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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Determination of Residual Stress in Composite Materials Using Ultrasonic Waves

The performance of high temperature composites can be significantly affected by the presence of residual stresses. These stresses arise during cooling processes from fabrication to room temperature due to mismatch of thermal expansion coefficients between matrix and fiber materials. This effect is especially pronounced in metal matrix and intermetallic composites. It can lead to plastic deformations, matrix cracking and fiber/matrix interface debonding. In this work the feasibility of ultrasonic techniques for residual stress assessment in composites is addressed. A novel technique for absolute stress determination in orthotropic materials from angular dependencies of ultrasonic velocities is described. The technique is applicable for determination of both applied and residual stresses and does not require calibration measurements on a reference sample. The important advantage of this method is that stress is determined simultaneously with stress-dependent elastic constants and is thus decoupled from the material texture. It is demonstrated that when the principal plane stress directions coincide with acoustical axes, the angular velocity data in the plane perpendicular to the stress plane may be used to determine both stress components. When the stress is off the acoustical axes, the shear and the difference of the normal stress components may be determined from the angular dependence of group velocities in the plane of stresses. Synthetic sets of experimental data corresponding to materials with different anisotropy and stress levels are used to check the applicability of the technique. The method is also verified experimentally. A high precision ultrasonic wave transmission technique is developed to measure angular dependence of ultrasonic velocities. Examples of stress determination from experimental velocity data are given. A method is presented for determination of velocities of ultrasonic waves propagating through the composite material with residual stresses. It is based on the generalized self-consistent multiple scattering model. Calculation results for longitudinal and shear ultrasonic wave velocities propagating perpendicular to the fibers direction in SCS-6/Ti composite with and without residual stresses are presented. They show that velocity changes due to presence of stresses are of order 1%.

Rokhlin, S. I.↗
DOE OSTI2021

Validity of Machine Learning in the Quantitative Analysis of Complex Scanning Near-Field Optical Microscopy Signals Using Simulated Data

Scattering-type scanning near-field optical microscope (s-SNOM) is a modern technique for subdiffractional optical imaging and spectroscopy. Over the past two decades, tremendous efforts have been devoted to modeling complex tip-sample interactions in s-SNOM, aimed at understanding the electrodynamics of materials at the nanoscale. However, due to complexities in analytical methods and the limited computation power for fully numerical simulations, compromises must be made to facilitate the modeling of tip-sample interaction, such as using quasistatic approximation or unrealistic tip geometries. Here, we apply a variety of widely utilized machine-learning methods, including k nearest neighbor and feedforward neural network etc. to study the phase-resolved spectroscopic near-field response. With only a small set of training data, which is simulated using the finite-dipole model, we demonstrate that the relation between the experimental near-field signal and sample optical constant can be one to one mapped without the need for tip modeling: for a given material with a moderate dielectric function, its complex near-field spectrum can be accurately determined within the mid-IR spectral range, and vice versa. Our preliminary study sets the stage for future exploration using real experimental data. Our method is beneficial for processing the increasing amount of data accumulated across many research groups and especially useful for user facilities such as synchrotron-based national laboratories where a large amount of data is generated on a daily basis.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Cold neutron-deuteron capture and Wigner-SU(4) symmetry

We calculate the cold neutron-deuteron (nd) capture cross section,σ nd to next-to-next-to leading order (NNLO) using the model-independent approach of pionless effective-field theory [EFT(π)]. At leading order we find σ nd = 0.314 ± 0.217 mb, while the experimental result is 0.508(15) mb for a laboratory neutron velocity of 2200 m/s. At next-to-leading-order (NLO), we show that σnd is sensitive to the low-energy constant (LEC) $L$$^{(0)}_{1}$ of the two-nucleon isovector current appearing at NLO. A fit of $L$$^{(0)}_{1}$ at NLO to the triton magnetic moment yields a NLO prediction of σ nd = 0.393 ± 0.164 mb, where the error comes from propagating the error from the $L$$^{(0)}_{1}$ fit. At NNLO, we find that a new three-nucleon magnetic moment counterterm is required for renormalization-group invariance of both σnd and the triton magnetic moment. Fitting the NNLO correction to $L$$^{(0)}_{1}$ (denoted $L$$^{(1)}_{1}$) to cold neutron-proton capture (σnp) yields a NNLO prediction of σ nd = 0.447 ± 0.130 mb, where the error comes from propagating the error from the $L$$^{(1)}_{1}$ fit. We also study different fittings of $L$$^{(0)}_{1}$ and $L$$^{(1)}_{1}$ to σ np , σ nd , and/or the triton magnetic moment. For example, fitting $L$$^{(0)}_{1}$ simultaneously to σ np , σ nd , and the triton magnetic moment at NLO, and fitting $L$$^{(1)}_{1}$ simultaneously to σ np and σnd at NNLO, yields σ nd = 0.480 ± 0.114 mb and 0.511 ± 0.042 mb, respectively, where errors are naively estimated from EFT(π) power counting. Additionally, we discuss how Wigner SU(4) symmetry may alter the naive EFT(π) expansion of σ nd .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1979

Empirical data on the origin of 'new' comets

The mass distribution of a group of 62 comets from the sample of Marsden et al (1978) was determined by assuming that the size of a comet is in proportion to the surface area of its vaporizing nucleus. A bimodal distribution was found, with a gap between magnitudes 8.1 and 9. The 50 brighter comets (magnitudes 1 to 8) have been tentatively identified as true 'new' comets; their size distribution cannot be fit to a constant slope on a log-log graph. These comets were apparently formed by a mechanism which differs from the fragmentation process. The 12 fainter may be fragments of comets which split or dimmed during their first passages. Results indicate that new comets could be identified with pristine planetesimals; they decay rapidly, probably by splitting when they enter the inner solar system.

Delsemme, A. H.↗
NASA NTRS2011

Electrochemical and mechanical polishing and shaping method and system

A method and system are provided for the shaping and polishing of the surface of a material selected from the group consisting of electrically semi-conductive materials and conductive materials. An electrically non-conductive polishing lap incorporates a conductive electrode such that, when the polishing lap is placed on the material's surface, the electrode is placed in spaced-apart juxtaposition with respect to the material's surface. A liquid electrolyte is disposed between the material's surface and the electrode. The electrolyte has an electrochemical stability constant such that cathodic material deposition on the electrode is not supported when a current flows through the electrode, the electrolyte and the material. As the polishing lap and the material surface experience relative movement, current flows through the electrode based on (i) adherence to Faraday's Law, and (ii) a pre-processing profile of the surface and a desired post-processing profile of the surface.

Engelhaupt, Darell E.↗
NASA NTRS1975

Regulation of body mass in rats exposed to chronic acceleration

Female rats approximately 6 mo old were chronically centrifuged for up to 30 days at 2.76 G or 3.18 G and sacrificed at intervals for body-composition study. Both fat and the fat-free body mass (FFBM) were reduced during the 1st wk of centrifugation, with the fat showing considerably more variation both within and between groups. The FFBM was reduced below control level to the same extent in rats fed commercial chow, a high-fat diet, or a high-protein diet or in rats prefasted to produce a body-mass deficit at the start of centrifugation. There were no centrifugation-associated changes in body water content. It was concluded that body fat showed no evidence of regulation, FFBM is regulated at any constant level of acceleration between 1 and 4.15 G, and the change in FFBM induced by a change in acceleration is probably not regulated.

Pitts, G. C.↗
NASA NTRS2001

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which removes a significant amount of the surface water. In this presentation, we report the results of measurements of the molecular packing and rates of kinetic exchange of the trisiloxane surfactants at the air/water interface in order to confirm our picture of trisiloxane packing, and provide additional insight into the superspreading process. We used the pendant bubble technique as a Langmuir trough to measure the trisiloxane equation of state which relates the tension to the surface concentration. From these measurements we obtain accurate values for the maximum packing density. We find that trisiloxanes with 4 and 8 ethoxylate groups have the same maximum packing concentration, indicating that the maximum packing is controlled by the cross section of the head group. For trisiloxanes with larger than eight ethoxylates, the maximum packing increases with ethoxylate number, indicating that the disposition of the ethoxylate chain (i.e., its effective size) is controlling. This supports our picture of superspreading: The superspreading ability of trisiloxanes decreases considerably for trisiloxanes with larger than eight ethoxylates; the packing measurements indicate that for the higher ethoxylate number trisiloxanes, the compact nonpolar head groups are pushed apart by the ethoxylate chain. They leave spaces of surface water on adsorption and do not lower the solid tension as much as their lower chain analogues. Finally the report measurements of the dynamic tension reduction accompanying the adsorption of trisiloxanes onto an initially clean interface using the pendant bubble technique, and we obtain from these relaxations, the equation of state and a mass transfer model, the rate constants for kinetic exchange. We find that the rate constants for desorption of trisiloxanes are generally much slower than for analogous aliphatic polyethoxylate surfactants with identical ethoxylate chain lengths. When an aqueous drop of a superspreader solution is placed on a hydrophobic surface and begins to spread, the lower desorption rates allows the tension at the drop center to remain reduced relative to the tension of the expanding periphery, thus strengthening Marangoni forces which can assist the spreading. Marangoni forces can be especially significant in the case of superspreaders because their maximum equilibrium reduction in tension is several dynes/cm lower than for aliphatic surfactants.

Kumar, Nitin↗
DOE OSTI2023

Electronic Tuning of Photoexcited Dynamics in Heteroleptic Cu(I) Complex Photosensitizers

Photoexcited dynamics of heteroleptic Cu(I) complexes as noble-metal-free photosensitizers are closely intertwined with the nature of their ligands. By utilizing ultrafast optical and X-ray transient absorption spectroscopies, we characterized a new set of heteroleptic Cu(I) complexes [Cu(PPh 3 )( 2 )(BPy R )] + (R = CH 3 , H, Br to COOCH 3 ), with an increase in the electron-withdrawing ability of the functional group (R). Here we found that after the transient photooxidation of Cu(I) to Cu(II), the increasing electron-withdrawing ability of R barely affects the internal conversion (IC) (e.g., Jahn-taller (JT) distortion) between singlet MLCT states. However, it does accelerate the dynamics of intersystem crossing (ISC) between singlet and triplet MLCT states and the subsequent decay from the triplet MLCT state to the ground state. The associated lifetime constants are reduced by up to 300%. Our understanding of the photoexcited dynamics in heteroleptic Cu(I) complexes through ligand electronic tuning provides valuable insight into the rational design of efficient Cu(I) complex photosensitizers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electron Transfer Theory Elucidates the Hidden Role Played by Triethylamine and Triethanolamine during Photocatalysis

Triethylamine (TEA) and triethanolamine (TEOA) are renowned, in part, for their ability to reductively quench excited states by outer-sphere electron transfer with vast and still growing applications as sacrificial electron donors for photocatalytic systems. Upon amine oxidation, the resulting TEA •+ and TEOA •+ radical cations undergo proton transfer (or hydrogen atom transfer), resulting in the formation of a chemical reductant that has an α-carbon centered radical adjacent to the nitrogen center (TEA • and TEOA • ). In this contribution, we have electrochemically and spectroscopically characterized a set of electron acceptors which, upon accepting an electron, are a series of photocatalysts, [ReCl(R 1 R 2 -bpy)(CO) 3 ] •– , where R 1 and R 2 are electron-donating and electron-withdrawing groups in the 4,4′- and 5,5′-positions on the bipyridyl ligand. Here, we substantiated the formation of the electron donors, TE(O)A • , by spin trapping electron paramagnetic resonance spectroscopy, where TE(O)A • reacts with 2,4,6-tri-tert-butylnitrosobenzene to generate N-centered and O-centered radical adducts. Having established the chemical behaviors of the electron acceptors and donors individually, the electron transfer rate constants were determined across a 1.43 V range in driving force. The redox potential of TEA • was benchmarked to within ±80 mV on an absolute scale in V vs Fc + /Fc in CH 3 CN by using an empirical rate vs free-energy correlation, electron transfer theory, and density functional theory calculations. The equilibrium potentials for TEA • and TEOA • were determined to be −1.98 V and −1.76 V, respectively. Based on the kinetic and thermochemical analysis presented for TEA • and TEOA • , these transient radicals can be broadly considered strong homogeneous chemical reductants within the wider context of photoredox potentials. Thus, this work clarifies a frequently unnoticed secondary function for these sacrificial electron donors during photocatalysis and rationalizes the possibility of a one-photon/two-electron conversion process that is dependent on the free-energy exchange between TE(O)A • and photocatalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Structural Basis of Ligand Selectivity by a Bacterial Adhesin Lectin Involved in Multispecies Biofilm Formation

Carbohydrate recognition by lectins governs critical host-microbe interactions. MpPA14 (Marinomonas primoryensis PA14 domain) lectin is a domain of a 1.5-MDa adhesin responsible for a symbiotic bacterium-diatom interaction in Antarctica. Here, we show that MpPA14 binds various monosaccharides, with l-fucose and N-acetylglucosamine being the strongest ligands (dissociation constant [K d ], ~150 μM). High-resolution structures of MpPA14 with 15 different sugars bound elucidated the molecular basis for the lectin’s apparent binding promiscuity but underlying selectivity. MpPA14 mediates strong Ca 2+ -dependent interactions with the 3,4-diols of l-fucopyranose and glucopyranoses, and it binds other sugars via their specific minor isomers. Thus, MpPA14 only binds polysaccharides like branched glucans and fucoidans with these free end groups. Consistent with our findings, adhesion of MpPA14 to diatom cells was selectively blocked by l-fucose, but not by N-acetyl galactosamine. The MpPA14 lectin homolog present in a Vibrio cholerae adhesin was produced and was shown to have the same sugar binding preferences as MpPA14. The pathogen’s lectin was unable to effectively bind the diatom in the presence of fucose, thus demonstrating the antiadhesion strategy of blocking infection via ligand-based antagonists.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Strain Effects in SrHfO 3 Films Grown by Hybrid Molecular Beam Epitaxy

Perovskite oxide heterostructures host a large number of interesting phenomena such as ferroelectricity, which are often driven by octahedral distortions in the crystal that may induce polarization. SrHfO 3 (SHO) is a perovskite oxide with a pseudocubic lattice parameter of 4.08 Å that previous density functional theory (DFT) calculations suggest can be stabilized in a ferroelectric P4mm phase when stabilized with sufficient compressive strain. Additionally, it is insulating and possesses a large band gap and a high dielectric constant, making it an ideal candidate for oxide electronic devices. Here, to test the viability of epitaxial strain as a driver of ferroic phase transitions, SHO films were grown by hybrid molecular beam epitaxy (hMBE) with a tetrakis(ethylmethylamino)hafnium(IV) source on GdScO 3 and TbScO 3 substrates. Strained SHO phases were characterized using X-ray diffraction, X-ray absorption spectroscopy, and scanning transmission electron microscopy to determine the space group of the strained films, with the results compared to those of DFT-optimized models of phase stability versus strain. Contrary to past reports, we find that compressively strained SrHfO 3 undergoes octahedral tilt distortions without associated ferroelectric polarization and most likely takes on the I4/mcm phase with the a 0 a 0 c – tilt pattern.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

A stochastic model of cumulus clumping

Observations show that cumulus clouds often occur in long-lived mesoscale groups, or clumps. Five possible explanations of clumping are surveyed. The 'mutual protection hypothesis,' that clumps occur because cumulus clouds create and maintain, in their near environments, relatively favorable conditions for the development of succeeding clouds, is examined at length. This idea is tested through the use of a simple time-dependent model in which clouds, triggered at randomly selected locations, tend to stabilize their environment in the face of a prescribed constant forcing. Results show that clumping occurs when the cloud-induced stabilization rate is strongest at an intermediate distance from a cloud, and that it does not occur when the stabilization rate decreases monotonically away from a cloud.

Randall, D. A.↗
NASA NTRS2000

Aerogel Projects Ongoing in MSFC's Engineering Directorate

When we speak of an aerogel material, we are referring more to process and structure am to a specific substance. Aerogel, considered the lightest solid material, has been made from silica for seventy years. Resorcinol-formaldehyde, organic aerogels have been developed more recently. However, aerogel can be made from almost any type of substance, even lead. Because an aerogel is mostly air (about 99 %), the solid substance used will affect the weight very little. The term "aerogel" connotes the sol-gel process used to manufacture the material. The aerogel begins as a liquid "sol," becomes a solid "alcogel," and is then dried to become an "aerogel." The final product has a unique structure, useful for exploitation. It is an "open pore" system with nano-sized particles and pores, has very high surface area, and is highly interconnected. Besides low weight, aerogels have ultimate (lowest) values in other properties: thermal conductivity, refractive index, sound speed, and dielectric constant. Aerogels were first prepared in 1931 by Steven Kistler, who used a supercritical drying step to replace the liquid in a gel with air, preserving the structure (1). Kistler's procedure involved a water-to-alcohol exchange step; in the 1970's, this step was eliminated when a French investigator introduced the use of tetramethylorthosilicate. Still, alcohol drying involved dangerously high temperatures and pressures. In the 1980's, the Microstructured Materials Group at Berkeley Laboratory found that the alcohol in the gel could be replaced with liquid carbon dioxide before supercritical drying, which greatly improved safety (2). 'Me most recent major contribution has been that of Deshpande, Smith and Brinker in New Mexico, who are working to eliminate the supercritical drying step (3). When aerogels were first being developed, they were evaporatively dried. However, the wet gel, when dried, underwent severe shrinkage and cracking; this product was termed "xerogel." When the autoclave drying step was introduced, the final product was without cracks and showed only minimal shrinkage; this product was termed "aerogel." In the 1990's, Deshpande, Smith and Brinker developed an evaporative drying procedure in which the wet gel is chemically "capped" so that the material, which undergoes shrinkage, springs back to its original size when evaporatively dried. This new type of xerogel, while uncracked and almost the same size as the wet gel, differs from the autoclave-dried product in that it is less porous (approximately 70%, as compared to 99% for aerogels).

Shular, David A.↗
NASA NTRS2006

Vivid Motor Imagery as an Adaptation Method for Head Turns on a Short-Arm Centrifuge

Artificial gravity (AG) has been proposed as a potential countermeasure to the debilitating physiological effects of long duration space flight. The most economical means of implementing AG may be through the use of a short-radius (2m or less) centrifuge. For such a device to produce gravitational forces comparable to those on earth requires rotation rates in excess of 20 revolutions per minute (rpm). Head turns made out of the plane of rotation at these rates, as may be necessary if exercise is combined with AG, result in cross-coupled stimuli (CCS) that cause adverse side effects including motion sickness, illusory sensations of motion, and inappropriate eye movements. Recent studies indicate that people can adapt to CCS and reduce these side effects by making multiple head turns during centrifuge sessions conducted over consecutive days. However, about 25% of the volunteers for these studies have difficulty tolerating the CCS adaptation paradigm and often drop out due to motion sickness symptoms. The goal of this investigation was to determine whether vivid motor imagery could be used as a pseudostimulus for adapting subjects to this unique environment. Twenty four healthy human subjects (14 males, 10 females), ranging in age from 21 to 48 years (mean 33, sd 7 years) took part in this study. The experimental stimuli were produced using the NASA JSC short-arm centrifuge (SAC). Subjects were oriented supinely on this device with the nose pointed toward the ceiling and head centered on the axis of rotation. Thus, centrifuge rotation was in the body roll plane. After ramp-up the SAC rotated clockwise at a constant rate of 23 rpm, producing a centrifugal force of approximately 1 g at the feet. Semicircular canal CCS were produced by having subjects make yaw head turns from the nose up (NU) position to the right ear down (RED) position and from RED to NU. Each head turn was completed in about one second, and a 30 second recovery period separated consecutive head movements. Participants were randomly assigned to one of three groups (n=8 per group): physical adapters (PA), mental adapters (MA), or a control group (CG). Each subject participated in a one hour test session on each of three consecutive days. Each test session consisted of an initial (preadaptation) period during which the subject performed six CCS maneuvers in the dark, followed by an adaptation period with internal lighting on the centrifuge, and a final (postadaptation) period during which six more CCS maneuvers were performed in the dark. For the PA group, the adaptation period consisted of performing 30 additional CCS maneuvers in the light. For the MA and CG group the centrifuge was ramped down to 0 rpm after the pre-adaptation period and ramped back up to 23 rpm before the post-adaptation period. For the both of these groups, the adaptation period consisted of making 30 CCS maneuvers in the light with the centrifuge stationary (so no cross-coupling occurred). MA group subjects were instructed to vividly imagine the provocative sensations produced by the preadaptation CCS maneuvers in terms of magnitude, duration, and direction of illusory body tilt, as well as any accompanying levels of motion sickness. CG group subjects were asked to answer low imagery content questions (trivial pursuit) during each adaptation period head turn. During the 30 second recovery following each head turn, psychophysical data were collected including self reports of motion sickness, magnitude and direction estimates of illusory body tilt, and the overall duration of these sensations. A multilevel mixed effects linear regression analysis performed on all response variables indicated that all three groups experienced some psychophysical adaptation across the three test sessions. For illusory tilt magnitude, the PA group exhibited the most overall adaptation, followed by the MA group, and the CG group. The slopes of these adaptation trajectories by group over day were significantly diffent from one another. For the perceived duration of sensations, the CG group again exhibited the least amount of adaptation. However, the rates of adaptation of the PA and the MA groups were indistinguishable, suggesting that the imagined pseudostimulus appeared to be just as effective a means of adaptation as the actual stimulus. The MA group's rate of adaptation to motion sickness symptoms was also comparable to the PA group. The use of vivid motor imagery may be an effective method for adapting to the illusory sensations and motion sickness symptoms produced by cross-coupled stimuli. For space-based AG applications, this technique may prove quite useful in retaining astronauts considered highly susceptible to motion sickness as it reduces the number of actual CCS required to attain adaptation.

Newby, N. J.↗
DOE OSTI2024

Mass gaps of a Z 3 gauge theory with three fermion flavors in 1 + 1 dimensions

We consider a Z 3 gauge theory coupled to three degenerate massive flavors of fermions, which we term Quantum Z(3) Dynamics, QZD. The spectrum can be computed in 1 + 1 dimensions using tensor networks. In weak coupling the spectrum is that of the expected mesons and baryons, although the corrections in weak coupling are nontrivial, analogous to those of nonrelativistic QED in 1 + 1 dimensions. In strong coupling, besides the usual baryon, the singlet meson is a baryon-antibaryon state. For two special values of the coupling constant, the lightest baryon is degenerate with the lightest octet meson, and the lightest singlet meson, respectively. Published by the American Physical Society 2024

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Reversible Ligand Protonation in Noninnocent Constrained-Geometry-Like Group 4 Complexes

The proligands C 5 H 5 CMe 2 CHPhOx R (R = Me 2 , CHMe 2 , and CMe 3 ) react with M(NMe 2 ) 4 (M = Ti, Zr, and Hf) to give monodeprotonated (Ox R CHPhCMe 2 C 5 H 4 )M(NMe 2 ) 3 , doubly deprotonated (C 5 H 4 CMe 2 CPhOx R )M(NMe 2 ) 2 , or a mixture of both. The observed products depend on reaction conditions, the oxazoline substituent, and the metal center, with 4-t-butyl-oxazoline or Ti giving only the monodeprotonated (Ox R CHPhCMe 2 C 5 H 4 )M(NMe 2 ) 3 . Amine elimination from (Ox R CHPhCMe 2 C 5 H 4 )M(NMe 2 ) 3 to give (C 5 H 4 CMe 2 CPhOx R )M(NMe 2 ) 2 is reversible for 4,4-dimethyl- and 4-isopropyl-oxazoline-based ligands in Zr or Hf complexes. Temperature-dependent kinetic studies of the equilibration of (C 5 H 4 CMe 2 CPhOx Me2 )Zr(NMe 2 ) 2 , HNMe 2 and (Ox Me2 CHPhCMe 2 C 5 H 4 )Zr(NMe 2 ) 3 provide the experimental thermodynamic parameters ΔS° = -17.4 ± 2.6 cal·mol –1 K –1 and ΔH° = -6.8 ± 0.8 kcal·mol –1 . An Eyring plot of the rate constants, determined from the system as it approaches equilibrium, gives the activation entropy and activation enthalpy for the addition of (C 5 H 4 CMe 2 CPhOx Me2 )Zr(NMe 2 ) 2 and HNMe 2 as -36 ± 4 cal·mol –1 K –1 and 8.9 ± 1.3 kcal·mol –1 , respectively; the elimination of HNMe 2 from (Ox Me2 CHPhCMe 2 C 5 H 4 )Zr(NMe 2 ) 3 is characterized by ΔS ‡ = -19 ± 5 cal·mol –1 K –1 and ΔH ‡ = 15.7 ± 1.5 kcal·mol –1 . DFT computational models indicate a single-step, nonlinear transfer of the H between the benzylic position of the noninnocent, oxazoline-coordinated ligand and NMe 2 . Computations also confirm the negative activation entropy and the trends in the barriers support the experimental results. Together, these studies indicate the importance of steric effects from the oxazoline ligand, metal center, ancillary ligands, and leaving group on the shuttling of the proton between HNMe 2 and the noninnocent ligand. Finally, these effects suggest that coordination of oxazoline to the metal center is a key part of the benzylic deprotonation and noninnocent behavior of the cyclopentadienyl-oxazoline ligand.

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

The mammalian retina as a clock

Many physiological, cellular, and biochemical parameters in the retina of vertebrates show daily rhythms that, in many cases, also persist under constant conditions. This demonstrates that they are driven by a circadian pacemaker. The presence of an autonomous circadian clock in the retina of vertebrates was first demonstrated in Xenopus laevis and then, several years later, in mammals. In X. laevis and in chicken, the retinal circadian pacemaker has been localized in the photoreceptor layer, whereas in mammals, such information is not yet available. Recent advances in molecular techniques have led to the identification of a group of genes that are believed to constitute the molecular core of the circadian clock. These genes are expressed in the retina, although with a slightly different 24-h profile from that observed in the central circadian pacemaker. This result suggests that some difference (at the molecular level) may exist between the retinal clock and the clock located in the suprachiasmatic nuclei of hypothalamus. The present review will focus on the current knowledge of the retinal rhythmicity and the mechanisms responsible for its control.

Review Literature↗
DOE OSTI2022

Influence of intermolecular interactions on the infrared complex indices of refraction for binary liquid mixtures

This paper investigates the accuracy of deriving the composite optical constants of binary mixtures from only the complex indices of refraction of the neat materials. These optical constants enable the reflectance spectra of the binary mixtures to be modeled for multiple scenarios (e.g., different substrates, thicknesses, volume ratios), which is important for contact and standoff chemical detection. Using volume fractions, each mixture's complex index of refraction was approximated via three different mixing rules. To explore the impact of intermolecular interactions, these predictions are tested by experimental measurements for two representative sets of binary mixtures: (1) tributyl phosphate combined with n-dodecane, a non-polar medium, to represent mixtures which primarily interact via dispersion forces and (2) tributyl phosphate and 1-butanol to represent mixtures with polar functional groups that can also interact via dipole–dipole interactions, including hydrogen bonding. The residuals and the root-mean-square error between the experimental and calculated index values are computed and demonstrate that for miscible liquids in which the average geometry of the cross-interactions can be considered isotropic (e.g., dispersion), the refractive indices of the mixtures can be modeled using composite n and k values derived from volume fractions of the neat liquids. Conversely, in spectral regions where the geometry of the cross-interactions is more restricted and anisotropic (e.g., hydrogen bonding), the calculated n and k values vary from the measured values. The impact of these interactions on the reflectance spectra are then compared by modeling a thin film of the binary mixtures on an aluminum substrate using both the measured and the mathematically computed indices of refraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗