Antioxidants containing diazirine functionalities, compositions comprising them and use thereof

Abstract

The present disclosure generally pertains to the field of functionalized-antioxidant compounds. In particular, the present disclosure pertains to antioxidant compounds covalently linked (conjugated) to one or more diazirine moieties. The invention further relates to the use and methods of attaching such antioxidant conjugates to biological or synthetic substrates, including but not limited to natural and synthetic polymers, tissues, tissue engineering constructs, and surfaces of articles, to impart free radical-scavenging and antioxidant properties.

Description

ANTIOXIDANTS CONTAINING DIAZIRINE FUNCTIONALITIES, COMPOSITIONS COMPRISING THEM AND USE THEREOFCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 661,354, filed on June 18, 2024, which is incorporated herein by reference in its entirety.TECHNICAL FIELD

[0002] The present disclosure generally pertains to the field of functionalized antioxidant compounds. In particular, the present disclosure pertains to antioxidant compounds covalently linked (conjugated) to one or more diazirine moieties. The invention further relates to the use and methods of attaching such antioxidant conjugates to biological or synthetic substrates, including but not limited to natural and synthetic polymers, tissues, tissue engineering constructs, and surfaces of articles, to impart free radical-scavenging and antioxidant properties.BACKGROUND

[0003] Oxidative degradation, triggered by formation of free radicals leads to degradation of organic compounds, including synthetic polymers, biological molecules, as well as cells. The effects of oxidative degradation are of significant concern across a broad range of industries, including but not limited to food preservation, polymers, fuels, lubricants, and pharmaceuticals. Antioxidants play a critical role in neutralizing free radicals by donating electrons, thereby preventing chain reactions that lead to material deterioration.

[0004] Antioxidants are organic compounds that inhibit oxidation reactions that lead to the production of free radicals. Antioxidants are used in several industrial applications, and are frequently added to synthetic and natural polymers, fuels, lubricants, food, packaging, medical devices and other industrial products to forestall degradation by neutralizing free radicals, giving up their own electrons to “quench” or switch off free radicals. The strategic use of antioxidants is vital in enhancing product performance, ensuring safety, and extending the operational life of materials and formulations across a wide spectrum of industrial applications.

[0005] To ensure effective and localized neutralization of free radicals, antioxidants must be in close proximity or direct association with the material or substrate that requires protection. Conventionally, this has been achieved either by physical application of antioxidants onto surfaces (e.g., coating, spraying, or blending) or by mixing antioxidants into the bulk material during formulation.

[0006] While such methods are widely practiced, they suffer from several notable limitations. Physical application often leads to poor adhesion of the antioxidant to the substrate and results in rapid depletion or leaching, especially when exposed to solvents, heat, or moisture. Similarly, mixing antioxidants into the bulk material may result in non-uniform distribution, reduced availability at the surface, and compromised effectiveness over time due to migration or degradation.

[0007] Substantial research has been carried out to chemically conjugate or immobilize antioxidant moieties onto various substrates to overcome these limitations. However, most known approaches either rely on non-covalent interactions or require harsh chemical conditions and reactive intermediates, many of which may be toxic, unstable, or environmentally undesirable. Moreover, these methods often lack specificity or durability, resulting in incomplete immobilization or leaching of the antioxidant component over time, especially in aqueous or high-stress environments.

[0008] These challenges underscore the unmet need in the art for a method that enables stable, efficient, and environmentally friendly conjugation of antioxidants to a wide range of substrates. There is a need to arrive at a method which ensures strong covalent bonding between the antioxidant and the substrate, minimizes leaching or migration of the antioxidant during use, and preserves the bioactivity or radical-scavenging efficiency of the antioxidant.

[0009] Accordingly, there remains a need for a conjugation strategy that effectively incorporates antioxidants onto or into substrates in a manner that ensures durable antioxidant performance, resistance to leaching, and broad applicability across industrial and biomedical domains.SUMMARY OF THE DISCLOSURE

[0010] This summary is intended to introduce, in simplified form, a selection of concepts that are further described in the detailed description. This summary is merely presented as a brief overview of the subject matter described and claimed herein and does not aid in determining the scope of the claimed subject matter.

[0011] In one aspect, the present disclosure provides a compound comprising an antioxidant moiety and one or more diazirine moieties covalently linked thereto. The diazirine moiety enables covalent attachment of the compound to a substrate upon activation.

[0012] In an embodiment, the compound is of formula (IA), or (IB):(IA), (IB), wherein:A is an antioxidant moiety;Ri, at each occurrence, is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkoxy, alkoxy alkyl, alkoxy alkynyl, arylalkyl, or perfluorinated or partly fluorinated alkyl, aryl, and arylalkyl group;R2may be absent, or selected from alkylene, arylene, arylalkylene and heteroarylene; or Ri and R2 taken together form a cycloalkyl, or a heterocycloalkyl group;L is a bond or linker selected from an amide, alkylene, ether, ketone, ester, sulfide, sulfone, amino, triazolyl, isoxazolyl optionally substituted with alkyl, and a combination thereof; and z is 1, 2, 3 or 4.

[0013] In another aspect, the present disclosure provides a composition comprising an antioxidant moiety and one or more diazirine moieties covalently linked thereto.

[0014] In yet another aspect, the present disclosure provides use of a compound according to any one of the preceding aspects or embodiments for covalently binding to a material or surface or substrate comprising C-H, N-H, and / or O-H bonds via UV irradiation or heating. The substrate is as disclosed or described herein.

[0015] In another aspect, the present disclosure provides a product, material, or an article comprising a substrate having covalently attached thereto a compound of formula (IA), or (IB).

[0016] In yet another aspect, the present disclosure provides a method for bonding a compound of formula (IA), or (IB) to a substrate comprising:• applying a compound of formula (IA) or (IB) to a substrate comprising C-H, N-H, and / or O-H functional groups; and• activating the compound by UV radiation or heat to form covalent bond(s) with the substrate.

[0017] In certain embodiments, the present disclosure provides a product, material, or article obtainable by the method of the preceding aspect.

[0018] In still another aspect, the present disclosure provides a process for preparing a compound, the process comprising:• providing an antioxidant moiety; and• covalently attaching one or more diazirine moieties to the antioxidant moiety.

[0019] In certain embodiments, the process of the preceding aspect comprises:• providing a diazirine moiety having at least one reactive functional group selected from the group comprising carboxylic acid, halide, acyl halide, ester, amine, amide, isocyanate, and hydroxyl; and• reacting the diazirine moiety with an antioxidant moiety containing at least one functional group selected from the group comprising carboxylic acid, halide, acyl halide, ester, amine, isocyanate, hydroxyl and N-hydroxysuccinimide ester under conditions effective to form a covalent bond between the diazirine moiety and the antioxidant moiety.DETAILED DESCRIPTION

[0020] The objective of the present disclosure is to arrive at compounds comprising an antioxidant moiety and one or more diazirine moieties covalently linked thereto, resulting in monofunctional or multifunctional diazirine-based compounds such as bis-diazirines, tris- diazirines, tetrakis-diazirines, oligomeric diazirines with radical scavenging properties, and their industrial and medical applications.

[0021] The present disclosure can be understood more readily by reference to the following description, taken in conjunction with the accompanying Figures and Examples, all of which form a part of this disclosure. At the very outset of the detailed description, it may be understood that the ensuing description only illustrates a particular form of this invention. However, such a particular form is only an exemplary embodiment, and without intending to imply any limitation on the scope of this invention. Accordingly, the description is to be understood as an exemplary embodiment and teaching of invention and not intended to be taken restrictively.

[0022] Before the present disclosure or methods of the present disclosure are described in greater detail, it is to be understood that the specific products, methods, processes, conditions, or parameters, are not limited to embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing embodiments only and is not intended to be limiting.

[0023] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the methods. Where the stated range includes one or both limits, ranges excluding either or both of those included limits are also included in the methods. Certain ranges are presented herein with numerical values being preceded by the term “about.” The term “about” is used herein to provide literal support for the exact number that it precedes, as well as a number that is near to or approximately the number that the term precedes. For example, "about" can mean within one or more standard deviations, or within ± 30%, 25%, 20%, 15%, 10% or 5% of the stated value.

[0024] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, preferred methods and materials are described. For the purposes of the present invention, the following terms are defined below.

[0025] It is appreciated that certain features of the methods, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the methods, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination. All combinations of the embodiments are specifically embraced by the present invention and are disclosed herein just as if each and every combination was individually and explicitly disclosed, to the extent that such combinations embrace operable processes and / or composites / scaffolds .

[0026] The articles "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, "an element" means one element or more than one element. As used herein, the term "comprises", "comprising", or “comprising of’ is generally used in the sense of include, that is to say permitting the presence of one or more features or components. The term "comprises", "comprising", or “comprising of’ when placed before the recitation of steps in a process or method means that the process or method encompasses one or more steps that are additional to those expressly recited, and that the additional one or more steps may be performed before, between, and / or after the recited steps.

[0027] Reference throughout this specification to “certain embodiments”, “further embodiments”, “specific embodiments”, “further specific embodiment”, “one embodiment”, “a non-limiting embodiment”, “an exemplary embodiment”, “some instances”, or “further instances”, means that a particular feature, structure or characteristic described in connection with the embodiment may be included in at least one embodiment of the present disclosure. As used herein, the terms ‘include’, ‘have’, ‘comprise’, ‘contain’ etc. or any form of said terms such as ‘having’, ‘including’, ‘containing’, ‘comprising’ or ‘comprises’ are inclusive and will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

[0028] The use of any and all examples, or exemplary language (e.g., “such as”) provided with respect to certain embodiments herein is intended merely to better illustrate the disclosure and does not pose a limitation on the scope of the disclosure otherwise claimed. As used herein,the term “invention”, “present invention”, “disclosure” or “present disclosure” as used herein is a non-limiting term and is not intended to refer to any single embodiment of the particular invention but encompasses all possible embodiments as described in the specification. The terms “process(es)” and “method(s)” are considered interchangeable within this disclosure.

[0029] The term “antioxidant moiety” as used herein refers to a chemical structure, functional group, or compound, either in its native form or as part of a larger molecule, that is capable of inhibiting or neutralizing oxidative reactions by scavenging free radicals. The term encompasses both natural and synthetic antioxidants. The antioxidant moiety may include functional groups such as phenol, polyphenol, thiol, amine, or imidazole, which confer redox activity.

[0030] The term “diazirine moiety” as used herein refers to organic molecules comprising carbon atom bonded to two nitrogen atoms, which are connected by a double bond. Upon heating or UV treatment, diazirines form reactive carbene species by the loss of a nitrogen molecule which enables insertion into various C-H, N-H and O-H bonds on the surface of articles or in bulk materials containing one or more of these bonds.

[0031] The term “substrate” as used herein refers to a solid, semi-solid, or structured material or surface to which a compound of the present disclosure may be covalently linked either on the surface or within the material matrix, such that the antioxidant remains functionally stable, accessible, and active over a desired period of use. The substrate provides a physical support and chemical environment that permits the stable immobilization of the antioxidant through chemical, biochemical, or photoactivated covalent bonding mechanisms.

[0032] As used herein, the symbol “” denotes a position at which the bonding takes place with another repeat unit or another atom or molecule or group or moiety as appropriate with the structure of the group as shown.

[0033] The term “alkyl” refers to a saturated, monovalent hydrocarbon group having a straightchain or branched structure and typically comprising 1 to 20 carbon atoms, or from 1 to 10 carbon atoms, or from 1 to 6 carbon atoms. The alkyl group may be straight-chain (e.g., methyl,ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl) or branched (e.g., isopropyl, sec-butyl, tert-butyl, isopentyl). Alkyl groups may be unsubstituted or substituted with one or more substituents.

[0034] The term “alkynyl” refers to a straight or branched hydrocarbon group having at least one carbon-carbon triple bond (-C=C-), typically containing from 2 to about 20 carbon atoms, or from 2 to 10 carbon atoms, or from 2 to 6 carbon atoms unless otherwise specified. Examples of alkynyl groups include, but are not limited to, ethynyl (-C=CH), propynyl (e.g., 1-propynyl, 2-propynyl), butynyl (e.g., 1-butynyl, 2-butynyl), and their branched isomers. Alkynyl groups may be optionally substituted with one or more substituents.

[0035] The term “alkoxy” refers to a group of the formula -OR, where R is a straight or branched alkyl group having from 1 to about 20 carbon atoms, or from 1 to 10 carbon atoms, or from 1 to 6 carbon atoms unless otherwise specified. The alkyl moiety may be straight-chain or branched and includes, for example, methoxy (-OCH3), ethoxy (-OCH2CH3), n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy. In certain embodiments, the alkyl portion of the alkoxy group is a lower alkyl (C1-C4). Alkoxy groups may be optionally substituted with non-interfering substituents.

[0036] The term “aryl” refers to aromatic hydrocarbon ring system containing one or more aromatic rings, which may be fused or unfused and which typically contain 6 to 14 carbon atoms, or from 6 to 12 carbon atoms, or 6 to 10 carbon atoms. In certain embodiments, aryl is a 6-membered aryl. The term “aryl” also encompasses substituted aryl groups, wherein one or more hydrogen atoms on the aromatic ring are replaced with one or more substituents. The term also encompasses “heteroaryl” groups containing one or more heteroatoms (such as nitrogen, oxygen, and sulfur) within the ring structure. In certain embodiments, heteroaryl is a 5- or 6-membered monocyclic heteroaryl. The term “monocyclic heteroaryl” refers to a heteroaryl group having only one aromatic ring, wherein heteroaryl is as defined herein.

[0037] The term “arylalkyl” refers to monovalent substituent in which an aryl group is bonded to a compound via an alkyl linker. The alkyl portion typically comprises a straight or branched saturated hydrocarbon chain comprising 1 to 20 carbon atoms, or from 1 to 10 carbon atoms, or from 1 to 6 carbon atoms, and serves as a spacer between the aryl ring and the point of attachment. The arylalkyl groups may be optionally substituted on the aryl ring and / or the alkyl chain with one or more substituents. Examples of arylalkyl groups include benzyl(phenylmethyl), phenethyl (phenylethyl), and naphthylmethyl. The aryl portion may be a phenyl, naphthyl, or other aryl as defined herein and may be optionally substituted with one or more substituents.

[0038] The term “perfluorinated” refers to moiety in which all hydrogen atoms that are bonded to carbon atoms in the corresponding hydrocarbon structure have been replaced by fluorine atoms.

[0039] The term “partly fluorinated alkyl” refers to hydrocarbon group in which one or more, but not all of the hydrogen atoms are replaced by fluorine atoms.

[0040] The term “alkylene” refers to divalent saturated hydrocarbon group derived from an alkane by the removal of two hydrogen atoms, typically one from each of two different carbon atoms. These groups can be linear or branched, and generally contain from 1 to 20 carbon atoms, or from 1 to 10 carbon atoms, or from 1 to 6 carbon atoms. The alkylene group may be straight-chain or branched and serves to link two other groups within a molecule. Examples include methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2- or - CH(CHS)CH2-), and butylene (e.g., -CH2CH2CH2CH2-). Alkylene groups may be optionally substituted with one or more non-interfering substituents.

[0041] The term “arylene” refers to a valent aromatic hydrocarbon group derived from an aryl group by removal of two hydrogen atoms, typically from adjacent or non-adjacent positions, and having from 6 to 14 carbon atoms, unless otherwise specified. In certain embodiments, arylene is a 6-membered arylene. Arylene groups may be monocyclic or fused polycyclic, and include, for example, phenylene. The arylene group may be optionally substituted with one or more non-interfering substituents.

[0042] The term “arylalkylene” refers to a divalent substituent comprising an alkylene linking an aryl group to another part of a molecule typically containing from 1 to 6 carbon atoms in the alkylene portion, unless otherwise specified. The aryl moiety may be monocyclic or polycyclic (e.g., phenyl, naphthyl) and may be optionally substituted with one or more substituents such as halo, alkyl, alkoxy, nitro, cyano, hydroxy, and amino.

[0043] The term “cycloalkyl” refers to a saturated, monovalent carbocyclic ring system having from 3 to 8 carbon atoms, which may be monocyclic or bicyclic. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and bicyclo[2.2.1]heptyl. The cycloalkyl group may be unsubstituted or substituted with one or more non-interfering substituents.

[0044] The term “heterocycloalkyl” refers to saturated or partially saturated monovalent ring system having from 3 to 8 ring atoms, wherein one or more ring atoms are heteroatoms selected from nitrogen, oxygen, and sulfur, and the remaining ring atoms are carbon. The heterocycloalkyl ring may be monocyclic or bicyclic and may be unsubstituted or substituted with one or more non-interfering substituents

[0045] The term “heteroatomic group” refers to atoms other than carbon and hydrogen. Common heteroatoms include, but are not limited to, nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), and halogens (fluorine (F), chlorine (Cl), bromine (Br), iodine (I).

[0046] The term “linker” refers to chemical moiety or group that covalently connects two parts of a molecule, such as two functional groups, substituents, or larger molecular fragments. A linker may be linear or branched, saturated or unsaturated, and can include heteroatoms (e.g., O, N, or S). Examples include, but are not limited to, amide, alkylene, ether, ketone, ester, sulfide, sulfone, amino, triazolyl, isoxazolyl optionally substituted with alkyl, and a combination thereof.

[0047] Unless stated otherwise, a group may be either substituted or unsubstituted. The term “optionally substituted” refers to a group that may be either unsubstituted or substituted with one or more substituents, including but not limited to, halogen (F, Cl, Br, I), alkyl (e.g., Ci-Ce alkyl), alkoxy (e.g., methoxy, ethoxy), hydroxy, nitro, cyano, amino, carboxy, ester; and sulfonyl, or other functional groups.

[0048] The terms “the compound”, “antioxidant-diazirine compound”, “compound of the present disclosure” are used interchangeably to refer to the compounds of the present invention wherein at least one antioxidant moiety and at least one diazirine moiety are covalently linked.

[0049] In one aspect, the present disclosure provides a compound comprising an antioxidant moiety and one or more diazirine moieties covalently linked thereto.

[0050] In certain embodiments, the antioxidant moiety is derived from compounds selected from a group comprising tocopherol or its derivative, trolox or its derivative, ascorbic acid or its derivative, beta-carotene, carotenoid, flavonoid, hindered phenol, and polyphenol.

[0051] In certain embodiments, any diazirine moiety or compound that can form a covalent bond with the antioxidant moiety or compound and retains its diazirine functionality capable of reacting with C-H, N-H, and / or O-H bonds of a substrate or surface upon activation by heat or UV radiation may be used.

[0052] In certain embodiments, the diazirine moiety or compound, which can be covalently linked to the antioxidant, has the following formula:Ri, at each occurrence, is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkoxy, alkoxy alkyl, alkoxy alkynyl, arylalkyl, or perfluorinated or partly fluorinated alkyl, aryl, and arylalkyl group;R2 may be absent, or selected from alkylene, arylene, arylalkylene and heteroarylene; or Ri and R2 taken together form a cycloalkyl, or a heterocycloalkyl group; andY is a group selected from carboxylic acid, halide, acyl halide, ester, amine, amide, isocyanate, hydroxyl and N-hydroxysuccinimide ester, and enables covalent bonding between the diazirine moiety and the antioxidant compound.

[0053] In certain embodiments, an amine-functionalized diazirine can react with activated carboxyl groups (e.g., acid chlorides or esters) on the antioxidant compound, forming an amide linkage. Similarly, a carboxyl group on the diazirine moiety can be converted to an activated carboxyl group, which reacts with amine groups on the antioxidant compound to form an amide bond. A diazirine bearing a sulfonyl chloride can react with amines on the antioxidant compound to form a sulfonamide bond, or vice versa. A person skilled in the art would readily understand that other reactive functional groups may also be used to form covalent linkages,without impairing the desired functional properties of the antioxidant compounds. Suitable reaction conditions (e.g., reagents, solvents, temperatures, catalysts, and reaction times) for these coupling reactions are well-known in the art and can be selected by a person skilled in the art without undue experimentation.

[0054] In the compounds of the present disclosure, a covalent bond is formed between a diazirine moiety and an antioxidant moiety. The resulting conjugated product comprises the diazirine group covalently linked to the antioxidant. The conjugated compound retains its photoactivation or crosslinking functionality rendered by the diazirine moiety, and antioxidant property rendered by the antioxidant moiety, while maintaining a stable chemical linkage to each other.

[0055] In certain embodiments, the one or more diazirine moieties present in the compounds of the present disclosure are reactive functional groups capable of binding to C-H, N-H, and / or O-H bonds upon activation by heat or UV radiation; and wherein the compound is configured to chemically bond to a surface or a substrate comprising C-H, N-H, and / or O-H bonds.

[0056] In certain embodiments, the one or more diazirine moieties present in the compounds of the present disclosure are capable of generating a carbene intermediate upon activation by heat or UV radiation, and wherein the carbene reacts with functional groups selected from C- H, N-H, and / or O-H groups present on a surface or substrate to form a covalent bond.

[0057] In an embodiment, the compound has a formula (IA), or (IB):wherein:A is an antioxidant moiety;Ri, at each occurrence, is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkoxy, alkoxy alkyl, alkoxy alkynyl, arylalkyl, or perfluorinated or partly fluorinated alkyl, aryl, and arylalkyl group;R2may be absent, or selected from alkylene, arylene, arylalkylene and heteroarylene; or Ri and R2 taken together form a cycloalkyl, or a heterocycloalkyl group; andL is a bond or linker selected from an amide, alkylene, ether, ketone, ester, sulfide, sulfone, amino, triazolyl, isoxazolyl optionally substituted with alkyl, and a combination thereof; and z is 1, 2, 3 or 4.

[0058] In certain embodiments, the compound has a formula (IA):(IA), wherein A, Ri, R2, L, and z are same as defined in any of the preceding aspects or embodiments.

[0059] In certain embodiments, the compound has a formula (IB):(IB), wherein A, Ri, R2, L, and z are same as defined in any of the preceding aspects or embodiments.

[0060] In certain embodiments, the substituents alkyl, aryl, arylalkyl, alkynyl, alkoxy, alkoxy alkynyl, perfluorinated or partly fluorinated alkyl, aryl, arylalkyl, alkylene, arylene, arylalkylene, heteroaryl group, amide, alkylene, ether, ketone, ester, sulfide, sulfone, amino, triazolyl, isoxazolyl, substituted, and linker groups are intended to have the general meanings commonly understood in the art, unless otherwise specified herein. These groups may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

[0061] In certain embodiments, the diazirine moiety or compound, which can be covalently linked to the active, has the following formula:FY-R2-ftR1wherein Ri, and R2 are same as defined in any of the preceding aspects or embodiments; andY is a group selected from carboxylic acid, halide, acyl halide, ester, amine, amide, isocyanate, hydroxyl and N-hydroxysuccinimide ester, which enable covalent bonding between the diazirine moiety and the antioxidant compound.

[0062] In certain embodiments, Ri, at each occurrence, is independently selected from hydrogen, C1-C12 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C12 aryl, Ce - C12 aryl Ci - C12 alkyl, C1-6 alkoxy, C1.3 alkoxy-Ci.3 alkyl, C1.2 alkoxy-C2-6 alkynyl, C2 - C 12 perfluoroalkyl, Ci - C12 alkyl or Ce - C12 aryl where portions of hydrogen on alkyl are replaced with fluorine, and Ce - C12 aryl Ci - C12 alkyl, where portions of hydrogen on alkyl are replaced with fluorine.

[0063] In certain embodiments, Ri, at each occurrence, is independently selected from hydrogen, methyl, trifluoromethyl, but-3-yn-l-yl and prop-2-yn-l-yloxy.

[0064] In certain embodiments, R2, at each occurrence, is independently selected from Ci-Ce alkylene, Ce-C 10 arylene, Ce-Cio aryl-Ci-Ce alkylene or 5-10 membered heteroarylene having N, or O or both heteroatoms.

[0065] In certain embodiments, R2, at each occurrence, is independently selected from methyl, ethyl, propyl, benzyl and phenyl.

[0066] In certain embodiments, Ri and R2 together form a C3-C12 cycloalkyl, or a heterocycloalkyl group having N or O as the heteroatom. The ring can be selected from cyclohexyl, cyclobutyl, cyclopentyl, azepanyl, pyrrolidinyl and azetidinyl.

[0067] In certain embodiments, L is a bond or a divalent linking or a spacer group selected from -R-, C(O)-, -C(O)O-R-OC(O)- , -C(O)-R-, -R-OC(O)R- , C(O)-R-OC(O)-, R-O-ROC(O)- , C(O)-NR-, R-NR, C(O)- R-, -C(O)-R-NR, -OR- wherein R is Ci-C6alkylene, or C2-C6alkenylene, or an C6-C12 arylene, each of which is optionally substituted.

[0068] In certain embodiments, the diazirine moiety is derived from a corresponding diazirine compound having a reactive functional group selected from the group comprising carboxylic acid, halide, acyl halide, ester, amine, amide, isocyanate, hydroxyl and N-hydroxysuccinimide ester.

[0069] In an embodiment, the diazirine moiety is derived from a diazirine compound selected from 3-(4-(bromomethyl)phenyl)-3-(trifluoromethyl)-3H-diazirine, 3-(4-bromophenyl)-3- (trifluoromethyl)-3H-diazirine, 3-(4-(bromoethyl)phenyl)-3-(trifluoromethyl)-3H-diazirine, 6- bromo-l,2-diazaspiro[2.5]oct-l-ene, 3-(2-bromoethyl)-3-methyl-3H-diazirine, 3-(2- bromomethyl)-3-methyl-3H-diazirine, (4-(3-(trifluoromethyl)-3H-diazirin-3- yl)phenyl)methanamine hydrochloride, l,2-diazaspiro[2.5]oct-l-en-5-amine hydrochloride, l,2-diazaspiro[2.3]hex-l-en-5-amine hydrochloride, 2-(3-(but-3-yn-l-yl)-3H-diazirin-3- yl)ethan-l -amine, (3 -methyl-3H-diazirin-3-yl)m ethanamine hydrochloride, 2-(3-methyl-3H- diazirin-3-yl)ethan-l -amine hydrochloride, (4-(3-(trifluoromethyl)-3H-diazirin-3- yl)phenyl)methanol, 2-(3 -(but-3 -yn- 1 -yl)-3H-diazirin-3 -yl)ethan- 1 -ol, 2-(3 -((prop-2 -yn- 1 - yloxy)methyl)-3H-diazirin-3-yl)ethan-l-ol, 3-(3H-diazirin-3-yl)propanoic acid, 3-(3-methyl- 3H-diazirin-3-yl)propionyl chloride, 4-(3H-diazirin-3-yl)butanoic acid, 2,5-dioxopyrrolidin-l- yl 3-(3-methyl-3H-diazirin-3-yl)propanoate, 2,5-dioxopyrrolidin-l-yl-3-((2-(3-(3-methyl-3H- diazirin-3-yl)propanamido)ethyl) disulfaneyl)propanoate, 2-(3-Methyl-3H-diazirin-3- yl)ethanol, l,2,6-triazaspiro[2.6]non-l-ene hydrochloride, l,2,6-triazaspiro[2.6]oct-l-ene hydrochloride, l,2,5-triazaspiro[2.4]hept-l-ene hydrochloride, l,2,5-triazaspiro[2.3]hex-l-ene hydrochloride; l,2-diazaspiro[2.4]hept-l-ene-5-carboxylic acid, l,2-diazaspiro[2.3]hex-l-ene- 5-carboxylic acid, and di[2-(3-methyl-3H-diazirin-3-yl)ethyl] (2S)-2-hydroxybutanedioate.

[0070] In certain embodiments, the diazirine moiety is derived from compounds selected from 2-(3-Methyl-3J7-diazirin-3-yl)ethanol, 3-[p-(bromomethyl)phenyl]-3-(trifluoromethyl)-3Z7- diazirine, 3-(3-Methyl-3Z7-diazirin-3-yl)propionic acid, 3-(3-Methyl-3Z7-diazirin-3- yl)propionyl chloride, 3-(2-bromoethyl)-3-methyl-3Z7-diazirine, and di[2-(3-methyl-3H- diazirin-3-yl)ethyl] (2S)-2-hydroxybutanedioate.

[0071] The antioxidant moiety is derived from compounds selected from a group comprising tocopherol or its derivative, trolox or its derivative, ascorbic acid or its derivative, betacarotene, carotenoid, flavonoid, hindered phenol, and polyphenol.

[0072] In certain embodiments, the antioxidant moiety which forms a part of the compound of formula (IA), or (IB) by linking to the linker L, or to the group R2 can be represented by the following formula:wherein R3, R4 and R5 are independently selected from hydrogen and alkyl; and the wavy line (Awd represents the point of attachment. In certain embodiments, R3, R4 and R5 are independently selected from hydrogen and methyl.

[0073] In certain embodiments, the antioxidant moiety which forms a part of the compound of formula (IA), or (IB) by linking to the linker L, or to the group R2 can be represented by the following formula:wherein Rs, R7, Rs, R9, and Rio are independently selected from hydrogen, hydroxyl, halide, alkyl, and haloalkyl; and the wavy line ( 'ww' ) represents the point of attachment. In some embodiments, Re, R7, Rs, R9, and Rio are independently selected from hydrogen, hydroxyl, halide (Cl, F, Br, I), and trifluoromethyl, and tert-butyl.

[0074] In certain embodiments, the antioxidant moiety which forms a part of the compound of formula (IA), or (IB) by linking to the linker L, or to the group R2 can be represented by the following formula:

[0075] In certain embodiments, the antioxidant moiety is derived from a corresponding antioxidant compound having a reactive functional group selected from the group comprising carboxylic acid, acyl halide, ester, halide, amine, amide, isocyanate, and hydroxyl.

[0076] In certain embodiments, the antioxidant moiety is derived from compounds selected from 6-hydroxy-2,5,7,8-tetramethyl-2-chromancarboxylic acid, 3-(6-hydroxy-2, 5,7,8- tetramethyl-2-chromanyl)propionic acid, 6-hydroxy-2,5,7,8-tetramethyl-2-chroman acyl chloride, 3-(6-hydroxy-2,5,7,8-tetramethyl-2-chromanyl)propionyl chloride; 2,6-di-tert- butylphenol, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), 2,6-di-tert- butyl-4-methylphenol, 2,6-diisopropylphenol, 4-(bromomethyl)-2,6-di- / c / 7-butylphenol, 4- bromophenol, 4-bromobenzene-l,2-diol, 5-bromobenzene-l,2,3-triol, 2,4-dibromophenol, 4,5- dibromobenzene-l,2-diol, 2,4,6-tribromophenol, 2,4,6-tribromo-5-pentylbenzene-l,3-diol, 4- amino-2,6-di- / c77-butylphenol, 4-methylamino-2,6-di-tert-butylphenol, 4-aminophenol, 2,6- diaminophenol, 2,4-diaminophenol, 2,4,6-triaminophenol, 4-aminobenzene-l,2-diol, 5- aminobenzene- 1,3 -diol, 4-aminobenzene-l,2-diol, 4-aminobenzene- 1,3 -diol, 5- aminoethylbenzene-l,2,3-triol, 5-aminobenzene-l,2,3-triol, 4-hydroxybenzamide, 2- hydroxybenzamide, 3,5-dihydroxybenzamide, 3,4,5-trihydroxybenzamide, aniline, 4, d'methylenedianiline, 4,4'-(perfluoropropane-2-2-diyl)bisaniline, 3,5- bis(trifluoromethyl)aniline, (5R)-[(1 S)-l,2-dihydroxyethyl]-3,4-dihydroxyfuran-2(5H)-one or its derivatives, and l-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine.

[0077] In certain embodiments, the compounds are selected from 6-hydroxy-2, 5,7,8- tetramethyl-2-chromancarboxylic acid, 6-hydroxy-2,5,7,8-tetramethyl-2-chromancarbonyl chloride, 4-amino-2,6-di-tert-butylphenol, 4-(bromomethyl)-2,6-di-tert-butylphenol, 4- methylamino-2,6-di-tert-butylphenol, 3-(6-hy droxy -2,5,7, 8-tetramethyl-2- chromanyl)propionic acid, 3,5-bis(trifluoromethyl)phenylaniline, and 4-(bromomethyl)-2,6- di -tert-butyl phenol .

[0078] In certain embodiments, the compounds of formula (IA), and (IB) are selected from 2,6-di-tert-butyl-4-{[({4-[(trifluoromethyl)-3H-diazirin-3-yl]phenyl}methyl)amino]methyl} phenol, 2-(3-methyl-3JH-diazirin-3-yl)ethyl 6-hydroxy -2,5,7, 8-tetramethyl-2- chromancarboxylate, 2,6-Di- / c / 7-butyl-4-[([ / 9-[3-(trifluorornethyl)-3 / / -diazirin-3- yl]benzyl}amino]phenol, 2,6-Di-tert-butyl-4-[({p-[3-(trifluoromethyl)-3H-diazirin-3- yl]benzyl}methyl)amino]phenol, 2,6-Di- / c77-butyl-4-[ [2-(3-methyl-3 / / -diazirin-3- yl)ethoxy]methyl (phenol, 2-(3-Methyl-3Z7-diazirin-3 -yl)ethyl-3 -(6-hydroxy -2, 5,7,8- tetramethyl-2-chromanyl) propionate, l-Hydroxy-2,2,6,6-tetramethyl-4-piperidyl 3-(3- methyl-3Z7-diazirin-3-yl)propionate, l-Hydroxy-2,2,6,6-tetramethyl-4-piperidyl 3-(3-methyl- 3Z7-diazirin-3-yl)propionate, 2,2,6,6-tetramethyl-4-[2-(3-methyl-3JH-diazirin-3-yl)ethoxy]-l- piperidinol, 4-hydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)benzamide, 3,5- dihydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)benzamide, 3,4,5-trihydroxy-N- (4-(3-(trifluoromethyl)-3H-diazirin-3-yl) benzyl)benzamide, 4-((4-(3-(trifluoromethyl)-3H- diazirin-3-yl)benzyl)amino)phenol, 4-((4-(3-(trifluoromethyl)-3H-diazirin-3- yl)benzyl)amino)benzene-l,2-diol, 5-((4-(3-(trifluoromethyl)-3H-diazirin-3- yl)benzyl)amino)benzene-l,3-diol, 5-(2-((4-(3-(trifluoromethyl)-3H-diazirin-3- yl)benzyl)amino)ethyl)benzene-l,2,3-triol, 4-hydroxy-N-(2-(3-methyl-3H-diazirin-3- yl)ethyl)benzamide, 3,5-dihydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide, 3,4,5- trihydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;4-(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol, 4-((2-(3-methyl-3Z7-diazirin-3- yl)ethyl)amino)benzene-l,2-diol, 5-((2-(3-methyl-3JH-diazirin-3-yl)ethyl)amino)benzene-l,3- diol, 5-(2-((2-(3-methyl-3JH-diazirin-3-yl)ethyl)amino)ethyl)benzene-l,2,3-triol, 2,4-bis((4- (3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol, 2,6-bis((4-(3-(trifluoromethyl)- 3H-diazirin-3-yl)benzyl)amino)phenol, 2,4,6-tris((4-(3-(trifluoromethyl)-3H-diazirin-3- yl)benzyl)amino)phenol, 2,6-bis(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol, 2,4,6- tris(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol, N-phenyl-4-(3-(trifluoromethyl)-3H- diazirin-3-yl)aniline, 3,5-bis(trifluoromethyl)-N-(4-(3-(trifluoromethyl)-3H-diazirin-3- yl)phenyl)aniline, 4,4’-methylenebis(N-(4-(3-(trifluoromethyl)-3H-diaziri-3- yl)phenyl)aniline); 4,4’-(perfluoropropane-2,2-diyl)bis(N-(4-3-(trifluoromethyl)-3H-diazirin- 3-yl)benzyl)aniline), and di[2-(methyl-3H-diazirin-3-yl)ethyl] (2S)-2-(6-hydroxy-2, 5,7,8- tetram ethyl chroman-2-y 1 carb ony 1 oxy )butanedi oate .

[0079] In certain embodiments, the compounds are selected from 2-(3 -Methyl -3 / / -diazirin-3- yl)ethyl 6-hydroxy-2,5,7,8-tetramethyl-2-chromancarboxylate, 2,6-Di- / c / 7-butyl-4-[([ / ?-[3- (trifluoromethy^-SZZ-diazirin-S-ylJbenzylJaminoJphenol, 2,6-Di-tert-butyl-4-[({p-[3- (trifluoromethyl)-3H-diazirin-3-yl]benzyl}methyl)amino]phenol, 2,6-Di-tert-butyl-4-{[2-(3- methyl-3JH-diazirin-3-yl)ethoxy]methyl}phenol, 2-(3-Methyl-3J7-diazirin-3-yl)ethyl 3-(6- hydroxy-2,5,7,8-tetramethyl-2-chromanyl)propionate, 1 -Hydroxy -2,2,6, 6-tetramethyl-4- piperidyl 3-(3-methyl-3Z7-diazirin-3-yl)propionate, 2,2,6,6-Tetramethyl-4-[2-(3-methyl-3Z7- diazirin-3-yl)ethoxy]-l-piperidinol, and di[2-(methyl-3H-diazirin-3-yl)ethyl] (2S)-2-(6- hydroxy-2,5,7,8-tetramethylchroman-2-ylcarbonyloxy)butanedioate.

[0080] In certain embodiments, the compound of Formula (IA) or (IB) can be selected from:The compounds of the present disclosure are capable of chemically binding to any material or surface comprising C-H, N-H and / or O-H bonds upon exposure to UV light or heat.

[0081] Accordingly, in certain embodiments, the present disclosure provides the use of a compound according to any one of the preceding aspects or embodiments for covalently binding the antioxidant to a material or surface or substrate comprising C-H, N-H, and / or O- H bonds via UV irradiation or heating. In some embodiments, the present disclosure provides a compound according to any one of the preceding aspects or embodiments for use in covalently binding the antioxidant to a material or surface or substrate comprising C-H, N-H, and / or O-H bonds via UV irradiation or heating. In certain embodiments, the substrate is selected from the group comprising monomers, polymers, biomolecules, tissues, tissueengineering constructs, tissue allografts, tissue autografts, pharmaceutical compounds, medical devices, metal surfaces, ceramic surfaces, and combinations thereof.

[0082] The major advantage of such a chemically bindable compound comprising an antioxidant is its versatility in imparting antioxidant property to the bulk, the surface (or both), of any article comprising C-H, N-H and / or O-H bonds without any concerns of the compounds leaching out of the article or device.

[0083] In another embodiment, the present disclosure provides a composition comprising an antioxidant moiety and one or more diazirine moieties covalently linked thereto.

[0084] In certain embodiments, the compositions are selected from compositions for packaging materials, for medical appliances, polymeric compositions, pharmaceutical compositions, and tissue engineering constructs.

[0085] In another aspect, the present disclosure provides a product, material, or an article comprising a substrate having covalently attached thereto a compound of formula (IA), or (IB). The substrate can be selected from the group comprising polymers, biomolecules, tissues, tissue engineering constructs, tissue allografts, tissue autografts, pharmaceutical compounds, medical devices, metal surfaces, ceramic surfaces, and combinations thereof.

[0086] Monomers or polymers which can be employed as substrate may include, but are not limited to, both natural and synthetic materials such as ethylene, lactic acid, polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), polyethylene glycol (PEG), and copolymers thereof.

[0087] In certain embodiments, the compounds of the present disclosure can be reacted to chemical bonds that are present in monomers that do not participate in inducing antioxidant properties into the monomers. These monomers comprising antioxidant moieties can then be polymerized to form new oligomers or polymers. This approach is more effective when the polymerization occurs by condensation polymerization, rather than free radical methods where the free radical could be scavenged by the antioxidant moieties on the monomers, thus terminating the reaction.

[0088] In certain embodiments, the substrate is selected from degradable polymer like polylactic acid (PLA) or poly(lactic-co-glycolic acid) (PLGA) and the antioxidant-diazirine compounds are grafted to these polymers. The release of the antioxidant-diazirine compounds from the polymer particles is governed by degradation of the polymer matrix. The particles can optionally be further infused with a pharmaceutical compound to serve as a vehicle to deliver the injectable particles along with a pharmaceutical compound infused in it to certain internal organs for treatment.

[0089] In certain embodiments, the present disclosure provides ultra-high molecular weight polyethylene (UHMWPE) articles coated with the compound(s) of formula (IA) or (IB) as described herein. The diazirine moieties in the compound(s) of formula (IA) or (IB) are capable of forming covalent bonds with C-H, N-H, and / or O-H groups upon activation by heat or UV irradiation.

[0090] In certain embodiments, the compounds are coated onto UHMWPE particles prior to processing. The resulting coated UHMWPE powder may then be processed using compression molding, ram extrusion, or other melt-processing techniques, wherein the material is compressed and heated above the melting temperature of UHMWPE to achieve both particle fusion and covalent grafting of the compounds of formula (IA) or (IB). The covalent bonding may occur either predominantly at the particle surface or throughout the bulk polymer matrix, depending on the activation temperature of the di azirine moiety relative to the melting point of UHMWPE. In a typical fusion process, the coated UHMWPE powder particles are compressed under an applied pressure of about 10 MPa and heated to a temperature range of 180°C to 200°C, which is above the UHMWPE melting temperature (140°C). The pressure and temperature are maintained for a time period sufficient to allow particle fusion, typically ranging from 30 minutes to several hours, depending on article size and geometry.

[0091] By varying the molecular structure of one or more of the substituents (e.g., Ri, R2, and L), the activation temperature of the diazirine moiety may be adjusted to control the location of grafting. When the diazirine moiety activation temperature is below the UHMWPE melting temperature, activation occurs prior to or during the early stages of fusion, favoring grafting at particle surfaces. When the activation temperature approaches or exceeds the UHMWPE melting temperature, the compounds of formula (IA) or (IB) may diffuse into the molten UHMWPE bulk before activation, enabling grafting within the interior of the polymer matrix.Selection of diazirine moieties with multiple reactive sites (e.g., di-, tri-, or tetra- diazirine groups) allows for controlled crosslinking of UHMWPE chains. Crosslinking may be localized near the surface when diazirine activation occurs below the melt temperature, or distributed throughout the bulk polymer when activation occurs at or above the melt temperature.

[0092] Optionally, post-molding heat treatments may be performed to further promote diffusion of the compounds into the bulk UHMWPE, enabling additional grafting and / or crosslinking while preserving mechanical properties. In some embodiments, the UHMWPE may be heated to a temperature in the range of 250°C-325°C during or after compression molding to facilitate deeper diffusion of the antioxidant-compound having higher activation temperatures.

[0093] The described processes may also provide enhanced fusion quality, as partial thermal degradation of UHMWPE during molding may increase molecular mobility and promote fusion between powder particles or resin granules.

[0094] The resulting UHMWPE articles may exhibit superior oxidative stability due to the presence of covalently bound antioxidant moieties, improved mechanical performance via crosslinking, resistance to free radical degradation caused by sterilization processes, and non- leachable surface properties suitable for long-term implantable medical devices.

[0095] In certain embodiments, the UHMWPE article can be adhered to and inter-locked with a metal or ceramic component or bone cement by applying the antioxidant-diazirine compound containing more than one diazirine which enables the compound to form bonds with the surface of UHMWPE and to the metal or ceramic component or bone cement. The compound can also crosslink to itself forming a glue or adhesive compound that adheres the parts together. In the case of the metal or ceramic component, the article can be surface treated to produce C-H, O-H and / or N-H bonds or a mixture thereof to enable the antioxidant-diazirine compound to form a chemical bond with one or more of these bonds.

[0096] In certain embodiments, UHMWPE parts may be bonded to other UHMWPE parts or metal parts or ceramic parts or bone cement or tissue. Similarly, metal parts, ceramic parts or bone cement may be attached to other metal parts of ceramic parts or bone cement or peri- prosthetic tissue, as desired.

[0097] The present disclosure also provides microparticles, nanoparticles, or macroparticles fabricated from compounds of formula (IA) or (IB) containing multiple diazirine moieties, which are crosslinked by UV or heat activation while dispersed in an immiscible medium during synthesis. Surfactants may be used to control particle size. Alternatively, compounds of formula (IA) or (IB) compounds may be grafted onto degradable polymers such as polylactic acid (PLA) or poly(lactic-co-glycolic acid) (PLGA), where release of the compound is controlled by matrix degradation. The particles can optionally be further infused with a pharmaceutical compound to serve as a vehicle to deliver the injectable particles along with an pharmaceutical compound infused in it to certain internal organs for treatment; additionally, when the particles are comprised of compounds with di-, tri-, or tetra-diazirine functionality and when the particles are exposed to UV radiation only after injection and delivery to the treatment site, this exposure can provide adherence of the particles to the intended tissue, thereby providing local delivery of pharmaceutical compound.

[0098] In certain embodiments, antioxidant-diazirine compounds of the present disclosure or a mixture of antioxidant-diazirine compounds are bonded to polymers used in packaging applications, especially food packaging.

[0099] In certain embodiments, antioxidant-diazirine compounds of the present disclosure or a mixture of antioxidant-diazirine compounds are bonded to polymers used as additives in fuel, gasoline or lubricant applications.

[0100] In certain embodiments, antioxidant-diazirine compounds of the present disclosure or a mixture of antioxidant-diazirine compounds are applied to fibers used in industrial composite formulations, for example in aeronautics, construction, automotive and defense applications. The use of antioxidant-diazirine compounds containing more than one diazirine group can be used to adhere the fibers onto the polymer matrix of the composite. In the case of some fibers, such as carbon or glass fibers, the fiber may be pretreated to include C-H, O-H and / or N-H bonds or a mixture thereof, on their surface to facilitate adherence.

[0101] In certain embodiments, biomolecules which can be employed as substrate include, but are not limited to, proteins, peptides, polysaccharides, nucleic acids, and combinations thereof that may facilitate specific binding or interaction with antioxidants through chemicalor electrostatic affinity. Biological tissues such as skin, bone, cartilage, or vascular tissue whether used in their native form or as decellularized matrices can be modified or treated to incorporate antioxidant agents to mitigate oxidative stress during grafting or implantation.

[0102] In certain embodiments, tissue engineering constructs, whether synthetic, hybrid, or derived from extracellular matrices, provide a versatile platform for antioxidant integration to enhance cellular viability and regenerative outcomes. Tissue allografts and autografts, used in transplantation procedures, may be treated with antioxidants-diazirine compounds to reduce ischemia-reperfusion injury, enhance healing, and prolong graft viability.

[0103] In certain embodiments, pharmaceutical compounds may be functionalized with antioxidant-diazirine compounds to improve drug stability, bioavailability, or therapeutic efficacy, particularly in oxidative environments. Medical devices, including stents, catheters, implants, and prostheses, can be coated or embedded with antioxidants to reduce inflammation, prevent biofouling, or enhance biocompatibility.

[0104] In certain embodiments, the present disclosure provides coating and grafting antioxidant-diazirine compounds onto the wound surfaces of band-aids and other medical bandages.

[0105] In certain embodiments, the antioxidant-diazirine compounds can be bound to molecules and polymers used in cosmetic formulations, such as but not limited to skin creams, shampoo, hair spray, nail polish and others, to confer antioxidant properties to them. The polymers may include natural polymers used in cosmetic formulations such as collagen, elastic, keratin, chitosan, starch and other polysaccharides. Other examples of polymers are xanthan gum, guar gum, carrageenan, alginates, pectin, gelatin, agar, acacia, konjac powder and cellulose derivatives. Silicones are also common polymer used in cosmetic applications. The antioxidant-diazirine compounds may be incorporated by blending, coating, or grafting processes, followed by UV or heat activation to covalently attach to functional groups on the polymers.

[0106] In certain embodiments, the substrates include medical devices selected from heart valves, shunts, pacemakers, ocular devices, dental implants, oral and maxillofacial implants, implants used in trauma applications and hydrogels used to treat aneurysms and fill defects. Ineach case, the antioxidant-diazirine compound has the benefit of being non-leachable after activation while conferring antioxidant properties to the implant. The benefit can be to mitigate inflammation and also to prevent degradation from free radicals in situ or free radicals induced by sterilization by gamma or other ionizing radiation processes.

[0107] In certain embodiments, metal surfaces (e.g., titanium, stainless steel, cobalt-chrome alloys) and ceramic surfaces (e.g., hydroxyapatite, alumina, zirconia) used in implants or medical instruments may be functionalized via chemical bonding, plasma treatment, or surface modification techniques to allow for antioxidant attachment, thereby improving their biological performance.

[0108] These substrates may be used alone or in combination, allowing for tailored and synergistic applications depending on the intended medical, pharmaceutical, or industrial use of the antioxidant-modified product.

[0109] In certain embodiments, the antioxidant diazirine compounds of different compositions are mixed together when used to bind to small molecule compounds, macromolecules and surfaces of articles. This results in enhancement in the antioxidant properties rendered by the mixture of the antioxidant-diazirine compound compared to applying just one single antioxidant-compound.

[0110] In certain embodiments, the present disclosure provides coating and grafting antioxidant-diazirine compounds onto the surfaces of medical devices intended for long-term implantation. Example devices include, but are not limited to, polyether ether ketone (PEEK) spinal implants, polypropylene or polyester hernia meshes, polyester coverings of metal mesh stents and silicone airway stents. It is also possible to graft antioxidant-diazirine compounds within the bulk of an implanted polymeric material. For example, blending antioxidant- diazirine compounds with polypropylene or polyester resin and subsequently molding or thermoforming the hernia mesh device would graft the antioxidant-diazirine compound to the polymer molecules throughout the bulk of the device, provided the diazirine activation temperature is equal to or less than the molding temperature. A similar approach can be used for grafting antioxidant-diazirine compounds throughout the bulk of a silicone airway stent.The above surface and bulk descriptions both address needs for non-leachable antioxidants that prevent oxidative degradation of implanted polymeric devices.

[0111] In certain embodiments, the antioxidant-diazirine compounds can be grafted to silicone polymer, which finds application in finger prostheses, breast implants and other implant devices. When antioxidant-diazirine compounds contain more than one diazirine, the silicones can be crosslinked depending on the amount of antioxidant-diazirine dispersed in the silicone.

[0112] In certain embodiments, the antioxidant-diazirine compound may be dispersed in tissue engineering constructs. In certain embodiments, the tissue engineering constructs are scaffolds that may comprise natural or synthetic biomaterials such as collagen, glycosaminoglycans or synthetic polymers in hydrogel or fiber. The compound (antioxidant- diazirine compound) may be applied before or after scaffold fabrication via blending, dipcoating, or spray-coating, and subsequently activated by UV or heat to covalently bond to C- H, N-H, and / or O-H bonds on the biomaterial to confer antioxidant properties to them. A few selected examples of tissue engineering constructs that are not meant to be limiting are constructs used to fill bone defects, skin, cartilage defects, meniscus tears, ligament tears, repair of detached soft tissue such as rotator cuff, muscles, tendons or other musculoskeletal tissue.

[0113] In certain embodiments, antioxidant-diazirine compounds containing more than one diazirine crosslink with synthetic polymers, biomolecules, or biomacromolecules. The diazirines of one antioxidant-diazirine compound containing more than one diazirine will have the ability to chemically bond (crosslink) to other antioxidant-diazirine molecules or the same of different composition so that the compound will serve as a glue or adhesive to bond external surfaces or internal surfaces of articles together.

[0114] In certain embodiments, the compounds of the present disclosure contain the same antioxidant moieties (AO) but different molecular compositions of Ri and R2, wherein at least one of the groups has a different molecular composition, it is likely to activate the diazirine at different temperatures thereby generating and thereby binding to the surrounding molecule or macromolecule at different temperatures and at different time intervals as the antioxidant- diazirine compound is being heated, which can be advantageous if the compound is being usedto chemically bind to a mixture of different synthetic polymers or biomacromolecules or small molecules.

[0115] In yet another aspect, the present disclosure provides a method for bonding a compound of formula (IA), or (IB) to a substrate comprising:• applying a compound as claimed in claims 1 to 7 to a substrate comprising C-H, N-H, and / or O-H functional groups; and• activating the compound by UV radiation or heat to form covalent bond(s) with the substrate.

[0116] In certain embodiments of the preceding aspect, the substrate is the same as defined in the preceding embodiments.

[0117] The compound of Formula (IA) or (IB), when brought into contact with the substrate, may be applied through techniques such as dip coating, spray coating, spin coating, brushing, inkjet printing, microcontact printing, or drop casting, depending on the physical properties of both the compound and the substrate.

[0118] Following application, the treated substrate is subjected to an activation step wherein the compound is exposed to ultraviolet (UV) radiation and / or thermal energy. The activation serves to initiate a photochemical or thermally driven reaction, such as the generation of reactive intermediates including radicals or nitrenes from the compound of Formula (IA) or (IB). These intermediates subsequently undergo insertion or coupling reactions with the C-H, N-H, or O-H groups on the substrate surface, resulting in the formation of stable covalent bonds.

[0119] The choice of activation conditions such as the specific UV wavelength, exposure time, or heating temperature can be optimized based on the reactivity of the specific compound and the substrate material.

[0120] This method provides a robust and durable means for anchoring antioxidant compounds onto a wide range of substrates, thereby enabling long-lasting functionalization for biomedical, pharmaceutical, or industrial applications. The covalent nature of the bondingensures resistance to desorption or leaching under physiological or environmental conditions, thereby enhancing the stability, efficacy, and longevity of the antioxidant-functionalized substrate.

[0121] In certain embodiments, when the substrate is a tissue allograft, or autograft, the antioxidant-diazirine compound is applied to tissue allografts or autografts prior to placement at the target site and then UV treated, followed by implantation. If adherence to tissue is desired, the antioxidant-diazirine compound containing more than one-diazirine can be used and the UV treatment conducted after placement of the allograft or autograft at the target site in situ.

[0122] In certain embodiments, the present disclosure provides the product, material, or article obtainable by the method of the preceding embodiments.

[0123] In certain embodiment, the product, material, or article obtainable by the method of the preceding embodiment comprises a substrate as defined in the preceding embodiments.

[0124] In certain embodiments, the substrate in the product, material, or article, is a monomer or polymer selected from ethylene, lactic acid, polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), polyethylene glycol (PEG), and copolymers thereof, and ultra-high molecular weight polyethylene (UHMWPE) powder particles employed in packaging applications, as additives in fuels, as lubricants etc.; fibers used in industrial composite formulations, for example in aeronautics, construction, automotive and defense applications; biomolecules selected from proteins, peptides, polysaccharides, and nucleic acids; tissue engineering constructs selected from tissue allografts and autografts; pharmaceutical products such as medical devices, including stents, catheters, implants, and prostheses, band-aids and other medical bandages, cosmetic formulations.

[0125] In certain embodiments, the product, material, or article is selected from the group consisting of: a polymeric composition comprising a compound a compound of formula (IA) or (IB) blended with or grafted to a polymer selected from polylactic acid (PLA), poly(lactic-co-glycolic acid)(PLGA), polyethylene, polypropylene, polyester, polyether ether ketone (PEEK), silicone, and any combination thereof; a particulate composition comprising microparticles or nanoparticles of the compound of formula (IA) or (IB), wherein the particles are formed by dispersing the compound in an immiscible medium and crosslinking the compound within each particle by UV or heat activation, optionally in the presence of a surfactant to control particle size; a pharmaceutical composition comprising microparticles or nanoparticles of the compound of formula (IA) or (IB), for local or systemic drug delivery, wherein the particles adhere to tissue upon UV activation at a target site; a medical device comprising a surface coating of the compound of formula (IA) or (IB), wherein the coating is applied to the device and activated by UV or heat to chemically bind the compound to the surface, thereby providing non-leachable antioxidant properties to the device; an article comprising ultra-high molecular weight polyethylene (UHMWPE) having the compound of formula (IA) or (IB) grafted onto or into the UHMWPE; wherein the grafting is achieved by coating UHMWPE particles with the compound and subjecting the coated particles to compression and heating to cause particle fusion and chemical bonding of the compound to the UHMWPE; an article comprising ultra-high molecular weight polyethylene (UHMWPE) bonded to a second material via the compound of formula (IA) or (IB), wherein the compound chemically bonds to the UHMWPE and the second material, and the second material is selected from metal, ceramic, bone cement, or tissue; a tissue engineering material comprising a scaffold of biomolecules or synthetic polymers, wherein the scaffold has the compound of formula (IA) or (IB)chemically bonded or crosslinked to the biomolecules or polymers, optionally by UV or heat activation; a packaging or industrial material comprising a polymer bound to the compound of formula (IA) or (IB), wherein the material is used for food packaging, fuel additives, lubricants, aeronautical composites, construction materials, automotive parts, or defense applications; and a polymerizable monomer comprising a compound of formula (IA) or (IB)covalently bonded to a polymerizable moiety, wherein the monomer is polymerizable to form an oligomer or polymer comprising the compound.

[0126] In still another aspect, the present disclosure provides a process for preparing a compound, the process comprising:(a) providing an antioxidant moiety; and(b) covalently attaching one or more diazirine moieties to the antioxidant moiety.

[0127] In certain embodiments, the process comprises: providing a diazirine moiety having at least one reactive functional group selected from the group comprising carboxylic acid, halide, acyl halide, ester, amine, amide, isocyanate, hydroxyl and N-hydroxysuccinimide ester; and reacting the diazirine moiety with an antioxidant moiety containing at least one functional group selected from the group comprising carboxylic acid, halide, acyl halide, ester, amine, isocyanate, and hydroxyl under conditions effective to form a covalent bond between the diazirine moiety and the antioxidant moiety.

[0128] In certain embodiments, the diazirine moiety, the antioxidant moiety, and the compound prepared in this embodiment are the same as described in the preceding embodiments.

[0129] The selection of reactive functional groups from both components allows for multiple possible coupling strategies, including but not limited to esterification, amidation, urethane (carbamate) formation, and nucleophilic substitution, depending on the pairing of functional groups. For example, a diazirine bearing a carboxylic acid group may react with a phenol bearing a hydroxyl or amine group to form an ester or amide linkage, respectively. Similarly, an isocyanate-functionalized diazirine may react with a phenol or amine-functionalized phenol derivative to form a urethane or urea linkage.

[0130] The reaction may be facilitated using standard coupling reagents or catalysts commonly employed in organic synthesis, such as carbodiimides (e.g., l-Ethyl-3 -(3 -dimethyl aminopropyl) carbodiimide, N,N'-Dicyclohexyl carbodiimide), acid chlorides, or base / acid catalysis, and may be carried out in a suitable solvent system such as dimethylformamide (DMF), dichloromethane (DCM), tetrahydrofuran (THF), or ethanol, depending on the solubility and stability of the reactants. Reaction temperature may vary from ambient to elevated temperatures (e.g., 25°C to 80°C) to ensure sufficient conversion while maintaining the integrity of the diazirine ring structure, which is sensitive to excessive heat or UV prior to intended activation.

[0131] In certain embodiments, the steps to synthesize antioxidant-diazirine compounds include first combining the appropriate antioxidant and diazirine building blocks in a common solvent, with the appropriate stoichiometry. Often the solvent is degassed, allowing for oxygen removal. Then, while the reactant mixture is stirred and covered with a blanket of argon (Ar) or a stream of nitrogen (N2), chemical reaction between the antioxidant and diazirine building blocks is allowed to proceed. Next steps include workup or product stabilization, extraction and purification followed by characterization via nuclear magnetic resonance (NMR), liquid chromatography (LC), differential scanning calorimeter (DSC), mass spectrometer, optical absorbance spectroscopy or Fourier transform infrared spectroscopy (FTIR).

[0132] In accordance with the embodiments described herein, the compounds of the present disclosure may be synthesized using standard organic synthesis techniques or through specific processes as described in the present disclosure. Suitable reaction conditions (e.g., reagents, solvents, temperatures, catalysts, and reaction times) are well-known in the art and can be selected by a person skilled in the art without undue experimentation. The following table provides representative examples of starting materials and corresponding end products, which may be prepared using the synthetic procedures, reaction conditions, and intermediates disclosed herein.

[0133] The following example is provided to illustrate certain aspects of the disclosed invention and is not intended to limit the scope thereof. Unless explicitly stated otherwise, this example is prophetic in nature and is based on theoretical models or anticipated results rather than actual experimental data.

[0134] Prophetic Example: Synthesis of di[2-(methyl-3H-diazirin-3-yl)ethyl] (2S)-2-(6- hydroxy-2,5,7,8-tetramethylchroman-2-ylcarbonyloxy)butanedioate:

[0135] The synthesis begins by protecting the hydroxyl group of (2S)-2-hydroxybutanedioic acid (L-malic acid) to prevent undesired side reactions such as intramolecular lactonization.

[0136] In a dry round-bottom flask under an argon atmosphere, dissolve L-malic acid in anhydrous dichloromethane. To this solution, add imidazole and tert-butyldimethylsilyl chloride (TBSC1), and stir the reaction mixture at room temperature overnight to selectively form the TBS ether at the secondary alcohol. Upon completion, quench the reaction with water,extract with dichloromethane, then dry and concentrate the organic phase to afford the protected intermediate, (2S)-2-(tert-butyldimethylsilyloxy)butanedioic acid.

[0137] Esterify the TBS-protected malic acid with 2-(3-methyl-3H-diazirin-3-yl)ethanol.

[0138] Dissolve the protected diacid in dry dichloromethane or N,N-dimethylformamide, and add a slight excess (2.2 equivalents) of 2-(3-methyl-3H-diazirin-3-yl)ethanol. Cool the reaction mixture to 0 °C, and then introduce the l-ethyl-3-(3- dimethylaminopropyl)carbodiimide hydrochloride (EDC HQ) and catalytic 4- (dimethylamino)pyridine (DMAP) to mediate ester formation. After stirring at 0 °C for 30 minutes and then at room temperature for several hours, quench the reaction with saturated aqueous ammonium chloride, extract with dichloromethane, and then purify the product by silica gel chromatography. This yields the intermediate di[2-(3-methyl-3H-diazirin-3-yl)ethyl] (2S)-2-(tert-butyldimethylsilyloxy)butanedioate.

[0139] To expose the secondary alcohol, remove the TBS group by treatment with tetrabutylammonium fluoride (TBAF) in tetrahydrofuran at 0 °C to room temperature for 1-2 hours. Work up the reaction mixture to give the free alcohol intermediate, di[2-(3-methyl-3H- diazirin-3-yl)ethyl] (2S)-2-hydroxybutanedioate.

[0140] In the final step, couple this diester precursor to Trolox, formally known as (±)-6- hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid.

[0141] Dissolve the alcohol intermediate in dry dichloromethane and treat with Trolox, EDC HC1, and catalytic DMAP under ambient conditions. In this esterification, the carboxylic acid of Trolox selectively reacts with the secondary alcohol of malic acid, while the phenolic hydroxyl group remains unaltered. Stir the reaction overnight, then quench, extract, and purify by column chromatography to yield the final product, di[2-(methyl-3H-diazirin-3-yl)ethyl] (2S)-2-(6-hydroxy-2,5,7,8-tetramethylchroman-2-ylcarbonyloxy)butanedioate, featuring two photoreactive diazirine units and a covalently linked Trolox moiety that retains its antioxidant phenol functionality.

[0142] In an alternative protocol, the hydroxyl group of (2S)-2-hydroxybutanedioic acid (L- malic acid) is not unprotected, and careful control of reagent addition and stoichiometry is used to minimize side reactions such as intramolecular lactonization. First, dissolve the L-malic acid in anhydrous di chloromethane under an argon atmosphere, and cool the solution to 0 °C. To activate both carboxylic acid groups, add l-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC HC1) and a catalytic amount of 4-(dimethylamino)pyridine (DMAP). Immediately afterward, add 2 equivalents of 2-(3-methyl-3H-diazirin-3-yl)ethanol dropwise tofavor esterification of the carboxylic acid groups before the free hydroxyl group on the malic acid backbone can participate in side reactions. Stir the reaction at 0 °C for 30 minutes and then allow to warm to room temperature and continue stirring for several hours. Confirm the completion by thin-layer chromatography or LC-MS. Quench the reaction mixture with saturated ammonium chloride, extract with dichloromethane, and purify the product by silica gel chromatography to yield di[2-(3-methyl-3H-diazirin-3-yl)ethyl] (2S)-2- hydroxybutanedioate.

[0143] Dissolve this intermediate, bearing a free secondary alcohol at the 2-position in anhydrous dichloromethane and couple with (±)-6-hydroxy-2,5,7,8-tetramethylchroman-2- carboxylic acid (Trolox). Add EDC HQ and catalytic DMAP to mediate ester formation between the carboxylic acid of Trolox and the hydroxyl group of the malic acid derivative. The phenolic hydroxyl group on Trolox remains unreactive under these coupling conditions. Stir the reaction mixture at room temperature overnight, then quench, extract, and purify by column chromatography. The final product, di[2-(3-methyl-3H-diazirin-3-yl)ethyl] (2S)-2-(6-hydroxy- 2,5,7,8-tetramethylchroman-2-ylcarbonyloxy)butanedioate, features two diazirine- functionalized esters at the malic acid carboxylic acid groups and one ester linkage between the malic acid hydroxyl and the Trolox carboxylic acid. The antioxidant activity of Trolox is preserved via the intact 6-hydroxyphenyl group.

[0144] The resulting diazirine-phenol compound retains the photoreactive diazirine group, which can subsequently be activated via UV irradiation to form highly reactive carbene species that can insert into C-H, N-H, and / or O-H bonds on a substrate surface, enabling covalent surface modification.

[0145] In certain embodiments, the present disclosure provides a method for the synthesis of macroparticles, microparticles and nanoparticles of the antioxidant-diazirine compound containing more than one diazirine in each compound. Such particles can be synthesized by UV treatment of beads of the antioxidant-diazirine compounds dispersed in a medium that is immiscible in the compound. Surfactants can be added to decrease the size of the beads to the microscale or nanoscale during dispersion in the immiscible medium, such as non-solvent for the antioxidant-diazirine compound, prior to UV treatment to crosslink the antioxidant- diazirine compound within each particle, microparticle, nanoparticle or a mixture thereof.

[0146] In certain embodiments, the compounds of Formula (IA) or (IB) may be prepared by methods analogous to those described in prophetic examples. The preparation of other compounds within the scope of the present invention can be accomplished using appropriate starting materials, reagents, and reaction conditions known to those skilled in the art, without undue experimentation

[0147] The present disclosure is further described with reference to the following examples, which are only illustrative in nature and should not be construed to limit the scope of the present disclosure in any manner.

[0148] EXAMPLES:Example 1: Synthesis and characterization of 2,6-di-tert-butyl-4-{[({4-[(trifluoromethyl)-3H- diazirin-3-yl]phenyl}methyl)amino]methyl (phenol (DTBP-diazirine).Step 1:167 mg of 4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamine hydrochloride was suspended in 7 mL of anhydrous acetonitrile under an argon atmosphere and stirred at room temperature. After cooling the mixture to 0 °C, 97.6 μL of triethylamine was added dropwise to liberate the free amine. The mixture was stirred briefly, and 0.5 mL of diethyl ether was added to precipitate the tri ethylamine hydrochloride salt. Following centrifugation, the supernatant (~5.5 mL) was recovered and used immediately in the second step.Step 2:In the alkylation step, the amine-containing supernatant was transferred to a dry 20 mL roundbottom flask under argon. To this solution, 172 mg of potassium carbonate and 223 mg of 4- (bromomethyl)-2,6-di-tert-butylphenol were added, along with an additional 6 mL of acetonitrile, bringing the total volume to 11.5 mL. The reaction mixture was stirred at room temperature under argon and protected from light for 24 hours. Upon completion, the mixture was filtered to remove insoluble solids and diluted with 15 mL of ethyl acetate. The organic phase was sequentially washed with saturated sodium bicarbonate, deionized water, and brine. After drying over sodium sulfate, the solution was filtered and concentrated under reduced pressure to yield a pale-yellow material.>HNMR (399.78 MHz, chloroform-d) 5 7.44 (d, 1.00H), 7.16 (s, 2.03H), 7.11 (d, 1.10H), 5.07 (s, 0.99H), 4.11 (m, 0.58H), 3.49 (d, 3.00H),1.41 (m, 19.77H);13C NMR (100.52 MHz, chloroform-d) 152.60, 142.63, 135.54, 129.96, 129.05, 127.33, 126.29, 126.19, 125.06, 123.56, 120.82, 60.40, 58.30, 57.36, 34.27, 30.36; (19F NMR 376.17 MHz, chloroform-d) -65.127, - 65.154, -65.181. Minor peaks attributable to solvent or other impurities were not assigned.Analysis by NMR confirmed the formation of the desired product. In the1H NMR spectrum, aromatic resonances were observed at 7.44 ppm (d, 1.00H), 7.16 ppm (s, 2.03H), and 7.11 ppm (d, 1.1 OH), corresponding to the expected aromatic protons distributed between the diazirine- substituted phenyl ring and the hindered phenol ring. A singlet at 5.07 ppm integrating to approximately 1H is assigned to the N-H proton of the secondary amine bridge formed by SN2 coupling of the bromo hindered phenol and the diazirine-substituted aryl amine, confirming that the two aromatic moi eties were successfully joined. Two benzylic CH2 groups appear in distinct environments: a doublet at 3.49 ppm (3. OOH), corresponding to the CH> adjacent to the hindered phenol, and a multiplet centered at 4.11 ppm (0.58H), likely associated with the CH2 next to the diazirine-substituted aryl ring. The disparity in integration and multiplicity reflects conformational asymmetry and potential diastereotopic splitting. A broad multiplet at 1.41 ppm integrating to 19.77H is attributed to two tert-butyl groups, whose characteristic singlet is broadened due to electronic effects near the polar secondary amine and phenol functionalities.The13C NMR spectrum showed resonances between 152.6 and 120.8 ppm, assigned to aromatic and quaternary carbon atoms. Signals at 60.4, 58.3, and 57.3 ppm are consistent with the benzylic CH2 groups and the CFs-substituted carbon adjacent to the diazirine moiety. Peaksat 34.3 and 30.3 ppm represent the quaternary and methyl carbons of the tert-butyl substituents. The19F NMR spectrum displayed a distinctive set of three closely spaced peaks at -65.127, - 65.154, and -65.181 ppm. This well-defined triplet-like splitting pattern is characteristic of a trifluoromethyl group attached to a rigid diazirine ring and is attributed to long-range coupling interactions or conformational restriction. The preservation of this CFs splitting pattern strongly suggests that the diazirine ring remained intact through the reaction and was not activated or decomposed.Altogether, the1H,13C, and19F NMR data are consistent with the proposed structure of DTBP- diazirine. The chemical shifts, multiplicities, and integration values reflect the presence of key structural features including the diazirine-functionalized aryl group, the hindered phenol core, and the secondary amine linker. The singlet corresponding to the N-H proton and the defined fluorine splitting provide evidence that the coupling reaction succeeded and that the diazirine moiety was preserved. Minor peaks attributable to residual solvent or trace impurities were not included in the analysis. These spectral data confirm both the structure and the integrity of the final compound.Following synthesis, specimens were prepared for oxidation induction time (OIT) studies using Differential Scanning Calorimetry (DSC). For each formulation, 10 mg of either the DTBP- diazirine compound or a commercially available tocopherol blend, known for its antioxidant properties, was dissolved in 6 mL of methanol. To each of these solutions, 2 g of UHMWPE powder (GUR1020, sourced from Celanese) was added and the mixtures were rotated for 30 minutes to ensure thorough contact between the antioxidant solution and the powder particles. The treated powders were poured into 100 mm diameter glass Petri dishes and left to dry overnight, allowing the methanol to fully evaporate. Based on this formulation approach, both the DTBP-diazirine and tocopherol -treated UHMWPE mixtures contained 0.5 weight percent antioxidant. Although the resulting powder appeared dry and free-flowing, the samples were subjected to additional vacuum drying for one hour to ensure complete solvent removal.The dried powders were subsequently heat- and compression-molded into discs measuring 4 mm in diameter and 3 mm in thickness using a molding temperature of 180 °C for 30 minutes. For oxidation induction time (OIT) measurements, small shards were cut from the molded discs and placed in open aluminum DSC pans without lids. These pans were positioned on the sample platform of a TA Instruments Q20 DSC system.For OIT studies, a DSC instrument is used to measure the exothermic heat released by a polymer sample during oxidative degradation. In a typical procedure, the sample is first held under an inert atmosphere (such as nitrogen) to stabilize the temperature profile, then exposed to an oxygen-rich environment. The oxidation induction time is defined as the time between the onset of oxygen exposure and the first significant rise in heat flow, which marks the beginning of the oxidative reaction within the material.The OIT result for the molded discs containing DTBP-diazirine and GUR1020 UHMWPE was 47.7 minutes. This value was intermediate between the OIT of 27.2 minutes for molded discs made from GUR1020E (Celanese UHMWPE pre-blended with 0.1 wt% tocopherols) and 81.6 minutes for the tocopherol blend at 0.5 wt%. For comparison, the OIT of GUR1020 UHMWPE powder without any antioxidant was measured between 30 seconds and 1.3 minutes, over several specimens, confirming the significant antioxidant effect conferred by both the DTBP- diazirine and tocopherol treatments.Example 2: Synthesis and characterization of 6-Hydroxy-2,5,7,8-tetramethylchroman-2- carboxylic acid 2-(3-methyl-3H-diazirin-3-yl)ethyl ester (Trolox-diazirine)A 50 mL round-bottom flask equipped with a magnetic stir bar was charged with 125 mg of 6- hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox) and 15 mL of anhydrous dichloromethane (DCM), and the mixture was stirred under an argon atmosphere. To this solution, 37 μL of 2-(3-methyl-3H-diazirin-3-yl)ethan-l-ol and 9.2 mg of 4- (dimethylamino)pyridine (DMAP) were added sequentially. The flask was then cooled in an ice bath, and 118 mg of l-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC HC1) was added. The mixture was stirred for 10 minutes at 0 °C before allowing the reaction to warm to room temperature. Stirring was continued under argon for 20 hours withprotection from light. Upon reaction completion, 10 mL of deionized water was added to quench the mixture. The contents were transferred to a separatory funnel, and the organic (DCM) layer was separated. The organic phase was then washed sequentially with 10 mL of saturated sodium bicarbonate solution followed by 10 mL of brine. The resulting organic layer was dried over 2 g of anhydrous sodium sulfate for 10 minutes, decanted, and concentrated under reduced pressure to afford the crude Trolox-diazirine ester as a pale yellow material.Following synthesis, samples were prepared for oxidation induction time (OIT) analysis using Differential Scanning Calorimetry (DSC). For each formulation, 10 mg of either the Trolox- diazirine compound or unmodified Trolox was dissolved in 6 mL of methanol. To each solution, 2 g of ultra-high molecular weight polyethylene (UHMWPE) powder (GUR1020, sourced from Celanese) was added. The mixtures were rotated for 30 minutes to ensure uniform distribution of the antioxidant across the polymer powder. The treated powders were then poured into 100 mm diameter glass Petri dishes and allowed to dry overnight to ensure complete evaporation of the methanol solvent. Based on the formulation, both Trolox-diazirine and Trolox were present at a concentration of 0.5 wt% relative to the UHMWPE powder. Although the dried powders appeared free-flowing and non-tacky, they were subjected to further vacuum drying for one hour to eliminate any residual solvent.The fully dried powders were subsequently compression-molded into discs measuring 4 mm in diameter and 3 mm in thickness by heating at 180 °C for 30 minutes. For OIT testing, small shards (several milligrams) were cut from the molded discs and placed in open aluminum DSC pans without lids. OIT measurements were performed using a TA Instruments QA20 DSC instrument.The OIT for the molded discs containing Trolox-diazirine and GUR1020 UHMWPE was determined to be 19.7 minutes. This was comparable to the OIT of 19.1 minutes for molded discs containing Trolox with GUR1020 UHMWPE. In contrast, the UHMWPE powder (GUR1020) without any antioxidant exhibited a markedly lower OIT of between 30 seconds and 1.3 minutes, as measured over several specimens. These results confirm the antioxidant activity of both Trolox-diazirine and Trolox when incorporated into UHMWPE formulations.

Claims

What is claimed is:

1. A compound comprising an antioxidant moiety and one or more diazirine moieties covalently linked thereto.

2. The compound as claimed in claim 1, wherein the compound is of formula (IA), or (IB):wherein:A is an antioxidant moiety;Ri, at each occurrence, is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkoxy, alkoxy alkyl, alkoxy alkynyl, arylalkyl, or perfluorinated or partly fluorinated alkyl, aryl, and arylalkyl group;R2may be absent, or selected from alkylene, arylene, arylalkylene and heteroarylene; or Ri and R2 taken together form a cycloalkyl, or a heterocycloalkyl group;L is a bond or linker selected from an amide, alkylene, ether, ketone, ester, sulfide, sulfone, amino, triazolyl, isoxazolyl optionally substituted with alkyl, and a combination thereof; and z is 1, 2, 3 or 4.

3. The compound as claimed in claim 1, wherein Ri at each occurrence is independently selected from hydrogen, C1-C12 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C12 aryl, Ce - C12 aryl Ci - C12 alkyl, Ci-6 alkoxy, C1.3 alkoxy-Ci.3 alkyl, C1.2 alkoxy-C2-6 alkynyl, C2-C12 perfluoroalkyl, Ci - C12 alkyl or Ce - C12 aryl where portions of hydrogen on alkyl are replaced with fluorine, and Ce - C12 aryl Ci - C12 alkyl, where portions of hydrogen on alkyl are replaced with fluorine; and, R2 at each occurrence is independently selected from Ci-Ce alkylene, Ce- C10 arylene, Ce-Cio aryl-Ci-Ce alkylene, or 5-10 membered heteroarylene having N, or O or both heteroatoms; or Ri and R2 together form a C3-C12 cycloalkyl, or a heterocycloalkyl group having N or O as the heteroatom.

4. The compound as claimed in claim 1, wherein Ri, at each occurrence, is independently selected from hydrogen, methyl, trifluoromethyl, but-3-yn-l-yl and prop-2-yn-l-yloxy; and R2 at each occurrence is independently selected from methyl, ethyl, propyl, benzyl and phenyl; orRi and R2 together form cyclohexyl, cyclobutyl, cyclopentyl, azepanyl, pyrrolidinyl or azetidinyl ring.

5. The compound as claimed in claim 1, wherein the antioxidant moiety is derived from compounds selected from a group comprising tocopherol or its derivative, ascorbic acid or its derivative, beta-carotene, carotenoid, flavonoid, hindered phenol, and polyphenol.

6. The compound as claimed in claim 5, wherein tocopherol or tocopherol derivative is selected from 6-hydroxy-2,5,7,8-tetramethyl-2-chromancarboxylic acid, 3-(6-hydroxy-2, 5,7,8- tetramethyl-2-chromanyl)propionic acid, 6-hydroxy-2,5,7,8-tetramethyl-2-chroman acyl chloride, 3-(6-hydroxy-2,5,7,8-tetramethyl-2-chromanyl)propionyl chloride; hindered phenols are selected from 4-(bromomethyl)-2,6-di- / c77-butylphenol, 4-bromophenol, 4-bromobenzene-1.2-diol, 5-bromobenzene-l,2,3-triol, 2,4-dibromophenol, 4,5-dibromobenzene-l,2-diol, 2,4,6-tribromophenol, 2,4,6-tribromo-5-pentylbenzene-l,3-diol, 4-amino-2,6-di- / c77- butylphenol, 4-methylamino-2,6-di- / c77-butylphenol, 4-aminophenol, 2,4-diaminophenol, 2,6- diaminophenol, 2,4,6-triaminophenol, 4-aminobenzene-l,2-diol, 4-aminobenzene- 1,3 -diol, 5- aminobenzene- 1,3 -diol, 5-aminobenzene-l,2,3-triol, 5-ethylaminobenzene-l,2,3-triol, 4- hydroxybenzamide, 2-hydroxybenzamide, 3,5-dihydroxybenzamide, and 3,4,5- trihydroxybenzamide.

7. The compound as claimed in claim 1, wherein one or more diazirine moi eties present in the compound are derived from compounds selected from: 3-(4-(bromomethyl)phenyl)-3-(trifluoromethyl)-3H-diazirine;3-(4-(bromoethyl)phenyl)-3-(trifluoromethyl)-3H-diazirine; 3-(4-bromophenyl)-3-(trifluoromethyl)-3H-diazirine;6-bromo- 1 ,2-diazaspiro[2.5 ] oct- 1 -ene;3-(2-bromoethyl)-3-methyl-3H-diazirine;3-(2-bromomethyl)-3-methyl-3H-diazirine;4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzylamine hydrochloride; (4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)methanamine hydrochloride;1.2-diazaspiro[2.5]oct-l-en-5-amine hydrochloride;1.2-diazaspiro[2.3]hex-l-en-5-amine hydrochloride, 2-(3 -(but-3 -yn- 1 -yl)-3H-diazirin-3 -yl)ethan- 1 -amine;(3-methyl-3H-diazirin-3-yl)methanamine hydrochloride;2-(3-methyl-3H-diazirin-3-yl)ethan-l -amine hydrochloride;1.2.6-triazaspiro[2.6]non-l-ene hydrochloride;1.2.6-triazaspiro[2.5]oct-l-ene hydrochloride;1.2.5-triazaspiro[2.4]hept- 1 -ene hydrochloride;1.2.5-triazaspiro[2.3]hex-l-ene hydrochloride;(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)methanol;2-(3 -(but-3 -yn- 1 -yl)-3H-diazirin-3 -yl)ethan- 1 -ol ;2-(3-((prop-2-yn-l-yloxy)methyl)-3H-diazirin-3-yl)ethan-l-ol;2-(3-methyl-3H-diazirin-3-yl)ethan-l-ol;1.2-diazaspiro[2.4]hept-l-ene-5-carboxylic acid;1.2-diazaspiro[2.3]hex-l-ene-5-carboxylic acid;3-(3H-diazirin-3-yl)propanoic acid;3-(3-methyl-3H-diazirin-3-yl)propionyl chloride;4-(3H-diazirin-3-yl)butanoic acid;2.5-dioxopyrrolidin-l-yl 3-(3-methyl-3H-diazirin-3-yl)propanoate;2.5-dioxopyrrolidin-l-yl-3-((2-(3-(3-methyl-3H-diazirin-3-yl)propanamido)ethyl) disulfaneyl)propanoate; and di[2-(3-methyl-3H-diazirin-3-yl)ethyl] (2S)-2-hydroxybutanedioate.

8. The compound as claimed in claim 1, wherein the compound is selected from:2.6-di-tert-butyl-4-{[({4-[(trifluoromethyl)-3H-diazirin-3-yl]phenyl}methyl)amino]methyl} phenol;2-(3-Methyl-3 / / -diazirin-3-yl)ethyl-6-hydroxy-2,5,7,8-tetramethyl-2-chromancarboxylate;2.6-Di- / c / 7-butyl-4-[([ / 9-[3-(trifluorornethyl)-3 / / -diazirin-3-yl]benzyl }amino]phenol;2.6-Di- / cv7-butyl-4-[([ / 9-[3-(trifluorornethyl)-3 / / -diazirin-3-yl]benzyl }methyl)amino]phenol;2.6-Di- / c77-butyl-4-[ [2-(3-methyl-3 / / -diazirin-3-yl)ethoxy]methyl [phenol;2-(3-Methyl-3J / -diazirin-3-yl)ethyl-3-(6-hydroxy-2,5,7,8-tetramethyl-2-chromanyl) propionate; l-Hydroxy-2,2,6,6-tetramethyl-4-piperidyl 3-(3-methyl-3J / -diazirin-3-yl)propionate;2.2.6.6-Tetramethyl-4-[2-(3-methyl-3J / -diazirin-3-yl)ethoxy]-l-piperidinol;4-hydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)benzamide;3,5-dihydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)benzamide;3.4.5-trihydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl) benzyl)benzamide; 4-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;4-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)benzene-l,2-diol;5-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)benzene-l,3-diol;5-(2-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)ethyl)benzene-l,2,3-triol; 4-hydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;3.5-dihydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;3.4.5-trihydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;4-(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol;4-((2-(3-methyl-3 / / -diazirin-3-yl)ethyl)amino)benzene-l,2-diol;5-((2-(3-methyl-3J / -diazirin-3-yl)ethyl)amino)benzene-l,3-diol; 5-(2-((2-(3-methyl-3 / / -diazirin-3-yl)ethyl)amino)ethyl)benzene-l,2,3-triol; 2,4-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;2.6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;2.4.6-tris((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;2.6-bis(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol;2.4.6-tris(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol; and di[2-(methyl-3H-diazirin-3-yl)ethyl] (2S)-2-(6-hydroxy-2,5,7,8-tetramethylchroman-2- y 1 carb ony 1 oxy )butanedi oate .

9. A product, material, or an article comprising a substrate having covalently attached thereto a compound as claimed in any one of claims 1 to 8.

10. The product, material, or article as claimed in claim 9, wherein the substrate is selected from the group comprising monomers, polymers, biomolecules, tissues, tissue engineering constructs, tissue allografts, tissue autografts, pharmaceutical compounds, medical devices, metal surfaces, ceramic surfaces, and combinations thereof.

11. The product, material, or article as claimed in claim 9, wherein the substrate is a monomer or polymer selected from ethylene, lactic acid, polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), polyethylene glycol (PEG), and copolymers thereof, and ultra-high molecular weight polyethylene (UHMWPE) powder particles employed in packaging applications, as additives in fuels, as lubricants etc.;fibers used in industrial composite formulations, for example in aeronautics, construction, automotive and defense applications; biomolecules selected from proteins, peptides, polysaccharides, and nucleic acids; tissue engineering constructs selected from tissue allografts and autografts; and pharmaceutical products such as medical devices, including stents, catheters, implants, and prostheses, band-aids and other medical bandages, cosmetic formulations.

12. The product, material, or article as claimed in claim 9, selected from the group consisting of a polymeric composition comprising a compound as claimed in any one of claims 1 to 8 blended with or grafted to a polymer selected from polylactic acid (PLA), poly(lactic-co- glycolic acid) (PLGA), polyethylene, polypropylene, polyester, polyether ether ketone (PEEK), silicone, and any combination thereof; a particulate composition comprising microparticles or nanoparticles of the compound as claimed in any one as claimed in claims 1 to 8, wherein the particles are formed by dispersing the compound in an immiscible medium and crosslinking the compound within each particle by UV or heat activation, optionally in the presence of a surfactant to control particle size; a pharmaceutical composition comprising microparticles or nanoparticles of the compound as claimed in any one as claimed in claims 1 to 8, for local or systemic drug delivery, wherein the particles adhere to tissue upon UV activation at a target site; a medical device comprising a surface coating of the compound as claimed in any one as claimed in claims 1 to 8, wherein the coating is applied to the device and activated by UV or heat to chemically bind the compound to the surface, thereby providing non-leachable antioxidant properties to the device; an article comprising ultra-high molecular weight polyethylene (UHMWPE) having the compound as claimed in any one as claimed in any one of claims 1 to 8 grafted onto or into the UHMWPE; wherein the grafting is achieved by coating UHMWPE particles with the compound and subjecting the coated particles to compression and heating to cause particle fusion and chemical bonding of the compound to the UHMWPE; an article comprising ultra-high molecular weight polyethylene (UHMWPE) bonded to a second material via the compound as claimed in in any one of claims 1 to 8, wherein thecompound chemically bonds to the UHMWPE and the second material, and the second material is selected from metal, ceramic, bone cement, or tissue; a tissue engineering material comprising a scaffold of biomolecules or synthetic polymers, wherein the scaffold has the compound as claimed in any one of claims 1 to 8 chemically bonded or crosslinked to the biomolecules or polymers, optionally by UV or heat activation; a packaging or industrial material comprising a polymer bound to the compound as claimed in any one of claims 1 to 8, wherein the material is used for food packaging, fuel additives, lubricants, aeronautical composites, construction materials, automotive parts, or defense applications; and a polymerizable monomer comprising a compound as claimed in any one of claims 1 to 8 covalently bonded to a polymerizable moiety, wherein the monomer is polymerizable to form an oligomer or polymer comprising the compound.

13. Use of a compound as claimed in any one of the claims 1 to 8, for covalently binding to a material or surface or substrate comprising C-H, N-H, and / or O-H bonds via UV irradiation or heating.

14. A method for bonding a compound to a substrate comprising:• applying a compound as claimed in claims 1 to 8 to a substrate comprising C-H, N-H, and / or O-H functional groups; and• activating the compound by UV radiation or heat to form covalent bond(s) with the substrate.

15. The method as claimed in claim 14, wherein the substrate is selected from the group comprising monomers, polymers, biomolecules, tissues, tissue engineering constructs, tissue allografts, tissue autografts, pharmaceutical compounds, medical devices, metal surfaces, ceramic surfaces, and combinations thereof.

16. The method as claimed in claim 14, wherein the compound comprises two or more diazirine moieties and crosslinks with the substrate upon activation.

17. A product, material, or an article obtainable by a method as claimed in claim 14.

18. The product, material, or an article as claimed in claim 18, wherein the product comprises a compound selected from:2.6-di-tert-butyl-4-{[({4-[(trifluoromethyl)-3H-diazirin-3-yl]phenyl}methyl)amino]methyl} phenol;2-(3-Methyl-3J7-diazirin-3-yl)ethyl 6-hydroxy-2,5,7,8-tetramethyl-2-chromancarboxylate;2.6-Di- / c / 7-butyl-4-[([ / 9-[3-(tritluoromethyl)-3 / / -diazirin-3-yl]benzyl }amino]phenol;2.6-Di- / c77-butyl-4-[([ / 9-[3-(trifluoromethyl)-3 / / -diazirin-3-yl]benzyl }methyl)amino]phenol;2.6-Di- / c77-butyl-4-[ [2-(3-methyl-3 / / -diazirin-3-yl)ethoxy]methyl [phenol;2-(3-Methyl-3J / -diazirin-3-yl)ethyl-3-(6-hydroxy-2,5,7,8-tetramethyl-2-chromanyl) propionate; l-Hydroxy-2,2,6,6-tetramethyl-4-piperidyl 3-(3-methyl-3J / -diazirin-3-yl)propionate; l-Hydroxy-2,2,6,6-tetramethyl-4-piperidyl 3-(3-methyl-3J / -diazirin-3-yl)propionate;2.2.6.6-Tetramethyl-4-[2-(3-methyl-3J / -diazirin-3-yl)ethoxy]-l-piperidinol;4-hydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)benzamide;3.5-dihydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)benzamide;3.4.5-trihydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl) benzyl)benzamide;4-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;4-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)benzene-l,2-diol;5-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)benzene-l,3-diol;5-(2-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)ethyl)benzene-l,2,3-triol;4-hydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;3.5-dihydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;3.4.5-trihydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;4-(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol;4-((2-(3-methyl-3J / -diazirin-3-yl)ethyl)amino)benzene-l,2-diol;5-((2-(3-methyl-3J / -diazirin-3-yl)ethyl)amino)benzene-l,3-diol;5-(2-((2-(3-methyl-3J / -diazirin-3-yl)ethyl)amino)ethyl)benzene-l,2,3-triol;2,4-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;2.6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;2.4.6-tris((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;2.6-bis(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol;2.4.6-tris(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol; anddi[2-(methyl-3H-diazirin-3-yl)ethyl] (2S)-2-(6-hydroxy-2,5,7,8-tetramethylchroman-2- y 1 carb ony 1 oxy )butanedi oate .

19. A process for preparing a compound, the process comprising:(a) providing an antioxidant moiety; and(b) covalently attaching one or more diazirine moieties to the antioxidant moiety.

20. The process as claimed in claim 19, comprising: providing a diazirine moiety having at least one reactive functional group selected from the group comprising carboxylic acid, acyl halide, ester, amine, amide, isocyanate, and hydroxyl; and reacting the diazirine moiety with an antioxidant moiety containing at least one functional group selected from the group comprising carboxylic acid, acyl halide, ester, amine, isocyanate, and hydroxyl under conditions effective to form a covalent bond between the diazirine moiety and the antioxidant moiety.

21. The process as claimed in claim 19, wherein one or more diazirine moieties are selected from:3-(4-(bromomethyl)phenyl)-3-(trifluoromethyl)-3H-diazirine;3-(4-bromophenyl)-3-(trifluoromethyl)-3H-diazirine;3-(4-(bromoethyl)phenyl)-3-(trifluoromethyl)-3H-diazirine;6-bromo- 1 ,2-diazaspiro[2.5 ] oct- 1 -ene;3-(2-bromoethyl)-3-methyl-3H-diazirine;3-(2-bromomethyl)-3-methyl-3H-diazirine;(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)methanamine hydrochloride;1.2-diazaspiro[2.5]oct-l-en-5-amine hydrochloride;1.2-diazaspiro[2.3]hex-l-en-5-amine hydrochloride, 2-(3-(but-3-yn-l-yl)-3H-diazirin-3- yl)ethan-l -amine;(3-methyl-3H-diazirin-3-yl)methanamine hydrochloride;2-(3-methyl-3H-diazirin-3-yl)ethan-l -amine hydrochloride;1.2.6-triazaspiro[2.6]non-l-ene hydrochloride;1.2.6-triazaspiro[2.5]oct-l-ene hydrochloride;1 ,2, 5-triazaspiro[2.4]hept- 1 -ene hydrochloride;1.2.5-triazaspiro[2.3]hex-l-ene hydrochloride;(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)methanol;2-(3 -(but-3 -yn- 1 -yl)-3H-diazirin-3 -yl)ethan- 1 -ol ;2-(3-((prop-2-yn-l-yloxy)methyl)-3H-diazirin-3-yl)ethan-l-ol;2-(3-methyl-3H-diazirin-3-yl)ethan-l-ol;1.2-diazaspiro[2.4]hept-l-ene-5-carboxylic acid;1.2-diazaspiro[2.3]hex-l-ene-5-carboxylic acid;3-(3H-diazirin-3-yl)propanoic acid;3-(3-methyl-3H-diazirin-3-yl)propionyl chloride;4-(3H-diazirin-3-yl)butanoic acid;2.5-dioxopyrrolidin-l-yl 3-(3-methyl-3H-diazirin-3-yl)propanoate;2.5-dioxopyrrolidin-l-yl-3-((2-(3-(3-methyl-3H-diazirin-3-yl)propanamido)ethyl) disulfaneyl)propanoate; and di[2-(3-methyl-3H-diazirin-3-yl)ethyl] (2S)-2-hydroxybutanedioate.

22. The process as claimed in claims 19, wherein the antioxidant moiety is selected from a group comprising tocopherol or its derivative, ascorbic acid or its derivative, beta-carotene, carotenoid, flavonoid, hindered phenol, and polyphenol.

23. The process as claimed in claim 19, wherein tocopherol or tocopherol derivative is selected from 6-hydroxy-2,5,7,8-tetramethyl-2-chromancarboxylic acid, 3-(6-hydroxy-2, 5,7,8- tetramethyl-2-chromanyl)propionic acid, 6-hydroxy-2,5,7,8-tetramethyl-2-chroman acyl chloride, 3-(6-hydroxy-2,5,7,8-tetramethyl-2-chromanyl)propionyl chloride; hindered phenols are selected from 4-(bromomethyl)-2,6-di-tert-butylphenol, 4-bromophenol, 4-bromobenzene-1.2-diol, 5-bromobenzene-l,2,3-triol, 2,4-dibromophenol, 4,5-dibromobenzene-l,2-diol,2.4.6-tribromophenol, 2,4,6-tribromo-5-pentylbenzene-l,3-diol, 4-amino-2,6-di- / c / 7- butylphenol, , 4-methylamino-2,6-di-tert-butylphenol, 4-aminophenol, 2,4-diaminophenol,2.6-diaminophenol, 2,4,6-triaminophenol, 4-aminobenzene-l,2-diol, 4-aminobenzene-l,3- diol, 5-aminobenzene-l,3-diol, 5-aminobenzene-l,2,3-triol, 5-ethylaminobenzene-l,2,3-triol,4-hydroxybenzamide, 2-hydroxybenzamide, 3,5-dihydroxybenzamide, and 3,4,5- trihydroxybenzamide.

24. The process as claimed in claim 19, wherein the compound is selected from:2.6-di-tert-butyl-4-{[({4-[(trifluoromethyl)-3H-diazirin-3-yl]phenyl}methyl)amino]methyl} phenol;2-(3-Methyl-3J7-diazirin-3-yl)ethyl 6-hydroxy-2,5,7,8-tetramethyl-2-chromancarboxylate;2.6-Di-terZ-butyl-4-[({p-[3-(trifluoromethyl)-3JH-diazirin-3-yl]benzyl)amino]phenol;2.6-Di-terZ-butyl-4-[({p-[3-(trifluoromethyl)-3JH-diazirin-3-yl]benzyl }methyl)amino]phenol;2.6-Di- / c77-butyl-4-[ [2-(3-methyl-37 / -diazirin-3-yl)ethoxy]methyl [phenol;2-(3-Methyl-37 / -diazirin-3-yl)ethyl-3-(6-hydroxy-2,5,7,8-tetramethyl-2-chromanyl) propionate; l-Hydroxy-2,2,6,6-tetramethyl-4-piperidyl 3-(3-methyl-3Z / -diazirin-3-yl)propionate; l-Hydroxy-2,2,6,6-tetramethyl-4-piperidyl 3-(3-methyl-3Z / -diazirin-3-yl)propionate;2.2.6.6-Tetramethyl-4-[2-(3-methyl-3JH-diazirin-3-yl)ethoxy]-l-piperidinol;4-hydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)benzamide;3.5-dihydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)benzamide;3.4.5-trihydroxy-N-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl) benzyl)benzamide;4-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;4-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)benzene-l,2-diol;5-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)benzene-l,3-diol;5-(2-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)ethyl)benzene-l,2,3-triol;4-hydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;3.5-dihydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;3.4.5-trihydroxy-N-(2-(3-methyl-3H-diazirin-3-yl)ethyl)benzamide;4-(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol;4-((2-(3-methyl-3JH-diazirin-3-yl)ethyl)amino)benzene-l,2-diol;5-((2-(3-methyl-3JH-diazirin-3-yl)ethyl)amino)benzene-l,3-diol;5-(2-((2-(3-methyl-3JH-diazirin-3-yl)ethyl)amino)ethyl)benzene-l,2,3-triol;2,4-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;2.6-bis((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;2.4.6-tris((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)amino)phenol;2.6-bis(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol;2.4.6-tris(((3-methyl-3H-diazirin-3-yl)methyl)amino)phenol; and di[2-(methyl-3H-diazirin-3-yl)ethyl] (2S)-2-(6-hydroxy-2,5,7,8-tetramethylchroman-2- y 1 carb ony 1 oxy )butanedi oate .

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