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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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As fundamental building blocks of proteins, helices take different forms including the 3 10 -, α-, and π-helices that feature distinct H-bond networks. The H-bond connectivity is shown to modulate energy transfer efficiency in protein helical structures.
This work describes the use of C–H∙∙∙F–C contacts in the solid-state from the stator towards the rotator to fine-tune their internal motion, by constructing a set of interactions that generate close-fitting cavities in three supramolecular rotors 1–3I. The crystal structures of these rotors, determined by synchrotron radiation experiments at different temperatures, show the presence of such C–H∙∙∙F–C contacts between extended carbazole stators featuring fluorinated phenyl rings and the 1,4-diazabicyclo[2.2.2]octane (DABCO) rotator. According to the 2 H NMR results, using deuterated samples, and periodic density functional theory computations, the rotators experience fast angular displacements (preferentially 120° jumps) due to their low rotational activation energies (E a = 0.8–2.0 kcal mol -1 ). The higher rotational barrier for 1 (2.0 kcal mol -1 ) is associated with a larger number of weak C–H∙∙∙F–C contacts generated by the stators. This strategy offers the possibility to explore the correlation among weak intermolecular forces, cavity shape, and internal dynamics, which has strong implications in the design of future fine-tuned amphidynamic crystals.
Solvent molecules interact with reactive species and alter the rates and selectivities of catalytic reactions by orders of magnitude. Specifically, solvent molecules can modify the free energies of liquid phase and surface species via solvation, participating directly as a reactant or co-catalyst, or competitively binding to active sites. These effects carry consequences for reactions relevant for the conversion of renewable or recyclable feedstocks, the development of distributed chemical manufacturing, and the utilization of renewable energy to drive chemical reactions. First, we describe the quantitative impact of these effects on steady-state catalytic turnover rates through a rate expression derived for a generic catalytic reaction (A → B), which illustrates the functional dependence of rates on each category of solvent interaction. Second, we connect these concepts to recent investigations of the effects of solvents on catalysis to show how interactions between solvent and reactant molecules at solid–liquid interfaces influence catalytic reactions. Furthermore, this discussion demonstrates that the design of effective liquid phase catalytic processes benefits from a clear understanding of these intermolecular interactions and their implications for rates and selectivities.
Molybdenum hexafluoride (MoF6) is used as a non-radioactive substitute for uranium to study the hydrolysis of metal hexafluorides. Molybdenum hexafluoride gas and water vapor, from the air, were sequentially layered onto a diamond substrate kept at liquid nitrogen temperature using a custom designed cryogenic cell with a copper cold finger. Reaction progress was monitored by transmission Fourier Transform Infrared Spectroscopy (FTIR) through the layers and diamond substrate over several hours while allowing the substrate to warm. Changes in the modes in the 500–1000 cm -1 region are tracked as the reaction progresses in order to identify intermediate species. Strong absorption features are also observed in the 1000–3000 cm -1 range, suggesting the presence of ionic dissociation intermediates trapped in a disordered H-bonded network of cryogenic hydrofluoric acid. Here, a possible reaction pathway is proposed and the final hydrolysis product is characterized by FTIR, UV-vis, and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS).
Choline based eutectic solvents are developed for CO 2 capture. The physical properties as a function of the H-bond donor and acceptor components are examined. Accordingly, molecular descriptors are identified for future property predictions.
This work highlights lignin-derivable, thermoplastic, non-isocyanate polyurethanes as potential alternatives to petroleum-derived analogues with increased toughness and processability due to the functionality of lignin-aromatics (methoxy groups).
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Combining results from impedance spectroscopy and oscillatory shear rheology, this study focuses on the relation between the mass and charge flows and on how these are affected by the H-bonding in viscous ionic liquids (ILs). In particular, we compare the relaxational behaviors of the paradigmatic IL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI) and its OH-functionalized counterpart 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (OHEMIM-TFSI). Our results and their analysis demonstrate that the presence of cationic OH-groups bears a strong impact on the overall dynamics of OHEMIM-TFSI, although no signatures of suprastructural relaxation modes could be identified in their dielectric and mechanical responses. To check whether at the origin of this strong variation is the H-bonding or merely the difference between the corresponding cation sizes (controlling both the hydrodynamic volume and the inter-charge distance), the present study includes 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (PMIM-TFSI), mixtures of EMIM-TFSI and PMIM-TFSI with lithium bis(trifluoromethylsulfonyl)imide (Li-TFSI), and mixtures of OHEMIM-TFSI with PMIM-TFSI. Their investigation clearly reveals that the dynamical changes induced by H-bonding are significantly larger than those that can be attributed to the change in the ion size. Moreover, in the mixtures of OHEMIM-TFSI with PMIM-TFSI, a dilution of the OH-groups leads to strong deviations from ideal mixing behavior, thus highlighting the common phenomenological ground of hydroxy-functionalized ILs and other H-bonded liquids.
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The primary goal of the proposed research was to explore the use of far-infrared (FIR) spectroscopy for providing new informal on about the solvation structure and dynamics of small ions such as Li + , Na + , and Mg 2+ in electrolyte solutions commonly used in energy-related applications. Classical and ab initio molecular dynamics simulations were to be carried out together with spectroscopic measurements to aid interpretation of the spectra generated.
Abstract not provided.
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Importance of H-bonding on stability of genetic code of DNA as expressed by Watson-Crick model and template idea