Diluted, complementary, click-reactive elastin-like recombinamer (ELR) solutions have been prepared and mixed at two different temperatures, one below and one above the characteristic transition temperature (T t ) of these chemically modified ELRs. Size, aspect ratio, zeta potential and microrheological measurements have been carried out on the nanostructures formed under these dilute conditions as a way to better understand the relationship between the final macroscopic properties of ELR-based hydrogels and the molecular conditions governing the initial stages of the chemical crosslinking process that occurs, especially its dependence on the preparation temperature relative to T t As a result, two different fractal modes of gel formation have been found at the two temperatures studied (above and below T t ). Thus, when the reaction mixture is prepared below T t , essentially onedimensional linear nanogels with a high aspect ratio are obtained. In contrast, 3D nanogels are formed above T t , with spherical shapes predominating. These different structures seem to reflect the two molecular organizations of the single components of the mixture under these conditions, namely extended chains below T t and a globular arrangement above T t . In addition to the interest in these nanogels as models for understanding the formation of microscopic structures and differential macroscopic properties under more conventional hydrogel-formation conditions, these nanogels are of interest due to their thermoresponsiveness and biocompatibility, which provide them with potential uses for drug delivery and other biomedical applications in living systems.
INTRODUCTIONNew materials, many of which are intended for use as gels, especially in the bioscience fields, are continuously coming to the fore.Elastin-like recombinamers (ELRs) are proteinaceous biomaterials based on the repetition of certain sequences from natural elastin 1,2 . These compounds are designed and produced by recombinant DNA technology, thus allowing complete control of their structure and amino acid sequence. ELRs can include different bioactive sequences3, such as those governing protease sensitivity or cell adhesion, etc. These ELRs exhibit cell friendly behavior, tunable mechanical properties, thermal sensitivity and an ability to self-assemble 3,4 . All these properties are interesting for the most cutting-edge applications in the fields of nanotechnology and biomedicine. Their thermal sensitivity is characterized by a critical temperature in aqueous solution, known as the transition temperature (T t ), which is associated with a conformational reorganization at the molecular level. Thus, whereas the polymer chains are soluble in water below T t , they self-assemble into nano-and microaggregates above this temperature, becoming insoluble. This process is completely reversible.We have recently, designed, synthesized, and bioproduced elastin-like recombinamer catalyst-free click gels (ELR-