Saccharide-based raft agents

Abstract

Compounds are provided of Formula I, as well as polymers formed from said compounds, wherein all variables are as defined herein. Methods of making and using said compounds and polymers are also provided.

Description

[0001] Attorney Docket No.103362-032WO1 SACCHARIDE-BASED RAFT AGENTS CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to United States Provisional Patent Application No. 63 / 693,869, filed September 12, 2024, the disclosure of which is incorporated herein by reference in its entirety. BACKGROUND Reversible addition-fragmentation chain-transfer polymerization (RAFT) is considered one of the most versatile and finely tunable strategies for synthesizing well-defined polymers across diverse architectures and functional domains. In RAFT polymerization, the resulting polymers typically exhibit low dispersity, primarily because the chain transfer agent (CTA) establishes a rapid equilibrium between active polymer chains and their dormant counterparts. (See F. Hatton, Polym. Chem., 2020, 11, 220-229). The CTA comprises Z and R groups, which are crucial for controlling the polymer's molecular weight and enabling diverse architectures. The R group of the CTA plays a pivotal role in governing polymerization and fragmentation rates, functioning as the reinitiating species and thereby significantly influencing both polymerization kinetics and the capacity for block copolymer formation. If the R group is overly stable, fragmentation is slowed, resulting in polymerization retardation; conversely, if it is too unstable, reinitiation is inefficient, compromising the overall control of the polymerization process. (See Coote, M.L., Krenske, E.H. and Izgorodina, E.I. Macromol. Rapid Commun., 2006, 27, 473-497). The Z group of the CTA plays a critical role in the polymerization process by modulating the stability of the intermediate radical and dictating the range of monomers that can be efficiently polymerized. Electron-withdrawing Z groups, such as aryl or carbonyl-containing moieties, preferentially facilitate the polymerization of more activated monomers like methacrylates, whereas electron-donating Z groups (e.g., alkylthio) are suitable for less activated monomers, such as vinyl esters. (See Macromolecules 2021, 54, 20, 9496–9509; Polym. Chem., 2024,15, 868-877). Among the various RAFT agents, dithioesters and trithiocarbonates are particularly effective in controlling the polymerization of more activated monomers (MAMs). In these agents, the Z group is connected via a carbon atom in dithioesters and via a Attorney Docket No.103362-032WO1 sulfur atom in trithiocarbonates, a structural feature that significantly influences their polymerization behavior. Recent advances demonstrate that incorporating specialized moieties into the Z group enables direct control over polymerization kinetics and facilitates the synthesis of polymers with tailored functionality. This approach provides access to materials with precisely engineered behaviors, including responsiveness, biocompatibility, and site-specificity. Foster et al. reported dithiocarbamate CTAs with norbornene- containing Z groups, which facilitate controlled polymerization for specific monomer classes. These findings underscore the pivotal role of Z-group structure in modulating RAFT efficiency and enabling dual polymerization strategies. (See Jeffrey C. Foster, Scott C. Radzinski, Sally E. Lewis, Matthew B. Slutzker, John B. Matson Polymer, 2015, 79, 205-211; S. Stace, G. Moad, C. Fellows and D. Keddie, Polym. Chem., 2015, 6, 7119-7126; M. Odnoroh, F. Desmoulin, O. Coutelier, C. Pestourie, C. Mingotaud, M. Destarac, J.-D. Marty, Nanoscale, 2025,17, 14164- 14171). Traditionally, saccharide units have been introduced into polymers solely as monomers, and not as components of RAFT agents. (See S. Haiting, L. Li, W. Xiaobei, L. Jingyi, Polym. Chem., 2012, 3, 1182-1188)( K. A. Green, A. Kulkarni, P. E. Jankoski, T. B. Newton, B. Derbigny, T. D. Clemons, D. Watkins, S. E. Morgan, Biomacromolecules 2024, 25, 10, 6681–6692). Glycosylated polymers have long been recognized for their critical roles in biological processes and their potential in the development of innovative therapeutic agents for biomedical applications. (See Farnaz Jafari, Gokhan Yilmaz, C. Remzi Becer, European Polymer Journal, 2021, 142, 110147; Chem. Soc. Rev., 2023, 52, 2617- 2642) Moreover, glycopolymers can be engineered as biosensors due to carbohydrate–lectin interactions, which are involved in numerous biological processes, and their ability to mimic natural carbohydrate–protein interactions further highlights their potential in biomedical research and therapeutics. (See Himshikha Malviya, Seema Thapa, Jay Singh, Carbohydrate Research, 2025, 555, 109561; Halji, M.R., Ibrahim, A.A., Chong, K.F. et al. Top Curr Chem, 2022, (Z) 380, 45) Ladmiral et al. reported the use of galactose-decorated monomers to generate biocompatible nano-objects (spheres, worms, vesicles) via RAFT polymerization, targeting galectin receptors to deliver cargo intracellularly, thereby highlighting the carbohydrate–protein specificity for biomedical delivery. (See J. Am. Chem. Soc. Attorney Docket No.103362-032WO1 2013, 135(36):13574–13581). In addition to biomedical uses, galactose-based organogelators have been explored for phase-selective solvent separation and cationic dye removal, demonstrating their wider applicability in remediation and related areas. (See Shubhra Goel, Josemon Jacob, Reactive and Functional Polymers, 2020, 157, 104766) In another report, they have demonstrated a powerful tool for fabricating assemblies with tunable morphologies. The galactose-functionalized methacrylate polymer synthesized via RAFT polymerization formed highly ordered “glyco-inside” nanoassemblies, thereby broadening prospects for targeted delivery and biosensing applications. (See Angew Chem Int Ed Engl. 2021, 60(20):11098– 11103). There is a clear need for methods allowing access to further glycosylated polymers. This disclosure addresses this as well as other needs. SUMMARY The present disclosure provides compounds, polymers formed from said compounds, particles formed from said monomers, and methods of making and using the same. More particularly, the present disclosure provides chain transfer agents for use in RAFT polymerization and the polymers formed from the same. In one aspect, a compound is provided of Formula I wherein all variables are as defined herein. In another aspect, a method of polymerizing a monomer is provided. In some aspects, the method includes subjecting a mixture including the monomer, a radical initiator, and the above compound to conditions suitable to generate a radical from the radical initiator. In another aspect, a method of preparing a block copolymer is provided. In some aspects, the method includes subjecting a mixture including a first monomer, radical initiator, and the above compound to conditions suitable to generate a radical from the radical initiator, allowing the first monomer to be consumed, and then adding a second monomer to the mixture. Attorney Docket No.103362-032WO1 In another aspect, a polymer is provided prepared according to a method described herein. In another aspect, a polymer is provided having the formula: , , wherein all variables are as defined herein. In another aspect, a particle is provided including a polymer as described herein. In another aspect, a method of making a particle is provided. In some aspects, the method includes subjecting a mixture including a solvent and a polymer described herein to conditions suitable to form a particle. In another aspect, a particle is provided prepared according to a method described herein. The details of one or more aspects of the disclosure are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the disclosure will be apparent from the description, the drawings, and the claims. Attorney Docket No.103362-032WO1 DESCRIPTION OF DRAWINGS FIG.1 is a scheme for the synthesis of homo polymers using Gal-RAFT reagent with either V50 or AIBN as the initiator, a temperature of 50-70 °C, and various solvents as described in the examples. FIG. 2 is a1H NMR spectrum of the hydrophobic polymer Gal-pBzMA using CDCl3 as solvent and containing ethyl acetate impurities. FIG.3 is a1H NMR of different molecular weights of Gal-pBzMA polymer synthesized using AIBN as initiator. FIGs. 4A-4B provide (FIG. 4A) monomer conversion versus time for Gal PBzMA polymerization, and (FIG. 4B) kinetics of the reaction of Gal RAFT reagent with BzMA to form PBzMA using spectra. FIG. 5 is a scheme for the synthesis of hydrophilic Gal-pDMAEMA polymer using Gal-RAFT reagent with 0.075 equiv. of AIBN, 30% w / v dry dioxane at 70 °C. FIG.6 is a1H NMR spectrum of hydrophilic GalpDMAEMA using CDCl3 as solvent. FIGs. 7A-7D provide (FIG. 7A) a scheme for the synthesis of block copolymer Gal- pBzMA-b-pDMAEMA with 0.075 equiv. of AIBN, 30% w / v dry dioxane at 70 °C for 5.5 h; (FIG.7B) GPC spectrum of the block copolymer; and (FIG.7C) DLS of the block copolymer; (FIG. 7D) a NMR spectrum of block copolymer Gal-pBZMA-b- pDMAEMA using CDCl3 as solvent. DETAILED DESCRIPTION Before the present methods and systems are disclosed and described, it is to be understood that the methods and systems are not limited to specific synthetic methods, specific components, or particular compositions. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from “about” one particular value, and / or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value. Similarly, Attorney Docket No.103362-032WO1 when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. Throughout the description and claims of this specification, the word “comprise” and variations of the word, such as “comprising” and “comprises,” mean “including but not limited to,” and is not intended to exclude, for example, other additives, components, integers, or steps. “Exemplary” means “an example of” and is not intended to convey an indication of a preferred or ideal aspect. “Such as” is not used in a restrictive sense, but for explanatory purposes. Disclosed are components that can be used to perform the disclosed methods and systems. These and other components are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these components are disclosed, that while specific reference of each various individual and collective combinations and permutations of these may not be explicitly disclosed, each is specifically contemplated and described herein, for all methods and systems. This applies to all aspects of this application including, but not limited to, steps in disclosed methods. Thus, if there are a variety of additional steps that can be performed, it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the disclosed methods. Compounds disclosed herein may be provided in the form of acceptable salts. Examples of such salts are acid addition salts formed with inorganic acids, for example, hydrochloric, hydrobromic, sulfuric, phosphoric, and nitric acids and the like; salts formed with organic acids such as acetic, oxalic, tartaric, succinic, maleic, fumaric, gluconic, citric, malic, methanesulfonic, p-toluenesulfonic, napthalenesulfonic, and polygalacturonic acids, and the like; salts formed from elemental anions such as chloride, bromide, and iodide; salts formed from metal hydroxides, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, and magnesium hydroxide; salts formed from metal Attorney Docket No.103362-032WO1 carbonates, for example, sodium carbonate, potassium carbonate, calcium carbonate, and magnesium carbonate; salts formed from metal bicarbonates, for example, sodium bicarbonate and potassium bicarbonate; salts formed from metal sulfates, for example, sodium sulfate and potassium sulfate; and salts formed from metal nitrates, for example, sodium nitrate and potassium nitrate. The term "alkyl" refers to a radical of a straight-chain or branched hydrocarbon group having a specified range of carbon atoms (e.g., a "C1-16alkyl" can have from 1 to 16 carbon atoms). An alkyl group can be a saturated alkyl group or an unsaturated alkyl group, i.e., an alkyl group having one or more carbon-carbon double / triple bonds, i.e., an alkenyl or alkynyl group. Unless specified to the contrary, an “alkyl” group includes both saturated alkyl groups and unsaturated alkyl groups. The term "heteroalkyl" refers to an alkyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur within (i.e., inserted between adjacent carbon atoms of) and / or placed at one or more terminal position(s) of the parent chain. By way of example, a heteroC1-6alkyl (which may also be designated a C1-6heteroalkyl) group includes, but is not limited to, the following structures: The term “heteroalkyl” preceded by a separate heteroatom refers to a heteroalkyl group bonded through the specified heteroatom. By way of example, a OC1-6heteroalkyl group includes, but it not limited to, the following structures: When a range of values is listed, it is intended to encompass each value and sub- range within the range. For example, "C1-6 alkyl" is intended to encompass C1, C2, C3, C4, C5, C6, C1-6, C1-5, C1-4, C1-3, C1-2, C2-6, C2-5, C2-4, C2-3, C3-6, C3-5, C3-4, C4-6, C4-5, and C5- 6 alkyl. Attorney Docket No.103362-032WO1 Affixing the suffix "-ene" to a group indicates the group is a polyvalent moiety, e.g., bonded to two or more groups. Alkylene is the polyvalent moiety of alkyl, alkenylene is the divalent moiety of alkenyl, alkynylene is the divalent moiety of alkynyl, heteroalkylene is the divalent moiety of heteroalkyl, heteroalkenylene is the divalent moiety of heteroalkenyl, heteroalkynylene is the divalent moiety of heteroalkynyl, carbocyclylene is the divalent moiety of carbocyclyl, heterocyclylene is the divalent moiety of heterocyclyl, arylene is the divalent moiety of aryl, and heteroarylene is the divalent moiety of heteroaryl (each of which parent groups as defined herein). The term "alkoxy" refers to an alkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom. The term "aryl" refers to a radical of a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 π electrons shared in a cyclic array) having 6-14 ring carbon atoms and zero heteroatoms provided in the aromatic ring system ("C6-14 aryl"). "Aryl" also includes ring systems wherein the aryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups wherein the radical or point of attachment is on the aryl ring, and in such instances, the number of carbon atoms continues to designate the number of carbon atoms in the aryl ring system. Unless otherwise specified, each instance of an aryl group is independently unsubstituted (an "unsubstituted aryl") or substituted (a "substituted aryl") with one or more substituents. "Aralkyl" is a subset of "alkyl" and refers to an alkyl group substituted by an aryl group, wherein the point of attachment is on the alkyl moiety. The term "heteroaryl" refers to a radical of a 5-14 membered monocyclic or polycyclic (e.g., bicyclic, tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 π electrons shared in a cyclic array) having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-14 membered heteroaryl"). In heteroaryl groups that contain one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom, as valency permits. Heteroaryl polycyclic ring systems can include one or more heteroatoms in one or both rings. "Heteroaryl" includes ring systems wherein the heteroaryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups wherein the point of attachment is on the Attorney Docket No.103362-032WO1 heteroaryl ring, and in such instances, the number of ring members continues to designate the number of ring members in the heteroaryl ring system. "Heteroaryl" also includes ring systems wherein the heteroaryl ring, as defined above, is fused with one or more aryl groups, wherein the point of attachment is either on the aryl or heteroaryl ring, and in such instances, the number of ring members designates the number of ring members in the fused polycyclic (aryl / heteroaryl) ring system. Polycyclic heteroaryl groups wherein one ring does not contain a heteroatom (e.g., indolyl, quinolinyl, carbazolyl, and the like), the point of attachment can be on either ring, i.e., either the ring bearing a heteroatom (e.g., 2-indolyl) or the ring that does not contain a heteroatom (e.g., 5-indolyl). Exemplary heteroaryl and heterocyclyl rings include: benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH carbazolyl, carbolinyl, chromanyl, chromenyL cirrnolinyl, decahydroquinolinyl, 2H,6H~ 1,5,2-dithiazinyl, dihydrofuro[2,3 b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, lH-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole, pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl, pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl, quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 6H-1,2,5-thiadiazinyl, 1,2,3-thiadiazolyl, 1,2,4- thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl, and xanthenyl. Unless specified to the contrary, the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl groups defined herein (and the “ene” versions of said groups) may be substituted or Attorney Docket No.103362-032WO1 unsubstituted. A substituted group includes a non-hydrogen substituent at a position where, in the unsubstituted version, a hydrogen atom would be found. Substituents include, but are not limited to, halogen, hydroxy, alkyl, alkoxy, nitro, cyano, oxo, carbocyclyl, carbocycloalkyl, heterocarbocyclyl, heterocarbocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, -NRaRb, -NRaC(=O)Rb, -NRaC(=O)NRaNRb, - NRaC(=O)ORb, - NRaSO2Rb, -C(=O)Ra, -C(=O)ORa, -C(=O)NRaRb, -OC(=O)NRaRb, - ORa, -SRa, -SORa, - S(=O)2Ra, -OS(=O)2Raand -S(=O)2ORa. Raand Rbin this context can be the same or different and independently hydrogen, halogen, hydroxyl, alkyl, alkoxy, alkyl, amino, alkylamino, dialkylamino, carbocyclyl, carbocycloalkyl, heterocarbocyclyl, heterocarbocycloalkyl, aryl, arylalkyl, heteroaryl, or heteroarylalkyl. As used herein, the designation of a polyvalent moiety without specifying the specific order of attachment is intended to cover all possible arrangements. By way of example, a compound represented by the formula: A-X-B, wherein X is NHC(=O) embraces both: O O B A A N N B H and H .As used herein, a chemical bond depicted: represents either a single, double, ortriple bond, valency permitting. By way of example, Unless stated to the contrary, a substituent drawn without explicitly specifying the point of attachment indicates that the substituent may be attached at any possible atom. For example, in a benzofuran depicted: , Attorney Docket No.103362-032WO1 the substituent may be present at any one of the six possible carbon atoms. As used herein, the term “null,” when referring to a possible identity of a chemical moiety, indicates that the group is absent, and the two adjacent groups are directly bonded to one another. By way of example, for a genus of compounds having the formula CH3-X-CH3, if X is null, then the resulting compound has the formula CH3- CH3. A group having the subscript ‘0’ is understood to represent a null group as well. By way of example, in the compound CH3-(X)z-CH3, if X is CH2and z is 0, then the compound has the formula CH3-CH3. A bracketed functional group with a subscripted variable should be understood to denote the number of repeated bracketed groups present. For example, a number that is selected from 0 or 1 should be interpreted as follows: .In certain instances, two or more variable groups may together form a ring. It is understood that any depicted atoms separated from the identified groups will themselves form part of the ring: When the variable groups are substituted on an aromatic system, the new ring will be a fused ring, and unless specified to the contrary, may be either aromatic or non- aromatic, carbocyclic or heterocyclic: The ring may further be defined by the number of carbon atoms in the specific ring formed by the variable groups, which includes the atoms separating the variable groups: Attorney Docket No.103362-032WO1 Each of the above results occurs when R1and R2together form a six-membered (or six-atom) ring. Other rings, including 3, 4, 5, 7, and 8-member rings, may also be formed, and may be further limited by a specified number of carbon atoms. Although the singular “a ring” may be used to define the group, unless specified to the contrary, both monocyclic and polycyclic rings are possible: Unless stated to the contrary, a formula with chemical bonds shown only as solid lines and not as wedges or dashed lines contemplates each possible isomer, e.g., each enantiomer, diastereomer, and meso compound, and a mixture of isomers, such as a racemic or scalemic mixture. Unless stated to the contrary, a formula depicting one or more stereochemical features does not exclude the presence of other isomers. Some compounds disclosed herein may exist as one or more tautomers. Tautomers are interconvertible structural isomers that differ in the position of one or more protons or other labile atoms. By way of example: . The prevalence of one tautomeric form over another will depend on the specific chemical compound as well as its local chemical environment. Unless specified to the contrary, the depiction of one tautomeric form is inclusive of all possible tautomeric forms. As used herein, the term “(meth)acrylate” embraces both methacrylate and acrylate. The same convention is applicable to (meth)acrylamide and (meth)acrylic. The term “therapeutic agent” includes any synthetic or naturally occurring biologically active compound or composition of matter which, when administered to Attorney Docket No.103362-032WO1 an organism (either human or a nonhuman animal), induces a desired pharmacologic, immunogenic, and / or physiologic effect by local and / or systemic action. The term therefore encompasses those compounds or chemicals traditionally regarded as drugs, vaccines, and biopharmaceuticals, including molecules such as proteins, peptides, hormones, nucleic acids, gene constructs and the like. Examples of therapeutic agents are described in well-known literature references such as the Merk Index (14thEdition), the Physician’s Desk Reference (64thEdition), and The Pharmacological Basis of Therapeutics (12thEdition), and they include, without limitation, medicaments; vitamins; mineral supplements, substances used for the treatment, prevention, diagnosis, cure or mitigation of a disease or illness; substances that affect the structure or function of the body, or pro-drugs, which become biologically active or more active after they have been placed in a physiological environment. For example, the term “therapeutic agent” includes compounds or compositions for use in all of the major therapeutic areas including, but not limited to, adjuvants; anti-infectives such as antibiotics and antiviral agents; analgesics and analgesic combinations, anorexics, anti-inflammatory agents, anti- epileptics, local and general anesthetics, hypnotics, sedatives, antipsychotic agents, neuroleptic agents, antidepressants, anxiolytics, antagonists, neuron blocking agents, anticholinergic and cholinomimetic agents, antimuscarinic and muscarinic agents, antiandrenergics, antiarrhythmics, antihypertensive agents, hormones, and nutrients, antiarthritics, antiasthmatic agents, anticonvulsants, antihistamines, antinauseants, antineoplastics, antipruritics, antipyretics, antispasmodics, cardiovascular preparations (including calcium channel blockers, beta blockers, and beta-agonists), antihypertensives, diuretics, vasodilators, central nervous system stimulants, cough and cold preparations, decongestants, diagnostics, bone growth stimulants and bone resorption inhibitors, immunosuppressives, muscle relaxants, psychostimulants, sedatives, tranquilizers, proteins, peptides, and fragments thereof (whether naturally occurring, chemically synthesized or recombinantly produced), and nucleic acid molecules (polymeric forms of two or more nucleotides, either ribonucleotides (RNA) or deoxyribonucleotides (DNA) including both double and single-stranded molecules, gene constructs, expression vectors, antisense molecules and the like), small molecules and other biologically active macromolecules such as, for examples, proteins and enzymes. The agent may be a biologically active agent Attorney Docket No.103362-032WO1 used in medical, including veterinary, applications, and in agriculture, such as with plants, as well as other areas. Disclosed herein are compounds of Formula I: wherein: Rcis a carbohydrate; Ra1and Ra2are independently selected from H, CH3, Ph, and CN; X1is selected from L2SC(=S)S, L2SC(=S), or L2NRNC(=S)S wherein L2is null, (CH2)0,or [CH2CH2O]o, wherein o is 1-5, and RNis H, C1-4alkyl, aryl, heteroaryl, or CH2Ph; L1is null or (CH2)n, wherein n is 1-3; and X2is L3ORe, L3CN, L3COORe, wherein L3is null, CH(Ph), C(Ph)(CH3), CH(CH3), or C(CH3)2, and Reis H, C1-4alkyl, C1-4alkylene-OH, CH2Ph, or [CH2CH2O]pRp, wherein p is 1-5 and Rpis H or CH3. In some aspects, Rccan be a glucose residue, a galactose residue, or a mannose residue. In some aspects, Rchas the formula: , wherein one of R2, R3, R4, or R6represents a bond to X1; R1is OH, OCH3, or OP, and the remaining of R2, R3, R4, or R6are selected from H, OH, OP, wherein P represents a protecting group or a further carbohydrate, wherein any two or more of the remaining of R1, R2, R3, R4, or R6can together form a ring. In some aspects, P in each case is independently selected from CH2aryl, C(=O)Rp, SiRs3, or C(Rz1)(Rz2)-*, wherein Rpis independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rsis independently selected from C1-4alkyl or phenyl, * represents a bond to a further P group, Rz1and Rz2are independently selected from Attorney Docket No.103362-032WO1 H and C1-4alkyl, preferably from CH3, and CH2CH3, or Rz1is H and Rz2is optionally substituted aryl or alkaryl, or Rz1and Rz2together form a carbonyl. In certain aspects, R4and R3together form an acetal or carbonate; and R2and R1together form an acetal or carbonate. In some aspects, Rchas the formula: In some aspects, Rchas the formula: In certain aspects, Rchas the formula: . In certain aspects, R6represents a bond to X1. In certain aspects, the compound has the formula: Attorney Docket No.103362-032WO1 , wherein P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, wherein Rp1*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs1*is independently selected from C1-4alkyl or phenyl; P2is selected from CH2aryl, C(=O)Rp2*, and SiRs2*3, wherein Rp2*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs2*is independently selected from C1-4alkyl or phenyl; P3is selected from CH2aryl, C(=O)Rp3*, and SiRs3*3, wherein Rp3*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs3*is independently selected from C1-4alkyl or phenyl; P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3, wherein Rp4*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs4*is independently selected from C1-4alkyl or phenyl; or wherein any pair of P1and P2, P2and P3, or P3and P4may together be -C(Rz1)(Rz2)-, wherein Rz1and Rz2are independently selected from H and C1-4alkyl, preferably CH3or CH2CH3, or Rz1is H and Rz2is optionally substituted aryl or alkaryl, or Rz1and Rz2together form a carbonyl. In certain aspects, P1and P2together are -C(Rz1)(Rz2)- and P3and P4together are - C(Rz1)(Rz2)-. In other aspects, P2and P3together are -C(Rz1)(Rz2)-, P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, and P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3. In some aspects, P1and P4can be independently selected from C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS). In some aspects, the compound has the formula: Attorney Docket No.103362-032WO1 , In some aspects, the compound has the formula: In further aspects, the compound has the formula: . In certain aspects, P1is CH3, C(=O)CH3, C(=O)phenyl, benzyl, or paramethoxybenzyl; P2is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); P3is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); and P4is C(=O)CH3, C(=O)phenyl, benzyl, Attorney Docket No.103362-032WO1 paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS). In some aspects, the compound has the formula: In some aspects, Rz1and Rz2are each CH3or CH2CH3. In some aspects, Rz1is H and Rz2is benzyl or paramethoxybenzyl. In some aspects, Rz1and Rz2together form a carbonyl. In some aspects, the compound has the formula: . In certain aspects X1is L2SC(=S)S or L2SC(=S). In some aspects, L2is null or OCH2CH2. In some aspects, the compound has the formula: Attorney Docket No.103362-032WO1 In some aspects, the compound has the formula: . where Z, Rz1, and Rz2are as defined above. In some aspects, the compound has the formula: Attorney Docket No.103362-032WO1 where Z is as defined above. In certain aspects, Ra1and Ra2are each CH3; Ra1is H and Ra2is CH3; or Ra1is CN and Ra2is CH3. In certain aspects, L3is null or C(CH3)2. In certain aspects, L1is null, CH2, or CH2CH2. In certain aspects, X2is CN, COOH, OCH3, or OH. In some aspects X1is L2N(RN)C(=S)S, and RNis CH3, pyridine-4-yl, phenyl, 4- fluorophenyl, or 4-cyanophenyl. In some aspects, the compound has the structure: Also disclosed herein are methods of polymerizing a monomer using the disclosed compounds (which may be designated as a RAFT agent). In some aspects, the disclosed compound may be combined with a polymerizable monomer and radical initiator, and then exposed to conditions suitable to generate a radical compound from the radical initiator. In some aspects, the mixture is heated. In some aspects, the mixture is irradiated. In some aspects, the polymerizable monomer includes a reactive double bond or reactive triple bond, for example, a (meth)acrylate, (meth)acrylamide, (meth)acrylic acid, an α-olefin, or a combination thereof. Attorney Docket No.103362-032WO1 In some alternative aspects, the polymerizable monomer can include a (meth)acrylate, (meth)acrylamide, acrylonitrile, styrene or a derivative thereof, butadiene, vinyl acetate, or N-vinylpyrrolidone. In some aspects, the polymerizable monomer can have the formula: wherein Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl, or In an alternative aspect, Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, heteroaryl, NH2, NH(C1-C6 alkyl), or N(independently C1-C6 alkyl)2. In an alternative aspect, the polymerizable monomer can have the formula ,wherein Rq**is H, F, Cl, Br, cyano, C1-C16alkyl, -O(C1-C16alkoxy), -O(C=O)C1-C16alkoxy, aryl, or heteroaryl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl. In some aspects, the compound, polymerizable monomer, and radical initiator can be combined in a solvent, for example, one or more of water, toluene, benzene, acetonitrile, acetone, ethyl acetate, methanol, DMF, and the like. When the polymerizable monomer is a liquid under relevant conditions, the polymerization may be carried out in the absence of a solvent. The polymerizable monomer and RAFT agent may be combined in a variety of ratios. In some aspects, the RAFT agent may be present in an amount from 0.1-25 mol%, from 1-25 mol, from 5-25 mol%, or from 10-25 mol% (relative to polymerizable monomer). In some aspects, the RAFT agent may be present in an amount from 0.1- 1 mol%, from 1-5 mol%, from 1-10 mol%, from 5-15 mol%, or from 10-25 mol%, Attorney Docket No.103362-032WO1 In some aspects, the radical initiator is an azo compound. In some aspects, the radical initiator is a thermal initiator (i.e., radical generating upon heating). In some aspects, the radical initiator is a photoinitiator. In certain aspects, the radical initiator can be AIBN, ACHN, V50, ACP, ABVN, or K2S2O8. Also disclosed herein are methods of preparing block copolymers, including the step of conducting a polymerization with a first monomer and RAFT agent under the conditions described above, followed by adding a second monomer to the reaction mixture after the first monomer has been consumed. In some aspects, the first polymerizable monomer can be a hydrophilic (meth)acrylate, (meth)acrylamide, (meth)acrylic acid, an α-olefin, or a combination thereof, and the second polymerizable monomer includes a hydrophobic (meth)acrylate, (meth)acrylamide, (meth)acrylic acid, an α-olefin, or a combination thereof. In some aspects, the first polymerizable monomer can be a hydrophobic (meth)acrylate, (meth)acrylamide, (meth)acrylic acid, an α-olefin, or a combination thereof, and the second polymerizable monomer includes a hydrophilic (meth)acrylate, (meth)acrylamide, (meth)acrylic acid, an α-olefin, or a combination thereof. In some alternative aspects, the first polymerizable monomer can include a (meth)acrylate, (meth)acrylamide, acrylonitrile, styrene or a derivative thereof, butadiene, vinyl acetate, or N-vinylpyrrolidone. In some alternative aspects, the second polymerizable monomer can include a (meth)acrylate, (meth)acrylamide, acrylonitrile, styrene or a derivative thereof, butadiene, vinyl acetate, or N- vinylpyrrolidone. In some aspects, following completion of the polymerization reaction, the oxygen protecting groups in the carbohydrate residue can be removed, i.e., each OP group in Rcis converted to OH. Also disclosed herein are polymers having the formula: Attorney Docket No.103362-032WO1 , , wherein: z is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50- 100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; z* is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50-100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl; or, in an alternative aspect, Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, heteroaryl, NH2, NH(C1-C6alkyl), or N(independently C1-C6alkyl)2; Rm*is H or CH3, Xm*is O or NH, and Rq*is H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl; Attorney Docket No.103362-032WO1 or, in an alternative aspect, and Rq*is H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, heteroaryl, NH2, NH(C1-C6 alkyl), or N(independently C1-C6 alkyl)2; Rcis a carbohydrate; Ra1and Ra2are independently selected from H, CH3, Ph, and CN; X1is selected from L2SC(=S)S, L2SC(=S), or L2NRNC(=S)S wherein L2is null, (CH2)o, or [CH2CH2O]o, wherein o is 1-5, and RNis H, C1-4alkyl, aryl, heteroaryl, or CH2Ph; L1is null or (CH2)n, wherein n is 1-3; and X2is L3ORe, L3CN, L3COORe, wherein L3is null, CH(Ph), C(Ph)(CH3), CH(CH3), or C(CH3)2, and Reis H, C1-4alkyl, C1-4alkylene-OH, CH2Ph, or [CH2CH2O]pRp, wherein p is 1-5 and Rpis H or CH3. In some alternative aspects, disclosed herein are polymers having the formula: , , wherein: z is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50- 100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; z* is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50-100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; Rq**is H, F, Cl, Br, cyano, C1-C16alkyl, -O(C1-C16alkoxy), -O(C=O)C1-C16alkoxy, aryl, or heteroaryl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl; Br, cyano, C1-C16 alkyl, -O(C1-C16 alkoxy), -O(C=O)C1-C16 alkoxy, aryl, or heteroaryl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl; Rcis a carbohydrate; Attorney Docket No.103362-032WO1 Ra1and Ra2are independently selected from H, CH3, Ph, and CN; X1is selected from L2SC(=S)S, L2SC(=S), or L2NRNC(=S)S wherein L2is null, (CH2)o, or [CH2CH2O]o, wherein o is 1-5, and RNis H, C1-4alkyl, aryl, heteroaryl, or CH2Ph; L1is null or (CH2)n, wherein n is 1-3; and X2is L3ORe, L3CN, L3COORe, wherein L3is null, CH(Ph), C(Ph)(CH3), CH(CH3), or C(CH3)2, and Reis H, C1-4alkyl, C1-4alkylene-OH, CH2Ph, or [CH2CH2O]pRp, wherein p is 1-5 and Rpis H or CH3. In certain aspects, the polymer has the formula: , Attorney Docket No.103362-032WO1 P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, wherein Rp1*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs1*is independently selected from C1-4alkyl or phenyl; P2is selected from CH2aryl, C(=O)Rp2*, and SiRs2*3, wherein Rp2*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs2*is independently selected from C1-4alkyl or phenyl; P3is selected from CH2aryl, C(=O)Rp3*, and SiRs3*3, wherein Rp3*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs3*is independently selected from C1-4alkyl or phenyl; P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3, wherein Rp4*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs4*is independently selected from C1-4alkyl or phenyl; or wherein any pair of P1and P2, P2and P3, or P3and P4may together be -C(Rz1)(Rz2)-, wherein Rz1and Rz2are independently selected from H and C1-4alkyl, preferably CH3 or CH2CH3, or Rz1is H and Rz2is optionally substituted aryl or alkaryl, or Rz1and Rz2together form a carbonyl. In certain aspects, P1and P2together are -C(Rz1)(Rz2)- and P3and P4together are - C(Rz1)(Rz2)-. In other aspects, P2and P3together are -C(Rz1)(Rz2)-, P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, and P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3. In some aspects, P1and P4can be independently selected from C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS). In further aspects, the polymer has the formula: , Attorney Docket No.103362-032WO1 . In certain aspects, P1is CH3, C(=O)CH3, C(=O)phenyl, benzyl, or paramethoxybenzyl; P2is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); P3is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); and P4is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS). In some aspects, the polymer has the formula: . In some aspects, the polymer has the formula: Attorney Docket No.103362-032WO1 . In some aspects, the polymer has the formula: . In some aspects, the polymer has the formula: , Attorney Docket No.103362-032WO1 . In another aspect, a particle is provided including a polymer as described herein. In the context of this disclosure, a “particle” refers to a physically discrete unit of matter, such as a granule, bead, flake, colloid, or droplet, having a defined dimension or size range (for example, an average diameter between 1 nanometer and 100 micrometers), and may comprise inorganic, organic, or composite materials, whether present individually or in agglomerated form, unless otherwise specified. The particle may be of any shape, morphology, or composition, and may include, but is not limited to, spheres, rods, plates, flakes, or irregular shapes. Particle size can be defined, for example, by a characteristic dimension such as diameter, length, or equivalent spherical diameter determined by appropriate measurement methods (such as laser diffraction, electron microscopy, or dynamic light scattering) and Attorney Docket No.103362-032WO1 specified as an average or range Particle size, shape, and composition are determined by standard industry methods, including but not limited to electron microscopy, sieving, or particle sizing instruments. In some aspects, the particle can be a microparticle. A “microparticle” refers to a discrete particle having a characteristic dimension, such as a mean diameter or width, in the range from about 1 micrometer to about 1000 micrometers. In some aspects, the particle can be a nanoparticle. In some aspects, the particle can be a nanoparticle. A ‘nanoparticle’ refers to a discrete particle having a characteristic dimension, such as mean diameter or width, in the range of about 1 nanometer to about 100 nanometers. In some aspects, the particle can be a micelle. Also disclosed herein are methods of making a particle by combining the disclosed polymers in a solvent under conditions suitable to form a particle. In some aspects, the polymer includes an unprotected carbohydrate residue (i.e., each P = H). In some aspects, the polymer includes a protected carbohydrate residue (i.e., each P ≠ H). In such aspects, some or all of the protecting groups may be removed following formation of the particle. For example, at least the carbohydrate residues present on the surface of the particle can be deprotected. Particles described herein can be generated by any suitable method known in the art. As a non-limiting example, particles described herein may be generated via precipitation (i.e., formation of particles by causing a solute to come out of solution, typically via chemical reaction or solvent change, resulting in solid particle formation from a supersaturated solution), emulsification (i.e., creating droplets of a dispersed liquid phase within another immiscible liquid, usually followed by solidification (via solvent evaporation, thermal or photochemical curing, or crosslinking) to create solid particles), spray drying or atomization (i.e., creating droplets from a solution or suspension and rapidly drying or solidifying them, often by hot gas stream or via UV curing for polymers in mid-air), milling and comminution (i.e., mechanically reducing the size of bulk materials into particles using devices such as ball mills, jet mills, or high-shear mixers), solvent evaporation / extraction (i.e., generating particles by removing solvent from emulsified droplets or from a solution, leaving behind solidified particles), supercritical fluid techniques (i.e., using rapid expansion of supercritical solutions (RESS) or supercritical antisolvent (SAS) methods to precipitate particles by changing pressure or solvent environment), high-pressure Attorney Docket No.103362-032WO1 homogenization (i.e., employing piston-gap or high-shear homogenizers to break down materials into fine particles), coacervation and phase separation (i.e., inducing polymer-rich and polymer-poor phases, then collecting the phase-separated material as particles), microfluidic and template-assisted methods (i.e., producing monodisperse or defined-shape particles using microfluidic devices or by templating against a patterned surface or mold), solid state reaction or synthesis: Directly mixing reagents in the solid state (with or without heating) to form particulate products), chemical vapor deposition (CVD) (i.e., depositing material from a vapor phase onto nucleation sites to grow particulate products), or additive manufacturing / layer-by- layer deposition (i.e., forming particles by building up material in discrete steps, including stereolithography and related 3D printing methodologies). In another aspect, a particle is provided prepared according to a method described herein. Other materials which may include or be formed from a polymer described herein include, but are not limited to, hydrogels, membranes, conductive or responsive polymers, molecularly imprinted polymers, and glycopolymer brushes or gels. The polymers described herein can be used in drug, gene, and antigen delivery systems, tissue engineering scaffolds, anti-biofouling or antifouling coating, diagnostic and biosensor platforms, and flexible energy storage devices. In view of the described compounds, compositions, and methods, certain more particular aspects of the disclosure are described below. These particularly recited aspects should not, however, be interpreted to have any limiting effect on any different claims containing different or more general teachings described herein, or that the “particular” aspects are somehow limited in some way other than the inherent meanings of the language and formulae literally used therein. Aspect 1. A compound having of Formula I) wherein: Rcis a carbohydrate; Ra1and Ra2are independently selected from H, CH3, Ph, and CN; Attorney Docket No.103362-032WO1 X1is selected from L2SC(=S)S, L2SC(=S), or L2NRNC(=S)S wherein L2is null, (CH2)0,or [CH2CH2O]o, wherein o is 1-5, and RNis H, C1-4alkyl, aryl, heteroaryl, or CH2Ph; L1is null or (CH2)n, wherein n is 1-3; and X2is L3ORe, L3CN, L3COORe, wherein L3is null, CH(Ph), C(Ph)(CH3), CH(CH3), or C(CH3)2, and Reis H, C1-4alkyl, C1-4alkylene-OH, CH2Ph, or [CH2CH2O]pRp, wherein p is 1-5 and Rpis H or CH3. Aspect 2. The compound according to any aspect described herein, for example aspect 1, wherein Rcis a glucose residue, a galactose residue, or a mannose residue. Aspect 3. The compound according to any aspect described herein, for example aspect 1 or aspect 2, wherein Rchas the formula: , wherein one of R2, R3, R4, or R6represents a bond to X1; R1is OH, OCH3, or OP, and the remaining of R2, R3, R4, or R6are selected from H, OH, OP, wherein P represents a protecting group or a further carbohydrate, wherein any two or more of the remaining of R1, R2, R3, R4, or R6can together form a ring. Aspect 4. The compound according to any aspect described herein, for example aspect 3, wherein P in each case is independently selected from CH2aryl, C(=O)Rp, SiRs3, or C(Rz1)(Rz2)-*, wherein Rpis independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rsis independently selected from C1-4alkyl or phenyl, * represents a bond to a further P group, Rz1and Rz2are independently selected from H and C1-4alkyl, preferably from CH3, and CH2CH3, or Rz1is H and Rz2is optionally substituted aryl or alkaryl, or Rz1and Rz2together form a carbonyl. Aspect 5. The compound according to any aspect described herein, for example any one of aspects 1-4, wherein R4and R3together form an acetal or carbonate; and R2and R1together form an acetal or carbonate. Attorney Docket No.103362-032WO1 Aspect 6. The compound according to any aspect described herein, for example any one of aspects 1-5, wherein Rchas the formula: Aspect 7. The compound according to any aspect described herein, for example any one of aspects 1-6, wherein Rchas the formula: Aspect 8. The compound according to any aspect described herein, for example any one of aspects 1-7, wherein, Rchas the formula: . Aspect 9. The compound according to any aspect described herein, for example any one of aspects 3-8, wherein R6represents a bond to X1. Aspect 10. The compound according to any aspect described herein, for example any one of aspects 1-9, wherein the compound has the formula: Attorney Docket No.103362-032WO1 , wherein P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, wherein Rp1*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs1*is independently selected from C1-4alkyl or phenyl; P2is selected from CH2aryl, C(=O)Rp2*, and SiRs2*3, wherein Rp2*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs2*is independently selected from C1-4alkyl or phenyl; P3is selected from CH2aryl, C(=O)Rp3*, and SiRs3*3, wherein Rp3*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs3*is independently selected from C1-4alkyl or phenyl; P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3, wherein Rp4*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs4*is independently selected from C1-4alkyl or phenyl; or wherein any pair of P1and P2, P2and P3, or P3and P4may together be -C(Rz1)(Rz2)-, wherein Rz1and Rz2are independently selected from H and C1-4alkyl, preferably CH3or CH2CH3, or Rz1is H and Rz2is optionally substituted aryl or alkaryl, or Rz1and Rz2together form a carbonyl. Aspect 11. The compound according to any aspect described herein, for example aspect 10, wherein: P1and P2together are -C(Rz1)(Rz2)- and P3and P4together are -C(Rz1)(Rz2)-; or P2and P3together are -C(Rz1)(Rz2)-, P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, and P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3. Aspect 12. The compound according to any aspect described herein, for example aspect 10, wherein P1and P4are independently selected from C(=O)CH3, Attorney Docket No.103362-032WO1 C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS). Aspect 13. The compound according to any aspect described herein, for example any one of aspects 10-12, wherein the compound has the formula: Aspect 14. The compound according to any aspect described herein, for example any one of aspects 10-13, wherein the compound has the formula: Aspect 15. The compound according to any aspect described herein, for example any one of aspects 10-14, wherein the compound has the formula: Attorney Docket No.103362-032WO1 . Aspect 16. The compound according to any aspect described herein, for example any one of aspects 10-15, wherein P1is CH3, C(=O)CH3, C(=O)phenyl, benzyl, or paramethoxybenzyl; P2is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); P3is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); and P4is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS). Aspect 17. The compound according to any aspect described herein, for example any one of aspects 10-16, wherein the compound has the formula: Aspect 18. The compound according to any aspect described herein, for example any one of aspects 10-17, wherein Rz1and Rz2are each CH3 or CH2CH3. Attorney Docket No.103362-032WO1 Aspect 19. The compound according to any aspect described herein, for example any one of aspects 10-17, wherein Rz1is H and Rz2is benzyl or paramethoxybenzyl. Aspect 20. The compound according to any aspect described herein, for example any one of aspects 10-17, Rz1and Rz2together form a carbonyl. Aspect 21. The compound according to any aspect described herein, for example any one of aspects 1-20, wherein compound has the formula: . Aspect 22. The compound according to any aspect described herein, for example any one of aspects 1-21, wherein X1is L2SC(=S)S or L2SC(=S). Aspect 23. The compound according to any aspect described herein, for example any one of aspects 1-22, wherein L2is null or OCH2CH2. Aspect 24. The compound according to any aspect described herein, for example any of aspects 10-20, wherein the compound has the formula: Attorney Docket No.103362-032WO1 Aspect 25. The compound according to any aspect described herein, for example 24, wherein the compound has the formula: . Aspect 26. The compound according to any aspect described herein, for example aspect 24 or aspect 25, wherein the compound has the formula: Aspect 27. The compound according to any aspect described herein, for example any one of aspects 1-26, wherein Ra1and Ra2are each CH3; Ra1is H and Ra2is CH3; or Ra1is CN and Ra2is CH3. Aspect 28. The compound according to any aspect described herein, for example any one of aspects 1-27, wherein L3is null or C(CH3)2. Aspect 29. The compound according to any aspect described herein, for example any one of aspects 1-28, wherein L1is null, CH2, or CH2CH2. Attorney Docket No.103362-032WO1 Aspect 30. The compound according to any aspect described herein, for example any one of aspects 1-29, wherein X2is CN, COOH, OCH3, or OH. Aspect 31. The compound according to any aspect described herein, for example any one of aspects 1-20, wherein X1is L2N(RN)C(=S)S, and RNis CH3, pyridine-4-yl, phenyl, 4-fluorophenyl, or 4-cyanophenyl. Aspect 32. A method of polymerizing a monomer, including subjecting a mixture including the monomer, a radical initiator, and the compound according to any aspect described herein, for example any one of aspects 1-31 to conditions suitable to generate a radical from the radical initiator. Aspect 33. The method according to any aspect described herein, for example aspect 32, wherein the monomer includes a (meth)acrylate, (meth)acrylamide, (meth)acrylic acid, an α-olefin, or a combination thereof. Aspect 34. The method according to any aspect described herein, for example aspect 32, wherein the monomer can have the formula: wherein Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl. Aspect 35. The method according to any aspect described herein, for example aspect 32, wherein the monomer can have the formula: wherein Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, heteroaryl, NH2, NH(C1-C6alkyl), or N(independently C1- C6 alkyl)2. Attorney Docket No.103362-032WO1 Aspect 36. The method according to any aspect described herein, for example any one of aspects 32-35, wherein the compound is present in an amount from 0.1-25 mol%, from 1-25 mol, from 5-25 mol%, or from 10-25 mol% (relative to the monomer). Aspect 37. The method according to any aspect described herein, for example any one of aspects 32-36, wherein the radical initiator includes an azo compound. Aspect 38. The method according to any aspect described herein, for example any one of aspects 32-37, wherein the radical initiator includes a thermal initiator, a photoinitiator, or a combination thereof. Aspect 39. The method according to any aspect described herein, for example any one of aspects 32-38, wherein the radical initiator can be AIBN, ACHN, V50, ACP, ABVN, or K2S2O8. Aspect 40. A method of preparing a block copolymer, including subjecting a mixture including a first monomer, radical initiator, and compound according to any aspect described herein, for example any one of aspects 1-31 to conditions suitable to generate a radical from the radical initiator, allowing the first monomer to be consumed, and then adding a second monomer to the mixture. Aspect 41. The method according to any aspect described herein, for example aspect 40, wherein the first monomer includes a hydrophobic monomer and the second monomer includes a hydrophilic monomer, or wherein the first monomer includes a hydrophilic monomer and the second monomer includes a hydrophobic monomer. Aspect 42. The method according to any aspect described herein, for example any one of aspects 32-41, further including converting each of R1, R2, R3, and R4to OH. Aspect 43. A polymer prepared according to any aspect described herein, for example the method of any one of aspects 32-42. Aspect 44. A polymer having the formula: Attorney Docket No.103362-032WO1 , wherein: z is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50- 100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; z* is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50-100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl; Rm*is H or CH3, Xm*is O or NH, and Rq*is H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl; Rcis a carbohydrate; Ra1and Ra2are independently selected from H, CH3, Ph, and CN; Attorney Docket No.103362-032WO1 X1is selected from L2SC(=S)S, L2SC(=S), or L2NRNC(=S)S wherein L2is null, (CH2)o, or [CH2CH2O]o, wherein o is 1-5, and RNis H, C1-4alkyl, aryl, heteroaryl, or CH2Ph; L1is null or (CH2)n, wherein n is 1-3; and X2is L3ORe, L3CN, L3COORe, wherein L3is null, CH(Ph), C(Ph)(CH3), CH(CH3), or C(CH3)2, and Reis H, C1-4alkyl, C1-4alkylene-OH, CH2Ph, or [CH2CH2O]pRp, wherein p is 1-5 and Rpis H or CH3. Aspect 45. A polymer having the formula: , wherein: z is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50- 100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; z* is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50-100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; Attorney Docket No.103362-032WO1 Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, heteroaryl, NH2, NH(C1-C6 alkyl), or N(independently C1-C6 alkyl)2; Rm*is H or CH3, Xm*is O or NH, and Rq*is H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1- 4alkyl, aryl, heteroaryl, NH2, NH(C1-C6 alkyl), or N(independently C1-C6 alkyl)2; Rcis a carbohydrate; Ra1and Ra2are independently selected from H, CH3, Ph, and CN; X1is selected from L2SC(=S)S, L2SC(=S), or L2NRNC(=S)S wherein L2is null, (CH2)o, or [CH2CH2O]o, wherein o is 1-5, and RNis H, C1-4alkyl, aryl, heteroaryl, or CH2Ph; L1is null or (CH2)n, wherein n is 1-3; and X2is L3ORe, L3CN, L3COORe, wherein L3is null, CH(Ph), C(Ph)(CH3), CH(CH3), or C(CH3)2, and Reis H, C1-4alkyl, C1-4alkylene-OH, CH2Ph, or [CH2CH2O]pRp, wherein p is 1-5 and Rpis H or CH3. Aspect 46. The polymer according to any aspect described herein, for example aspect 44 or aspect 45, wherein the polymer has the formula: Attorney Docket No.103362-032WO1 wherein P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, wherein Rp1*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs1*is independently selected from C1-4alkyl or phenyl; P2is selected from CH2aryl, C(=O)Rp2*, and SiRs2*3, wherein Rp2*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs2*is independently selected from C1-4alkyl or phenyl; P3is selected from CH2aryl, C(=O)Rp3*, and SiRs3*3, wherein Rp3*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs3*is independently selected from C1-4alkyl or phenyl; P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3, wherein Rp4*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs4*is independently selected from C1-4alkyl or phenyl; or wherein any pair of P1and P2, P2and P3, or P3and P4may together be -C(Rz1)(Rz2)-, wherein Rz1and Rz2are independently selected from H and C1-4alkyl, preferably CH3 or CH2CH3, or Rz1is H and Rz2is optionally substituted aryl or alkaryl, or Rz1and Rz2together form a carbonyl. Aspect 47. The polymer according to any aspect described herein, for example aspect 46, wherein P1and P2together are -C(Rz1)(Rz2)- and P3and P4together are - C(Rz1)(Rz2)-, or P2and P3together are -C(Rz1)(Rz2)-, P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, and P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3. Attorney Docket No.103362-032WO1 Aspect 48. The polymer according to any aspect described herein, for example aspect 46, wherein P1and P4are independently selected from C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS). Aspect 49. The polymer according to any aspect described herein, for example any one of aspects 46-48, wherein the polymer has the formula: . Aspect 50. The polymer according to any aspect described herein, for example any one of aspects 46-49, wherein P1is CH3, C(=O)CH3, C(=O)phenyl, benzyl, or paramethoxybenzyl; P2is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); P3is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); and P4is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS). Aspect 51. The polymer according to any aspect described herein, for example any one of aspects 46-50, wherein the polymer has the formula: Attorney Docket No.103362-032WO1 . Aspect 52. The polymer according to any aspect described herein, for example any one of aspects 44-51, wherein the polymer has the formula: . Aspect 53. The polymer according to any aspect described herein, for example any one of aspects 44-48, wherein the polymer has the formula: Attorney Docket No.103362-032WO1 . Aspect 54. The polymer according to any aspect described herein, for example aspect 53, wherein the polymer has the formula: , , Attorney Docket No.103362-032WO1 . Aspect 55. The polymer according to any aspect described herein, for example any one of aspects 44-54, wherein Ra1and Ra2are each CH3; Ra1is H and Ra2is CH3; or Ra1is CN and Ra2is CH3. Aspect 56. The polymer according to any aspect described herein, for example any one of aspects 44-55, wherein L3is null or C(CH3)2. Aspect 57. The polymer according to any aspect described herein, for example any one of aspects 44-56, wherein L1is null, CH2, or CH2CH2. Aspect 58. The polymer according to any aspect described herein, for example any one of aspects 44-57, wherein X2is CN, COOH, OCH3, or OH. Aspect 59. The polymer according to any aspect described herein, for example any one of aspects 44-58, wherein X1is L2N(RN)C(=S)S, and RNis CH3, pyridine-4-yl, phenyl, 4-fluorophenyl, or 4-cyanophenyl. Aspect 60. A particle including a polymer according to any aspect described herein, for example any one of aspects 44-59. Aspect 61. A method of making a particle, including subjecting a mixture including a solvent and the polymer of any aspect described herein, for example one of aspects 44-59, to conditions suitable to form a particle. Aspect 62. The method of any aspect described herein, for example aspect 61, wherein the mixture further includes a therapeutic agent. Attorney Docket No.103362-032WO1 A number of aspects of the disclosure have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the disclosure. Accordingly, other aspects are within the scope of the following claims. By way of non-limiting illustration, examples of certain aspects of the present disclosure are given below. EXAMPLES The following examples are set forth below to illustrate the compounds, compositions, and methods claimed herein, along with associated methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present disclosure, which are apparent to one skilled in the art. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of reaction conditions, e.g., component concentrations, temperatures, pressures, and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described processes. Only reasonable and routine experimentation will be required to optimize such process conditions. Synthesis of RAFT reagent for controlled radical polymerization of functionalized polymeric materials In this example, we describe a chain transfer agent (CTA) derived from D-galactose and evaluate its potential as a reversible addition–fragmentation chain-transfer (RAFT) agent. Using this galactose-based CTA, both hydrophilic and hydrophobic monomers were successfully polymerized along with their amphiphilic polymer, demonstrating its broad applicability. Additionally, we investigated the optimal reaction conditions, including initiator type and concentration, solvent, and Attorney Docket No.103362-032WO1 temperature. The resulting galactose-containing amphiphilic polymers self- assembled into polymeric nanoparticles (<150 nm, Dh) in aqueous media. These amphiphilic polymeric nanoparticles were subsequently characterized and investigated for their potential in biomedical applications. This example showcases the synthesis of end-functional macromolecules capable of complementing a range of synthetic routes towards functional polymeric materials. In this example, we describe a strategy by introducing D-galactose directly as the Z group in RAFT polymerization. The scope of this technique has been extended to functional polymers, including glycopolymers, for several biomedical applications. Traditionally, saccharide units have been introduced into polymers solely as monomers, and they have not often been used as components of RAFT agents (Biomacromolecules 2014, 15, 12, 4509–4519). The incorporation of the biologically significant molecule galactose as the Z group in RAFT reagents extends the role of sugars beyond their traditional function as monomers and generates inherently bioactive CTAs. This design enables controlled polymerization while providing a direct platform for glyco-functionalization, thereby opening opportunities in drug delivery, biomaterials, and glycopolymer research. To introduce the galactose moiety as the Z group in RAFT reagents, a galactose-based RAFT agent was synthesized, and its performance was evaluated for the polymerization of both hydrophilic and hydrophobic monomers. Using this RAFT agent, hydrophilic, hydrophobic, and amphiphilic polymers were synthesized under carefully optimized conditions to achieve the desired molecular weights with controlled polydispersity suitable for biomedical applications. The polymers were characterized by various techniques, confirming that the optimized conditions enabled precise control over polymerization with this innovative RAFT system. The results of this example, along with the demonstration of utility in forming saccharide- coated nanoparticles, significantly broaden the utility of RAFT, transforming it from a versatile polymerization technique into a design platform for next-generation functional materials with applications in nanomedicine. Results and Discussion Synthesis of RAFT Reagent Attorney Docket No.103362-032WO1 RAFT reagent governs the control, versatility, and fidelity of the polymerization process. The structure of the RAFT reagent typically contains a thiocarbonylthio moiety (Z–C(=S)–S–R). The Z and R group plays a crucial role in regulating chain growth by mediating a dynamic equilibrium between active and dormant chains. Fine-tuning these two groups enables the RAFT reagent to produce polymers with predictable molecular weights, narrow molecular weight distributions, and complex architectures. Here, we developed a galactose-based RAFT reagent based on a protected galactose unit as the Z group and an acid group with a spacer as the R group. Considering its ability to interact with specific receptors, we introduced the galactose unit into the RAFT reagent, making it a valuable building block for creating site- specific therapeutic agents. The synthesis of the galactose-based RAFT reagent included five steps. The synthesis of thiolated galactose was based on an established protocol where the secondary hydroxyls of D-galactose were protected using acetone in the presence of a catalytic amount of sulphuric acid to achieve (1) with a yield of 82%. The RAFT reagent was then synthesized by coupling with the 2,2-dimethyl bromo propionic acid, followed by tosylation (2)(yield 83%) and thiolation (3) (yield 38%) using tosyl chloride and thioacetate, respectively. Deacetylation of the thioacetate afforded intermediate 4 with 60% yield. The compound (4) was then treated with 2-bromomethyl propionic acid to obtain the desired galactose-based RAFT reagent (5)(yield 69%). Product 5 was confirmed by1H NMR spectroscopy. Characteristic signals for the protected galactose moiety were observed at 5.44, 4.55, 4.22, and 3.95 ppm, while the peaks at 3.57 and 3.33 ppm corresponded to the methyl protons adjacent to the thiocarbonylthio group CH2- S-C=S-S-. Resonance signals in the region between 1.24 –1.36 ppm confirmed the presence of the isopropylidene protecting group (CH3)2C- on the galactose unit. Additionally, a doublet at 1.65 ppm was attributed to methyl groups (CH3)2-S-C=S-S- located near the acid functionality. Collectively, these results confirmed the successful synthesis of the RAFT reagent. Polymerization Using Galactose-Based RAFT Reagent A protected galactose-based RAFT agent was employed in this example to introduce a structurally defined and functionalized end group without interfering with the Attorney Docket No.103362-032WO1 RAFT polymerization mechanism. The presence of protective groups (e.g., acetyl or benzyl) renders the galactose moiety hydrophobic, enhancing the solubility of the RAFT agent in organic solvents such as DMF or methanol. This hydrophobicity aligns well with the use of benzyl methacrylate (BzMA), a hydrophobic monomer, which ensures homogeneous reaction conditions and minimizes end-group aggregation. Additionally, the bulky sugar structure can impart subtle steric effects that may improve chain-end stability and reduce termination events. Notably, the galactose unit remains chemically latent during polymerization and can be deprotected post- synthetically to yield a bioactive saccharide-functional polymer chain end. Influence of Initiator on Polymerization The potential of the novel RAFT reagent was evaluated using benzyl methacrylate (BzMA) as a model monomer with V-50 (hydrophilic) and AIBN (hydrophobic) initiators, targeting polymers with a molecular weight of 10 kDa. BzMA was selected as the model monomer because it is the most frequently used monomer in RAFT polymerization, allowing the construction of polymers with controlled molecular weight, specific morphologies, and properties. Importantly, BzMA polymers exhibit favorable mechanical and self-assembling properties, thereby preventing the kinetic trapping of self-assembled molecules. V-50 was examined at multiple concentrations (0.02, 0.05, 0.1M) and in different solvent systems (DMF, MeOH, and MeOH / DMF mixtures at 70 °C) at a fixed [M]:[CTA] ratio of 54:1. Across all conditions, the polymerizations exhibited poor molecular weight control, broad dispersities, or negligible conversion. These observations are attributed to the limited solubility of V-50 in organic media, the decreased polarity associated with hydrophobic BzMA, and an elevated radical flux at higher temperatures, leading to uncontrolled chain initiation. Reactions conducted in anhydrous methanol proceeded more slowly and likewise failed to improve control, likely due to hydrogen-bonding effects that reduce methacrylate propagation, particularly for hydrophobic monomers that rely on optimal solvation. Based on the results from V50, we employed an alternative initiator, AIBN. AIBN is a common, hydrophobic initiator and typically works well in organic solvents. We maintained the initiator concentration at 0.1 M, the solution concentration at 25% w / v, and the reaction temperature at 50°C. The molecular weight evolution was Attorney Docket No.103362-032WO1 studied at different time points. After 5 h, the PDI of the polymer formed was 2.00, and the Mn (18,507 Da) and Mw (37,092 Da) values remained higher, which did not align with the theoretical molecular weight. The reaction was further incubated overnight, and it was observed that the Mn and Mw values were slightly lower than those of the 5 h samples, which were 14,626 and 34,430 Da, respectively. However, the dispersity (2.35) was higher than that of the polymerization reaction after 5 h. Table 1: Influence of reaction conditions on polymerization of BzMA using Gal RAFT reagent with AIBN Conditions: M: I: CTA= 1: 0.15 / 0.1 / 0.075 / 0.05: 54, solvent used is anhydrous solvent, ON: overnight samples (12-16 h). Attorney Docket No.103362-032WO1

[0002] Attorney Docket No.103362-032WO1 Interestingly, when the RAFT polymerization of benzyl methacrylate (BzMA) in anhydrous DMF at 70 °C was allowed to proceed overnight, a slight decrease in molecular weight (Mn) was observed compared to earlier time points. This phenomenon is consistent with RAFT end-group degradation and bimolecular termination events, which are known to occur under prolonged radical exposure and elevated temperatures. As reported by Moad et al., extended heating in polar solvents can compromise the thiocarbonylthio end group of RAFT agents, leading to chain fragmentation or loss of living character. Perrier also highlighted that when monomer conversion is high, continued radical generation can cause termination between active chains, producing dead polymers and shifting the molecular weight distribution. Attorney Docket No.103362-032WO1 Additionally, radical-induced backbone scission reactions may occur during prolonged thermal exposure, especially in methacrylate systems in polar environments. We next increased the solvent concentration to 50% w / v, maintaining the initiator concentration, monomer-to-initiator ratio, and temperature as in the previous reaction. The change in solvent concentration resulted in polymerization within 2 hours. The molecular weight, as determined by GPC (Mn 19,000, Mw 22,277 Da), was higher than theoretical, but the PDI (1.17) was lower (Table 1). The reaction was further allowed to run, and after 4 hours, the molecular weight decreased (Mn 13897, Mw 18391 Da), but with an increase in the PDI (1.32). This decrease in molecular weight can be attributed to several reasons mentioned above, such as chain fragmentation and RAFT reagent degradation. Interestingly, when the initiator concentration was increased to 0.15 M under identical conditions at different time points, the Mn value obtained after 3 hours via GPC agreed with the theoretical molecular weight. However, the polymer obtained had a higher polydispersity index of 1.55 Ð. For the overnight sample, the molecular weight increased as expected. However, the polydispersity was drastically improved (1.14 Ð), indicating that a higher radical flux under these specific conditions may have overcome oxygen inhibition or maintained a sufficient population of active chains, thus delaying degradation and supporting continued propagation. Over time, as more chains propagate and dormant chains re-enter the RAFT equilibrium, the system undergoes chain-length equalization, resulting in a narrower molecular weight distribution. These observations are consistent with recent findings by Taylor et al., who demonstrated that high initiator concentrations in RAFT polymerization promote oxygen tolerance and lead to improved polymer control with time. The effect of varying AIBN concentration on the RAFT polymerization of benzyl methacrylate (BzMA) was evaluated under constant conditions: 70 °C, 50% w / v solvent concentration, and galactose-based RAFT agent. At a lower initiator concentration (0.05 M), polymerization was only observed after 3 hours, indicating delayed initiation, likely due to insufficient radical flux. In contrast, increasing the initiator concentration to 0.075 M and 0.1 M led to rapid polymerization, initiating within the first hour. The molecular weight increased with time at lower initiator concentrations (0.05 M and 0.075 M), but showed poor control, with PDI values Attorney Docket No.103362-032WO1 ranging from 1.41 to 1.45. At a higher initiator concentration (0.1 M), the molecular weight decreased over time, and the dispersity broadened significantly, with the polydispersity index (PDI) increasing from 1.49 to 1.69 after 4 h. These results confirm that AIBN concentration critically influences not only the rate of polymerization initiation but also molecular weight buildup and control, with higher concentration leading to increased radical termination events and reduced control over the RAFT process. Based on these findings, we proceeded with an initiator concentration of 0.075 M and aimed to achieve the desired molecular weight by reducing the solvent concentration to 30% w / v. The reaction was maintained for 5.5 hours. The ¹H NMR spectrum displayed a broad peak corresponding to the benzyl proton (-CH2-O-) signal at 4.8 ppm and the aromatic proton (-CH-) signals at 7.2 ppm, confirming the polymerization. A doublet at 5.4 ppm indicated the presence of the Gal-RAFT reagent (-CH-O-) and remained stable during the reaction, as no additional peak was observed. We successfully achieved the targeted molecular weight (Mn 10,931 Da) with a well-dispersed polydispersity index of 1.05. (Table 2) The improved control is attributed to the optimized balance between radical flux and monomer concentration, along with the consistent chain-transfer behavior of the RAFT agent. Although the galactose moiety was protected, it provides a chemically versatile handle for post-polymerization modifications, making the system suitable for designing functional glycopolymers. We expanded our synthesis towards targeted molecular weights of 20 kDa with [M]: [CTA]: [I] = 111: 1: 0.075 and 30 kDa with [M]: [CTA]: [I] = 167: 1: 0.075 respectively under the same optimized conditions used for the 10 kDa polymer (i.e., 0.075 M AIBN concentration and 30 % w / v dioxane). In both cases, we achieved polymers with molecular weights in close agreement with theoretical values and narrow polydispersity indices (Table 2), indicating excellent control over polymerization. The synthesized polymers were studied using ¹H NMR, and these results confirmed that the protected galactose-functionalized RAFT reagent was suitable for the controlled polymerization of hydrophobic monomers, such as benzyl methacrylate. Its efficient chain-transfer behavior and compatibility with the reaction medium support the synthesis of well-defined polymers across a range of target molecular weights. Attorney Docket No.103362-032WO1 Table 2: Synthesis of different molecular weights p(BzMA) polymer using AIBN as initiator Kinetics Study using BzMA The kinetics of RAFT polymerization of BzMA involve several key steps, including initiation, pre-equilibrium, reinitiation, main equilibrium, propagation, and termination. Factors such as solvent composition, RAFT agent concentration, and temperature influence each step. Here, the kinetics of the polymerization of BzMA were observed in anhydrous dioxane at 70 °C with a CTA to benzyl methacrylate ratio [CTA]:[M]:[I] = 0.075:45:1. Where in the rate of polymerization was influenced by initiator concentration, monomer concentration, propagation rate (kp), and the structure of leaving group and stabilizing group of the CTA. The kinetics profile of Gal-pBzMA homopolymer demonstrated this to be an example of classic RAFT with approx.98% conversion within 5.5 hrs. Influence of Monomers After applying the galactose-based RAFT reagent for the polymerization of BzMA, a hydrophobic monomer, we optimized the performance of the galactose-based RAFT reagent for the polymerization of hydrophilic monomers. DMAEMA was selected as the model hydrophilic monomer because its tertiary amine imparts pH- and temperature-responsive behavior, it is highly soluble in aqueous / organic media, and Attorney Docket No.103362-032WO1 it readily undergoes controlled radical polymerization, affording stimuli-responsive platforms and functional polymer architectures. Similar reaction conditions were maintained for the hydrophobic monomer. AIBN was used as the initiator, anhydrous dioxane as the solvent, with a 30 % w / v solution concentration. The reaction was maintained at 70°C for 5.5 h, with a theoretical molecular weight of 20 kDa. NMR confirmed the polymerization of DMEMA with the Gal-RAFT reagent, denoting a broad peak at 4.04 ppm corresponding to the CH₂- OC=O group. The polymerization of DMEMA was not controlled, as observed from the molecular weight calculated by NMR and GPC. Mn (NMR), Mn and Mw values obtained were 21,343 Da, 18,263 Da, and 22,060 Da with a PDI of 1.21, respectively. The GPC spectra displayed a unimodal peak with a minor shoulder, suggesting that some chains were shorter than expected, which resulted from degradation of end group fidelity. This was further supported by the NMR spectrum, which showed an additional doublet at 5.5 ppm corresponding to the anomeric proton of galactose, confirming partial degradation of the RAFT reagent. As a result, some polymer chains are terminated prematurely, which accounts for the slight reduction in molecular weight observed by GPC compared to the theoretical value. The degradation is likely due to the nature of DMAEMA, which may promote side reactions of the RAFT end-group under thermal conditions. These findings align with previous reports, where monomers bearing basic functional groups have been shown to compromise RAFT end-group integrity, resulting in chain termination and lower- than-expected molecular weights. Hafliger et. al. reported that extended heating can degrade RAFT end-groups, leading to a measurable decrease in molecular weight. Similarly, Stace et. al. observed that RAFT polymers lose their thiocarbonyl end- groups at temperatures below those required for backbone degradation, notably affecting molecular weight control. Hence, the type of monomer and temperature can affect the molecular weight built up in RAFT polymerization. Block Copolymer Synthesis After evaluating RAFT polymerization of individual monomers, we synthesized amphiphilic block copolymers of benzyl methacrylate (BzMA, hydrophobic) and DMAEMA (hydrophilic). The 10 kDa BzMA macro-CTA was chain-extended with DMAEMA (target 10 kDa) to yield a 20 kDa block copolymer. Polymerization used Attorney Docket No.103362-032WO1 dioxane (30% w / v), 0.075 equiv. initiator, at 70 °C for 5.5 h under previously optimized conditions. NMR confirmed the polymerization, with a degree of polymerization (DP) of 65 hydrophobic units and 62 hydrophilic units contributing to a molecular weight of 21,220 Da, which is slightly higher than the theoretical value. In comparison, the molecular weights obtained by GPC agreed with the theoretical values, with Mn = 20,453 Da and Mw = 24,544 Da, respectively. The peak obtained by GPC was unimodal, indicating that both units had similar molecular weights. Self-Assembly and Deprotection of Gal-pBZMA-b-PDMAEMA Block Copolymers With the amphiphilic polymer in hand, nanoparticles via polymer self-assembly were formed. Based on the block architecture, micelles are expected, with pBzMA forming the core and pDMAEMA constituting the corona. The particle size was analyzed in aqueous media using DLS, which affords the hydrodynamic diameter (Dh). Protected Gal-pBZMA-b-PDMAEMA has a particle size with an intensity average diameter of 190.04 ± 1.53 nm, with 0.11 PDI and a zeta potential of 27.72 ± 0.23 mV. In parallel, the block copolymer Gal-pBZMA-b-PDMAEMA was treated with 8% (v / v) TFA in chloroform for 4 hours to deprotect the isopropylidene groups present on the galactose moiety. These nanoparticles resulted in an intensity average diameter of 102.1 ± 0.44 nm, with 0.096 PDI and a zeta potential of 25.98 ± 0.70 mV. The size of the nanoparticles decreased upon deprotection, which may have resulted from the removal of the isopropylidene groups. These protecting groups result in the aggregation of the polymer chains or adoption of a more extended conformation, hence a higher hydrodynamic volume. Whereas the deprotection created a more compact, soluble polymer, resulting in a smaller hydrodynamic radius observed in DLS measurements. A similar result was obtained by Wu et al., in which the deprotection of the acetate group from the sugars resulted in the shrinkage of the nanoparticles. As they mentioned, the fast reaction of acetate makes the assemblies with more kinetically trapped features. The zeta potential values after deprotection of the galactose unit decreased slightly. This could be because deprotection results in attracting water molecules that form a hydrophilic neutral layer, which may further Attorney Docket No.103362-032WO1 shield the charges captured by the zeta potential measurements, leading to a decrease in the measured zeta potential values. Conclusion Here, we describe a galactose-based CTA and demonstrate its utility in aqueous RAFT polymerization. Using this CTA, hydrophilic, hydrophobic, and amphiphilic polymers were successfully synthesized. AIBN, with a 0.075 concentration in dry dioxane, seemed to be suitable for the polymerization of the BzMA reaction using this galactose-based CTA. The amphiphilic polymers self-assembled into nanoparticles in aqueous media, and both the protected and deprotected forms were thoroughly characterized and evaluated for biomedical applications. Dynamic light scattering (DLS) analysis revealed nanoparticle sizes of 190 nm (protected) and 102 nm (deprotected), with corresponding zeta potentials of +27.72 mV and +25.98 mV. The observed decrease in size and slight reduction in zeta potential upon deprotection are attributed to a slight increase in water affinity resulting from the hydroxyl groups formed, which enhances hydration and polymer assembly, thereby altering the hydrodynamic diameter and partially shielding surface charges. Materials D-galactose, lithium aluminum hydride (LAH) in 2M THF, 2-bromo-2-methyl propionic acid, benzyl methacrylate, 2-(Dimethylamino)ethyl methacrylate (DMAEMA), AIBN (2,2'-Azobis(2-methylpropionitrile), carbon disulfide, and K3PO4were procured from Sigma, 2-(hydroxymethyl)-2-methylpropanoic acid, 2- (hydroxyethyl)methacrylate, para toluene sulfonic chloride (pTSCl), V50(2,2'- Azobis(2-methylpropionamidine) dihydrochloride), sulfuric acid were supplied by thermo fisher scientific. Potassium thioacetate was obtained from TCI. All the solvents used were anhydrous. All chemicals were used as received, unless otherwise specified. General equipment Nuclear Magnetic Resonance Spectroscopy.1H NMR spectroscopy was performed using a 400 MHz Bruker AVANCE III spectrometer. Chain transfer agent and monomer spectra were acquired with 32-64 co-added scans and a delay time of Attorney Docket No.103362-032WO1 5 s. Polymer spectra were acquired using 64 co-added scans and a delay time of 2 seconds. All spectra were obtained using the appropriate deuterated solvents (CDCl3, DMSO-d6, or MeOH-d4) and were processed and analyzed using MNova software. Gel Permeation Chromatography Protected glycopolymer weight- and number-average molecular weights were determined using an Agilent Technologies 1260 Infinity multidetector suite (refractive index detector only) and an Agilent Technologies 1260 ISO pump fitted with a 1260 ALS autosampler. The GPC eluent was HPLC-grade DMF containing 0.01% LiBr and was filtered prior to use. GPC / SEC was equipped with a 300 x 8 mm PSS GRAM analytical column and 50 x 8 mm guard column. HPLC-grade DMF was used as the eluent at a flow rate of 0.5 mL / min, operating at 55 °C with a sample concentration of 5 mg / mL and an injection volume of 100 μL. The instrument was calibrated with linear poly(methyl methacrylate) standards (800 Da - 40kDa). All samples were passed through 0.2 μm nylon filters prior to GPC measurements. Preparation and Characterization of Nanoparticles Polymer systems were formed into nanoparticles via a previously reported nanoprecipitation method.1 mg of the polymer was dissolved in THF (200 µL), and the resulting solution was added dropwise to a vial containing MilliQ water (2 mL) while sonicating. THF was allowed to evaporate under constant nitrogen flow. Nanoformulations were allowed to equilibrate for 12 h before testing. Particle size and zeta potential (ζ-potential) measurements were carried out on a Zetasizer Nano ZS (Malvern Instrument) using a He−Ne laser (633 nm) detector angle of 173° at 25 °C. Concentration was maintained at 0.5 mg / mL for all systems, and all measurements were performed in triplicate to ensure consistency. Environmental TEM obtained morphologies of the nanoparticles. Kinetics Experiments Kinetic studies were performed to monitor monomer conversion during RAFT polymerization. Polymerizations were conducted under the standard conditions as described below. At predetermined time intervals, small aliquots (0.20 mL) of the reaction mixture were withdrawn using a degassed syringe under a nitrogen Attorney Docket No.103362-032WO1 atmosphere. Each aliquot was rapidly quenched by cooling and exposed to air. The quenched samples were diluted with a deuterated solvent and analyzed by1H NMR spectroscopy to determine monomer conversion by integrating the characteristic resonances of the monomer and polymer. Spectra of the aliquots were analyzed to determine the evolution of molecular weight (Mn vs. conversion) and degree of polymerization (DP). Plots of ln([M]₀ / [M]) vs. time were generated to evaluate pseudo-first-order kinetics, while Mn and Ð vs. monomer conversion were plotted to assess molecular weight evolution and control over dispersity. Synthesis Procedures Synthesis of 1,2:3,4-Di-O-isopropylidene-α-D-galactopyranose (1). This product was synthesized using a previously reported procedure with slight modifications. Briefly, D-(+)-galactose (7 g, 38.85 mmol) was suspended in dry acetone (250 mL) followed by parallel addition of conc. H2SO4 (7.7 mL) at 0 °C in the presence of Argon. The reaction mixture was allowed to stir at room temperature for 5 hours, after which it was neutralized using a saturated solution of Na2CO3, monitored using pH paper. The formed precipitate was filtered using Celite. The filtrate was concentrated under reduced pressure. The crude diacetonide-protected d-(+)-galactose (1) (8.25 g, 82%) was used without further purification.1H NMR (400 MHz, CDCl3) δ 5.59 (d, J = 5.39 Hz, 1H), 4.64 (dd, J1 = 7.85 Hz, J2 =2.42 Hz, Attorney Docket No.103362-032WO1 iH), 4.36 (dd, J = 5.09 Hz, J = 2.38 Hz, 1H), 4.29 ( d, J = 7.8 Hz, 1H), 3.89 (m, 2H), 3.77 (m, 1H), 1.56 (s, 3H), 1.48 (s, 3H), 1.36 109.47, 108.69, 96.30, 71.60, 70.76, 70.57, 68.10, 62.32, 26.03, 25.93, 24.94, 24.30. Synthesis of 1,2:3,4-Di-O-isopropylidene-6-O-tosyl-α-D-galactopyranose (2). Diisopropylidene galactose 1 (8.25 g, 31.70 mmol) and pTsCl (12.09 g, 63.39 mmol) were stirred in anhydrous pyridine (70 mL) under argon for 1 h and then kept overnight at ice temperature. The reaction mixture was stirred overnight at room temperature. After which, the reaction was filtered, and the filtrate was poured over water. A workup was then performed using ether. The reaction mixture was worked up with 1 M HCl and brine, dried over sodium sulfate, concentrated, and the NMR was recorded. Column chromatography was performed, and the product was separated at 10% ethyl acetate: hexane mixture (11.81 g, 83 % yield).1H NMR (400 MHz, CDCl3) δ 7.81 (m, 2H), 7.33 (m, 2H), 5.45 (d, J = 5 Hz, 1H), 4.58 (dd, J= 7.82 and 2.52 Hz, 1H), 4.29 (dd, J = 5.0 and 2.59 Hz, 1H ), 4.20 (m, 2H), 4.07 (m, 2H), 2.53 (s, 3H), 1.50 (S, 3H), 1.34 (S, 3H), 1.31 δ 21.65, 24.36, 24.93, 25.82, 25.99, 65.88, 68.20, 70.38, 70.41,70.53, 96.14, 108.96, 109.60, 128.14, 129.76, 132.83, 144.77. Synthesis of 6-Thioacetate-1,2:3,4-di-O-iso-propylidene-D- galactopyranose (3). The galactose tosylate (2) (10.81 g, 26.08 mmol) was treated with potassium thioacetate (6 g, 2 equiv, 52.16 mmol), dissolved in dry DMF (70 mL), and heated at 50 °C for 10 h, as per the reported protocol. Afterward, the reaction mixture was poured into water, followed by extraction using dichloromethane. The organic phase was then dried over sodium sulfate and concentrated. Column chromatography was performed and the sample was separated using a 5% ethyl acetate-hexane mixture. (yield: 6.7 g, 81% yield) NMR (400 MHz) δ 5.51 (d, J = 4.88 Hz, 1H), 4.61 (dd, J1 = 7.91 Hz, J2 = 2.5 Hz, 1H), 4.29 (dd, J1 = 4.96 Hz, J2 = 2.42 Hz, 1H), 4.26 (dd, J1= 7.81 Hz, J2= 1.89 Hz, 1H), 3.85 (m, J1= 8.58 Hz, J2= 5.05 Hz, J3 = 1.82 Hz, 1H), 3.16 (dd, J1 = 13.79 Hz, J2 = 5.26 Hz, 1H), 3.03 (dd, J1 = 13.99 Hz, J2= 8.7 Hz, 1H), 2.34 (s, 3H), 1.48 (s, 3H), 1.45 (s, 3H), 1.35 (s, 3H), 1.32 (S, 3H).13C NMR (400 MHz) δ 24.44, 24.99, 25.95, 29.71, 30.53,66.84, 70.53, 70.96, 72.07, 96.54, 108.80, 109.49,195.83. Synthesis of 6-Thio-1,2:3,4-di-O-iso-propylidene-D-galactopyranose (4). Following the known procedure with a modification, 6.7 g of (3) was dissolved in Attorney Docket No.103362-032WO1 anhydrous THF, and 2 M of LAH (in THF) was added dropwise at 0°C. After stirring for 1 h, complete conversion was observed. The reaction was quenched with water, and THF was evaporated. The remaining aqueous phase was treated with chloroform three times, concentrated, and dried. The reaction was subjected to column chromatography, and the pure product was obtained using a 5% ethyl acetate: hexane mixture. (yield: 3.69 g, 56%).1H NMR (400 MHz) δ 5.46 (d, J = 5.09 Hz, 1H), 4.56 (dd, J1= 7.95 Hz, J2= 2.49 Hz, 1H), 4.28 (dd, J1= 7.70 Hz, J2= 2.28 Hz, 1H), 4.25 (dd, J1 = 5 Hz, J2 = 2.5 Hz, 1H), 3.72 (M, 1H), 2.64 (m, 2H), 1.55 (dd, J1 = 7.65 Hz, J2 = 2.5 Hz, 1H), 1.48 (s, 3H), 1.37 (s, 3H), 1.28 (s, 3H), 1.27 MHz) δ 24.45, 24.48, 24.94, 25.98, 26.05,69.91, 70.57, 70.90, 71.29, 96.64, 108.72, 109.51. Synthesis of the RAFT CTA (chain transfer agent). 2.83 g (1.1 equiv, 13.35 mmol) of K3PO4was suspended in anhydrous acetone in a round-bottom flask. Argon was purged for 30 minutes. (4) (3.69 g, 1.1 eq, 13.35 mmol) was dissolved separately in dry acetone, purged, and added dropwise to the RBF under Argon for over 30 min. Followed by the dropwise addition of carbon disulfide (2.2 mL, 3 eq, 36.42 mmol) (1mL in 3 min), and lastly, 2-bromo-2-methyl propionic acid (2.03 g, 1.0 eq, 12.14 mmol) was added to the mixture. The reaction was allowed to stir overnight, after which acetone was removed from the reaction mixture under vacuum. A yellow solid was obtained and dissolved in 1 M HCl, then extracted with DCM. The DCM layer was further washed with 200 mL of water, 200 mL of brine, dried over sodium sulfate, and purified by column chromatography using 20% ethyl acetate in hexanes. (Yield: 5.1 g, 88%). ESI-MS: 439.0919 m / z.1H NMR (400 MHz) δ 5.44 (d, J = 5.3 Hz, 1H), 4.55 (dd, J1= 7.86 Hz, J2= 2.5 Hz, 1H), 4.21 (m, J1= 8.9 Hz, J2= 5.14 Hz, J3= 2.5 Hz, 2H), 3.94 (m, J1= 8.72 Hz, J2= 4.45 Hz, J3= 2.15 Hz, 1H), 3.57 (dd, J1= 13.95 Hz, J2 = 4.75 Hz, 1H), 3.33 (dd, J = 13.93 Hz, J = 8.59 Hz, 1H), 1.65 (s, 6H), 1.39 (s, 3H), 1.36 (d, J = Hz, 3H), 1.26 (s, 3H), 1.24 24.45, 24.48, 24.94, 25.98, 26.05,69.91, 70.57, 70.90, 71.29, 96.64, 108.72, 109.51. Attorney Docket No.103362-032WO1 RAFT polymerization of BzMA. Galactose-containing BzMA homopolymers (pGalBzMA) were synthesized using previously published literature procedures. Glycopolymers with a target degree of polymerization (DP) of 54 (molecular weight = 10,930 g / mol), 111 (molecular weight = 22,310 g / mol), and 167 (molecular weight = 29,074 g / mol) were synthesized by RAFT polymerization. The galactose- containing chain transfer agent, thermal initiator (AIBN), and BzMA were dissolved in anhydrous dioxane in a 25-mL round-bottom flask equipped with a magnetic stirring bar, and the mixture was degassed with ultrapure argon for 45 minutes while stirring. All polymerizations were carried out at an initial monomer concentration of 1.7 M. The [M]0:[CTA]0 varied depending on the target molecular weight for each reaction, while the [CTA]0:[I]0was maintained at 13:1. Reactions were carried out for 5.5 hours to achieve a final monomer conversion of 95%. To determine the reaction times required to achieve the desired molecular weights, kinetic studies were performed, where the appearance of the benzyl peak (4.8 ppm, 2H) was monitored by ¹H NMR spectroscopy and compared to the sugar peak (5.4 ppm, 1H) of the MCTA at various reaction times. After the target molecular weights were achieved, the reaction was quenched by opening the RBF to air and precipitating the reaction mixture into a 6:3:1 hexane, diethyl ether, and MeOH solution. The reaction mixture was redissolved in CHCl3, and precipitation was performed four times. The liquid was decanted, leaving behind a pale yellow solid (pGalBzMA). RAFT polymerization of DMAEMA. Galactose-containing DMAEMA homopolymer (pGalDMAEMA) was synthesized using an established synthesis procedure. Glycopolymers with a target degree of polymerization of 124 (molecular weight = 21,343 g / mol) were synthesized by RAFT polymerization. The galactose- containing chain transfer agent, thermal initiator (AIBN), and DMAEMA were dissolved in anhydrous dioxane in a 25-mL round-bottom flask equipped with a magnetic stirring bar. The mixture was degassed with ultrapure argon for 45 minutes while stirring. The polymerization was carried out at an initial monomer concentration of 1.7 M. The [M]0:[CTA]0:[I] was maintained at 124:1:0.075. Reactions were carried out for 5.5 hours to achieve a final monomer conversion of 93%. After the target molecular weight was achieved, the reaction was quenched by opening the RBF to air and precipitating the reaction mixture into a cold hexane solution. The reaction mixture was redissolved in CHCl3, and precipitation was Attorney Docket No.103362-032WO1 performed four times. The liquid was decanted, leaving behind a colorless amorphous solid (pGalDMAEMA). RAFT polymerization for diblock copolymer synthesis. A galactose- containing diblock copolymer (Gal-pBzMA-b-DMAEMA) was synthesized using a procedure similar to previous syntheses. A diblock copolymer with a target molecular weight = 20,000 g / mol was synthesized by RAFT polymerization. The galactose- containing macro chain transfer agent (pBzMA homopolymer), thermal initiator (AIBN), and DMAEMA were dissolved in anhydrous dioxane in a 25-mL round- bottom flask equipped with a magnetic stirring bar. The mixture was degassed with ultrapure argon for 45 minutes, stirring continuously. The polymerization was carried out at an initial monomer concentration of 1.7 M. The [M]0:[CTA]0:[I] was maintained at 124:1:0.075. Reactions were carried out for 5.5 hours to achieve a final monomer conversion of 82%. After the target molecular weight was achieved, the reaction was quenched by opening the RBF to air and precipitating the reaction mixture into a cold hexane solution. The reaction mixture was redissolved in CHCl3, and precipitation was performed four times. The liquid was decanted, leaving behind a white solid (Gal-BzMA-b-DMAEMA). References F. Hatton, Polym. Chem., 2020, 11, 220-229. Macromol. Rapid Commun., 27: 473-497. Macromolecules 2021, 54, 20, 9496–9509. Polym. Chem., 2024, 15, 868-877. Polymer,79, 2015, 205-211. Polym. Chem., 2015, 6, 7119-7126. Attorney Docket No.103362-032WO1 Nanoscale, 2025, 17, 14164-14171. Polym. Chem., 2012, 3, 1182-1188. European Polymer Journal, 142, 2021, 110147. Chem. Soc. Rev., 2023, 52, 2617-2642. Carbohydrate Research, 555, 2025 ,109561. Top Curr Chem (Z) 380, 45 (2022). J. Am. Chem. Soc.2013, 135(36):13574–13581. Polymers, 157, 2020, 104766. Angew Chem Int Ed Engl.2021; 60(20):11098–11103. J. Mater. Chem. B, 2016, 4, 4696-4706. Angew. Chem. Int. Ed.2021, 60, 11098. European Polymer Journal, 2021, Vol: 159, Page: 110713. Macromol. Chem. Phys.2024, 226, 2400354. Macromolecules, 2014, 47, 28, 9380–9388. Polym. Chem., 2022,13, 3696-3704. Molecules 2023, 28(6), 2588. Macromolecules 2004, 37, 24, 8941–8950. Polymer Journal, Vol.13, No. I, pp 41-50 (1981). Polym. Chem., 2022, 13, 4798-4808. Polym. Chem., 2022, 13, 3696-3704. Chem. Rev.2009, 109 (11), 663–676. New J. Chem., 2022, 46, 15321-15333. ACS Macro Lett.2023, 12, 9, 1207–1212. Macromol. Rapid Commun.2018, 1800228. Polymers 2022, 14(3), 570. Attorney Docket No.103362-032WO1 The references cited herein are hereby incorporated by reference to disclose and describe the methods or materials in connection with which the publications are cited or to provide background for the present disclosure. Any incorporation by reference of documents herein is limited such that no subject matter is incorporated by reference that is contrary to the explicit disclosure herein. In the event of inconsistent usages between this document and those documents so incorporated by reference herein, the use in the incorporated references should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims, and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods, in addition to those shown and described herein, are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.

Claims

Attorney Docket No.103362-032WO1 WHAT IS CLAIMED IS:

1. A compound of Formula I:wherein: Rcis a carbohydrate; Ra1and Ra2are independently selected from H, CH3, Ph, and CN; X1is selected from L2SC(=S)S, L2SC(=S), or L2NRNC(=S)S wherein L2is null, (CH2)0,or [CH2CH2O]o, wherein o is 1-5, and RNis H, C1-4alkyl, aryl, heteroaryl, or CH2Ph; L1is null or (CH2)n, wherein n is 1-3; and X2is L3ORe, L3CN, L3COORe, wherein L3is null, CH(Ph), C(Ph)(CH3), CH(CH3), or C(CH3)2, and Reis H, C1-4alkyl, C1-4alkylene-OH, CH2Ph, or [CH2CH2O]pRp, wherein p is 1-5 and Rpis H or CH3.

2. The compound according to claim 1, wherein Rcis a glucose residue, a galactose residue, or a mannose residue.

3. The compound according to claim 1 or claim 2, wherein Rchas the formula:, wherein one of R2, R3, R4, or R6represents a bond to X1; R1is OH, OCH3, or OP, and the remaining of R2, R3, R4, or R6are selected from H, OH, OP, wherein P represents a protecting group or a further carbohydrate, wherein any two or more of the remaining of R1, R2, R3, R4, or R6can together form a ring.

4. The compound according to claim 3, wherein P in each case is independently selected from CH2aryl, C(=O)Rp, SiRs3, or C(Rz1)(Rz2)-*, wherein Rpis independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rsis independently selectedAttorney Docket No.103362-032WO1 from C1-4alkyl or phenyl, * represents a bond to a further P group, Rz1and Rz2are independently selected from H and C1-4alkyl, preferably from CH3, and CH2CH3, or Rz1is H and Rz2is optionally substituted aryl or alkaryl, or Rz1and Rz2together form a carbonyl.

5. The compound according to any one of claims 1-4, wherein R4and R3together form an acetal or carbonate; and R2and R1together form an acetal or carbonate.

6. The compound according to any one of claims 1-5, wherein Rchas the formula:

7. The compound according to any one of claims 1-6, wherein Rchas the formula:

8. The compound according to any one of claims 1-7, wherein, Rchas the formula:.

9. The compound according to any one of claims 3-8, wherein R6represents a bond to X1.Attorney Docket No.103362-032WO1 10. The compound according to any one of claims 1-9, wherein the compound has the formula:, wherein P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, wherein Rp1*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs1*is independently selected from C1-4alkyl or phenyl; P2is selected from CH2aryl, C(=O)Rp2*, and SiRs2*3, wherein Rp2*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs2*is independently selected from C1-4alkyl or phenyl; P3is selected from CH2aryl, C(=O)Rp3*, and SiRs3*3, wherein Rp3*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs3*is independently selected from C1-4alkyl or phenyl; P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3, wherein Rp4*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs4*is independently selected from C1-4alkyl or phenyl; or wherein any pair of P1and P2, P2and P3, or P3and P4may together be -C(Rz1)(Rz2)-, wherein Rz1and Rz2are independently selected from H and C1-4alkyl, preferably CH3or CH2CH3, or Rz1is H and Rz2is optionally substituted aryl or alkaryl, or Rz1and Rz2together form a carbonyl.

11. The compound according to claim 10, wherein: P1and P2together are -C(Rz1)(Rz2)- and P3and P4together are -C(Rz1)(Rz2)-; or P2and P3together are -C(Rz1)(Rz2)-, P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, and P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3.Attorney Docket No.103362-032WO1 12. The compound according to claim 10, wherein P1and P4are independently selected from C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS).

13. The compound according to any one of claims 10-12, wherein the compound has the formula:

14. The compound according to any one of claims 10-13, wherein the compound has the formula:

15. The compound according to any one of claims 10-14, wherein the compound has the formula:Attorney Docket No.103362-032WO1.

16. The compound according to any one of claims 10-15, wherein P1is CH3, C(=O)CH3, C(=O)phenyl, benzyl, or paramethoxybenzyl; P2is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); P3is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); and P4is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS).

17. The compound according to any one of claims 10-16, wherein the compound has the formula:.

18. The compound according to any one of claims 10-17, wherein Rz1and Rz2are each CH3 or CH2CH3.

19. The compound according to any one of claims 10-17, wherein Rz1is H and Rz2is benzyl or paramethoxybenzyl.Attorney Docket No.103362-032WO1 20. The compound according to any one of claims 10-17, Rz1and Rz2together form a carbonyl.

21. The compound according to any one of claims 1-20, wherein compound has the formula:.

22. The compound according to any one of claims 1-21, wherein X1is L2SC(=S)S or L2SC(=S).

23. The compound according to any one of claims 1-22, wherein L2is null or OCH2CH2.

24. The compound according to any of claims 10-20, wherein the compound has the formula:Attorney Docket No.103362-032WO125. The compound according to 24, wherein the compound has the formula:.

26. The compound according to claim 24 or claim 25, wherein the compound has the formula:.

27. The compound according to any one of claims 1-26, wherein Ra1and Ra2are each CH3; Ra1is H and Ra2is CH3; or Ra1is CN and Ra2is CH3.

28. The compound according to any one of claims 1-27, wherein L3is null or C(CH3)2.

29. The compound according to any one of claims 1-28, wherein L1is null, CH2, or CH2CH2.

30. The compound according to any one of claims 1-29, wherein X2is CN, COOH, OCH3, or OH.

31. The compound according to any one of claims 1-20, wherein X1is L2N(RN)C(=S)S, and RNis CH3, pyridine-4-yl, phenyl, 4-fluorophenyl, or 4- cyanophenyl.Attorney Docket No.103362-032WO1 32. A method of polymerizing a monomer, comprising subjecting a mixture comprising the monomer, a radical initiator, and the compound according to any one of claims 1-31 to conditions suitable to generate a radical from the radical initiator.

33. The method according to claim 32, wherein the monomer comprises a (meth)acrylate, (meth)acrylamide, (meth)acrylic acid, an α-olefin, or a combination thereof.

34. The method according to claim 32, wherein the monomer can have the formula:wherein Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl.

35. The method according to claim 32, wherein the monomer can have the formula:wherein Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, heteroaryl, NH2, NH(C1-C6alkyl), or N(independently C1- C6 alkyl)2.

36. The method according to any one of claims 32-35, wherein the compound is present in an amount from 0.1-25 mol%, from 1-25 mol, from 5-25 mol%, or from 10- 25 mol% (relative to the monomer).

37. The method according to any one of claims 32-36, wherein the radical initiator comprises an azo compound.

38. The method according to any one of claims 32-37, wherein the radical initiator comprises a thermal initiator, a photoinitiator, or a combination thereof.Attorney Docket No.103362-032WO1 39. The method according to any one of claims 32-38, wherein the radical initiator can be AIBN, ACHN, V50, ACP, ABVN, or K2S2O8.

40. A method of preparing a block copolymer, comprising subjecting a mixture comprising a first monomer, radical initiator, and compound according to any one of claims 1-31 to conditions suitable to generate a radical from the radical initiator, allowing the first monomer to be consumed, and then adding a second monomer to the mixture.

41. The method according to claim 40, wherein the first monomer comprises a hydrophobic monomer and the second monomer comprises a hydrophilic monomer, or wherein the first monomer comprises a hydrophilic monomer and the second monomer comprises a hydrophobic monomer.

42. The method according to any one of claims 32-41, further comprising converting each of R1, R2, R3, and R4to OH.

43. A polymer prepared according to the method of any one of claims 32-42.

44. A polymer having the formula: ,wherein:Attorney Docket No.103362-032WO1 z is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50- 100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; z* is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50-100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl; Rm*is H or CH3, Xm*is O or NH, and Rq*is H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, or heteroaryl; Rcis a carbohydrate; Ra1and Ra2are independently selected from H, CH3, Ph, and CN; X1is selected from L2SC(=S)S, L2SC(=S), or L2NRNC(=S)S wherein L2is null, (CH2)o, or [CH2CH2O]o, wherein o is 1-5, and RNis H, C1-4alkyl, aryl, heteroaryl, or CH2Ph; L1is null or (CH2)n, wherein n is 1-3; and X2is L3ORe, L3CN, L3COORe, wherein L3is null, CH(Ph), C(Ph)(CH3), CH(CH3), or C(CH3)2, and Reis H, C1-4alkyl, C1-4alkylene-OH, CH2Ph, or [CH2CH2O]pRp, wherein p is 1-5 and Rpis H or CH3.

45. A polymer having the formula:, ,Attorney Docket No.103362-032WO1wherein: z is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50- 100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; z* is from 2-2,000, 2-100, 2-50, 2-25, 2-15, 5-15, 5-25, 5-50, 10-25, 10-50, 25-100, 50-100, 50-150, 50-250, 100-500, 250-500, 250-1,000, 500-1,000, 500-2,000, or 1,000-2000; Rmis H or CH3, Xmis O or NH, and Rqis H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, heteroaryl, NH2, NH(C1-C6alkyl), or N(independently C1-C6alkyl)2; Rm*is H or CH3, Xm*is O or NH, and Rq*is H or C1-16alkyl, C2-16alkenyl, or C2-16alkynyl, optionally substituted one or more times by F, Cl, Br, OH, N3, epoxy, COOH, CO2C1-4alkyl, aryl, heteroaryl, NH2, NH(C1-C6 alkyl), or N(independently C1-C6 alkyl)2; Rcis a carbohydrate; Ra1and Ra2are independently selected from H, CH3, Ph, and CN; X1is selected from L2SC(=S)S, L2SC(=S), or L2NRNC(=S)S wherein L2is null, (CH2)o, or [CH2CH2O]o, wherein o is 1-5, and RNis H, C1-4alkyl, aryl, heteroaryl, or CH2Ph; L1is null or (CH2)n, wherein n is 1-3; and X2is L3ORe, L3CN, L3COORe, wherein L3is null, CH(Ph), C(Ph)(CH3), CH(CH3), or C(CH3)2, and Reis H, C1-4alkyl, C1-4alkylene-OH, CH2Ph, or [CH2CH2O]pRp, wherein p is 1-5 and Rpis H or CH3.Attorney Docket No.103362-032WO1 46. The polymer according to claim 44 or claim 45, wherein the polymer has the formula:wherein P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, wherein Rp1*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs1*is independently selected from C1-4alkyl or phenyl; P2is selected from CH2aryl, C(=O)Rp2*, and SiRs2*3, wherein Rp2*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs2*is independently selected from C1-4alkyl or phenyl;Attorney Docket No.103362-032WO1 P3is selected from CH2aryl, C(=O)Rp3*, and SiRs3*3, wherein Rp3*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs3*is independently selected from C1-4alkyl or phenyl; P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3, wherein Rp4*is independently selected from C1-4alkyl, C1-4haloalkyl, aryl, heteroaryl, Rs4*is independently selected from C1-4alkyl or phenyl; or wherein any pair of P1and P2, P2and P3, or P3and P4may together be -C(Rz1)(Rz2)-, wherein Rz1and Rz2are independently selected from H and C1-4alkyl, preferably CH3 or CH2CH3, or Rz1is H and Rz2is optionally substituted aryl or alkaryl, or Rz1and Rz2together form a carbonyl.

47. The polymer according to claim 46, wherein P1and P2together are - C(Rz1)(Rz2)- and P3and P4together are -C(Rz1)(Rz2)-, or P2and P3together are - C(Rz1)(Rz2)-, P1is selected from CH3, CH2aryl, C(=O)Rp1*, and SiRs1*3, and P4is selected from CH2aryl, C(=O)Rp4*, and SiRs4*3.

48. The polymer according to claim 46, wherein P1and P4are independently selected from C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS).

49. The polymer according to any one of claims 46-48, wherein the polymer has the formula:.

50. The polymer according to any one of claims 46-49, wherein P1is CH3, C(=O)CH3, C(=O)phenyl, benzyl, or paramethoxybenzyl; P2is C(=O)CH3,Attorney Docket No.103362-032WO1 C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); P3is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS); and P4is C(=O)CH3, C(=O)phenyl, benzyl, paramethoxybenzyl, or a silyl protecting group (TMS, TES, TBDMS, TBDPS, or TIPS).

51. The polymer according to any one of claims 46-50, wherein the polymer has the formula:.

52. The polymer according to 44-51, wherein the polymer has the formula:Attorney Docket No.103362-032WO1.

53. The polymer according to any one of claims 44-48, wherein the polymer has the formula:.

54. The polymer according to claim 53, wherein the polymer has the formula: ,,Attorney Docket No.103362-032WO1.

55. The polymer according to any one of claims 44-54, wherein Ra1and Ra2are each CH3; Ra1is H and Ra2is CH3; or Ra1is CN and Ra2is CH3.

56. The polymer according to any one of claims 44-55, wherein L3is null or C(CH3)2.

57. The polymer according to any one of claims 44-56, wherein L1is null, CH2, or CH2CH2.

58. The polymer according to any one of claims 44-57, wherein X2is CN, COOH, OCH3, or OH.

59. The polymer according to any one of claims 44-58, wherein X1is L2N(RN)C(=S)S, and RNis CH3, pyridine-4-yl, phenyl, 4-fluorophenyl, or 4- cyanophenyl.

60. A particle comprising the polymer of any one of claims 44-59.

61. A method of making a particle, comprising subjecting a mixture comprising a solvent and the polymer of any one of claims 44-59 to conditions suitable to form a particle.Attorney Docket No.103362-032WO1 62. The method of claim 61, wherein the mixture further comprises a therapeutic agent.

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