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Low molecular weight gelators (LMWGs) are the subject of intense research for a range of biomedical and engineering applications. Peptides are a special class of LMWG, which offer infinite sequence possibilities and, therefore, engineered properties. This work examines the propensity of the GxG peptide family, where x denotes a guest residue, to self-assemble into fibril networks via changes in pH and ethanol concentration. These triggers for gelation are motivated by recent work on GHG and GAG, which unexpectedly self-assemble into centimeter long fibril networks with unique rheological properties. The propensity of GxG peptides to self-assemble, and the physical and chemical properties of the self-assembled structures are characterized by microscopy, spectroscopy, rheology, and X-ray diffraction. Interestingly, we show that the number, length, size, and morphology of the crystalline self-assembled aggregates depend significantly on the x-residue chemistry and the solution conditions, i.e. pH, temperature, peptide concentration, etc. The different x-residues allow us to probe the importance of different peptide interactions, e.g. π–π stacking, hydrogen bonding, and hydrophobicity, on the formation of fibrils. We conclude that fibril formation requires π–π stacking interactions in pure water, while hydrogen bonding can form fibrils in the presence of ethanol–water solutions. These results validate and support theoretical arguments on the propensity for self-assembly and leads to a better understanding of the relationship between peptide chemistry and fibril self-assembly. Overall, GxG peptides constitute a unique family of peptides, whose characterization will aid in advancing our understanding of self-assembly driving forces for fibril formation in peptide systems. 

The tripeptide glycyl-histidyl-glycine (GHG) self-assembles into long, crystalline fibrils forming a strong hydrogel ( G ′ ∼ 50 kPa) above a critical concentration of 40 mM upon the deprotonation of its imidazole group. Spectroscopic data reveal a mixture of helically twisted β-sheets and monomers to coexist in the gel phase. 

Cationic glycylalanylglycine (GAG) self-assembles into a gel in a 55 mol% ethanol/45 mol% water mixture. The gel exhibits a network of crystalline fibrils grown to lengths on a 10 −4 –10 −5 m scale (Farrel et al. , Soft Matter , 2016, 12 , 6096–6110). Rheological data are indicative of a rather strong gel with storage moduli in the 10 kPa regime. Spectroscopic data revealed the existence of two gel phases; one forms below T = 15 °C (phase I) while the other one forms in a temperature range between 15 °C and the melting temperature of ca. 35 °C (phase II). We explored the reformation of the cationic GAG gel in 55 mol% ethanol/45 mol% water after thermal annealing by spectroscopic and rheological means. Our data reveal that even a short residence time of 5 minutes in the sol phase at 50 °C produced a delay of the gelation process and a gel of lesser strength. These observations suggest that the residence time at the annealing temperature can be used to adjust the strength of both gel phases. Our spectroscopic data show that the annealing process does not change the chirality of peptide fibrils in the two gel phases and that the initial aggregation state of the reformation process is by far more ordered for phase I than it is for phase II. In the gel phases of GAG/ethanol/water mixtures, ethanol seems to function as a sort of catalyst that enables the self-assembly of the peptide in spite of its low intrinsic propensity for aggregation. 

Abstract A parallel automated track collector is integrated with a rationally designed centrifugal spinning head to collect aligned polyacrylonitrile (PAN) nanofibers. Centrifugal spinning is an extremely promising nanofiber fabrication technology due to high production rates. However, continuous oriented fiber collection and processing presents challenges. Engineering solutions to these two challenges are explored in this study. A 3D‐printed head design, optimized through a computational fluid dynamics simulation approach, is utilized to limit unwanted air currents that disturb deposited nanofibers. An automated track collecting device has pulled deposited nanofibers away from the collecting area. This results in a continuous supply of individual aligned nanofibers as opposed to the densely packed nanofiber mesh ring that is deposited on conventional static post collectors. The automated track collector allows for simple integration of the postdraw processing step that is critical to polymer fiber manufacturing for enhancing macromolecular orientation and mechanical properties. Postdrawing has enhanced the mechanical properties of centrifugal spun PAN nanofibers, which have different crystalline properties compared with conventional PAN microfiber. These technological developments address key limitations of centrifugal spinning that can facilitate high production rate commercial fabrication of highly aligned, high‐performance polymer nanofibers.