Protein‐based fibers are used by nature as high‐performance materials in a wide range of applications, including providing structural support, creating thermal insulation, and generating underwater adhesives. Such fibers are commonly generated through a hierarchical self‐assembly process, where the molecular building blocks are geometrically confined and aligned along the fiber axis to provide a high level of structural robustness. Here, this approach is mimicked by using a microfluidic spinning method to enable precise control over multiscale order during the assembly process of nanoscale protein nanofibrils into micro‐ and macroscale fibers. By varying the flow rates on chip, the degree of nanofibril alignment can be tuned, leading to an orientation index comparable to that of native silk. It is found that the Young's modulus of the resulting fibers increases with an increasing level of nanoscale alignment of the building blocks, suggesting that the mechanical properties of macroscopic fibers can be controlled through varying the level of ordering of the nanoscale building blocks. Capitalizing on strategies evolved by nature, the fabrication method allows for the controlled formation of macroscopic fibers and offers the potential to be applied for the generation of further novel bioinspired materials.

The determination of in situ structural information of soft matter under flow is challenging, as it depends on many factors, such as temperature, concentration, confinement, channel geometry, and type of imposed flow. Here, we combine microfluidics and scanning small-angle X-ray scattering (scanning-SAXS) to create a two-dimensional spatially resolved map, which represents quantitatively the variation of molecular properties under flow. As application examples, mappings of confined amyloid fibrils and wormlike micelles under flow into various channel geometries are compared. A simple process to fabricate X-rays resistant chips, based on polyimide and UV-curing resin, is discussed. During experiments, these chips remained in high-energy synchrotron radiation for more than 24 hours, causing constant low background scattering. Thus, sufficient statistics were obtained from sample scattering at exposure times as low as 0.1 s, even with the small scattering volumes in microfluidic channels. Scanning-SAXS of microfluidic flows has many potential applications from biology to fundamental soft matter physics. In general, any fluid which has enough contrast for X-ray scattering can be measured to obtain the dependence of molecular shape, conformation, alignment and size on the flow field. Besides, dynamic processes of soft matter caused by flow, temperature, concentration gradient, and confinement, for example self-assembling, aggregation, mixing, diffusion, and disintegration of macromolecules, can be quantified and visualized on a single image by this mapping technique.

During the anisotropic growth from globular to wormlike micelles, the basic interactions among distinct parts of the surfactant monomer, its counterion, and additives are fundamental to tune molecular self-assembly. We investigate the addition of sodium salicylate (NaSal) to hexadecyltrimethylammonium chloride and bromide (CTAC and CTAB), 1-hexadecylpyridinium chloride and bromide (CPyCl and CPyBr), and benzyldimethylhexadecylammonium chloride (BDMC), which have the same hydrophobic tail. Their potential to enhance viscoelasticity by anisotropic micellar growth upon salt addition was compared in terms of (i) the influence of the headgroup structure, and (ii) the influence of surfactant counterion type. Employing proton nuclear magnetic resonance ((1)H NMR), we focused on the molecular conformation of surfactant monomers in the core and polar shell regions of the micelles and their interactions with increasing concentration of NaSal. The viscoelastic response was investigated by rotational and oscillatory rheology. We show that micellar growth rates can be tuned by varying the flexibility and size of the surfactant headgroup as well as the dissociation degree of the surfactant counterion, which directly influences the strength of headgroup-counterion pairing. As a consequence, the morphological transitions depend directly on charge neutralization by electrostatic screening. For example, the amount of salt necessary to start the rodlike-to-wormlike micelle growth depends directly on the number of dissociated counterions in the polar shell.

Metal-coordinated hydrogels are physical hydrogels entirely crosslinked by complexes between ligand decorated polymers and metal ions. The mechanical properties of these hydrogels strongly depend on the density and dynamics of...