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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Cooperativity in the Aldol Condensation Using Bifunctional Mesoporous Silica–Poly(styrene) MCM-41 Organic/Inorganic Hybrid Catalysts

This work explores the efficacy of silica/organic hybrid catalysts, where the organic component is built from linear aminopolymers appended to the silica support within the support mesopores. Specifically, the role of molecular weight and polymer chain composition in amine-bearing atom transfer radical polymerization-synthesized poly(styrene-co-2-(4-vinylbenzyl)isoindoline-1,3-dione) copolymers is probed in the aldol condensation of 4-nitrobenzaldehyde and acetone. Controlled polymerization produces protected amine-containing poly(styrene) chains of controlled molecular weight and dispersity, and a grafting-to thiol–ene coupling approach followed by a phthalimide deprotection step are used to covalently tether and activate the polymer hybrid catalysts prior to the catalytic reactions. Site-normalized batch kinetics are used to assess the role of polymer molecular weight and chain composition in the cooperative catalysis. Lower-molecular-weight copolymers are demonstrated to be more active than catalysts built from only molecular organic components or from higher-molecular-weight chains. Molecular dynamics simulations are used to probe the role of polymer flexibility and morphology, whereby it is determined that higher-molecular-weight hybrid structures result in congested pores that inhibit active site cooperativity and the diffusivity of reagents, thus resulting in lower rates during the reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Metal–Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO 2 Reduction at Low Overpotentials

Biological and heterogeneous catalysts for the electrochemical CO 2 reduction reaction (CO 2 RR) often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over the hydrogen evolution reaction (HER). Here, we report a molecular iron(II) system that captures this design concept in a homogeneous setting through the use of a redox non-innocent terpyridine-based pentapyridine ligand (tpyPY2Me). As a result of strong metal-ligand exchange coupling between the Fe(II) center and ligand, [Fe(tpyPY2Me)] 2+ exhibits redox behavior at potentials 640 mV more positive than the isostructural [Zn(tpyPY2Me)] 2+ analog containing the redox-inactive Zn(II) ion. This shift in redox potential is attributed to the requirement for both an open-shell metal ion and a redox non-innocent ligand. The metal-ligand cooperativity in [Fe(tpyPY2Me)] 2+ drives the electrochemical reduction of CO 2 to CO at low overpotentials with high selectivity for CO 2 RR (>90%) and turnover frequencies of 100,000 s -1 with no degradation over 20 h. The decrease in the thermodynamic barrier engendered by this coupling also enables homogeneous CO 2 reduction catalysis in water without compromising selectivity or rates. Synthesis of the two-electron reduction product, [Fe(tpyPY2Me)] o , and characterization by X-ray crystallography, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), variable temperature NMR, and density functional theory (DFT) calculations, support assignment of an open-shell singlet electronic structure that maintains a formal Fe(II) oxidation state with a doubly reduced ligand system. Furthermore, this work provides a starting point for the design of systems that exploit metal-ligand cooperativity for electrocatalysis where the electrochemical potential of redox non-innocent ligands can be tuned through secondary metal-dependent interactions.

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

Controlled Single-Electron Transfer via Metal–Ligand Cooperativity Drives Divergent Nickel-Electrocatalyzed Radical Pathways

Electrocatalysis enables the construction of C-C bonds under mild conditions via controlled formation of carbon-centered radicals. For sequences initiated by alkyl halide reduction, coordinatively unsaturated Ni complexes commonly serve as single-electron transfer agents, giving rise to the foundational question of whether outer- or inner-sphere electron transfer oxidative addition prevails in redox mediation. Indeed, rational design of electrochemical processes requires the discrimination of these two electron transfer pathways, as they can have outsized effects on the rate of substrate bond activation and thus impact radical generation rates and downstream product selectivities. We present results from combined synthetic, electroanalytical, and computational studies that examine the mechanistic differences of single electron transfer to alkyl halides imparted by Ni metal-ligand cooperativity. Electrogenerated reduced Ni species, stabilized by delocalized spin density onto a redox-active tpyPY2Me polypyridyl ligand, activates alkyl iodides via outer-sphere electron transfer, allowing for the selective activation of alkyl iodide substrates over halogen atom donors and the controlled generation and sequestration of electrogenerated radicals. In contrast, the Ni complex possessing a redox-innocent pentapyridine congener activates the substrates in an inner-sphere fashion owning to a purely metal-localized spin, thereby activating both substrates and halogen atom donors in an indiscriminate fashion, generating a high concentration of radicals and leading to unproductive dimerization. Overall, our data establish that controlled electron transfer via Ni-ligand cooperativity can be used to limit undesired radical recombination products and promote selective radical processes in electrochemical environments, providing a generalizable framework for designing redox mediators with distinct rate and potential requirements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Finite momentum Cooper pairing in three-dimensional topological insulator Josephson junctions

Abstract Unconventional superconductivity arising from the interplay between strong spin–orbit coupling and magnetism is an intensive area of research. One form of unconventional superconductivity arises when Cooper pairs subjected to a magnetic exchange coupling acquire a finite momentum. Here, we report on a signature of finite momentum Cooper pairing in the three-dimensional topological insulator Bi 2 Se 3 . We apply in-plane and out-of-plane magnetic fields to proximity-coupled Bi 2 Se 3 and find that the in-plane field creates a spatially oscillating superconducting order parameter in the junction as evidenced by the emergence of an anomalous Fraunhofer pattern. We describe how the anomalous Fraunhofer patterns evolve for different device parameters, and we use this to understand the microscopic origin of the oscillating order parameter. The agreement between the experimental data and simulations shows that the finite momentum pairing originates from the coexistence of the Zeeman effect and Aharonov–Bohm flux.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Colloidal fibers and rings by cooperative assembly

Abstract Janus colloids with one attractive patch on an otherwise repulsive particle surface serve as model systems to explore structure formation of particles with chemically heterogeneous surfaces such as proteins. While there are numerous computer studies, there are few experimental realizations due to a lack of means to produce such colloids with a well-controlled variable Janus balance. Here, we report a simple scalable method to precisely vary the Janus balance over a wide range and selectively functionalize one patch with DNA. We observe, via experiment and simulation, the dynamic formation of diverse superstructures: colloidal micelles, chains, or bilayers, depending on the Janus balance. Flexible dimer chains form through cooperative polymerization while trimer chains form by a two-stage process, first by cooperative polymerization into disordered aggregates followed by condensation into more ordered stiff trimer chains. Introducing substrate binding through depletion catalyzes dimer chains to form nonequilibrium rings that otherwise do not form.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Thermoelectric current in a graphene Cooper pair splitter

Generation of electric voltage in a conductor by applying a temperature gradient is a fundamental phenomenon called the Seebeck effect. This effect and its inverse is widely exploited in diverse applications ranging from thermoelectric power generators to temperature sensing. Recently, a possibility of thermoelectricity arising from the interplay of the non-local Cooper pair splitting and the elastic co-tunneling in the hybrid normal metal-superconductor-normal metal structures was predicted. Here, we report the observation of the non-local Seebeck effect in a graphene-based Cooper pair splitting device comprising two quantum dots connected to an aluminum superconductor and present a theoretical description of this phenomenon. The observed non-local Seebeck effect offers an efficient tool for producing entangled electrons.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Defective internal allosteric network imparts dysfunctional ATP/substrate-binding cooperativity in oncogenic chimera of protein kinase A

An aberrant fusion of the DNAJB1 and PRKACA genes generates a chimeric protein kinase (PKA-C DNAJB1 ) in which the J-domain of the heat shock protein 40 is fused to the catalytic α subunit of cAMP-dependent protein kinase A (PKA-C). Deceivingly, this chimeric construct appears to be fully functional, as it phosphorylates canonical substrates, forms holoenzymes, responds to cAMP activation, and recognizes the endogenous inhibitor PKI. Nonetheless, PKA-C DNAJB1 has been recognized as the primary driver of fibrolamellar hepatocellular carcinoma and is implicated in other neoplasms for which the molecular mechanisms remain elusive. Here we determined the chimera’s allosteric response to nucleotide and pseudo-substrate binding. We found that the fusion of the dynamic J-domain to PKA-C disrupts the internal allosteric network, causing dramatic attenuation of the nucleotide/PKI binding cooperativity. Our findings suggest that the reduced allosteric cooperativity exhibited by PKA-C DNAJB1 alters specific recognitions and interactions between substrates and regulatory partners contributing to dysregulation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Confinement and asymptotic freedom with Cooper pairs

One of the most profound aspects of the standard model of particle physics, the mechanism of confinement binding quarks into hadrons, is not sufficiently understood. The only known semiclassical mechanism of confinement, mediated by chromo-electric strings in a condensate of magnetic monopoles still lacks experimental evidence. Here we show that the infinite resistance superinsulating state, which emerges on the insulating side of the superconductor insulator transition in superconducting films offers a realization of confinement that allows for a direct experimental access. We find that superinsulators realize a single-color version of quantum chromodynamics and establish the mapping of quarks onto Cooper pairs. We reveal that the mechanism of superinsulation is the linear binding of Cooper pairs into neutral “mesons” by electric strings. Here, our findings offer a powerful laboratory for exploring and testing the fundamental implications of confinement, asymptotic freedom, and related quantum chromodynamics phenomena via the desktop experiments on superconductors.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Direct Probe of the Interior of an Electric Pion in a Cooper Pair Superinsulator.

The nature of hadrons is one of the most fundamental mysteries of physics. It is generally agreed that they are made of "colored" quarks, which move nearly free at short scales but are confined inside hadrons by strong interactions at large distances. Because of confinement, quarks are never directly observable and, experimentally, their properties can be tested only indirectly, via high energy collisions. Here we show that superinsulating films realize a complete, one-color model system of hadron physics with Cooper pairs playing the role of quarks. We report measurements on highly controlled NbTiN films that provide a window into the interior of "Cooper pair mesons" and present the first direct evidence of asymptotic freedom, `t Hooft's dual superconductivity confinement mechanism, and magnetic monopoles.

Diamantini, M. C.↗
DOE OSTI2022

Long-range cooperative resonances in rare-earth ion arrays inside photonic resonators

Engineering arrays of active optical centers to control the interaction Hamiltonian between light and matter has been the subject of intense research recently. Collective interaction of atomic arrays with optical photons can give rise to directionally enhanced absorption or emission, which enables engineering of broadband and strong atom-photon interfaces. Here, we report on the observation of long-range cooperative resonances in an array of rare-earth ions controllably implanted into a solid-state lithium niobate micro-ring resonator. We show that cooperative effects can be observed in an ordered ion array extended far beyond the light’s wavelength. We observe enhanced emission from both cavity-induced Purcell enhancement and array-induced collective resonances at cryogenic temperatures. Engineering collective resonances as a paradigm for enhanced light-matter interactions can enable suppression of free-space spontaneous emission. The multi-functionality of lithium niobate hosting rare-earth ions can open possibilities of quantum photonic device engineering for scalable and multiplexed quantum networks.

42 ENGINEERING↗
DOE OSTI2015

Resonant tunneling of fluctuation Cooper pairs

Superconducting fluctuations have proved to be an irreplaceable source of information about microscopic and macroscopic material parameters that could be inferred from the experiment. According to common wisdom, the effect of thermodynamic fluctuations in the vicinity of the superconducting transition temperature, T c , is to round off all of the sharp corners and discontinuities, which otherwise would have been expected to occur at T c . Here we report the current spikes due to radiation-induced resonant tunneling of fluctuation Cooper pairs between two superconductors which grow even sharper and more pronounced upon approach to T c . This striking effect offers an unprecedented tool for direct measurements of fluctuation Cooper pair lifetime, which is key to our understanding of the fluctuation regime, most notably to nature of the pseudogap state in high-temperature superconductors. Lastly, our finding marks a radical departure from the conventional view of superconducting fluctuations as a blurring and rounding phenomenon.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Cooperative valorization of lignin and residual sugar to polyhydroxyalkanoate (PHA) for enhanced yield and carbon utilization in biorefineries

Lignin valorization is essential for a sustainable and economically viable biorefinery. Despite the recent efforts, it is still unclear how the reactivity of native lignin can be improved by pretreatment in a biorefinery and how different components in biorefinery residue especially residual sugar contribute to bioconversion in biorefineries. In the present study, co-utilization of lignin and limited glucose was first evaluated and proved to facilitate lignin conversion and polyhydroxyalkanoate (PHA) production. A new integrated biorefinery was then designed to cooperatively valorize lignin and residual sugar for improving the PHA yield and utilization efficiency of biorefinery residue. By the design of integrated biorefinery, the glucose and xylose yield were 91% and 73%, respectively, which increased by 18% and 12% compared with that only using sodium hydroxide pretreatment. Approximately 85% of the lignin was dissolved into a liquid stream with the integrated biorefinery, corresponding to an increase of 69% compared with that only using sodium hydroxide pretreatment. More than 70% of the residual sugar was released from the biorefinery residue, producing the soluble lignin stream that contains both lignin and residual sugar for synergistic bioconversion. Bioconversion of the soluble lignin stream with Pseudomonas putida KT2440 produced 1.5 g l -1 PHA, representing the record titer of PHA from biorefinery residue. The lignin characterization results from nuclear magnetic resonance and gel-permeation chromatography showed that the integrated process significantly reduced the lignin molecular weight, broke down more β-O-4 and β-5 linkages, and enriched the H-lignin content. Alongside the increased residual sugar concentration, the bioconversion performance of soluble lignin to PHA was significantly improved. Altogether, the integrated biorefinery increased the fermentable sugar yield and improved the PHA production from biorefinery waste by cooperative valorization of lignin and residual sugar, which shows potential advantages for biorefinery sustainability.

09 BIOMASS FUELS↗
DOE OSTI2013

Cooperative effect of ultraviolet and near-infrared beams in laser-induced condensation

We demonstrate the cooperative effect of near infrared (NIR) and ultraviolet (UV) beams on laser-induced condensation. Launching a UV laser after a NIR pulse yields up to a 5-fold increase in the production of nanoparticles (25–300 nm) as compared to a single NIR beam. This cooperative effect exceeds the sum of those from the individual beams and occurs for delays up to 1 μs. We attribute it to the UV photolysis of ozone created by the NIR pulses. The resulting OH radicals oxidize NO{sub 2} and volatile organic compounds, producing condensable species.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Lattice architecture effect on the cooperativity of spin transition coordination polymers

We have investigated in the framework of the Ising-like model, by means of Monte Carlo Metropolis method with open boundary condition, the architecture effect on the cooperativity of spin transition coordination polymers. We have analyzed the influence of several physical parameters (size, pressure, and edge effects) on different lattice architectures which were in good agreement with reported experimental data. We show that the cooperativity of a spin crossover system, characterized by the same number of molecules and the same short- and long-range interaction parameters, is progressively enhanced when going from a 1D chain to a 1D ladder type lattice and to a 2D square lattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Maskless direct laser writing with visible light: Breaking through the optical resolving limit with cooperative manipulations of nonlinear reverse saturation absorption and thermal diffusion

In this work, the resolving limit of maskless direct laser writing is overcome by cooperative manipulation from nonlinear reverse saturation absorption and thermal diffusion, where the nonlinear reverse saturation absorption can induce the formation of below diffraction-limited energy absorption spot, and the thermal diffusion manipulation can make the heat quantity at the central region of energy absorption spot propagate along the thin film thickness direction. The temperature at the central region of energy absorption spot transiently reaches up to melting point and realizes nanolithography. The sample “glass substrate/AgInSbTe” is prepared, where AgInSbTe is taken as nonlinear reverse saturation absorption thin film. The below diffraction-limited energy absorption spot is simulated theoretically and verified experimentally by near-field spot scanning method. The “glass substrate/Al/AgInSbTe” sample is prepared, where the Al is used as thermal conductive layer to manipulate the thermal diffusion channel because the thermal diffusivity coefficient of Al is much larger than that of AgInSbTe. The direct laser writing is conducted by a setup with a laser wavelength of 650 nm and a converging lens of NA=0.85, the lithographic marks with a size of about 100 nm are obtained, and the size is only about 1/10 the incident focused spot. The experimental results indicate that the cooperative manipulation from nonlinear reverse saturation absorption and thermal diffusion is a good method to realize nanolithography in maskless direct laser writing with visible light.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Elastically Cooperative Activated Barrier Hopping Theory of Relaxation in Viscous Fluids. II. Thermal Liquids

Building on the elastically collective nonlinear Langevin equation theory developed for hard spheresin Paper I, we propose and implement a quasi-universal theory for the alpha relaxation of thermalliquids based on mapping them to an effective hard sphere fluid via the dimensionless compressibility.The result is a zero adjustable parameter theory that can quantitatively address in a unifiedmanner the alpha relaxation time over 14 or more decades. The theory has no singularities abovezero Kelvin, and relaxation in the equilibrium low temperature limit is predicted to be of a roughlyArrhenius form. The two-barrier (local cage and long range collective elastic) description results ina rich dynamic behavior including apparent Arrhenius, narrow crossover, and deeply supercooledregimes, and multiple characteristic or crossover times and temperatures of clear physical meaning.Application of the theory to nonpolar molecules, alcohols, rare gases, and liquids metals is carriedout. Overall, the agreement with experiment is quite good for the temperature dependence of thealpha time, plateau shear modulus, and Boson-like peak frequency for van der Waals liquids, thoughless so for hydrogen-bonding molecules. The theory predicts multiple growing length scales uponcooling, which reflect distinct aspects of the coupled local hopping and cooperative elastic physics.Calculations of the growth with cooling of an activation volume, which is strongly correlated with ameasure of dynamic cooperativity, agree quantitatively with experiment. Comparisons with elastic,entropy crisis, dynamic facilitation, and other approaches are performed, and a fundamental basisfor empirically extracted crossover temperatures is established. The present work sets the stage foraddressing distinctive glassy phenomena in polymer melts, and diverse liquids under strong confinement.

Mirigian, Stephen↗
DOE OSTI2014

Two color laser fields for studying the Cooper minimum with phase-matched high-order harmonic generation

We experimentally study the observation of the Cooper minimum in a semi-infinite argon-filled gas cell using two-color laser fields at wavelengths of 1400 nm and 800 nm. The experimental results show that the additional 800 nm field can change the macroscopic phase-matching condition through change of the atomic dipole phase associated with the electron in the continuum state and that this approach can be used to control the appearance of the Cooper minimum in the high-order harmonic spectrum in order to study the electronic structure of atoms and molecules.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Enhancing efficiency and power of quantum-dots resonant tunneling thermoelectrics in three-terminal geometry by cooperative effects

We propose a scheme of multilayer thermoelectric engine where one electric current is coupled to two temperature gradients in three-terminal geometry. This is realized by resonant tunneling through quantum dots embedded in two thermal and electrical resisting polymer matrix layers between highly conducting semiconductor layers. There are two thermoelectric effects, one of which is pertaining to inelastic transport processes (if energies of quantum dots in the two layers are different), while the other exists also for elastic transport processes. These two correspond to the transverse and longitudinal thermoelectric effects, respectively, and are associated with different temperature gradients. We show that cooperation between the two thermoelectric effects leads to markedly improved figure of merit and power factor, which is confirmed by numerical calculation using material parameters. Such enhancement is robust against phonon heat conduction and energy level broadening. Therefore, we demonstrated cooperative effect as an additional way to effectively improve performance of thermoelectrics in three-terminal geometry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗