Growing environmental awareness imposes on polymer scientists the development of novel materials that show a longer lifetime and that can be easily recycled. These challenges were largely met by vitrimers, a new class of polymers that merges properties of thermoplastics and thermosets. This is achieved by the incorporation of dynamic covalent bonds into the polymer structure, which provides high stability at the service temperature, but enables the processing at elevated temperatures. Numerous types of dynamic covalent bonds have been utilized for the synthesis of vitrimers. Amongst them, boronic acid-based linkages, namely boronic acid esters and boroxines, are distinguished by their quick exchange kinetics and the possibility of easy application in various polymer systems, from commercial thermoplastics to low molecular weight thermosetting resins. This review covers the development of dynamic cross-links. This review is aimed at providing the state of the art in the utilization of boronic species for the synthesis of covalent adaptable networks. We mainly focus on the synthetic aspects of boronic linkages-based vitrimers construction. Finally, the challenges and future perspectives are provided.

Polyglycidol (or polyglycerol) is a biocompatible polymer with a main chain structure similar to that of poly(ethylene oxide) but with a –CH₂OH reactive side group in every structural unit. The hydroxyl groups in polyglycidol not only increase the hydrophilicity of this polymer but also allow for its modification, leading to polymers with carboxyl, amine, and vinyl groups, as well as to polymers with bonded aliphatic chains, sugar moieties, and covalently immobilized bioactive compounds in particular proteins. The paper describes the current state of knowledge on the synthesis of polyglycidols with various topology (linear, branched, and star-like) and with various molar masses. We provide information on polyglycidol-rich surfaces with protein-repelling properties. We also describe methods for the synthesis of polyglycidol-containing copolymers and the preparation of nano- and microparticles that could be derived from these copolymers. The paper summarizes recent advances in the application of polyglycidol and polyglycidol-containing polymers as drug carriers, reagents for diagnostic systems, and elements of biosensors.

Programmable hydrogels are an emerging class of intelligent materials engineered to respond precisely to specific stimuli, offering tailored functionalities with significant potential for biomedical applications, including drug delivery, tissue engineering, and wound healing. This review comprehensively explores various programmable hydrogels responsive to diverse triggers, including temperature, gene expression, color, shape, and mechanical force. The design and fabrication methods underlying these systems are detailed, highlighting the roles of crosslinkers, adhesion groups, and photosensitive functional groups. Furthermore, the key physical, chemical, and biological properties that govern the performance and functionality of hydrogels are analyzed. The review further examines the mechanisms and recent advancements in self‐executing hydrogels, such as self‐activated, self‐oxygenated, self‐expandable, and self‐powered systems, demonstrating how these innovative designs drive the development of next‐generation programmable hydrogels. The main challenges in hydrogel design, including complexity, reproducibility, and clinical translation, are also addressed. Finally, a perspective on future research directions, highlighting the integration of the latest technologies to realize programmable hydrogels with dynamic closed‐loop responsiveness, bionic synergy, and robust clinical applicability, is offered.

The review is focused on the hydrogel systems dedicated to the intravaginal delivery of antibacterial, antifungal and anti-Trichomonas vaginalis activity drugs for the treatment of gynaecological infections. The strategies for the enhancement of the hydrophobic drug solubility in the hydrogel matrix based on the formation of bigel systems and the introduction of nano- and microparticles as a drug reservoir are presented. Hydrogel carriers of natural and synthetic pharmacological substances, drug-free systems displaying antimicrobial activity thanks to the hydrogel building elements and systems combining the antimicrobial activity of both drug and polymer building components are distinguished. The design of hydrogels facilitating their administration and proper distribution in the vaginal mucosa and the vagina based on thermoresponsive systems capable of gelling at vaginal conditions and already-cross-linked injectable systems after reaching the yield stress are discussed. In addition, the mechanisms of hydrogel bioadhesion that regulate the retention time in the vagina are indicated. Finally, the prospects for the further development of hydrogel-based drug carriers in gynaecological therapies are highlighted.

Injectable, self-healing hydrogels with enhanced solubilization of hydrophobic drugs are urgently needed for antimicrobial intravaginal therapies. Here, we report the first hydrogel systems constructed of dynamic boronic esters cross linking unimolecular micelles, which are a reservoir of antifungal hydrophobic drug molecules. The selective hydrophobization of hyperbranched polyglycidol with phenyl units in the core via ester or urethane bonds enabled the solubilization of clotrimazole, a water-insoluble drug of broad antifungal properties. The encapsulation efficiency of clotrimazole increases with the degree of the HbPGL core modification; however, the encapsulation is more favorable in the case of urethane derivatives. In addition, the rate of clotrimazole release was lower from HbPGL hydrophobized via urethane bonds than with ester linkages. In this work, we also revealed that the hydrophobization degree of HbPGL significantly influences the rheological properties of its hydrogels with poly(acrylamide-ran-2-acrylamidephenylboronic acid). The elastic strength of networks (G(N)) and the thermal stability of hydrogels increased along with the degree of HbPGL core hydrophobization. The degradation of the hydrogel constructed of the neat HbPGL was observed at approx. 40 degrees C, whereas the hydrogels constructed on HbPGL, where the monohydroxyl units were modified above 30 mol %, were stable above 50 degrees C. Moreover, the flow and self healing ability of hydrogels were gradually decreased due to the reduced dynamics of macromolecules in the network as an effect of increased hydrophobicity. The changes in the rheological properties of hydrogels resulted from the engagement of phenyl units into the intermolecular hydrophobic interactions, which besides boronic esters constituted additional cross-links. This study demonstrates that the HbPGL core hydrophobized with phenyl units at 30 mol % degrees via urethane linkages is optimal in respect of the drug encapsulation efficiency and rheological properties including both self-healable and injectable behavior. This work is important because of a proper selection of a building component for the construction of a therapeutic hydrogel platform dedicated to the intravaginal delivery of hydrophobic drugs.