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Abstract The development and understanding of antifreezing hydrogels are crucial both in principle and practice for the design and delivery of new materials. The current antifreezing mechanisms in hydrogels are almost exclusively derived from their incorporation of antifreezing additives, rather than from the inherent properties of the polymers themselves. Moreover, developing a computational model for the independent yet interconnected double-network (DN) structures in hydrogels has proven to be an exceptionally difficult task. Here, we develop a multiscale simulation platform, integrating ‘random walk reactive polymerization’ (RWRP) with molecular dynamics (MD) simulations, to computationally construct a physically-chemically linked PVA/PHEAA DN hydrogels from monomers that mimic a radical polymerization and to investigate water structures, dynamics, and interactions confined in PVA/PHEAA hydrogels with various water contents and temperatures, aiming to uncover antifreezing mechanism at atomic levels. Collective simulation results indicate that the antifreezing property of PVA/PHEAA hydrogels arises from a combination of intrinsic, strong water-binding networks and crosslinkers and tightly crosslinked and interpenetrating double-network structures, both of which enhance polymer-water interactions for competitively inhibiting ice nucleation and growth. These computational findings provide atomic-level insights into the interplay between polymers and water molecules in hydrogels, which may determine their resistance to freezing. 

Polymer brushes have witnessed extensive utilization and progress, driven by their distinct attributes in surface modification, tethered group functionality, and tailored interactions at the nanoscale, enabling them for various scientific and industrial applications of coatings, sensors, switchable/responsive materials, nanolithography, and lab-on-a-chips. Despite the wealth of experimental investigations into polymer brushes, this review primarily focuses on computational studies of antifouling polymer brushes with a strong emphasis on achieving a molecular-level understanding and structurally designing antifouling polymer brushes. Computational exploration covers three realms of thermotical models, molecular simulations, and machine-learning approaches to elucidate the intricate relationship between composition, structure, and properties concerning polymer brushes in the context of nanotribology, surface hydration, and packing conformation. Upon acknowledging the challenges currently faced, we extend our perspectives toward future research directions by delineating potential avenues and unexplored territories. Our overarching objective is to advance our foundational comprehension and practical utilization of polymer brushes for antifouling applications, leveraging the synergy between computational methods and materials design to drive innovation in this crucial field. 

Antifreezing hydrogels are essential for materials design and practical applications, but their development and understanding have been challenging due to their high-water content. Current antifreezing hydrogels typically rely on organic solvents or the addition of antifreezing agents. In this study, we present a novel crosslinking strategy to fabricate antifreezing hydrogels without the need for additional antifreezing agents. We introduce a new crosslinker, PEGn-EGINA, which combines highly hydrophilic EGINA with polyethylene glycol (PEG) of varying molecular weights. Utilizing PEGn-EGINA as the crosslinker, we synthesize Agar/Polyacrylamide (Agar/PAAm) double-network hydrogels, alongside conventional MBAA-crosslinked hydrogels for comparison. The resulting PEGn-EGINA-crosslinked hydrogels exhibit inherent antifreezing properties and retain their mechanical integrity even at subzero temperatures for extended periods. Molecular dynamics (MD) simulations further reveal that the antifreezing behavior observed in the PEGn-EGINA-crosslinked hydrogels can be attributed to their highly hydrophilic and tightly crosslinked double-network structures. These structures enable strong bindings between water and the hydrogel network, thus effectively preventing the formation of ice crystals within the hydrogels. Notably, PEGn-EGINA-crosslinked hydrogels not only demonstrate superior mechanical performance compared to MBAA-crosslinked hydrogels, but also maintain their mechanical properties even in frozen conditions, making them suitable for a wide range of applications. This study presents a simple yet effective design concept for highlighting the role of novel crosslinker in enhancing antifreezing and mechanical properties, showcasing their potential for various applications that require both antifreezing capabilities and robust mechanical performance. 

Bilayer hydrogels encoded with smart functions have emerged as promising soft materials for engineered biological tissues and human-machine interfaces, due to the versatility and flexibility in designing their mechanical and chemical properties. However, conventional fabrication strategies often require multiple complicated steps to create an anisotropic bilayer structure with poor interfaces, which significantly limit the scope of bilayer hydrogel applications. Here, we reported a general, one-pot, macrophase separation strategy to fabricate a family of bilayer hydrogels made of vinyl and styryl monomers with a seamless interface and a controllable layer separation efficiency (20–99%). The working principle of a macrophase separation strategy allows for the decoupling of the two gelation processes to form distinct vinyl- and styryl-enriched layers by manipulating competitive polymerization reactions between vinyl and styryl monomers. This work presents a straightforward approach and a diverse range of radical monomers, which can be utilized to create next-generation bilayer hydrogels, beyond a few available today.