Search for: All records

Abstract Spiders amplify their physical capabilities by synthesizing multiple high performing silks. Renowned for its toughness, major ampullate (MA) silk composes the spiderweb frame, providing support and absorbing high-energy impacts. In ecribellate orb-weavers, proline-rich motifs in MaSp2 proteins of MA silk are linked to a range of mechanical properties, including extensibility, elasticity, stiffness, and supercontraction. We show a modification of these motifs outside of this clade in a spider that constructs a spring-loaded web. The triangle weaver spider Hyptiotes cavatus (family Uloboridae) stores energy in the support lines of its triangular web, then rapidly releases the tension to catapult forward, collapsing the web around prey. Hyptiotes has an expanded set of MaSp2 genes which encode proteins with far higher proline contents than typical MaSp2. The predominant GPGPQ motifs present in Hyptiotes spidroins also occur abundantly in MaSp sequences of distantly related spiders that produce the most extensible dragline, implying silk protein convergence. Proline-rich MaSp2 proteins constitute half of all MA gland expression in Hyptiotes, and we show that the resulting fibers are the most proline-rich spider silk measured to date. This unique silk composition suggests a functional importance that may facilitate the spring-loaded prey capture mechanism of this species' web and may inspire the design of novel biomaterials using protein engineering. 

Marine δ¹⁸O data reveal astronomical forcing of the climate and cryosphere during the Miocene, when atmosphericPco₂was on par with emissions scenarios over the next century. This inspired hypotheses for how Milankovitch cycles, ice-ocean interactions, and greenhouse gases influence ice volume. Mass balance controls for marine and terrestrial ice sheets differ, and proxy data collected far from Antarctica provide valuable but limited insight into regional processes. We evaluate clast abundance data from Antarctic marine sedimentary records, observing a strong signal of eccentricity and precession coincident with a terrestrial ice sheet and a clear obliquity signal at the margins of a marine ice sheet. These analyses are integrated with a synthesis of proxy data, and we argue that high variance in obliquity forcing (mediated and enhanced by the ocean and atmosphere) can inhibit ice sheet growth, even when insolation forcing is conducive to glaciation. This “obliquity disruption” explains cryosphere variability before the existence of large northern hemisphere ice sheets. 

Poly- and Perfluorinated alkyl substances (PFAS) pose environmental and public health concerns. While incineration remains the most common PFAS remediation method, the complete combustion and pyrolysis mechanism of PFAS is unknown. This study aims to expand our understanding of the kinetics of gas-phase PFAS incineration by measuring the effect of difluoromethane (CHF) on propane ignition delay times (IDTs). The ignition delay times were measured by OH* emission and end-wall pressure time histories behind the reflected shock wave. Different concentrations of CH2F2 were mixed with fuel-lean propane-oxygen mixtures diluted in argon. Experiments were conducted at a nominal reflected shock pressure of P5 = 1 atm and reflected shock temperatures of 1200 < T5 < 1800 K. A new detailed chemical kinetic mechanism is presented. 135 new rate constants were computed using RRKM/ME theory, based upon stationary points computed using ANL0. The new mechanism is in excellent agreement with the measured ignition delay time. A novel sensitivity analysis helps to explain the elementary steps by which CH2F2 increases the ignition delay time. 

Mean-field microkinetic modeling is a powerful tool for catalyst design and the simulation of catalytic processes. The reaction enthalpies in a microkinetic model often need to be adjusted when changing species’ binding energies to model different catalysts, when performing thermodynamic sensitivity analyses, and when fitting experimental data. When altering reaction enthalpies, the activation energies should also be reasonably altered to ensure realistic reaction rates. The Blowers–Masel approximation (BMA) relates the reaction barrier to the reaction enthalpy. Unlike the Brønsted–Evans–Polani relationship, the BMA requires less data because only one parameter, the intrinsic activation energy, needs to be determined. We validate this application of BMA relations to model surface reactions by comparing against density functional theory data taken from the literature. By incorporating the BMA rate description into the open-source Cantera software, we enable a new workflow, demonstrated herein, allowing rapid screening of catalysts using linear scaling relationships and BMA kinetics within the process simulation software. For demonstration purposes, a catalyst screening for catalytic methane partial oxidation on 81 hypothetical metals is conducted. We compared the results with and without BMA-corrected rates. The heat maps of various descriptors (e.g., CH4 conversion, syngas yield) show that using BMA rates instead of Arrhenius rates (with constant activation energies) changes which metals are most active. Heat maps of sensitivity analyses can help identify which reactions or species are the most influential in shaping the descriptor map patterns. Our findings indicate that while using BMA-adjusted rates did not markedly affect the most sensitive reactions, it did change the most influential species.