reaction, improving simplicity and efficiency for the method.

[0024] The invention provides a broad scope for synthesizing diversely functional biomolcculcs, such as biopolymers, from a range of proteins, amino acids, lipids and carbohydrates at low cost whilst maintaining a minimal carbon footprint.

[0025] In a second aspect of the present invention, there is provided a functionalised molecule obtainable using the method of the first aspect. The molecule is characterized in that it comprises a functionalising group attached to the surface of the molecule via an amide bond, and in that it includes trace amounts of both the first metal and the second metal from the mixed metal oxide catalyst. The first metal may, for example, be present in amounts of 0.01 ppm or more, or from 0.05 ppm or more, such as from 0.01 to 2 ppm or from 0.05 to 1 ppm (e.g. from 0.10 to 1 ppm, in some embodiments) and the second metal may, for example, be present in amounts of 0.01 ppm or more, or from 0.05 ppm or more, such as from 0.01 to 2 ppm or from 0.05 to 1 ppm (e.g. from 0.10 to 1 ppm, in some embodiments) . The amounts may be determined by inductively coupled plasma optical emission spectroscopy (ICP-OES).

[0026] The molecule and the functionalising group and the metals from the catalyst may each be according to the definitions as provided herein.

[0027] In one embodiment, the functionalised molecule according to the second aspect is: N-Lauroyl functionalised chitosan, betaine functionalised chitosan, N-Lauroyl-betaine functionalised chitosan, dodecylamine functionalised alginate, N-Lauroyl functionalised arginine, N-Steroyl functionalised arginine, butyric acid functionalised chitosan, tartrazine functionalised chitosan, caproic acid functionalised chitosan, caprylic acid functionalised chitosan, dodecylamine functionalised carboxy pullulan, lauric acid functionalised keratin protein hydrolysed, 1 ,4-diamino 9, 10-anthraquinone functionalised keratin protein hydrolysed, tartrazine functionalised keratin protein hydrolysed, 6,8-difluoro-7-hydroxy-2-oxo-2H-l - benzopyran-3-carhoxyltc acid functionalised keratin protein hydrolysed , dodecylamine functionalised hyaluronic acid, or lauric acid functionalised hyaluronic acid, these molecules arc all illustrated in the examples.

[0028] In a third aspect of the present invention, there is provided a method of producing a product, such as a consumer product. The method comprises providing a functionalised molecule as obtainable by the method of the first aspect ; and combining the functionalised molecule with a carrier. In one embodiment, the method comprises providing a functionalised molecule according to the second aspect; and combining the functionalised molecule with a carrier.

[0029] In one embodiment, the method comprises carrying out the method of the first aspect, to provide a functionalised molecule; and then combining the functionalised molecule with a carrier.

[0030] The product may, for example, have use in biomedical applications, cosmetic applications, home care products, agriculture application, food products, or environmental remediation, including water purification.

[0031] In one embodiment, the product is a consumer product which is a skin or hair care product.

[0032] The functionalisation provided by the present invention may, for example, provide enhanced skin barrier function through reduction of moisture loss. There may also be improved hydration.

[0033] A further benefit may be skin barrier enhancement. The consumer product may prevent the penetration of external irritants and pollutants, thus reducing the risk of skin sensitivity and / or damage.

[0034] When the molecule has been functionalised in a manner which enhances the hydrophobicity, the consumer product may exhibit enhanced water resistance. The consumer product may additionally exhibit improved delivery and bioavailability of hydrophobic active ingredients , such as antioxidants, vitamins, and humectants.

[0035] The molecule as functionalised may provide preservative characteristics. In one embodiment, therefore, the product is a cosmetics product, personal care product, home care product, or food product and the functionalised molecule provides preservative characteristics for the product. In a fourth aspect of the present invention, there is provided a product, such as a consumer product, comprising a functionalised molecule and a carrier, wherein the functionalised molecule is obtainable by the method of the first aspect. In one embodiment, the functionalised molecule is according to the second aspect. In one embodiment, the product of the fourth aspect is obtainable by the method of the third aspect.

[0036] Detailed description of the invention

[0037] The first aspect of the present invention involves functionalising a molecule, such as a macromolecule or a biomolecule, by surface modification. In the present invention, this surface modification is via an amidation reaction. An amide bond formation involves the reaction between an amine (-NH2) and a carboxylic acid (-COOH) or a derivative thereof, such as an acyl chloride or acid anhydride

[0038] This reaction results in the formation of an amide linkage (-CONH-), which is both stable and biocompatible.

[0039] Thus, in one embodiment, the molecule to be functionalised comprises a reactive group that is a carboxylic acid or salt thereof or derivative thereof (such as an acyl chloride or an anhydride or a lactone) and the linker group of the surface modifying agent is an amine or salt thereof. For example, alginate and hyaluronic acid each include a reactive group that is a carboxylic acid.

[0040] In another embodiment, the molecule to be functionalised comprises a reactive group that is an amine or salt thereof and the linker group of the surface modifying agent is a carboxylic acid or salt thereof or derivative thereof (such as an acyl chloride or an anhydride or a lactone). For example, chitosan and arginine each include a reactive group that is an amine.

[0041] The skilled person will be able to identify molecules that include a reactive group that is a carboxylic acid or salt thereof or derivative thereof or that include a reactive group that is an amine or salt thereof. Any such molecule can be used in the present invention.

[0042] When the reactive group is a carboxylic acid or salt thereof or derivative thereof, the following applies. Suitable derivatives include an acyl chloride, an acid anhydride, an ester, a lactone. a thioester, or an acyl phosphate. Suitable salts include alkali metal salts and alkaline earth metal salts, for example sodium or potassium salts. In one embodiment, the reactive group is a carboxylic acid or an alkali metal salt thereof or an alkaline earth metal salt thereof or an acyl chloride or an acid anhydride. In one embodiment, the reactive group is a carboxylic acid or an alkali metal salt thereof or an alkaline earth metal salt thereof or an acyl chloride. The reactive group may, for example, be represented as -COzRxwhere Rxis H or Cl-12 alkyl such as Cl -6 alkyl (linear or branched or cyclic, where it will be appreciated a branched chain must have at least C3 and a cyclic chain must have at least C3) or an alkali metal or alkaline earth metal. In one embodiment, the reactive group is a saturated or unsaturated carboxylic acid or a sodium or potassium salt thereof. Acid anhydrides are also envisaged, and are illustrated in the examples.

[0043] When the reactive group is an amine or salt thereof, the following applies. The group may be a secondary amine, a tertiary amine, or an amine salt. The salt may be a halogen salt, e.g. Cl or Br. The reactive group may be a saturated or unsaturated amine. The reactive group may, for example, be represented as -NRb or -NRV where each Rymay be the same or different and may be selected from H and Cl-12 alkyl such as Cl -6 alkyl (linear or branched or cyclic, where it will be appreciated a branched chain must have at least C3 and a cyclic chain must have at least C3).

[0044] The molecule to be functionalised is provided in the form of a first aqueous precursor composition comprising the molecule, which may be a macromolecule.

[0045] The molecule to be functionalised may suitably be a biomolecule. In other words, it may be a molecule that is produced by a living organism or that is found in a living organism. It may be provided in isolated form. It may be that the biomolecule is modified before use, for example the biomolcculc may have undergone a reaction to add a carboxylic acid group, or salt thereof or derivative thereof, or the biomolecule may have undergone a reaction to add an amine group or salt thereof.

[0046] Biomolecules include carbohydrates, proteins, amino acids, lipids and nucleic acids.

[0047] In one embodiment, the molecule to be functionalised is a biomolecule that is a carbohydrate, a protein, or an amino acid. The molecule may, in one embodiment, be an amino acid. The molecule may, in one embodiment, be a biopolymer, such as a protein or a polysaccharide. Tn one preferred embodiment, the molecule is a carbohydrate. The carbohydrate may be a monosaccharide, a disaccharidc, an oligosaccharide, or a polysaccharide. Preferably, the carbohydrate is a polysaccharide.

[0048] Examples of polysaccharides that can be chosen for use include alginate, cellulose, chitosan, pullulan, callose, laminarin, chrysolaminarin, xylan, arabinoxylan, mannan, fucoidan , galactomannan, carrageenan, ulvan and agarose. Another example is hyaluronic acid. Further examples of polysaccharides that can be chosen for use include pectin, carboxyl functionalised xanthan gum, carboxy pullulan, and chondroitin sulfate, each of which have carboxyl functional groups. Yet further examples of polysaccharides that can be chosen for use include carboxymethyl cellulose, carboxymethyl chitosan, carboxymethyl starch, carboxymethyl dextran, carboxy methyl inulin, carboxymethyl pullulan, or derivatives thereof, each of which have carboxymethyl functional groups .

[0049] In one embodiment, the polysaccharide is hyaluronic acid or alginate or chitosan. The polysaccharide may also be chondroitin sulfate or pectin. These polysaccharides naturally include a carboxylic acid group or an amine group.

[0050] In another embodiment, the molecule is a polysaccharide derivative, wherein the polysaccharide is selected from cellulose, pullulan, callose, laminarin, chrysolaminarin, xylan, arabinoxylan, mannan, fucoidan, galactomannan, carrageenan, ulvan and agarose, and wherein the polysaccharide has been modified to add a carboxylic acid group or salt thereof or derivative thereof (such as an acyl chloride or anhydride) or an amine group or salt thereof. In further such embodiments, the molecule is a polysaccharide derivative, wherein the polysaccharide is selected from xanthan gum, starch, dextran, and inulin, and wherein the polysaccharide has been modified to add a carboxylic acid group or salt thereof or derivative thereof (such as an acyl chloride or anhydride) or an amine group or salt thereof.

[0051] The skilled person would be able to produce a synthetic derivative of naturally occurring molecules whereby a reactive group that is a carboxylic acid group or an amine group is added. The carboxylic acid group may, for example, be a carboxyl functional group or a carboxymethyl functional group.

[0052] In another embodiment, the molecule to be functionalised is a protein, e.g. keratin. In general, non-limiting examples of proteins that can be chosen for use include keratin, pea protein, rice protein, and antibodies. In one embodiment, the molecule to be functionalised is selected from natural or synthetic fibres, which may be formed from protein or from protein-polysaccharides or from protein- lipid or from protein-polysaccharide-lipid or from polysaccharide-lipid. It will be appreciated that keratin is one protein found in fibres, but the present invention is not limited to keratin.

[0053] In another embodiment, the molecule to be functionalised is an amino acid, e.g. arginine.

[0054] In another embodiment, the molecule to be functionalised is a biomolecule that is a lipid, wherein the lipid is a fatty acid, fatty amine, aromatic acid, aromatic amine, or a salt or derivative thereof.

[0055] In one embodiment, the molecule to be functionalised is selected from chitosan, alginate, arginine, keratin, hyaluronic acid, and carboxy modified pullulan (e.g. carboxymethyl pullulan).

[0056] In one embodiment, the molecule to be functionalised is selected from hyaluronic acid, alginate, chitosan, keratin, and arginine.

[0057] In one embodiment, the functionalised molecule as obtained by the method can be further functionalised by repeating the method steps a)-c). Thus, a functionalised molecule as obtained by the method can be provided in aqueous solution or suspension, as the first precursor composition, to thereby by carry out repeat step a) and repeat steps b) and c) can then be carried out. Clearly, the functionalised molecule as obtained must include a reactive group that is a carboxylic acid or salt thereof or derivative thereof (such as an acyl chloride or anhydride) or a reactive group that is an amine or salt thereof. The surface modifying agent provided in repeat step b) may be the same as or different to that used in the original step b). For example, as shown in the worked examples, functionalization with a betaine can be followed by functionalization with a fatty acid.

[0058] The first aqueous precursor composition may be in the form of an aqueous solution or an aqueous suspension. In one preferred embodiment, the first aqueous precursor composition is a solution. The first aqueous precursor composition may suitably comprise from 25 to 99.5wt% water, such as from 30 to 99wt% water, or from 35 to 98wt% water, or from 40 to 95wt% water. In one embodiment it comprises from 50 to 99.5wt% water, such as from 60 to 99.5wt% water, or from 65 to 99wt% water, or from 75 to 99wt% water.

[0059] The first precursor composition may suitably be neutral or acidic, i.e., it may have a pH of about 7 or less, such as from about 3 to about 7, or from about 4 to about 6.

[0060] The second precursor solution comprises a surface modification agent, and may optionally include two or more different surface modification agents, such as two or three or four different surface modification agents.

[0061] The second precursor composition may, in one embodiment, be in the form of an aqueous solution or an aqueous suspension. In one preferred embodiment, the second precursor composition is an aqueous solution. In another preferred embodiment, the second precursor composition is provided as a solution in a water-miscible organic solvent, such as alcohol (e.g. methanol or ethanol) or THF (and / or 2-Methyltetrahydrofuran, meTHF). It may be that the second precursor composition is provided as a solution in a mixture of water and organic solvent. The solvent may, for example, be a mixture of water and water-miscible organic solvent, such as from 10-90 v / v% organic solvent in water.

[0062] The second precursor composition may suitably comprise from 25 to 99.5wt% solvent, such as from 30 to 99wt% solvent, or from 35 to 98wt% solvent, or from 40 to 95wt% solvent. In one embodiment it comprises from 50 to 99.5wt% solvent, such as from 60 to 99.5wt% solvent, or from 65 to 99wt% solvent, or from 75 to 99wt% solvent. The solvent may usefully be water or comprise water.

[0063] The second precursor composition may suitably be neutral or acidic, i.e., it may have a pH of about 7 or less, such as from about 3 to about 7, or from about 4 to about 6.

[0064] The linker group of the surface modification agent may be a carboxylic acid group, or a salt thereof or a derivative thereof. Suitable derivatives include an acyl chloride, an acid anhydride, an ester, a lactone, a thioester, or an acyl phosphate. Suitable salts include alkali metal salts and alkaline earth metal salts , for example sodium or potassium salts. In one embodiment, the linker group is a carboxylic acid or an alkali metal salt thereof or an alkaline earth metal salt thereof or an acyl chloride. The linker group may, for example, be represented as -CCbR* where Rxis H or C1 -12 or C 1 -6 alkyl (linear or branched or cyclic, where it will be appreciated a branched chain must have at least C3 and a cyclic chain must have at least C3) or an alkali metal or alkaline earth metal. In one embodiment, the linker group is a saturated or unsaturated carboxylic acid or a sodium or potassium salt thereof.

[0065] The linker group of the surface modification agent may be an amine or a salt thereof, such as a secondary amine, a tertiary amine, or an amine salt. The salt may be a halogen salt, e.g. Cl or Br. For example, the linker group may be a saturated or unsaturated amine. The linker group may, for example, be represented as -NRy2 or -NRY where each Rymay be the same or different and may be selected from H and Cl -6 alkyl (linear or branched).

[0066] The functionalising group of the surface modification agent may be any group that imparts a desired functionality.

[0067] Functionalising groups that can be contemplated may have one or more of the following properties: amphiphilic, hydrophobic, hydrophilic, oleophobic, oleophilic, anti -microbial, antiviral, hydrogen bonding, electro -dispersive and hygroscopic.

[0068] In one embodiment, the surface modification agent may be any molecule with a carboxylic acid group, such as a carboxylic acid containing dye, small molecules, actives, bioactives, carboxylic acid containing drugs (small molecule or macromolecule), carboxylic acid containing fibre (e.g. natural and / or synthetic fibres and derivatives thereof, including cotton, hair, wood and the like), and carboxylic acid containing solid nanoparticles.

[0069] In one embodiment, the surface modification agent may be any molecule with an amine functional group, such as an amine containing dye, small molecules, actives, bioactives, amine containing drugs (small molecule or macromolecule), amine containing fibre (e.g. natural and / or synthetic fibres and derivatives thereof, including cotton, hair, wood and the like), and amine containing solid nanoparticles.

[0070] In one embodiment, the functionalising group includes one or more hydrophilic moiety, e.g. selected from hydroxyl moieties, carbonyl moieties, carboxyl moieties, and amino moieties.

[0071] The surface modification agent may, in one embodiment, be a betaine. In one embodiment, it is trimethyl glycine (glycine betaine) or a salt thereof. Tn one embodiment, the functionalising group includes one or more hydrophobic moiety, e.g. selected from aliphatic chains, which may be saturated or unsaturated, and which may for example be a C2-50 or C2-28 straight chain or branched alkyl or alkenyl group, such as (i) a C2-24 or C2-18 straight chain or branched alkyl or alkenyl group, or (ii) a C4-24 or C6-18 straight chain or branched alkyl or alkenyl group .

[0072] The surface modification agent may therefore, in one embodiment, be a fatty acid group or a fatty amine group.

[0073] The surface modification agent may, in one embodiment, be selected from saturated and unsaturated acids, such as saturated and unsaturated fatty acids, having the general formula CH3(CH2)nCC>2 Rxwhere Rxis H or Cl-12 such as Cl -6 alkyl or alkenyl (linear or branched or cyclic, where it will be appreciated a branched chain must have at least C3 and a cyclic chain must have at least C3) or an alkali metal or alkaline earth metal, n is an integer value of up to 50. In one embodiment, n is from 2 to 40, or from 2 to 30, or from 2 to 28, or from 4 to 24, such as from 6 to 18 or from 6 to 12. In one embodiment, n is from 6 to 16 or from 6 to 14. In one embodiment, n is from 1 to 30, or from 1 to 28, or from 1 to 26, or from 1 to 24, or from 1 to 22. In one embodiment, the surface modification agent has the general formula CH3(CH2)nCO2 Rxwhere Rxis H or C l-6 alkyl or alkenyl (linear or branched).

[0074] The surface modification agent may be selected from saturated and unsaturated amines, such as saturated and unsaturated fatty amines having the general formula CH3(CH2)nNRy2 or CH3(CH2)nNRy3+where each Rymay be the same or different and may be selected from H and Cl-12 such as Cl-6 alkyl or alkenyl (linear or branched or cyclic, where it will be appreciated a branched chain must have at least C3 and a cyclic chain must have at least C3 ). n is an integer value of up to 50. Tn one embodiment, n is from 2 to 40, or from 2 to 30, or from 2 to 28, or from 4 to 24, such as from 6 to 18 or from 6 to 12. In one embodiment, n is from 1 to 30, or from 1 to 28, or from 1 to 26, or from 1 to 24, or from 1 to 22. In one embodiment, n is from 4 to 26 or from 4 to 24. In one embodiment, n is from 6 to 16 or from 6 to 14. In one embodiment, the surface modification agent has the general formula CH3(CH2)nNRy2 or CH3(CH2)uNRy3+where each Rymay be the same or different and may be selected from H and Cl-6 alkyl or alkenyl (linear or branched).

[0075] In one embodiment, the surface modification agent is selected from: a saturated or unsaturated acid, or salt thereof; a saturated or unsaturated acid anhydride, or salt thereof; • a saturated or unsaturated ester;

[0076] • a saturated or unsaturated amine or salt thereof;

[0077] • a dye or salt thereof, whereby the dye is a carboxylic acid containing dye or an amine containing dye.

[0078] Tn one embodiment, the surface modification agent is selected from:

[0079] • a saturated or unsaturated fatty acid, or salt thereof;

[0080] • a betaine, such as trimethyl glycine, or salt thereof;

[0081] • a saturated or unsaturated acid anhydride, or salt thereof;

[0082] • a saturated or unsaturated ester;

[0083] • a saturated or unsaturated fatty amine or salt thereof;

[0084] • a dye or salt thereof, whereby the dye is a carboxylic acid containing dye or an amine containing dye.

[0085] In one embodiment, the surface modification agent has up to 50 carbon atoms, such as up to 40 carbon atoms, or up to 30 carbon atoms.

[0086] In one example, the surface modification agent may be a saturated fatty acid, or derivative or salt thereof. The hydrocarbon chain may, for example, be a C1 -C30 straight chain or branched alkyl group, such as C2-28, or C2-24, or C2-18. Examples are pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecenoic acid, heptadecanoic acid, octadecanoic acid, acetic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, propionic acid, or combinations thereof or salts or derivatives thereof. Further examples include propanoic acid, butanoic acid, beta-retinolic acid, and lignoceric acid, or salts or derivatives thereof.

[0087] In another example, the surface modification agent may be an unsaturated fatty acid, or derivative or salt thereof. The hydrocarbon chain may, for example, be a C1 -C30 straight chain or branched alkenyl group, such as C2-28, or C2-24. Examples are oleic acid, linoleic acid, docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), arachidonic fatty acid, or combinations thereof or salts or derivatives thereof.

[0088] In yet another example, the surface modification agent may be a dye or colorant or derivatives or salts thereof, whereby the dye is a carboxylic acid containing dye or an amine containing dye. Examples include azo-dyes, including tartrazine, rhodamine B, lithol rubine BK; fluorophores, such as 3-carboxy-6,8-difluoro-7-hydroxycoumarin; anthraquinones, such as l ,4-diamino-9, 10-anthraquinonc; nitrobenzenes, such as 2-amino-5-(2-hydroxycthylamino) nitrobenzene; and combinations thereof or salts or derivatives thereof.

[0089] In a further example, the surface modification agent may be a saturated or unsaturated acid anhydride, or derivative or salt thereof. The hydrocarbon chain may, for example, be a Cl - C30 straight chain or branched alkyl or alkenyl group , such as C2-28, or C2-24, or C2-18. In one embodiment, the hydrocarbon chain is saturated. Examples include butyric anhydride, hexanoic anhydride, octanoic anhydride, dodccanoic anhydride, stcric anhydride, or combinations thereof or salts or derivatives thereof.

[0090] In another example, the surface modification agent may be a saturated or unsaturated ester , or derivative thereof. The hydrocarbon chain may, for example, be a C1 -C30 straight chain or branched alkyl or alkenyl group, such as C2-28, or C2-24, or C2-18. In one embodiment, the hydrocarbon chain is saturated. Examples include methyl butyrate, methyl hexanoate, methyl dodecanoate; combinations thereof or derivatives thereof.

[0091] In another example, the surface modification agent may be a saturated fatty amine or derivative or salt thereof. The hydrocarbon chain may, for example, be a C1 -C30 straight chain or branched alkyl or alkenyl group, such as C2-28, or C2-24, or C2-18. In one embodiment, the hydrocarbon chain is saturated. Examples include pentyl amine, hexyl amine, heptyl amine, octyl amine, nonyl amine, decyl amine, undecyl amine, dodecyl amine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine, heptadecyl amine, octadecyl amine; combinations thereof or salts or derivatives thereof.

[0092] The catalyst is a mixed metal oxide (MMO) catalyst. The invention uses a mixed metal catalyst that comprises a first transition metal and a second metal that is a transition metal or Group 13 or 14 metal. The Group 13 or 14 metal may be selected from the group consisting of: aluminium, gallium, indium, germanium, tin, and lead; for example, it may be germanium or tin.

[0093] The metal catalyst may be Lewis acidic. As the skilled person will understand, for a metal oxide, where there are exposed coordinatively unsaturated metal cations these can form Lewis acid sites on the surface. The number of metals in the mixed metal catalyst may be two or more, such as three or more , or four or more. In one embodiment the number of metals in the catalyst is two or three or four, such as two or three.

[0094] In one embodiment, therefore, the invention may use a mixed metal catalyst that includes two metals; there may be a first transition metal and a second metal that is a transition metal; or there may be a first transition metal and a second metal that is a Group 13 or 14 metal (such as tin).

[0095] In another embodiment, the invention may use a mixed metal catalyst that includes three metals. It may be that when the mixed-oxide catalyst comprises a third metal, the third metal is a transition metal, such as a Group 4-8 transition metal, e.g. titanium, zirconium, vanadium, chromium, manganese or iron; or is a Group 13 or 14 metal, such as germanium or tin.

[0096] In one embodiment the mixed-oxide catalyst comprises a first transition metal, a second metal that is a transition metal, and a third metal that is a Group 13 or 14 metal (such as tin). In one embodiment the mixed-oxide catalyst comprises a first transition metal, a second metal that is a transition metal, and a third metal that is a transition metal. In one embodiment the mixed- oxide catalyst comprises a first transition metal, a second metal that is tin, and a third metal that is a transition metal.

[0097] In the embodiment where the catalyst comprises a first transition metal and a second metal that is a transition metal, the first transition metal and the second transition metal are different. Likewise, in the embodiment where a third metal is present that is a transition metal, the third transition metal is different from the first and second metal. In all embodiments, it may be preferred that the transition metals that are present are independently selected from Group 4-8 transition metals.

[0098] In the embodiment where the mixed metal catalyst includes a Group 13 or 14 metal, it may be that this is selected from the group consisting of: aluminium, gallium, indium, germanium, tin, and lead; for example, it may be selected from the group consisting of: aluminium, gallium, indium, germanium and tin. In one embodiment, it is germanium or tin. In one preferred embodiment, it is tin.

[0099] Tn one embodiment, the first transition metal is selected from manganese, iron, cobalt, zinc, nickel and titanium. In one embodiment, the first transition metal is a Group 4-8 metal, such as titanium, vanadium, manganese or iron. In one preferred embodiment, the first transition metal is selected from manganese, iron, and titanium. In one such embodiment, the first transition metal is titanium or iron.

[0100] In one embodiment, the second metal is a transition metal, or tin or germanium.

[0101] In one embodiment, the second metal is selected from zirconium, titanium, vanadium , germanium, tin, iron, and chromium.

[0102] In one embodiment, the second metal is a Group 4-8 metal, such as titanium, zirconium, vanadium, chromium, manganese or iron, or a Group 13 or 14 metal such as germanium or tin. In one preferred embodiment, the second metal is selected from zirconium, titanium, vanadium, tin, iron, and chromium.

[0103] In one preferred embodiment, the second metal is selected from zirconium, titanium, vanadium, tin, and iron. In one such embodiment, the second metal is selected from titanium, tin, and iron.

[0104] In one embodiment the catalyst is selected from a mixed-oxide catalyst that is: Fe-Ti, Sn-Ti, Sn-Fe-Ti, Zn-Sn, Zn-Ti, Mn-Sn, Zn-Fe, Mn-Ti, Zn-Ge, Fe-Ge, or Ti-Ge. In one embodiment the catalyst is selected from a mixed-oxide catalyst that is: Fe-Ti, Zn-Sn, Zn-Ti, Mn-Sn, Zn- Fe, Mn-Ti, Zn-Ge, Fe-Ge, or Ti-Ge. In one embodiment the catalyst is selected from a mixed- oxide catalyst that is: Fe-Ti, Sn-Ti, Sn-Fe-Ti, or Zn-Sn. In one embodiment the catalyst is an iron-titanium mixed oxide (Fe-Ti-oxide) catalyst.

[0105] The catalyst may be provided on a support material.

[0106] In one embodiment the catalyst may be coupled with an enzyme, e.g. lipase. Lipase immobilisation is of course well known in the art. Thus, in one embodiment, the mixed metal oxide catalyst is coupled with an enzyme such as lipase. This results in the enzyme being immobilised on the catalyst. By immobilising an enzyme such as lipase on the MMO catalyst, there is the potential to achieve better specificity and improved catalytic activity. The skilled person will appreciate that the enzyme that is coupled with the catalyst may be a genetically or structurally engineered enzyme and therefore may have a sequence that differs from the enzyme (e.g. lipase) as found in nature, for example there may be 70% or more sequence identity, or 80% or more, such as 90% or more, or 95% or more.

[0107] The metal catalyst may be porous and preferably mesoporous. The catalyst may, in one embodiment, have a pore size distribution in the range of from 1 to 5 nm, preferably from 2 to 4 nm or from 2.5 to 4 nm, such as from 3 to 3.5 nm. In one embodiment, the catalyst has a narrow pore size distribution, e.g. in the range of 3.1 to 3.4 nm. Na adsorption-desorption studies can be used to determine the pore size distribution.

[0108] In one embodiment, the mixed oxide catalyst is a highly ordered two-dimensional (2D) mesoporous material. TEM imaging of the material can be used to establish the presence of a 2D-mesophase.

[0109] In one embodiment, the catalyst may be provided in the form of nanoparticles. The catalyst may, in particular, comprise very fine nanoparticles. A preferred size range is primary particles with diameters of from lOnm to 80nm, such as from 15nm to 70nm, preferably from 20nm to 50nm. The primary particles may aggregate to form larger secondary particles, e.g. with diameters of from 90nm to 400nm, such as from lOOnm to 250nm. The primary particles may be spherical. The secondary particles may be spherical.

[0110] In one embodiment, the catalyst suitably has a surface area in the range from 100 to 500 m2 / g, such as from 120 to 385 m2 / g. Na adsorption-desorption studies can be used to determine the surface area.

[0111] The catalyst may, in one embodiment, be prepared at acidic pH (e.g. at a pH of 1-2).

[0112] In one embodiment, the catalyst is a TiOz-FczOa mixcd-oxidc. In one embodiment, both a- FejOa and anatase TiOz phases are present. This can be seen via analysis through UV-vis and DRS spectra, as well as wide-angle powder XRD patterns. In one embodiment, the TiOz— FezOa mixed-oxide catalyst is provided in the form of nanoparticles, e.g. as described above. In one embodiment, the TiOz-FezOa mixed-oxide catalyst is porous and preferably mesoporous, e.g. as described above.

[0113] In general, the skilled person will be aware of processes in the literature to make mixed oxide catalysts and these can be used to make a make mixed oxide catalyst for use in the present invention. Tn particular, a sol-gel process may be used, especially a sol-gel process using a template directing agent.

[0114] The manufacture of mixed metal oxide catalysts is, for example, described in “The enhancement of direct amide synthesis reaction rate over TiO2@SiC>2@NiFe2O4 magnetic catalysts in the continuous flow under radiofrequency heating”, Liu Y. et al, Journal of Catalysis 355 (2017) 120-130.

[0115] “Interactions between Metal Oxides and Biomolcculcs: from Fundamental Understanding to Applications” Limo, Marion J. et al, Chem. Rev. 2018, 118, 11118-11193, includes a detailed discussion of metal oxides.

[0116] Reference is also made to “Mesoporous Titania-Iron (III) Oxide with Nanoscale Porosity and High Catalytic Activity for the Synthesis of P-Amino Alcohols and Benzimidazole Derivative” ChemCatChem 2015, 7, 2689 - 2697, which includes details of the manufacture of a TiO2_Fe2O3 mixed-oxide catalyst.

[0117] In one embodiment, the catalyst is a mesoporous mixed-oxide material which can be prepared via a sol-gel process. In an exemplary sol-gel process, a template directing agent (e.g. sodium dodecyl sulfate (SDS) or cetrimonium bromide (CTAB), polyethylene glycol - polypropylene glycol - polyethylene glycol (PEG-PPG-PEG), also known as Pl 23 or another surfactant that can act as a template directing agent) is dissolved in distilled water (e.g. 25-30 wt%) to provide a micellar solution. A source of the first metal, e.g. Fe, such as Fe(III) anhydrous FeCL dissolved in distilled water (e.g. 15-20 wt%) is added dropwise to the micellar solution. The resulting mixture is stirred, e.g. for 30 minutes. Then, a source of the second metal, e.g. Ti, such as titanium isopropoxide or titanium butoxide or titanium (IV) chloride, is dissolved in isopropanol (e.g. 50-60 wt%) is added slowly to the stirred mixture. The pH of the solution is then maintained at 1.0, by adding acid, e.g. 2N HC1 solution. The resulting solution is stirred, e.g. for 2-5 hours. The mixture is then kept under freezing conditions (e.g. 4 °C) for about 24-48 hours. The resultant solid is then collected by filtration. The solid product is washed, e.g. with deionised water, followed by ethanol washing (e.g. with 20% and 80% ethanol). The resultant product was dried; for example, it may be dried under vacuum and further dried in an oven at about 60-75 °C. The dry powder solid is then extracted, e.g. in dilute HCl-containing ethanol medium. This provides dry mesoporous iron-titanium mixed oxide material that can be used as the catalyst. Tn the method of the present invention, i n step c), the first aqueous precursor composition, the second aqueous precursor composition, and the mixed metal oxide catalyst arc mixed and the linker group of the surface modifying agent is allowed to react with the molecule.

[0118] During step c) the mixture may be agitated. Agitating the reaction mixture may comprise the use of a mechanical agitator, static agitator, rotating tank agitator, paddle type agitator, or combinations thereof. Agitation may be continuous, during step c), or intermittent.

[0119] Step c) may suitably take place for a period of time from 10 minutes up to 24 hours, such as from 15 minutes up to 12 hours, or from 30 minutes up to 10 hours. In one embodiment, the reaction takes from 1 to 8 hours such as from 1 to 6 hours.

[0120] Step c) may be carried out where the mixture is neutral or acidic, i.e., it may have a pH of about 7 or less, such as from about 3 to about 7, or from about 4 to about 6.

[0121] The extent of functionalisation of the macromolecule may be termed grafting density. The grafting density may be expressed as a percentage of functionalised sites on the macromolecule divided by the total functional! sable sites on the macromolecule.

[0122] The method may optionally further include step d) of recovering the functionalised macromolecule from the mixture.

[0123] In one embodiment, step d) may comprise cooling the mixture.

[0124] The step of recovering the functionalised macromolecule from the mixture may alternatively or additionally comprise extracting the functionalised macromolecule from the mixture via filtration or centrifugation. Suitable filtration techniques include gravity filtration, vacuum filtration, hot filtration.

[0125] The method may optionally further include step e) of recovering the catalyst. This may, for example, be by filtration or centrifugation.

[0126] In a second aspect of the present invention, there is provided a functionalised molecule obtainable using the method of the first aspect, wherein the functionalised molecule is N - Lauroyl functionalised chitosan, betaine functionalised chitosan, N -Lauroyl -betaine functionalised chitosan, dodccylaminc functionalised alginate, N -Lauroyl functionalised arginine, butyric acid functionalised chitosan, tartrazine functionalised chitosan, caproic acid functionalised chitosan, caprylic acid functionalised chitosan, dodccylaminc functionalised carboxy pullulan, lauric acid functionalised keratin protein hydrolysed, 1,4-Diamino 9,10- anthraquinone functionalised keratin protein hydrolysed, tartrazine functionalised keratin protein hydrolysed, 6,8-Difluoro-7-hydroxy-2-oxo-2H-l-benzopyran-3-carboxylic acid functionalised keratin protein hydrolysed , dodecylamine functionalised hyaluronic acid , or lauric acid functionalised hyaluronic acid

[0127] In a third aspect of the present invention, there is provided a method of producing a product, such as a consumer product. The method comprises providing a functionalised macromolecule as obtainable by the method of the first aspect; and combining the functionalised macromolecule with a carrier.

[0128] The carrier may be a cosmetically acceptable carrier, for example a topologically acceptable carrier. The carrier may be a pharmaceutically acceptable carrier. The carrier may be an edible carrier.

[0129] The carrier may be oil or wax based and / or water based.

[0130] For example, the carrier may be water based and may comprise de-ionized water, purified water, natural spring water, or the like. In one embodiment de-ionized or purified water is used.

[0131] In another embodiment, the carrier may be oil or wax based. The oil may be natural oil or synthetic oil, but preferably is natural oil such as a vegetable oil or a nut oil. The wax is preferably a natural wax.

[0132] The product according to the fourth aspect may further comprise at least one active ingredient.

[0133] The product according to the fourth aspect may comprise at least one, at least two, at least three, or at least four active ingredients.

[0134] The Personal Care Product Council's International Cosmetic Ingredient Dictionary and Handbook, Thirteenth Edition, and the CTFA Cosmetic Ingredient Handbook, Second Edition (1992) each describe a wide variety of non -limiting cosmetic and pharmaceutical ingredients commonly used in the skin care industry, which arc suitable optional components for use in the compositions of the present invention. Examples of these ingredient classes include: conditioning agents, surfactants and emulsifiers, abrasives, absorbents, aesthetic components such as fragrances, pigments, colorings / colorants, plant extracts including essential oils, anti - caking agents, antifoaming agents, antimicrobials, binders, biological additives, buffering agents, bulking agents, chelating agents, colorants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, emollients, external analgesics, film formers or materials, opacifying agents, pH adjusters, preservatives, propellants, reducing agents, sequestrants, skin cooling agents, skin protectants, thickeners / viscosity modifiers, vitamins, anti-oxidant, moisturizer, hydrating agent, gelling agent, and combinations thereof.

[0135] In one embodiment, the at least one active ingredient may, for example, be selected from conditioning agents, surfactants and emulsifiers.

[0136] The composition may include one or more conditioning agents, such as polyquatermium-10, polyquatermium-11 , quaternium-80, polyquatermium-7, cetrimonium chloride, or stearamidopropyl dimethylamine. Alternatively, or additionally, conditioning oil, such as paraffinum liquidum may be included.

[0137] The composition may include one or more surfactant, such as cosmetically acceptable salts of alkyl ether sulphates (such as ammonium laureth sulphate or sodium laureth sulphate), alkyl and alkylamidoalkyl betaines (such as cocamidopropyl betaine), ethoxylated alcohols, polyethyleneglycol carboxylates, acceptable salts of alkyl sulphates (such as ammonium lauryl sulphate or sodium lauryl sulphate), sulphosuccinates (such as disodium laureth sulphosuccinate), amphoacetates and amphodiacetates (such as disodium cocoamphodiacetates), alkylglucosides and alcohol sulphonates.

[0138] When an emulsifier is present, the or each emulsifier may be any emulsifier known in the art for use in water-in-oil or oil-in-water emulsions. Non-limiting examples include: sesquioleates such as sorbitan sesquioleate, or polyglyceryl-2-sesquioleate; ethoxylated esters of derivatives of natural oils; silicone emulsifiers such as silicone polyols; anionic emulsifiers such as fatty acid soaps e.g. potassium stearate, and fatty acid sulphates e.g. sodium cetostearyl sulphate; ethoxylated fatty alcohols; sorbitan esters; ethoxylated sorbitan esters; ethoxylated fatty acid esters such as ethoxylated stearates; ethoxylated mono-, di- and triglycerides; non-ionic self-emulsifying waxes; ethoxylated fatty acids; or mixtures thereof.

[0139] An emulsifying agent such as cocamidopropyl betaine or cctcarcth-20 may be included. In one embodiment, the at least one active ingredient may, for example, be selected from antioxidants, vitamins and derivatives thereof, humectants, preservatives, and combinations thereof.

[0140] The antioxidant may be selected from ascorbic acid and derivatives thereof, erythorbic acid and derivatives thereof, and tocopherols (vitamin E forms) and derivatives thereof.

[0141] Examples of ascorbic acid or derivatives thereof include ascorbic acid, sodium ascorbate, potassium ascorbate, calcium ascorbate, L-ascorbic acid phosphate ester, magnesium ascorbyl phosphate, sodium ascorbyl phosphate, ascorbyl sulfate, sodium ascorbyl 2 phosphate salt and ascorbyl-2-glucoside, and the like.

[0142] Examples of erythorbic acid or derivatives thereof include erythorbic acid or derivative thereof, such as erythorbic acid, sodium erythorbate, potassium erythorbate, calcium erythorbate, erythorbic acid phosphate, erythorbic acid sulfate and the like.

[0143] In general, suitable tocopherols include naturally occurring vitamin E, synthetic vitamin E, enantiomerically pure forms of vitamin E (e.g. (+) -alpha-tocopherol), vitamin E derivatives such as acetates, succinates, linoleate, more water-soluble forms of vitamin E such as tocophereth-5, tocophereth-10, tocophereth-12, tocophereth-18, tocophereth-50, D-alpha- tocopherol polyethylene glycol 1000 -succinates. Specifica examples of tocopherol or derivatives thereof include a-tocopherol, P-tocopherol, y-tocopherol, 5-tocopherol, acetic acid-a-tocopherol, nicotinic acid-a-tocopherol, linoleic acid-a-tocopherol, succinic acid -a- tocopherol, as well as a-tocotrienol, -tocotrienol, y-tocotrienol, and 5-tocotrienol.

[0144] Other antioxidants that can be mentioned include flavonoids (catechin, anthocyanin, flavone, isoflavone, flavan, flavanone and rutin), phenolic acids (chlorogenic acid, ellagic acid, gallic acid and propyl gallate), lignans, curcumins and coumarins.

[0145] Examples of suitable vitamins may be vitamin A, vitamin C, vitamin E, vitamin B or a vitamin B complex (e.g. B l , B2, B3, B5, B6, B7, B9, and / or B 12 and combinations thereof), vitamin D, vitamin K, or combinations thereof. Derivatives of vitamins, such as reduced or oxidised forms and precursors, can also be used. For example, Vitamin A derivatives include retinol and retinolic acid and Vitamin C derivatives include ascorbic acid and ethyl ascorbic acid. Examples of suitable humectants may be tricthylcnc glycol, tripropylcnc glycol, propylene glycol, polypropylene glycol, glycerin, sorbitol, hexylene, butylene glycol, urea, collagen , or combinations thereof.

[0146] The product may comprise a preservative selected from any of the group comprising phenoxyethanol; salicylic acid; potassium sorbate; DMDM hydantoin; benzyl alcohol; sodium benzoate; formaldahyde; chlorphenism; triclosan; imidazolidinyl urea; diazolidinyl urea; sorbic acid; mcthylisothiazolinonc; sodium dchydroacctatc; dchydroacctic acid; quatcrnium- 15; stearalkonium chloride; zinc pyrithione; sodium metabisulfite; 2 -bromo-2-nitropropane; chlorhexidine digluconate; polyaminopropyl biguanide; benzalkonium chloride; sodium sulfite; sodium salicylate; citric acid; grapefruit seed extract; neem oil; essential oil; lactic acid; and vitamin E (tocopherol); or combinations thereof.

[0147] In one embodiment, the product comprises one or more plant extract. The plant extract may be selected from essential oils, extracts from leaves, extracts from stems, extracts from petals, extracts from seeds, extracts from roots and extracts from pollen.

[0148] The product may be a water-based composition, an oil-based composition, or an emulsion, or an anhydrous composition.

[0149] Examples of a water-based composition include skin lotions, beauty essences, water-based gels, and the like, while examples of the oil-based composition include cleansing oil and oilbased gels, and the like. Examples of emulsion composition include creams , skin milks and sunscreen lotions, and the like, where the types of emulsion include oil in water emulsion (o / w), water in oil emulsion (w / o) and multilayer emulsion (e.g. w / o / w, o / w / o).

[0150] The product may be a topical composition that can be provided in a variety of forms, including but not limited to lotions, milks, mousses, serums, sprays, aerosols, foams, sticks, gels, creams and ointments. In one embodiment, the composition is in the form of a spray or gel and in another embodiment the composition is in the form of a lotion, milk or cream.

[0151] In one embodiment, the product is a consumer product, e.g. a skin or hair care product. Examples of personal care products that can be provided include but are not limited to: shampoo; face mask (c.g. peel off mask); sunscreen; hair styling gel; conditioner; body lotion, face cream and other moisturizers.

[0152] In one embodiment, the product is a water purification product, such as a membrane; a coating or packaging product; a drug delivery product; a food product or additive, such as a food preservative; or an anti-microbial product.

[0153] The molecule as functionalised may provide preservative characteristics. In one embodiment, therefore, the product is a cosmetics product, personal care product, home care product, or food product and the functionalised molecule provides preservative characteristics for the product.

[0154] The invention will now be further described by the following non -limiting examples.

[0155] Examples

[0156] Example la: Preparation of TiOs-FezCh mixed-oxide catalyst (Catalyst 1)

[0157] The mixed metal oxide material was synthesized via a sol -gel process. First, sodium dodecyl sulfate (SDS) was dissolved in distilled water (25 -30 wt%). After that, anhydrous FcCl dissolved in distilled water (15-20 wt%) was added dropwise to the micellar solution. The resulting mixture was stirred for 30 minutes. Then, titanium isopropoxide was dissolved in isopropanol (50-60 wt%) and was added slowly to the premixed solution. The pH of the solution was then maintained at 1.0 by the adding 2N HC1 solution. The resulting solution was stirred for 2-5 hours, and the mixture was kept under freezing conditions (4 °C) for 24 - 48 hours. After that, the resultant solid was collected by filtration. The solid product was washed with deionised water, followed by 20% and 80% ethanol washing. The resultant product was dried under vacuum and further dried in an oven at 60-75 °C. The dry powder solid was extracted in dilute HCl-containing ethanol medium.

[0158] This template-free, dry mesoporous iron-titanium mixed oxide material was used as a catalyst in the following examples.

[0159] Example lb: Preparation of Sn-TiOa mixed-oxide catalyst (Catalyst 2)

[0160] Mesoporous Sn-TiO2 catalysts are synthesized as follows. In a typical synthesis process, 8 g of PEG-PPG-PEG (P123), 3.0 g of citric acid and 7.0 ml of hydrochloric acid were dissolved into 1 50 ml of anhydrous ethanol. Then, 15 g of titanium isopropoxide and 1 .5 g of tin tetrachloride were simultaneously added into above-mentioned solution and vigorously stirred at 30 °C for 24 h. The solution was transferred to a petri dish to evaporate at 45 °C for 48 h and then thermally treated at 100 °C for another 24 h. The catalyst was collected by calcination in air at 500 °C for 5 h to remove the organic template and was defined as Sn- TiOz.

[0161] This mixed oxide material was used as a catalyst in the following examples.

[0162] Example 1c: Preparation of Fe-Sn-Ti mixed-oxide catalyst (Catalyst 3)

[0163] Mesoporous Fe-Sn-Ti mixed oxide catalyst was synthesized as follows. In a typical synthesis process, 8 g of PEG-PPG-PEG (P123), 3.0 g of citric acid and 7.0 ml of hydrochloric acid were dissolved into 150 ml of anhydrous ethanol. The add 4.35 g of anhydrous FeC13 dissolved in 50 ml of anhydrous ethanol, followed by 15 g of titanium isopropoxide and 1.5 g of tin tetrachloride were simultaneously added into above-mentioned solution and vigorously stirred at 30 °C for 24 h. The solution was transferred to a petri dish to evaporate at 45 °C for 48 h and then thermally treated at 100 °C for another 24 h. The catalyst was collected by calcination in air at 500 °C for 5 h to remove the organic template and was defined as Fe-Sn-TiOz

[0164] This mixed oxide material was used as a catalyst in the following examples.

[0165] Example Id: Preparation of lipase immobilized Fe-Ti mixed oxide catalyst (Catalyst 4) 100 mL of 2 mg / mL lipase solution was combined with 100 mL of 2 mg / mL Fe-Ti mesoporous catalyst (as made in Example la) in the form of a suspension, and the pH was adjusted to 7. The mixture was sonicated for 10 minutes at 35 °C, then incubated for 4 hours at the same temperature. Afterward, the mixture was centrifuged, washed multiple times with distilled water, and dried at 40 °C for 24 hours.

[0166] This mixed oxide material was used as a catalyst in the following examples.

[0167] Example le: Preparation of lipase immobilized Sn-Ti mixed oxide catalyst (Catalyst 5) 100 mL of 2 mg / mL lipase solution was combined with 100 mL of 2 mg / mL Sn-Ti mesoporous catalyst (as made in Example lb) in the form of a suspension, and the pH was adjusted to 7. The mixture was sonicated for 10 minutes at 35 °C, then incubated for 4 hours at the same temperature. Afterward, the mixture was centrifuged, washed multiple times with distilled water, and dried at 40 °C for 24 hours.

[0168] This mixed oxide material was used as a catalyst in the following examples.

[0169] Example If: Preparation of lipase immobilized Fe-Sn-Ti mixed oxide catalyst (Catalyst 6}

[0170] 100 mL of 2 mg / mL lipase solution was combined with 100 mL of 2 mg / mL Fe-Sn-Ti mcsoporous catalyst (as made in Example 1c) in the form of a suspension, and the pH was adjusted to 7. The mixture was sonicated for 10 minutes at 35 °C, then incubated for 4 hours at the same temperature. Afterward, the mixture was centrifuged, washed multiple times with distilled water, and dried at 40 °C for 24 hours.

[0171] This mixed oxide material was suitable for use as a catalyst in the following examples.

[0172] Example 2a: Preparation of N-Lauroyl functionalised chitosan

[0173] Scheme 1 : Functionalisation of chitosan with fatty acids (lauric acid) via amide bond formation

[0174] Reaction conditions: HzO, 10-20% MeOH, 7-9 hr, Catalyst 1 (iron-titanium mesoporous mixed metal oxide catalyst)

[0175] Chitosan of 10-20 kDa molecular weight and 90% degree of deacetylation (DDA%) was chosen for hydrophobic functionalisation. Chitosan (12 g / 1) dissolved in water at pH 4. -5.5 (pH adjusted using 2(N) HC1) and fatty acids (1.5 mg-12 mg / ml) (dissolved in 10-40% mcthanol / cthanol) arc reacted in the presence of catalyst in water-alcohol medium (pH 5.5-7.0) at 55-70 °C for 6-7 hours to obtain a fatty acid functionalised chitosan.

[0176] The reaction was effective over the range of tested pH values, but the best yield was obtained at pH 5.8.

[0177] The modified chitosan was subjected to cooling. The catalyst was separated through multiple rounds of filtration / centrifugation. Then, the filtered product was freeze -dried successively to obtain pure fatty acid functionalised chitosan (yield 50-60%). The freeze-dried powder product was washed with hexane / ethanol to remove unreacted free fatty acid and was dried in air.

[0178] The addition of lauric acid functionalization onto the chitosan (CH) backbone was confirmed by FT-IR spectroscopy. The FT-IR spectra absorption peaks of chitosan and fatty acid functionalised CH polymers at 1651 cm1can be attributed to the carbonyl stretching of secondary amides. Upon conjugation, the 1651 peak became more prominent and broader. The absorption peaks present in chitosan at around 866 cm1are attributed to the -CHz groups of N-acyl moiety. In the lauric acid functionalised chitosan, two characteristic absorption bands at 2843 and 2917 cm-1appeared that are assigned to vibrational bands corresponding to CHz group of the fatty acid long chain.

[0179] NMR spectroscopy further confirmed these results. The ring protons of chitosan were observed to resonate at 3.4-4.0 ppm. Two protons (H2) of glucosamine residue were observed at 1 .8 ppm and 2.9 ppm, respectively. The characteristic chemical shifts of lauric acid in CH - LA conjugate were at 1.2 ppm, and the protons of the fatty acyl residue associated with the amide bond ((-CO)-CH2-) resonated around 2.4 ppm. The new proton peaks at 0.8 - 1.1 ppm can be associated to the resonances of -CH and -CH2- groups of the fatty acyl residues.

[0180] CHN analysis allowed the grafting density of CH-LA with respect to chitosan to be established: [(C / N)m - (C / N)u] / N, where, (C / N)m = C / N ration of modified product; (C / N)u = C / N ration of unmodified product; N = number of carbon introduced during modification (here we took Lauric Acid C12H24O2, so the number of carbons was 12) = [(47. 19 / 6.71 )-(40.35 / 7.51 )] / 12 = 0.1 3834 = 13.83 %

[0181] A DSC thermogram was obtained using a Shimadzu spectrophotometer (TA instruments Q 20-DSC). 5.0 mg of chitosan sample was crimped in a standard aluminum pan was heated from 20 to 200°C at heating constant rate of 10°C / min under constant purging of nitrogen at 20 ml / min. The DSC curves for chitosan showed a large endothermic peak resolved with TP value of 133.93°C. Upon functionalization with fatty acid, the decomposition temperature drops to 108°C. Example 2b: Further preparation of N-Lauroyl chitosan

[0182] The following further different chitosan products were used for hydrophobic functionalization of the chitosan surface, using the same process as Example 2a.

[0183] In each case, the process successfully obtained a fatty acid functionalised chitosan. f Betaine Functionalised chitosan

[0184] Chitosan Betaine HCI Betaine-Chitosan

[0185] Scheme 2: Reaction of chitosan with betaine HCI (trimethylglycine HCI)

[0186] Reaction conditions: H2O, 5-9 hr, Catalyst 1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst), Temp: 50-75 °C

[0187] Betaine-functionalised chitosan polymers were prepared using an amidation reaction.

[0188] Tn this reaction, chitosan (10 g / L) was dissolved at pH 4.5 -5.5. Then, betaine HCI (trimcthylglycinc HCI) solution in water (10 g / L) was added to the chitosan solution at room temperature. After mixing both solutions, catalyst 1 (0.5-5 wt%) was added to the mixture, and the final pH of the solution was adjusted to pH 5.8. The reaction mixture was stirred for 5-9 hr at 50-75 °C in a glass reactor.

[0189] The excess betaine HCI and water-soluble by-products were removed by dialysis against deionized water. The product was dried using spray dry technology.

[0190] The final modified chitosan has improved water solubility at neutral pH compared to the starting chitosan which was soluble at pH 5 and below.

[0191] This reaction was found to be most efficient at an acidic pH (pH 5.0 - 7.2). This reaction was repeated successfully using four further alternative catalysts, in Examples 3b-3c, which followed the protocol of Example 3a but changed the catalyst as follows.

[0192] Example 4a: Preparation of N-Lauroyl-Betaine functionalised chitosan

[0193] Scheme 3: Reaction of betaine functionalised chitosan with lauric acid

[0194] Reaction conditions: HzO, 10-40% McOH, 5-8 hr, Catalyst 1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst), Temp: 50-75 °C

[0195] Betaine-functionalised chitosan as made in Example 3 (20 g / L) was dissolved in water at pH 5.5-6. This was reacted with lauric acid (lOg / L) (dissolved in 10-40% methanol / ethanol in the presence of the catalyst 1 in water-alcohol medium (pH 5.5-7.5) at 55-70 °C for 6-9 hours to obtain a N-Lauryl-Betaine functionalised chitosan.

[0196] The reaction was effective over the range of tested pH values, but the best yield was obtained at pH 5.5-6.8 and especially at pH 5.8.

[0197] The modified chitosan was subjected to cooling. The catalyst was separated through multiple rounds of filtration / centrifugation.

[0198] The filtered product was freeze-dried successively to obtain pure fatty acid functionalised chitosan (yield 60-80%). The freeze-dried powder product was washed with hexane / ethanol to remove unreacted free fatty acid and dried in air.

[0199] This reaction was repeated successfully using four further alternative catalysts, in Examples 4b-4e, which followed the protocol of Example 4a but changed the catalyst as follows.

[0200] Example 5: Preparation of fatty acid modified sodium alginate Scheme 4: Reaction of Na Alginate with dodecyl amine via amide bond formation

[0201] Reaction conditions: H2O, 20% THF, 7-9 hr, Catalyst 1 (iron-titanium mixed oxide (Fe-Ti- oxide) catalyst) Example 6a: Preparation of N-Lauroyl functionalised arginine

[0202]

[0203] Scheme 5: Reaction of arginine with fatty acids (lauric acid) via amide bond formation

[0204] Reaction conditions: H2O, 20% THF, 7-9 hr, Catalyst 1 (iron-titanium mixed oxide (Fc-Ti- oxide) catalyst), at 60-70 °C

[0205] This reaction was repeated successfully using four further alternative catalysts, in Examples 6b-6e, which followed the protocol of Example 6a but changed the catalyst as follows.

[0206] Example 6f and g: Preparation of N-steroyl-functionalised arginine

[0207] The reaction of Example 6a was repeated but using arginine and steric acid as the reagents. This reaction of arginine with fatty acids (steric acid) via amide bond formation was successful when carried out with:

[0208] 6f: Fe-Ti mixed oxide catalyst (Catalyst 1)

[0209] 6g. lipase immobilised mixed Fe-Ti catalyst (Catalyst 4)

[0210] Example 6g gave a better yield than 6f.

[0211] Example 7a: Preparation of butyric acid functionalised chitosan

[0212] Scheme 6: Reaction of chitosan with fatty acids (butyric acid) via amide bond formation

[0213] Reaction conditions: 10ml butyric acid liquid was mixed with 5g chitosan powder in round bottom flask. 1 g Catalyst-1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst) was added. The resultant mixture was heated to 90°C for 8-12 hours.

[0214] A water insoluble butyric acid grafted chitosan product was formed.

[0215] This reaction was repeated successfully using four further alternative catalysts, in Examples 7b-7e, which followed the protocol of Example 7a but changed the catalyst as follows.

[0216] Example 8a: Preparation of tartrazine functionalised chitosan

[0217] Scheme 7: Reaction of chitosan with tartrazine dye via amide bond formation

[0218] Reaction conditions: 200mg Tartrazine due dissolved in 50ml water and mixed with 2g chitosan powder dissolved in 200ml water at pH 5.8 in round bottom flask. 150 mg Catalyst - 1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst) was added. The resultant mixture was heated to 70°C for 12 hours. Tartrazine dye was removed by dialysis against water. A yellow-color chitosan derivative was formed.

[0219] This reaction was repeated successfully using four further alternative catalysts, in Examples 8b-8e, which followed the protocol of Example 8a but changed the catalyst as follows.

[0220] Example 9a: Anhydrous preparation of butyric acid functionalised chitosan

[0221] Scheme 8: Reaction of chitosan with butyric anhydride via amide bond formation

[0222] Reaction conditions: 10 ml Butyric anhydride liquid was mixed with 5g chitosan powder in round bottom flask under ‘"solvent-free” reaction condition. 200 mg Catalyst-1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst) was added in presence of mild base. The resultant mixture was heated to 90 °C for 8-12 hours under stirring at 400-500 rpm. A water insoluble butyric acid grafted chitosan slurry product formed.

[0223] After removing unreacted butyric anhydride, the modified chitosan became insoluble in 1 % acetic acid. This resulted in the hydrophobic modified chitosan product being obtained.

[0224] This reaction was repeated successfully using four further alternative catalysts, in Examples 9b-9c, which followed the protocol of Example 9a but changed the catalyst as follows.

[0225] Example 10a: Anhydrous preparation of caproic acid functionalised chitosan

[0226] Scheme 9: Reaction of chitosan with hexanoic anhydride via amide bond formation

[0227] Reaction conditions: 10 ml Hexanoic anhydride liquid was mixed with 5g chitosan powder in round bottom flask under “solvent-free” reaction condition. 200 mg Catalyst-1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst) was added in presence of mild base. The resultant mixture was heated to 90°C for 8-12 hours under stirring at 400-500 rpm. A water insoluble caproic acid grafted chitosan slurry product formed.

[0228] After removing unreacted hexanoic anhydride, the modified chitosan became insoluble in i % acetic acid. This resulted in the hydrophobic modified chitosan product being obtained.

[0229] This reaction was repeated successfully using four further alternative catalysts, in Examples lOb-lOe, which followed the protocol of Example 10a but changed the catalyst as follows.

[0230] Example Ila: Anhydrous preparation of caprylic acid functionalised chitosan

[0231] Scheme 10: Reaction of chitosan with octanoic anhydride via amide bond formation

[0232] Reaction conditions: 10 ml Octanoic anhydride liquid was mixed with 5g chitosan powder in round bottom flask under “solvent-free” reaction condition. 200 mg Catalyst-1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst) was added in presence of mild base. The resultant mixture was heated to 90 °C for 8-12 hours under stirring at 400-500 rpm. A water insoluble caprylic acid grafted chitosan slurry product formed. After removing unreacted octanoic anhydride, the modified chitosan became insoluble in 1% acetic acid. This resulted in the hydrophobic modified chitosan product being obtained.

[0233] This reaction was repeated successfully using four further alternative catalysts, in Examples l lb-l le, which followed the protocol of Example I la but changed the catalyst as follows.

[0234] Example 12a: Preparation, of dodecylamine functionalised carboxy pullulan Scheme 11 : Reaction of carboxy pullulan with dodecylamine vi a amide bond formation

[0235] Reaction conditions: 5g carboxymethyl pullulan was dissolved in water and mixed with 1g Dodecvlamine dissolved in THF at pH 5.8 in round bottom flask. 100 mg Catalyst-1 (iron- titanium mixed oxide (Fe-Ti-oxide) catalyst) was added. The resultant mixture was heated to 65 °C for 8-12 hours. Unrcactcd dodccylaminc was removed by ethanol wash.

[0236] A fully water-soluble pullulan turned into a turbid solution, due to the modification of the molecule.

[0237] This reaction was repeated successfully using four further alternative catalysts, in Examples 12b-12e, which followed the protocol of Example 12a but changed the catalyst as follows.

[0238] Example 13a: Preparation of lauric acid functionalised keratin protein (hydrolysed)

[0239] Scheme 12: Reaction of keratin protein (hydrolysed) with lauric acid via amide bond formation

[0240] Reaction conditions: 2g keratin protein (hydrolysed) was dissolved in 50 ml water and mixed with 700 mg lauric acid dissolved in 20 ml methanol at pH 5.8 in round bottom flask. 200 mg Catalyst-1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst) was added. The resultant mixture was heated to 65-70 °C for 8-10 hours. Unrcactcd lauric acid was removed by dialysis against (1 : 1) ethanol: water mixture twice followed by removing the ethanol by dialyzed against DI water.

[0241] A fully water-soluble keratin protein solution turned into a turbid solution, due to the modification of the molecule.

[0242] This reaction was repeated successfully using four further alternative catalysts, in Examples 13b-l 3e, which followed the protocol of Example 13a but changed the catalyst as follows.

[0243] Example 14a: Preparation of 1,4-diamino 9.10-anthraquinone functionalised keratin

[0244] Scheme 13: Reaction of keratin protein (hydrolysed) with 1 ,4-diamino 9,10- anthraquinone via amide bond formation

[0245] Reaction conditions: lOOmg 1 ,4-diamino 9,10-anthraquinone dye was dissolved in 20 ml methanol and mixed with 2g keratin protein powder dissolved in 50 ml water at pH 5.8 in round bottom flask. 200 mg Catalyst-1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst) was added. The resultant mixture was heated to 70-80 °C for 8-12 hours. The unreacted 1 ,4- Diamino 9, 10-anthraquinone dye was removed by dialysis against (1 : 1) ethanol: water mixture twice followed by removing the ethanol by dialyzed against DI water.

[0246] A colorless keratin protein solution turned into violet solution, due to the dye modification of the molecule.

[0247] This reaction was repeated successfully using four further alternative catalysts, in Examples 14b-14e, which followed the protocol of Example 14a but changed the catalyst as follows.

[0248] Example 15a: Preparation of tartrazine functionalised keratin protein (hydrolysed)

[0249] Scheme 14: Reaction of keratin protein hydrolysed with tartrazine via amide bond formation

[0250] Reaction conditions: 200mg tartrazine dye dissolved in water and mixed with 2g keratin powder dissolved in water at pH 5.8 in round bottom flask. 100 mg Catalyst-1 (iron-titanium mixed oxide (Fe-Ti-oxide) catalyst) was added. The resultant mixture was heated to 65 °C for 8-12 hours. Tartrazine dye was removed by dialysis against water over 3 days with 3 time change of water.

[0251] A yellow color keratin-dye derivative was formed.

[0252] This reaction was repeated successfully using four further alternative catalysts, in Examples 15b-15e, which followed the protocol of Example 15a but changed the catalyst as follows. of 6,8-difluoro-7-hydroxy-2-oxo-2H-l-benzopyran-3- carboxylic ACLdJunctipnaHsed k

[0253] Scheme 15: Reaction of keratin protein (hydrolysed) with 6,8-Difluoro-7-hydroxy-2-oxo-2H- l-benzopyran-3-carboxylic acid via amide bond formation

[0254] Reaction conditions: 200mg 6,8-Difluoro-7-hydroxy-2-oxo-2H-1 -ben zopyran-3 -carboxy lie acid dissolved in water and mixed with 2g keratin powder dissolved in water at pH 5.8 in a round bottom flask. 100 mg Catalyst-1 (iron-titanium mixed oxide (Fc-Ti-oxidc) catalyst) was added. The resultant mixture was heated to 65 °C for 8-12 hours. 6,8-Difluoro-7-hydroxy-2- oxo-2H-l-benzopyran-3-carboxylic acid dye was removed by dialysis against water over 3 days with 3 time change of water.

[0255] A blue color keratin -dye derivative was formed.

[0256] This reaction was repeated successfully using four further alternative catalysts, in Examples 16b-l 6e, which followed the protocol of Example 16a but changed the catalyst as follows.

[0257] Scheme 16: Reaction of dodecylamine with hyaluronic acid via amide bond formation Reaction conditions: 5g hyaluronic acid was dissolved in water and mixed with 1 g dodccylaminc dissolved in THF at pH 5.8 in round bottom flask. 100 mg Fc-Ti catalyst-1 was added. The resultant mixture was heated to 65°C for 8-12 hours. Unreacted dodecylamine was removed by ethanol or methanol wash.

[0258] A fully water-soluble hyaluronic acid solution turned into a slightly turbid solution due to the formation of the modified molecule.

[0259] This reaction was repeated successfully using four further alternative catalysts, in Examples 17b-17e, which followed the protocol of Example 17a but changed the catalyst as follows.

[0260] Applications:

[0261] Functionalised molecules according to the invention have a wide range of potential applications. The following are illustrative and non-limiting.

[0262] N-Lauroyl functionalised chitosan can be used in multiple applications, including:

[0263] 1. emulsifiers

[0264] 2. cosmetic products, including moisturizers

[0265] 3. anti-microbial polymers

[0266] 4. antioxidant and anti-ageing products

[0267] 5. moisturization and hydrating products

[0268] 6. film forming, sunscreen products,

[0269] 7. coating and packaging applications

[0270] 8. water treatment and purification

[0271] 9. skin healing products

[0272] 10. anti-ageing products

[0273] 11. micro and nano-encapsulation and drug / gene delivery applications 12. preservatives in cosmetics, personal care, home care, and food - e.g. food preservation, including water resistant coatings

[0274] Betaine functionalised chitosan can be used in multiple applications, including:

[0275] 1. water-soluble film former

[0276] 2. cationic conditioning biopolymer

[0277] 3. thickener and gelling agent

[0278] 4. antimicrobial coating, anti-microbial polymer

[0279] 5. water-soluble coating and packaging applications, biopolymer for encapsulation; food packaging

[0280] 6. wound healing products

[0281] 7. antioxidant and anti-ageing products

[0282] 8. moisturization and hydrating products

[0283] 9. sunscreen products

[0284] 10. micro and nano-encapsulation and drug / gene delivery applications

[0285] 11. preservatives in cosmetics, personal care, home care, and food - e.g. food preservation

[0286] 12. cosmetic products, including moisturizer; body lotion; colour cosmetics - e.g. makeup product, foundation, lipstick

[0287] 13. anti-inflammatory products; anti-fungal products

[0288] 14. anti-acne products

[0289] 15. haircare products including conditioners; shampoo; hair styling products

[0290] 16. home care and disinfectant - kitchen and floor cleaning; laundry care

[0291] 17. biomedical and pharmaceutical applications

[0292] 18. agricultural applications

[0293] 19. water treatment and purification

[0294] 20. battery / energy storage, and electrochemical applications

[0295] N-Lauroyl-betaine functionalised chitosan can be used in multiple applications, including:

[0296] 1. emulsifiers (o / w)

[0297] 2. anti-microbial biopolymers, anti-acne, e.g. anti-acne face wash or cream

[0298] 3. coating and packaging applications

[0299] 4. water treatment and purification

[0300] 5. wound healing products

[0301] 6. antioxidant and anti-ageing products

[0302] 7. moisturization and hydrating products

[0303] 8. sunscreen products 9. micro and nano-encapsulation and drug / gene delivery application

[0304] 10. preservatives in cosmetics, personal care, home care, and food - c.g. food preservation

[0305] 11. cosmetic products, including moisturizers; colour cosmetics - e.g. makeup product, foundation, lipstick

[0306] 12. haircare products including conditioners; shampoo; hair styling products

[0307] 13. anti-inflammatory products; anti-fungal products

[0308] 14. home care and disinfectant - kitchen and floor cleaning; laundry care

[0309] 15. battery / energy storage, and electrochemical applications

[0310] N-Lauroyl functionalised alginate can be used in multiple applications, including:

[0311] 1. cosmetic products, including moisturizers

[0312] 2. emulsifiers, stabilizers

[0313] 3. thickeners, gelling agents, and texture modifiers

[0314] 4. films and coatings

[0315] 5. controlled release, encapsulation

[0316] 6. tissue engineering

[0317] 7. bio-ink

[0318] 8. preservatives in cosmetics, personal care, home care, and food

[0319] N-Lauroyl functionalised arginine can be used in multiple applications, including:

[0320] 1. cosmetic products, including moisturizers

[0321] 2. haircare products including conditioners

[0322] 3. antimicrobial products, antimicrobial agent, biofilm control in industrial settings

[0323] 4. foam forming agents

[0324] 5. solubilizers

[0325] 6. baby and hygiene care applications

[0326] 6. biosurfactant for cleaning products (shampoo, hand wash, body wash, male and female hygiene products, baby body wash)

[0327] 7. preservatives in cosmetics, personal care, home care, and food - e.g. food preservation

[0328] 8. food packaging

[0329] 9. biomedical applications (e.g. nasal sprays) and pharmaceuticals

[0330] 10. feed additives for livestock and aquatic animals Butyric acid functionalised chitosan, Caproic acid functionalised chitosan, Caprylic acid functionalised chitosan can be used in multiple applications, including :

[0331] 1. cosmetic products, including moisturizers

[0332] 2. haircare products including conditioners

[0333] 3. agriculture (biopesticides, plant growth enhancers, antimicrobial)

[0334] 4. environmental applications (including wastewater treatment)

[0335] 5. textile industry applications

[0336] 6. packaging materials applications

[0337] 7. anti-cancer and anti-inflammatory applications

[0338] 8. wound healing products

[0339] 9. food industry applications

[0340] 10. preservatives in cosmetics, personal care, home care, and food

[0341] Tartrazine functionalised chitosan can be used in multiple applications, including :

[0342] 1. coloration of cosmetics

[0343] 2. personal care

[0344] 3. food industry applications

[0345] 4. fibre and textiles applications

[0346] 5. pharmaceuticals and biomarkers

[0347] 6. clinical use applications

[0348] 7. imaging use applications

[0349] 8. preservatives in cosmetics, personal care, home care, and food

[0350] Dodecylamine functionalised carboxypullulan can be used in multiple applications, including:

[0351] 1. drug delivery systems and gene delivery

[0352] 2. antimicrobial agents

[0353] 3. tissue engineering scaffolds

[0354] 4. emulsifying agents

[0355] 5. film forming agents

[0356] 6. preservatives in cosmetics, personal care, home care, and food

[0357] Lauric acid functionalised keratin protein (hydrolysed) can be used in multiple applications, including:

[0358] 1. haircare products including: conditioners; shampoo; hair styling products

[0359] 2. cosmetic products, including moisturizers

[0360] 3. wound healing products 4. antimicrobial coatings

[0361] 5. controlled drug delivery systems

[0362] 6. cosmetic emulsifiers

[0363] 7. textile coatings

[0364] 8. food packaging materials

[0365] 9. agricultural films

[0366] 10. biomedical implants and tissue engineering scaffolds

[0367] 11. acne treatment formulations

[0368] 12. nutritional supplements

[0369] 13. preservatives in cosmetics, personal care, home care, and food

[0370] 1,4-Diamino 9, 10-anthraquinone functionalised keratin protein (hydrolysed) can be used in multiple applications, including:

[0371] 1. textile dyeing

[0372] 2. cosmetic formulations

[0373] 3. biodegradable films

[0374] 4. leather treatment

[0375] 5. paper coatings

[0376] 6. 3D printing materials

[0377] Tartrazine functionalised keratin protein (hydrolysed) can be used in multiple applications, including:

[0378] 1. textile dyeing

[0379] 2. cosmetic formulations

[0380] 3. biocompatible hydrogels

[0381] 4. biosensors

[0382] 5. food packaging

[0383] 6. wound dressings

[0384] 7. 3D printing materials

[0385] 8. leather treatment

[0386] 9. preservatives in cosmetics, personal care, home care, and food

[0387] 6,8-Difluoro-7-hydroxy-2-oxo-2H-l-benzopyran-3-carboxylic acid functionalised keratin protein (hydrolysed) can be used in multiple applications, including :

[0388] 1 . coloration of cosmetics

[0389] 2. personal care 3. food industry applications

[0390] 4. fibers and textiles

[0391] 5. pharmaceuticals and biomarkers

[0392] 6. clinical use

[0393] 7. imaging use

[0394] 8. preservatives in cosmetics, personal care, home care, and food

[0395] Lauric acid functionalised hyaluronic acid (HL) can be used in multiple applications, including:

[0396] 1. cosmetic products, including moisturizer; body lotion

[0397] 2. emulsifiers and co- emulsifiers

[0398] 4. hair care products, including hair styling products and hair repair and regeneration

[0399] 5. preservatives in cosmetics, personal care, home care, and food

[0400] Exemplary Product Formulation

[0401] Characterization of Functionalised Molecules

[0402] Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) was used to analyse the functionalised molecules produced using the method of the invention.

[0403] This technique detects a trace of the catalyst used in preparation of the functionalised molecules, indicating that the functionalised molecule has been prepared using the claimed method. Thus, functionalised molecules made according to the invention can be distinguished from molecules made by an alternative route.

[0404] Method: 100 mg of the powder samples were dissolved in 100 ml 2% nitric acid solution, mixed well, and sonicated for 60 min at 75°C. The resulting solution was then filtered to prepare the final test sample. Solution was not diluted further and injected directly onto the mass spectrometer. TCP-OES instrument model : Agilent®, TCP-OES, 5900

[0405] Mobile phase: 2% nitric acid

[0406] Sample concentration: Img / ml

[0407] Dilution factor = 1

[0408] Flow rate: 10 rpm

[0409] Nebulizer temperature: 25°C

[0410] Elemental analysis was carried out on:

[0411] • a control sample (2% nitric acid, used to digest and extract elements from a sample)

[0412] • unmodified chitosan

[0413] • two functionalised molecules prepared by the method of the invention using Catalyst-

[0414] 1 (heterogeneous solid Fe-Ti mixed metal oxide)

[0415] The results are set out below:

[0416] Elemental analysis of the final products, N-Lauroyl-Bctainc functionalised chitosan and N- Lauroyl functionalised chitosan, confirmed an increase in trace amounts of Fe and Ti, indicating successful functionalization with the proposed catalyst, compared to the initial levels in chitosan.

[0417] Advantages:

[0418] Functionalised molecules according to the invention have a wide range of advantages. The following are illustrative and non -limiting.

[0419] 1. Enhanced skin barrier function: By forming a protective film on the skin, N-Lauroyl- functionalised chitosan, betaine functionalised chitosan, and N-Lauroyl betaine functionalised chitosan can reduce moisture loss, improves hydration, and prolongs moisturization.

[0420] 2. Skin barrier enhancement: Applying N-Lauroyl functionalised chitosan creates a water-resistant coating that prevents the penetration of external irritants and pollutants. This helps reduce the risk of skin sensitivity or damage , and delays skin ageing.

[0421] 3. Long-lasting effects: The hydrophobic modification of N-Lauroyl functionalised chitosan enhances the water resistance of leave-on products such as sunscreen, foundations, concealers, and lipsticks. This makes it ideal for prolonged outdoor application, even when exposed to water or sweat.

[0422] 4. Improved delivery and bioavailability of hydrophobic actives: N-Lauroyl functionalised chitosan, betaine functionalised chitosan, and N-Lauroyl betaine functionalised chitosan each facilitate the effective delivery and bioavailability of hydrophobic active ingredients, such as antioxidants, vitamins, and humectants.

[0423] 5. Health benefits: Betaine functionalised chitosan and N-Lauroyl functionalised chitosan offer excellent bioactivities, as well as its functional properties. It has been found to reduce inflammation, acne, exhibit anti-ageing and anti-wrinkle properties, and promote skin healing. Natural chitosan already possesses skin healing properties, and the hydrophobic functionalisation further enhances these properties. Betaine functionalised chitosan and N-Lauroyl Betaine functionalised chitosan protect cells from dying, and delay ageing.

[0424] 6. N-Lauroyl functionalised chitosan, betaine functionalised chitosan, and N-Lauroyl betaine functionalised chitosan each act as a natural antimicrobial agent. The functionalisation improves the antimicrobial properties of chitosan.

[0425] 7. Preservative effects: the functionalised molecules can provide preservative characteristics and so can improve the shelf life of products.

[0426] References:

[0427] 1. Synthesis and Characterization of Fatty Acid Grafted Chitosan Polymeric Micelles for Improved Gene Delivery of VGF to the Brain through Intranasal Route, Biomedicines 2022, 10, 493.

[0428] 2. Hydrophobic Modification of Chitosan via Reactive Solvent-Free Extrusion. Polymers 2021 , 13, 2807.

[0429] 3. Enzymatic Grafting of Hexyloxyphenol onto Chitosan to Alter Surface and Rheological Properties, Tianhong Chen, Guneet Kumar, Michael T. Harris, Paul .1. Smith, Gregory F. Payne, BIOTECHNOLOGY AND BIOENGINEERING, VOL. 70, NO. 5, DECEMBER 5, 2000

[0430] 4. Enzymatic Grafting of a Natural Product onto Chitosan to Confer Water Solubility Under Basic Conditions, Guneet Kumar, Paul J. Smith, Gregory F. Payne, BIOTECHNOLOGY AND BIOENGINEERING, VOL. 63, NO. 2, APRIL 20, 1999

[0431] 5. Enzymatic synthesis of chitosan derivatives and their potential applications, Abdulhadi Aljawish Isabelle Chevalot Jordane, Jasniewski Joel Scher Lionel Muniglia, Journal of Molecular Catalysis B: Enzymatic, 112, 25-39.

[0432] 6. Q.H. Zeng, Y. Tian, C.R. Zhou, B.H. Luo, Acta Polymcrica Sinica, (2012) 593 -598.

[0433] 7. A New Horizon in Modifications of Chitosan: Syntheses and Application, Therapeutic Drug Carrier Systems, 30(2), 91-181 (2013)

[0434] 8. V. M. Bykova, L. I. Krivosheina, O. I. Glazunov, and E. A. Ezhova, in Proceedings of 6th AllRussia Conference “New Perspectives in Chitin and Chitosan Investi gation,” Shchelkovo, 2001, p. 147

[0435] 9. Souza, V.G.L.; Pires, J.R.A.; Rodrigues, C.; Coelhoso, I.M.; Fernando, A.L. Chitosan Composites in Packaging Industry — Current Trends and Future Challenges. Polymers 2020, 12, 417.

[0436] 10. Prashanth, K.V.H.; Tharanathan, R.N. Chitin / chitosan: Modifications and their unlimited application potential — an overview. Trends Food Sci. Technol. 2007

[0437] 11. Dowling, M.B.; Smith, W.; Balogh, P.; Duggan, M.J.; Maclntire, EC.; Harris, E.; Mesar, T.; Raghavan, S.R.; King, D.R.

[0438] 12. Hydrophobically-modified chitosan foam: Description and hemostatic efficacy. J. Surg. Res. 2015, 193, 316-323.

[0439] 13. L. Xing, L.N. Du, C.Q. Luo, T.J. Zhou, Y. Zhu, J.H. Gong, Y.G. Jin, H.L. Jiang, Chitosan and its derivatives as chemical drug delivery, Curr. Org. Chem. 22(7) (2018) 690- 707

Claims

CLAIMS1 . A method of producing a functionalised molecule, wherein the method comprises: a) providing a first aqueous precursor composition comprising a molecule in aqueous solution or suspension, wherein the molecule has a reactive group; b) providing a second precursor composition comprising a surface modifying agent in solution or suspension, wherein the surface modifying agent has a linker group and a functionalising group; c) forming a reaction mixture comprising the first aqueous precursor composition, the second precursor composition, and a mixed metal catalyst that comprises a first transition metal and a second metal that is a transition metal or Group 13 or 14 metal; and allowing the linker group of the surface modifying agent to react with the reactive group of the molecule in the presence of the catalyst, to thereby provide a functionalised molecule; wherein: i. the reactive group of the molecule comprises a carboxylic acid or salt thereof or derivative thereof and the linker group of the surface modifying agent is an amine or salt thereof; or ii. the reactive group of the molecule comprises an amine or salt thereof and the linker group of the surface modifying agent is a carboxylic acid or salt thereof or derivative thereof; such that the functionalising group is attached to the surface of the molecule via the formation of an amide bond.

2. The method of claim 1, wherein the second metal is a transition metal or is tin or germanium.

3. The method of claim 1 or claim 2, wherein the second metal is a Group 4-8 metal, such as titanium, zirconium, vanadium, chromium, manganese or iron, or a Group 13 or 14 metal such as germanium or tin.

4. The method of claim 3, wherein the second metal is selected from:(a) zirconium, titanium, vanadium, germanium, tin, iron, and chromium ; or(b) zirconium, titanium, vanadium, tin, iron, and chromium; or(c) zirconium, titanium, vanadium, tin, and iron; or(d) titanium, tin, and iron.

5. The method of any preceding claim, wherein the mixed metal catalyst is Lewis acidic.

6. The method of any preceding claim, wherein the first transition metal is a Group 4-8 metal, such as titanium, vanadium, manganese or iron.

7. The method of any preceding claim, wherein the first transition metal is selected from :(a) manganese, iron, cobalt, zinc, nickel and titanium; or(b) manganese, iron, and titanium; or(c) titanium and iron.

8. The method of any preceding claim, wherein the mixed-oxide catalyst further comprises a third metal, optionally wherein said third metal is a Group 4-8 metal, such as titanium, zirconium, vanadium, chromium, manganese or iron, or a Group 13 or 14 metal such as germanium or tin.

9. The method of any preceding claim, wherein the catalyst is selected from a mixed- oxide catalyst that is:(a) Fe-Ti, Sn-Ti, Sn-Fe-Ti, Zn-Sn, Zn-Ti, Mn-Sn, Zn-Fe, Mn-Ti, Zn-Ge, Fe-Ge, or Ti-Ge; or(b): Fe-Ti, Zn-Sn, Zn-Ti, Mn-Sn, Zn-Fe, Mn-Ti, Zn-Ge, Fe-Ge, or Ti-Ge; or(c) Fe-Ti, Sn-Ti, or Sn-Fe-Ti ; or(d) a porous iron-titanium mixed oxide (Fc-Ti-oxidc) catalyst in the form of nanoparticlcs.

10. The method of any preceding claim, wherein the molecule as provided in step a) is a biomolecule.

11. The method of any preceding claim, wherein the molecule as provided in step a) is selected from carbohydrates, proteins, and amino acids, and derivatives thereof.

12. The method of claim 1 1 , wherein the molecule is a polysaccharide or derivative thereof, or is a protein, or is an amino acid.

13. The method of claim 11 or claim 12, wherein the molecule is selected from: alginate, cellulose, chitosan, pullulan, callose, laminarin, chrysolaminarin, xylan, arabinoxylan, mannan, fucoidan, galactomannan, carrageenan, ulvan, agarose, hyaluronic acid, pectin, carboxyl functionalised xanthan gum, chondroitin sulfate, carboxymethyl cellulose,carboxymethyl chitosan, carboxymethyl starch, carboxymethyl dextran, carboxymethyl inulin, carboxymethyl pullulan, or derivatives thereof.

14. The method of claim 13, wherein the molecule is a polysaccharide selected from: hyaluronic acid, alginate, chitosan, chondroitin sulfate and pectin.

15. The method of claim 12, wherein the molecule is a polysaccharide derivative, wherein the polysaccharide is selected from cellulose, pullulan, callose, laminarin, chrysolaminarin, xylan, arabinoxylan, mannan, fucoidan, galactomannan, carrageenan, ulvan , agarose, xanthan gum, starch, dextran, and inulin, and wherein the polysaccharide has been modified to add a carboxylic acid group or salt thereof or derivative thereof (such as an acyl chloride or anhydride) or an amine group or salt thereof.

16. The method of any one of the preceding claims, wherein the molecule as provided in step a) is selected from: i) chitosan, alginate, arginine, keratin, hyaluronic acid, and carboxy modified pullulan (e.g. carboxymethyl pullulan); or ii) hyaluronic acid, alginate, chitosan, keratin, and arginine.

17. The method of any one of the preceding claims, wherein the first precursor composition is neutral or acidic.

18. The method of any one of the preceding claims, wherein the second precursor composition is neutral or acidic.

19. The method of any one of the preceding claims, wherein the linker group is of formula: a) -COzR* where Rxis H or Cl-12 alkyl (linear or branched or cyclic) or an alkali metal or alkaline earth metal; or b) -NRy2 or -NRY where each Rymay be the same or different and each is independently selected from H and C1 -1 2 alkyl (linear or branched or cyclic); or c) -COzR* where Rxis H or Cl -6 alkyl (linear or branched) or an alkali metal or alkaline earth metal; or d) -NRy2 or -NRY where each Rymay be the same or different and each is independently selected from H and Cl -6 alkyl (linear or branched).

20. The method of any one of the preceding claims, wherein the functionalising group includes: a) one or more hydrophilic moiety, e.g. selected from hydroxyl moieties, carbonyl moictics, carboxyl moieties, and amino moieties; or b) one or more hydrophobic moiety, e.g. selected from aliphatic chains, which may be saturated or unsaturated, and which may for example be a C2-50 or C2-28 straight chain or branched alkyl or alkenyl group.

21. The method of claim 20, wherein the one or more hydrophobic moiety includes:(i) a C2-24 or C2-18 straight chain or branched or cyclic alkyl or alkenyl group, or(ii) a C4-24 or C6-18 straight chain or branched or cyclic alkyl or alkenyl group, or(iii) a C2-24 or C2-1 8 straight chain or branched alkyl or alkenyl group, or(iv) a C4-24 or C6-18 straight chain or branched alkyl or alkenyl group.

22. The method of any one of the preceding claims, wherein the surface modification agent is selected from:• a saturated or unsaturated acid, or salt thereof;• a saturated or unsaturated acid anhydride, or salt thereof;• a saturated or unsaturated ester;• a saturated or unsaturated amine or salt thereof;• a dye or salt thereof, whereby the dye is a carboxylic acid containing dye or an amine containing dye.

23. The method of any one of the preceding claims, wherein the surface modification agent is selected from:• a saturated or unsaturated fatty acid, or salt thereof;• a betaine, such as trimethyl glycine, or salt thereof;• a saturated or unsaturated acid anhydride, or salt thereof;• a saturated or unsaturated ester;• a saturated or unsaturated fatty amine or salt thereof;• a dye or salt thereof, whereby the dye is a carboxylic acid containing dye or an amine containing dye.

24. The method of claim 22 or claim 23, wherein the surface modification agent has up to 50 carbon atoms, such as up to 40 carbon atoms, or up to 30 carbon atoms.

25. The method of any one of the preceding claims, wherein the surface modification agent is selected from: a) saturated fatty acids having the general formula CH3(CH2)nCO2Rxwhere Rxis H or C1 -6 alkyl (linear or branched) or an alkali metal or alkaline earth metal , and where n is an integer value from 1 to 50; or b) saturated fatty amines having the general formula CH3(CH2)nNRy2 where each Rymay be the same or different and may be selected from H and Cl -6 alkyl (linear or branched) and where n is an integer value from 1 to 50.

26. The method of any preceding claim wherein step c) takes place for a period of time from 10 minutes up to 24 hours, such as from 1 to 6 hours.

27. The method of any preceding claim wherein step c) takes place under neutral or acidic conditions.

28. The method of any preceding claim wherein the method further includes step d) of recovering the functionalised molecule from the mixture.

29. The method of claim 28, wherein step d) comprises cooling the mixture.

30. The method of claim 28 or claim 29, wherein step d) comprises extracting the functionalised molecule from the mixture via filtration or centrifugation.

31. The method of any preceding claim wherein the method further includes step e) of recovering the catalyst.

32. A functionalised molecule obtainable by (or obtained by) carrying out the method of any one of claims 1 -31.

33. The functionalised molecule of claim 32, wherein the functionalised molecule is N- Lauroyl functionalised chitosan, betaine functionalised chitosan, N-Lauroyl-bctainc functionalised chitosan, dodecylamine functionalised alginate, N-Lauroyl functionalised arginine, N-Steroyl functionalised arginine, butyric acid functionalised chitosan, tartrazine functionalised chitosan, caproic acid functionalised chitosan, caprylic acid functionalised chitosan, dodecylamine functionalised carboxy pullulan, lauric acid functionalised keratin protein (hydrolysed), 1 ,4-diamino 9,10-anthraquinone functionalised keratin proteinhydrolysed, tartrazine functionalised keratin protein (hydrolysed), 6,8-difluoro-7-hydroxy-2- oxo-2H-l-benzopyran-3-carboxylic acid functionalised keratin protein (hydrolysed), dodecyl amine functionalised hyaluronic acid, or lauric acid functionalised hyaluronic acid.

34. A method of producing a product, such as a consumer product, wherein the method comprises: a) providing a functionalised molecule as obtainable by the method of any one of claims 1- 31 ; and b) combining the functionalised molecule with a carrier.

35. The method of claim 34, wherein step a) comprises carrying out the method of any one of claims 1 -31 .

36. A product obtainable by the method of claim 34 or claim 35.

37. The method of claim 34 or claim 35 or the product of claim 36, wherein the product is a consumer product, e.g. a skin or hair care product.

38. The method or product of claim 37, wherein the product is selected from: shampoo; face mask (e.g. peel off mask); sunscreen; hair styling gel; conditioner; body lotion, face cream and other moisturizers; baby care products.

39. The product of claim 36, wherein the product is a water purification product, such as a membrane; a coating or packaging product; a drug delivery product; a food product or additive, such as a food preservative; or an anti-microbial product.

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