Compositions and materials for bone regeneration
Polymer and oligomer compositions releasing citrate, glutamine, and magnesium enhance bone regeneration by mimicking native bone structure and composition, addressing integration and stability issues in bone graft materials, and offering imaging capabilities for monitoring.
Patent Information
- Application Number
- PCT/US2025/029291
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-05-14
- Filing Date
- 2025-05-14
- Publication Date
- 2025-11-20
AI Technical Summary
Current bone graft materials face challenges such as limited availability, complications, ethical issues, variable quality, immunogenicity, and poor integration with surrounding tissue, along with difficulties in shaping and maintaining structural stability during bone regeneration.
Development of polymer and oligomer compositions that release citrate, glutamine, and magnesium synergistically, incorporating hydroxyapatite to mimic native bone inorganic composition, with photoluminescent and photoacoustic properties for imaging, to create biocements, cements, and scaffolds that support bone regeneration.
The compositions provide enhanced osteoconduction, angiogenesis, and vascularization, while maintaining structural integrity and enabling non-invasive monitoring of implant presence and tissue regeneration.
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Figure US2025029291_20112025_PF_FP_ABST
Abstract
Description
[0001] Attorney Docket No.11196-115WO1 COMPOSITIONS AND MATERIALS FOR BONE REGENERATION CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to United States Provisional Patent Application No.63 / 647,285, filed May 14, 2024, the disclosure of which is incorporated herein by reference in its entirety. BACKGROUND When trauma, infection, congenital malformation, tumor growth, or degenerative diseases impair bone integrity, grafting procedures are employed to encourage new bone growth in the defect area. The demand for a readily available bone graft material is highlighted by the fact that there are millions of operations involving bone substitutes performed annually worldwide2. The preferred choice of graft material is currently autogenous bone tissue, which contains a limited number of viable osteoblasts and osteogenic precursor cells to contribute to new bone formation after implantation. However, this advantage is not fully realized in clinical practice because the procurement and processing techniques used result in the death of these vital cellular elements3. In addition to loss of cellular function, the harvesting of autologous bone is associated with complication rates of up to 30%, including prolonged wound drainage, large hematoma formation, the need for reoperation, enterocutaneous fistula, long-lasting pain, harvest site failure, and heterotopic bone formation3. Even in the absence of these avoidable complications, unavoidable complications associated with autograft harvesting include limited availability, high costs, disruption of the donor-site structure, increased operative time, and added operative blood loss3. To circumvent the use of autograft bone tissue, allogenic and xenogenic bone sources offer advantages of an unlimited supply and the absence of donor site complications4. Unfortunately, allogenic and xenogenic bone tissue is highly variable in quality, which is largely dependent on the donor source. Their use also raises ethical problems, the risk of virus transmission, and the potential for immunologic rejection of the graft material5. In addition, the extensive cleaning and processing techniques required are not cost-effective and compromise the mechanical properties and osteoinductive potential of the graft material4. Due to their immunogenicity, xenograft preparations harvested from other species have generally been impractical for clinical use, and to guarantee viral inactivation, all cells and proteins must be removed, which eliminates their osteogenic and osteoinductive potential3. Attorney Docket No.11196-115WO1 Therefore, the search for a readily available grafting material as an alternative to autograft remains an important topic in orthopedic medical research. To address the limitations of biologically derived materials, readily available and fully synthetic inorganic bioactive ceramics, such as tricalcium phosphate Ca3(PO4)2 and hydroxyapatite Ca10(PO4)6(OH)2, have been used for bone grafting procedures. Although biodegradable and naturally osteogenic, these materials are inherently difficult to shape, brittle, and can be easily fractured, causing difficulties during implantation6,7. To ease surgical implantation into irregularly shaped defects, bioceramics have been fabricated in the form of particles of various shapes and dimensions and approved for use by the FDA for use in the clinic4,8. Although easier to implant, they are difficult to contain in the defect area and migrate over time, offering little to no structural stability6,7,9. To prevent the migration of bioactive ceramic particles, materials such as poly (methyl methacrylate) (PMMA) have been hybridized with calcium phosphate particles to create bioactive cements with varying degrees of porosity6. Although PMMA is the most commonly used binding material, its use raises several concerns, including high exothermic polymerization, nonadhesive anchorage to native bone, significant inflammatory response, and fibrous encapsulation, which results in possible infection, loosening, and exposure of the implant7,10. Additional disadvantages of PMMA include time- consuming preparations, minimal working times before material hardening, and radiolucency of the cement, making widely used imaging techniques difficult10–14. Furthermore, PMMA cannot be degraded. After implantation, it is poor at integrating with the surrounding bone tissue and eventually needs to be removed with another surgery. The masquelet technique represents a recent addition of bone defect reconstruction in treating nonunion fractures, even infected nonunion fractures. It is a two-stage process. The first stage involves an accurate debridement of all septic and devitalized tissues. The residual void is then filled with an antibiotic-loaded PMMA spacer. The spacer prevents soft tissue invasion of the bone defect. It also acts as a foreign body and stimulates the formation of a pseudosynovial membrane all around the spacer. Then, during the second stage, performed at least 6-8 weeks after the former, cement is removed and replaced with a huge fresh autologous cancellous bone graft. The membrane, which is essential for the revascularization of the bone grafts, must be maintained intact to cover the autograft completely. The creation of a bone scaffold with intricate morphologies resembling native bone tissue has posed a challenge in bone tissue engineering. The diaphysis region, spanning between the proximal and distal ends of a long bone, forms a hollow tubular structure. This tube encases Attorney Docket No.11196-115WO1 the medullary cavity, filled with bone marrow. The outer wall of the diaphysis consists of dense and rigid cortical bone. Within the cortical bone, Haversian canals are longitudinally arranged, running parallel to the length of the long bone, while Volkmann's canals are transversely oriented, running perpendicular to the Haversian canals. These canals create a complex network in the cortical bone, hosting blood vessels and nerves, essential for oxygenating and nourishing the bone, and facilitating interactions among various resident cells such as mesenchymal stem cells, osteocytes, endothelial cells, and Schwann cells. Ideally, a bone scaffold that mimics the native network structure of cortical bone, as opposed to a solid and simple piece, would be more effective in supporting angiogenesis, innervation, and bone regeneration in the setting of nonunion bone fracture. An ideal bone substitute material should meet the following general requirements: be readily available, highly osteoconductive, support the angiogenesis and vascularization of tissue regeneration, absorb in a predictable manner in concert with bone growth, be malleable to be adapted to irregular geometries, provide a surface conducive to gone growth, be sterilizable, and cause no detrimental effects to the surrounding tissue15,16. In addition to these general requirements, an ideal bone substitute should match the native organic and inorganic composition of bone. It is widely known that bone is a natural nanocomposite consisting of 60- 65 wt.% HA embedded in a collagen matrix17–25. Citrate also plays a significant role in bone development. Citrate is a dissolved calcium-solubilizing agent, which is strongly bound and an integral part of the bone nanocomposite, playing roles in regulating apatite nanocrystal formation and controlling its thickness26–29. Although the role of citrate in bone formation is still largely unknown, exogenous citrate, whether presented on a biomaterial or supplemented into culture media, can enhance alkaline phosphatase (ALP) and osterix (OSX) gene expression, osteoblast phenotype progression, implant osteoinductivity, and osteointegration both in vitro and in vivo30. The majority of essential and non-essential amino acids are known to be required for bone healing. They not only provide building blocks for protein synthesis but also play other critical roles in bone regeneration. For example, lysine and arginine have long been reported to promote fracture healing in multiple animal models through stimulating vascularization and bone cell differentiation. Polar and charged amino acids are heavily expressed in non- collagenous proteins and are involved in HA mineralization. Another example is glutamine. Glutamine, normally present at a concentration of 400 to 600 μM in human serum, is the most abundant amino acid in circulation31. It serves as the major energy source other than glucose. Attorney Docket No.11196-115WO1 Glutamine is converted into alpha-ketoglutarate and then participates in the tricarboxylic cycle (TCA) cycle and in adenosine triphosphate (ATP) generation in mitochondria. Besides direct contribution to protein synthesis as a building block, glutamine is an indispensable carbon and nitrogen donor for the synthesis of many essential amino acids, nucleotides, and lipids. It is also the precursor of reduced glutathione (GSH) and participates in cellular oxidative stress control32. Glutamine can also act as a signaling molecule to activate the mTORC1 pathway and stimulate cell proliferation and differentiation in general33. Studies have supported that glutamine metabolism is critical in tissue regeneration, including angiogenesis, immune regulation, and stem cell proliferation and differentiation34,35. Recently, glutamine has gained increasing attention in its role in promoting bone regeneration, including both osteogenesis and chondrogenesis36,37. Although glutamine can be synthesized in mammalian cells through glutamate, abundant evidence suggests that it becomes a conditionally essential amino acid in illness and injuries. During stress, the body’s needs for glutamine greatly exceed the individual’s ability to produce enough of this amino acid. It has also been reported that the proliferation and differentiation of human endothelial cells were largely enhanced with glutamine supplementation above the physiological glutamine concentration38. Traditionally, amino acids, including glutamine, are supplemented through diet. Unfortunately, dietary glutamine intake, even with supplementation, can hardly elevate the circulating amino acids to the ideal concentration required for optimal tissue regeneration and angiogenesis39. Different metals and their corresponding ions, such as calcium, cobalt, copper, zinc, iron, magnesium, etc., are integral components of bone tissue, playing multiple and critical functional roles in the physiological cellular environment, as well as in the course of bone healing. Taking magnesium (Mg) as an example, magnesium is the fourth most abundant element in the human body. Approximately 67% of Mg in the body is stored in bone tissues, and 30% is exchangeable on the crystal surface of bone, providing a dynamic supply for maintaining intra- and extracellular Mg concentrations. Studies have suggested that magnesium ions (Mg2+) have an effect on the overall rate of calcium phosphate crystallization and the subsequent growth of HA40. Mg2+also participates in energy production. Adenosine monophosphate (AMP) bonds to Mg2+before converting into ATP, and ATP must be bonded to Mg2+to become biologically active41. Moreover, Mg-based biomaterials have been found to promote bone regeneration through activating MAPK / ERK pathway in bone marrow stem cells (BMSCs), participating in the cross-talk between dorsal root ganglia (DRG) and periosteum- derived stem cells (PSCs), prompting the adhesion and motility of osteoblasts and inhibiting Attorney Docket No.11196-115WO1 osteoclast differentiation42–44. In vivo, Mg2+can potentially promote angiogenesis by stimulating VEGF, angiogenin, and other crucial chemoattractants production in bone marrow- derived stem cells (BMSCs)40. Furthermore, incorporating metal ions into fully synthetic biomaterials can greatly improve the mechanical properties and increase the load-bearing capacity of said materials. SUMMARY The present disclosure provides polymer and / or oligomer compositions, prepolymer compositions, and polymerizable compositions which can be used in the manufacture of biomaterials for bone regeneration and / or grafting, as well as other biotherapeutic applications. The presently disclosed compositions are capable of releasing citrate, glutamine, and magnesium in a fashion that was surprisingly found to be synergistic in promoting bone regeneration. The presently disclosed compositions have also been found to be capable of incorporating a higher proportion of inorganic materials (such as hydroxyapatite) to more closely match the inorganic composition found in native bone, which was not possible with previously described materials. The presently disclosed compositions were also surprisingly found to have intrinsic photoluminescent and photoacoustic properties, allowing for the disclosed compositions to also have an imaging aspect (including dual imaging techniques) which may aid in monitoring of implant presence and tissue regeneration. In one aspect, a composition is provided including a polymer or oligomer. In some aspects, the polymer or oligomer can be formed from one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt. In some aspects, the polymer or oligomer can also be formed from one or more monomers B comprising a polyol or polyamine. In some aspects, the polymer or oligomer can also be formed from one or more monomers C comprising glutamine or a salt or derivative thereof. In some aspects, the polymer or oligomer can also be formed from one or more magnesium salts. In some aspects, the polymer or oligomer can also be optionally formed from one or more additional monomers. In another aspect, a prepolymer composition is provided. In some aspects, the prepolymer composition can be formed from one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt. In some aspects, the prepolymer composition can also be formed from one or more monomers B comprising a polyol or polyamine. In some aspects, the prepolymer composition can also be formed from one or more monomers C comprising glutamine or a salt or derivative thereof. In some aspects, the prepolymer composition can also Attorney Docket No.11196-115WO1 be formed from one or more magnesium salts. In some aspects, the prepolymer composition can also be optionally formed from one or more additional monomers. In another aspect, a polymerizable composition is provided. In some aspects, the polymerizable composition can include one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt. In some aspects, the polymerizable composition can also include one or more monomers B comprising a polyol or polyamine. In some aspects, the polymerizable composition can also include one or more monomers C comprising glutamine or a salt or derivative thereof. In some aspects, the polymerizable composition can also include one or more magnesium salts. In some aspects, the polymerizable composition can also optionally include one or more additional monomers. In another aspect, a bone fixation device including a composition as described herein. In another aspect, a bone substitute is provided including a composition as described herein. In another aspect, a particle is provided including a composition as described herein. In another aspect, a biocement or bioadhesive is provided including a composition as described herein. In another aspect, a tissue engineering scaffold is provided including a composition as described herein. In another aspect, a fiber is provided including a composition as described herein. In another aspect, a hydrogel is provided including a composition as described herein. In another aspect, a method of promoting and / or accelerating bone regeneration in a bone site is provided. In some aspects, the method can include delivering a composition described herein to the bone site. 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. DESCRIPTION OF DRAWINGS FIG.1 depicts a scheme regarding how BPLP-Glutamine is synthesized via a simple one-step reaction: BPLP-Glutamine polymers are synthesized via the esterification reaction of Citric Acid and 1,8 Octanediol concurrent to the formation of DPR fluorophores from Citric Acid and L-Glutamine, which are then incorporated into the polymer network. FIG. 2 depicts a scheme regarding how BPLP-Glutamine Magnesium is synthesized via a simple one-step reaction: BPLP-Glutamine Magnesium polymers are synthesized via the esterification reaction of Citric Acid and 1,8 Octanediol concurrent to the formation of DPR Attorney Docket No.11196-115WO1 fluorophores from Citric Acid and L-Glutamine, which are then incorporated into the polymer network and the reaction of Magnesium Nitrate with the carboxyl groups of Citric Acid. FIG. 3A provides a schematic representation showing the proposed use of biodegradable, citrate-based, fluorescent and metal-ion incorporated composites (BCFMC) in non-union bone fracture. FIG. 3B provides a schematic representation of the natural long bone and the transverse section. FIG. 3C depicts a representative biphasic bone substitute scaffold. Transverse canals are introduced into the outer wall of the hollow tubular bone scaffold. The outer wall material serves as a long-lasting mechanical support, slowly degrading over an extended period (greater than 6 months) while releasing Mg2+, citrate, and glutamine. Within the hollow tube, a rapidly degrading (citrate) material is incorporated, releasing Mg2+, citrate, and glutamine and degrading within one month. FIG. 3D depicts a bone scaffold with canals positioned both longitudinally and transversely in the outer wall. FIG. 4A depicts representative solid cylinders made from BCFMC with different glutamine ratios and the visual effect of the addition of magnesium ions into the materials. FIG. 4B depicts representative porous cylinders made from BCFMC. FIG.5 depicts how biodegradable, citrate-based, fluorescent and metal-ion incorporated films (BCFMFs) synthesized with citric acid, L-glutamine, 1,8-octanediol, and magnesium ion are inherently fluorescent to offer an additional means of non-invasive imaging to quantitatively monitor the material presence, degradation, and tissue regeneration once implanted in the body. FIGs.6A-6B depicts and provides data regarding how Fourier-transform infrared spectroscopy (FTIR) demonstrated the incorporation of glutamine (FIG.6A) and magnesium (FIG.6B) into BCFMFs as described in the examples. FIGs. 7A-7B depicts and provides data regarding how proton nuclear magnetic resonance demonstrated the incorporation of glutamine (FIG. 7A) and magnesium (FIG. 7B) into BCFMFs at different glutamine concentrations as described in the examples. FIGs. 8A-8B depict and provide data regarding the compressive mechanical properties of (FIG. 8A) Hexamethylene diisocyanate (HDI) crosslinked (2x HDI) and (FIG. 8B) thermo- crosslinked (80 °C for 3 days) BCFMCs as described in the examples. (n=6 composites per group). FIG. 9 provides data regarding the compressive mechanical properties of BCFMCs (POC- 0.3glutamine-Mg-50% HA) post-polymerized with increasing HDI ratios as described in the examples. (n=6 composites per group). Attorney Docket No.11196-115WO1 FIG.10 provides data regarding the comparison of peak stress of 0.3glutamine BCFMCs with and without magnesium post-polymerized with 2x HDI ratio and different thermos- crosslinking conditions as described in the examples. (n=6 composites per group). FIG. 11 provides data regarding the accelerated degradation analysis of BCFMCs with and without magnesium post-polymerized with increasing HDI ratios or thermally crosslinked BCFMCs as described in the examples. (n=6 composites per group). FIG. 12 provides data regarding the cell proliferation of hMSCs with treatment of increasing concentrations of glutamine determined by cell counting kit-8 (CCK8 assay) as described in the examples. (n=6 biological replicates per group). FIG. 13 provides data regarding the cell migration of hMSCs with treatment of increasing concentrations of glutamine determined by wound healing assay as described in the examples. (n=4 biological replicates per group). FIG. 14 provides data regarding the osteogenic differentiation of hMSCs with treatment of increasing concentrations of glutamine evaluated by measurement of ALP activity as described in the examples. (n=4 biological replicates per group). FIG. 15 depicts and provides data regarding the osteogenic differentiation of hMSCs with treatment of increasing concentrations of glutamine evaluated by measurement of extracellular calcium deposition as described in the examples. Extracellular calcium is detected by Alizarin Red Staining. (n=4 biological replicates per group). FIG. 16 provides data regarding the osteogenic differentiation of hMSCs with treatment of increasing concentrations of magnesium evaluated by measurement of ALP activity as described in the examples. (n=4 biological replicates per group). FIG. 17 depicts and provides data regarding the osteogenic differentiation of hMSCs with treatment of increasing concentrations of magnesium evaluated by measurement of extracellular calcium deposition as described in the examples. Extracellular calcium is detected by Alizarin Red Staining. (n=4 biological replicates per group). FIG. 18 provides data regarding the osteogenic differentiation of hMSCs with treatment of increasing concentrations of glutamine with or without supplementation of 8mM magnesium ions. OG is evaluated by measurement of ALP activity as described in the examples. (n=4 biological replicates per group). Attorney Docket No.11196-115WO1 FIGs.19A-19I depict and provide data regarding the osteogenic differentiation of hMSCs with treatment of glutamine, magnesium and CA individually or in combinations as described in the examples. OG is evaluated by measurement of (FIG.19A) ALP activity at day 7, (FIG.19B) Runx2 gene expression at day 3, (FIG. 19C) Spp1, ALPL and BMP2 gene expression at day 7, (FIGs. 16D-16E) Calcium nodule formation, immunofluorescence staining of ALP (FIGs. 19F-19G) and OCN (FIGs.19H-19I) protein. FIG. 20 provides data regarding the intracellular ATP determination of undifferentiated hMSCs treated with increasing concentrations of glutamine as described in the examples. FIG. 21 provides data regarding the intracellular ATP determination of undifferentiated hMSCs treated with increasing concentrations of magnesium ions under 2mM or 4mM glutamine supplementations as described in the examples. FIG. 22 provides data regarding the intracellular ATP determination of osteogenically differentiated hMSCs treated with increasing concentrations of glutamine after OG differentiation for 3 or 7 days, as described in the examples. FIG. 23 provides data regarding the intracellular ATP determination of osteogenically differentiated hMSCs with treatment of 2mM glutamine, 2mM magnesium and 200uM CA individually or in combinations after OG differentiation for 3 days or 7 days as described in the examples. FIG. 24 provides data regarding how the treatment of citrate, glutamine and Magnesium individually or in combination in osteogenically differentiated MSCs enhances the mitochondrial TCA cycle activity as described in the examples, as evidenced by the increased intracellular concentration of TCA cycle metabolites. FIGs.25A-25B provide data regarding how the treatment of citrate, glutamine and magnesium in combination compared with glutamine and citrate treatment only in osteogenically differentiated MSCs enhances the oxygen consumption rate (OCR), as evidenced by the increased basal respiration, maximal respiration and ATP production. FIGs.26A-26E provide data regarding how the treatment of citrate, glutamine and Magnesium individually or in combination in osteogenically differentiated MSCs activates both mTORC1 pathway and AMPK pathway as described in the examples. (FIGs. 26A-26B) S6K1, AMPK, and AKT phosphorylation; (FIG. 26C) Inhibition of CaMKK activity via STO609 blocks the glutamine / Magnesium / citrate-mediated AMPK pathway activation. (FIG. 26D) mTOR inhibitor, Torin1, blocks the glutamine / Magnesium / citrate-mediated mTORC1 pathway Attorney Docket No.11196-115WO1 activation. (FIG. 26E) AKT inhibitor, MK2206, blocks the glutamine / Magnesium / citrate- mediated mTORC1 pathway activation. FIGs. 27A-27C provide data regarding how (FIG. 27A) STO609 or (FIG. 27B) MK2206 or (FIG. 27C) Torin 1 treatment reduced MSC OG differentiation as measured by ALP activity as described in the examples. FIGs.28A-28C depict and provide data regarding how DPR fluorophores are synthesized via the one-step reaction of Citric Acid and L-Glutamine as described in the examples. CA- Glutamine small molecules are formed via the one-step reaction of Citric Acid and L- Glutamine (FIG.28A), resulting in fluorophores with excitation and emission ranges primarily from 300 to 600nm (FIG. 28B) and excitation dependent emission (intrinsic bandshifting) (FIG. 28C), readily visualized in solution under UV illumination. CA-Glutamine was dissolved in 1,4 Dioxane at 0.3 wt%. FIG. 29 depicts how the monomers utilized in BPLP-Glutamine synthesis lack absorbance as described in the examples. The primary monomers utilized in BPLP-Glutamine synthesis, Citric Acid, L-Glutamine, and 1,8 Octanediol, lack significant absorbance, as indicated by white color. FIGs. 30A-30E provide data regarding how glutamine addition increases the absorbance of prepolymers as described in the examples. Prepolymers containing increasing amounts of L- Glutamine demonstrate a concentration dependent increase in absorbance, particularly within the NIR-I range (700-1000nm) from (FIG. 30A) POC through (FIG. 30B) BPLP-Glutamine 0.01, (FIG. 30C) BPLP-Glutamine 0.03, (FIG. 30D) BPLP-Glutamine 0.05, and (FIG. 30E) BPLP-Glutamine 0.07, validating the role of the CA-Glutamine monomer in the manifestation of long wavelength absorbance. All prepolymers were dissolved in 1,4-Dioxane. FIGs. 31A-31D depict and provide data regarding how glutamine addition increases the absorbance of prepolymers as described in the examples. NIR-I absorbance progressively increases compared to POC with increased Glutamine content, particularly 0.05 and 0.07 molar ratios (FIGs. 31A-31C), manifesting as a progressive increase in color from clear to dark brown at 3 wt% concentration (FIG.27D). All prepolymers were dissolved in 1,4-Dioxane. FIGs. 32A-32C provide data regarding how magnesium addition preserves the developed absorbance of BPLP-Glutamine prepolymers as described in the examples. Prepolymers containing Magnesium (0.02 mole ratio) display similar progressive increases in NIR-I absorbance to BPLP-Glutamine with increased Glutamine content and concentration (FIGs. Attorney Docket No.11196-115WO1 32A-32C), validating the ability to incorporate ions into prepolymer without compromising absorbance. All prepolymers were dissolved in 1,4-Dioxane. FIGs. 33A-33C depict and provide data regarding how glutamine addition increases the absorbance of prepolymers as described in the examples. NIR-I absorbance progressively increases in BPLP-Glutamine Magnesium prepolymers (FIG. 33A-33C). All prepolymers were dissolved in 1,4 Dioxane. FIG.34 depicts and provides data regarding the color difference among BPLP-Glutamine and BPLP-Glutamine Magnesium prepolymers at 3 wt% concentration. All prepolymers were dissolved in 1,4 Dioxane. FIGs. 35A-35D depict and provide data regarding how varying the Magnesium feeding ratio modulates prepolymer absorbance as described in the examples. Varying Magnesium feeding ratios in BPLP-Glutamine 0.03 (Q0.03) resulted in prepolymers maintaining concentration dependent absorbance (FIGs.35A-35D). FIGs. 36A-36C depict and provide data regarding how varying the Magnesium feeding ratio modulates absorbance as described in the examples. BPLP-Glutamine Magnesium prepolymers all display concentration-dependent absorbance in the NIR-I range. FIGs.37A-37E provide data regarding how the fluorescence of BPLP-Glutamine prepolymers is dependent on Glutamine content and concentration as described in the examples. Incorporation of the DPR fluorophore (CA-Glutamine) results in increased fluorescence compared to POC, with fluorescence intensity varying according to both Glutamine content and prepolymer concentration while maintaining fluorescence over a broad range of wavelengths. FIG. 38 provides data regarding the expanded concentration dependence of BPLP-Glutamine 0.07 as described in the examples. Concentration displays a significant effect on fluorescence of BPLP-Glutamine 0.07. FIG.39 provides data regarding how the relative fluorescence intensity varies with Glutamine content at an equivalent concentration as described in the examples. Increasing Glutamine content results in a plateau of both excitation and emission at Q0.05, followed by decreased intensity for Q0.07 when prepolymer concentration is held constant at 0.3 wt%. FIGs. 40A-40E provide data regarding how BPLP-Glutamine prepolymers maintain band shifting and broad emission wavelengths regardless of formulation, as described in the Attorney Docket No.11196-115WO1 examples. Excitation-dependent emission (band shifting) occurs in all BPLP-Glutamine prepolymers, allowing imaging over a broad wavelength range. FIGs. 41A-41B depict and provide data regarding how the BPLP-Glutamine prepolymer displays broad wavelength fluorescence as described in the examples. Intrinsic bandshifting of Q0.03 prepolymer from 250 to 650nm (FIGs. 41A-41B), indicating suitability for imaging even in vivo. FIGs.42A-42C provide data regarding how the fluorescence of BPLP-Glutamine Magnesium prepolymers is dependent on Glutamine content and concentration as described in the examples. Similar to Magnesium-free prepolymers, Mg0.02-containing prepolymers display varying fluorescence intensities due to both Glutamine content and concentration for Q0.03 Mg0.02 (FIG.42A), Q0.05 Mg0.02 (FIG.42B), and Q0.07 Mg0.02 (FIG.42C). FIG. 43 provides data regarding the expanded concentration dependence of BPLP-Glutamine 0.07 Mg0.02 as described in the examples. Concentration displays a significant effect on fluorescence of BPLP-Glutamine 0.07 Mg0.02. FIG.44 provides data regarding how the relative fluorescence intensity varies with Glutamine content at an equivalent concentration as described in the examples. Increasing Glutamine content results in a plateau of both excitation and emission at Q0.05 Mg0.02, followed by decreased intensity for Q0.07 Mg0.02 when prepolymer concentration is held constant at 0.3 wt%. FIGs. 45A-45C provide data regarding how BPLP-Glutamine Mg0.02 prepolymers maintain band shifting and broad emission wavelengths regardless of formulation, as described in the examples. Excitation-dependent emission (band shifting) occurs in all BPLP-Glutamine Mg0.02 prepolymers, allowing imaging over a broad wavelength range. FIGs. 46A-46B provide data regarding how the fluorescence Intensity is decreased with Magnesium Addition as described in the examples. Excitation (FIG.46A) and Emission (FIG. 46B) intensities are decreased by the addition of Magnesium in Q0.03 and Q0.05, while slightly increasing in Q0.07. FIG. 47 provides data regarding how BPLP-Glutamine prepolymers display high photostability as described in the examples. Both Q0.03 and Q0.03 Mg0.02 prepolymers display approximately 95% stability after 3 hours, similar to commercial Fluorescein and much higher than commercial Rhodamine B. Attorney Docket No.11196-115WO1 FIGs. 48A-48D provide data regarding how the addition of Magnesium reduces fluorescent intensity as described in the examples. The addition of Mg at 0.01 (FIG. 48B), 0.02 (FIG. 48C), and 0.03 (FIG. 48D) moles reduces fluorescence compared to Magnesium free Q0.03 (FIG.48A) while still maintaining similar fluorescence profiles. FIGs. 49A-49B provide data regarding how NIR Absorbance increases with increased Glutamine content in crosslinked films as described in the examples. Transmittance decreases (FIG. 49A) with increased Glutamine feeding ratio from POC to Q0.07 with concomitant increase in NIR-I absorbance (FIG.49B). FIGs. 50A-50B provide data regarding how NIR Absorbance increases with increased Glutamine content in Glutamine Magnesium crosslinked films as described in the examples. Transmittance decreases (FIG. 50A) with increased Glutamine feeding ratio from Q0.03 to Q0.07 with concomitant increase in NIR-I absorbance (FIG.50B) when Magnesium is present (Mg0.02). FIGs. 51A-51B provide data regarding how NIR Absorbance is decreased with Magnesium incorporation as described in the examples. Addition of Magnesium (0.02) results in increased transmittance (FIG. 51A) and decreased absorbance (FIG. 51B) compared to corresponding Magnesium free formulations. FIGs. 52A-52B provide data regarding how NIR Absorbance is decreased with increasing Magnesium feeding ratio, as described in the examples. Increasing Magnesium incorporation from 0 to 0.03 molar feeding ratio results in increased transmittance (FIG.52A) and decreased absorbance (FIG.52B). FIG. 53 provides data regarding how fluorescence is diminished with increased Glutamine incorporation in crosslinked films as described in the examples. FIG.54 provides data regarding how BPLP-Glutamine 0.03 films display reduced fluorescence with increased crosslinking time as described in the examples. FIGs. 55A-55B depict and provide data regarding how BPLP-Glutamine 0.03 film displays broad wavelength fluorescence as described in the examples. Intrinsic bandshifting of Q0.03 films from 250 to 650nm (FIGs.55A) results in fluorescence from 480 to 680nm (blue to red) (FIG.55B). FIG. 56 provides data regarding how fluorescence is diminished with increased Glutamine incorporation in Magnesium containing crosslinked films as described in the examples. Attorney Docket No.11196-115WO1 FIGs.57A-57B depict and provide data regarding how the BPLP-Glutamine 0.03 Mg0.02 film displays broad wavelength fluorescence as described in the examples. Intrinsic bandshifting of Q0.03 Mg0.02 films from 250 to 650nm, indicating suitability for imaging even in vivo. FIGs.58A-58B provide data regarding how Magnesium incorporation decreases fluorescence except in Q0.07 as described in the examples. Excitation (FIG.58A) and Emission (FIG.58B) decrease when Magnesium is incorporated in Q0.03 and Q0.05 but increase when Magnesium is incorporated in Q0.07. FIG. 59 provides data regarding how BPLP-Glutamine films display high photostability as described in the examples. Both Q0.03 and Q0.03 Mg0.02 films display approximately high stability after 3 hours, particularly Q0.03 Mg0.02. FIG. 60 provides data regarding how fluorescence is diminished with Magnesium incorporation in crosslinked films as described in the examples. FIGs. 61A-61C depict and provide data regarding how BPLP-Glutamine Magnesium porous scaffolds allow broad wavelength imaging as described in the examples. Band shifting (FIG. 61A) of BPLP-Glutamine 0.05 Magnesium 0.02 / Hydroxyapatite porous scaffolds with bright fluorescence (FIG. 61B) allows imaging from blue to red (FIG. 61C), with potential for in vivo imaging. FIGs. 62A-62B provide data regarding the effect of Glutamine incorporation on prepolymer fluorescence and absorbance as described in the examples. Increasing Glutamine results in increased NIR-I absorbance with concurrent decreases in fluorescence without (FIG. 62A) or with (FIG.62B) Magnesium incorporation. FIGs. 63A-63B provide data regarding the effect of BPLP-Glutamine 0.07 concentration on prepolymer fluorescence and absorbance as described in the examples. Increasing concentration results in increased NIR-I absorbance with concurrent decreases in fluorescence without (FIG. 63A) or with (FIG. 63B) Magnesium incorporation, except from 0.03% to 0.15%, likely a result of increased fluorophore concentration without a significant increase in absorbance at between these two concentrations. FIG. 64 provides data regarding the effect of Magnesium incorporation in BPLP-Glutamine 0.03 on prepolymer fluorescence and absorbance as described in the examples. Increasing magnesium incorporation results in a biphasic response in absorbance, increasing to Mg0.02 and then decreasing, with fluorescence also decreasing except between Mg0.02 and Mg0.03. Additionally, although absorbance of Mg0.03 is similar to Q0.03, fluorescence remains much Attorney Docket No.11196-115WO1 lower, likely due to the reduction in fluorophore per gram in Mg0.03 compared to Q0.03, counteracting the expected role of decreased absorbance. FIG. 65 provides data regarding the effect of Glutamine incorporation on crosslinked film fluorescence and absorbance as described in the examples. Increasing Glutamine results in increased NIR-I absorbance with concurrent decreases in fluorescence without (left) or with (right) Magnesium incorporation, although fluorescence is less affected by increasing from Q0.05 to Q0.07 when Magnesium is present. FIG.66 depicts the visualization of the effect of Glutamine Incorporation on film absorbance and fluorescence as described in the examples. Increased Glutamine feeding ratio results in increasingly dark films with diminished fluorescence (nearly absent in Q0.07). FIG.67 depicts the visualization of the effect of Magnesium incorporation in films as described in the examples. Magnesium films display a lighter color and increased fluorescence. FIG.68 provides data regarding the effect of crosslinking condition on BPLP-Glutamine 0.03 films as described in the examples. Increased crosslinking time and temperature result in decreased fluorescence and increased absorbance, with slightly higher fluorescence at 3,3 compared to 3,1, likely due to the effect of increased polymer density on fluorophore density counteracting the increase in absorbance. FIG. 69 provides data regarding the effect of Magnesium incorporation in BPLP-Glutamine 0.03 on film fluorescence and absorbance as described in the examples. Increasing Magnesium incorporation results in a decrease in absorbance, with fluorescence also decreasing from Q0.03 to Mg0.01, then partially recovering between Mg0.02 and Mg0.03, likely the result of the combination of decreased absorbance with increasing Magnesium incorporation being counteracted by the concurrent decrease in fluorophore compared to Q0.03. FIG.70 depicts the visualization of the effect of magnesium incorporation on Glutamine 0.03 films as described in the examples. Increased magnesium incorporation results in a lighter color and decreased fluorescence. FIGs. 71A-71B provide data regarding how the crosslinked BPLP-Glutamine and BPLP- Glutamine Mg films display increased PAUS signal as described in the examples. BPLP- Glutamine films (FIG. 71A) and BPLP-Glutamine Mg films (FIG. 71B) demonstrate increasing photoacoustic / ultrasound (PAUS) signal intensity corresponding to increased absorbance of their prepolymers and crosslinked films, with Magnesium containing films performing similarly to the corresponding Magnesium free formulations. PAUS imaging was Attorney Docket No.11196-115WO1 conducted within agar phantoms at a 2.5cm depth. All films were crosslinked for 3 days at 80 °C followed by 3 days at 120°C under vacuum (<2 inches of Hg). DETAILED DESCRIPTION The following description of the disclosure is provided as an enabling teaching of the disclosure in its best, currently known aspects. Many modifications and other aspects disclosed herein will come to mind to one skilled in the art to which the disclosed compositions and methods pertain, benefiting from the teachings presented in the descriptions herein and the associated drawings. Therefore, it is understood that the disclosures are not limited to the specific aspects disclosed and that modifications and other aspects are intended to be included within the scope of the appended claims. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. As apparent to those of skill in the art upon reading this disclosure, each of the individual aspects described and illustrated herein has discrete components and features that may be readily separated from or combined with the features of any of the other several aspects without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not explicitly state in the claims or descriptions that the steps are to be limited to a particular order, it is in no way intended that an order be inferred in any respect. This holds for any possible non-express basis for interpretation, including logic concerning arrangement of steps or operational flow, meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification. All publications mentioned herein are incorporated by reference to disclose and describe the methods or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure before the filing date of the present Attorney Docket No.11196-115WO1 application. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation. It is also to be understood that the terminology herein describes particular aspects only and is not intended to be limiting. Unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. It can be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein. Before describing the various aspects of the present disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in the present disclosure. Definitions As used herein, “comprising” is interpreted as specifying the presence of the stated features, integers, steps, or components but does not preclude the presence or addition of one or more features, integers, steps, components, or groups thereof. Moreover, each of the terms “by,” “comprising,” “comprises,” “comprised of,” “including,” “includes,” “included,” “involving,” “involves,” “involved,” and “such as” are used in their open, non-limiting sense and may be used interchangeably. Further, the term “comprising” is intended to include examples and aspects encompassed by the terms “consisting essentially of” and “consisting of.” Similarly, “consisting essentially of” is intended to include examples encompassed by the term “consisting of.” As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context dictates otherwise. Ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. Further, the endpoints of each of the ranges are significant both in relation to the other endpoint and independently of the other endpoint. There are many values disclosed herein, and each value is also disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value and to “about” another particular value. Similarly, when values are expressed as approximations, using the antecedent “about,” the Attorney Docket No.11196-115WO1 particular value forms a further aspect. For example, if the value “about 10” is disclosed, then “10” is also disclosed. When a range is expressed, a further aspect includes from the one particular value and to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g., the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’. The range can also be expressed as an upper limit, e.g. ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x,’ ‘about y,’ and ‘about z’ as well as the ranges of ‘less than x,’ ‘less than y.’ and ‘less than z.’ Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x,’ ‘about y,’ and ‘about z’ as well as the ranges of ‘greater than x,’ greater than y,’ and ‘greater than z.’ In addition, the phrase “about ‘x’ to ‘y’,” where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’.” Such a range format is used for convenience and brevity and thus, should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1% to 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range. As used herein, the terms “about,” “approximate,” “at or about,” and “substantially” mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact but may be approximate, larger or smaller, as desired, reflecting tolerances, conversion factors, rounding, measurement error, and the like, and other factors known to those of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In such cases, as used herein, “about” and “at or about” mean the nominal value indicated ±10% variation unless otherwise indicated or inferred. In general, an amount, size, formulation, parameter, or other quantity or characteristic is “about,” “approximate,” or “at or about,” whether or not expressly stated to be Attorney Docket No.11196-115WO1 such. Where “about,” “approximate,” or “at or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself unless expressly stated otherwise. As used herein, the term “therapeutically effective amount” refers to an amount sufficient to achieve the desired therapeutic result or to have an effect on undesired symptoms but generally insufficient to cause adverse side effects. The specific therapeutically effective dose level for any particular patient will depend upon a variety of factors, including the disorder being treated and the severity of the disorder; the specific composition employed; the age, body weight, general health, sex, and diet of the patient; the time of administration; the route of administration; the rate of excretion of the specific compound employed; the duration of the treatment; drugs used in combination or coincidental with the particular compound employed and like factors within the knowledge and expertise of the health practitioner and which may be well known in the medical arts. In the case of treating a particular disease or condition, in some instances, the desired response can be inhibiting the progression of the disease or condition. This may involve only slowing the progression of the disease temporarily. However, in other instances, it may be desirable to permanently halt the progression of the disease. This can be monitored by routine diagnostic methods known to one of ordinary skill in the art for any particular disease. The desired response to treatment of the disease or condition can also be delaying the onset or even preventing the onset. For example, it is well within the skill of the art to start doses of a compound at levels lower than those required to achieve the desired therapeutic effect and to increase the dosage gradually until the desired effect is achieved. If desired, the effective daily dose can be divided into multiple doses for administration. Consequently, single dose compositions can contain such amounts or submultiples thereof to make up the daily dose. The individual physician can adjust the dosage in the event of any contraindications. It is generally preferred that a maximum dose of the pharmacological agents of the disclosure (alone or in combination with other therapeutic agents) be used, that is, the highest safe dose according to sound medical judgment. However, a patient may insist on a lower or tolerable dose for medical reasons, psychological reasons, or virtually any other reason. A response to a therapeutically effective dose of a disclosed compound or composition can be measured by determining the physiological effects of the treatment or medication, such as the decrease or lack of disease symptoms following the administration of the treatment or pharmacological agent. Other assays will be known to one of ordinary skill in the art and can be employed for measuring the level of the response. The amount of a treatment may be varied, Attorney Docket No.11196-115WO1 for example, by increasing or decreasing the amount of a disclosed compound or pharmaceutical composition, changing the disclosed compound or pharmaceutical composition administered, changing the route of administration, changing the dosage timing, and so on. Dosage can vary and can be administered in one or more doses daily for one or several days. Guidance can be found in the literature for appropriate dosages for given classes of pharmaceutical products. As used herein, “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur. The description includes instances where said event or circumstance occurs and those where it does not. As used interchangeably herein, “subject,” “individual,” or “patient” can refer to a vertebrate organism, such as a mammal (e.g., human). “Subject” can also refer to a cell, a population of cells, a tissue, an organ, or an organism, preferably to a human and constituents thereof. As used herein, “treating” and “treatment” generally refer to obtaining a desired pharmacological or physiological effect. The effect can be but does not necessarily have to be prophylactic in preventing or partially preventing a disease, symptom, or condition. The effect can be therapeutic regarding a partial or complete cure of a disease, condition, symptom, or adverse effect attributed to the disease, disorder, or condition. The term “treatment” as used herein can include any treatment of a disorder in a subject, particularly a human. It can include any one or more of the following: (a) preventing the disease from occurring in a subject who may be predisposed to the disease but has not yet been diagnosed as having it; (b) inhibiting the disease, i.e., arresting its development; and (c) relieving the disease, i.e., mitigating or ameliorating the disease or its symptoms or conditions. The term “treatment,” as used herein, can refer to both therapeutic treatment alone, prophylactic treatment alone, or both therapeutic and prophylactic treatment. Those in need of treatment (i.e., subjects in need thereof) can include those already with the disorder or those in which the disorder is to be prevented. As used herein, the term “treating” can include inhibiting the disease, disorder, or condition, e.g., impeding its progress; and relieving the disease, disorder, or condition, e.g., causing regression of the disease, disorder, or condition. Treating the disease, disorder, or condition can include ameliorating at least one symptom of the particular disease, disorder, or condition, even if the underlying pathophysiology is not affected, e.g., such as treating the pain of a subject by administration of an analgesic agent even though such agent does not treat the cause of the pain. Attorney Docket No.11196-115WO1 As used herein, “dose,” “unit dose,” or “dosage” can refer to physically discrete units suitable for use in a subject, each unit containing a predetermined quantity of a disclosed compound or a pharmaceutical composition thereof calculated to produce the desired response or responses in association with its administration. As used herein, “therapeutic” can refer to treating, healing, or ameliorating a disease, disorder, condition, or side effect or decreasing the rate of advancement of a disease, disorder, condition, or side effect. As used herein, the term or phrase “effective,” “effective amount,” or “conditions effective to” refers to such amount or condition that is capable of performing the function or property for which an effective amount or condition is expressed. As will be pointed out below, the exact amount or particular condition required will vary from one aspect to another, depending on recognized variables such as the materials employed and the processing conditions observed. Thus, it is not always possible to specify an exact “effective amount” or “condition effective to.” However, it should be understood that an appropriate effective amount will be readily determined by one of ordinary skill in the art using only routine experimentation. Although the operations of exemplary aspects of the disclosed method may be described in a particular sequential order for convenient presentation, it should be understood that disclosed aspects can encompass an order of operations other than the particular sequential order disclosed. For example, operations described sequentially may, in some cases, be rearranged or performed concurrently. Further, descriptions and disclosures provided in association with one particular aspect are not limited to that aspect and may be applied to any aspect disclosed. The terms “coupled” and “associated” generally mean electrically, electromagnetically, and / or physically (e.g., mechanically or chemically) coupled or linked and do not exclude the presence of intermediate elements between the coupled or associated items. It will be understood that when an element is referred to as being "connected" or "coupled" to another element, it can be directly connected or coupled to the other element, or intervening elements can be present. In contrast, when an element is referred to as being "directly connected" or "directly coupled" to another element, there are no intervening elements present. Other words used to describe the relationship between elements or layers should be interpreted in a like fashion (e.g., "between" versus "directly between," "adjacent" versus "directly adjacent," "on" versus "directly on"). Attorney Docket No.11196-115WO1 It will be understood that although the terms "first," "second," etc., can be used herein to describe various elements, components, regions, layers, and / or sections. These elements, components, regions, layers, and / or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of exemplary aspects. Spatially relative terms, such as,“ "beneath," "below," "lower," "above," "upper," “upward,” “downward,” “top,” “bottom,” and the like, can be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "below" or "beneath" other elements or features would then be oriented "above" the other elements or features. Thus, the term "below" can encompass both an orientation of above and below. The device can be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein are interpreted accordingly. Terms such as “proximal,” “distal,” “radially outward,” “radially inward,” “outer,” “inner,” and “side” describe the orientation and / or location of portions of the components or elements within a consistent but arbitrary frame of reference which is made clear by reference to the text and the associated drawings describing the components or elements under discussion. Such terminology can include the words specifically mentioned above, derivatives thereof, and words of similar import. Similarly, the terms “first,” “second,” and other such numerical terms referring to structures neither imply a sequence nor order unless clearly indicated by the context. As used herein, the term "substantially" means that the subsequently described event or circumstance completely occurs or that the subsequently described event or circumstance generally, typically, or approximately occurs. Still further, the term “substantially” can, in some aspects, refer to at least about 90 %, at least about 91 %, at least about 92 %, at least about 93 %, at least about 94 %, at least about 95 %, at least about 96 %, at least about 97 %, at least about 98 %, at least about 99 %, or about 100 Attorney Docket No.11196-115WO1 % of the stated property, component, composition, or other condition for which substantially is used to characterize or otherwise quantify an amount. As used herein, the term “substantially,” in, for example, the context “substantially identical” or “substantially similar,” refers to a method or a system, or a component that is at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, or about 100% by similar to the method, system, or the component it is compared to. Compounds are described using standard nomenclature. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this disclosure belongs. The compounds described herein include enantiomers, mixtures of enantiomers, diastereomers, tautomers, racemates, and other isomers, such as rotamers, as if each is specifically described unless otherwise indicated or otherwise excluded by context. It is to be understood that the compounds provided herein may contain chiral centers. Such chiral centers may be of either the (R) or (S) configuration. The compounds provided herein may either be enantiomerically pure or be diastereomeric or enantiomeric mixtures. It is to be understood that the chiral centers of the compounds provided herein may undergo epimerization in vivo. As such, one of ordinary skill in the art will recognize that administering a compound in its (R) form is equivalent, for compounds that undergo epimerization in vivo, to administering the compound in its (S) form. 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. Compounds described herein may contain one or more double bonds and, thus, potentially give rise to cis / trans (E / Z) isomers, as well as other conformational isomers unless stated to the contrary; all such possible isomers are contemplated, as well as mixtures of such isomers. Compounds described herein may also be present as an equilibrium of tautomers. For example, ketones with an α-hydrogen can exist in an equilibrium of the keto form and the enol form. Likewise, amides with an N-hydrogen can exist in an equilibrium of the amide form and the imidic acid form. Unless stated to the contrary, all possible tautomers of the compounds described herein are contemplated. Attorney Docket No.11196-115WO1 A dash (“-”) that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -(C=O)NH2is attached through the carbon of the keto (C=O) group. The term “substituted,” as used herein, means that any one or more hydrogens on the designated atom or group are replaced with a moiety selected from the indicated group, provided that the designated atom’s normal valence is not exceeded and the resulting compound is stable. For example, when the substituent is oxo (i.e., =O), two hydrogens on the atom are replaced. For example, a pyridyl group substituted by an oxo is a pyridine. Combinations of substituents and / or variables are permissible only if such combinations result in stable compounds or useful synthetic intermediates. A stable active compound refers to a compound that can be isolated and / or formulated into a form with a shelf life of at least one month. A stable manufacturing intermediate or precursor to an active compound is stable if it does not degrade within the period needed for reaction or other use. A stable moiety or substituent group is one that does not degrade, react, or fall apart within the period necessary for use. Non-limiting examples of unstable moieties are those that combine heteroatoms in an unstable arrangement, as typically known and identifiable to those of skill in the art. Any suitable group may be present on a “substituted” or “optionally substituted” position that forms a stable molecule and meets the desired purpose of the disclosure and includes, but is not limited to: halo, nitro, cyano, azido, oxo, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2- C6 alkynyl, (C3-C7 cycloalkyl)(C0-C3 alkyl)-, (3- to 8-membered monocyclic or bicyclic heterocycle)-(C0-C6alkyl)-, (6- to 10-membered monocyclic or bicyclic aryl)-(C0-C6alkyl)-, (5- to 10-membered monocyclic or bicyclic heteroaryl)-(C0-C6 alkyl)-, AxO-(C0-C6 alkyl)-, AxS-(C0-C6alkyl)-, (AxAyN)-(C0-C6alkyl)-, AzC(O)-(C0-C6alkyl)-, AzC(N)-(C0-C6alkyl)-, and AzS(O)-(C0-C6 alkyl)-, and AzS(O)2-(C0-C6 alkyl)-, wherein Axand Ayare independently selected at each occurrence from Aa, AzC(O)-, AzC(N)-, AzS(O)-, and AzS(O)2-, each of which may be optionally substituted with one or more B groups as allowed by valency; wherein Azis independently selected at each occurrence from hydrogen, halo, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6alkynyl, (C3-C7 cycloalkyl)-(C0-C3 alkyl)-, (4- to 6-membered heterocycle)-(C0-C3alkyl)-, (5- to 10-membered monocyclic or bicyclic aryl)-(C0-C3alkyl)-, (5- to 10-membered monocyclic or bicyclic heteroaryl)-(C0-C3 alkyl)-, -OAa, -SAa, and - NAaAb, each of which may be optionally substituted with one or more B groups as allowed by valency; wherein Aaand Abare independently selected at each occurrence from hydrogen, C1- C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6alkynyl, (C3-C7 cycloalkyl)-(C0-C3 alkyl)-, (4- to Attorney Docket No.11196-115WO1 6-membered heterocycle)-(C0-C3alkyl)-, (5- to 10-membered monocyclic or bicyclic aryl)- (C0-C3alkyl)-, (5- to 10-membered monocyclic or bicyclic heteroaryl)-(C0-C3alkyl)-, each of which may be optionally substituted by one or more B groups as allowed by valency; and wherein B is independently selected at each occurrence from hydrogen, halo, nitro, cyano, azido, oxo, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, (C3-C7 cycloalkyl)(C0- C3alkyl)-, (3- to 8-membered monocyclic or bicyclic heterocycle)-(C0-C6alkyl)-, (6- to 10- membered monocyclic or bicyclic aryl)-(C0-C6 alkyl)-, (5- to 10-membered monocyclic or bicyclic heteroaryl)-(C0-C6alkyl)-, ApO-, ApS-, ApAqN-, AoC(O)-, AoC(O)-O-, AoC(O)-NAq-, AoS(O)2-, AoS(O)2-O-, and AoS(O)2-NAq-, wherein Aois independently selected at each occurrence from Ap, halo, ApO-, and ApAqN-, and wherein Apand Aqare independently selected at each occurrence from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, (C3-C7 cycloalkyl)(C0-C3 alkyl)-, (3- to 8-membered monocyclic or bicyclic heterocycle)-(C0- C6 alkyl)-, (6- to 10-membered monocyclic or bicyclic aryl)-(C0-C6 alkyl)-, and (5- to 10- membered monocyclic or bicyclic heteroaryl)-(C0-C6 alkyl)-. The terms for various functional groups as used herein are not intended to be limited to monovalent radicals and may include polyvalent radical groups as appropriate, such as divalent, trivalent, tetravalent, pentavalent, and hexavalent groups, and the like, based on the position and location of such groups in the compounds described herein as would be readily understood by the skilled person in the context in which said functional groups are recited.As used herein, the symbol “ ” (which hereinafter can be referred to as “a point ofattachment bond”) denotes a bond that is a point of attachment between two chemical entities, one of which is depicted as being attached to the point of attachment bond and the other of which is not depicted as being attached to the point of attachment bond. For example, “ ” indicates that the chemical entity “XY” is bonded to another chemical entity via the point of attachment bond. Furthermore, the specific point of attachment to the non-depicted chemical entity can be specified by inference. For example, the compound CH3-R3, wherein R3is H or “ ,” infers that when R3 is “XY”, the point of attachment bond is the same bondas the bond by which R3is depicted as being bonded to CH3. “Halo” or “halogen” independently indicates any of fluoro, chloro, bromo, or iodo. The term “nitro,” as used herein, is represented by the formula —NO2. The term “cyano,” as used herein, is represented by the formula —CN Attorney Docket No.11196-115WO1 The term “azido,” as used herein, is represented by the formula –N3. The term “oxo,” as used herein, is represented by the formula =O. “Alkyl” is a straight chain or branched saturated aliphatic hydrocarbon group. In certain aspects, the alkyl is C1-C2, C1-C3, or C1-C6 (i.e., the alkyl chain can be 1, 2, 3, 4, 5, or 6 carbons in length). The specified ranges as used herein indicate an alkyl group with the length of each member of the range described as an independent species. For example, C1-C6alkyl, as used herein, indicates an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms and is intended to mean that each of these is described as an independent species, and C1-C4alkyl, as used herein, indicates an alkyl group having 1, 2, 3, or 4 carbon atoms and is intended to mean that each of these is described as an independent species. When C0-Cnalkyl is used herein in conjunction with another group, for example (C3-C7 cycloalkyl)C0-C4alkyl, or -C0-C4(C3-C7 cycloalkyl), the indicated group, in this case cycloalkyl, is either directly bound by a single covalent bond (C0alkyl), or attached by an alkyl chain, in this case 1, 2, 3, or 4 carbon atoms. Alkyls can also be attached via other groups such as heteroatoms, such as -O-C0-C4alkyl(C3-C7cycloalkyl). Examples of alkyl include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2- methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane. In some aspects, the alkyl group is optionally substituted as described herein. “Haloalkyl” refers to an alkyl group that is substituted with one or more halo groups, e.g., fluoro, chloro, bromo, iodo, or combinations thereof. “Cycloalkyl” is a saturated or partially unsaturated mono- or multicyclic hydrocarbon ring system. When composed of two or more rings, the rings may be joined together in a fused or bridged fashion. Non-limiting examples of typical cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. In some aspects, the cycloalkyl group is optionally substituted as described herein. “Alkenyl” is a straight or branched chain aliphatic hydrocarbon group having one or more carbon-carbon double bonds, each of which is independently either cis or trans, that may occur at a stable point along the chain. Non-limiting examples include C2-C4alkenyl and C2-C6alkenyl (i.e., having 2, 3, 4, 5, or 6 carbons). The specified ranges as used herein indicate an alkenyl group, with each member of the range described as an independent species, as described above for the alkyl moiety. Examples of alkenyl include, but are not limited to, ethenyl and propenyl. In one aspect, the alkenyl group is optionally substituted as described herein. Attorney Docket No.11196-115WO1 “Alkynyl” is a straight or branched chain aliphatic hydrocarbon group having one or more carbon-carbon triple bonds that may occur at any stable point along the chain, for example, C2- C4alkynyl or C2-C6alkynyl (i.e., having 2, 3, 4, 5, or 6 carbons). The specified ranges as used herein indicate an alkynyl group, with each member of the range described as an independent species, as described above for the alkyl moiety. Examples of alkynyl include, but are not limited to, ethynyl, propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3- pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, and 5-hexynyl. In one aspect, the alkynyl group is optionally substituted as described herein. “Aryl” indicates an aromatic group containing only carbon in the aromatic ring or rings. In one aspect, the aryl group contains 1 to 3 separate or fused rings and is 6 to 14 or 18 ring atoms, without heteroatoms as ring members. When indicated, such aryl groups may be further substituted with carbon or non-carbon atoms or groups. Such substitution may include the fusion to a 4- to 7- or 5- to 7-membered saturated or partially unsaturated cyclic group that optionally contains 1, 2, or 3 heteroatoms independently selected from N, O, B, P, Si, and S, to form, for example, a 3,4-methylenedioxyphenyl group. Aryl groups include, for example, phenyl and naphthyl, including 1-naphthyl and 2-naphthyl. In one aspect, aryl groups are pendant. An example of a pendant ring is a phenyl group substituted with a phenyl group. In one aspect, the aryl group is optionally substituted as described herein. The term “heterocycle” refers to saturated and partially saturated heteroatom-containing ring radicals, where the heteroatoms may be selected from N, O, and S. The term heterocycle includes monocyclic 3-12 members rings, as well as bicyclic 5-16 membered ring systems (which can include fused, bridged, or spiro bicyclic ring systems). It does not include rings containing -O-O-, -O-S-, and -S-S- portions. Examples of saturated heterocycle groups, including saturated 4- to 7-membered monocyclic groups containing 1 to 4 nitrogen atoms [e.g., pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, azetidinyl, piperazinyl, and pyrazolidinyl]; saturated 4- to 6-membered monocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms [e.g., morpholinyl]; and saturated 3- to 6-membered heteromonocyclic groups containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms [e.g., thiazolidinyl]. Examples of partially saturated heterocycle radicals include, but are not limited to, dihydrothienyl, dihydropyranyl, dihydrofuryl, and dihydrothiazolyl. Examples of partially saturated and saturated heterocycle groups include, but are not limited to, pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, pyrazolidinyl, piperazinyl, morpholinyl, tetrahydropyranyl, thiazolidinyl, dihydrothienyl, 2,3-dihydro-benzo[1,4]dioxanyl, indolinyl, Attorney Docket No.11196-115WO1 isoindolinyl, dihydrobenzothienyl, dihydrobenzofuryl, isochromanyl, chromanyl, 1,2- dihydroquinolyl, 1,2,3,4-tetrahydro-isoquinolyl, 1,2,3,4-tetrahydro-quinolyl, 2,3,4,4a,9,9a- hexahydro-1H-3-aza-fluorenyl, 5,6,7-trihydro-1,2,4-triazolo[3,4-a]isoquinolyl, 3,4-dihydro- 2H-benzo[1,4]oxazinyl, benzo[1,4]dioxanyl, 2,3,-dihydro-1H-benzo[d]isothazol-6-yl, dihydropyranyl, dihydrofuryl, and dihydrothiazolyl. Bicyclic heterocycle includes groups wherein the heterocyclic radical is fused with an aryl radical, and the point of attachment is the heterocycle ring. Bicyclic heterocycle also includes heterocyclic radicals that are fused with a carbocyclic radical. Representative examples include but are not limited to, partially unsaturated condensed heterocyclic groups containing 1 to 5 nitrogen atoms, for example, indoline and isoindoline, partially unsaturated condensed heterocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, partially unsaturated condensed heterocyclic groups containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms, and saturated condensed heterocyclic groups containing 1 to 2 oxygen or sulfur atoms. In one aspect, the heterocycle group is optionally substituted as described herein. “Heteroaryl” refers to a stable monocyclic, bicyclic, or multicyclic aromatic ring that contains from 1 to 4, or in some aspects 1, 2, or 3 heteroatoms selected from N, O, S, B, and P (and typically selected from N, O, and S) with remaining ring atoms being carbon, or a stable bicyclic or tricyclic system containing at least one 5, 6, or 7 membered aromatic ring which contains from 1 to 4, or in some aspects from 1 to 3 or from 1 to 2, heteroatoms selected from N, O, S, B, or P, with remaining ring atoms being carbon. In one aspect, the only heteroatom is nitrogen. In one aspect, the only heteroatom is oxygen. In one aspect, the only heteroatom is sulfur. Monocyclic heteroaryl groups typically have from 5 to 6 ring atoms. In some aspects, bicyclic heteroaryl groups are 8- to 10-membered heteroaryl groups, that is groups containing 8 or 10 ring atoms in which one 5-, 6-, or 7-membered aromatic ring which contains from 1 to 4 heteroatoms selected from N, O, S, B, or P is fused to a second aromatic or non-aromatic ring, wherein the point of attachment is an aromatic ring. When the total number of S and O atoms in the heteroaryl ring exceeds 1, these heteroatoms are not adjacent to one another within the ring. In one aspect, the total number of S and O atoms in the heteroaryl ring is not more than 2. In another aspect, the total number of S and O atoms in the heteroaryl ring is not more than 1. Examples of heteroaryl groups include, but are not limited to, pyridinyl, imidazolyl, imidazopyridinyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, furyl, thienyl, isoxazolyl, thiazolyl, oxadiazolyl, oxazolyl, isothiazolyl, pyrrolyl, quinolinyl, isoquinolinyl, tetrahydroisoquinolinyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, Attorney Docket No.11196-115WO1 indolizinyl, phthalazinyl, pyridazinyl, triazinyl, isoindolyl, pteridinyl, purinyl, triazolyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, and furopyridinyl. In one aspect, the heteroaryl group is optionally substituted as described herein. Certain materials, compounds, compositions, and components disclosed herein can be obtained commercially or readily synthesized using techniques generally known to those of skill in the art. For example, the starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers, such as Sigma-Aldrich (formally MilliporeSigma, Burlington, MA) or Thermo Fisher Scientific Inc. (Waltham, MA), or are prepared by methods known to those skilled in the art following procedures set forth in references such as Fieser and Fieser's Reagents for Organic Synthesis (John Wiley and Sons, 2007); Organic Reactions (John Wiley and Sons, 2004); March's Advanced Organic Chemistry, (John Wiley and Sons, 8thEdition); and Larock's Comprehensive Organic Transformations (John Wiley and Sons, 3rdedition, 2017). The present disclosure also includes compounds described herein with at least one desired isotopic substitution of an atom, at an amount above the natural abundance of the isotope, i.e., enriched. Examples of isotopes that can be incorporated into compounds of the present disclosure include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorous, fluorine, and chlorine, such as2H,3H,11C,13C,15N,17O,18O,18F,31P, 32P,35S,36Cl, and125I, respectively. In one aspect, isotopically labeled compounds can be used in metabolic studies (with14C), reaction kinetic studies (with, for example2H or3H), detection or imaging techniques, such as positron emission tomography (PET) or single-photon emission computed tomography (SPECT) including drug and substrate tissue distribution assays, or in radioactive treatment of patients. In particular, an18F-labeled compound may be particularly desirable for PET or SPECT studies. Isotopically labeled compounds of this disclosure and prodrugs thereof can generally be prepared by carrying out the procedures disclosed herein by substituting a readily available isotopically labeled reagent for a non-isotopically labeled reagent. By way of general example and without limitation, isotopes of hydrogen, for example, deuterium (2H) and tritium (3H), may optionally be used anywhere in the described structures that achieve the desired result. Alternatively, or in addition, isotopes of carbon, e.g.,13C and14C, may be used. In one aspect, the isotopic substitution is replacing hydrogen with a Attorney Docket No.11196-115WO1 deuterium at one or more locations on the molecule to improve the performance of the molecule as a drug, for example, the pharmacodynamics, pharmacokinetics, biodistribution, half-life, stability, AUC, Tmax, Cmax, etc. For example, the deuterium can be bound to carbon in the allocation of bond breakage during metabolism (an alpha-deuterium kinetic isotope effect) or next to or near the site of bond breakage (a beta-deuterium kinetic isotope effect). Isotopic substitutions, such as deuterium substitutions, can be partial or complete. Partial deuterium substitution means that at least one hydrogen is substituted with deuterium. In certain aspects, the isotope is 80, 85, 90, 95, or 99% or more enriched in an isotope at any location of interest. In some aspects, deuterium is 80, 85, 90, 95, or 99% enriched at a desired location. Unless otherwise stated, the enrichment at any point is above natural abundance, and, in an aspect, is enough to alter a detectable property of the compounds as a drug in a human. The compounds of the present disclosure may form a solvate with solvents (including water). Therefore, in one aspect, the disclosure includes a solvated form of the active compound. The term “solvate” refers to a molecular complex of a compound of the present disclosure (including a salt thereof) with one or more solvent molecules. Non-limiting examples of solvents are water, ethanol, dimethyl sulfoxide, acetone, and other common organic solvents. The term “hydrate” refers to a molecular complex comprising a disclosed compound and water. Pharmaceutically acceptable solvates in accordance with the disclosure include those wherein the solvent of crystallization may be isotopically substituted, e.g., D2O, d6-acetone, or d6- DMSO. A solvate can be in a liquid or solid form. A “prodrug” as used herein means a compound which, when administered to a host in vivo, is converted into a parent drug. As used herein, the term “parent drug” means any of the presently described compounds herein. Prodrugs can be used to achieve any desired effect, including enhancing the properties of the parent drug or improving the pharmaceutical or pharmacokinetic properties of the parent, including increasing the half-life of the drug in vivo. Prodrug strategies provide choices in modulating the conditions for the in vivo generation of the parent drug. Non-limiting examples of prodrug strategies include covalent attachment of removable groups, or removable portions of groups, for example, but not limited to, acylating, phosphorylation, phosphonylation, phosphoramidate derivatives, amidation, reduction, oxidation, esterification, alkylation, other carboxy derivatives, sulfoxy or sulfone derivatives, carbonylation, or anhydrides, among others. In certain aspects, the prodrug renders the parent compound more lipophilic. In certain aspects, a prodrug can be provided that has several prodrug moieties in a linear, branched, or cyclic manner. For example, non-limiting aspects Attorney Docket No.11196-115WO1 include the use of a divalent linker moiety such as a dicarboxylic acid, amino acid, diamine, hydroxycarboxylic acid, hydroxyamine, di-hydroxy compound, or other compound that has at least two functional groups that can link the parent compound with another prodrug moiety and is typically biodegradable in vivo. In some aspects, 2, 3, 4, or 5 prodrug biodegradable moieties are covalently bound in a sequence, branched, or cyclic fashion to the parent compound. Non- limiting examples of prodrugs according to the present disclosure are formed with: a carboxylic acid on the parent drug and a hydroxylated prodrug moiety to form an ester; a carboxylic acid on the parent drug and an amine prodrug to form an amide; an amino on the parent drug and a carboxylic acid prodrug moiety to form an amide; an amino on the parent drug and a sulfonic acid to form a sulfonamide; a sulfonic acid on the parent drug and an amino on the prodrug moiety to form a sulfonamide; a hydroxyl group on the parent drug and a carboxylic acid on the prodrug moiety to form an ester; a hydroxyl on the parent drug and a hydroxylated prodrug moiety to form an ester; a phosphonate on the parent drug and a hydroxylated prodrug moiety to form a phosphonate ester; a phosphoric acid on the parent drug and a hydroxylated prodrug moiety to form a phosphate ester; a hydroxyl on the parent drug and a phosphonate on the prodrug to form a phosphonate ester; a hydroxyl on the parent drug and a phosphoric acid prodrug moiety to form a phosphate ester; a carboxylic acid on the parent drug and a prodrug of the structure HO-(CH2)2-O-(C2-24 alkyl) to form an ester; a carboxylic acid on the parent drug and a prodrug of the structure HO-(CH2)2-S-(C2-24alkyl) to form a thioester; a hydroxyl on the parent drug and a prodrug of the structure HO-(CH2)2-O-(C2-24 alkyl) to form an ether; a hydroxyl on the parent drug and a prodrug of the structure HO-(CH2)2-O-(C2-24alkyl) to form an thioether; and a carboxylic acid, oxime, hydrazide, hydrazine, amine or hydroxyl on the parent compound and a prodrug moiety that is a biodegradable polymer or oligomer including but not limited to polylactic acid, polylactide-co-glycolide, polyglycolide, polyethylene glycol, polyanhydride, polyester, polyamide, or a peptide. In some aspects, a prodrug is provided by attaching a natural or non-natural amino acid to an appropriate functional moiety on the parent compound, for example, oxygen, nitrogen, or sulfur, and typically oxygen or nitrogen, usually in a manner such that the amino acid is cleaved in vivo to provide the parent drug. The amino acid can be used alone or covalently linked (straight, branched, or cyclic) to one or more other prodrug moieties to modify the parent drug to achieve the desired performance, such as increased half-life, lipophilicity, or other drug delivery or pharmacokinetic properties. The amino acid can be any compound with an amino group and a carboxylic acid, which includes an aliphatic amino acid, alkyl amino acid, aromatic Attorney Docket No.11196-115WO1 amino acid, heteroaliphatic amino acid, heteroalkyl amino acid, heterocyclic amino acid, or heteroaryl amino acid. This disclosure describes the compositions and methods of a family of citrate-based, biodegradable, fluorescent, and metal ion incorporated orthopedic biomaterials, which can be used as a graft material in orthopedic applications. Non-union bone fractures (NUBF), with an estimated global prevalence of 9 million annually, represent a fundamental therapeutic challenge for orthopedic and reconstructive surgeons. The large lesion exceeds the intrinsic capacity of self-regeneration; consequently, bone repair is delayed and impaired, resulting in patients living with pain, facing high risks of infection, and a reduced quality of life1. In order to maximally restore the pre-existing function, effective bone grafting is required for NUBF treatment. The preferred clinical approach to treat critical-sized bone defects is the transplantation of autogenous bone grafts; however, several major restrictions limit its application, such as the volume of bone needed, possible donor site complications, and uncontrollable graft resorption and infection. Thus, the development of fully synthetic bone substitutes that are readily available, cost-effective, osteopromotive, and biodegradable is particularly encouraged to address the unmet medical needs. Disclosed herein are family of biodegradable, citrate-based, fluorescent / photoacoustic and metal-ion incorporated composites (BCFMCs) with the following advantages over the pre- existing orthopedic biomaterials: 1) BCFMCs are all derived from citric acid, which recently has been shown to play a critical role in the physiology, metabolism, and nanocomposite structure formation of bone development and regeneration; 2) BCFMCs are synthesized from United States Food and Drug Administration (FDA) approved compounds; 3) BCFMCs inherently contains valuable pendant carboxylic acid chemistry for metal ion chelation without the need for any additional chemical modification to incorporate multiple metal ions to the biopolymer with controlled release for enhanced bioactivity and mechanical properties; 4) BCFMCs are superior at polymer-bioceramic binding with the ability to incorporate 50 wt.-% hydroxyapatite (HA) to match the native inorganic bone composition, which is not possible with previous materials; 5) BCFMCs are intrinsically photoluminescent / photoacoustic to introduce an exclusive imaging aspect into the current orthopedic applications in addition to radiographic techniques to monitor implant presence and tissue regeneration; 6) BCFMCs, combining the chemistry of citrate and different diols, provide not only rich pendant carboxyl, but also hydroxyl groups, both allowing the efficient incorporation of various amino acids to the biopolymer to deliver essential nutrients and support better vascularization and tissue Attorney Docket No.11196-115WO1 regeneration; 7) Using hexamethylene diisocyanate (HDI) as the crosslinker, BCFMCs can incorporate many temperature-sensitive small molecules, such as antibiotics and be used as a localized drug delivery vehicle; and 8) the ability to match the native citrate and inorganic composition of bone allows for the development of highly biomimetic composite materials that can modulate the immune environment, promote bone regeneration and fully integrate with the surrounding tissue. Through these unique advantages, BCFMCs can be useful for multiple applications in orthopedics. BCFMCs also show great versatility as an osteogenic fluorescent / photoacoustic platform biomaterial and can be easily modified to fit a particular application. For example, BCFMCs can be easily fabricated into a wide array of scaffolds and applied in orthopaedics as artificial joints, plates and screws, orthodontics as braces and dental implants. BCFMCs can also be fabricated into porous and hollow bone substitutes for large bone defect reconstruction. Metal ions incorporated into BCFMCs greatly improved the mechanical properties of citrate- based biopolymers and expanded the applications of BCFMCs. When combined with the masquelet-induced membrane technique, BCFMC-based large bone substitutes can potentially replace both polymethyl methacrylate (PMMA) and autologous cancellous bone graft, greatly shorten and simplify the original two-stage operative procedure into a single-stage process. In its simplest form, BCFMCs without post-polymerization can be made into a malleable, putty- like consistency and can be used as an osteoconductive material to fill and aid in the repair of irregular-shaped bone defects. Furthermore, BCFMCs can be modified to function as an in situ crosslinkable cement to assist in bone bonding or as an adhesive to secure other implant devices to skeletal tissues. Finally, BCFMCs not only serve as an implant material to induce bone regeneration, but also as a powerful bioimaging tool due to their unique intrinsic fluorescent / photoacoustic property. All BCFMC forms emit fluorescence in a wide spectrum of colors and can be exploited to monitor the presence, stability, and degradation of the implant in situ to circumvent the need for animal sacrifice and tedious histological procedures while composites containing higher glutamine content also exhibit strong photoacoustic signal, with superior imaging capability at greater depths compared to fluorescence. Overall, the development of BCFMCs should set new requirements of an ideal orthopedic biomaterial and provide a readily available, fully synthetic adjunct or replacement to autologous bone grafting. This disclosure describes how a citrate-based, amino acid, and metal-containing fluorescent / photoacoustic composite can be used as substitutes for autologous bone grafts. The rationale behind this approach is that 1) A citrate-based composite offers a means to replicate Attorney Docket No.11196-115WO1 the native organic citrate content in bone; 2) The use of citric acid as a multifunctional monomer provides free pendant carboxylic acid chemistry for enhanced HA binding through calcium chelation, allowing for the incorporation of up to 65 wt% HA and the incorporation of various other metal ions, which not only enhance the mechanical properties of material, but also play essential roles in facilitating tissue regeneration; 3) Combination of the chemistry of citrate and different diols, provide not only rich pendant carboxyl, but also hydroxyl groups to allow the incorporation of various amino acids to the biopolymer to deliver essential nutrients and support better vascularization and tissue regeneration; Taken together, the use of citrate, amino acids and metal ions will allow us to create extremely biomimetic materials to enhance bone development and integration for orthopedic applications; 4) A composite with fluorescent imaging capabilities can offer an additional means to non-invasively monitor material degradation and tissue regeneration; 5) Using hexamethylene diisocyanate (HDI) as the crosslinker, BCFMCs can incorporate many temperature-sensitive small molecules, such as antibiotics and be used as a localized drug delivery vehicle; 6) Utilizing a variety of crosslinking methods, BCFMCs can be engineered into intricate structures to meet the requirements for bone repair at different anatomical sites; and 6) A fully synthetic polymer formulation is cost-effective, easy to synthesize, and readily available to meet the current demands. The following sections will provide a detailed description of the preparation, characterization, and potential use of BCFMCs in orthopedic applications. Using the biodegradable and osteoconductive BCFMC-based bone substitutes described herein, it is possible to shorten the lengthy, two-stage masquelet technique into a single-stage operation. Low-level cross-linked BCFMCs can also act as a localized antibiotic delivery vehicle in treating infected large bone defects. These features would save patients a second surgical procedure to remove the PMMA spacer and fill the membrane-concealed chamber with autologous bone graft. Polymer and / or Oligomer Compositions In one aspect, the present disclosure provides compositions including a polymer or oligomer. In some aspects, the polymer or oligomer can be formed from one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt. In some aspects, the one or more monomers A can include an alkoxylated, alkenoxylated, or non-alkoxylated and non- alkenoxylated citric acid, citrate, or ester or amide of citric acid. In some aspects, the one or more monomers A can include citric acid or a citrate salt (such as sodium citrate, potassium Attorney Docket No.11196-115WO1 citrate, calcium citrate, magnesium citrate, lithium citrate, or ammonium citrate). In some aspects, the citric acid can comprise a citrate ester (such as triethyl citrate). In some aspects, the one or more monomers A can include citric acid, trimethyl citrate, triethyl citrate, monosodium citrate, disodium citrate, trisodium citrate, calcium citrate, or combinations thereof. In some particular aspects, the one or more monomers A include citric acid. In some aspects, the one or more monomers A can include a compound of Formula (A1), ; X1, X2, and X3are each independently -O- or -NH-; R1, R2, and R3are each independently -H, C1-C22 alkyl, C2-C22 alkenyl, or M+; R4is H or M+; and M+is a cation. In some aspects of Formula A1, X1can be -O-. In some aspects of Formula A1, X2can be -O- . In some aspects of Formula A1, X3can be -O-. In some aspects of Formula A1, X1, X2, and X3can be each -O-. In some aspects of Formula A1, R1, R2, and R3can be each independently -H, -CH3, or -CH2CH3. In some aspects of Formula A1, R1, R2and R3can be each independently -H or M+. In some aspects of Formula A1, R4is -H. In some aspects of Formula A1, R4can be M+. In some aspects of Formula A1, M+can be independently at each occurrence Na+or K+. In some aspects, the polymer or oligomer can be further formed from one or more monomers B comprising a polyol or polyamine. Non-limiting examples of suitable polyols and polyamines suitable include C2-C20, C2-C12, or C2-C6 aliphatic alkane diols / diamines, including α,ω-η-alkane diols / diamines, or α,ω-alkene diols / diamines. For instance, in some aspects, a polyol / polyamine comprises 1,4-butanediol / diamine, 1,6-hexanediol / diamine, 1,8- octanediol / diamine, 1,10-decanediol / diamine, 1,12-dodecanediol / diamine, 1,16- hexadecanediol / diamine, or 1,20-icosanediol / diamine. Branched α,ω-alkane diols / diamines or α,ω-alkene diols / diamines can also be used. Additionally, a polyol / polyamine can also be an Attorney Docket No.11196-115WO1 aromatic diol / diamine. Further, in some aspects, a polyol / polyamine can include a poly(ethylene glycol) (PEG) or poly(propylene glycol) (PPG) having terminal hydroxyl or amine groups. Any such PEG or PPG that is not inconsistent with the objectives of the present disclosure may be used. In some aspects, for instance, a PEG or PPG has a weight average molecular weight between about 100 and about 5000, or between about 200 and about 1000, or between 200 and about 100,000. In some aspects, the one or more monomers B can include a diol or diamine. In some aspects, the one or more monomers B can include a poly(alkylene glycol). In some aspects, the one or more monomers B can include poly(ethylene glycol), poly(propylene glycol), or combinations thereof. In some aspects, the one or more monomers B can include an alkylene diol. In some aspects, the one or more monomers B can include 1,2-ethylene glycol, 1,3-propanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12- dodecanediol, or combinations thereof. In some aspects, the one or more monomers B comprise 1,8-octanediol. In some aspects, the one or more monomers B can include a compound of Formula (B1) , R6is -NH2, -OH, -OCH3, or -OCH2CH3; R7is -H, C1-C23 alkyl, or C2-C23 alkenyl; R8is -H, C1-C23 alkyl, C2-C23 alkenyl, -CH2CH2OH, or -CH2CH2NH2; and m is an integer ranging from 1 to 2000. In some aspects of Formula (B1), R6can be -OH. In some aspects of Formula (B1), R7can be -H. In some aspects of Formula (B1), R7can be -CH3. In aspects of Formula (B1), R8can be - H. In some aspects of Formula (B1), m can be an integer from 1 to 2000, including exemplary values of 1 to 100, or 1 to 250, or 1 to 500, or 1 to 750 or 1 to 1000, or 1 to 1250, or 1-1500, or 1 to 1750. In yet other aspects of Formula (B1), m can be an integer between 1 and 20, including exemplary values of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19 In some aspects, the one or more monomers B can include a compound of Formula (B2) Attorney Docket No.11196-115WO1 , X4and X5are independently -O- or -NH; and n is an integer ranging from 1 to 2000. In some aspects of Formula (B2), X4can be -O. In some aspects of Formula (B2), X4can be - NH-. In some aspects of Formula (B2), X5can be -O-. In some aspects of Formula (B2), X5can be -NH-. In some aspects of Formula (B2), X4and X5can be each -O-. In some aspects of Formula (B2), X4and X5can be each -NH-. In some aspects of Formula (B2), one of X4and X5can be -O- and the other of X4and X5can be -NH-. In some aspects of Formula (B2), n can be an integer from 1 to 2000, including exemplary values of 1 to 100, or 1 to 250, or 1 to 500, or 1 to 750 or 1 to 1000, or 1 to 1250, or 1-1500, or 1 to 1750. In yet other aspects of Formula (B2), n can be an integer between 1 and 20, including exemplary values of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19 In some aspects, the polymer or oligomer can be further formed from one or more monomers C including glutamine or a salt or derivative thereof. In some aspects, the one or more monomers C can include glutamine, a glutamine salt, or an ester or amide of glutamine. In some aspects, the one or more monomers C comprise glutamine. In some aspects, the one or more monomers A and the one or more monomers C can be present in a molar ratio from about 20:1 to about 1:20, including exemplary values of about 20:1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, or any subrange formed from the above exemplary values. In some aspects, the one or more monomers B and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:20, including exemplary values of about 20:1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, Attorney Docket No.11196-115WO1 about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, or any subrange formed from the above exemplary values. In some aspects, the polymer or oligomer can be further formed from one or more magnesium salts. Representative examples of suitable magnesium salts include, but are not limited to, magnesium acetate, magnesium benzoate, magnesium bicarbonate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium citrate, magnesium fluoride, magnesium gluconate, magnesium diglutamate, magnesium glycinate, magnesium hydroxide, magnesium iodide, magnesium lactate, magnesium levulinate, magnesium malate, magnesium nitrate, magnesium orotate, magnesium oxalate, magnesium oxide, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium pidolate, magnesium salicylate, magnesium sulfate, magnesium taurate, and magnesium threonate, or combinations thereof. In some particular aspects, the one or more magnesium salts can include magnesium nitrate. In some aspects, the one or more monomers A and the one or more magnesium salts can be present in a molar ratio from about 10:1 to about 1:10, including exemplary values of about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, or any subrange formed from the above exemplary values. In some aspects, the one or more monomers B and the one or more magnesium salts can be present in a molar ratio from about 10:1 to about 1:10, including exemplary values of about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, or any subrange formed from the above exemplary values. In some aspects, the polymer or oligomer can be optionally further formed from one or more additional monomers. In some aspects, the polymer or oligomer can be further formed from one or more monomers D comprising a catechol-containing species. The catechol-containing species can include any catechol-containing species that are not inconsistent with the objectives of the present disclosure. In some aspects, a catechol-containing species comprises at least one moiety that can form an ester or amide bond with another chemical species used to form the compositions described herein. For example, in some aspects, a catechol-containing species comprises an Attorney Docket No.11196-115WO1 alcohol moiety, an amine moiety, a carboxylic acid moiety, or combinations thereof. Further, in some aspects, a catechol-containing species comprises a hydroxyl moiety that is not part of the catechol moiety. In some aspects, a catechol-containing species comprises dopamine. In other aspects, a catechol-containing species comprises L-3,4-dihydroxyphenylalanine (L- DOPA) or D-3,4-dihydroxyphenylalanine (D-DOPA). In still other aspects, a catechol- containing species comprises gallic acid or caffeic acid. In some aspects, a catechol-containing species comprises 3,4-dihydroxycinnamic acid. Additionally, a catechol-containing species may also comprise a naturally occurring species or a derivative thereof, such as tannic acid or a tannin. Moreover, in some aspects, a catechol-containing species is coupled to the backbone of the polymer or oligomer through an amide bond. In other aspects, a catechol-containing species is coupled to the backbone of the polymer or oligomer through an ester bond. Further examples of catechol-containing species which can be used can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the catechol-containing species is a compound of Formula (D1): R9 ; R9, R10, R11, and R12are each independently selected from -H, -OH, -CH2(CH2)xNH2, -CH2(CHR13)NH2, -CH2(CH2)xOH, -CH2(CHR13)OH, and -CH2(CH2)xCOOH; R13is -COOH or –(CH2)yCOOH; and x and y are independently an integer ranging from 1 to 10. In some aspects, the catechol-containing species can be selected from dopamine, L-DOPA, D- DOPA, gallic acid, caffeic acid, 3,4-dihydroxyhydrocinnamic acid, and tannic acid. In some aspects, the polymer or oligomer is further formed from one or more monomers E comprising an isocyanate. In some aspects, an isocyanate comprises an alkane diisocyanate having four to twenty carbon atoms. An isocyanate described herein may also include a Attorney Docket No.11196-115WO1 monocarboxylic acid moiety. Further examples of various isocyanates which can be used are described in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the isocyanate is a compound selected from Formula (E1), Formula (E2), Formula (E3), and Formula (E4): , In some aspects, the polymer or oligomer is further formed from one or more monomers F comprising a polycarboxylic acid. In some aspects, the polycarboxylic acid can be a dicarboxylic acid, or a functional equivalent of a polycarboxylic acid, such as a cyclic anhydride or an acid chloride of a polycarboxylic acid. In some aspects, the polycarboxylic acid or functional equivalent thereof can be saturated or unsaturated. In some aspects, for example, the polycarboxylic acid or functional equivalent thereof comprises maleic acid, maleic anhydride, fumaric acid, or fumaryl chloride. In some aspects, a vinyl-containing polycarboxylic acid or functional equivalent thereof may also be used, such as allylmalonic acid, allylmalonic chloride, itaconic acid, or itaconic chloride. Further, in some aspects, the polycarboxylic acid or functional equivalent thereof can be at least partially replaced with an olefin-containing monomer that may or may not be a polycarboxylic acid. In some aspects, for instance, an olefin-containing monomer comprises an unsaturated polyol such as a vinyl- containing diol. Further examples can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. Attorney Docket No.11196-115WO1 In some aspects, the polycarboxylic acid is a compound selected from Formula (F1) and Formula (F2): ; and -Cl. In some aspects, the polymer or oligomer is further formed from one or more monomers G comprising one or more azide moieties. The monomer comprising one or more azide moieties used to form a polymer described herein can comprise any azide-containing chemical species not inconsistent with the objectives of the present disclosure. Additional examples of monomers containing azide moieties can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the one or more monomers G can be selected from a compound of Formula (G1), Formula (G2), and Formula (G3): X6is independently selected at each occurrence from -O- or -NH-; R16is -CH3 or -CH2CH3; and R17and R18are each independently -CH2N3, -CH3, or -CH2CH3. In some aspects, the polymer or oligomer is further formed from one or more monomers H comprising one or more alkyne moieties. The monomer comprising one or more alkyne moieties used to form a polymer described herein can comprise any alkyne-containing chemical species that are not inconsistent with the objectives of the present disclosure. Additional examples of monomers containing alkyne moieties can be found in U.S. Patent Attorney Docket No.11196-115WO1 Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the one or more monomers H can be selected from a compound of Formula (H1), Formula (H2), Formula (H3), Formula (H4), Formula (H5), and Formula (H6): ; X7and Y are independently -O- or -NH-; R19and R20are each independently -CH3 or -CH2CH3; R21is -OC(O)CCH, -CH3, or -CH2CH3; and R22is -CH3, -OH, or -NH2. In some aspects, the polymer or oligomer is crosslinked. In some aspects, the polymer or oligomer can be thermally crosslinked, radically crosslinked, chemically crosslinked, ionically crosslinked, or combinations thereof. In some aspects, the polymer or oligomer can be chemically crosslinked with a crosslinker. Any crosslinker that is not inconsistent with the objectives of the present disclosure may be used. In some cases, for example, a crosslinker comprises one or more olefins or olefinic Attorney Docket No.11196-115WO1 moieties that can be used to crosslink polymers containing ethylenically unsaturated moieties. In some aspects, a crosslinker comprises an acrylate or polyacrylate, including a diacrylate. In other aspects, a crosslinker comprises one or more of 1,3-butanediol diacrylate, 1,6-hexanediol diacrylate, glycerol 1,3-diglyerolate diacrylate, d(ethylene glycol) diacrylate, poly(ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, and propylene glycol glycerolate diacrylate. In still other aspects, a crosslinker comprises a “click chemistry” reagent, such as an azide or an alkyne. In some aspects, a crosslinker comprises an ionic crosslinker. For instance, in some aspects, a polymer is crosslinked with a multivalent metal ion, such as a transition metal ion. In some aspects, a multivalent metal ion used as a crosslinker of the polymer comprises one or more of Fe, Ni, Cu, Zn, or Al, including in the +2 or +3 state. In some aspects, the polymer or oligomer is chemically crosslinked by a diisocyanate (such as butanediisocyanate (BDI), 1,6-hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI)). In some aspects, the composition further comprises an inorganic material. In some aspects, the inorganic material comprises a particulate inorganic material. Any particulate inorganic material that is not inconsistent with the objectives of the present disclosure may be used. In some aspects, the particulate inorganic material comprises one or more of hydroxyapatite, tricalcium phosphate (including alpha- and beta-tricalcium phosphate), biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particles. Other particular materials may also be used. In addition, a particular inorganic material described herein can have any particle size and / or particle shape that is not inconsistent with the objective of the present disclosure. In some aspects, for instance, a particulate material has an average particle size in at least one dimension of less than about 1000 µm, less than about 800 µm, less than about 500 µm, less than about 300 µm, less than about 100 µm, less than about 50 µm, less than about 30 µm, or less than about 10 µm. In some aspects, a particular material has an average particle size in at least one dimension of less than about 1 µm, less than about 500 nm, less than about 300 nm, less than about 100 nm, less than about 50 nm, or less than about 30 nm. In some aspects, a particulate material has an average particle size recited herein in two dimensions or three dimensions. Moreover, a particulate material can be formed of substantially spherical particles, plate-like particles, needle-like particles, or a combination thereof. Particulate materials having other shapes may also be used Attorney Docket No.11196-115WO1 In some aspects, the composition further comprises an antioxidant, a therapeutic agent (such as an antibiotic), a biomolecule (such as a peptide or a protein), a cell, or combinations thereof. As used herein, the term “therapeutic agent” includes any synthetic or naturally occurring biologically active compound or composition of matter which, when administered to 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 Attorney Docket No.11196-115WO1 may be a biologically active agent used in medical, including veterinary, applications and in agriculture, such as with plants, as well as in other areas. As used herein, a “biomolecule” is a molecule produced by a living organism and essential to one or more typically biological processes. Biomolecules can include, but are not limited to, lipids, fatty acids, glycolipids, sterols, monosaccharides, oligosaccharides, polysaccharides, vitamins, hormones, neurotransmitters, metabolites, amino acids, oligopeptides, polypeptides / proteins, terpenes, nucleosides, nucleotides, DNA, RNA, lignin, and the like. In some aspects, the composition is luminescent. In some cases, such luminescence is photoluminescence and can be observed by exposing the composition to a suitable wavelength of light, such as light having a peak or average wavelength between 400 nm and 600 nm. Moreover, in some embodiments, the luminescence intensity of the composition, measured in arbitrary or relative units, can be used as a measure of degradation of the scaffold over time, thereby indicating biodegradability or clearance from a site, such as a bone site. In some aspects, the composition is fluorescent. In some aspects, the composition further comprises a fluorescence / absorbance enhancer. Representative examples of fluorescence / absorbance enhancers include a metal (such as gold, silver, or a lanthanide), a carbon nanostructure, or an inorganic phosphate. In some aspects, the composition displays near-infrared (NIR) absorbance. In some aspects, the composition displays absorbance at an average wavelength from about 700 nm to 1000 nm. The fluorescence and / or absorbance properties of the compositions described herein may be used for imaging purposes, for example, to track degradation of the composition (e.g., in an associated article or device) in vivo, to track integration of the composition (e.g., in an associated article or device) into tissues in vivo, or to track motion or migration over time of the composition (e.g., in an associated article or device) in vivo. In other aspects, the fluorescence and / or absorbance properties of the compositions described herein may be used for therapeutic purposes, for example, via photodynamic therapy or by promoting release of a therapeutic agent from the compositions. In some aspects, the composition exhibits photoacoustic properties. The photoacoustic properties of the compositions described herein may be used either for imaging purposes, for example, to track degradation of the composition (e.g., in an associated article or device) in vivo, to track integration of the composition (e.g., in an associated article or device) into tissues in vivo, or to track motion or migration over time of the composition (e.g., in an associated Attorney Docket No.11196-115WO1 article or device) in vivo. In other aspects, the photoacoustic properties of the compositions described herein may be used for therapeutic purposes, for example, via targeted heating of the compositions when present in vivo. In some aspects, the composition is biodegradable. In some aspects, the composition is capable of releasing citrate, glutamine, and / or magnesium upon degradation. In some aspects, the composition is capable of releasing citrate, glutamine, and / or magnesium upon degradation in the presence of a biological tissue; in such aspects, the released citrate, glutamine, and / or magnesium are capable of providing a beneficial therapeutic effect (e.g., such as improved bone regeneration) to the biological tissue. The polymer or oligomers in the compositions described herein may be formed using any suitable polymerization method as would be readily understood by one of ordinary skill in the art. For example, the polymers or oligomers described herein may be formed by condensation polymerization. Alternatively, the polymers or oligomers described herein may be formed by radical polymerization, including but not limited to, ultraviolet, gamma, and photon irradiation using photoinitiators such as Irgacure 2959, Irgacure 784, Esacure DP 250, phosphine oxide methylpropriophenone, dimethoxyphenylacetophenone, or any other photoinitiators that work for photopolymerization. Prepolymer Compositions In one aspect, the present disclosure provides prepolymer compositions comprising a prepolymer. As used herein, a “prepolymer” refers to a polymer or oligomer, the molecules of which are capable of entering, through the presence of one or more reactive groups, into further polymerization and thereby can contribute to more than one structural unit to at least one type of final polymer. In some aspects, the prepolymer composition can be formed from one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt. In some aspects, the one or more monomers A can include an alkoxylated, alkenoxylated, or non-alkoxylated and non- alkenoxylated citric acid, citrate, or ester or amide of citric acid. In some aspects, the one or more monomers A can include citric acid or a citrate salt (such as sodium citrate, potassium citrate, calcium citrate, magnesium citrate, lithium citrate, or ammonium citrate). In some aspects, the citric acid can comprise a citrate ester (such as triethyl citrate). In some aspects, the one or more monomers A can include citric acid, trimethyl citrate, triethyl citrate, monosodium citrate, disodium citrate, trisodium citrate, calcium citrate, or combinations Attorney Docket No.11196-115WO1 thereof. In some particular aspects, the one or more monomers A include citric acid. In some aspects, the one or more monomers A can include a compound of Formula (A1), ; X1, X2, and X3are each independently -O- or -NH-; R1, R2, and R3are each independently -H, C1-C22 alkyl, C2-C22 alkenyl, or M+; R4is H or M+; and M+is a cation. In some aspects of Formula A1, X1can be -O-. In some aspects of Formula A1, X2can be -O- . In some aspects of Formula A1, X3can be -O-. In some aspects of Formula A1, X1, X2, and X3can be each -O-. In some aspects of Formula A1, R1, R2, and R3can be each independently -H, -CH3, or -CH2CH3. In some aspects of Formula A1, R1, R2and R3can be each independently -H or M+. In some aspects of Formula A1, R4is -H. In some aspects of Formula A1, R4can be M+. In some aspects of Formula A1, M+can be independently at each occurrence Na+or K+. In some aspects, the prepolymer composition can be further formed from one or more monomers B comprising a polyol or polyamine. Non-limiting examples of suitable polyols and polyamines include C2-C20, C2-C12, or C2-C6 aliphatic alkane diols / diamines, including α,ω- η-alkane diols / diamines, or α,ω-alkene diols / diamines. For instance, in some aspects, a polyol / polyamine comprises 1,4-butanediol / diamine, 1,6-hexanediol / diamine, 1,8- octanediol / diamine, 1,10-decanediol / diamine, 1,12-dodecanediol / diamine, 1,16- hexadecanediol / diamine, or 1,20-icosanediol / diamine. Branched α,ω-alkane diols / diamines or α,ω-alkene diols / diamines can also be used. Additionally, a polyol / polyamine can also be an aromatic diol / diamine. Further, in some aspects, a polyol / polyamine can include a poly(ethylene glycol) (PEG) or poly(propylene glycol) (PPG) having terminal hydroxyl or amine groups. Any such PEG or PPG not inconsistent with the objectives of the present disclosure may be used. In some aspects, for instance, a PEG or PPG has a weight average Attorney Docket No.11196-115WO1 molecular weight between about 100 and about 5000 or between about 200 and about 1000, or between 200 and about 100,000. In some aspects, the one or more monomers B can include a diol or diamine. In some aspects, the one or more monomers B can include a poly(alkylene glycol). In some aspects, the one or more monomers B can include poly(ethylene glycol), poly(propylene glycol), or combinations thereof. In some aspects, the one or more monomers B can include an alkylene diol. In some aspects, the one or more monomers B can include 1,2-ethylene glycol, 1,3-propanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12- dodecanediol, or combinations thereof. In some aspects, the one or more monomers B comprise 1,8-octanediol. In some aspects, the one or more monomers B can include a compound of Formula (B1) , R6is -NH2, -OH, -OCH3, or -OCH2CH3; R7is -H, C1-C23 alkyl, or C2-C23 alkenyl; R8is -H, C1-C23alkyl, C2-C23alkenyl, -CH2CH2OH, or -CH2CH2NH2; and m is an integer ranging from 1 to 2000. In some aspects of Formula (B1), R6can be -OH. In some aspects of Formula (B1), R7can be -H. In some aspects of Formula (B1), R7can be -CH3. In aspects of Formula (B1), R8can be - H. In some aspects of Formula (B1), m can be an integer from 1 to 2000, including exemplary values of 1 to 100, or 1 to 250, or 1 to 500, or 1 to 750 or 1 to 1000, or 1 to 1250, or 1-1500, or 1 to 1750. In yet other aspects of Formula (B1), m can be an integer between 1 and 20, including exemplary values of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19 In some aspects, the one or more monomers B can include a compound of Formula (B2) Attorney Docket No.11196-115WO1 X4and X5are independently -O- or -NH; and n is an integer ranging from 1 to 2000. In some aspects of Formula (B2), X4can be -O. In some aspects of Formula (B2), X4can be - NH-. In some aspects of Formula (B2), X5can be -O-. In some aspects of Formula (B2), X5can be -NH-. In some aspects of Formula (B2), X4and X5can be each -O-. In some aspects of Formula (B2), X4and X5can be each -NH-. In some aspects of Formula (B2), one of X4and X5can be -O- and the other of X4and X5can be -NH-. In some aspects of Formula (B2), n can be an integer from 1 to 2000, including exemplary values of 1 to 100, or 1 to 250, or 1 to 500, or 1 to 750 or 1 to 1000, or 1 to 1250, or 1-1500, or 1 to 1750. In yet other aspects of Formula (B2), n can be an integer between 1 and 20, including exemplary values of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19 In some aspects, the prepolymer composition can be further formed from one or more monomers C including glutamine or a salt or derivative thereof. In some aspects, the one or more monomers C can include glutamine, a glutamine salt, or an ester or amide of glutamine. In some aspects, the one or more monomers C comprise glutamine. In some aspects, the one or more monomers A and the one or more monomers C can be present in a molar ratio from about 20:1 to about 1:20, including exemplary values of about 20:1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, or any subrange formed from the above exemplary values. In some aspects, the one or more monomers B and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:20, including exemplary values of about 20:1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, or any subrange formed from the above exemplary values. Attorney Docket No.11196-115WO1 In some aspects, the prepolymer composition can be further formed from one or more magnesium salts. Representative examples of suitable magnesium salts include, but are not limited to, magnesium acetate, magnesium benzoate, magnesium bicarbonate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium citrate, magnesium fluoride, magnesium gluconate, magnesium diglutamate, magnesium glycinate, magnesium hydroxide, magnesium iodide, magnesium lactate, magnesium levulinate, magnesium malate, magnesium nitrate, magnesium orotate, magnesium oxalate, magnesium oxide, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium pidolate, magnesium salicylate, magnesium sulfate, magnesium taurate, and magnesium threonate, or combinations thereof. In some particular aspects, the one or more magnesium salts can include magnesium nitrate. In some aspects, the one or more monomers A and the one or more magnesium salts can be present in a molar ratio from about 10:1 to about 1:10, including exemplary values of about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, or any subrange formed from the above exemplary values. In some aspects, the one or more monomers B and the one or more magnesium salts can be present in a molar ratio from about 10:1 to about 1:10, including exemplary values of about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, or any subrange formed from the above exemplary values. In some aspects, the prepolymer composition can be optionally further formed from one or more additional monomers. In some aspects, the prepolymer composition can be further formed from one or more monomers D comprising a catechol-containing species. The catechol-containing species can include any catechol-containing species not inconsistent with the objectives of the present disclosure. In some aspects, a catechol-containing species comprises at least one moiety that can form an ester or amide bond with another chemical species used to form the compositions described herein. For example, in some aspects, a catechol-containing species comprises an alcohol moiety, an amine moiety, a carboxylic acid moiety, or combinations thereof. Further, in some aspects, a catechol-containing species comprises a hydroxyl moiety that is not part of the catechol moiety. In some aspects, a catechol-containing species comprises dopamine. In Attorney Docket No.11196-115WO1 other aspects, a catechol-containing species comprises L-3,4-dihydroxyphenylalanine (L- DOPA) or D-3,4-dihydroxyphenylalanine (D-DOPA). In still other aspects, a catechol- containing species comprises gallic acid or caffeic acid. In some aspects, a catechol-containing species comprises 3,4-dihydroxycinnamic acid. Additionally, a catechol-containing species may also comprise a naturally-occurring species or a derivative thereof, such as tannic acid or a tannin. Moreover, in some aspects, a catechol-containing species is coupled to the backbone of the prepolymer composition through an amide bond. In other aspects, a catechol-containing species is coupled to the backbone of the prepolymer composition through an ester bond. Further examples of catechol-containing species which can be used can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the catechol-containing species is a compound of Formula (D1): R9 ; R9, R10, R11, and R12are each independently selected from -H, -OH, -CH2(CH2)xNH2, -CH2(CHR13)NH2, -CH2(CH2)xOH, -CH2(CHR13)OH, and -CH2(CH2)xCOOH; R13is -COOH or –(CH2)yCOOH; and x and y are independently an integer ranging from 1 to 10. In some aspects, the catechol-containing species can be selected from dopamine, L-DOPA, D- DOPA, gallic acid, caffeic acid, 3,4-dihydroxyhydrocinnamic acid, and tannic acid. In some aspects, the prepolymer composition is further formed from one or more monomers E comprising an isocyanate. In some aspects, an isocyanate comprises an alkane diisocyanate having four to twenty carbon atoms. An isocyanate described herein may also include a monocarboxylic acid moiety. Further examples of various isocyanates which can be used are described in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Attorney Docket No.11196-115WO1 Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the isocyanate is a compound selected from Formula (E1), Formula (E2), Formula (E3), and Formula (E4): , In some aspects, the prepolymer composition is further formed from one or more monomers F comprising a polycarboxylic acid. In some aspects, the polycarboxylic acid can be a dicarboxylic acid, or a functional equivalent of a polycarboxylic acid, such as a cyclic anhydride or an acid chloride of a polycarboxylic acid. In some aspects, the polycarboxylic acid or functional equivalent thereof can be saturated or unsaturated. In some aspects, for example, the polycarboxylic acid or functional equivalent thereof comprises maleic acid, maleic anhydride, fumaric acid, or fumaryl chloride. In some aspects, a vinyl-containing polycarboxylic acid or functional equivalent thereof may also be used, such as allylmalonic acid, allylmalonic chloride, itaconic acid, or itaconic chloride. Further, in some aspects, the polycarboxylic acid or functional equivalent thereof can be at least partially replaced with an olefin-containing monomer that may or may not be a polycarboxylic acid. In some aspects, for instance, an olefin-containing monomer comprises an unsaturated polyol such as a vinyl- containing diol. Further examples can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the polycarboxylic acid is a compound selected from Formula (F1) and Formula (F2): Attorney Docket No.11196-115WO1 ; and -Cl. In some aspects, the prepolymer composition is further form from one or more monomers G comprising one or more azide moieties. The monomer comprising one or more azide moieties used to form a prepolymer composition described herein can comprise any azide-containing chemical species not inconsistent with the objectives of the present disclosure. Additional examples of monomers containing azide moieties can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the one or more monomers G is selected from a compound of Formula (G1), Formula (G2), and Formula (G3): X6is independently selected at each occurrence from -O- or -NH-; R16is -CH3 or -CH2CH3; and R17and R18are each independently -CH2N3, -CH3, or -CH2CH3. In some aspects, the prepolymer composition is further formed from one or more monomers H comprising one or more alkyne moieties. The monomer comprising one or more alkyne moieties used to form a prepolymer composition described herein can comprise any alkyne- containing chemical species not inconsistent with the objectives of the present disclosure. Additional examples of monomers containing alkyne moieties can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. Attorney Docket No.11196-115WO1 In some aspects, the one or more monomers H can be selected from a compound of Formula (H1), Formula (H2), Formula (H3), Formula (H4), Formula (H5), and Formula (H6): ; X7and Y are independently -O- or -NH-; R19and R20are each independently -CH3or -CH2CH3; R21is -OC(O)CCH, -CH3, or -CH2CH3; and R22is -CH3, -OH, or -NH2. In some aspects, the prepolymer composition further comprises an inorganic material. In some aspects, the inorganic material comprises a particulate inorganic material. Any particulate inorganic material that is not inconsistent with the objectives of the present disclosure may be used. In some aspects, the particulate inorganic material comprises one or more of hydroxyapatite, tricalcium phosphate (including alpha- and beta-tricalcium phosphate), biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particle. Other particular materials may also be used. Attorney Docket No.11196-115WO1 In addition, a particular inorganic material described herein can have any particle size and / or particle shape that is not inconsistent with the objective of the present disclosure. In some aspects, for instance, a particulate material has an average particle size in at least one dimension of less than about 1000 µm, less than about 800 µm, less than about 500 µm, less than about 300 µm, less than about 100 µm, less than about 50 µm, less than about 30 µm, or less than about 10 µm. In some aspects, a particular material has an average particle size in at least one dimension of less than about 1 µm, less than about 500 nm, less than about 300 nm, less than about 100 nm, less than about 50 nm, or less than about 30 nm. In some aspects, a particulate material has an average particle size recited herein in two dimensions or three dimensions. Moreover, a particulate material can be formed of substantially spherical particles, plate-like particles, needle-like particles, or a combination thereof. Particulate materials with other shapes may also be used. In some aspects, the prepolymer composition further comprises an antioxidant, a therapeutic agent (such as an antibiotic), a biomolecule (such as a peptide or a protein), a cell, or combinations thereof. In some aspects, the prepolymer composition is luminescent. In some cases, such luminescence is photoluminescence and can be observed by exposing the composition to a suitable wavelength of light, such as light having a peak or average wavelength between 400 nm and 600 nm. Moreover, in some embodiments, the luminescence intensity of the composition, measured in arbitrary or relative units, can be used as a measure of degradation of the scaffold over time, thereby indicating biodegradability or clearance from a site, such as a bone site. In some aspects, the composition is fluorescent. In some aspects, the prepolymer composition further comprises a fluorescence / absorbance enhancer. Representative examples of fluorescence / absorbance enhancers include a metal (such as gold, silver, or a lanthanide), a carbon nanostructure, or an inorganic phosphate. Polymerizable Compositions In another aspect, the present disclosure provides polymerizable compositions. As used herein, a “polymerizable composition” refers to a composition including one or more monomers, and optionally one or more additional components, capable of being polymerized to form a polymer, oligomer, or prepolymer as described herein. Attorney Docket No.11196-115WO1 In some aspects, the polymerizable composition can include one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt. In some aspects, the one or more monomers A can include an alkoxylated, alkenoxylated, or non-alkoxylated and non- alkenoxylated citric acid, citrate, or ester or amide of citric acid. In some aspects, the one or more monomers A can include citric acid or a citrate salt (such as sodium citrate, potassium citrate, calcium citrate, magnesium citrate, lithium citrate, or ammonium citrate). In some aspects, the citric acid can comprise a citrate ester (such as triethyl citrate). In some aspects, the one or more monomers A can include citric acid, trimethyl citrate, triethyl citrate, monosodium citrate, disodium citrate, trisodium citrate, calcium citrate, or combinations thereof. In some particular aspects, the one or more monomers A include citric acid. In some aspects, the one or more monomers A can include a compound of Formula (A1), ; X1, X2, and X3are each independently -O- or -NH-; R1, R2, and R3are each independently -H, C1-C22 alkyl, C2-C22 alkenyl, or M+; R4is H or M+; and M+is a cation. In some aspects of Formula A1, X1can be -O-. In some aspects of Formula A1, X2can be -O- . In some aspects of Formula A1, X3can be -O-. In some aspects of Formula A1, X1, X2, and X3can be each -O-. In some aspects of Formula A1, R1, R2, and R3can be each independently -H, -CH3, or -CH2CH3. In some aspects of Formula A1, R1, R2and R3can be each independently -H or M+. In some aspects of Formula A1, R4is -H. In some aspects of Formula A1, R4can be M+. In some aspects of Formula A1, M+can be independently at each occurrence Na+or K+. In some aspects, the polymerizable composition can further include one or more monomers B comprising a polyol or polyamine. Non- limiting examples of suitable polyols and polyamines suitable include C2-C20, C2-C12, or C2-C6 aliphatic alkane diols / diamines, including α,ω-η- Attorney Docket No.11196-115WO1 alkane diols / diamines, or α,ω-alkene diols / diamines. For instance, in some aspects, a polyol / polyamine comprises 1,4-butanediol / diamine, 1,6-hexanediol / diamine, 1,8- octanediol / diamine, 1,10-decanediol / diamine, 1,12-dodecanediol / diamine, 1,16- hexadecanediol / diamine, or 1,20-icosanediol / diamine. Branched α,ω-alkane diols / diamines or α,ω-alkene diols / diamines can also be used. Additionally, a polyol / polyamine can also be an aromatic diol / diamine. Further, in some aspects, a polyol / polyamine can include a poly(ethylene glycol) (PEG) or poly(propylene glycol) (PPG) having terminal hydroxyl or amine groups. Any such PEG or PPG not inconsistent with the objectives of the present disclosure may be used. In some aspects, for instance, a PEG or PPG has a weight average molecular weight between about 100 and about 5000 or between about 200 and about 1000, or between 200 and about 100,000. In some aspects, the one or more monomers B can include a diol or diamine. In some aspects, the one or more monomers B can include a poly(alkylene glycol). In some aspects, the one or more monomers B can include poly(ethylene glycol), poly(propylene glycol), or combinations thereof. In some aspects, the one or more monomers B can include an alkylene diol. In some aspects, the one or more monomers B can include 1,2-ethylene glycol, 1,3-propanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12- dodecanediol, or combinations thereof. In some aspects, the one or more monomers B comprise 1,8-octanediol. In some aspects, the one or more monomers B can include a compound of Formula (B1) , or -OCH2CH3; R7is -H, C1-C23alkyl, or C2-C23alkenyl; R8is -H, C1-C23alkyl, C2-C23alkenyl, -CH2CH2OH, or -CH2CH2NH2; and m is an integer ranging from 1 to 2000. In some aspects of Formula (B1), R6can be -OH. In some aspects of Formula (B1), R7can be -H. In some aspects of Formula (B1), R7can be -CH3. In aspects of Formula (B1), R8can be - H. In some aspects of Formula (B1), m can be an integer from 1 to 2000, including exemplary Attorney Docket No.11196-115WO1 values of 1 to 100, or 1 to 250, or 1 to 500, or 1 to 750 or 1 to 1000, or 1 to 1250, or 1-1500, or 1 to 1750. In yet other aspects of Formula (B1), m can be an integer between 1 and 20, including exemplary values of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19 In some aspects, the one or more monomers B can include a compound of Formula (B2) , X4and X5are independently -O- or -NH; and n is an integer ranging from 1 to 2000. In some aspects of Formula (B2), X4can be -O. In some aspects of Formula (B2), X4can be - NH-. In some aspects of Formula (B2), X5can be -O-. In some aspects of Formula (B2), X5can be -NH-. In some aspects of Formula (B2), X4and X5can be each -O-. In some aspects of Formula (B2), X4and X5can be each -NH-. In some aspects of Formula (B2), one of X4and X5can be -O- and the other of X4and X5can be -NH-. In some aspects of Formula (B2), n can be an integer from 1 to 2000, including exemplary values of 1 to 100, or 1 to 250, or 1 to 500, or 1 to 750 or 1 to 1000, or 1 to 1250, or 1-1500, or 1 to 1750. In yet other aspects of Formula (B2), n can be an integer between 1 and 20, including exemplary values of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19 In some aspects, the polymerizable composition can further include one or more monomers C including glutamine or a salt or derivative thereof. In some aspects, the one or more monomers C can include glutamine, a glutamine salt, or an ester or amide of glutamine. In some aspects, the one or more monomers C comprise glutamine. In some aspects, the one or more monomers A and the one or more monomers C can be present in a molar ratio from about 20:1 to about 1:20, including exemplary values of about 20:1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, or any subrange formed from the above exemplary values. Attorney Docket No.11196-115WO1 In some aspects, the one or more monomers B and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:20, including exemplary values of about 20:1, about 19:1, about 18:1, about 17:1, about 16:1, about 15:1, about 14:1, about 13:1, about 12:1, about 11:1, about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, or any subrange formed from the above exemplary values. In some aspects, the polymerizable composition can further include one or more magnesium salts. Representative examples of suitable magnesium salts include, but are not limited to, magnesium acetate, magnesium benzoate, magnesium bicarbonate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium citrate, magnesium fluoride, magnesium gluconate, magnesium diglutamate, magnesium glycinate, magnesium hydroxide, magnesium iodide, magnesium lactate, magnesium levulinate, magnesium malate, magnesium nitrate, magnesium orotate, magnesium oxalate, magnesium oxide, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium pidolate, magnesium salicylate, magnesium sulfate, magnesium taurate, and magnesium threonate, or combinations thereof. In some particular aspects, the one or more magnesium salts can include magnesium nitrate. In some aspects, the one or more monomers A and the one or more magnesium salts can be present in a molar ratio from about 10:1 to about 1:10, including exemplary values of about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, or any subrange formed from the above exemplary values. In some aspects, the one or more monomers B and the one or more magnesium salts can be present in a molar ratio from about 10:1 to about 1:10, including exemplary values of about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, or any subrange formed from the above exemplary values. In some aspects, the polymerizable composition can optionally further include one or more additional monomers. Attorney Docket No.11196-115WO1 In some aspects, the polymerizable composition can further include one or more monomers D comprising a catechol-containing species. The catechol-containing species can include any catechol-containing species not inconsistent with the objectives of the present disclosure. In some aspects, a catechol-containing species comprises at least one moiety that can form an ester or amide bond with another chemical species as found in the polymerizable compositions described herein. For example, in some aspects, a catechol-containing species comprises an alcohol moiety, an amine moiety, a carboxylic acid moiety, or combinations thereof. Further, in some aspects, a catechol-containing species comprises a hydroxyl moiety that is not part of the catechol moiety. In some aspects, a catechol-containing species comprises dopamine. In other aspects, a catechol-containing species comprises L-3,4-dihydroxyphenylalanine (L- DOPA) or D-3,4-dihydroxyphenylalanine (D-DOPA). In still other aspects, a catechol- containing species comprises gallic acid or caffeic acid. In some aspects, a catechol-containing species comprises 3,4-dihydroxycinnamic acid. Additionally, a catechol-containing species may also comprise a naturally-occurring species or a derivative thereof, such as tannic acid or a tannin. Moreover, in some aspects, a catechol-containing species is capable of coupling to a backbone of a polymer or oligomer described herein through an amide bond. In other aspects, a catechol-containing species is capable of coupling to a backbone of a polymer or oligomer described herein through an ester bond. Further examples of catechol-containing species which can be used can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the catechol-containing species is a compound of Formula (D1): R9 ; R9, R10, R11, and R12are each independently selected from -H, -OH, -CH2(CH2)xNH2, -CH2(CHR13)NH2, -CH2(CH2)xOH, -CH2(CHR13)OH, and -CH2(CH2)xCOOH; R13is -COOH or –(CH2)yCOOH; and Attorney Docket No.11196-115WO1 x and y are independently an integer ranging from 1 to 10. In some aspects, the catechol-containing species is selected from dopamine, L-DOPA, D- DOPA, gallic acid, caffeic acid, 3,4-dihydroxyhydrocinnamic acid, and tannic acid. In some aspects, the polymerizable composition can include one or more monomers E comprising an isocyanate. In some aspects, an isocyanate comprises an alkane diisocyanate having four to twenty carbon atoms. An isocyanate described herein may also include a monocarboxylic acid moiety. Further examples of various isocyanates which can be used are described in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the isocyanate is a compound selected from Formula (E1), Formula (E2), Formula (E3), and Formula (E4): , In some aspects, the polymerizable composition can include one or more monomers F comprising a polycarboxylic acid. In some aspects, the polycarboxylic acid can be a dicarboxylic acid, or a functional equivalent of a polycarboxylic acid, such as a cyclic anhydride or an acid chloride of a polycarboxylic acid. In some aspects, the polycarboxylic acid or functional equivalent thereof can be saturated or unsaturated. In some aspects, for example, the polycarboxylic acid or functional equivalent thereof comprises maleic acid, maleic anhydride, fumaric acid, or fumaryl chloride. In some aspects, a vinyl-containing polycarboxylic acid or functional equivalent thereof may also be used, such as allylmalonic acid, allylmalonic chloride, itaconic acid, or itaconic chloride. Further, in some aspects, the Attorney Docket No.11196-115WO1 polycarboxylic acid or functional equivalent thereof can be at least partially replaced with an olefin-containing monomer that may or may not be a polycarboxylic acid. In some aspects, for instance, an olefin-containing monomer comprises an unsaturated polyol such as a vinyl- containing diol. Further examples can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the polycarboxylic acid is a compound selected from Formula (F1) and Formula (F2): ; and -Cl. In some aspects, the polymerizable composition can include one or more monomers G comprising one or more azide moieties. The monomer comprising one or more azide moieties can comprise any azide-containing chemical species that are not inconsistent with the objectives of the present disclosure. Additional examples of monomers containing azide moieties can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the one or more monomers G can be selected from a compound of Formula (G1), Formula (G2), and Formula (G3): X6is independently selected at each occurrence from -O- or -NH-; R16is -CH3 or -CH2CH3; and R17and R18are each independently -CH2N3, -CH3, or -CH2CH3. Attorney Docket No.11196-115WO1 In some aspects, the polymerizable composition can include one or more monomers H comprising one or more alkyne moieties. The monomer comprising one or more alkyne moieties can comprise any alkyne-containing chemical species that are not inconsistent with the objectives of the present disclosure. Additional examples of monomers containing alkyne moieties can be found in U.S. Patent Application Publication No. 2020 / 0140607 and International Patent Application Publication No. WO2018 / 227151, the contents of which are incorporated herein in their entirety. In some aspects, the one or more monomers H can be selected from a compound of Formula (H1), Formula (H2), Formula (H3), Formula (H4), Formula (H5), and Formula (H6): ; X7and Y are independently -O- or -NH-; R19and R20are each independently -CH3 or -CH2CH3; R21is -OC(O)CCH, -CH3, or -CH2CH3; and R22is -CH3, -OH, or -NH2. Attorney Docket No.11196-115WO1 In some aspects, the polymerizable composition further comprises an inorganic material. In some aspects, the inorganic material comprises a particulate inorganic material. Any particulate inorganic material that is not inconsistent with the objectives of the present disclosure may be used. In some aspects, the particulate inorganic material comprises one or more of hydroxyapatite, tricalcium phosphate (including alpha- and beta-tricalcium phosphate), biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particles. Other particular materials may also be used. In addition, a particular inorganic material described herein can have any particle size and / or particle shape that is not inconsistent with the objective of the present disclosure. In some aspects, for instance, a particulate material has an average particle size in at least one dimension of less than about 1000 µm, less than about 800 µm, less than about 500 µm, less than about 300 µm, less than about 100 µm, less than about 50 µm, less than about 30 µm, or less than about 10 µm. In some aspects, a particular material has an average particle size in at least one dimension of less than about 1 µm, less than about 500 nm, less than about 300 nm, less than about 100 nm, less than about 50 nm, or less than about 30 nm. In some aspects, a particulate material has an average particle size recited herein in two dimensions or three dimensions. Moreover, a particulate material can be formed of substantially spherical particles, plate-like particles, needle-like particles, or a combination thereof. Particulate materials having other shapes may also be used. In some aspects, the polymerizable composition further comprises an antioxidant, a therapeutic agent (such as an antibiotic), a biomolecule (such as a peptide or a protein), a cell, or combinations thereof. In some aspects, the polymerizable composition further comprises a fluorescence / absorbance enhancer. Representative examples of fluorescence / absorbance enhancers include a metal (such as gold, silver, or a lanthanide), a carbon nanostructure, or an inorganic phosphate. Uses of Disclosed Compositions The compositions disclosed herein may be incorporated or used in the manufacture of appropriate articles or devices used in biomedical applications. In particular aspects, the compositions described herein may be used in biomedical articles or devices intended for use in promoting or accelerating bone regeneration in a subject. Attorney Docket No.11196-115WO1 In some aspects, the article may comprise a bone fixation device, for example a screw, a pin, a rod, or a plate. The bone fixation devices may be manufactured either by molding or machining the compositions described herein. In some aspects, the article may comprise a bone substitute. In some aspects, the article may comprise a long bone substitute. In such aspects, the long bone substitute may at least partially replicate the intricate structure of the native diaphysis region. In some aspects, the long bone substitute may comprise a hollow tube structure with an outer wall and an insert. In some aspects, the insert may comprise a material different from the compositions described herein. The insert may help secure the implants to the distal and proximal ends of a long bone defect. In further aspects, the outer wall can be disposed with both longitudinal (Haversian) and transverse (Volkmann’s) canals. The Haversian canals can be organized into concentric rings, interconnected by Volkmann’s canals. The quantity and the size of both Haversian and Volkmann’s canals can be tailored based on the specific application of the long bone substitute. The hollow tubes can be filled with materials (for example, porous materials, particles, or hydrogels as described herein) that may degrade faster and release necessary ingredients such as citrate, magnesium ions, and / or glutamine, which aid bone regeneration. In some aspects, the article may comprise a tissue engineering scaffold. In some aspects, the tissue engineering scaffold comprises a three-dimensional scaffold. The tissue engineering scaffold may be manufactured using any appropriate method, as understood by the skilled person, such as salt leaching, freeze-drying, or three-dimensional printing. In some aspects, particles (such as nanoparticles or microparticles) are provided, including a composition as described herein. In some aspects, the particles may further include one or more additional components, such as a therapeutic agent, a biomolecule, or a cell. In some aspects, the particles encapsulate the therapeutic agent, biomolecule, or cell. In other aspects, the composition as found in the particles can be conjugated to the therapeutic agent, the biomolecule, or the cell. In some aspects, the particles are fabricated so as to be injectable in vivo. In some aspects, the compositions described herein may be used in a biocement or bioadhesive. In some aspects, the compositions described herein may be used in a malleable putty to fill and regenerate bone defects. In some aspects, the article may comprise fibers. The compositions described herein may be manufactured into fibers in micro- and nano-size ranges. The fiber structures can act as a Attorney Docket No.11196-115WO1 scaffold to closely resemble the extracellular matrix for biomedical applications. The biodegradable fibers can also be used in any woven or non-woven applications. In some aspects, the compositions described may be used in a hydrogel. In such aspects, the compositions described herein can be synthesized using hydrophilic macrodiols such as poly (ethylene glycols) of various molecular weights to create water-soluble formulations, which can act as in situ crosslinkable hydrogels or as an injectable cell encapsulation vehicle for use in tissue regeneration. In some aspects, the compositions described herein can be used to fabricate osteoconductive scaffolds for non-union bone fracture repair using Masquelet induced membrane technique. Such scaffolds can be used to replace the first-stage PMMA or the second-stage autologous cancellous bone graft, or both. In some aspects, the compositions described herein can be used to fabricate osteoconductive scaffolds for reconstruction of non-union bone defects. In some aspects, the compositions described herein can undergo surface modification, for example, with collagen, laminin, RGD, and various peptide chains to support cell adhesion, proliferation, and differentiation. The compositions, articles, or devices described herein can be used in fluorescent or photoacoustic imaging. In some aspects, the compositions, articles, or devices described herein may be used in both fluorescent and photoacoustic imaging, i.e., in a dual imaging modality. These imaging modalities may be used to track the composition, article, or device in vivo or to track the properties of the composition, article, or device in vivo. In some aspects, the compositions of the present disclosure can have multiple potential uses in tissue engineering, including in situ setting, formation of anatomically correct scaffolds when combined with molding, and 3D printing of scaffolds utilizing the rapid setting potential of the system. Additionally, the compositions of the present disclosure have potential uses in the orthopedic field as void fillers and as anchoring for surgical implants and scaffolds, as well as, when combined with porogens and other additives, as anatomically correct scaffolds based on patient specific anatomy. In still further aspects, the composition is injectable. In yet other aspects, the composition is configured to fill a void, wherein the void can be physiological. In yet further aspects, the composition is a wound closing composition. Attorney Docket No.11196-115WO1 In still further aspects, the use of the disclosed herein compositions include but is not limited to the following: orthopedic tissue engineering materials including composites and porous scaffolds for critical size segmental defect repair and fixation and spinal fusion and films for periosteum repair and barrier functionality; antibacterial capable materials for preventing and controlling infection; hemostat capable materials for controlling bleeding in wounds and surgical implantation procedures; self-setting materials for void filling and fracture fixation; and self-setting materials for the generation of molded or 3D printed scaffolds. In another aspect, a method of promoting and / or accelerating bone regeneration in a bone site is provided. In some aspects, the method includes delivering a composition, article, or device as described herein to the bone site. In some aspects, the composition, article, or device can be delivered before and / or during a proliferation stage of osteogenesis at the bone site. In some aspects, the method may further include delivering stem cells to the bone site. In some aspects, the bone site is an intramembranous ossification site. In other aspects, the bone site is an endochondral ossification site. The compositions described herein can be useful for promoting and / or accelerating bone regeneration, including bone growth, bone healing, and / or bone repair as further described herein. It should be understood that one or more compositions described herein can be used in one or more methods of promoting and / or accelerating bone regeneration described herein, including for bone growth, bone healing, and / or bone repair. In some embodiments, the compositions described herein that are useful for promoting bone growth can comprise a graft or scaffold. A “graft” or “scaffold”, for reference purposes herein, can refer to any structure usable as a platform or implant for the replacement of missing bone or for promotion of growth of new bone. Moreover, as utilized herein, a “graft” or “scaffold” may be synonymous. For example, a graft or scaffold composition described herein can be used in the repair of a bone defect, the replacement of missing or removed bone, or for the promotion of new bone growth, as in the case of a bone fusion procedure. Further, it is to be understood that grafts or scaffolds consistent with compositions and methods described herein can have any structure or be formed in any shape, configuration, or orientation not inconsistent with the objectives of the present disclosure. For example, in some aspects, a graft or scaffold can be shaped, configured, or oriented in such a manner as to correspond to a defect or bone growth site to be repaired. For example, in some aspects, a graft or scaffold utilized in the repair of a bone defect, such as a cranial defect of condyle defect, may be formed, molded, or resized to a Attorney Docket No.11196-115WO1 size and / or shape corresponding to the defect. In certain other aspects, such as in a bone fusion procedure, a graft or scaffold in composition and methods described herein can have a shape, configuration, orientation, or dimensions adapted to traverse a gap between the bones to be fused and / or to reinforce a bone growth site. In this manner, particular shapes, sizes, orientations and / or configurations of grafts or scaffolds described herein are not intended to be limited to a particular set or subset of modalities on, within, or adjacent to a bone growth site. A “bone site”, as referenced herein, can be any area in which bone regeneration, bone ossification, bone growth, or bone repair may be desired. In certain non-limiting aspects, a bone site can comprise or include a bone defect, a site in which bone has been removed or degraded, and / or a site of desired new bone growth or regeneration, as in the case of a spine or other bone fusion. Various components of compositions that may form part or all of a graft or scaffold utilized for promoting bone regeneration have been described herein. It is to be understood that a composition according to the present disclosure can comprise any combination of components and features that are not inconsistent with the objectives of the present disclosure. For example, in some aspects, a composition forming part or all of a graft or scaffold utilized in a composition described herein can comprise a combination, mixture, or blend of polymers or oligomers described herein. Additionally, in some aspects, such a combination, mixture, or blend can be selected to provide a graft or scaffold having any osteo-promoting property, biodegradability, mechanical property, and / or chemical functionality described herein. Further, one or more polymers or oligomers described herein can be present in a composition forming part or all of a graft or scaffold utilized in any amount not inconsistent with the objectives of the present disclosure. In some aspects, a graft or scaffold consists or consists essentially of the one or more polymers or oligomers described herein. In other aspects, a graft or scaffold comprises up to about 95 weight percent, up to about 90 weight percent, up to about 80 weight percent, up to about 70 weight percent, up to about 60 weight percent, up to about 50 weight percent, up to about 40 weight percent, or up to about 30 weight percent polymer or oligomer, based on the total weight of the graft or scaffold. In some aspects, the balance of a graft or scaffold described herein can be water, an aqueous solution, and / or an inorganic material as described further below. In some aspects, the composition can further comprise an inorganic material. In some aspects, the inorganic material comprises a particulate inorganic material. Any particulate inorganic material not inconsistent with the objectives of the present disclosure may be used. In some Attorney Docket No.11196-115WO1 cases, the particulate inorganic material comprises one or more of hydroxyapatite, tricalcium phosphate (including alpha- and beta-tricalcium phosphate), biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particles. Other particular materials may also be used. A particular inorganic material can be present in the compositions (such as a graft or scaffold) described herein in any amount not inconsistent with the objective of the present disclosure. For example, in some aspects, a composition utilized as a graft or scaffold described herein comprises up to about 30 weight percent, up to about 40 weight percent, up to about 50 weight percent, up to about 60 weight percent, or up to about 70 weight percent particular materials, based on the total weight of the composition. In some aspects, a composition comprises between about 1 and about 70 weight percent, between about 10 and about 70 weight percent, between about 15 and about 60 weight percent, between about 25 and about 65 weight percent, between about 26 and about 50 weight percent, between about 30 and about 70 weight percent, or between about 50 and about 70 weight percent particulate material, based on the total weight of the composition. For example, a composition described herein may comprise up to about 65 weight percent hydroxyapatite. In some aspects, the graft or scaffold may be itself a particulate. The particulate graft or scaffold may include or contain a liquid or be substantially “dry” or free of liquid. Moreover, a liquid that is included in (or mostly excluded from) such a particular graft or scaffold can be any liquid that is not inconsistent with the objectives of the present disclosure. In some aspects, for instance, the liquid is water or an aqueous solution or mixture, such as saline. Moreover, in some aspects, the liquid can be a carrier liquid for introducing other species to the particulate graft or scaffold. For example, in some aspects, the liquid comprises one or more biomolecules, bioactive materials, or other biomaterials, as described further herein. In some aspects, the liquid comprises a hyaluronate or hyaluronic acid. In other aspects, the liquid comprises blood or plasma. Additionally, the particulate graft or scaffold, in some aspects, is a paste. More particularly, such a paste can include the particulate graft or scaffold and a liquid (as opposed to being a “dry” material). Such a “paste” can be a viscous or shape-stable material (at standard temperature and pressure conditions) and can have a viscosity suitable for handling or manipulation, such as scooping, with a microspatula. The liquid component of a paste, in some aspects, is an isotonic solution, and the paste is a biologically sterile paste. For example, in some aspects, a paste described herein can be formed from a salt solution, such as saline, or Attorney Docket No.11196-115WO1 other biologically active solutions, such as sodium hyaluronate or blood. In some aspects, the biologically active solution can comprise additional biological molecules or factors suitable to promote and / or accelerate bone regeneration. For example, the solution can comprise growth factors or signaling molecules, such as osteogenic factors. Non-limiting examples of biological factors that may be used in some embodiments described herein include osteopontin (OPN), osteocalcin (OCN), bone morphogenetic protein-2 (BMP-2), transforming growth factor β3 (TGFβ3), stromal cell-derived factor-1α (SDF-1α), erythropoietin (Epo), vascular endothelial growth factor (VEGF), insulin-like growth factor-1 (IGF-1), platelet derived growth factor (PDGF), fibroblast growth factor (BGF), nerve growth factor (NGF), neurotrophin-3 (NT-3), and glial cell-derived neurotrophic factor (GDNF). Other therapeutic proteins and chemical species may also be used. In some aspects, the graft or scaffold described herein is a polymer network. The polymer network can comprise any combination of compositions described above. Further, in some aspects, the polymer network comprises an inorganic material (such as a particulate inorganic material). For example, compositions as described above can be cross-linked to encapsulate or otherwise bond to the inorganic material. Cross-linking can be performed, for example, by exposing the polymer to heat and / or UV light. The compositions described herein, or articles or devices incorporating the same, may be administered in such amounts, time, and route deemed necessary in order to achieve the desired result. The exact amount will vary from subject to subject, depending on the species, age, and general condition of the subject, the severity of the medical disorder, the particular implants or polymers or oligomers used, their mode of administration, their mode of activity, and the like. The specific therapeutically effective dose level for any particular subject will depend upon a variety of factors including the disorder being treated and the severity of the disorder; the activity of the specific composition, article, or device employed; the specific composition of the composition, article, or device employed; the age, body weight, general health, sex and diet of the patient; the time of administration, route of administration, and rate of excretion of the specific composition, article, or device employed; the duration of the treatment; drugs used in combination or coincidental with the specific compsotion, article, or device employed; and like factors well known in the medical arts. The exact amount of the compositions described herein, or articles or devices incorporating the same, required to achieve a therapeutically effective amount will vary from subject to subject, depending on species, age, and general condition of a subject, severity of the side effects or Attorney Docket No.11196-115WO1 disorder, identity of the particular compound(s), mode of administration, and the like. The amount to be administered to, for example, a child or an adolescent can be determined by a medical practitioner or person skilled in the art and can be lower or the same as that administered to an adult. Useful dosages can be determined by comparing their in vitro activity and in vivo activity in animal models. Methods for the extrapolation of effective dosages in mice, and other animals, to humans are known to the art. The dosage ranges for the administration of the compositions described herein, or articles or devices incorporating the same, are those large enough to produce the desired effect in which the symptoms or disorder are affected. The dosage should not be so large as to cause adverse side effects, such as unwanted cross-reactions, anaphylactic reactions, and the like. Generally, the dosage will vary with the patient's age, condition, sex, and extent of the disease, as can be determined by one skilled in the art. The dosage can be adjusted by the individual physician in the event of any contraindications. Dosage can vary and can be administered in one or more doses. Additional Aspects In view of the described compositions, articles, devices, and methods, herein below are described certain more particular aspects of the disclosure. 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 composition comprising a polymer or oligomer formed from: one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt; one or more monomers B comprising a polyol or polyamine; one or more monomers C comprising glutamine or a salt or derivative thereof; one or more magnesium salts; and optionally one or more additional monomers. Attorney Docket No.11196-115WO1 Aspect 2. The composition of aspect 1, wherein the one or more monomers A comprise citric acid, trimethyl citrate, triethyl citrate, monosodium citrate, disodium citrate, trisodium citrate, calcium citrate, or combinations thereof. Aspect 3. The composition of aspect 1, wherein the one or more monomers A comprise citric acid. Aspect 4. The composition of aspect 1, wherein the one or more monomers A comprise a compound of Formula (A1), ; wherein: X1, X2, and X3are each independently -O- or -NH-; R1, R2, and R3are each independently -H, C1-C22 alkyl, C2-C22 alkenyl, or M+; R4is H or M+; and M+is a cation. Aspect 5. The composition of aspect 4, wherein X1, X2, and X3are each -O-. Aspect 6. The composition of aspect 4 or aspect 5, wherein R4is -H. Aspect 7. The composition of any one of aspects 1-6, wherein the one or more monomers B comprise a diol or diamine. Aspect 8. The composition of any one of aspects 1-6, wherein the one or more monomers B comprise a poly(alkylene glycol). Aspect 9. The composition of any one of aspects 1-6, wherein the one or more monomers B comprise poly(ethylene glycol), poly(propylene glycol), or combinations thereof. Aspect 10. The composition of any one of aspects 1-6, wherein the one or more monomers B comprise an alkylene diol. Attorney Docket No.11196-115WO1 Aspect 11. The composition of any one of aspects 1-6, wherein the one or more monomers B comprise 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol, or combinations thereof. Aspect 12. The composition of any one of aspects 1-6, wherein the one or more monomers B comprise 1,8-octanediol. Aspect 13. The composition of any one of aspects 1-6, wherein the one or more monomers B comprise a compound of Formula (B1) , wherein: R6is -NH2, -OH, -OCH3, or -OCH2CH3; R7is -H, C1-C23 alkyl, or C2-C23 alkenyl; R8is -H, C1-C23alkyl, C2-C23alkenyl, -CH2CH2OH, or -CH2CH2NH2; and m is an integer ranging from 1 to 2000. Aspect 14. The composition of any one of aspects 1-6, wherein the one or more monomers B comprise a compound of Formula (B2) , wherein: X4and X5are independently -O- or -NH; and n is an integer ranging from 1 to 2000. Aspect 15. The composition of any one of aspects 1-14, wherein the one or more monomers C comprise glutamine. Aspect 16. The composition of any one of aspects 1-15, wherein the one or more magnesium salts are selected from magnesium acetate, magnesium benzoate, magnesium bicarbonate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium citrate, magnesium fluoride, magnesium gluconate, magnesium diglutamate, magnesium glycinate, magnesium hydroxide, magnesium iodide, magnesium lactate, magnesium Attorney Docket No.11196-115WO1 levulinate, magnesium malate, magnesium nitrate, magnesium orotate, magnesium oxalate, magnesium oxide, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium pidolate, magnesium salicylate, magnesium sulfate, magnesium taurate, and magnesium threonate, or combinations thereof. Aspect 17. The composition of any one of aspects 1-16, wherein the one or more magnesium salts comprise magnesium nitrate. Aspect 18. The composition of any one of aspects 1-17, wherein the one or more monomers A and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:20. Aspect 19. The composition of any one of aspects 1-18, wherein the one or more monomers B and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:20. Aspect 20. The composition of any one of aspects 1-19, wherein the one or more monomers A and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:10. Aspect 21. The composition of any one of aspects 1-20, wherein the one or more monomers B and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:10. Aspect 22. The composition of any one of aspects 1-21, wherein the polymer or oligomer is further formed from one or more monomers D comprising a catechol-containing species. Aspect 23. The composition of aspect 22, wherein the catechol-containing species is a compound of Formula (D1): R9 ; R9, R10, R11, and R12are each independently selected from -H, -OH, -CH2(CH2)xNH2, -CH2(CHR13)NH2, -CH2(CH2)xOH, -CH2(CHR13)OH, and -CH2(CH2)xCOOH; R13is -COOH or –(CH2)yCOOH; and Attorney Docket No.11196-115WO1 x and y are independently an integer ranging from 1 to 10. Aspect 24. The composition of aspect 22, wherein the catechol-containing species is selected from dopamine, L-DOPA, D-DOPA, gallic acid, caffeic acid, 3,4- dihydroxyhydrocinnamic acid, and tannic acid. Aspect 25. The composition of any one of aspects 1-24, wherein the polymer or oligomer is further formed from one or more monomers E comprising an isocyanate. Aspect 26. The composition of aspect 25, wherein the isocyanate is a compound selected from Formula (E1), Formula (E2), Formula (E3), and Formula (E4): , Aspect 27. The composition of any one of aspects 1-26, wherein the polymer or oligomer is further formed from one or more monomers F comprising a polycarboxylic acid. Aspect 28. The composition of aspect 27, wherein the polycarboxylic acid is a compound selected from Formula (F1) and Formula (F2): ; and -Cl. Aspect 29. The composition of any one of aspects 1-28, wherein the polymer or oligomer is further form from one or more monomers G comprising one or more azide moieties. Aspect 30. The composition of aspect 29, wherein the one or more monomers G is selected from a compound of Formula (G1), Formula (G2), and Formula (G3): Attorney Docket No.11196-115WO1 X6is independently selected at each occurrence from -O- or -NH-; R16is -CH3or -CH2CH3; and R17and R18are each independently -CH2N3, -CH3, or -CH2CH3. Aspect 31. The composition of any one of aspects 1-30, wherein the polymer or oligomer is further form from one or more monomers H comprising one or more alkyne moieties. Aspect 32. The composition of aspect 31, wherein the one or more monomers H is selected from a compound of Formula (H1), Formula (H2), Formula (H3), Formula (H4), Formula (H5), and Formula (H6): ; Attorney Docket No.11196-115WO1 wherein: X7and Y are independently -O- or -NH-; R19and R20are each independently -CH3or -CH2CH3; R21is -OC(O)CCH, -CH3, or -CH2CH3; and R22is -CH3, -OH, or -NH2. Aspect 33. The composition of any one of aspects 1-32, wherein the polymer or oligomer is crosslinked. Aspect 34. The composition of aspect 33, wherein the polymer or oligomer is chemically crosslinked. Aspect 35. The composition of aspect 34, wherein the polymer or oligomer is chemically crosslinked by a diisocyanate (such as butanediisocyanate (BDI), 1,6-hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI). Aspect 36. The composition of any one of aspects 33-35, wherein the polymer or oligomer is thermally crosslinked. Aspect 37. The composition of any one of aspects 1-36, wherein the composition further comprises an inorganic material. Aspect 38. The composition of aspect 37, wherein the inorganic material comprises a particular inorganic material. Aspect 39. The composition of aspect 37 or aspect 38, wherein the inorganic material is selected from hydroxyapatite, tricalcium phosphate, biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particles. Aspect 40. The composition of any one of aspects 1-39, wherein the composition further comprises an antioxidant, a therapeutic agent (such as an antibiotic), a biomolecule (such as a peptide or a protein), a cell, or combinations thereof. Aspect 41. The composition of any one of aspects 1-40, wherein the composition is fluorescent. Aspect 42. The composition of aspect 41, wherein the composition further comprises a fluorescence / absorbance enhancer. Attorney Docket No.11196-115WO1 Aspect 43. The composition of aspect 42, wherein the fluorescence / absorbance enhancer is selected from a metal (such as gold, silver, or a lanthanide), a carbon nanostructure, or an inorganic phosphate. Aspect 44. The composition of any one of aspects 1-41, wherein the composition displays near-infrared (NIR) absorbance. Aspect 45. The composition of any one of aspects 1-44, wherein the composition exhibits photoacoustic properties. Aspect 46. The composition of any one of aspects 1-45, wherein the composition exhibits photodynamic properties. Aspect 47. The composition of any one of aspects 1-46, wherein the composition is biodegradable. Aspect 48. The composition of aspect 47, wherein the composition is capable of releasing citrate, glutamine, and / or magnesium cations upon degradation. Aspect 49. A prepolymer composition formed from: one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt; one or more monomers B comprising a polyol or polyamine; one or more monomers C comprising glutamine or a salt or derivative thereof; one or more magnesium salts; and optionally one or more additional monomers. Aspect 50. The prepolymer composition of aspect 49, wherein the one or more monomers A comprise citric acid, trimethyl citrate, triethyl citrate, monosodium citrate, disodium citrate, trisodium citrate, calcium citrate, or combinations thereof. Aspect 51. The prepolymer composition of aspect 49, wherein the one or more monomers A comprise citric acid. Aspect 52. The prepolymer composition of aspect 49, wherein the one or more monomers A comprise a compound of Formula (A1), Attorney Docket No.11196-115WO1 ; wherein: X1, X2, and X3are each independently -O- or -NH-; R1, R2, and R3are each independently -H, C1-C22alkyl, C2-C22alkenyl, or M+; R4is H or M+; and M+is a cation. Aspect 53. The prepolymer composition of aspect 52, wherein X1, X2, and X3are each -O- . Aspect 54. The prepolymer composition of aspect 52 or aspect 53, wherein R4is -H. Aspect 55. The prepolymer composition of any one of aspects 49-54, wherein the one or more monomers B comprise a diol or diamine. Aspect 56. The prepolymer composition of any one of aspects 49-54, wherein the one or more monomers B comprise a poly(alkylene glycol). Aspect 57. The prepolymer composition of any one of aspects 49-54, wherein the one or more monomers B comprise poly(ethylene glycol), poly(propylene glycol), or combinations thereof. Aspect 58. The prepolymer composition of any one of aspects 49-54, wherein the one or more monomers B comprise an alkylene diol. Aspect 59. The prepolymer composition of any one of aspects 49-54, wherein the one or more monomers B comprise 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5- pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol, or combinations thereof. Aspect 60. The prepolymer composition of any one of aspects 49-54, wherein the one or more monomers B comprise 1,8-octanediol. Aspect 61. The prepolymer composition of any one of aspects 49-54, wherein the one or more monomers B comprise a compound of Formula (B1) Attorney Docket No.11196-115WO1 , wherein: R6is -NH2, -OH, -OCH3, or -OCH2CH3; R7is -H, C1-C23 alkyl, or C2-C23 alkenyl; R8is -H, C1-C23 alkyl, C2-C23 alkenyl, -CH2CH2OH, or -CH2CH2NH2; and m is an integer ranging from 1 to 2000. Aspect 62. The prepolymer composition of any one of aspects 49-54, wherein the one or more monomers B comprise a compound of Formula (B2) , wherein: X4and X5are independently -O- or -NH; and n is an integer ranging from 1 to 2000. Aspect 63. The prepolymer composition of any one of aspects 49-62, wherein the one or more monomers C comprise glutamine. Aspect 64. The prepolymer composition of any one of aspects 49-63, wherein the one or more magnesium salts are selected from magnesium acetate, magnesium benzoate, magnesium bicarbonate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium citrate, magnesium fluoride, magnesium gluconate, magnesium diglutamate, magnesium glycinate, magnesium hydroxide, magnesium iodide, magnesium lactate, magnesium levulinate, magnesium malate, magnesium nitrate, magnesium orotate, magnesium oxalate, magnesium oxide, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium pidolate, magnesium salicylate, magnesium sulfate, magnesium taurate, and magnesium threonate, or combinations thereof. Aspect 65. The prepolymer composition of any one of aspects 49-64, wherein the one or more magnesium salts comprise magnesium nitrate. Attorney Docket No.11196-115WO1 Aspect 66. The prepolymer composition of any one of aspects 49-65, wherein the one or more monomers A and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:20. Aspect 67. The prepolymer composition of any one of aspects 49-66, wherein the one or more monomers B and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:20. Aspect 68. The prepolymer composition of any one of aspects 49-67, wherein the one or more monomers A and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:10. Aspect 69. The prepolymer composition of any one of aspects 49-68, wherein the one or more monomers B and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:10. Aspect 70. The prepolymer composition of any one of aspects 49-69, wherein the prepolymer composition is further formed from one or more monomers D comprising a catechol-containing species. Aspect 71. The prepolymer composition of aspect 70, wherein the catechol-containing species is a compound of Formula (D1): R9 ; R9, R10, R11, and R12are each independently selected from -H, -OH, -CH2(CH2)xNH2, -CH2(CHR13)NH2, -CH2(CH2)xOH, -CH2(CHR13)OH, and -CH2(CH2)xCOOH; R13is -COOH or –(CH2)yCOOH; and x and y are independently an integer ranging from 1 to 10. Attorney Docket No.11196-115WO1 Aspect 72. The prepolymer composition of aspect 70, wherein the catechol-containing species is selected from dopamine, L-DOPA, D-DOPA, gallic acid, caffeic acid, 3,4- dihydroxyhydrocinnamic acid, and tannic acid. Aspect 73. The prepolymer composition of any one of aspects 49-72, wherein prepolymer composition is further formed from one or more monomers E comprising an isocyanate. Aspect 74. The prepolymer composition of aspect 73, wherein the isocyanate is a compound selected from Formula (E1), Formula (E2), Formula (E3), and Formula (E4): , Aspect 75. The prepolymer composition of any one of aspects 49-74, wherein the prepolymer composition is further formed from one or more monomers F comprising a polycarboxylic acid. Aspect 76. The prepolymer composition of aspect 75, wherein the polycarboxylic acid is a compound selected from Formula (F1) and Formula (F2): ; and -Cl. Aspect 77. The prepolymer composition of any one of aspects 49-76, wherein the prepolymer composition is further form from one or more monomers G comprising one or more azide moieties. Attorney Docket No.11196-115WO1 Aspect 78. The prepolymer composition of aspect 77, wherein the one or more monomers G is selected from a compound of Formula (G1), Formula (G2), and Formula (G3): X6is independently selected at each occurrence from -O- or -NH-; R16is -CH3 or -CH2CH3; and R17and R18are each independently -CH2N3, -CH3, or -CH2CH3. Aspect 79. The prepolymer composition of any one of aspects 49-78, wherein the prepolymer composition is further form from one or more monomers H comprising one or more alkyne moieties. Aspect 80. The prepolymer composition of any one of aspects 79, wherein the one or more monomers H is selected from a compound of Formula (H1), Formula (H2), Formula (H3), Formula (H4), Formula (H5), and Formula (H6): , , Attorney Docket No.11196-115WO1 ; X7and Y are independently -O- or -NH-; R19and R20are each independently -CH3 or -CH2CH3; R21is -OC(O)CCH, -CH3, or -CH2CH3; and R22is -CH3, -OH, or -NH2. Aspect 81. The prepolymer composition of any one of aspects 49-80, wherein the prepolymer composition further comprises an inorganic material. Aspect 82. The prepolymer composition of aspect 81, wherein the inorganic material comprises a particular inorganic material. Aspect 83. The prepolymer composition of aspect 81 or aspect 82, wherein the inorganic material is selected from hydroxyapatite, tricalcium phosphate, biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particles. Aspect 84. The prepolymer composition of any one of aspects 49-83, wherein the prepolymer composition further comprises an antioxidant, a therapeutic agent (such as an antibiotic), a biomolecule (such as a peptide or a protein), a cell, or combinations thereof. Aspect 85. A polymerizable composition comprising: one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt; one or more monomers B comprising a polyol or polyamine; one or more monomers C comprising glutamine or a salt or derivative thereof; one or more magnesium salts; and optionally one or more additional monomers. Attorney Docket No.11196-115WO1 Aspect 86. The polymerizable composition of aspect 85, wherein the one or more monomers A comprise citric acid, trimethyl citrate, triethyl citrate, monosodium citrate, disodium citrate, trisodium citrate, calcium citrate, or combinations thereof. Aspect 87. The polymerizable composition of aspect 85, wherein the one or more monomers A comprise citric acid. Aspect 88. The polymerizable composition of aspect 85, wherein the one or more monomers A comprise a compound of Formula (A1), ; wherein: X1, X2, and X3are each independently -O- or -NH-; R1, R2, and R3are each independently -H, C1-C22 alkyl, C2-C22 alkenyl, or M+; R4is H or M+; and M+is a cation. Aspect 89. The polymerizable composition of aspect 88, wherein X1, X2, and X3are each - O-. Aspect 90. The polymerizable composition of aspect 88 or aspect 89, wherein R4is -H. Aspect 91. The polymerizable composition of any one of aspects 85-90, wherein the one or more monomers B comprise a diol or diamine. Aspect 92. The polymerizable composition of any one of aspects 85-90, wherein the one or more monomers B comprise a poly(alkylene glycol). Aspect 93. The polymerizable composition of any one of aspects 85-90, wherein the one or more monomers B comprise poly(ethylene glycol), poly(propylene glycol), or combinations thereof. Aspect 94. The polymerizable composition of any one of aspects 85-90, wherein the one or more monomers B comprise an alkylene diol. Attorney Docket No.11196-115WO1 Aspect 95. The polymerizable composition of any one of aspects 85-90, wherein the one or more monomers B comprise 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5- pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol, or combinations thereof. Aspect 96. The polymerizable composition of any one of aspects 85-90, wherein the one or more monomers B comprise 1,8-octanediol. Aspect 97. The polymerizable composition of any one of aspects 85-90, wherein the one or more monomers B comprise a compound of Formula (B1) , wherein: R6is -NH2, -OH, -OCH3, or -OCH2CH3; R7is -H, C1-C23alkyl, or C2-C23alkenyl; R8is -H, C1-C23 alkyl, C2-C23 alkenyl, -CH2CH2OH, or -CH2CH2NH2; and m is an integer ranging from 1 to 2000. Aspect 98. The polymerizable composition of any one of aspects 85-90, wherein the one or more monomers B comprise a compound of Formula (B2) , wherein: X4and X5are independently -O- or -NH; and n is an integer ranging from 1 to 2000. Aspect 99. The polymerizable composition of any one of aspects 85-98, wherein the one or more monomers C comprise glutamine. Aspect 100. The polymerizable composition of any one of aspects 85-99, wherein the one or more magnesium salts are selected from magnesium acetate, magnesium benzoate, magnesium bicarbonate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium citrate, magnesium fluoride, magnesium gluconate, magnesium diglutamate, magnesium Attorney Docket No.11196-115WO1 glycinate, magnesium hydroxide, magnesium iodide, magnesium lactate, magnesium levulinate, magnesium malate, magnesium nitrate, magnesium orotate, magnesium oxalate, magnesium oxide, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium pidolate, magnesium salicylate, magnesium sulfate, magnesium taurate, and magnesium threonate, or combinations thereof. Aspect 101. The polymerizable composition of any one of aspects 85-100, wherein the one or more magnesium salts comprise magnesium nitrate. Aspect 102. The polymerizable composition of any one of aspects 85-101, wherein the one or more monomers A and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:20. Aspect 103. The polymerizable composition of any one of aspects 85-102, wherein the one or more monomers B and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:20. Aspect 104. The polymerizable composition of any one of aspects 85-103, wherein the one or more monomers A and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:10. Aspect 105. The polymerizable composition of any one of aspects 85-104, wherein the one or more monomers B and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:10. Aspect 106. The polymerizable composition of any one of aspects 85-105, further comprising one or more monomers D comprising a catechol-containing species. Aspect 107. The polymerizable composition of aspect 106, wherein the catechol-containing species is a compound of Formula (D1): R9
[0002] Attorney Docket No.11196-115WO1 R9, R10, R11, and R12are each independently selected from -H, -OH, -CH2(CH2)xNH2, -CH2(CHR13)NH2, -CH2(CH2)xOH, -CH2(CHR13)OH, and -CH2(CH2)xCOOH; R13is -COOH or –(CH2)yCOOH; and x and y are independently an integer ranging from 1 to 10. Aspect 108. The polymerizable composition of aspect 106, wherein the catechol-containing species is selected from dopamine, L-DOPA, D-DOPA, gallic acid, caffeic acid, 3,4- dihydroxyhydrocinnamic acid, and tannic acid. Aspect 109. The polymerizable composition of any one of aspects 85-108, wherein further comprising one or more monomers E comprising an isocyanate. Aspect 110. The polymerizable composition of aspect 109, wherein the isocyanate is a compound selected from Formula (E1), Formula (E2), Formula (E3), and Formula (E4): , Aspect 111. The polymerizable composition of any one of aspects 85-110, further comprising one or more monomers F comprising a polycarboxylic acid. Aspect 112. The polymerizable composition of aspect 111, wherein the polycarboxylic acid is a compound selected from Formula (F1) and Formula (F2): Attorney Docket No.11196-115WO1 Aspect 113. The polymerizable composition of any one of aspects 85-112, further comprising one or more monomers G having one or more azide moieties. Aspect 114. The polymerizable composition of aspect 113, wherein the one or more monomers G is selected from a compound of Formula (G1), Formula (G2), and Formula (G3): X6is independently selected at each occurrence from -O- or -NH-; R16is -CH3or -CH2CH3; and R17and R18are each independently -CH2N3, -CH3, or -CH2CH3. Aspect 115. The polymerizable composition of any one of aspects 85-114, further comprising one or more monomers H having one or more alkyne moieties. Aspect 116. The polymerizable composition of any one of aspects 115, wherein the one or more monomers H is selected from a compound of Formula (H1), Formula (H2), Formula (H3), Formula (H4), Formula (H5), and Formula (H6): , , Attorney Docket No.11196-115WO1 ; X7and Y are independently -O- or -NH-; R19and R20are each independently -CH3 or -CH2CH3; R21is -OC(O)CCH, -CH3, or -CH2CH3; and R22is -CH3, -OH, or -NH2. Aspect 117. The polymerizable composition of any one of aspects 85-116, wherein the polymerizable composition further comprises an inorganic material. Aspect 118. The polymerizable composition of aspect 117, wherein the inorganic material comprises a particular inorganic material. Aspect 119. The polymerizable composition of aspect 117 or aspect 118, wherein the inorganic material is selected from hydroxyapatite, tricalcium phosphate, biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particles. Aspect 120. The polymerizable composition of any one of aspects 85-119, wherein the polymerizable composition further comprises an antioxidant, a therapeutic agent (such as an antibiotic), a biomolecule (such as a peptide or a protein), a cell, or combinations thereof. Aspect 121. A bone fixation device comprising a composition of any one of aspects 1-48. Aspect 122. The bone fixation device of aspect 121, wherein the bone fixation device comprises a screw, a pin, a rod, or a plate. Aspect 123. A bone substitute comprising a composition of any one of aspects 1-48. Aspect 124. A particle comprising a composition of any one of aspects 1-48. Aspect 125. The particle of aspect 124, wherein the particle is a nanoparticle or a microparticle. Attorney Docket No.11196-115WO1 Aspect 126. The particle of aspect 124 of aspect 125, further comprising a therapeutic agent, a biomolecule, or a cell. Aspect 127. The particle of aspect 126, wherein the composition is conjugated to the therapeutic agent, the biomolecule, or the cell. Aspect 128. A biocement or bioadhesive comprising a composition of any one of aspects 1- 120. Aspect 129. A tissue engineering scaffold comprising a composition of any one of aspects 1-120. Aspect 130. A fiber comprising a composition of any one of aspects 1-48. Aspect 131. A hydrogel comprising a composition of any one of aspects 1-120. Aspect 132. A method of promoting and / or accelerating bone regeneration in a bone site, the method comprising delivering a composition of any one of aspects 1-120 to the bone site. Aspect 133. The method of aspect 132, wherein the composition is delivered before and / or during a proliferation stage of osteogenesis at the bone site. Aspect 134. The method of aspects 132 or 133, further comprising delivering stem cells to the bone site. Aspect 135. The method of any one of aspects 132-134, wherein the bone site is an intramembranous ossification site. Aspect 136. The method of any one of aspects 132-134, wherein the bone site is an endochondral ossification site. 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 compositions, articles, devices, and methods claimed herein, along with associated methods and results according to the disclosed subject matter. These examples are not intended to include all aspects of the subject matter Attorney Docket No.11196-115WO1 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 process. Only reasonable and routine experimentation will be required to optimize such process conditions. Glutamine and Magnesium Ion-Incorporated Citrate-Based Composites for Bone Regeneration Materials and Methods Synthesis of Biodegradable Photoluminescent Citrate-Based Prepolymer For POC-Glutamine synthesis, citric acid, 1,8-octanediol, and L-glutamine at molar ratios as outlined in Table 1 were mixed in a round-bottomed flask. After melting at 160 °C for 10 min, the temperature was lowered to 140 °C, and the mixture was stirred continuously with the stirring speed lowered gradually from 800 rpm to 80 rpm to produce the BPLP-Glutamine prepolymer (FIG. 1). The prepolymer was then dissolved in 1,4-dioxane and purified by precipitation in water, followed by freeze-drying and storage in brown bottles at −20 °C. For POC-Gln-Mg synthesis, the same procedures are followed, except magnesium nitrate hexahydrate was added at 140 °C (FIG.2) at the molar ratios outlined in Table 2. Citric Acid 1,8-octanediol L-Glutamine Magnesium Attorney Docket No.11196-115WO1 BPLP- 0.1 0.11 0.03 0 Glutamine Citric Acid 1,8-octanediol L-Glutamine Magnesium Attorney Docket No.11196-115WO1 BPLP- 0.1 0.11 0.03 0.03 Glutamine Preparation of Polymer Films via Thermal Crosslinking Method To prepare polymer films, pre-polymer with above mentioned formulations was dissolved in 1,4-dioxane to obtain a 30 wt. % solution and then was casted into a Teflon mold followed by solvent evaporation and thermal cross-linking at 80 °C for 3 days, 80 °C for 3 days, 120 °C for 1 day under vacuum, or 3 days, or 80 °C for 3 days, 120 °C for 3 days under vacuum. Crosslinked polymers were then cut into appropriate shapes for further testing. Nittany Lion logo polymer film samples were cut using a LS-1630 CO2 Laser Cutter and Engraver (Boss Laser, Sanford, FL, USA) from laser paths generated in SolidWorks 20223 (Dassault Systems, France) software. Silicon Mold Preparation Desired structures were printed using a 3D printer (Formlabs Form2) using clear resin V4 (F5- F2-GPCL-O4). Obtained structures were then used to prepare silicone mold. Following manufacturing instructions, Smooth-On Silicone Mold Making kit was used for the preparation of silicone mold for scaffold making. Preparation of Polymer Films and Polymer / HA Composite Scaffolds via HDI Crosslinking Method To prepare polymer films, pre-polymer with above mentioned formulations was dissolved in 1,4-dioxane to obtain a 30 wt. % solution and then pour into a Teflon dish followed by solvent evaporation until a sticky consistency is achieved, then HDI at various molar ratio is added and immediately followed by continuous mixing for a homogenous mixture. The mixture was crosslinked overnight at room temperature. To prepare polymer / HA composites, 30 wt. % pre- polymer solution was mixed with 50 wt. % HA and stirred in teflon dishes to prepare homogenous mixture. Following solvent evaporation, sticky polymer / HA mixture was transferred into a 10mL syringe. Designated HDI concentration was added into the syringe and Attorney Docket No.11196-115WO1 followed by immediate mixing for a homogenous mixture. Polymer / HA / HDI mixture was then injected into the silicone mold as described herein. Material Characterization FTIR Characterization Fourier transform infrared (FTIR) spectra were obtained at room temperature using a FTS40 Fourier transform infrared spectrometer (BioRad Hercules, CA). Cross-linked BCFMC films (5 mm-thick) were cut using a microtome and placed on a KBr crystal. Mechanical Testing Compression testing of cylindrical composites: To test the compressive strength of polymer / HA composites, cylindrical samples were first prepared by mixing prepolymers with various amount of HA particles to prepare composites of 50 wt. % HA. Once the prepolymer-HA mixtures became clay-like, they were then inserted into PTFE tubing molds followed by post- polymerization of 80 °C for 3 days. Next, compression tests were performed on the cylindrical shaped specimens using a Instron 5966 machine equipped with a 10kN load (Instron, Norwood, MA) at a rate of 1.3 mm / min to failure. The initial modulus was calculated by measuring the gradient at 10% of compression of the stress-strain curve. Accelerated Degradation Study For accelerated degradation studies, polymer films were cut into round disks weighing ~50 mg (d=10 mm; Thickness~0.5 mm) and placed in tubes containing 10 mL of 0.05 M NaOH solutions. All samples were incubated at 37 for predetermined times. At each time point, the samples were taken out, washed thoroughly with deionized water and subsequently lyophilized. Film degradation was measured by mass remaining according to equation 1: W1 / W0×100% (1) where W0 refers to the original scaffold weight and W1 represents the remaining film weight. Cell Studies Cell Culture and Medium Attorney Docket No.11196-115WO1 Human mesenchymal stem cells (hMSCs; Lonza) were cultured in low glucose Dulbecco's Modified Eagle Medium (DMEM) with 10 vol. % fetal bovine serum (FBS) (Atlanta Biologicals; Flowery Branch, GA) and designated L-glutamine (Sigma). Cells were cultured in a humidified atmosphere with 5% CO2 at 37 °C. For osteogenic differentiation, cells at ∼80% confluence were treated with an established OG medium (low-glucose DMEM with 10−7 M dexamethasone, 0.05 mM ascorbate-2-phosphate, and 0.01 M β-glycerophosphate) supplemented with Gln, Mg, and CA alone or in combination at different concentrations to initiate differentiation. hMSCs Proliferation Studies To evaluate whether Gln could promote hMSCs proliferation, hMSCs were treated with 0, 0.5, 1, 2, 4, 8, 16 mM of glutamine supplementation in GM medium. According to manufacturer instruction, Cell Counting Kit-8 (CCK8) was used to quantify the number of cells at Day 0, Day 1, Day 3, and Day 5. hMSCs Differentiation Studies To evaluate whether Gln, Mg, or combination of Gln, Mg, and CA could promote osteogenic differentiation, hMSCs were treated with 0, 0.5, 1, 2, 4, 8, 16 mM of glutamine supplementation in OG medium, and cultured with cells for predetermined time periods. To evaluate the effect of Mg on osteogenesis, 8 mM of Mg supplementation was added in addition to 0.5, 2, 4, and 8 mM of Gln supplementation in OG medium, and cultured with cells for predetermined time periods. To determine whether Gln, Mg, and CA supplementation could have synergistic effect on osteogenic differentiation, hMSCs were treated with 2mM of Gln, 2mM of Mg, and 200 uM of CA in OG medium. For osteo-phenotype progression assessment, cells were lysed after 7 days of culture in OG medium, and alkaline phosphatase (ALP) production was quantified by using p-nitrophenyl phosphate (PNPP) as its substrate. Alizarin Red was used to stain the calcium nodules formed by the differentiating cells, and the calcium content in the nodules was quantified by Calcium Assay Kit (Sigma-Aldrich, St. Louis, MO). ALP Assay and DNA Quantification For ALP expression analysis, cell samples were lysed using RIPA buffer, and the cell lysate was centrifuged to remove debris. Then ALP activity measurement was performed by utilizing p-nitrophenyl phosphate (PNPP) which is hydrolyzed by ALP into a yellow-colored product. Attorney Docket No.11196-115WO1 Briefly, the PNPP stock solution (1M) was diluted with ALP assay buffer at a ratio of 1:100, 50 μL of which was subsequently added to 50 μL of lysate sample. After 10-30 min of incubation at 37oC, the plates were measured at 405 nm on a plate reader (TECAN, Männedorf, Switzerland). The same cell lysate solutions were used to determine DNA amount via a PicoGreen dsDNA quantification kit (Invitrogen, Carlsbad, CA) according to the manufacturer’s instructions. Alizarin Red Staining and Calcium Quantification For Alizarin Red staining, cell samples were fixed with 4% paraformaldehyde, and 40 mM Alizarin red solutions were used to stain calcium nodules for 30 min with gentle shaking. After thoroughly washing, the stained cells were observed on a Microscope (Nikon, Tokyo, Japan). For calcium quantification, cell samples were washed with PBS and decalcified in 0.6 N HCl for 12 h with gentle shaking. Calcium content in the supernatants was determined calorimetrically by using the Calcium assay kit (Sigma-Aldrich, St. Louis, MO). Would Healing Assay hMSCs were cultured on 48-well plates until confluence. Cells were starved for 12 hrs with 1% FBS. A straight scratch was made with a 200uL pipette tip per well. Wells were washed with PBS to clear cell debris. Bright field images were taken for initial boarder, then GM with 1% FBS and 0, 0.5, 1, 2, 4, 8 mM of glutamine supplementations same Glutamine concentrations were used for cultured for 8.5 hrs. After 8.5 hrs, cells were stain with DAPI and fluorescent images were taken for counting the cells that were migrated. Fluorescent Characterization Photoluminescent properties of prepolymers and films were studied using a Horiba FluoroMax- 4 spectrofluorometer (Horiba Scientific, Edison, NJ) with excitation and emission slit sizes of 1.5 nm by 1.5 nm and step size of 10nm. Fluorescent spectra of prepolymers were measured using prepolymer solution in 1,4 dioxane and a quartz zero background cuvette (Horiba Scientific, Edison, NJ). The fluorescent spectra of crosslinked polymers (16mm diameter x 0.5mm thickness) were measured using a solid-state holder (Horiba Scientific, Edison NJ).3D spectra and single wavelength excitation / emission spectra were obtained, with excitation / emission wavelengths of 354nm and 425nm, respectively for single wavelength measurements (max excitation / emission for BPLP-Glutamine). Photostability was measured Attorney Docket No.11196-115WO1 as above for 3 hours at the max excitation / emission wavelength). Fluorescent images of prepolymers were also obtained using an in vivo fluorescent imaging system (MaestroTM EX, Woburn, MA) with excitation and emission wavelengths as specified. Fluorescence of polymer films or laser cut shapes was further demonstrated using either a handheld torch or the above Maestro imaging system. Absorbance Characterization Prepolymer absorbance was measured using serially diluted solutions in 1,4 dioxane and a quartz zero background cuvette (Horiba Scientific, Edison, NJ) with a plate reader (infinite M200 PRO, TECAN, Männedorf, Switzerland) from 250-1000nm. Absorbance and transmission of crosslinked films was measured using a UV-2450 spectrometer (Shimadzu, Japan) with a minimum wavelength resolution of 0.2 nm from 250-2500nm. Photoacoustic / Ultrasound (PAUS) Characterization Photoacoustic properties of BPLP-Glutamine and BPLP-Glutamine Magnesium films were measured using a custom probe combining a high-resolution ultrasound probe with a fiber optic laser irradiation probe. The crosslinked polymer disks (6mm diameter x 0.5mm thickness) were embedded in a tissue phantom (1.5% agarose, 1% silica and 0.1% Intralipid) at a depth of approximately 2.5cm. The tissue phantom was then submerged in DI water and the ultrasound and photoacoustic (PAUS) signal from 700nm to 950nm was measured. PAUS signal intensities were calculated using MATLAB (MathWorks, Natick, MA, USA). Statistical Methods Data are expressed as the mean ± standard deviation. The statistical significance between two sets of data was calculated using a two-tail Student’s t-test. Analysis of variance (ANOVA) with Newman-Keuls multiple comparisons test post-hoc analysis was used to determine significant differences among three or more groups. Data was considered to be significant when a P-value of 0.05 or less was obtained. Results and Discussion Citrate-Based Fluorescent Metal-Incorporated Composite Intended Use, Fluorescent / Photoacoustic Imaging, and Handling Characteristics Attorney Docket No.11196-115WO1 In this example, a citrate-based fluorescent / photoacoustic metal-incorporated composite (BCFMC) was created to address the limitations of previous graft materials. We disclose using amino acid and metal ion incorporated, citrate-based polymer with inherent fluorescent / photoacoustic properties to composite with hydroxyapatite (HA) and creating a next-generation citrate-based material for bone regeneration in orthopedic applications. BCFMCs are easily molded into biomimetic biphasic bone substitute with complex structure and variable forms (FIGs.3A-3D and 4A-4B), offer chemistry amenable for HA interactions, and allow for a non-invasive means of fluorescently / photoacoustically monitoring the material presence, degradation, and tissue regeneration (FIGs.4A-4B). BCFMCs are all synthesized based on citric acid, which is a historically known metabolic by product of the Kreb’s cycle and acts as a robust multifunctional monomer to provide valuable carboxylic acid chemistry without the need for any additional chemical modifications. The intrinsic carboxyl chemistry provides hydrogen bonding and sites for calcium chelation with hydroxyapatite for enhanced polymer-ceramic interactions. BCFMCs are advantageous in that the resulting material can match the native inorganic composition of bone while providing amino acid and metal ions, which are nutrients and trace elements essential for optimal bone regeneration. Bone is a natural nanocomposite composed of 60-65 wt.-% HA embedded in a collagen matrix. The existing materials available for orthopedics are limited in the total amount of HA that can be incorporated into the composite before becoming brittle in nature. For example, many of the currently FDA approved composite materials in market can incorporate a maximum of 30 wt.-% HA or β-TCP, which is far less than that of native bone tissue. BCFMCs can incorporate up to 65 wt.-% HA, with an optimal HA ratio at 50 wt.-%, into the composite while still maintaining its mechanical properties, matching the native inorganic composition of bone (60-65 wt.-% HA) due to the enhanced polymer / HA interactions from the chelating ability of the free carboxylic acid chemistry of the polymer with the calcium of HA. This feature allows for increased HA concentrations in BCFMCs without becoming brittle like previous materials. Meanwhile, carboxyl groups provided by citrate make it very easy to incorporate amino acid into the materials through the reaction between the amine group of amino acid and the carboxyl group of citrate. Bivalent metal ions, such as magnesium ions, are bound to citrate-based materials through the chelating ability of the free carboxyl group from citrate. Stably adding amino acids and metal ions individually or in combination, in tunable and significant amounts (FIGs.4A-4B and 6A-6B), thus, become a unique feature of BCFMCs not achieved by other orthopedic materials. Attorney Docket No.11196-115WO1 Using hexamethylene diisocyanate (HDI) as the cross-linking reagent to post-polymerize BCFMC prepolymers, porous BCFMC scaffolds are easily made at room temperature without salt leaching. The size of pores and the porosity levels are modulated through regulating the pressure within the casting molds (FIGs. 1 and 2). Making porous scaffolds without salt leaching and post-polymerization under room temperature are two key conditions that enable incorporation of soluble and / or temperature-sensitive bioactive small molecules or protein- based growth factors, cytokines and chemokines into BCFMCs, a feature never achieved previously for citrate-based materials. When reacting citrate with any one of the twenty L-amino acids, BCFMCs gain an inherent fluorescent property. The amino acid reacts with the citrate to form a conjugated cyclic ring, which provides the fluorescent properties without the need for toxic quantum dots or dyes. Through the choice of amino acid used during pre-polymer synthesis, the fluorescent properties the resulting material can be fine-tuned to emit a wide array of wavelengths. Once implanted, BCFMCs can emit strong fluorescence when exposed to ultraviolet wavelengths to allow for a non-invasive means to monitor the material presence (FIG.5). The ability to offer a fluorescent imaging capability is a property that can be exploited to aid the currently used radiographic techniques. For example, material degradation can be correlated with the fluorescent intensity to quantitatively measure the presence of the material in vivo without the need for animal sacrifice. This allows for a better method to predict the necessary material resorption rate in various skeletal anatomic locations in different animal models to better design appropriate compositions for clinical use. Composite Mechanical Strength To assess the compressive mechanical properties of BCFMCs, cylindrical shaped specimens were tested in dry conditions and evaluated for their respective peak compressive stress, peak strain and initial modulus, which was determined from 0-10% strain. To determine the effects of amino acid and metal ions, BCFMC prepolymers were synthesized using citric acid, L- glutamine at 0.3 and 0.5 molar ratio relative to citric acid, and magnesium ions at 0.2 molar ratio relative to citric acid, which were all composited with 50 wt.-% HA. Prepolymers were post-polymerized using HDI as cross-linking reagent at 2x molar ratio relative to citrate, or thermo-crosslinked for 3 days at 80 °C or 3 days at 80 °C and 1 day at 120 °C. The samples were then tested in a dry state, and the results in FIGs. 8A-8B show a significant variation in compressive mechanical properties under different cross-linking conditions with various Attorney Docket No.11196-115WO1 compositions. BCFMC with 0.3 glutamine and 0.2 magnesium exhibits the highest peak stress. HDI cross-linking results in more flexible materials with lower initial moduli. Compressive mechanical properties of BCFMCs can also be modified by changing the ratios of HDI with a trend of increased peak stresses and initial moduli and decreased peak strains when HDI ratio increases (FIG.9). In a word, with increased crosslinking density, the resulted BCFMCs become harder and tougher. Similarly, increasing crosslinking density by thermal cross-linking of BCFMCs followed after HDI cross-linking can greatly increase the peak stress of the materials, while varying the thermal conditions didn’t affect the peak stresses when the materials have been crosslinked with HDI first (FIG.10). Taken together, the mechanical properties of BCFMCs can be tuned by HDI concentrations and crosslinking method. Stiffer and stronger composites can be created with increased HDI concentrations. Similarly, combination of HDI and thermal crosslinking can increase peak stress of the composites when compared with HDI crosslinking alone. Especially for POC / 0.3Gln / Mg formulation. The peak stress reached 400MPa after thermal crosslinked at 80C for 3 days in addition to 2x HDI crosslink. Further crosslinking at 120C for 3 days did not increase the peak stress for both formulations. This might indicate that the composites reached highest crosslinking density. Interestingly, the peak strain of BCFMCs composites was reaching 60% indicating the flexibility of the composites (FIGs. 8A-8B and 9). This is beneficial for the proposed non-inion bone fracture model. In addition to the physical structure design (FIG. 1), the unique mechanical property, flexibility, can further provide a stable condition after implantation as it can be securely compressed between the fracture gaps. Accelerated Degradation of BCFMs Films To access the accelerated degradation of BCFMs in 0.05 NaOH, 1x, 2x, 4x HDI crosslinked and thermal crosslinked films were used for each BCFMs formulation mentioned above. As shown in FIG. 11, as HDI concentrations increase, the degradation rate decreases. Thermal crosslinked films presented similar degradation rate as 4x HDI crosslinked films. Except for POC / 0.3Gln / Mg, all other formulations exhibited similar degradation trend where complete degradation was achieved around week 4 and 8 for 1x and 2x HDI respectively. POC / 0.3Gln / Mg exhibited a slower degradation rate. Even at week 24, there was still about 20% mass remaining. Effect of Glutamine on hMSC Proliferation and Migration Attorney Docket No.11196-115WO1 hMSC Proliferation with Glutamine Supplementation We first evaluated whether glutamine supplementation could promote hMSCs proliferation. As shown in FIG. 12, supplementation of 0.5 mM to 8mM of glutamine profoundly promotes hMSCs proliferation. Too high of concentration of glutamine will decrease its effect on hMSCs proliferation, but still enhanced hMSCs proliferation compared to 0 mM Glutamine supplementation. hMSCs Migration with Glutamine Supplementation During bone healing, hMSCs migration to the injury site is critical. Thus, we examined whether Gln supplementation can enhanced hMSCs motility. As shown in FIG. 13, Gln supplementation promoted hMSCs motility, and 2mM of Gln presented the optimal effect. Effects of Glutamine, Mg, CA Supplementation on Osteogenic Differentation of hMSCs Motivated by the recent published studies about glutamine, magnesium, and citrate in bone homeostasis, we explored the effect of glutamine, magnesium, and citrate supplementations on the osteogenic differentiation of hMSCs. As shown in FIG. 14, glutamine demonstrates a strong positive dose dependent effect on promoting the progression of osteoblast phenotype by presenting elevated alkaline phosphatase activity. Too high of a concentration of glutamine, at 16mM, started to decrease ALP activity. Consistently, calcium deposition also exhibits a promotive effect of glutamine supplementations, as shown in FIG. 15. All these data suggest an optimal exogenous glutamine supplementation concentration range, which is 2mM to 8mM. Thus, by supplementing glutamine above physiological concentration, 0.5mM, markedly supported hMSCs osteogenic differentiation. Next, we examined whether magnesium can further enhance osteogenesis. As shown in FIG. 18, supplementation of 8mM magnesium at various glutamine can further enhance osteogenesis. Moreover, we observed a synergistic effect of glutamine, magnesium, and citrate on human mesenchymal stem cells (hMSCs) osteogenesis. This was evident through heightened alkaline phosphatase (ALP) activity (FIG. 19A), augmented gene expression of key osteogenic regulators and effectors such as Runx2 (Day 3, FIG. 19B), SPP1, ALP1, and BMP2 (Day 7, FIG. 19C), and increased calcium deposition in late-stage osteogenic-differentiating hMSCs (FIGs. 19D-19E). Additionally, through fluorescent immunostaining, we demonstrated enhanced Runx2 protein expression in citrate, glutamine, and magnesium-treated osteogenic-differentiating MSCs (FIGs.19F-19I). Attorney Docket No.11196-115WO1 Effects of Glutamine, Mg, CA Supplementation on hMSC Energy Metabolism We further investigated how glutamine, magnesium, and citrate impact osteogenesis. We started to look at energy metabolism because hMSCs osteogenesis is an energy demanding process. Thus, we started with the examination of the effect of glutamine, magnesium, and citrate supplementations on ATP level during growth. As FIGs. 20-21 show, both glutamine and magnesium supplementations during cell growth can elevate ATP levels after 24 hrs. During osteogenesis, glutamine supplementation did not show a dose dependent effect at day 3 of osteogenesis, however, we see a dose dependent effect at day 7 (FIG. 22). Interestingly, we also observed a trend of synergistic effect of glutamine, magnesium, and citrate for ATP production at day 3 of osteogenesis. At day 7, the synergistic effect on osteogenesis greatly increased and the ATP production is significantly elevated (FIG. 23). These results indicate that there is a synergistic pathway for glutamine, magnesium, and citrate to promote the progression of osteogenic differentiation of hMSCs. Through metabolomic study, we further confirmed that most of metabolites in the TCA cycle were increased in citrate (FIG. 24), glutamine and magnesium treated and osteogenic-differentiating hMSCs, which demonstrated that these supplementations promoted intracellular ATP production through increased oxidative phosphorylation in mitochondria. The Signaling Pathways Orchestrated by Glutamine, Mg, CA Supplementation in Osteogenic-Differentiating MSCs The mammalian target of rapamycin (mTOR) serves as a crucial signaling hub, integrating signals from nutrients, oxygen, energy, amino acids, and growth factors to regulate metabolic pathways controlling cell proliferation and stem cell differentiation. Within this framework, two distinct mTOR complexes, known as mTOR complex 1 (mTORC1) and mTOR complex 2 (mTORC2), play pivotal roles. mTORC1, in particular, centrally regulates protein, lipid, and nucleotide synthesis in response to environmental conditions.46Previously, it was observed that exogenous citrate mediated mTOR-dependent protein synthesis in undifferentiated mesenchymal stem cells (MSCs).45Additionally, glutamine has been known to activate mTORC1 in various tissues and cell types, promoting cell growth.47However, whether exogenous citrate or glutamine can activate the mTORC1 signaling pathway in MSCs undergoing osteogenic differentiation remains unexplored. While magnesium has been found to enhance MSC osteogenic differentiation through the activation of the MAPK / ERK pathway and the classical Wnt pathway, its effect on the mTORC1 pathway has Attorney Docket No.11196-115WO1 not been reported.48However, according to findings in a human normal hepatocyte cell line (LO2), magnesium supplementation was identified as an mTORC1 inhibitor.49This example demonstrates that citrate, glutamine, and magnesium supplementation, individually or in combination, all mediated mTORC1 activation in osteogenic-differentiating MSCs. This activation was evidenced by the phosphorylation of the mTORC1 downstream target, Ribosomal protein S6 kinase beta-1 (S6K1), leading to increased protein synthesis and cell proliferation. The combinational supplementation demonstrated a synergistic enhancement effect on mTORC1 activation (FIG. 26A). Notably, mTOR inhibition by Torin1 highlighted the requirement of mTOR activity for proper MSC osteogenic differentiation, as Torin1 treatment resulted in diminished S6K1 phosphorylation even with citrate, glutamine and magnesium supplementation (FIG. 26B) and significantly reduced ALP activity in MSCs undergoing osteogenic differentiation (FIG.27B). To unravel the mechanism behind citrate, glutamine, and magnesium-mediated mTORC1 activation, we investigated the phosphorylation of adenosine monophosphate-activated protein kinase (AMPK), a crucial energy sensor. Normally, under low intracellular ATP levels, AMP and ADP bind directly to AMPK, prompting its activating phosphorylation. Once activated, AMPK inhibits mTORC1 activity, leading to a reduction in anabolic metabolism.50Given our observations of increased ATP production in citrate, glutamine, and magnesium-treated OG- differentiating MSCs and heightened mTORC1 activity, we initially hypothesized that the elevated intracellular ATP level would inhibit AMPK activation, consequently releasing the brake on mTORC1 activation. Contrary to this expectation, we found that AMPK phosphorylation was enhanced in citrate, glutamine, and magnesium-treated OG-differentiating MSCs, with the combinational supplementation exhibiting the most pronounced effect (FIG.26A). This unexpected outcome suggested that elevated ATP levels did not necessarily lead to reduced AMPK activity in our experiments. Meanwhile, our findings indicated that increased mTORC1 activity was not regulated through the conventional ATP / AMPK / mTORC1 pathway. In addition to sensing intracellular ATP levels, AMPK can be phosphorylated by Ca2+ / calmodulin-dependent kinase CaMKK2. To further explore this alternative pathway, we employed the CaMKK2 inhibitor, STO609, which remarkably attenuated the effect of citrate, glutamine, and magnesium on AMPK phosphorylation (FIG. 26B). Consequently, this reduction in AMPK phosphorylation diminished their osteogenic-promoting effects (FIG. 27A). Attorney Docket No.11196-115WO1 In summary, our study identified a proposed molecular mechanism in osteogenic- differentiating MSCs following citrate, glutamine, and magnesium treatment. The synergistic action of these supplements enhanced intracellular ATP production, providing the energy required for increased cellular activities in differentiating stem cells. Furthermore, citrate, glutamine, and magnesium activated mTORC1 in an AMPK-independent manner, promoting MSC proliferation crucial in the early stages of osteogenic differentiation. In the meantime, the supplements mediated AMPK activation in a CaMKK-dependent manner, essential for enhanced MSC osteogenic differentiation. This simultaneous increase in ATP production, mTORC1 activity, and AMPK phosphorylation represents a mechanism not previously reported in the literature. Emergence of NIR Absorbance and Photoacoustic Imaging Potential in BLPL-Glutamine Materials and Its Application in Dual Imaging Materials The ability to image biomaterial implants in vivo greatly expands the utility of said materials, allowing non-invasive tracking of both location within and interaction with the targeted and / or regenerating tissue (i.e. in tissue regeneration applications, anti-cancer targeting applications, or targeted delivery of drugs or other bioactive agents). Particularly, the ability to engineer completely biodegradable and biocompatible imaging agents is a cornerstone of biomaterials research, motivating the development of the intrinsically photoluminescent BPLP polymer family. Synthesized via the simple and catalyst free reaction of citric acid and amino acids or other similar amine containing monomers (as shown for the small molecule CA-Glutamine contained within the disclosed polymers) (FIGs.28A-28C), BPLPs have amply demonstrated strong fluorescence and utility in biomaterial nanoparticles, scaffolds, and composites, negating the drawbacks of typical imaging agents (including but not limited to synthetic dyes, carbon or quantum dots) such as high cost, complexity of synthesis, difficulty of incorporation within bulk materials, poor or non-degradability, and toxicity. Further, utilization of biologically relevant amino acids, typified in this disclosure by Glutamine, offers the additional benefit of straightforward conjugation of bioactive molecules capable of withstanding the harsh crosslinking and / or processing conditions (i.e., thermal crosslinking) necessary to attain high strength materials for bone regeneration, allowing release as a bioactive “drug” in synergy with released citrate and inorganic ions (as detailed in the above sections), creating an intrinsically proregenerative material combined with intrinsic imaging capability. Taking Glutamine as the example, it is well demonstrated that its reaction with citrate, forming our previously disclosed Attorney Docket No.11196-115WO1 DPR fluorophore (FIG. 28A) results in broad, intrinsically band shifting fluorescence from blue to red (250-650nm), with clearly visible fluorescence under UV illumination (FIGs.28B- 28C), enabling potential in vivo imaging. However, despite the utility of fluorescence, relatively low depth penetration through tissue (typically around 1cm maximum), limits its application, particularly in bone and other deeper tissues. Photoacoustic ultrasound (PAUS) imaging, relying on stimulation of absorbent materials by laser light at NIR (700nm+ wavelengths), which vibrate due to laser induced thermal expansion, generating detectable ultrasound waves, in contrast is capable of imaging at greater depths, with correspondingly increased utility in vivo. Additionally, heat generated by vibrations can be used therapeutically (photothermal effect) to promote tissue regeneration at mild temperatures or to kill cancer or bacterial cells at higher temperatures. Similar to fluorescence, photothermal imaging is usually enabled via the incorporation of expensive, complex, toxic and / or poorly degradable materials such as graphene, carbon dyes, precious metals (gold, silver), black / red phosphorous, copper, iron, or manganese oxides or sulfides, etc. Therefore, there is an equivalent driving force in research to develop improved PAUS biomaterials as there is toward the development of fluorescent biomaterials, with dual imaging (combining both modalities) being more critical yet. Thus, based on our existing BPLP family, we sought to achieve the combination of dual imaging, high biocompatibility / bioactivity, stable release of multiple bioactive compounds, and improved processing within a single material. As mentioned above, the fluorescence of BPLPs is well established; however, their NIR absorbent and photoacoustic potential emerged as an unexpected property, evidenced in the most basic sense that the starting monomers (citric acid, 1,8 octanediol, and glutamine) display no significant color at longer wavelengths (FIG. 29), standing in contrast to many commonly utilized NIR materials such as poly(aniline), graphene, or carbon, which themselves are visually dark. However, it was first observed that upon reaction of glutamine (or other amino acids) with citric acid, a dark color developed (whether reacting only the small molecular fluorophore or fluorophore containing polymers), therefore revealing additional potential of BPLPs in PAUS imaging and motivating further analysis. Beginning with BPLP-Glutamine prepolymers (dissolved in Dioxane solvent), a detailed systematic study was thus undertaken to develop the relation between polymer composition and absorbance properties and provide evidence that development of said absorbance is due to the reaction of citric acid and glutamine. As shown in FIGs. 30A-30E, a direct correlation between both concentration and glutamine feeding ratio was evidenced, with POC (without Attorney Docket No.11196-115WO1 glutamine) displaying minimal absorbance within the NIR-I (700-1000nm) range (equivalent to pure dioxane), while progressive increase in glutamine from 0.01 to 0.07 mole ratios resulted in development of increased absorbance, with higher concentration additionally leading to higher concentrations. More clearly, in FIGs.31A-31D, it can be seen that at all concentrations increasing glutamine increases absorbance, with marked enhancement (FIG.31D), correlating with visual color development. Next, addition of magnesium was studied to determine its effect. As shown in FIGs.32A-32C, a similar trend of increased absorbance was observed with increased glutamine when combined with magnesium at 0.02 mole ratios, further evidenced in FIGs. 33A-33C as distinct visual color development corresponding to increased absorbance. In FIG.34, it is demonstrated that although magnesium incorporation leads to a minor decrease in absorbance, both magnesium containing and magnesium free formulations maintain significant absorbance. Finally, testing the effect of addition of different feeding ratios of magnesium (0.01, 0.02, and 0.03 moles) revealed a more complicated trend whereby a biphasic trend was observed with increased absorbance maximizing at 0.02 mole ratio followed by a decrease at 0.03 mole ratio, which was particularly evidenced at higher concentrations (FIGs. 35A-35D and 36A-36C). Finally, utilizing 0.07 ratio of glutamine over a wider range of concentrations, the powerful effect of concentration on absorbance is evidenced, with magnesium incorporation giving similar results to the magnesium free formulation. Taken together, strong evidence was attained that absorbance is an emergent property of glutamine incorporation dependent on both feeding ratio and concentration (correlating to concentration of the absorber CA-Glutamine) and that similar results can be attained with or without magnesium incorporation. Particularly, aside from establishing the premise of NIR absorbance and imaging, these results indicate that nano or microparticles (themselves highly concentrated prepolymer particles within a non-solvent) have potential for PAUS imaging, similar to previously described fluorescent nanoparticles. In consideration of the negative effect of high absorbance on fluorescent intensity, particularly when fluorescence and absorbance profiles overlap, the effect of glutamine incorporation and prepolymer concentration on fluorescence was next examined to establish theoretical dual imaging potential. In a similar manner to the above, the effect of glutamine and concentration was well evidenced, with BPLPs displaying increased fluorescence compared to the fluorophore free POC while maintaining similar excitation / emission spectra (FIGs.37A-37E). However, there is more complex, biphasic response compared to that obtained with absorbance, whereby increasing fluorophore concentration initially leads to increased fluorescence before Attorney Docket No.11196-115WO1 reaching a point where absorbance dominates, reducing fluorescence intensity, as seen in many fluorescence systems. FIG. 38 further demonstrates the strong effect of concentration-based absorbance in glutamine 0.07, where fluorescence is strongly inhibited at even .3% and abolished by 1.5%, while FIG. 39 further demonstrates the effect fluorophore content at equivalent concentration, where initial increase leads to greater fluorescence to glutamine 0.05 followed by decrease. FIGs. 40A-40E further illustrate the overall effect at multiple wavelengths, with all polymers maintaining broad emission spectra but demonstrating reduced intensity. However, as demonstrated in FIGs.41A-41B, BPLP-Glutamine displays significant fluorescence from blue to red via its bandshifting, with potential in in vivo imaging. In FIGs. 42A-42C, magnesium incorporation is shown to also affect fluorescence, with similar trends to magnesium free formulations, again showing maximum intensity dependent on both glutamine and concentration, with study of glutamine 0.07 Mg0.02 again revealing the stark effect of concentration (FIG.43), with fluorescence again largely abolished at 1.5%. FIG. 44 also reveals a similar trend to magnesium free formulations, with glutamine 0.05 having max intensity at equivalent concentrations, while FIGs. 45A-45C demonstrate again the broad emission spectra of BPLP-Glutamine with magnesium 0.02. Finally, it is seen in FIGs. 46A- 46B that at 0.03 and 0.05 glutamine ratios, fluorescence is diminished with magnesium incorporation while at 0.07 ratio, fluorescence is slightly increased, which can be understood as the conflicting effects of magnesium incorporation reducing the overall concentration of glutamine in the final prepolymer as well as potentially interfering with CA-Glutamine formation via competing reactions with citrate and its effect on reduction of absorbance at lower concentrations (again via reduction of overall glutamine content), particularly in the extreme case of 0.07 (most absorptive). Photostability was also studied in FIG.47, with BPLPs maintaining high photo stabilities for up to 3 hours, equivalent to and exceeding commercial dyes Fluorescein and Rhodamine B, respectively, indicating better conservation of intensity at extended imaging times (for instance in vivo where locating / collecting images may be time consuming or where light therapies may be used for extended times). Effect of magnesium content was again studied in FIGs. 48A-48D, again indicating that magnesium content diminishes fluorescence, with magnesium 0.02 attaining the minimal fluorescence with a slight rebound at 0.03, while maintaining similar broad emission spectra, this biphasic trend correlating again with the conflict between magnesium’s effect on fluorophore content and on overall absorbance. Concluding, it is demonstrated that similar to absorbance, fluorescence is clearly affected by both glutamine content and concentration as well as magnesium incorporation, with different formulations favoring either maximized fluorescence or Attorney Docket No.11196-115WO1 maximized absorbance, validating the potential for dual imaging with careful selection of formulation. While results obtained for prepolymers were promising, establishment of similar trends of absorbance and fluorescence in solid materials is critical as most applications rely on utilization of solid films or scaffolds to promote tissue regeneration. In this context, absorbance of thermally crosslinked films was next studied. Beginning in FIGs. 49A-49B, the effect of glutamine content matches the trend seen in prepolymer, from near total transmittance and negligible NIR absorbance in POC to near 0 transmittance and maximum absorbance at glutamine 0.07. As crosslinking condition can also affect film absorbance via increased polymer density (being the solid-state analog to increasing concentration in solution), glutamine 0.03 films were studied. It was thus revealed that addition of high temperature crosslinking (120C) under vacuum for 3 days increased absorbance, there was negligible effect of 1 day at the elevated temperature, indicating that polymer density may only increase slowly via a strong polymerization driving force (temperature and vacuum); however, absorbance is maintained even at mild conditions, giving greater freedom to tune crosslinking dependent polymer attributes such as mechanics and degradation rate to the desired application. Assessing magnesium incorporation in FIGs.50A-50B, it is seen that trends remain similar to magnesium free formulations as above, again indicating the dominance of glutamine content toward absorbance, while in FIGs.51A-51B it is seen that magnesium films have lower absorbances compared to magnesium free formulations, likely due to the role in magnesium again reducing the content of glutamine within the film volume. This is supported in FIGs. 52A-52B by the reduction in absorbance with increasing magnesium feeding ratio from 0.01 to 0.03. In summary, film testing revealed preservation of trends observed in prepolymer and indicated the impressive potential for BPLP-Glutamine solid films as PAUS materials. Finally, as stated above, study of fluorescence in the solid state was undertaken to establish suitability for dual imaging. Again, results in the solid state mirrored those of prepolymer, with increased glutamine content resulting in reduced fluorescence (FIGs. 53), being largely abolished in glutamine 0.07, the key difference being POC’s high fluorescence, understandable in the context of its differing fluorescence mechanism compared to BPLP. While BPLP relies on a distinct fluorophore to generate fluorescence (leading to the demonstrated interference of the resulting absorbance of said fluorophore at concentrated conditions), POC relies solely on inter / intramolecular interactions between its backbone carboxyl and carbonyl groups, which is enhanced with greater polymer density sans significant absorbance increase compared to BPLP Attorney Docket No.11196-115WO1 (POC films remain “clear”). Further, broad emission is preserved in films, while in FIG. 54, greater thermal crosslinking time is shown to have a negative (though relatively minimal) effect on fluorescence, again indicating material tunability as stated above. In summary, FIGs.55A- 55B again indicate that BPLP-Glutamine films display full spectrum fluorescence from blue to red toward imaging in vivo (where longer wavelength >650nm enhance tissue penetration and diminish the interference of tissue autofluorescence. FIG. 56 again indicates that magnesium incorporating films perform similarly to magnesium free, maintaining broad wavelength imaging potential (FIGs. 57A-57B). FIGs. 58A-58B again indicate lower fluorescence with glutamine incorporation due to the diminished concentration of the fluorophore, except in 0.07, where reduced absorbance is enough to reverse the trend. Photostability of films again revealed significant retention of intensity over the 3 hour period (FIG. 59), with magnesium films performing better compared to magnesium free formulations, which may be due to lower absorbance of the magnesium film leading to greater penetration of the excitation laser into the bulk, exposing more fluorophores, whereas only the surface fluorophores of BPLP-Glutamine 0.03 are exposed, more rapidly bleaching the surface. Finally, increasing magnesium content from 0.01 to 0.03 again increased fluorescence due to decreased absorbance, while all formulations displayed reduced intensity compared to glutamine 0.03 due to reduced fluorophore density. These results again demonstrate the possibility to combine dual imaging properties or to maximize either fluorescence or PAUS via formulation control. As a further demonstration, porous scaffolds were fabricated from composites of BPLP- Glutamine 0.05 Mg 0.02 with hydroxyapatite toward orthopedic regeneration, again demonstrating fluorescence within wavelengths suitable for in vivo imaging (FIGs.61A-61C). In totality, these examples revealed the capability of the BPLP-Glutamine Magnesium system for both fluorescence and absorbance-based imaging, with potential for dual imaging via tuning of formulation with the following major trends: 1. Absorbance is increased with increased glutamine feeding ratio with a concurrent diminishment of fluorescence intensity regardless of magnesium incorporation in prepolymer, a function of the dual role of CA-Glutamine in contributing to both fluorescence and absorbance over similar wavelength ranges (FIGs.62A-62B). 2. Absorbance and fluorescence are concentration dependent in prepolymers, with fluorescence increasing initially due to increased fluorophore concentration followed Attorney Docket No.11196-115WO1 by diminished fluorescence as a function of the dominant role of absorbance (FIGs. 63A-63B), these trends being particularly dramatic in glutamine 0.07. 3. Fluorescence decreased with magnesium incorporation from 0 to 0.02 moles with a slight increase from 0.02 to 0.03 moles, while absorbance maximizes at Mg0.02, revealing a more complicated role for magnesium modulating absorbance while diminishing fluorescence due to reduction in fluorophore content (FIG.64). 4. Crosslinked films display similar trends to prepolymer with increased absorbance and decreased fluorescence with increased glutamine incorporation (FIGs.65 and 66), with magnesium incorporation resulting in increased fluorescence and decreased absorbance compared to magnesium free versions (FIG.67). 5. Crosslinking time has a more modest effect on absorbance and fluorescence, with 120C vacuum resulting at extended time periods (3 days) resulting in increased absorbance and decreased fluorescence (FIG.68). 6. Increasing magnesium content decreases both absorbance and fluorescence compared to magnesium free films, with some fluorescence recovery from 0.01 to 0.03 mole ratios, indicating the reduction of both CA-Glutamine based absorbance and fluorescence due to reduction of overall CA-Glutamine content per film volume (FIGs. 69-70). Motivated by the impressive absorbances attained in BPLP-Glutamine films, study of PAUS imaging in agar tissue phantoms was conducted at 2.5cm depth. Results conformed to the above observations, with a progressive increase in PAUS signal in the NIR-I range from Q0.01 (similar to POC) to Q0.07 (FIG.71A), while FIG.71B demonstrated similar effectiveness of the magnesium containing films with Q0.03 and Q0.05 incorporated. These results establish that BPLP-Glutamine Magnesium has significant potential for PAUS imaging even at depth in vivo, validating the dual imaging approach. BPLP-Glutamine Magnesium polymers thus achieve the valuable combination of biocompatibility / bioactivity, release of multiple bioactive factors (citrate, glutamine, and magnesium), dual fluorescent and PAUS imaging potential, and potential for fabrication as nano / microparticles, solid or porous films, bulks, or composites, and self-setting materials via HDI crosslinking, with significant potential in biomaterial research. Further, we demonstrate for the first time the capability of the reaction products of citric acid and amine containing molecules not only as fluorescent moieties but also as potent absorbance enhancers for Attorney Docket No.11196-115WO1 photoacoustic / photothermal applications via progressive incorporation of Glutamine. With this understanding, it is expected that a family of highly potent, bioactive and functional materials will be developed via a single step, catalyst free, low cost reaction with enormous potential for mix and match properties via incorporation of specific amine containing moieties, inorganic ions, and other components. The described fluorescent / photoacoustic and biodegradable composites can be commercialized for a wide variety of orthopedic applications. In putty form, BCFMCs can be used as a malleable osteoconductive material to fill and aid in the repair of skeletal defects. As in situ crosslinkable materials, BCFMCs can be commercialized as an adhesive or cement to bond orthopedic devices to bone tissue. BCFMCs can also be machined or molded into a wide variety of prefabricated bone fixation devices including, but not limited to, screws, pins, rods, and plates. They can also be used in other orthopedic applications areas such as tissue engineered scaffolding, fluorescent imaging probes, and controlled drug delivery devices. References The references cited below 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 below 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 below, the use in the incorporated references should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls. (1) Sk, S. Fracture Non-Union: A Review of Clinical Challenges and Future Research Needs. Malays Orthop J 2019, 13 (2), 1–10. 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Implant-Derived Magnesium Induces Local Neuronal Production of CGRP to Improve Bone-Fracture Healing in Rats. Nat Med 2016, 22 (10), 1160–1169. Attorney Docket No.11196-115WO1 (44) Chen, S.; Guo, Y.; Liu, R.; Wu, S.; Fang, J.; Huang, B.; Li, Z.; Chen, Z.; Chen, Z. Tuning Surface Properties of Bone Biomaterials to Manipulate Osteoblastic Cell Adhesion and the Signaling Pathways for the Enhancement of Early Osseointegration. Colloids Surf B Biointerfaces 2018, 164, 58–69. (45) Ma, C.; Tian, X.; Kim, J. P.; Xie, D.; Ao, X.; Shan, D.; Lin, Q.; Hudock, M. R.; Bai, X.; Yang, J. Citrate-Based Materials Fuel Human Stem Cells by Metabonegenic Regulation. Proc Natl Acad Sci U S A 2018, 115 (50), E11741–E11750. (46) Panwar, V.; Singh, A.; Bhatt, M.; Tonk, R. K.; Azizov, S.; Raza, A. S.; Sengupta, S.; Kumar, D.; Garg, M. Multifaceted Role of MTOR (Mammalian Target of Rapamycin) Signaling Pathway in Human Health and Disease. Sig Transduct Target Ther 2023, 8 (1), 375. (47) Bodineau, C.; Tomé, M.; Courtois, S.; Costa, A. S. H.; Sciacovelli, M.; Rousseau, B.; Richard, E.; Vacher, P.; Parejo-Pérez, C.; Bessede, E.; Varon, C.; Soubeyran, P.; Frezza, C.; Murdoch, P. D. S.; Villar, V. H.; Durán, R. V. Two Parallel Pathways Connect Glutamine Metabolism and MTORC1 Activity to Regulate Glutamoptosis. Nat Commun 2021, 12 (1), 4814. (48) Zhou, H.; Liang, B.; Jiang, H.; Deng, Z.; Yu, K. Magnesium-Based Biomaterials as Emerging Agents for Bone Repair and Regeneration: From Mechanism to Application. Journal of Magnesium and Alloys 2021, 9 (3), 779–804. (49) Chen, S.; Luo, S.; Zou, B.; Xie, J.; Li, J.; Zeng, Y. Magnesium Supplementation Stimulates Autophagy to Reduce Lipid Accumulation in Hepatocytes via the AMPK / MTOR Pathway. Biol Trace Elem Res 2023, 201 (7), 3311–3322. (50) González, A.; Hall, M. N.; Lin, S.-C.; Hardie, D. G. AMPK and TOR: The Yin and Yang of Cellular Nutrient Sensing and Growth Control. Cell Metabolism 2020, 31 (3), 472– 492. 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 Attorney Docket No.11196-115WO1 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.11196-115WO1 WHAT IS CLAIMED IS:
1. A composition comprising a polymer or oligomer formed from: one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt; one or more monomers B comprising a polyol or polyamine; one or more monomers C comprising glutamine or a salt or derivative thereof; one or more magnesium salts; and optionally one or more additional monomers.
2. The composition of claim 1, wherein the one or more monomers A comprise citric acid, trimethyl citrate, triethyl citrate, monosodium citrate, disodium citrate, trisodium citrate, calcium citrate, or combinations thereof.
3. The composition of claim 1, wherein the one or more monomers A comprise citric acid.
4. The composition of claim 1, wherein the one or more monomers A comprise a compound of Formula (A1), ; wherein:X1, X2, and X3are each independently -O- or -NH-; R1, R2, and R3are each independently -H, C1-C22alkyl, C2-C22alkenyl, or M+; R4is H or M+; and M+is a cation.
5. The composition of claim 4, wherein X1, X2, and X3are each -O-.
6. The composition of claim 4 or claim 5, wherein R4is -H.
7. The composition of any one of claims 1-6, wherein the one or more monomers B comprise a diol or diamine.Attorney Docket No.11196-115WO1 8. The composition of any one of claims 1-6, wherein the one or more monomers B comprise a poly(alkylene glycol).
9. The composition of any one of claims 1-6, wherein the one or more monomers B comprise poly(ethylene glycol), poly(propylene glycol), or combinations thereof.
10. The composition of any one of claims 1-6, wherein the one or more monomers B comprise an alkylene diol.
11. The composition of any one of claims 1-6, wherein the one or more monomers B comprise 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol, or combinations thereof.
12. The composition of any one of claims 1-6, wherein the one or more monomers B comprise 1,8-octanediol.
13. The composition of any one of claims 1-6, wherein the one or more monomers B comprise a compound of Formula (B1) , wherein:R6is -NH2, -OH, -OCH3, or -OCH2CH3; R7is -H, C1-C23 alkyl, or C2-C23 alkenyl; R8is -H, C1-C23 alkyl, C2-C23 alkenyl, -CH2CH2OH, or -CH2CH2NH2; and m is an integer ranging from 1 to 2000.
14. The composition of any one of claims 1-6, wherein the one or more monomers B comprise a compound of Formula (B2) , wherein:X4and X5are independently -O- or -NH; and n is an integer ranging from 1 to 2000.Attorney Docket No.11196-115WO1 15. The composition of any one of claims 1-14, wherein the one or more monomers C comprise glutamine.
16. The composition of any one of claims 1-15, wherein the one or more magnesium salts are selected from magnesium acetate, magnesium benzoate, magnesium bicarbonate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium citrate, magnesium fluoride, magnesium gluconate, magnesium diglutamate, magnesium glycinate, magnesium hydroxide, magnesium iodide, magnesium lactate, magnesium levulinate, magnesium malate, magnesium nitrate, magnesium orotate, magnesium oxalate, magnesium oxide, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium pidolate, magnesium salicylate, magnesium sulfate, magnesium taurate, and magnesium threonate, or combinations thereof.
17. The composition of any one of claims 1-16, wherein the one or more magnesium salts comprise magnesium nitrate.
18. The composition of any one of claims 1-17, wherein the one or more monomers A and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:
20.
19. The composition of any one of claims 1-18, wherein the one or more monomers B and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:
20.
20. The composition of any one of claims 1-19, wherein the one or more monomers A and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:
10.
21. The composition of any one of claims 1-20, wherein the one or more monomers B and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:
10.
22. The composition of any one of claims 1-21, wherein the polymer or oligomer is further formed from one or more monomers D comprising a catechol-containing species.
23. The composition of claim 22, wherein the catechol-containing species is a compound of Formula (D1): R9Attorney Docket No.11196-115WO1 wherein: R9, R10, R11, and R12are each independently selected from -H, -OH, -CH2(CH2)xNH2, -CH2(CHR13)NH2, -CH2(CH2)xOH, -CH2(CHR13)OH, and -CH2(CH2)xCOOH; R13is -COOH or –(CH2)yCOOH; and x and y are independently an integer ranging from 1 to 10.
24. The composition of claim 22, wherein the catechol-containing species is selected from dopamine, L-DOPA, D-DOPA, gallic acid, caffeic acid, 3,4-dihydroxyhydrocinnamic acid, and tannic acid.
25. The composition of any one of claims 1-24, wherein the polymer or oligomer is further formed from one or more monomers E comprising an isocyanate.
26. The composition of claim 25, wherein the isocyanate is a compound selected from Formula (E1), Formula (E2), Formula (E3), and Formula (E4): ,27. The composition of any one of claims 1-26, wherein the polymer or oligomer is further formed from one or more monomers F comprising a polycarboxylic acid.
28. The composition of claim 27, wherein the polycarboxylic acid is a compound selected from Formula (F1) and Formula (F2): ;Attorney Docket No.11196-115WO1 wherein R14is selected from -OH, -OCH3, -OCH2CH3, and -Cl.
29. The composition of any one of claims 1-28, wherein the polymer or oligomer is further form from one or more monomers G comprising one or more azide moieties.
30. The composition of claim 29, wherein the one or more monomers G is selected from a compound of Formula (G1), Formula (G2), and Formula (G3):X6is independently selected at each occurrence from -O- or -NH-; R16is -CH3or -CH2CH3; and R17and R18are each independently -CH2N3, -CH3, or -CH2CH3.
31. The composition of any one of claims 1-30, wherein the polymer or oligomer is further form from one or more monomers H comprising one or more alkyne moieties.
32. The composition of claim 31, wherein the one or more monomers H is selected from a compound of Formula (H1), Formula (H2), Formula (H3), Formula (H4), Formula (H5), and Formula (H6): , ,Attorney Docket No.11196-115WO1 ;X7and Y are independently -O- or -NH-; R19and R20are each independently -CH3 or -CH2CH3; R21is -OC(O)CCH, -CH3, or -CH2CH3; and R22is -CH3, -OH, or -NH2.
33. The composition of any one of claims 1-32, wherein the polymer or oligomer is crosslinked.
34. The composition of claim 33, wherein the polymer or oligomer is chemically crosslinked.
35. The composition of claim 34, wherein the polymer or oligomer is chemically crosslinked by a diisocyanate (such as butanediisocyanate (BDI), 1,6-hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI).
36. The composition of any one of claims 33-35, wherein the polymer or oligomer is thermally crosslinked.
37. The composition of any one of claims 1-36, wherein the composition further comprises an inorganic material.
38. The composition of claim 37, wherein the inorganic material comprises a particular inorganic material.
39. The composition of claim 37 or claim 38, wherein the inorganic material is selected from hydroxyapatite, tricalcium phosphate, biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particles.
40. The composition of any one of claims 1-39, wherein the composition further comprises an antioxidant, a therapeutic agent (such as an antibiotic), a biomolecule (such as a peptide or a protein), a cell, or combinations thereof.Attorney Docket No.11196-115WO1 41. The composition of any one of claims 1-40, wherein the composition is fluorescent.
42. The composition of claim 41, wherein the composition further comprises a fluorescence / absorbance enhancer.
43. The composition of claim 42, wherein the fluorescence / absorbance enhancer is selected from a metal (such as gold, silver, or a lanthanide), a carbon nanostructure, or an inorganic phosphate.
44. The composition of any one of claims 1-41, wherein the composition displays near- infrared (NIR) absorbance.
45. The composition of any one of claims 1-44, wherein the composition exhibits photoacoustic properties.
46. The composition of any one of claims 1-45, wherein the composition exhibits photodynamic properties.
47. The composition of any one of claims 1-46, wherein the composition is biodegradable.
48. The composition of claim 47, wherein the composition is capable of releasing citrate, glutamine, and / or magnesium cations upon degradation.
49. A prepolymer composition formed from: one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt; one or more monomers B comprising a polyol or polyamine; one or more monomers C comprising glutamine or a salt or derivative thereof; one or more magnesium salts; and optionally one or more additional monomers.
50. The prepolymer composition of claim 49, wherein the one or more monomers A comprise citric acid, trimethyl citrate, triethyl citrate, monosodium citrate, disodium citrate, trisodium citrate, calcium citrate, or combinations thereof.
51. The prepolymer composition of claim 49, wherein the one or more monomers A comprise citric acid.
52. The prepolymer composition of claim 49, wherein the one or more monomers A comprise a compound of Formula (A1),Attorney Docket No.11196-115WO1 ; wherein:X1, X2, and X3are each independently -O- or -NH-; R1, R2, and R3are each independently -H, C1-C22alkyl, C2-C22alkenyl, or M+; R4is H or M+; and M+is a cation.
53. The prepolymer composition of claim 52, wherein X1, X2, and X3are each -O-.
54. The prepolymer composition of claim 52 or claim 53, wherein R4is -H.
55. The prepolymer composition of any one of claims 49-54, wherein the one or more monomers B comprise a diol or diamine.
56. The prepolymer composition of any one of claims 49-54, wherein the one or more monomers B comprise a poly(alkylene glycol).
57. The prepolymer composition of any one of claims 49-54, wherein the one or more monomers B comprise poly(ethylene glycol), poly(propylene glycol), or combinations thereof.
58. The prepolymer composition of any one of claims 49-54, wherein the one or more monomers B comprise an alkylene diol.
59. The prepolymer composition of any one of claims 49-54, wherein the one or more monomers B comprise 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol, or combinations thereof.
60. The prepolymer composition of any one of claims 49-54, wherein the one or more monomers B comprise 1,8-octanediol.
61. The prepolymer composition of any one of claims 49-54, wherein the one or more monomers B comprise a compound of Formula (B1)Attorney Docket No.11196-115WO1 , wherein:R6is -NH2, -OH, -OCH3, or -OCH2CH3; R7is -H, C1-C23 alkyl, or C2-C23 alkenyl; R8is -H, C1-C23 alkyl, C2-C23 alkenyl, -CH2CH2OH, or -CH2CH2NH2; and m is an integer ranging from 1 to 2000.
62. The prepolymer composition of any one of claims 49-54, wherein the one or more monomers B comprise a compound of Formula (B2) , wherein:X4and X5are independently -O- or -NH; and n is an integer ranging from 1 to 2000.
63. The prepolymer composition of any one of claims 49-62, wherein the one or more monomers C comprise glutamine.
64. The prepolymer composition of any one of claims 49-63, wherein the one or more magnesium salts are selected from magnesium acetate, magnesium benzoate, magnesium bicarbonate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium citrate, magnesium fluoride, magnesium gluconate, magnesium diglutamate, magnesium glycinate, magnesium hydroxide, magnesium iodide, magnesium lactate, magnesium levulinate, magnesium malate, magnesium nitrate, magnesium orotate, magnesium oxalate, magnesium oxide, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium pidolate, magnesium salicylate, magnesium sulfate, magnesium taurate, and magnesium threonate, or combinations thereof.
65. The prepolymer composition of any one of claims 49-64, wherein the one or more magnesium salts comprise magnesium nitrate.Attorney Docket No.11196-115WO1 66. The prepolymer composition of any one of claims 49-65, wherein the one or more monomers A and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:
20.
67. The prepolymer composition of any one of claims 49-66, wherein the one or more monomers B and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:
20.
68. The prepolymer composition of any one of claims 49-67, wherein the one or more monomers A and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:
10.
69. The prepolymer composition of any one of claims 49-68, wherein the one or more monomers B and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:
10.
70. The prepolymer composition of any one of claims 49-69, wherein the prepolymer composition is further formed from one or more monomers D comprising a catechol-containing species.
71. The prepolymer composition of claim 70, wherein the catechol-containing species is a compound of Formula (D1): R9 ;R9, R10, R11, and R12are each independently selected from -H, -OH, -CH2(CH2)xNH2, -CH2(CHR13)NH2, -CH2(CH2)xOH, -CH2(CHR13)OH, and -CH2(CH2)xCOOH; R13is -COOH or –(CH2)yCOOH; and x and y are independently an integer ranging from 1 to 10.Attorney Docket No.11196-115WO1 72. The prepolymer composition of claim 70, wherein the catechol-containing species is selected from dopamine, L-DOPA, D-DOPA, gallic acid, caffeic acid, 3,4- dihydroxyhydrocinnamic acid, and tannic acid.
73. The prepolymer composition of any one of claims 49-72, wherein prepolymer composition is further formed from one or more monomers E comprising an isocyanate.
74. The prepolymer composition of claim 73, wherein the isocyanate is a compound selected from Formula (E1), Formula (E2), Formula (E3), and Formula (E4): ,75. The prepolymer composition of any one of claims 49-74, wherein the prepolymer composition is further formed from one or more monomers F comprising a polycarboxylic acid.
76. The prepolymer composition of claim 75, wherein the polycarboxylic acid is a compound selected from Formula (F1) and Formula (F2): ;and -Cl.
77. The prepolymer composition of any one of claims 49-76, wherein the prepolymer composition is further form from one or more monomers G comprising one or more azide moieties.Attorney Docket No.11196-115WO1 78. The prepolymer composition of claim 77, wherein the one or more monomers G is selected from a compound of Formula (G1), Formula (G2), and Formula (G3):X6is independently selected at each occurrence from -O- or -NH-; R16is -CH3 or -CH2CH3; and R17and R18are each independently -CH2N3, -CH3, or -CH2CH3.
79. The prepolymer composition of any one of claims 49-78, wherein the prepolymer composition is further form from one or more monomers H comprising one or more alkyne moieties.
80. The prepolymer composition of any one of claims 79, wherein the one or more monomers H is selected from a compound of Formula (H1), Formula (H2), Formula (H3), Formula (H4), Formula (H5), and Formula (H6): , ,Attorney Docket No.11196-115WO1 ;X7and Y are independently -O- or -NH-; R19and R20are each independently -CH3 or -CH2CH3; R21is -OC(O)CCH, -CH3, or -CH2CH3; and R22is -CH3, -OH, or -NH2.
81. The prepolymer composition of any one of claims 49-80, wherein the prepolymer composition further comprises an inorganic material.
82. The prepolymer composition of claim 81, wherein the inorganic material comprises a particular inorganic material.
83. The prepolymer composition of claim 81 or claim 82, wherein the inorganic material is selected from hydroxyapatite, tricalcium phosphate, biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particles.
84. The prepolymer composition of any one of claims 49-83, wherein the prepolymer composition further comprises an antioxidant, a therapeutic agent (such as an antibiotic), a biomolecule (such as a peptide or a protein), a cell, or combinations thereof.
85. A polymerizable composition comprising: one or more monomers A comprising citric acid, an ester or amide of citric acid, or a citrate salt; one or more monomers B comprising a polyol or polyamine; one or more monomers C comprising glutamine or a salt or derivative thereof; one or more magnesium salts; and optionally one or more additional monomers.Attorney Docket No.11196-115WO1 86. The polymerizable composition of claim 85, wherein the one or more monomers A comprise citric acid, trimethyl citrate, triethyl citrate, monosodium citrate, disodium citrate, trisodium citrate, calcium citrate, or combinations thereof.
87. The polymerizable composition of claim 85, wherein the one or more monomers A comprise citric acid.
88. The polymerizable composition of claim 85, wherein the one or more monomers A comprise a compound of Formula (A1), ; wherein:X1, X2, and X3are each independently -O- or -NH-; R1, R2, and R3are each independently -H, C1-C22 alkyl, C2-C22 alkenyl, or M+; R4is H or M+; and M+is a cation.
89. The polymerizable composition of claim 88, wherein X1, X2, and X3are each -O-.
90. The polymerizable composition of claim 88 or claim 89, wherein R4is -H.
91. The polymerizable composition of any one of claims 85-90, wherein the one or more monomers B comprise a diol or diamine.
92. The polymerizable composition of any one of claims 85-90, wherein the one or more monomers B comprise a poly(alkylene glycol).
93. The polymerizable composition of any one of claims 85-90, wherein the one or more monomers B comprise poly(ethylene glycol), poly(propylene glycol), or combinations thereof.
94. The polymerizable composition of any one of claims 85-90, wherein the one or more monomers B comprise an alkylene diol.
95. The polymerizable composition of any one of claims 85-90, wherein the one or more monomers B comprise 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol,Attorney Docket No.11196-115WO1 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol, or combinations thereof.
96. The polymerizable composition of any one of claims 85-90, wherein the one or more monomers B comprise 1,8-octanediol.
97. The polymerizable composition of any one of claims 85-90, wherein the one or more monomers B comprise a compound of Formula (B1) , wherein:R6is -NH2, -OH, -OCH3, or -OCH2CH3; R7is -H, C1-C23 alkyl, or C2-C23 alkenyl; R8is -H, C1-C23 alkyl, C2-C23 alkenyl, -CH2CH2OH, or -CH2CH2NH2; and m is an integer ranging from 1 to 2000.
98. The polymerizable composition of any one of claims 85-90, wherein the one or more monomers B comprise a compound of Formula (B2) , wherein:X4and X5are independently -O- or -NH; and n is an integer ranging from 1 to 2000.
99. The polymerizable composition of any one of claims 85-98, wherein the one or more monomers C comprise glutamine.
100. The polymerizable composition of any one of claims 85-99, wherein the one or more magnesium salts are selected from magnesium acetate, magnesium benzoate, magnesium bicarbonate, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium citrate, magnesium fluoride, magnesium gluconate, magnesium diglutamate, magnesium glycinate, magnesium hydroxide, magnesium iodide, magnesium lactate, magnesium levulinate, magnesium malate, magnesium nitrate, magnesium orotate, magnesium oxalate,Attorney Docket No.11196-115WO1 magnesium oxide, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium pidolate, magnesium salicylate, magnesium sulfate, magnesium taurate, and magnesium threonate, or combinations thereof.
101. The polymerizable composition of any one of claims 85-100, wherein the one or more magnesium salts comprise magnesium nitrate.
102. The polymerizable composition of any one of claims 85-101, wherein the one or more monomers A and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:
20.
103. The polymerizable composition of any one of claims 85-102, wherein the one or more monomers B and the one or more monomers C are present in a molar ratio from about 20:1 to about 1:
20.
104. The polymerizable composition of any one of claims 85-103, wherein the one or more monomers A and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:
10.
105. The polymerizable composition of any one of claims 85-104, wherein the one or more monomers B and the one or more magnesium salts are present in a molar ratio from about 10:1 to about 1:
10.
106. The polymerizable composition of any one of claims 85-105, further comprising one or more monomers D comprising a catechol-containing species.
107. The polymerizable composition of claim 106, wherein the catechol-containing species is a compound of Formula (D1): R9 ;R9, R10, R11, and R12are each independently selected from -H, -OH, -CH2(CH2)xNH2, -CH2(CHR13)NH2, -CH2(CH2)xOH, -CH2(CHR13)OH, and -CH2(CH2)xCOOH;Attorney Docket No.11196-115WO1 R13is -COOH or –(CH2)yCOOH; and x and y are independently an integer ranging from 1 to 10.
108. The polymerizable composition of claim 106, wherein the catechol-containing species is selected from dopamine, L-DOPA, D-DOPA, gallic acid, caffeic acid, 3,4- dihydroxyhydrocinnamic acid, and tannic acid.
109. The polymerizable composition of any one of claims 85-108, wherein further comprising one or more monomers E comprising an isocyanate.
110. The polymerizable composition of claim 109, wherein the isocyanate is a compound selected from Formula (E1), Formula (E2), Formula (E3), and Formula (E4): ,111. The polymerizable composition of any one of claims 85-110, further comprising one or more monomers F comprising a polycarboxylic acid.
112. The polymerizable composition of claim 111, wherein the polycarboxylic acid is a compound selected from Formula (F1) and Formula (F2): ;and -Cl.
113. The polymerizable composition of any one of claims 85-112, further comprising one or more monomers G having one or more azide moieties.Attorney Docket No.11196-115WO1 114. The polymerizable composition of claim 113, wherein the one or more monomers G is selected from a compound of Formula (G1), Formula (G2), and Formula (G3):X6is independently selected at each occurrence from -O- or -NH-; R16is -CH3 or -CH2CH3; and R17and R18are each independently -CH2N3, -CH3, or -CH2CH3.
115. The polymerizable composition of any one of claims 85-114, further comprising one or more monomers H having one or more alkyne moieties.
116. The polymerizable composition of any one of claims 115, wherein the one or more monomers H is selected from a compound of Formula (H1), Formula (H2), Formula (H3), Formula (H4), Formula (H5), and Formula (H6): , ,Attorney Docket No.11196-115WO1 ;X7and Y are independently -O- or -NH-; R19and R20are each independently -CH3 or -CH2CH3; R21is -OC(O)CCH, -CH3, or -CH2CH3; and R22is -CH3, -OH, or -NH2.
117. The polymerizable composition of any one of claims 85-116, wherein the polymerizable composition further comprises an inorganic material.
118. The polymerizable composition of claim 117, wherein the inorganic material comprises a particular inorganic material.
119. The polymerizable composition of claim 117 or claim 118, wherein the inorganic material is selected from hydroxyapatite, tricalcium phosphate, biphasic calcium phosphate, bioglass, ceramic, magnesium powder, pearl powder, magnesium alloy, and decellularized bone tissue particles.
120. The polymerizable composition of any one of claims 85-119, wherein the polymerizable composition further comprises an antioxidant, a therapeutic agent (such as an antibiotic), a biomolecule (such as a peptide or a protein), a cell, or combinations thereof.
121. A bone fixation device comprising a composition of any one of claims 1-48.
122. The bone fixation device of claim 121, wherein the bone fixation device comprises a screw, a pin, a rod, or a plate.
123. A bone substitute comprising a composition of any one of claims 1-48.
124. A particle comprising a composition of any one of claims 1-48.
125. The particle of claim 124, wherein the particle is a nanoparticle or a microparticle.
126. The particle of claim 124 of claim 125, further comprising a therapeutic agent, a biomolecule, or a cell.Attorney Docket No.11196-115WO1 127. The particle of claim 126, wherein the composition is conjugated to the therapeutic agent, the biomolecule, or the cell.
128. A biocement or bioadhesive comprising a composition of any one of claims 1-120.
129. A tissue engineering scaffold comprising a composition of any one of claims 1-120.
130. A fiber comprising a composition of any one of claims 1-48.
131. A hydrogel comprising a composition of any one of claims 1-120.
132. A method of promoting and / or accelerating bone regeneration in a bone site, the method comprising delivering a composition of any one of claims 1-120 to the bone site.
133. The method of claim 132, wherein the composition is delivered before and / or during a proliferation stage of osteogenesis at the bone site.
134. The method of claims 132 or 133, further comprising delivering stem cells to the bone site.
135. The method of any one of claims 132-134, wherein the bone site is an intramembranous ossification site.
136. The method of any one of claims 132-134, wherein the bone site is an endochondral ossification site.
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