Engineering topics

Herbert, Katie M.

Publications and source records attributed to Herbert, Katie M..

3 records

DOE OSTI2024

Stiffness anisotropy coordinates supracellular contractility driving long-range myotube-ECM alignment

The ability of cells to organize into tissues with proper structure and function requires the effective coordination of proliferation, migration, polarization, and differentiation across length scales. Skeletal muscle is innately anisotropic; however, few biomaterials can emulate mechanical anisotropy to determine its influence on tissue patterning without introducing confounding topography. Here, we demonstrate that substrate stiffness anisotropy coordinates contractility-driven collective cellular dynamics resulting in C2C12 myotube alignment over millimeter-scale distances. When cultured on mechanically anisotropic liquid crystalline polymer networks (LCNs) lacking topography, C2C12 myoblasts collectively polarize in the stiffest direction. Cellular coordination is amplified through reciprocal cell-ECM dynamics that emerge during fusion, driving global myotube-ECM ordering. Conversely, myotube alignment was restricted to small local domains with no directional preference on mechanically isotropic LCNs of the same chemical formulation. These findings provide valuable insights for designing biomaterials that mimic anisotropic microenvironments and underscore the importance of stiffness anisotropy in orchestrating tissue morphogenesis.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Circularity in polymers: addressing performance and sustainability challenges using dynamic covalent chemistries

The circularity of current and future polymeric materials is a major focus of fundamental and applied research, as undesirable end-of-life outcomes and waste accumulation are global problems that impact our society. The recycling or repurposing of thermoplastics and thermosets is an attractive solution to these issues, yet both options are encumbered by poor property retention upon reuse, along with heterogeneities in common waste streams that limit property optimization. Dynamic covalent chemistry, when applied to polymeric materials, enables the targeted design of reversible bonds that can be tailored to specific reprocessing conditions to help address conventional recycling challenges. In this review, we highlight the key features of several dynamic covalent chemistries that can promote closed-loop recyclability and we discuss recent synthetic progress towards incorporating these chemistries into new polymers and existing commodity plastics. Next, we outline how dynamic covalent bonds and polymer network structure influence thermomechanical properties related to application and recyclability, with a focus on predictive physical models that describe network rearrangement. Finally, we examine the potential economic and environmental impacts of dynamic covalent polymeric materials in closed-loop processing using elements derived from techno-economic analysis and life-cycle assessment, including minimum selling prices and greenhouse gas emissions. Throughout each section, we discuss interdisciplinary obstacles that hinder the widespread adoption of dynamic polymers and present opportunities and new directions toward the realization of circularity in polymeric materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Metastable doubly threaded [3]rotaxanes with a large macrocycle

Ring size is a critically important parameter in many interlocked molecules as it directly impacts many of the unique molecular motions that they exhibit. Reported herein are studies using one of the largest macrocycles reported to date to synthesize doubly threaded [3]rotaxanes. A large ditopic 46 atom macrocycle containing two 2,6-bis(N-alkyl-benzimidazolyl)pyridine ligands has been used to synthesize several metastable doubly threaded [3]rotaxanes in high yield (65–75% isolated) via metal templating. Macrocycle and linear thread components were synthesized and self-assembled upon addition of iron(II) ions to form the doubly threaded pseudo[3]rotaxanes that could be subsequently stoppered using azide–alkyne cycloaddition chemistry. Following demetallation with base, these doubly threaded [3]rotaxanes were fully characterized utilizing a variety of NMR spectroscopy, mass spectrometry, size-exclusion chromatography, and all-atom simulation techniques. Critical to the success of accessing a metastable [3]rotaxane with such a large macrocycle was the nature of the stopper group employed. By varying the size of the stopper group it was possible to access metastable [3]rotaxanes with stabilities in deuterated chloroform ranging from a half-life of <1 minute to ca. 6 months at room temperature potentially opening the door to interlocked materials with controllable degradation rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗