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Results for “molecular controller”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Molecular-Weight-Controlled, End-Capped Polybenzimidazoles

Novel molecular-weight-controlled end-capped poly(arylene ether benzimidazole)s (PAEBI's) prepared by nucleophilic displacement reaction of di(hydroxyl)benzimidazole monomers with activated aromatic dihalides. Polymers prepared at various molecular weights by upsetting stoichiometry of monomers and end-capped with monohydroxybenzimidazole. Exhibit favorable physical and mechanical properties, improved solubility in polar aprotic solvents and better compression moldability. Potential applications as adhesives, coatings, films, fibers, membranes, moldings, and composite matrix resins.

Connell, John W.↗
DOE OSTI2021

Surface equilibration mechanism controls the molecular packing of glassy molecular semiconductors at organic interfaces

Significance Because glasses are nonequilibrium materials, even a single-component system has an enormous number of distinct glass structures. Physical vapor deposition (PVD) is an important tool for preparing a wide range of these glasses. While the substrate can influence structure for hundreds of nanometers for crystalline and liquid crystalline systems, little is known about the structure of PVD glasses near an underlying substrate. This is important for organic electronics, as layers of PVD glasses as thin as 10 nm are used as active elements in organic light-emitting diodes, and molecular packing is vital to performance. We show that the free surface controls molecular packing of PVD glasses near a buried interface rather than the substrate, in sharp contrast with crystalline systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Closing the Gap Between Modeling and Experiments in the Self-assembly of Biomolecules at Interfaces and in Solution

Molecular self-assembly is a powerful tool in materials design, wherein non-covalent interactions like electrostatic, hydrophobic, hydrogen bonding, and van der Waals can be exploited to produce supramolecular nanostructures that are functional and highly tunable. Biomolecules are attractive building blocks, as they are biocompatible, biodegradable and adopt a wide array of higher order structures. Moreover, naturally occurring protein systems display a manifold of structures and interactions that can be replicated in synthetic biomolecules. In this perspective, we highlight advances in multiscale simulation techniques across broad spatiotemporal scales that can aid in characterizing self-assembly of hybrid and hierarchical bionanomaterial systems, with an emphasis on physics-based simulation approaches currently employed to study biomolecules at mineral interfaces. The power of these approaches is highlighted across a few recent areas where molecular simulations have advanced our understanding of self-assembly spanning peptides to protein self-assembly. Looking forward, we discuss how in the near future emerging methods in statistical and machine learning will advance this research field in all areas from expanding the capabilities of physics-based simulation methods to enabling new analyses of high throughput experiments. These advances will pave the way for understanding the molecular recognition patterns in systems that are dictated by self-assembly - biomineralizing peptides, hierarchical peptoids, and large protein assemblies, and will aid in the development of a new synthesis science for achieving precise molecular control in materials design

Sampath, Janani↗
NASA NTRS1992

Polyimide molding powder, coating, adhesive, and matrix resin

The invention is a polyimide prepared from 3,4'-oxydianiline (3,4'-ODA) and 4,4'-oxydiphthalic anhydride (ODPA), in 2-methoxyethyl ether (diglyme). The polymer was prepared in ultra high molecular weight and in a controlled molecular weight form which has a 2.5 percent offset in stoichiometry (excess diamine) with a 5.0 percent level of phthalic anhydride as an endcap. This controlled molecular weight form allows for greatly improved processing of the polymer for moldings, adhesive bonding, and composite fabrication. The higher molecular weight version affords tougher films and coatings. The overall polymer structure groups in the dianhydride, the diamine, and a metal linkage in the diamine affords adequate flow properties for making this polymer useful as a molding powder, adhesive, and matrix resin.

St.clair, Terry L.↗
DOE OSTI2022

All-optical nanoscopic spatial control of molecular reaction yields on nanoparticles

Molecular adsorbate reactions on nanoparticles play a fundamental role in areas such as nano-photocatalysis, atmospheric, and astrochemistry. They can be induced, enhanced, and controlled by field localization and enhancement on the nanoparticle surface. In particular, the ability to perform highly controlled near-field-mediated reactions is key to deepening our understanding of surface photoactivity on nanosystems. Here, using reaction nanoscopy, we experimentally demonstrate all-optical nanoscopic control of surface reaction yields by tailoring the near fields on nanoparticles with waveform-controlled linear and bicircular two-color laser pulses, respectively. We observe site-selective proton emission from the dissociative ionization of adsorbate molecules on Si O 2 nanoparticles as a function of the polarization and relative phase of the two-color pulses. The angularly resolved close-to-uniform mapping between the surface reaction yields and the measured ion momentum enables the observation and spatial control of molecular reactions on the nanoparticle surface with nanoscopic resolution. The experimental results are modeled and reproduced qualitatively by classical trajectory Monte Carlo simulations. Our work paves the way toward reliable all-optical control of photocatalytic chemical reactions on nanoscale surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Control of Molecular Bonding Strength on Metal Catalysts with Organic Monolayers for CO 2 Reduction

The development of separate levers for controlling the bonding strength of different reactive species on catalyst surfaces is challenging but essential for the design of highly active and selective catalysts. For example, during CO 2 reduction, production of CO often requires balancing a trade-off between the adsorption strength of the reactant and product states: weak binding of CO is desirable from a selectivity perspective, but weak binding of CO 2 leads to low activity. Here in this paper, we demonstrate a new method of controlling both CO 2 adsorption and CO desorption over supported metal catalysts by employing a single self-assembly step where organic monolayer films were deposited on the catalyst support. Binding of phosphonic acid monolayers on supported Pt and Pd catalysts weakened CO binding via a through-support effect. The weakened CO adsorption was generally accompanied by decreased adsorption and reactivity of CO 2 . However, by the incorporation of basic amine functions at controlled positions in the modifying film, strong CO 2 adsorption and hydrogenation reactivity could be restored. Thus, both through-surface and through-space interactions could be manipulated by design of the organic modifiers. After surface modification, the catalysts exhibited significantly improved selectivity (up to ~99% at conversions near 50%) and activity toward CO production. Moreover, the rate of deactivation was notably reduced due to prevention of CO poisoning.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Determining Key Factors for the Open-Loop Control of Molecular Fragmentation Using Shaped Strong Fields

Pulse shaping has long been employed for tailoring femtosecond laser pulses to study and control the fragmentation of polyatomic molecules. In many cases, a physical explanation connecting the properties of the field to the observed control is difficult to ascertain. We utilized 80 bit binary spectral phase functions to parametrize and map the search space, gaining insight into which pulse parameters most impact the ion yield and fragmentation pattern for the relatively large triethylamine [N(C 2 H 5 ) 3 ] molecule. Pulse structures used to control the m/z 86 branching ratio beyond a simple intensity dependence are identified and compared to pump–probe results. All of these findings are explained in terms of control via a dissociative Rydberg state in the neutral molecule. This methodology may be used to discover new control mechanisms and shed light onto which pulse parameters most influence the interaction between strong field lasers and matter.

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

Engineering Structural Transitions in a Multilevel Molecular Switch via Intermolecular Coupling

Controlling molecular conformations with atomic precision is essential for advancing molecular functional electronics, as well as our understanding of molecular dynamics. While switching between bistable molecular conformers is common in nature, creating systems with multiple, addressable states remains synthetically challenging. Here, we demonstrate a bottom-up strategy in which intermolecular interactions give rise to multilevel functionality within a simple two-molecule assembly. Using low-temperature scanning tunneling microscopy, we show that a pyrrolidine dimer on Cu(100) exhibits six distinct adsorption conformations, exceeding the four expected from two independent bistable units. This unusual complexity arises from the interplay between intermolecular van der Waals attraction and steric repulsion, which reshapes the potential energy landscape and changes a single high-energy transition into a sequential two-step pathway. Each step is driven by low-energy inelastic electron excitations, achieving a switching efficiency an order of magnitude higher than that of the monomer. Here, by tuning the bias voltage and tip–molecule distance, we achieve deterministic control over multiple stable states, establishing a general design principle for on-demand engineering of collective molecular behavior and energy-efficient multilevel molecular devices.

Molecular interactions↗
DOE OSTI2022

Molecular speciation controls arsenic and lead bioaccessibility in fugitive dusts from sulfidic mine tailings

Communities nearby mine wastes in arid and semi-arid regions are potentially exposed to high concentrations of toxic metal(loid)s from fugitive dusts deriving from impoundments. To assess the relation between potentially lofted particles and human health risk, we studied the relationship between pharmacokinetic bioaccessibility and metal(loid) molecular speciation for mine tailings dust particulate matter (PM), with elevated levels of arsenic and lead (up to 59 and 34 mmol kg -1 , respectively), by coupling in vitro bioassay (IVBA) with X-ray absorption spectroscopy (XAS). Mine tailing efflorescent salts (PM ES ) and PM from the surface crust (0–1 cm, PM SC ) and near surface (0–25 cm) were isolated to <10 μm and <150 μm effective spherical diameter (PM 10 and PM 150 ) and reacted with synthetic gastric and lung fluid for 30 s to 100 h to investigate toxic metal(loid) release kinetics. Bioaccessible (BAc) fractions of arsenic and lead were about 10 and 100 times greater in gastric than in lung fluid simulant, respectively, and 10–100% of the maximum gastric BAc from PM 10 and PM 150 occurred within 30 s, with parabolic dissolution of fine, highly-reactive particles followed by slower release from less soluble sources. Evaporite salts were almost completely solubilized in gastric-fluid simulants. Arsenate within jarosite and sorbed to ferrihydrite, and lead from anglesite, were identified by XAS as the principal contaminant sources in the near surface tailings. In the synthetic lung fluid, arsenic was released continuously to 100 h, suggesting that residence time in vivo must be considered for risk determination. Analysis of pre- and post-IVBA PM indicated the release of arsenic in lung fluid was principally from arsenic-substituted jarosite, whereas in synthetic gastric fluid arsenic complexed on ferrihydrite surfaces was preferentially released and subsequently repartitioned to jarosite-like coordination at extended exposures. Lead dissolved at 30 s was subsequently repartitioned back to the solid phase as pyromorphite in phosphate rich lung fluid. The bioaccessibility of lead in surface tailings PM was limited due to robust sequestration in plumbojarosite. Kinetic release of toxic elements in both synthetic biofluids indicated that a single IVBA interval may not adequately describe release dynamics.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2023

Scattering solution of an interacting Hamiltonian for the electronic control of molecular spin qubits

We theoretically study how a scattered electron can entangle molecular spin qubits (MSQs). This requires solving the inelastic transport of a single electron through a scattering region described by a tight-binding interacting Hamiltonian. We accomplish this using a Green's-function solution. We can model realistic physical implementations of MSQs by parametrizing the tight-binding Hamiltonian with first-principles descriptions of magnetic anisotropy and exchange interactions. As a result, we find that, for two-MSQ systems with inversion symmetry, projective measurement of the spin degree of freedom of the scattered electron offers probabilistic control of the degree of entanglement between the MSQs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Molecular-Level Control over Ionic Conduction and Ionic Current Direction by Designing Macrocycle-Based Ionomers

Poor ionic conductivity of the catalyst-binding, submicrometer- thick ionomer layers in energy conversion and storage devices is a huge challenge. However, ionomers are rarely designed keeping in mind the specific issues associated with nanoconfinement. Here, we designed nature-inspired ionomers (calix-2) having hollow, macrocyclic, calix[4]arene-based repeat units with precise, sub-nanometer diameter. In ≤100 nm-thick films, the in-plane proton conductivity of calix-2 was up to 8 times higher than the current benchmark ionomer Nafion at 85% relative humidity (RH), while it was 1-2 orders of magnitude higher than Nafion at 20-25% RH. Confocal laser scanning microscopy and other synthetic techniques allowed us to demonstrate the role of macrocyclic cavities in boosting the proton conductivity. The systematic self-assembly of calix-2 chains into ellipsoids in thin films was evidenced from atomic force microscopy and grazing incidence small-angle X-ray scattering measurements. Moreover, the likelihood of alignment and stacking of macrocyclic units, the presence of one-dimensional water wires across this macrocycle stacks, and thus the formation of long-range proton conduction pathways were suggested by atomistic simulations. We not only did see an unprecedented improvement in thin-film proton conductivity but also saw an improvement in proton conductivity of bulk membranes when calix-2 was added to the Nafion matrices. Nafion-calix-2 composite membranes also took advantage of the asymmetric charge distribution across calix[4]arene repeat units collectively and exhibited voltage-gating behavior. The inclusion of molecular macrocyclic cavities into the ionomer chemical structure can thus emerge as a promising design concept for highly efficient ion-conducting and ion-permselective materials for sustainable energy applications.

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

Polariton Control of Molecular Charge Transfer in Perylene Diimide Semiconductors

We report the modulation of molecular charge transfer in a bay-substituted perylene diimide derivative embedded in a planar distributed Bragg reflector microcavity. Angle-resolved reflectance spectra confirm the formation of upper and lower polaritons with clear Rabi splitting, indicating strong coupling between the cavity mode and molecular excitons. Using broadband transient absorption spectroscopy, we compare the ultrafast dynamics of cavity and non-cavity films. While excited-state absorption and stimulated emission pathways remain largely unchanged, kinetic modeling reveals a moderate increase in the charge transfer rate and yield under strong coupling. This enhancement is attributed to a reduction in the effective driving force via the formation of the lower polariton, placing the system deeper into the Marcus inverted regime. Our results demonstrate a promising non-chemical method leveraging cavity quantum electrodynamics to modulate charge separation processes in molecular semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗