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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Crystallization and Preliminary X-ray Analysis of Der f 2, a Potent Allergen Derived from the House Dust Mite

Although a number of allergens have been identified and isolated, the underlying molecular basis for the potent immune response is poorly understood. House dust mites (Dermatophugoides sp.) are particularly ubiquitous contributors to atopy in developed countries. The rhinitis, dermatitis, and asthma associated with allergic reactions to these arthropods are often caused by relatively small (125-129 amino acids) mite proteins of unclear biological function. Der f 2, a major allergen from the mite Dermatophagoides farinae, has been recombinantly expressed and characterized. The Der f 2 protein has been crystallized in our laboratory and a native data set collected at a synchrotron source. The crystals belong to the orthorhombic space group I422 with unit cell parameters of a = 95.2 Angstroms, b = 95.2 Angstroms, and c = 103.3 Angstroms. An essentially complete (97.2%) data set has been collected to 2.4 Angstroms. Attempts to solve the crystal structure of Der f 2 by molecular replacement using the available NMR coordinates for either Der f 2 or Der p 2 (the homologous protein from D. pterovssinus) failed to reveal a creditable solution.

Roeber, Dana↗
NASA NTRS2003

Crystallization and preliminary X-ray analysis of Der f 2, a potent allergen derived from the house dust mite (Dermatophagoides farinae)

Although a number of allergens have been identified and isolated, the underlying molecular basis for the potent immune response is poorly understood. House dust mites (Dermatophagoides sp.) are ubiquitous contributors to atopy in developed countries. The rhinitis, dermatitis and asthma associated with allergic reactions to these arthropods are frequently caused by relatively small (125-129 amino acids) mite proteins of unknown biological function. Der f 2, a major allergen from the mite D. farinae, has been recombinantly expressed, characterized and crystallized. The crystals belong to the tetragonal space group I4(1)22, with unit-cell parameters a = b = 95.2, c = 103.3 A. An essentially complete (97.2%) data set has been collected to 2.4 A at a synchrotron source. Attempts to solve the crystal structure of Der f 2 by molecular replacement using the NMR coordinates for either Der f 2 or Der p 2 (the homologous protein from D. pteronyssinus) failed, but preliminary searches using the crystalline Der p 2 atomic coordinates appear to be promising.

Pyroglyphidae/chemistry/immunology↗
NASA NTRS1994

Preliminary crystallographic studies of four crystal forms of serum albumin

Several crystal forms of serum albumin suitable for three-dimensional structure determination have been grown. These forms include crystals of recombinant and wild-type human serum albumin, baboon serum albumin, and canine serum albumin. The intrinsic limits of X-ray diffraction for these crystals are in the range 0.28-0.22 nm. Two of the crystal forms produced from human and canine albumin include incorporated long-chain fatty acids. Molecular replacement experiments have been successfully conducted on each crystal form using the previously determined atomic coordinates of human serum albumin illustrating the conserved tertiary structure.

Serum Albumin/chemistry↗
NASA NTRS1989

On the Nature of Navier-stokes Turbulence

Several turbulent and nonturbulent solutions of the Navier-Stokes equations are obtained. The unaveraged equations are used numerically in conjunction with tools and concepts from nonlinear dynamics, including time series, phase portraits, Poincare sections, largest Liapunov exponents, power spectra, and strange attractors. Initially neighboring solutions for a low-Reynolds-number fully developed turbulence are compared. The solutions, separate exponentially with time, having a positive Liapunov exponent. Thus the turbulence is characterized as chaotic. In a search for solutions which contrast with the turbulent ones, the Reynolds number is reduced. Several qualitatively different flows are noted. These are, fully chaotic, complex period, weakly chaotic, simple periodic, and fixed-point. Of these, only the fully chaotic flows are classified as turbulent. Those flows have both a positive Liapunov exponent and Poincare sections without pattern. By contrast, the weakly chaotic flows have some pattern in their Poincare sections. The fixed-point and periodic flows are nonturbulent, since turbulence, is both time-dependent and aperiodic. Turbulent solutions are obtained in which energy cascades from large to small-scale motions. In general, the spectral energy transfer takes place between wavenumber bands that are considerably separated. The special transfer can occur either as a result of nonlinear turbulence self-interaction or by interaction of turbulence with mean gradients. Turbulent systems are compared with those studied in kinetic theory. The two types of systems are fundamentally different (continuous and dissipative as opposed to discrete and conservative), but there are similarities. For instance, both are nonlinear and show sensitive dependence on initial conditions. Also, the turbulent and molecular stress tensors are identical if the macroscopic velocities for the turbulent stress are replaced by molecular velocities.

Deissler, Robert G.↗
DOE OSTI2021

Replacing Pyridine with Pyrazine in Molecular Cobalt Catalysts: Effects on Electrochemical Properties and Aqueous H2 Generation

Four new molecular Co(II)tetrapyridyl complexes were synthesized and evaluated for their activity as catalysts for proton reduction in aqueous environments. The pyridine groups around the macrocycle were substituted for either one or two pyrazine groups. Single crystal X-ray analysis shows that the pyrazine groups have minimal impact on the Co(II)–N bond lengths and molecular geometry in general. X-band EPR spectroscopy confirms the Co(II) oxidation state and the electronic environment of the Co(II) center are only very slightly perturbed by the substitution of pyrazine groups around the macrocycle. The substitution of pyrazine groups has a substantial impact on the observed metal- and ligand-centered reduction potentials as well as the overall H2 catalytic activity in a multimolecular system using the [Ru(2,2′-bipyridine)3]Cl2 photosensitizer and ascorbic acid as a sacrificial electron donor. The results reveal interesting trends between the H2 catalytic activity for each catalyst and the driving force for electron transfer between either the reduced photosensitizer to catalyst step or the catalyst to proton reduction step. The work presented here showcases how even the difference of a single atom in a molecular catalyst can have an important impact on activity and suggests a pathway to optimize the photocatalytic activity and stability of molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

High Spectral Resolution Lidar Measurements of Extinction and Particle Size in Clouds

The University of Wisconsin High Spectral Resolution Lidar (HSRL) measures optical properties of the atmosphere by separating the Doppler broadened molecular backscatter return from the unbroadened aerosol return. In the past, the HSRL employed a 150 mm diameter Fabry-Perot etalon to separate the aerosol and molecular signals. The replacement of the etalon with an I2 absorption filter significantly improved the ability of the HSRL to separate weak molecular signals inside dense clouds.

Eloranta, E. W.↗
DOE OSTI2025

Exploring Microphase Separation in Semi-Fluorinated Diblock Copolymers: A Combined Experimental and Modeling Investigation

We report the combined experimental and theoretical study of the bulk self-assembly behavior of polystyrene-blockpoly( 2,3,4,5,6-pentafluorostyrene) diblock copolymers. These block copolymers were designed to create highly antagonistic blocks (with a high Flory−Huggins interaction parameter, χ) with minimum disruption to the molecular construct (i.e., only replacing five hydrogen atoms with five fluorine atoms). A large library of diblock copolymers (41 samples) was synthesized by reversible addition− fragmentation chain transfer (RAFT) polymerization to map out a major portion of the phase space. All block copolymers exhibited narrow molecular weight distributions with dispersity (D) values between 1.07 and 1.32, and subsequent thermal annealing revealed phase separation into well-defined nanoscale morphologies depending on their molecular composition, as determined from small-angle X-ray scattering and transmission electron microscopy analyses, with an experimental phase diagram being constructed. The χ value at 25 °C for this block copolymer was estimated to be 0.2 using strong segregation theory, based on trends in phase-separated domain spacing and interfacial width. When applying theoretical approaches, the majority of the domain spacing data trends were captured by a coil−coil diblock copolymer model; however, a better fit to the data for samples with shorter fluorinated blocks was obtained with a rod−coil model, indicating that the chains in these fluorinated blocks likely have a higher inherent stiffness and were thus rod-like. This observation demonstrates that, due to the very high value of χ, a transition from coil−coil to rod−coil behavior can be obtained purely by reducing the length of the stiffer of the two blocks and without varying temperature or the chemical composition of the polymers. Here, this work showcases the presence of strong microphase separation within AB diblock copolymers despite the relatively similar chemical composition of the constituent “A” and “B” units, with a clear transition from rod−coil to coil−coil segregation behavior.

RAFT polymerization↗
DOE OSTI2024

Synthesis and characterization of biobased copolyesters based on pentanediol: (2) Poly(pentylene adipate–co–terephthalate)

Traditionally, most flexible food packaging is made of linear low-density polyethylene (LLDPE) which cannot easily be recycled, nor will it degrade in a reasonable timescale. In this work, a biobased biodegradable polyester alternative was investigated as a possible replacement for LLDPE. High molecular weight poly (pentylene adipate-co-terephthalate) with a 40/60 adipic acid/terephthalic acid mole ratio was synthesized using direct esterification and polycondensation. Glycerol and hexane-1,2,5,6-tetrol were added as branching agents to better match the structure of the LLDPE which in turn might help the ability of these materials in film-blowing. Thermal, mechanical, and rheological properties of the copolyesters were thoroughly investigated. All copolyesters had a weight-average molecular weight of over 140,000 g/mol, which is necessary for proper rheology, and were thermally stable up to 350°C. Here, the addition of branching agents led to a slight decrease in crystallinity, d-spacing, melting temperature, enthalpy of melting, stress at break, and elongation at break. However, an increase in Young's modulus and complex viscosity at high frequency were observed compared to PPeAT60 without branching agent added. Although the improved crystallinity and mechanical properties of the copolyesters made them viable for film-blowing, the slow crystallization rate creates a major challenge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

The HITRAN2016 Molecular Spectroscopic Database

This paper describes the contents of the 2016 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2012 and its updates during the intervening years. The HITRAN molecular absorption compilation is composed of five major components: the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, collision-induced absorption data, aerosol indices of refraction, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, added line-shape formalisms, and validity. Moreover, molecules, isotopologues, and perturbing gases have been added that address the issues of atmospheres beyond the Earth. Of considerable note, experimental IR cross-sections for almost 300 additional molecules important in different areas of atmospheric science have been added to the database. The compilation can be accessed through www.hitran.org. Most of the HITRAN data have now been cast into an underlying relational database structure that offers many advantages over the long-standing sequential text-based structure. The new structure empowers the user in many ways. It enables the incorporation of an extended set of fundamental parameters per transition, sophisticated line-shape formalisms, easy user-defined output formats, and very convenient searching, filtering, and plotting of data. A powerful application programming interface making use of structured query language (SQL) features for higher-level applications of HITRAN is also provided.

HITRAN↗
DOE OSTI2021

Mechanistic Duality of Bacterial Efflux Substrates and Inhibitors: Example of Simple Substituted Cinnamoyl and Naphthyl Amides

Antibiotic resistance poses an immediate and growing threat to human health. Multidrug efflux pumps are promising targets for overcoming antibiotic resistance with small-molecule therapeutics. Previously, we identified a diaminoquinoline acrylamide, NSC-33353, as a potent inhibitor of the AcrAB–TolC efflux pump in Escherichia coli. This inhibitor potentiates the antibacterial activities of novobiocin and erythromycin upon binding to the membrane fusion protein AcrA. It is also a substrate for efflux and lacks appreciable intrinsic antibacterial activity of its own in wild-type cells. Here, we have modified the substituents of the cinnamoyl group of NSC-33353, giving rise to analogs that retain the ability to inhibit efflux, lost the features of the efflux substrates, and gained antibacterial activity in wild-type cells. The replacement of the cinnamoyl group with naphthyl isosteres generated compounds that lack antibacterial activity but are both excellent efflux pump inhibitors and substrates. Surprisingly, these inhibitors potentiate the antibacterial activity of novobiocin but not erythromycin. Surface plasmon resonance experiments and molecular docking suggest that the replacement of the cinnamoyl group with naphthyl shifts the affinity of the compounds away from AcrA to the AcrB transporter, making them better efflux substrates and changing their mechanism of inhibition. These results provide new insights into the duality of efflux substrate/inhibitor features in chemical scaffolds that will facilitate the development of new efflux pump inhibitors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Tribological studies of a novel high-performance aromatic thermosetting copolyester containing carbon nanotubes for artificial hip joints

A high-performance aromatic thermosetting copolyester containing multi-walled carbon nanotubes (ATSP-MWNTs) was synthesized, characterized, and tribologically tested against cobalt-chromium-molybdenum (CoCrMo) alloy) as a potential replacement for ultra-high molecular weight polyethylene (UHMWPE) in artificial joints. By investigating the tribological properties of ATSP-MWNTs, crosslinked UHMWPE vs CoCrMo alloy, it was found that ATSP-MWNTs exhibited a lower and more stable friction coefficient and negligible wear. Further, unlike the case of ATSP-MWNTs, an obvious wear was present for UHMWPE. It is believed that transfer films in ATSP-MWNTs help to stabilize and decrease friction and wear. In addition, large and aggregated particles of UHMWPE seem to contribute to an increase in friction and wear.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1966

Approximation of molecular integrals.

Approximation method for molecular integrals that depends on replacement of two-center charge distributions by single-center distributions, giving results in terms of Coulomb type integrals

COULOMB POTENTIAL↗
DOE OSTI2025

Emergent Above-Gap Photoluminescence in Molecularly Engineered Hybrid Bilayer Crystals

Bilayer crystals, built by stacking two-dimensional (2D) covalent monolayers, give rise to coupled excitonic states whose properties are constrained by fixed lattice symmetry and orientation. Replacing one covalent monolayer with a 2D molecular crystal––held together by non-covalent forces––overcomes this limitation, as molecular functional groups afford tunable in-plane lattice geometry, intermolecular spacing, and interlayer coupling, providing a powerful knob for exciton engineering. Here, in this study, we report four-atom-thick hybrid bilayer crystals (HBCs) synthesized by directly growing single-crystalline PDI molecular crystal atop WS 2 monolayers, which exhibit a robust photoluminescence (PL) peak 120 meV above the WS 2 optical band gap alongside a belowgap emission. Both peaks display strong polarization anisotropy—nearing unity for the above-gap emission—and maintain a perfectly linear power-law dependence up to an excitation density of ~10 7 mW/cm 2 , indicative of coexisting localized and delocalized excitonic states. Substituting PDI with a PTCDA monolayer on WS 2 fully quenches PL, demonstrating molecular control over excitonic emission. Lattice scale ab initio GW and GW-BSE calculations reveal a significantly hybridized bilayer band structure in PDI/WS 2 that supports interlayer excitonic species both above and below the WS 2 gap with strong polarization anisotropy, in excellent agreement with experiment. Our work introduces a molecule-based bilayer platform for the bottom-up design and control of excitonic phenomena in atomically thin optoelectronic and quantum materials.

2D materials↗
DOE OSTI2022

Supervised learning and the finite-temperature string method for computing committor functions and reaction rates

A central object in the computational studies of rare events is the committor function. Though costly to compute, the committor function encodes complete mechanistic information of the processes involving rare events, including reaction rates and transition-state ensembles. Under the framework of transition path theory, Rotskoff et al. [Proceedings of the 2nd Mathematical and Scientific Machine Learning Conference, Proceedings of Machine Learning Research (PLMR, 2022), Vol. 145, pp. 757–780] proposes an algorithm where a feedback loop couples a neural network that models the committor function with importance sampling, mainly umbrella sampling, which collects data needed for adaptive training. Here, in this work, we show additional modifications are needed to improve the accuracy of the algorithm. The first modification adds elements of supervised learning, which allows the neural network to improve its prediction by fitting to sample-mean estimates of committor values obtained from short molecular dynamics trajectories. The second modification replaces the committor-based umbrella sampling with the finite-temperature string (FTS) method, which enables homogeneous sampling in regions where transition pathways are located. We test our modifications on low-dimensional systems with non-convex potential energy where reference solutions can be found via analytical or finite element methods, and show how combining supervised learning and the FTS method yields accurate computation of committor functions and reaction rates. We also provide an error analysis for algorithms that use the FTS method, using which reaction rates can be accurately estimated during training with a small number of samples. The methods are then applied to a molecular system in which no reference solution is known, where accurate computations of committor functions and reaction rates can still be obtained.

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

Enhanced Catalytic Activity of a Vanadium-Doped Mesoporous Octahedral Molecular Sieve-2 (K-OMS-2) toward Hydrogen Evolution Reaction

Hydrogen evolution reaction (HER) is the cathodic reaction in electrochemical water splitting that produces H 2 in a renewable pathway, primarily to be used in fuel cells. K-OMS-2, a manganese octahedral molecular sieve, has the potential to replace Pt as a catalyst for HER due to its redox and electrochemical properties, which can be further improved by doping metal cations into the K-OMS-2 framework. In this work, we synthesized 1, 5, and 10% vanadium- (V) doped mesoporous K-OMS-2 under mild acidic reaction conditions. Here, the mesoporous nature of the samples was confirmed by BET analysis. X-ray photoelectron spectroscopy confirmed that Mn has 2+, 3 +, and 4+ oxidation states, and V is present as V 4+ in V-K-OMS-2 samples. HER performance of 1% V-K-OMS-2 in an acidic medium shows the best activity with -0.32 V overpotential. The overpotential was lowered by 0.56 V upon doping 1% V into the K-OMS-2 framework. The 1% V-K-OMS-2 material has a Tafel slope of 129 mV/decay and an electrochemically active surface area (ECSA) of 127.5 cm 2 ECSA .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

Biomaterials and scaffolds in reparative medicine

Most approaches currently pursued or contemplated within the framework of reparative medicine, including cell-based therapies, artificial organs, and engineered living tissues, are dependent on our ability to synthesize or otherwise generate novel materials, fabricate or assemble materials into appropriate 2-D and 3-D forms, and precisely tailor material-related physical and biological properties so as to achieve a desired clinical response. This paper summarizes the scientific and technological opportunities within the fields of biomaterials science and molecular engineering that will likely establish new enabling technologies for cellular and molecular therapies directed at the repair, replacement, or reconstruction of diseased or damaged organs and tissues.

Non-NASA Center↗
NASA NTRS2007

Resistively Heated SiC Nozzle for Generating Molecular Beams

An improved nozzle has been developed to replace nozzles used previously in an apparatus that generates a substantially unidirectional beam of molecules passing through a vacuum at speeds of several kilometers per second. The basic principle of operation of the apparatus is the same for both the previous and the present nozzle designs. The main working part of the nozzle is essentially a cylinder that is closed except that there is an inlet for a pressurized gas and, at one end, the cylinder is closed by a disk that contains a narrow central hole that serves as an outlet. The cylinder is heated to increase the thermal speeds of the gas molecules into the desired high-speed range. Heated, pressurized gas escapes through the outlet into a portion of the vacuum chamber that is separated, by a wall, from the rest of the vacuum chamber. In this portion of the vacuum chamber, the gas undergoes a free jet expansion. Most of the expanded gas is evacuated and thus does not become part of the molecular beam. A small fraction of the expanded beam passes through a narrow central orifice in the wall and thereby becomes a needle- thin molecular beam in the portion of the vacuum on the downstream side of the wall.

Cagiano, Steven↗
NASA NTRS1994

Solar system formation and the distribution of volatile species

To understand how the solar system formed we must understand the compositional distribution of the current system. Volatile species are particularly important in that their stability as condensed phases is limited in temperature-pressure space, and hence variations in their distribution at present potentially contain an imprint of processes by which temperature and pressure varied in the solar nebula. In this talk we restrict ourselves to species more volatile than water ice, and address issues related to processes in the outer solar system and the formation of bodies there; others in this conference will cover volatile species relevant to inner solar system processes. Study of the outer solar system is relevant both to understanding the interface between the solar nebula and the progenitor giant molecular cloud (since the chemical links to present-day observables in molecular clouds are species like methane, carbon monoxide, etc.), as well as the origin of terrestrial planet atmospheres and oceans (the latter to be covered by Owen). The wealth of compositional information on outer solar system bodies which has become available from spacecraft and ground-based observations challenges traditional simplistic views of the composition and hence dynamics of the solar nebula. The basic assumption of thermochemical equilibrium, promulgated in the 1950's, in which methane and ammonia dominate nitrogen- and carbon-bearing species, is demonstrably incorrect on both observational and theoretical grounds. However, the kinetic inhibition model which replaced it, in which carbon monoxide and molecular nitrogen dominate a nebula which is fully mixed and hence cycles outer solar system gases through a hot, chemically active zone near the disk center, is not supported either by observations. Instead, a picture of the outer solar system emerges in which the gas and grains are a mixture of relatively unaltered, or modestly altered, molecular cloud material, along with a fraction which has been chemically altered in the solar nebula itself (and perhaps giant planet nebulae).

Lunine, Jonathan I.↗