Experimental tests of reaction rate theory: Mu+H2 and Mu+D2

Copyright @ 1987 American Institute of Physics.Bimolecular rate constants for the thermal chemical reactions of muonium (Mu) with hydrogen and deuterium—Mu+H2→MuH+H and Mu+D2→MuD+D—over the temperature range 473–843 K are reported. The Arrhenius parameters and 1σ uncertainties for the H2 reaction are log A (cm3 molecule-1 s-1)=-9.605±0.074 and Ea =13.29±0.22 kcal mol-1, while for D2 the values are -9.67±0.12 and 14.73±0.40, respectively. These results are significantly more precise than those reported earlier by Garner et al. For the Mu reaction with H2 our results are in excellent agreement with the 3D quantum mechanical calculations of Schatz on the Liu–Siegbahn–Truhlar–Horowitz potential surface, but the data for both reactions compare less favorably with variational transition-state theory, particularly at the lower temperatures.NSERC (Canada) and the Petroleum Research Foundation of the Americal Chemical Society

Reaction kinetics of muonium with the halogen gases (F2, Cl2, and Br2)

Copyright @ 1989 American Institute of PhysicsBimolecular rate constants for the thermal chemical reactions of muonium (Mu) with the halogen gases—Mu+X2→MuX+X—are reported over the temperature ranges from 500 down to 100, 160, and 200 K for X2=F2,Cl2, and Br2, respectively. The Arrhenius plots for both the chlorine and fluorine reactions show positive activation energies Ea over the whole temperature ranges studied, but which decrease to near zero at low temperature, indicative of the dominant role played by quantum tunneling of the ultralight muonium atom. In the case of Mu+F2, the bimolecular rate constant k(T) is essentially independent of temperature below 150 K, likely the first observation of Wigner threshold tunneling in gas phase (H atom) kinetics. A similar trend is seen in the Mu+Cl2 reaction. The Br2 data exhibit an apparent negative activation energy [Ea=(−0.095±0.020) kcal mol−1], constant over the temperature range of ∼200–400 K, but which decreases at higher temperatures, indicative of a highly attractive potential energy surface. This result is consistent with the energy dependence in the reactive cross section found some years ago in the atomic beam data of Hepburn et al. [J. Chem. Phys. 69, 4311 (1978)]. In comparing the present Mu data with the corresponding H atom kinetic data, it is found that Mu invariably reacts considerably faster than H at all temperatures, but particularly so at low temperatures in the cases of F2 and Cl2. The current transition state calculations of Steckler, Garrett, and Truhlar [Hyperfine Interact. 32, 779 (986)] for Mu+X2 account reasonably well for the rate constants for F2 and Cl2 near room temperature, but their calculated value for Mu+Br2 is much too high. Moreover, these calculations seemingly fail to account for the trend in the Mu+F2 and Mu+Cl2 data toward pronounced quantum tunneling at low temperatures. It is noted that the Mu kinetics provide a crucial test of the accuracy of transition state treatments of tunneling on these early barrier HX2 potential energy surfaces.NSERC (Canada), Donors of the Petroleum Research Fund, administered by the American Chemical Society, for their partial support of this research and the Canada Council

Specificity in transmembrane helix-helix interactions defines a hierarchy of stability for sequence variants,

The folding, stability, and oligomerization of helical membrane proteins depend in part on a precise set of packing interactions between transmembrane helices. To understand the energetic principles of these helix-helix interactions, we have used alaninescanning mutagenesis and sedimentation equilibrium analytical ultracentrifugation to quantitatively examine the sequence dependence of the glycophorin A transmembrane helix dimerization. In all cases, we found that mutations to alanine at interface positions cost free energy of association. In contrast, mutations to alanine away from the dimer interface showed free energies of association that are insignificantly different from wild-type or are slightly stabilizing. Our study further revealed that the energy of association is not evenly distributed across the interface, but that there are several ''hot spots'' for interaction including both glycines participating in a GxxxG motif. Inspection of the NMR structure indicates that simple principles of protein-protein interactions can explain the changes in energy that are observed. A comparison of the dimer stability between different hydrophobic environments suggested that the hierarchy of stability for sequence variants is conserved. Together, these findings imply that the protein-protein interaction portion of the overall association energy may be separable from the contributions arising from protein-lipid and lipid-lipid energy terms. This idea is a conceptual simplification of the membrane protein folding problem and has implications for prediction and design. G enome sequencing efforts reveal that approximately 20% of ORFs in complex organisms may encode proteins containing at least one helical transmembrane segment (1). Despite these numbers, as well as the fact that membrane proteins carry out many essential cell functions, our understanding of the sequence-structure-function relationships for this class of proteins lags far behind that of soluble proteins. These realities underscore the importance of biophysical and structural work aimed toward understanding chemical principles of helical membrane protein structural stability. Because the phospholipid bilayer places structural constraints on a helical membrane protein, the folding of a polypeptide sequence into a helical membrane protein can be considered, experimentally and theoretically, in separable thermodynamic steps (2, 3). The usefulness of this framework arises from the fact that individual energetic processes can be independently studied. The principal features of a polypeptide sequence that will give rise to the formation of an independently stable transmembrane ␣-helix are generally known (3). This information has been used extensively in computational search algorithms with reasonable accuracy rates to identify potential helical transmembrane proteins (reviewed in ref. 3). Once this is accomplished, however, the helical membrane protein folding problem then becomes focused on understanding and predicting the side-to-side associations in which these preformed transmembrane ␣-helices will participate. It is this final thermodynamic step in helical membrane protein folding that we investigate in this study. In a continuing effort to understand the structural and energetic principles of the side-to-side interactions of transmembrane ␣-helices, we have quantitatively examined the sequence dependence of the glycophorin A transmembrane helix dimerization. The propensity of the glycophorin A transmembrane domain to dimerize in a sequence-specific manner has been a paradigm for study of transmembrane helix-helix association in hydrophobic environments (4-9). An additional advantage for detailed thermodynamic analysis of the GpA transmembrane segment (TMS) dimerization is the fact that a solution NMR structure has been solved (10). Together with considerations of principles of stability of helices in membranes, the NMR structure provides a three-dimensional model for interpretation of potential structural consequences due to mutation. Understanding the chemical principles driving the selfassociation of the glycophorin transmembrane ␣-helix is of particular interest because both the NMR structure and the exquisite sequence dependence determined by SDS͞PAGE suggest that a detailed geometry of van der Waals interactions specify and stabilize the dimer (4, 8, 10). Only one residue with a polar side-chain, Thr 87 , is found at the dimer interface. The solution NMR structure of the glycophorin A transmembrane dimer in dodecylphosphocholine micelles reveals no interhelical hydrogen bond at this position (10), although the recent solid state NMR data from Smith and coworkers (11) hints that Thr 87 might participate in an intermonomer hydrogen bond in lipid bilayers. Nevertheless, the energetic stabilization from such a hydrogen bond is uncertain. Recent studies on the introduction of polar side chains into model transmembrane peptides find that residues containing two polar side-chain atoms (such as asparagine) have a much greater tendency to drive transmembrane helix association than residues containing only one polar sidechain atom (threonine or serine; refs. 12 and 13). It has been proposed that side-chain rotamer entropy is not expected to play a large role in the self-association of the glycophorin A transmembrane ␣-helix (10). The interacting surface of the glycophorin A TMS contains only three residues with some rotamer freedom in an ␣-helix (Leu Abbreviations: TMS, transmembrane segment; C8E5, pentaoxylethylene-octylether. † To whom reprint requests should be addressed

The PuZZling Li-Rich Red Giant Associated With NGC 6819

A Li-rich red giant (RG) star (2M19411367+4003382) recently discovered in the direction of NGC 6819 belongs to the rare subset of Li-rich stars that have not yet evolved to the luminosity bump, an evolutionary stage where models predict Li can be replenished. The currently favored model to explain Li enhancement in first-ascent RGs like 2M19411367+4003382 requires deep mixing into the stellar interior. Testing this model requires a measurement of C-12/C-13, which is possible to obtain from Apache Point Observatory Galactic Evolution Experiment (APOGEE) spectra. However, the Li-rich star also has abnormal asteroseismic properties that call into question its membership in the cluster, even though its radial velocity and location on color-magnitude diagrams are consistent with membership. To address these puzzles, we have measured a wide array of abundances in the Li-rich star and three comparison stars using spectra taken as part of the APOGEE survey to determine the degree of stellar mixing, address the question of membership, and measure the surface gravity. We confirm that the Li-rich star is a RG with the same overall chemistry as the other cluster giants. However, its log g is significantly lower, consistent with the asteroseismology results and suggestive of a very low mass if the star is indeed a cluster member. Regardless of the cluster membership, the C-12/C-13 and C/N ratios of the Li-rich star are consistent with standard first dredge-up, indicating that Li dilution has already occurred, and inconsistent with internal Li enrichment scenarios that require deep mixing.National Science Foundation AST1109888NSF AST-1358862, AST 1109718, AST 1312863Alfred P. Sloan FoundationNational Science FoundationU.S. Department of Energy Office of ScienceUniversity of ArizonaBrazilian Participation GroupBrookhaven National LaboratoryCarnegie Mellon UniversityUniversity of FloridaFrench Participation GroupGerman Participation GroupHarvard UniversityInstituto de Astrofisica de CanariasMichigan State/NotreDame/JINA Participation GroupJohns Hopkins UniversityLawrence Berkeley National LaboratoryMax Planck Institute for AstrophysicsMax Planck Institute for Extraterrestrial PhysicsNew Mexico State UniversityNew York UniversityOhio State UniversityPennsylvania State UniversityUniversity of PortsmouthPrinceton UniversitySpanish Participation GroupUniversity of TokyoUniversity of UtahVanderbilt UniversityUniversity of VirginiaUniversity of WashingtonYale UniversityNational Aeronautics and Space AdministrationTwo Micron All Sky SurveyUniversity of MassachusettsInfrared Processing and Analysis Center/California Institute of TechnologyU.S. Government NAG W-2166Astronom

Somatostatin neuron contributions to cortical slow wave dysfunction in adult mice exposed to developmental ethanol

IntroductionTransitions between sleep and waking and sleep-dependent cortical oscillations are heavily dependent on GABAergic neurons. Importantly, GABAergic neurons are especially sensitive to developmental ethanol exposure, suggesting a potential unique vulnerability of sleep circuits to early ethanol. In fact, developmental ethanol exposure can produce long-lasting impairments in sleep, including increased sleep fragmentation and decreased delta wave amplitude. Here, we assessed the efficacy of optogenetic manipulations of somatostatin (SST) GABAergic neurons in the neocortex of adult mice exposed to saline or ethanol on P7, to modulate cortical slow-wave physiology.MethodsSST-cre × Ai32 mice, which selectively express channel rhodopsin in SST neurons, were exposed to ethanol or saline on P7. This line expressed similar developmental ethanol induced loss of SST cortical neurons and sleep impairments as C57BL/6By mice. As adults, optical fibers were implanted targeting the prefrontal cortex (PFC) and telemetry electrodes were implanted in the neocortex to monitor slow-wave activity and sleep-wake states.ResultsOptical stimulation of PFC SST neurons evoked slow-wave potentials and long-latency single-unit excitation in saline treated mice but not in ethanol mice. Closed-loop optogenetic stimulation of PFC SST neuron activation on spontaneous slow-waves enhanced cortical delta oscillations, and this manipulation was more effective in saline mice than P7 ethanol mice.DiscussionTogether, these results suggest that SST cortical neurons may contribute to slow-wave impairment after developmental ethanol

Kepler-503b: An Object at the Hydrogen Burning Mass Limit Orbiting a Subgiant Star

Using spectroscopic radial velocities with the APOGEE instrument and Gaia distance estimates, we demonstrate that Kepler-503b, currently considered a validated Kepler planet, is in fact a brown-dwarf/low-mass star in a nearly circular 7.2-day orbit around a subgiant star. Using a mass estimate for the primary star derived from stellar models, we derive a companion mass and radius of $0.075\pm0.003 \ M_{\odot}$ ($78.6\pm3.1 \ M_{Jup}$) and $0.099^{+0.006}_{-0.004}\ R_{\odot}$ ($0.96^{+0.06}_{-0.04}\ R_{Jup}$), respectively. Assuming the system is coeval, the evolutionary state of the primary indicates the age is $\sim6.7$ Gyr. Kepler-503b sits right at the hydrogen burning mass limit, straddling the boundary between brown dwarfs and very low-mass stars. More precise radial velocities and secondary eclipse spectroscopy with James Webb Space Telescope will provide improved measurements of the physical parameters and age of this important system to better constrain and understand the physics of these objects and their spectra. This system emphasizes the value of radial velocity observations to distinguish a genuine planet from astrophysical false positives, and is the first result from the SDSS-IV monitoring of Kepler planet candidates with the multi-object APOGEE instrument.Comment: Accepted for publication in ApJL, 12 pages, 3 figures, 2 table

Kepler-730: A hot Jupiter system with a close-in, transiting, Earth-sized planet

Kepler-730 is a planetary system hosting a statistically validated hot Jupiter in a 6.49-day orbit and an additional transiting candidate in a 2.85-day orbit. We use spectroscopic radial velocities from the APOGEE-2N instrument, Robo-AO contrast curves, and Gaia distance estimates to statistically validate the planetary nature of the additional Earth-sized candidate. We perform astrophysical false positive probability calculations for the candidate using the available Kepler data and bolster the statistical validation by using radial velocity data to exclude a family of possible binary star solutions. Using a radius estimate for the primary star derived from stellar models, we compute radii of $1.100^{+0.047}_{-0.050}\ R_{Jup}$ and $0.140\pm0.012\ R_{Jup}$ ($1.57\pm0.13\ R_{\oplus}$) for Kepler-730b and Kepler-730c, respectively. Kepler-730 is only the second compact system hosting a hot Jupiter with an inner, transiting planet.Comment: 13 pages, 2 figures, 3 tables, published in ApJ

The First Extrasolar Planet Discovered with a New Generation High Throughput Doppler Instrument

We report the detection of the first extrasolar planet, ET-1 (HD 102195b), using the Exoplanet Tracker (ET), a new generation Doppler instrument. The planet orbits HD 102195, a young star with solar metallicity that may be part of the local association. The planet imparts radial velocity variability to the star with a semiamplitude of $63.4\pm2.0$ m s$^{-1}$ and a period of 4.11 days. The planetary minimum mass ($m \sin i$) is $0.488\pm0.015$ $M_J$.Comment: 42 pages, 11 figures and 5 tables, Accepted for publication in Ap

TOI-150: A transiting hot Jupiter in the TESS southern CVZ

We report the detection of a hot Jupiter ($M_{p}=1.75_{-0.17}^{+0.14}\ M_{J}$,$R_{p}=1.38\pm0.04\ R_{J}$) orbiting a middle-aged star ($\log g=4.152^{+0.030}_{-0.043}$) in the Transiting Exoplanet Survey Satellite (TESS) southern continuous viewing zone ($\beta=-79.59^{\circ}$). We confirm the planetary nature of the candidate TOI-150.01 using radial velocity observations from the APOGEE-2 South spectrograph and the Carnegie Planet Finder Spectrograph, ground-based photometric observations from the robotic Three-hundred MilliMeter Telescope at Las Campanas Observatory, and Gaia distance estimates. Large-scale spectroscopic surveys, such as APOGEE/APOGEE-2, now have sufficient radial velocity precision to directly confirm the signature of giant exoplanets, making such data sets valuable tools in the TESS era. Continual monitoring of TOI-150 by TESS can reveal additional planets and subsequent observations can provide insights into planetary system architectures involving a hot Jupiter around a star about halfway through its main-sequence life.Comment: 13 pages, 3 figures, 2 tables, accepted to ApJ