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Creators/Authors contains: "Lima, Thamires"

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  1. Abstract Laser zone‐drawing is shown to significantly enhance control over nanofiber properties. This study investigates the dynamics of nanofiber laser zone‐drawing. It is hypothesized that the equilibrium between heating and cooling guides fiber temperature. The high heating rate of laser irradiation and the high convective cooling rate of nanofibers facilitate fast heating and cooling kinetics. Results showed fiber thinning in the presence of laser irradiation until reaching a steady‐state diameter. Final fiber diameter is correlated to laser power independent of initial fiber diameter. The relationship between final fiber diameter and laser power is used to estimate the heat transfer coefficient, which is used to create a computational model of the thermodynamic system. These simulations predict rapid heating and cooling up to 36 000 K min−1for the lowest fiber diameters tested experimentally. While laser‐induced softening of polymer nanofibers is described in detail, the forces driving fiber drawing, particularly under different thermal kinetics, remain unexplored. This research showcases the capabilities of laser zone‐drawing in nanofiber manufacturing and facilitates future investigations aimed at enhancing fiber processing by producing highly aligned molecular structures via rapid cooling. This work signifies a pivotal methodological leap, promising transformative nanofiber materials useful across multiple industries including aerospace, electronics, and biomedicine. 
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  2. 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. 
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  3. Post-drawn PCL nanofibers can be molecularly tuned to have a variety of mechanical properties and drug release profiles depending on the temperature and time of annealing, which has implications for regenerative medicine and drug delivery applications. Post-drawing polycaprolactone (PCL) nanofibers has previously been demonstrated to drastically increase their mechanical properties. Here the effects of annealing on post-drawn PCL nanofibers are characterized. It is shown that room temperature storage and in vivo temperatures increase crystallinity significantly on the order of weeks, and that high temperature annealing near melt significantly increases crystallinity and molecular orientation on the order of minutes. The kinetics of crystallization were assessed using an anneal and quench approach. High temperature annealing also increased the ultimate tensile strength and toughness of the fibers and changed the release profile of a model drug absorbed in PCL nanofibers from first-order to zero-order kinetics. 
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  6. 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. 
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