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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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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Control of Peptide Amphiphile Supramolecular Nanostructures by Isosteric Replacements

Supramolecular nanostructures with tunable properties can have applications in medicine, pharmacy, and biotechnology. In this work, we show that the self-assembly behavior of peptide amphiphiles (PAs) can be effectively tuned by replacing the carboxylic acids exposed to the aqueous media with isosteres, functionalities that share key physical or chemical properties with another chemical group. Transmission electron microscopy, atomic force microscopy, and small-angle X-ray scattering studies indicated that the nanostructure’s morphologies are responsive to the ionization states of the side chains, which are related to their pK a values. Circular dichroism studies revealed the effect of the isosteres on the internal arrangement of the nanostructures. The interactions between diverse surfaces and the nanostructures and the effect of salt concentration and temperature were assessed to further understand the properties of these self-assembled systems. These results indicate that isosteric replacements allow the pH control of supramolecular morphology by manipulating the pK a of the charged groups located on the nanostructure’s surface. Theoretical studies were performed to understand the morphological transitions that the nanostructures underwent in response to pH changes, suggesting that the transitions result from alterations in the Coulomb forces between PA molecules. Furthermore, this work provides a strategy for designing biomaterials that can maintain or change behaviors based on the pH differences found within cells and tissues.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Supramolecular Interactions and Morphology of Self-Assembling Peptide Amphiphile Nanostructures

The morphology of supramolecular peptide nanostructures is difficult to predict given their complex energy landscapes. We investigated peptide amphiphiles containing β-sheet forming domains that form twisted nanoribbons in water. We explained the morphology based on a balance between the energetically favorable packing of molecules in the center of the nanostructures, the unfavorable packing at the edges, and the deformations due to packing of twisted β-sheets. We find that morphological polydispersity of PA nanostructures is determined by peptide sequences, and the twisting of their internal β-sheets. Here, we also observed a change in the supramolecular chirality of the nanostructures as the peptide sequence was modified, although only amino acids with l-configuration were used. Upon increasing charge repulsion between molecules, we observed a change in morphology to long cylinders and then rodlike fragments and spherical micelles. Understanding the self-assembly mechanisms of peptide amphiphiles into nanostructures should be useful to optimize their well-known functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Symmetric nanostructuring and plasmonic excitation of gold nanostructures by femtosecond Laguerre – Gaussian laser beams

Femtosecond low-energy Laguerre – Gaussian pulses of tightly focused visible laser radiation were employed for single-pulse ablative nanostructuring of a 50-nm thick gold film. Similar pulses of lower energy were employed for the efficient plasmonic photoluminescence excitation of a rhodamine 6G dye monolayer in the fabricated nanostructures. The consistency between the shape and polarisation symmetries of the low-energy laser beam, on the one hand, and the gold nanostructures produced by the same beam at a high radiation energy, on the other hand, opens the way to consistent nanostructuring and surface-enhanced analytical spectroscopy with the use of nanostructures. (interaction of laser radiation with matter)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Electrolyte-phobic Surface for the Next-Generation Nanostructured Battery Electrodes

Nanostructured electrodes are among the most important candidates rationally designed to enable high capacity battery chemistry. Nanostructures can solve issues such as the volume change and mechanical fragmentations. However, the high surface area they usually possess would decrease the Coulombic efficiencies, since the side chemical reactions scale with surface area. Moreover, electrodes comprised of nanomaterials have significant intakes of liquid electrolytes, which reduces the overall energy density and increases the cost of the battery. Here we present a new strategy of limiting effective surface area by introducing an “electrolyte-phobic surface”. In this study, a porous Si anode functions as a model material to demonstrate this concept. Silicon boasts high theoretical capacity, but experiences large volume change during its lithiation and delithiation processes. Porous Si can address this volume change problem with the buffer effect of its inner pores. However, porous silicon shows low initial Coulombic efficiencies and high irreversible lithium loss, owing to its intrinsic high surface area. In this report, a covalently linked perfluorinated surface coating layer on porous Si particles serves as an electrolyte-phobic protection layer, minimizing the accessible surface area for the electrolytes, decreasing the side reactions between the electrolyte and Si surface, and thus significantly enhancing the initial Coulombic efficiencies, up to ~88% compared to ~60% for the pristine porous silicon. Meanwhile, the electrolyte-phobic protection layer of Si particles keeps the silicon surface compatible with the conventional polyvinylidene fluoride (PVDF) binder, which helps to stabilize the Si electrode for long-term battery cycling.

Qian, Chenxi↗
DOE OSTI2021

Flow and extraction of energy and charge carriers in hybrid plasmonic nanostructures

Strong interactions of electromagnetic fields with plasmonic nanomaterials have been exploited in various applications. These applications have centred on plasmon-enhanced scattering rates in nearby molecules or plasmon-induced heating. A question that has emerged recently is whether it is possible to use plasmonic nanostructures in a range of hot electron (hole) applications, including photocatalysis, photovoltaics and photodetection. These applications require coupling of a plasmonic component, which amplifies the interaction of light with the material, to an attached non-plasmonic component that extracts this energy in the form of electronic excitations to perform a function. Here, in this Perspective, we discuss recent work in the emerging field of hybrid plasmonics. We focus on fundamental questions related to the nanoscopic flow of energy and excited charge carriers in these multicomponent materials. We also address critical misconceptions, challenges and opportunities that require more attention.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

In situ TEM observation of calcium silicate hydrate nanostructure at high temperatures

Fire poses a substantial threat to concrete structures because calcium silicate hydrate (C-S-H) is not thermally stable at high temperatures. Herein, in situ TEM at temperatures from 20 to 800 °C was conducted to study the thermal-induced structural changes in C-S-H. We captured C-S-H shrinks at an average rate of 0.02 μm{sup 2}/{sup o}C upon heating with three stages observed, including induction, constant, and rapid periods. Our observation revealed that an 800 nm pore could be healed during pore structure evolution owing to the reconstruction and deformation among C-S-H blocks. The Ca/Si ratio was dropped at higher temperatures because of the leakage of calcium ions from the C-S-H structure to form CaO precipitates. The temperature-driven phase transformation and degradation were also detected using electron diffraction that C-S-H was transformed into metastable calcium silicate minerals above 800 °C. This work provides insights into the nanoscale transformation of C-S-H at high temperatures.

36 MATERIALS SCIENCE↗