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Alginate (Alg) polymers have received much attention due to the mild conditions required for gel formation and their good bio-acceptability. However, due to limited interactions with cells, many drugs, and biomolecules, chemically modified alginates are of great interest. Sulfated alginate (S-Alg) is a promising heparin-mimetic that continues to be investigated both as a drug molecule and as a component of biomaterials. Herein, the S-Alg literature of the past five years (2017-2023) is reviewed. Several methods used to synthesize S-Alg are described, with a focus on new advances in characterization and stereoselectivity. Material fabrication is another focus and spans bulk materials, particles, scaffolds, coatings, and part of multicomponent biomaterials. The new application of S-Alg as an antitumor agent is highlighted together with studies evaluating safety and biodistribution. The high binding affinity of S-Alg for various drugs and heparin-binding proteins is exploited extensively in biomaterial design to tune the encapsulation and release of these agents and this aspect is covered in detail. Recommondations include publishing key material properties to allow reproducibility, careful selection of appropriate sulfation strategies, the use of cross-linking strategies other than ionic cross-linking for material fabrication, and more detailed toxicity and biodistribution studies to inform future work., (© 2024 The Author(s). Macromolecular Bioscience published by Wiley‐VCH GmbH.)

Over the past two decades, deep eutectic solvents (DESs) have captured significant attention as an emergent class of solvents that have unique properties and applications in differing fields of chemistry. One area where DES systems find utility is the design of polymeric gels, often referred to as "eutectogels," which can be prepared either using a DES to replace a traditional solvent, or where monomers form part of the DES themselves. Due to the extensive network of intramolecular interactions (e.g., hydrogen bonding) and ionic species that exist in DES systems, polymeric eutectogels often possess appealing material properties-high adhesive strength, tuneable viscosity, rapid polymerization kinetics, good conductivity, as well as high strength and flexibility. In addition, non-covalent crosslinking approaches are possible due to the inherent interactions that exist in these materials. This review considers several key applications of polymeric eutectogels, including organic electronics, wearable sensor technologies, 3D printing resins, adhesives, and a range of various biomedical applications. The design, synthesis, and properties of these eutectogels are discussed, in addition to the advantages of this synthetic approach in comparison to traditional gel design. Perspectives on the future directions of this field are also highlighted., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Solvent-free photopolymerization of vinyl monomers to produce high modulus materials with applications in 3D printing and photoswitchable materials is demonstrated. Polymerizable eutectic (PE) mixtures are prepared by simply heating and stirring various molar ratios of N-isopropylacrylamide (NIPAM), acrylamide (AAm) and 2-hydroxyethyl methacrylate (HEMA). The structural and thermal properties of the resulting mixtures are evaluated by 1D and 2D NMR spectroscopy as well as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). UV photocuring kinetics of the PE mixtures is evaluated via in situ photo-DSC and photorheology measurements. The PE mixtures cure rapidly and display storage moduli that are orders of magnitude greater than equivalent copolymers cured in an aqueous medium. The versatility of these PE systems is demonstrated through the addition of a photoswitchable spiropyran acrylate monomer, as well as applying the PE formulation as a stereolithography (SLA)-based 3D printing resin. Due to the hydrogen-bonding network in PE systems, 3D printing of the eutectic resin is possible in the absence of crosslinkers. The addition of a RAFT agent to reduce average polymer chain length enables 3D printing of materials which retain their shape and can be dissolved on demand in appropriate solvents., (© 2024 The Authors. Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Direct comparison of the sulfating agents H 2 SO 4 -DCC and SO 3 ·py for the synthesis of sulfated alginate (S-Alg) as well as detailed characterisation of the products that form is lacking. This study involving three researchers used the tributylammonium salt of alginate (T-Alg) as a common substrate for the sulfation reactions. It was found that the use of H 2 SO 4 -DCC resulted in poor control of the degree of sulfation (DS) and that the S-Alg polymers contained nitrogen (determined by elemental analysis) as a result of formation of an unwanted N-acylurea adduct. Additionally, a large reduction in chain length was confirmed. In contrast, the use of SO 3 ·py gave reasonable control over DS, resulted in high yields, showed no contamination and no clear change in chain length. Detailed characterisation of such S-Alg polymers by 1 H NMR, 13 C NMR and 1 H, 13 C-HSQC NMR confirmed sulfation at C2 and C3 with a preference for C2., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Injectable self-healing hydrogels are attractive materials for use as wound dressings. To prepare such hydrogels, the current study used quaternized chitosan (QCS) to improve the solubility and antibacterial activity and oxidized pectin (OPEC) to introduce aldehyde groups for Schiff's base reaction with the amine groups from QCS. Self-healing hydrogels were made by co-injection of polymer solutions at specific polymer concentrations and reagent ratios that optimized both Schiff's base reactions and ionic interactions. The optimal hydrogel displayed self-healing 30 min after cutting and continuous self-healing during continuous step strain analysis, rapid gelation (< 1 min), a storage modulus of 394 Pa, and hardness of 700 mN, and compressibility of 162 mN s. The adhesiveness of this hydrogel (133 Pa) was within a suitable range for application as a wound dressing. The extraction media from the hydrogel displayed no cytotoxicity to NCTC clone 929 cells and higher cell migration than the control. While the extraction media from the hydrogel was found not to have antibacterial properties, QCS was verified as having MIC 50 of 0.04 mg/mL against both E. coli and S. aureus. Therefore, this injectable self-healing QCS/OPEC hydrogel has the potential use as a biocompatible hydrogel material for wound management., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Surface modification of biomaterials is a strategy used to improve cellular and in vivo outcomes. However, most studies do not evaluate the lifetime of the introduced surface layer, which is an important aspect affecting how a biomaterial will interact with a cellular environment both in the short and in the long term. This study evaluated the surface layer stability in vitro in buffer solution of materials produced from poly(lactic-co-glycolic acid) (50:50) and polycaprolactone modified by hydrolysis and/or grafting of hydrophilic polymers using grafting from approaches. The data presented in this study highlight the shortcomings of using model substrates (e.g., spun-coated films) rather than disks, particles, and scaffolds. It also illustrates how similar surface modification strategies in some cases result in very different lifetimes of the surface layer, thus emphasizing the need for these studies as analogies cannot always be drawn.

The design of current implants produced from biodegradable polyesters is based on strength and rate of degradation and tailored by the choice of polyester used. However, detailed knowledge about the degradation mechanism of surface modified materials with applications in biomaterials science and tissue engineering is currently lacking. This perspective aims to outline the need for a greater focus on analyzing the degradation of modified polyesters to ensure they can fulfil their intended function and that degradation products can effectively be cleared from the body. The status of the literature regarding surface modified polyesters is summarized to illustrate the main aspects investigated in recent studies and specifically the number of studies investigating the fate of the materials upon degradation.