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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 1,441 records · Page 80
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Polyalkenamers as Drop-In Additives for Ring-Opening Metathesis Polymerization: A Promising Upcycling Paradigm

Here we report a distinct strategy to upcycle waste polyalkenamers such as polybutadiene into new, performance-advantaged materials by using them as drop-in additives for ring-opening metathesis polymerization (ROMP). The polyalkenamers serve as competent chain-transfer agents in ROMPs of common classes of cyclic olefin monomers, facilitating good molecular weight control, allowing low Ru catalyst loadings, and enabling efficient incorporation of the polyalkenamer into the synthesized polymeric material. We successfully demonstrate ROMP using model polyalkenamers and translate these learnings to leverage commercial polybutadiene and acrylonitrile butadiene styrene (ABS) as chain transfer agents for ROMP copolymerizations. Critically, our strategy is shown to be highly efficient and operationally simple, quantitatively incorporating the polyalkenamer and inheriting aspects of its thermomechanical performance. Our results highlight a promising pathway for the upcycling of polyalkenamers and provide an alternative to existing deconstruction and functional upcycling strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Quantifying the Influences of Epoxide Binding in Epoxide/CO 2 Ring Opening Copolymerization Catalysis

Understanding and predicting the effect of epoxide structure on the rate of polymerization in epoxide/CO 2 ring opening copolymerization catalysis is a long-standing challenge. Here, a known highly active Co(III)K(I) catalyst is used to investigate the influences of six different epoxides' binding strengths on their rates of copolymerization. Since calculations and experiments indicate that studying the catalytically relevant Co(III)−epoxide adduct directly is experimentally challenging, epoxide−catalyst binding interactions are quantified using a Co(II)K(I) complex to model the key catalytic intermediate. Epoxide−catalyst coordination is investigated using UV−vis spectroscopy titrations which provide fast and effective determination of association or binding constants. The epoxide−catalyst equilibrium constants show a clear exponential correlation with copolymerization rates and a new catalyst performance linear free energy relationship is revealed. Epoxides exhibiting stronger catalyst binding constants show higher copolymerization rates. The structure−activity correlation is consistent with the polymerization kinetics, mechanism and DFT calculations. Both the methods to investigate epoxide−catalyst coordination and the linear free energy relationship are shown to apply to the series of six epoxides and a second Co(III)K(I) catalyst. These structure− performance relationships are likely applicable to other transition metal catalysts and should expedite future epoxide and catalyst selection to make useful poly(carbonate) materials.

catalysts↗
DOE OSTI2021

Small footprint optoelectrodes using ring resonators for passive light localization

The combination of electrophysiology and optogenetics enables the exploration of how the brain operates down to a single neuron and its network activity. Neural probes are in vivo invasive devices that integrate sensors and stimulation sites to record and manipulate neuronal activity with high spatiotemporal resolution. State-of-the-art probes are limited by tradeoffs involving their lateral dimension, number of sensors, and ability to access independent stimulation sites. Here, we realize a highly scalable probe that features three-dimensional integration of small-footprint arrays of sensors and nanophotonic circuits to scale the density of sensors per cross-section by one order of magnitude with respect to state-of-the-art devices. For the first time, we overcome the spatial limit of the nanophotonic circuit by coupling only one waveguide to numerous optical ring resonators as passive nanophotonic switches. With this strategy, we achieve accurate on-demand light localization while avoiding spatially demanding bundles of waveguides and demonstrate the feasibility with a proof-of-concept device and its scalability towards high-resolution and low-damage neural optoelectrodes.

42 ENGINEERING↗
DOE OSTI2021

Structural basis of the stereoselective formation of the spirooxindole ring in the biosynthesis of citrinadins

Prenylated indole alkaloids featuring spirooxindole rings possess a 3 R or 3 S carbon stereocenter, which determines the bioactivities of these compounds. Despite the stereoselective advantages of spirooxindole biosynthesis compared with those of organic synthesis, the biocatalytic mechanism for controlling the 3 R or 3 S -spirooxindole formation has been elusive. Here, we report an oxygenase/semipinacolase CtdE that specifies the 3 S -spirooxindole construction in the biosynthesis of 21 R -citrinadin A. High-resolution X-ray crystal structures of CtdE with the substrate and cofactor, together with site-directed mutagenesis and computational studies, illustrate the catalytic mechanisms for the possible β-face epoxidation followed by a regioselective collapse of the epoxide intermediate, which triggers semipinacol rearrangement to form the 3 S -spirooxindole. Comparing CtdE with PhqK, which catalyzes the formation of the 3 R -spirooxindole, we reveal an evolutionary branch of CtdE in specific 3 S spirocyclization. Our study provides deeper insights into the stereoselective catalytic machinery, which is important for the biocatalysis design to synthesize spirooxindole pharmaceuticals.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Optomechanical ring resonator for efficient microwave-optical frequency conversion

Phonons traveling in solid-state devices are emerging as a universal excitation for coupling different physical systems. Phonons at microwave frequencies have a similar wavelength to optical photons in solids, enabling optomechanical microwave-optical transduction of classical and quantum signals. It becomes conceivable to build optomechanical integrated circuits (OMIC) that guide both photons and phonons and interconnect photonic and phononic devices. Here, we demonstrate an OMIC including an optomechanical ring resonator (OMR), where co-resonant infrared photons and GHz phonons induce significantly enhanced interconversion. The platform is hybrid, using wide bandgap semiconductor gallium phosphide (GaP) for waveguiding and piezoelectric zinc oxide (ZnO) for phonon generation. The OMR features photonic and phononic quality factors of >1 × 10 5 and 3.2 × 10 3 , respectively. The optomechanical interconversion between photonic modes achieved an internal conversion efficiency $η_i$ = (2.1 ± 0.1)% and a total device efficiency $η_{tot}$ = 0.57 x 10 -6 at a low acoustic pump power of 1.6 mW. The efficient conversion in OMICs enables microwave-optical transduction for quantum information and microwave photonics applications.

42 ENGINEERING↗
DOE OSTI2025

Active light-controlled frontal ring-opening metathesis polymerization

Frontal ring-opening metathesis polymerization (FROMP) is a promising energy-efficient approach to fabricate polymeric materials. Recent advances have demonstrated FROMP for diverse applications, including additive manufacturing, composites, and foams. However, the characteristic properties of the front are currently controlled primarily by varying the resin composition or the environmental conditions. In this work we present an approach to control FROMP of dicyclopentadiene (DCPD) using photochemical methods. A photobase generator is used to inhibit FROMP of DCPD with UV light while a photosensitizer and co-initiator are used to accelerate FROMP with blue light, enabling orthogonal active photocontrol of front velocity. In addition, photoinhibition-enabled lithographic patterning of frontal polymerizations is demonstrated. Frontal polymerizations are spatially controlled, redirected, and even split into diverging fronts. This work establishes a foundation for advanced control of frontal polymerizations, enabling innovation in traditional and additive manufacturing, as well as emerging processes like morphogenic manufacturing.

Polymer synthesis↗
DOE OSTI2025

4f-orbital covalency enables a single-crystal-to-single-crystal ring-opening isomerization in a CeIV–cyclopropenyl complex

Metal–ligand bonding interactions for f-element compounds are typically highly polarized with only minor covalent character. Whereas the 5d/6d orbitals are known to be chemically accessible for dative bonding, recent quantum chemical and spectroscopic analyses have indicated appreciable 4f/5f-orbital involvement in certain metal–ligand bonds. However, 4f-orbital covalency has not been compellingly linked to distinctive modes of chemical reactivity via rigorous comparative study and mechanistic investigation. Here a series of MIV–cyclopropenyl complexes (M = Ti, Zr, Ce, Hf, Th) are described, wherein the cerium congener exhibits a 4f-covalent Ce=Cα interaction, causing a ring-opening isomerization reaction through a single-crystal-to-single-crystal transformation. The results provide evidence for 4f-orbital covalency by demonstrating its expression in the reactivity of an f-element complex within an isostructural series of tetravalent d- and f-block metal complexes. They also provide new directions for the study of orbital covalency effects of molecular compounds in solid-state chemical transformations.

Vincenzini, Brett D↗
DOE OSTI2024

Achieving 19% efficiency in non-fused ring electron acceptor solar cells via solubility control of donor and acceptor crystallization

Non-fused ring electron acceptors (NFREAs) potentially have lower synthetic costs than their fused counterparts. However, the low backbone planarity and the presence of bulky substituents adversely affect the crystallinity of NFREAs, impeding charge transport and the formation of bicontinuous morphology in organic solar cells. Here we show that a binary solvent system can individually control the crystallization and phase separation of the donor polymer (for example, D18) and the NFREA (for example, 2BTh-2F-C 2 ). We select solvents such as chloroform and o -xylene that evaporate at different temperatures and rates and have different solubility for D18. Upon evaporation of chloroform, D18 starts to assemble into fibrils. Then, the evaporation of o-xylene induces the rapid formation of a fibril network that phase segregates 2BTh-2F-C 2 into pure domains and leads to a bicontinuous morphology. In conclusion, the well-defined interpenetrating network morphology affords an efficiency of 19.02% on small-area cells and 17.28% on 1 cm 2 devices.

14 SOLAR ENERGY↗
DOE OSTI2020

Investigating off-Hugoniot states using multi-layer ring-up targets

Abstract Laser compression has long been used as a method to study solids at high pressure. This is commonly achieved by sandwiching a sample between two diamond anvils and using a ramped laser pulse to slowly compress the sample, while keeping it cool enough to stay below the melt curve. We demonstrate a different approach, using a multilayer ‘ring-up’ target whereby laser-ablation pressure compresses Pb up to 150 GPa while keeping it solid, over two times as high in pressure than where it would shock melt on the Hugoniot. We find that the efficiency of this approach compares favourably with the commonly used diamond sandwich technique and could be important for new facilities located at XFELs and synchrotrons which often have higher repetition rate, lower energy lasers which limits the achievable pressures that can be reached.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Rotaxane rings promote oblique packing and extended lifetimes in DNA-templated molecular dye aggregates

Abstract Molecular excitons play a central role in natural and artificial light harvesting, organic electronics, and nanoscale computing. The structure and dynamics of molecular excitons, critical to each application, are sensitively governed by molecular packing. Deoxyribonucleic acid (DNA) templating is a powerful approach that enables controlled aggregation via sub-nanometer positioning of molecular dyes. However, finer sub-Angstrom control of dye packing is needed to tailor excitonic properties for specific applications. Here, we show that adding rotaxane rings to squaraine dyes templated with DNA promotes an elusive oblique packing arrangement with highly desirable optical properties. Specifically, dimers of these squaraine:rotaxanes exhibit an absorption spectrum with near-equal intensity excitonically split absorption bands. Theoretical analysis indicates that the transitions are mostly electronic in nature and only have similar intensities over a narrow range of packing angles. Compared with squaraine dimers, squaraine:rotaxane dimers also exhibit extended excited-state lifetimes and less structural heterogeneity. The approach proposed here may be generally useful for optimizing excitonic materials for a variety of applications ranging from solar energy conversion to quantum information science.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Theoretical H + O 3 rate coefficients from ring polymer molecular dynamics on an accurate global potential energy surface: assessing experimental uncertainties

Thermal rate coefficients and kinetic isotope effects have been calculated for an important atmospheric reaction H/D + O 3 → OH/OD + O2 based on an accurate permutation invariant polynomial-neural network potential energy surface, using ring polymer molecular dynamics (RPMD), quasi-classical trajectory (QCT) and variational transition-state theory (VTST) with multidimensional tunneling. The RPMD approach yielded results that are generally in better agreement with experimental rate coefficients than the VTST and QCT ones, especially at low temperatures, attributable to its capacity to capture quantum effects such as tunneling and zero-point energy. Additionally, the theoretical results support one group of existing experiments over the other. In addition, rate coefficients for the D + O 3 → OD + O 2 reaction are also reported using the same methods, which will allow a stringent assessment of future experimental measurements, thus helping to reduce the uncertainty in the recommended rate coefficients of this reaction.

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

Conductive and anti-freezing hydrogels constructed by pseudo-slide-ring networks

In this work, stretchable, tough, and anti-freezing hydrogels were prepared using partially carboxymethylated polyrotaxanes and polyacrylamides. The carboxylic acid groups of α-cyclodextrins in the polyrotaxane and the amide groups in polyacrylamide are hydrogen-bonded, affording a pseudo-slide-ring network, greatly enhancing the hydrogels’ macroscale mechanical properties, anti-freezing features, and electrical conductivity for the fabrication of a cold-temperature strain sensor.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Silver salt enabled H/D exchange at the β-position of thiophene rings: synthesis of fully deuterated thiophene derivatives

Here, we disclose a silver catalyzed H/D exchange reaction, which can introduce the deuterium atom at the β position of thiophene rings without the assistance of any coordinating groups. The advantages of this reaction include operation in open air, usage of D 2 O as the deuterium source, good tolerance to a range of functional groups and obtaining high atom% deuterium incorporation. In addition, this H/D exchange reaction is employed for direct deuteration of a thiophene based monomer, which is usually prepared by multistep synthesis from expensive deuterated starting materials.

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

Lithium calix[4]arenes: structural studies and use in the ring opening polymerization of cyclic esters

We have structurally characterized a number of lithiated calix[4]arenes, where the bridge in the calix[4]arene is thia (–S–, L S H 4 ), sulfinyl (–SO–, L SO H 4 ), sulfonyl (–SO 2 –, L SO2 H 4 ), dimethyleneoxa (–CH 2 OCH 2 –, L COC H 4 ) or methylene (–CH 2 –, LH 4 ). In the case of L 4S H 4 , interaction with LiO t Bu led to the isolation of the complex [Li 8 (L 4S ) 2 (THF) 4 ]·5THF ( 1 ·5THF), whilst similar interaction of L 4SO H 4 led to the isolation of [Li 6 (L 4SO H) 2 (THF) 2 ]·5(THF) ( 2 ·5THF). Interestingly, the mixed sulfinyl/sulfonyl complexes [Li 8 (calix[4]arene(SO)(SO 2 )(SO 1.68 ) 2 ) 2 (THF) 6 ]·8(THF) ( 3 ·8THF) and [Li 5 Na(L SO/3SO2 H) 2 (THF) 5 ]·7.5(THF) ( 4 ·7.5(THF) have also been characterized. Interaction of LiO t Bu with L SO2 H 4 and L COC H 4 afforded [Li 5 L 4SO2 (OH)(THF) 4 ]·2THF ( 5 ·2THF) and [Li 6 (L COC ) 2 (HO t Bu) 2 ]·0.78THF·1.22hexane ( 6 ·0.78THF·1.22hexane), respectively. In the case of LH 4 , reaction with LiO t Bu in THF afforded a monoclinic polymorph [LH 2 Li 2 (thf)(OH 2 ) 2 ]·3THF ( 7 ·3THF) of a known triclinic form of the complex, whilst reaction of the de-butylated analogue of LH 4 , namely de-BuLH 4 , afforded a polymeric chain structure {[Li 5 (de-BuL)(OH)(NCMe) 3 ]·2MeCN} n ( 8 ·2MeCN). For comparative catalytic studies, the complex [Li 6 (L Pr ) 2 (H 2 O) 2 ]·hexane ( 9 hexane), where L Pr2 H 2 = 1,3-di- n -propyloxycalix[4]areneH 2 , was also prepared. The molecular crystal structures of 1–9 are reported, and their ability to act as catalysts for the ring opening (co-)/polymerization (ROP) of the cyclic esters ε-caprolactone, δ-valerolactone, and rac -lactide has been investigated. In most of the cases, complex 6 outperformed the other systems, allowing for higher conversions and/or greated polymer M n .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗