Mechanical Reinforcement of Lamellar Bilayer Hydrogels by Small Amounts of Co-surfactants.

Anisotropic photonic hydrogels with alternatively stacked poly(dodecyl glyceryl itaconate) (PDGI) bilayers and polyacrylamide (PAAm) gel layers are unique soft materials with various functions. It is known that to form the lamellar phase of bilayers, a small amount of co-surfactant sodium dodecyl sulfate (SDS) should be present in the precursor monomer solutions of the gels. However, little is known about the influence of the co-surfactant on the structure of bilayers and on the mechanical properties of such photonic hydrogels. Herein, we chose several co-surfactants and studied the effect of the co-surfactants on the self-assembly behavior of the bilayers and on the mechanical properties of the resulting photonic hydrogels. A macroscopically aligned lamellar phase could be induced for all the co-surfactants. Interestingly, the mechanical response of the photonic hydrogels sensitively depends on the chemical structure of the co-surfactant, especially at large deformation. We hypothesize that doping by small amounts of co-surfactants dramatically changes the anchoring strength and density of PAAm strands onto the bilayer surface, thereby influencing the load transfer efficiency from the bilayer to the PAAm gel layer at large deformation and the rupture of the bilayer. This work provides new understanding in the molecular mechanisms of deformation and strengthening in this soft and anisotropic nanocomposite, helping to design more robust photonic hydrogels.

Biomimetic Tough Gels with Weak Bonds Unravel the Role of Collagen from Fibril to Suprafibrillar Self-Assembly.

Biological tissues rich in type I collagen exhibit specific hierarchical fibrillar structures together with remarkable mechanical toughness. However, the role of collagen alone in their mechanical response at different structural levels is not fully understood. Here, it is proposed to rationalize such challenging interplay from a materials science perspective through the subtle control of this protein self-assembly in vitro. It is relied on a spray-processing approach to readily use the collagen phase diagram and set a palette of biomimetic self-assembled collagen gels in terms of suprafibrillar organization. Their mechanical responses unveil the involvement of mechanisms occurring either at fibrillar or suprafibrillar scales. Noticeably, both modulus at early stage of deformations and tensile toughness probe the suprafibrillar organization, while durability under cyclic loading and stress relaxation reflect mechanisms at the fibril level. By changing the physicochemical environment, the interfibrillar interactions are modified toward more biomimetic mechanical responses. The possibility of making tissue-like materials with versatile compositions and toughness opens perspectives in tissue engineering.

Origin of transparency in scattering biomimetic collagen materials.

Living tissues, heterogeneous at the microscale, usually scatter light. Strong scattering is responsible for the whiteness of bones, teeth, and brain and is known to limit severely the performances of biomedical optical imaging. Transparency is also found within collagen-based extracellular tissues such as decalcified ivory, fish scales, or cornea. However, its physical origin is still poorly understood. Here, we unveil the presence of a gap of transparency in scattering fibrillar collagen matrices within a narrow range of concentration in the phase diagram. This precholesteric phase presents a three-dimensional (3D) orientational order biomimetic of that in natural tissues. By quantitatively studying the relation between the 3D fibrillar network and the optical and mechanical properties of the macroscopic matrices, we show that transparency results from structural partial order inhibiting light scattering, while preserving mechanical stability, stiffness, and nonlinearity. The striking similarities between synthetic and natural materials provide insights for better understanding the occurring transparency.

Self-Assembled Collagen Microparticles by Aerosol as a Versatile Platform for Injectable Anisotropic Materials.

Extracellular matrices (ECM) rich in type I collagen exhibit characteristic anisotropic ultrastructures. Nevertheless, working in vitro with this biomacromolecule remains challenging. When processed, denaturation of the collagen molecule is easily induced in vitro avoiding proper fibril self-assembly and further hierarchical order. Here, an innovative approach enables the production of highly concentrated injectable collagen microparticles, based on collagen molecules self-assembly, thanks to the use of spray-drying process. The versatility of the process is shown by performing encapsulation of secretion products of gingival mesenchymal stem cells (gMSCs), which are chosen as a bioactive therapeutic product for their potential efficiency in stimulating the regeneration of a damaged ECM. The injection of collagen microparticles in a cell culture medium results in a locally organized fibrillar matrix. The efficiency of this approach for making easily handleable collagen microparticles for encapsulation and injection opens perspectives in active tissue regeneration and 3D bioprinted scaffolds.