Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “CHIRALITY”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Controlled cyclization of peptoids to form chiral diketopiperazines

The present disclosure provides improved methods for controlled cyclization of peptoid dimers to form N,N′-2,5-diketopiperazines (N,N′-2,5-DKPs) with significant selectivity. In at least some examples, selectivity is based on a serendipitous conglomeration of slow exchange of amide rotamers, steric repulsion from the degree of α-substitution, and the geometric bulk of an amine nucleophile. By varying reaction conditions, the selectivity of the reaction and formation of a particular N,N′-2,5-DKP can be switched. The cyclization works in the presence of a variety of protection groups and diverse functionalities. The teachings herein provide techniques for synthesizing N,N′-2,5-DKPs that can be readily docked with drug candidates for shuttling across the blood brain barrier. This method provides a facile way to produce substituted DKPs containing groups ready for post-modification to include docking drug candidates.

Williams, Robert F.↗
DOE OSTI2025

Ordinary and exotic mesons in the extended Linear Sigma Model

The extended Linear Sigma Model (eLSM) is a hadronic model based on the global symmetries of QCD and the corresponding explicit, anomalous, and spontaneous breaking patterns. In its basic three-flavor form, its mesonic part contains the dilaton/glueball as well as the nonets of pseudoscalar, scalar, vector, and axial–vector mesons, thus chiral symmetry is linearly realized. In the chiral limit and neglecting the chiral anomaly, only one term – within the dilaton potential – breaks dilatation invariance, and all terms are chirally symmetric. Spontaneous symmetry breaking is implemented by a generalization of the Mexican-hat potential, with explicit symmetry breaking responsible for its tilting. The overall mesonic phenomenology up to ~2 GeV is in agreement with the PDG compilation of masses and partial and total decay widths. The eLSM was enlarged in a straightforward way to include other conventional quark–antiquark nonets (pseudovector and orbitally excited vector mesons, tensor and axial-tensor mesons, radially excited (pseudo)scalar mesons, etc.), as well as two nonets of hybrid mesons, the lightest one with exotic quantum numbers J $\mathscr{PC}$ = 1 -+ not allowed for $\bar{q}q$ objects, such as the resonance π 1 (1600) and the recently discovered η 1 (1855) . In doing so, different types of chiral multiplets are introduced: heterochiral and homochiral multiplets, which differ in the way they transform under chiral transformations. Moreover, besides the scalar glueball that is present from the beginning as dilaton, other glueballs, the tensor, the pseudoscalar and the vector glueballs were coupled to the eLSM: the scalar resonance ƒ 0 (1710) turns out to be mostly gluonic, the tensor glueball couples strongly to vector mesons, and the pseudoscalar glueball couples sizably to $ππη'$ and can be assigned to X (2370) or X (2600). In all cases above, masses and decays can be analyzed allowing for a better understanding of both conventional and non-conventional mesons: whenever data are available, a comparison is performed and, when this is not the case, predictions of decay widths and decay ratios are outlined. The eLSM contains chiral partners on an equal footing and is therefore well suited for studies of chiral symmetry restoration at nonzero temperature and densities: this is done by coupling it to the Polyakov loop. Finally, the QCD phase diagram and the location of the critical endpoint were investigated within this framework.

Chiral symmetry↗
DOE OSTI2024

Giant Apparent Optical Circular Dichroism in Thin Films of Bismuth-Based Hybrid Organic-Inorganic Metal Halide Semiconductor Through Preferred Orientation

Introducing chirality into organic/inorganic hybrid materials can impart chiroptical properties such as circular dichroism. The ability to tune chiroptical properties in self-assembled materials can have important implications for spintronic and optoelectronic applications. Here, a chiral organic cation, (R/S)-4-methoxy-a-methylbenzylammonium, is incorporated to synthesize the bismuth-based hybrid organic-inorganic metal halide semiconductor, (R/S-MeOMePMA)BiI4. Thin films of this Bi-based compound demonstrate large chiroptical responses, with circular dichroism anisotropy (gCD) values up to ˜0.1, close to the highest value observed in another chiral metal-halide semiconductor, (R-MBA2CuCl4). Detailed investigation reveals that this large gCD in (R/S-MeOMePMA)BiI4 is caused by the apparent CD effect. Careful selection of deposition conditions and the concomitant thin-film orientation enables the control of gCD, with maximum value observed when its thin film has a well-crystallized preferred (001) orientation parallel to the substrate. The results support a growing body of evidence that low symmetry plays an important role in achieving unusually large gCD in these chiral metal-halide materials and provides design rules for achieving large chiroptical response via morphology control.

chiroptic response↗
DOE OSTI2021

Twisted bilayer graphene. III. Interacting Hamiltonian and exact symmetries

We derive the explicit Hamiltonian of twisted bilayer graphene (TBG) with Coulomb interaction projected into the flat bands and study the symmetries of the Hamiltonian. First, we show that all projected TBG Hamiltonians can be written as positive semidefinite Hamiltonians, an example of which was found in work by Kang and Vafek [Phys. Rev. Lett. 122, 246401 (2019)]. We then prove that the interacting TBG Hamiltonian exhibits an exact U(4) symmetry in the exactly flat band (nonchiral-flat) limit. We further define, besides a first chiral limit where the AA stacking hopping is zero, a second chiral limit where the AB/BA stacking hopping is zero. In the first chiral-flat limit (or second chiral-flat limit) with exactly flat bands, the TBG is enhanced to have an exact U(4) × U(4) symmetry, whose generators are different between the two chiral limits. While in the first chiral limit and in the nonchiral case these symmetries have been found in work by Bultinck et al. [Phys. Rev. X 10, 031034 (2020)], for the eight lowest bands, we here prove that they are valid for projection into any 8 n max particle-hole symmetric TBG bands, with n max > 1 being the practical case for small twist angles < 1°. Furthermore, in the first or second chiral-nonflat limit without flat bands, an exact U(4) symmetry still remains. We also elucidate the link between the U(4) symmetry presented here and the similar but different U(4) of Kang and Vafek [Phys. Rev. Lett. 122, 246401 (2019)]. Additionally, we show that our projected Hamiltonian can be viewed as the normal-ordered Coulomb interaction plus a Hartree-Fock term from passive bands, and exhibits a many-body particle-hole symmetry which renders the physics symmetric around charge neutrality. We also provide an efficient parametrization of the interacting Hamiltonian. The existence of two chiral limits with an enlarged symmetry suggests a possible duality of the model yet undiscovered.

2-dimensional systems↗
DOE OSTI2023

THz Plasmonics and Topological Optics of Weyl Semimetals

THz magneto-optical properties of 3D topological Weyl semimetals were investigated with both THz spectroscopy and THz pump-probe measurements. The unique THz effects predicted in these materials may have important applications in THz technology. The electronic band structure was characterized spectroscopically through THz zero-field reflectance and/or cyclotron resonance measurements. The studies included the dynamic chiral pumping and the study of the predicted novel magneto-electric effects arising from the underlying Berry curvature and magneto plasmonic-like effects in the absence of an applied magnetic field. Chiral pumping in the extreme quantum limit was studied on Weyl semimetals to directly probe the chiral N=0 Landau level. Non-linear pump-probe measurements were used to measure the chiral pumping lifetime. Solids with topologically robust electronic states exhibit unusual electronic and optical transport properties that do not exist in other materials. A particularly interesting example is chiral charge pumping, the so-called chiral anomaly, in recently discovered topological Weyl and Dirac semimetals, where simultaneous application of parallel DC electric and magnetic fields creates an imbalance in the number of carriers of opposite topological charge (chirality). In an earlier study we investigated the Weyl metals Na 3 Bi and Cd 3 As 2 . In this grant we followed up with magneto-optical studies of TaAs, another Weyl semimetal. More recently, we have also characterized other Weyl and Dirac systems that have come on line. The Physics community is still looking for the “hydrogen atom” of the Weyl semimetal. CoSi is one promising new system which features Weyl node spacing comparable to the Brillouin zone size. This system may be suitable for study of the predicted chiral plasmons that arise from the Berry curvature in Weyl materials. In other experiments gates can be applied to the samples in order to study the Fermi arc surface states by modulation reflectance spectroscopy at THz frequencies.

36 MATERIALS SCIENCE↗
DOE OSTI2026

A Visual Understanding of Circular Dichroism Spectroscopy

Mapping chemical and structural properties to electronic and magnetic responses is critical to many applications such as quantum information science, where the precise storage and transmission of unique information is paramount. Specifically, constructing molecules and materials that provide strong polarized responses at tunable frequencies and with large anisotropies is key to optical processing of quantum information. Chiral molecules provide chiroptical response to circularly polarized light, making them attractive for quantum information science and other applications related to sensing, polarized photodetectors, and spintronics. Predicting a molecular design, a priori, with large anisotropies to circularly polarized light is challenging due to the complex interplay between electric and magnetic components of the optical response. In this work, we explore a visual representation of the electronic chiroptical response by decomposing the rotary strength into its constituent components. Here, we make use of the intuitive electronic oscillator framework to develop classical intuition regarding the rotary strength and its constituents. We explore three model chemical systems that exhibit local and global chirality. Our analysis reveals that local chirality necessarily exhibits competition between the local chiral center and chirality induced in other fragments of the molecule, resulting in both unexpected nonmonotonic trends and sign flips in chemically adjacent geometries. Furthermore, we can visually distinguish between local and global chirality via examination of the transition chiral tensor. Interestingly, we make strong connections to ferromagnetic and antiferromagnetic spin systems in that chiroptically inactive transitions exhibit antiferromagnetic-like alternating orbital patterns while active transitions show domain formation in an ferromagnetic-like alignment that produces a net chiroptical response.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Spin‐Polarized Interfaces Redirect CO 2 Reduction From CO to Formate

Achieving high product selectivity in electrocatalytic carbon dioxide reduction (CO 2 RR) remains a critical challenge due to competition between multiple proton-coupled electron-transfer pathways on catalyst surfaces. Meanwhile, chirality-induced spin selectivity (CISS), which enables spin-polarized electron transport through chiral interfaces, has recently emerged as a promising strategy to modulate interfacial electrochemical reactions. Although the CISS effect has been shown to enhance selectivity and efficiency in the spin-sensitive oxygen evolution reaction (OER), its role in regulating CO 2 RR pathways and in stabilizing intermediates remains largely unexplored. Here, chiral molecules (R- and S-1,1′-bi-2-naphthyl-2,2′-diyl hydrogen phosphate, BNP) were integrated with SnO 2 to construct chiral-modified catalysts (R-BNP/SnO 2 and S-BNP/SnO 2 ). Compared with bare SnO 2 and racemic BNP-modified SnO 2 (Rac-BNP/SnO 2 ), the chiral catalysts exhibited a pronounced shift in product selectivity from CO toward formate production. Importantly, in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) reveals that the chiral interface selectively stabilizes the O-bound *OCHO intermediate associated with the formate pathway and modulates interfacial water structure and hydrogen-bonding dynamics. These findings demonstrate that spin-polarized interfacial electron transfer can regulate CO 2 RR pathway selectivity by modulating the stabilization of key intermediates. More broadly, this work establishes chiral spin-selective interfaces as a new strategy for regulating competitive electrocatalytic reaction pathways.

14 SOLAR ENERGY↗