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Liquid embolic agents are widely used for the endovascular embolization of vascular conditions. However, embolization based on phase transition is limited by the adhesion of the microcatheter to the embolic agent, use of an organic solvent, unintentional catheter retention, and other complications. By mimicking thrombus formation, a water-soluble polymer that rapidly glues blood into a gel without triggering coagulation was developed. The polymer, which consists of cationic and aromatic residues with adjacent sequences, shows electrostatic adhesion with negatively charged blood substances in a physiological environment, while common polycations cannot. Aqueous polymer solutions are injectable through clinical microcatheters and needles. The formed blood gel neither adhered to the catheter nor blocked the port. Postoperative computed tomography imaging showed that the polymer can block the rat femoral artery in vivo and remain at the injection site without nontarget embolization. This study provides an alternative for the development of waterborne embolic agents.

Double network (DN) gels, consisting of two contrasting interpenetrated polymer networks, exhibit large resistances to crack initiation and propagation. For practical applications, crack resistances of materials in highly stretched states are important. In this study, we investigated the crack growth behaviors of DN gels in stretched states by inducing crack seeds into these gels under various degrees of tension. This examination enables the analysis of crack propagation for a wide range of bulk energy release rate G. The power-law elationship between G and crack growth velocity v was investigated for DN gels with different tensile behaviors. We found that for brittle and unnecking DN gels, the velocities changed from slow mode (quasi-stationary fracture) to fast mode (dynamic fracture) with an increase in G, similar to that of a single network gel; in contrast, for necking DN gels having higher crack resistances than those of the unnecking DN gels, only fast modes were observed once the G is above a threshold. Real-time birefringence observation reveals a large damage zone around the crack tip at G slightly lower than the threshold, while the damage zone is hardly observed at G higher than the threshold. The results indicate that, for the necking DN gels, crack initiation has a large energy barrier owing to the formation of the damage zone; once this barrier is overcome, the excess energy release accelerates the crack propagation and therefore the gels exhibit dynamic fracture.

Tuning the self-assembled structures in amorphous hydrogels will enrich the functionality of hydrogels. In this study, we tuned the structure of a photonic hydrogel, which consists of polymeric lamellar bilayers entrapped inside a polyacrylamide network, simply by molecular triggering using an ionic surfactant. Owing to the binding of ionic surfactants (sodium dodecyl sulfate), the lamellar bilayers comprising of non-ionic polymeric surfactants [poly(dodecyl glyceryl itaconate)] changed to micelles, whereas the unidirectional lamellar structure was preserved in the hydrogel. The bilayer-micelle structure transition caused a dramatic decrease in the swelling anisotropy and mechanical softening of the photonic gel. With the micelle structure, the softened gel shows fast (0.3 s) and reversible color change over the entire visible light range in response to a small mechanical pressure (5 kPa). This low stress-induced color-changing hydrogel could be applied as a visual tactile sensor in various fields, especially in biomedical engineering.

In this work, we succeeded in direct visualization of the network structure of synthetic hydrogels with TEM by developing a novel staining and network fixation method. Such a direct visualization had not been carried out because sample preparation and obtaining sufficient contrast are challenging for these soft materials. TEM images revealed robust heterogeneous network architectures at mesh size scale and defects at micro-scale. TEM images also revealed the presence of abundant dangling chains on the surface of the hydrogel network. The real space structural information provides a comprehensive perspective that links bulk properties with a nanoscale network structure, including fracture, adhesion, sliding friction, and lubrication. The presented method has the potential to advance the field.

We investigate the fatigue resistance of chemically cross-linked polyampholyte hydrogels with a hierarchical structure due to phase separation and find that the details of the structure, as characterized by SAXS, control the mechanisms of crack propagation. When gels exhibit a strong phase contrast and a low cross-linking level, the stress singularity around the crack tip is gradually eliminated with increasing fatigue cycles and this suppresses crack growth, beneficial for high fatigue resistance. On the contrary, the stress concentration persists in weakly phase-separated gels, resulting in low fatigue resistance. A material parameter, lambda(max), is identified, correlated to the onset of non-affine deformation of the mesophase structure in a hydrogel without crack, which governs the slow-to-fast transition in fatigue crack growth. The detailed role played by the mesoscale structure on fatigue resistance provides design principles for developing self-healing, tough, and fatigue-resistant soft materials.

The equilibrium swelling degree of a highly swollen charged gel has been thought to be determined by the balance between its elastic pressure and ionic osmotic pressure. However, the full experimental verification of this balance has not previously been conducted. In this study, we verified the balance between the elastic pressure and ionic osmotic pressure of charged gels using purely experimental methods. We used tetra-PEG gels created using the molecular stent method (St-tetra-PEG gels) as the highly swollen charged gels to precisely and separately control their network structure and charge density. The elastic pressure of the gels was measured through the indentation test, whereas the ionic osmotic pressure was determined by electric potential measurement without any strong assumptions or fittings. We confirmed that the two experimentally determined pressures of the St-tetra-PEG gels were well balanced at their swelling equilibrium, suggesting the validity of the aforementioned relationship. Furthermore, from single-strand level analysis, we investigated the structural requirements of the highly swollen charged gels in which the elasticity and ionic osmosis are balanced at their swelling equilibrium.

High modulus, toughness, and fatigue resistance are usually difficult to be obtained simultaneously in rubbery materials. Here, we report that by superimposing the nanophase separation structure in double network (DN) elastomers using immiscible polymers, the modulus, fracture energy, and energy release rate of fatigue threshold are enhanced all together by 13, 5, and 5 times, respectively. We reveal that the interplay between the DN structure and the nanophase separation structure brings two effects synergistically: (1) formation of nanoclusters overstresses and homogenizes the sacrificial network, thereby remarkably increasing the modulus and yielding stress and (2) the nanoclusters act as viscoelastic nanofillers dissipating energy and pinning the crack propagation, thereby significantly enhancing toughness and fatigue resistance. This work provides a facile approach to superimpose high-order structures in DN materials for excellent mechanical performance. The clarified synergetic effects should be universal for DN materials made of immiscible polymers. We believe that this work will facilitate more studies on elastomers and gels along this line.

The toughness of composite materials is size dependent below a critical load transfer length (lT). Fiber-reinforced viscoelastic polymers are uniquely suited to study the size-limited regime because the l(T)of these soft composites can be as high as several centimeters, in contrast to traditional composites where l(T) is extremely small, allowing a large window for macroscale characterization. In this work, we elucidate the parameters that influence the toughness of soft composites when failure is governed by a fiber pullout-induced matrix-fracture mechanism. We ultimately demonstrate three important points: (1) fiber-reinforced viscoelastic polymers can possess high toughness, even at dimensions well below l(T) , (2) significant toughness amplification occurs due to the presence of fibers, even when the fracture process consists solely of matrix rupture, and (3) the composite toughness in the fiber pullout region can be predicted from easily attainable component parameters.

The heterogeneous structure that exists in virtually all hydrogels has a significant influence on the resulting strength and toughness. While the internal structure has been observed with electron microscopy, it is difficult to measure the in situ local polymer concentration in the native swollen state. In this study, a modified microelectrode technique (MET) was employed to measure the Donnan potential of a heterogeneous hydrogel with a phase-separated structure. With this method, we succeeded in observing quantitative in situ polymer concentrations ranging from 10.2 mu mol/L to several hundred mmol/L. From the obtained concentration profiles, we could successfully evaluate the internal phase-separated structure with a resolution of less than 0.8 mu m. Using MET, we could estimate the average activity coefficient of the hydrogel, and we found a difference in concentration between the dense and sparse phases. We demonstrate that MET is a powerful method that can locally and quantitatively measure the polyelectrolyte concentration distribution within hydrogels. Furthermore, this method can be applied to cells and organs in vivo due to their similarities with polyelectrolytes. Enabling the in situ determination of the internal structures of biomaterials could have important implications toward the characterization of damaged and diseased tissues on the local scale.

The equilibrium swelling degree of a highly swollen charged gel has been thought to be determined by the balance between its elastic pressure and ionic osmotic pressure. However, the full experimental verification of this balance has not previously been conducted. In this study, we verified the balance between the elastic pressure and ionic osmotic pressure of charged gels using purely experimental methods. We used tetra-PEG gels created using the molecular stent method (St-tetra-PEG gels) as the highly swollen charged gels to precisely and separately control their network structure and charge density. The elastic pressure of the gels was measured through the indentation test, whereas the ionic osmotic pressure was determined by electric potential measurement without any strong assumptions or fittings. We confirmed that the two experimentally determined pressures of the St-tetra-PEG gels were well balanced at their swelling equilibrium, suggesting the validity of the aforementioned relationship. Furthermore, from single-strand level analysis, we investigated the structural requirements of the highly swollen charged gels in which the elasticity and ionic osmosis are balanced at their swelling equilibrium.

Applying the double network principle to develop tough hydrogels with different polymer chemistries is important for the potential application of hydrogel materials. Synthesis of the two interpenetrated networks with contrasting structure and properties required for double networks usually involves a two-step polymerization process. In this work, we present a new method to synthesize tough double network hydrogels by post-physical crosslinking of linear semi-rigid polyelectrolytes entrapped in a chemically crosslinked neutral network. Owing to their semi-rigid structure, the linear polyelectrolytes form a brittle physical network above their overlap concentration in multi-valent ZrCl2O ion solutions without macroscopic phase separation within the flexible neutral network. The double network hydrogels thus prepared exhibit high modulus (~1.7 MPa), strength (~1.3 MPa), fracture strain (~7.3), and strain energy density (~5.9 MJ/m3), while containing over 80% water. These materials also exhibit modest self-healing ability (~51% after 30 minutes), demonstrating an additional benefit of a physical sacrificial network. This method is simpler than the conventional two-step polymerization and could be applied to develop tough hydrogels from rigid polyelectrolytes, including biopolymers such as DNA, HA, and chondroitin sulfate.

Double network hydrogels (DN gels) exhibit extraordinarily high strength and toughness by interplay of the two contrasting networks: the rigid, brittle network serves as a sacrificial bond that fractures at a relatively low strain, while the soft, stretchable network serves as hidden length that sustains stress by large extension afterward. The internal fracture process of the brittle network strongly depends on the relative strength of the two networks. In this study, we study the internal fracturing process of typical DN gels that show yielding or necking under uniaxial stretching using in situ small-angle X-ray scattering. Two samples consisting of the same brittle first network from poly(2-acrylamido-2-methylpropanesulfonic acid) but stretchable second network from poly(N,N-dimethylacrylamide) of different concentrations were adopted. We found that (1) the brittle network shows nonaffine deformation even far below the yield strain by local fracture; (2) for the sample of low second network concentration, significant strain amplification occurs around the submicrometer-scale voids (defects) preexisting in the brittle network, which induces the fracture percolation of brittle network from voids to show the necking phenomenon; and (3) the strain amplification at voids is suppressed in the sample of high second network concentration, and fracture of brittle network occurs dispersedly, showing yielding without necking.

We report a method to create anisotropic double-network (DN) hydrogels, through the controlled orientation of a physical sacrificial network. A cross-linked polyacrylamide hydrogel is synthesized from a solution containing a semirigid anionic polyelectrolyte. Subsequently, the gel is stretched to orient the semirigid polyelectrolyte, which does not relax in the stretched state because of the high contour length in comparison to the mesh size of the polyacrylamide network. The polyelectrolyte is then physically cross-linked with a multivalent cation, ZrCl2O, to fix the anisotropy. Anisotropy was visualized by observing birefringence and quantified by small-angle X-ray scattering. By comparing the scattering in the oriented direction versus perpendicular to the oriented direction, a structural anisotropy factor was calculated. Uniaxial tensile testing was performed on samples of varying prestretch, both parallel and perpendicular to the stretching direction. Young's modulus, fracture stress, fracture strain, and work of extension were characterized, and the resulting mechanical anisotropy was compared to the structural anisotropy factor. We find that the anisotropy of Young's modulus and fracture stress is directly controlled by the anisotropy of the sacrificial network, while fracture strain and work of extension show little influence from structural anisotropy. The results of this work demonstrate that prestretching of a physical sacrificial network is a controllable and simple method to create anisotropic DN hydrogels.

Synthetic hydrogels possessing both macroscopic anisotropic structure and toughness, which are analogous to the load-bearing bio-tissues such as muscles and tendons, are rarely available. Studying the molecular mechanism of tough and anisotropic hydrogel under deformation is beneficial to understand the load-deformation functions of soft bio-tissues. In this work, the deformation-induced structure transformation of a macroscopically anisotropic and tough hydrogel has been investigated to understand the role of structure evolution for enhanced toughness. At rest, the hydrogel possesses a well-defined hierarchical structure in which self-assembled nanometer thick lamellar bilayers are alternatively stacked in hundred nanometer thick hydrogel matrixes. Stretching along the lamellar direction induces structure transformation from lamellar bilayers to hierarchical fibrous structures aligned along the deformation axis. The generated hierarchical structures consist of micrometer thick fiber bundles made from nanometer thick fibrils analogous to tropo-collagen bundles or microfibrils of the tendon. The fibrous structure formed at large elongation is associated with damage and rupture of the bilayers, which underpins the molecular mechanism of the unique mechanical behaviors of the tough lamellar hydrogel.

Polyelectrolyte gels exhibit intrinsic salt-sensitive swelling behaviour, which causes size instability in ionic environments. Thus, polyelectrolyte gels that show salt-insensitive swelling have been anticipated for applications in ionic environments, such as medical materials usedin vivo. We found that double-network (DN) gels consisting of both a polyelectrolyte network and a non-ionic network are resistant to salt-sensitive swelling. This resistance is attributed to their lower osmotic pressure originating from mobile ions relative to the osmotic pressure of mixing at swelling equilibrium. Our investigation indicated that the two contrasting network structures within the DN gels are vital for achieving these properties, where the structures include a highly prestretched and sparse polyelectrolyte network and a coiled and dense non-ionic network. The salt-insensitivity of the DN gels will lead to their unique applications in ionic environments.

Polyelectrolyte gels exhibit intrinsic salt-sensitive swelling behaviour, which causes size instability in ionic environments. Thus, polyelectrolyte gels that show salt-insensitive swelling have been anticipated for applications in ionic environments, such as medical materials usedin vivo. We found that double-network (DN) gels consisting of both a polyelectrolyte network and a non-ionic network are resistant to salt-sensitive swelling. This resistance is attributed to their lower osmotic pressure originating from mobile ions relative to the osmotic pressure of mixing at swelling equilibrium. Our investigation indicated that the two contrasting network structures within the DN gels are vital for achieving these properties, where the structures include a highly prestretched and sparse polyelectrolyte network and a coiled and dense non-ionic network. The salt-insensitivity of the DN gels will lead to their unique applications in ionic environments.