Subtle Regulation of Scaffold Stiffness for the Optimized Control of Cell Behavior

The rigidity of extracellular matrices can impact cell fate, guide tissue development, and initiate tumor formation. Scaffolds such as hydrogels with tunable levels of stiffness have been developed to control cell adhesion, migration, and differentiation, providing suitable microenvironments for different tissue outcomes. However, studies of cell–material interactions are largely confined to biomaterials with stiffness values that are coarsely regulated, so refinements in sensitive cellular responses and optimal stiffness values that determine cell fate remain elusive. Here, a freezing temperature, as a tunable regulating factor, was introduced to freeze-drying processes to form silk fibroin (SF) scaffolds with refined control of stiffness values. Due to this control of intermediate structural conformations of SF, the scaffolds exhibited differences in stiffness values to permit refined assessments of impact on cell behavior on cell-friendly surfaces. Both in vitro and in vivo results with these scaffolds exhibited gradually changeable cell migration and differentiation outcomes, as well as differences in tissue ingrowth, demonstrating the sensitivity of cellular responses to such refined mechanical cues. The optimal vascularization capacity of these SF scaffolds was in the 3–7.4 kPa range, suggesting a key range to develop bioactive biomaterials. Systematic fine regulation of scaffold rigidity based on the present strategy provides a platform for an improved understanding of cell–material interactions and also for generating optimized microenvironments for tissue regeneration

SERS Substrate with Silk Nanoribbons as Interlayer Template

The formation of hot spots is an effective approach to improve the performance of surface-enhanced Raman scattering (SERS). Silk nanoribbons (SNRs), with a height of about 1–2 nm, and Au nanoparticles (AuNPs) were assembled by electrostatic interactions to introduce sandwich hot spot structures. These sandwich structures were optimized by tuning the ratio of SNRs and AuNPs, resulting in strong SERS signals with a sensitivity of 10–13 M and enhancement factor (EF) of 5.8 × 106. Improved SERS spectrum uniformity with relative standard deviation (RSD) about 11.2% was also achieved due to the homogeneous distribution of these hot spot structures. The inherent biocompatibility of SNRs and facile fabrication processes utilized endowed the SERS substrates significant benefits toward biomedical applications, confirmed by cytocompatibility and improved SERS bioimaging capacity in vitro. The results of this study suggest the feasibility of forming high performance bioimaging systems through the use of naturally derived materials with special nanostructures

Multiscale Self-Assembly of Mobile-Ligand Molecular Nanoparticles for Hierarchical Nanocomposites

Multiscale hierarchical morphologies are greatly desired for fabricating nanocomposites with tunable macroscopic properties, but challenges remain in precisely manipulating the spatial arrangement of nanoparticles in polymer matrices across multiple length scales. Here, we demonstrate a class of mobile-ligand nanoparticle system built upon 1 nm anionic polyoxometalate molecular nanoparticles and cationic terminated polymer chains by electrostatic interaction. The highly rearrangeable polymer chains can serve as mobile ligands to direct the polyoxometalates to align into sub-10 nm anisotropic superlattice-like nanoarrays in the bulk state. Moreover, these nanoarrays can further serve as structural units to assemble into hierarchically ordered morphologies in polymer matrices, e.g., percolated networks over hundreds of micrometers which are comprised of cylindrically packed polyoxometalate superlattices down to sub-10 nm scale. These hierarchical morphologies enable the nanocomposites with reinforced mechanical performance. The presented mobile-ligand approach can provide a paradigm to design functional polymer nanocomposites with improved properties such as mechanical reinforcement and collective optical and electronic functions

Hybrid Liquid-Crystalline Electrolytes with High-Temperature-Stable Channels for Anhydrous Proton Conduction

Modern electrochemical and electronic devices require advanced electrolytes. Liquid crystals have emerged as promising electrolyte candidates due to their good fluidity and long-range order. However, the mesophase of liquid crystals is variable upon heating, which limits their applications as high-temperature electrolytes, e.g., implementing anhydrous proton conduction above 100 °C. Here, we report a highly stable thermotropic liquid-crystalline electrolyte based on the electrostatic self-assembly of polyoxometalate (POM) clusters and zwitterionic polymer ligands. These electrolytes can form a well-ordered mesophase with sub-10 nm POM-based columnar domains, attributed to the dynamic rearrangement of polymer ligands on POM surfaces. Notably, POMs can serve as both electrostatic cross-linkers and high proton conductors, which enable the columnar domains to be high-temperature-stable channels for anhydrous proton conduction. These nanochannels can maintain constant columnar structures in a wide temperature range from 90 to 160 °C. This work demonstrates the unique role of POMs in developing high-performance liquid-crystalline electrolytes, which can provide a new route to design advanced ion transport systems for energy and electronic applications