Hydrogels are hydrophilic 3D networks that are able to ingest large amounts of water or biological fluids, and are potential candidates for biosensors, drug delivery vectors, energy harvester devices, and carriers or matrices for cells in tissue engineering. Natural polymers, e.g., cellulose, chitosan and starch, have excellent properties that afford fabrication of advanced hydrogel materials for biomedical applications: biodegradability, biocompatibility, non-toxicity, hydrophilicity, thermal and chemical stability, and the high capacity for swelling induced by facile synthetic modification, among other physicochemical properties. Hydrogels require variable time to reach an equilibrium swelling due to the variable diffusion rates of water sorption, capillary action, and other modalities. In this study, the nature, transport kinetics, and the role of water in the formation and structural stability of various types of hydrogels comprised of natural polymers are reviewed. Since water is an integral part of hydrogels that constitute a substantive portion of its composition, there is a need to obtain an improved understanding of the role of hydration in the structure, degree of swelling and the mechanical stability of such biomaterial hydrogels. The capacity of the polymer chains to swell in an aqueous solvent can be expressed by the rubber elasticity theory and other thermodynamic contributions; whereas the rate of water diffusion can be driven either by concentration gradient or chemical potential. An overview of fabrication strategies for various types of hydrogels is presented as well as their responsiveness to external stimuli, along with their potential utility in diverse and novel applications. This review aims to shed light on the role of hydration to the structure and function of hydrogels. In turn, this review will further contribute to the development of advanced materials, such as “injectable hydrogels” and super-adsorbents for applications in the field of environmental science and biomedicine.

Supramolecular polysaccharide-based hydrogels have attracted considerable research interest recently due to their high structural functionality, low toxicity, and potential applications in foods, cosmetics, catalysis, drug delivery, tissue engineering and the environment. Modulation of the stability of hydrogels is of paramount importance, especially in the case of stimuli-responsive systems. This review will update the recent progress related to the rational design of supramolecular hydrogels with the objective of understanding the gelation process and improving their physical gelation properties for tailored applications. Emphasis will be given to supramolecular host–guest systems with reference to conventional gels in describing general aspects of gel formation. A brief account of the structural characterization of various supramolecular hydrogels is also provided in order to gain a better understanding of the design of such materials relevant to the nature of the intermolecular interactions, thermodynamic properties of the gelation process, and the critical concentration values of the precursors and the solvent components. This mini-review contributes to greater knowledge of the rational design of supramolecular hydrogels with tailored applications in diverse fields ranging from the environment to biomedicine.

Recent efforts have been directed towards the design of efficient and contaminant selective remediation technology for the removal of perfluorinated compounds (PFCs) from soils, sediments, and aquatic environments. While there is a general consensus on adsorption-based processes as the most suitable methodology for the removal of PFCs from aquatic environments, challenges exist regarding the optimal materials design of sorbents for selective uptake of PFCs. This article reviews the sorptive uptake of PFCs using cyclodextrin (CD)-based polymer adsorbents with nano- to micron-sized structural attributes. The relationship between synthesis of adsorbent materials and their structure relate to the overall sorption properties. Hence, the adsorptive uptake properties of CD-based molecularly imprinted polymers (CD-MIPs) are reviewed and compared with conventional MIPs. Further comparison is made with non-imprinted polymers (NIPs) that are based on cross-linking of pre-polymer units such as chitosan with epichlorohydrin in the absence of a molecular template. In general, MIPs offer the advantage of selectivity, chemical tunability, high stability and mechanical strength, ease of regeneration, and overall lower cost compared to NIPs. In particular, CD-MIPs offer the added advantage of possessing multiple binding sites with unique physicochemical properties such as tunable surface properties and morphology that may vary considerably. This mini-review provides a rationale for the design of unique polymer adsorbent materials that employ an intrinsic porogen via incorporation of a macrocyclic compound in the polymer framework to afford adsorbent materials with tunable physicochemical properties and unique nanostructure properties.