Heterobimetallic Complexes of Rhenium and Zinc: Potential Catalysts for Homogeneous Syngas Conversion

6-(Diphenylphosphino)-2,2′-bipyridine (PNN) coordinates to rhenium carbonyls in both κ^1(P) and κ^2(N,N) modes; in the former, the free bpy moiety readily binds to zinc alkyls and halides. [Re(κ^1(P)-PNN)(CO)_5][OTf] reacts with dialkylzinc reagents to form [Re(κ^1(P)-PNN·ZnR)(CO)_4(μ_(2-)C(O)R)][OTf] (R = Me, Et, Bn), in which an alkyl group has been transferred to a carbonyl carbon and the resulting monoalkyl Zn is bound both to the bpy nitrogens and the acyl oxygen. ZnCl_2 binds readily to the bpy group in Re(κ^1(P)-PNN)(CO)_4Me, and the resulting adduct undergoes facile migratory insertion, assisted by the Lewis acidic pendent Zn, to yield Re(κ^1(P)-PNN·ZnCl)(μ_(2-)Cl)(CO)_3(μ_(2-)C(O)Me), in which one of the chlorides occupies the sixth coordination site on Re. Migratory insertion is inhibited by THF or other ethers that can coordinate to ZnCl_2. Migratory insertion is also observed for Re(κ1(P)-PNN)(CO)_4(CH_2Ph) but not for Re(κ^1(P)-PNN)(CO)_4(CH_2OCH_3); coordination of the methoxy oxygen to Zn appears to block its ability to coordinate to the carbonyl oxygen and facilitate migratory insertion. Intramolecular Lewis acid promoted hydride transfer from [(dmpe)_2PtH][PF_6] to a carbonyl in [Re(κ^1(P)-PNN)(CO)_5][OTf] results in formation of a Re–formyl species; additional hydride transfer leads to a novel Re–Zn-bonded product along with some formal dehyde

Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme

A variety of C−H and C−C bond forming reactions of group 7 carbonyl complexes have been studied as potential steps in a homogeneously catalyzed conversion of syngas to C_(2+) compounds. The metal formyl complexes M(CO)_3(PPh_3)_2(CHO) (M = Mn, Re) are substantially stabilized by coordination of boranes BX_3 (X = F, C_6F_5) in the form of novel boroxycarbene complexes M(CO)_3(PPh_3)_2(CHOBX_3), but these boron-stabilized carbenes do not react with hydride sources to undergo further reduction to metal alkyls. The related manganese methoxycarbene cations [Mn(CO)_(5−x)(PPh_3)_x(CHOMe)]+ (x = 1 or 2), obtained by methylation of the formyls, do react with hydrides to form methoxymethyl complexes, which undergo further migratory insertion under an atmosphere of CO. The resulting acyls, cis- and trans-Mn(PPh_3)(CO)_4(C(O)CH_2OMe), can be alkylated to form the cationic carbene complex [Mn(PPh_3)(CO)_4(C(OR)CH_2OMe)]^+, which undergoes a 1,2 hydride shift to form 1,2-dialkoxyethylene, which is displaced from the metal, releasing triflate or diethyl ether adducts of [Mn(PPh_3)(CO)_4]^+. The acyl can also be protonated with HOTf to form a hydroxycarbene complex, which rearranges to Mn(PPh_3)(CO)_4(CH_2COOMe) and is protonolyzed to yield methyl acetate and [Mn(PPh_3)(CO)_4]^+; addition of L (L = PPh_3, CO) to the manganese cation regenerates [Mn(PPh_3)(CO)_4(L)]^+. Since the original formyl complex can be obtained by the reaction of [Mn(PPh_3)(CO)_5]^+ with [PtH(dmpe)_2]^+, which in turn can be generated from H_2, this set of transformations amounts to a stoichiometric cycle for selectively converting H_2 and CO into a C_2 compound under mild conditions

Hunting The Most Distant Stars in the Milky Way: Methods and Initial Results

We present a new catalog of 404 M giant candidates found in the UKIRT Infrared Deep Sky Survey (UKIDSS). The 2,400 deg$^2$ available in the UKIDSS Large Area Survey Data Release 8 resolve M giants through a volume four times larger than that of the entire Two Micron All Sky Survey. Combining near-infrared photometry with optical photometry and proper motions from the Sloan Digital Sky Survey yields an M giant candidate catalog with less M dwarf and quasar contamination than previous searches for similarly distant M giants. Extensive follow-up spectroscopy of this sample will yield the first map of our Galaxy's outermost reaches over a large area of sky. Our initial spectroscopic follow-up of $\sim$ 30 bright candidates yielded the positive identification of five M giants at distances $\sim 20-90$ kpc. Each of these confirmed M giants have positions and velocities consistent with the Sagittarius stream. The fainter M giant candidates in our sample have estimated photometric distances $\sim 200$ kpc (assuming $[Fe/H]$ = 0.0), but require further spectroscopic verification. The photometric distance estimates extend beyond the Milky Way's virial radius, and increase by $\sim 50\%$ for each 0.5 dex decrease in assumed $[Fe/H]$. Given the number of M giant candidates, initial selection efficiency, and volume surveyed, we loosely estimate that at least one additional Sagittarius-like accretion event could have contributed to the hierarchical build-up of the Milky Way's outer halo.Comment: 16 pages, 11 figures, emulateapj format. Accepted by A

The Most Distant Stars in the Milky Way

We report on the discovery of the most distant Milky Way (MW) stars known to date: ULAS J001535.72$+$015549.6 and ULAS J074417.48$+$253233.0. These stars were selected as M giant candidates based on their infrared and optical colors and lack of proper motions. We spectroscopically confirmed them as outer halo giants using the MMT/Red Channel spectrograph. Both stars have large estimated distances, with ULAS J001535.72$+$015549.6 at $274 \pm 74$ kpc and ULAS J074417.48$+$253233.0 at 238 $\pm$ 64 kpc, making them the first MW stars discovered beyond 200 kpc. ULAS J001535.72$+$015549.6 and ULAS J074417.48$+$253233.0 are both moving away from the Galactic center at $52 \pm 10$ km s$^{-1}$ and $24 \pm 10$ km s$^{-1}$, respectively. Using their distances and kinematics, we considered possible origins such as: tidal stripping from a dwarf galaxy, ejection from the MW's disk, or membership in an undetected dwarf galaxy. These M giants, along with two inner halo giants that were also confirmed during this campaign, are the first to map largely unexplored regions of our Galaxy's outer halo.Comment: Accepted and in print by ApJL. Seven pages, 2 figure

Kin discrimination, negative relatedness, and how to distinguish between selfishness and spite

Spiteful behaviors occur when an actor harms its own fitness to inflict harm on the fitness of others. Several papers have predicted that spite can be favored in sufficiently small populations, even when the harming behavior is directed indiscriminately at others. However, it is not clear that truly spiteful behavior could be favored without the harm being directed at a subset of social partners with relatively low genetic similarity to the actor (kin discrimination, causing a negative relatedness between actor and harmed recipient). Using mathematical models, we show that (1) the evolution of spite requires kin discrimination; (2) previous models suggesting indiscriminate spite involve scenarios where the actor gains a direct feedback benefit from harming others, and so the harming is selfish rather than spiteful; (3) extreme selfishness can be favored in small populations (or, more generally, under local competition) because this is where the direct feedback benefit of harming is greatest

Ares I Flight Control System Overview

This paper describes the control challenges posed by the Ares I vehicle, the flight control system design and performance analyses used to test and verify the design. The major challenges in developing the control system are structural dynamics, dynamic effects from the powerful first stage booster, aerodynamics, first stage separation and large uncertainties in the dynamic models for all these. Classical control techniques were employed using innovative methods for structural mode filter design and an anti-drift feature to compensate for translational and rotational disturbances. This design was coded into an integrated vehicle flight simulation and tested by Monte Carlo methods. The product of this effort is a linear, robust controller design that is easy to implement, verify and test

Spatial organization and time dependence of Jupiter's tropospheric temperatures, 1980-1993

The spatial organization and time dependence of Jupiter's temperature near 250-millibar pressure were measured through a jovian year by imaging thermal emission at 18 micrometers. The temperature field is influenced by seasonal radiative forcing, and its banded organization is closely correlated with the visible cloud field. Evidence was found for a quasi-periodic oscillation of temperatures in the Equatorial Zone, a correlation between tropospheric and stratospheric waves in the North Equatorial Belt, and slowly moving thermal features in the North and South Equatorial Belts. There appears to be no common relation between temporal changes of temperature and changes in the visual albedo of the various axisymmetric bands

An approach for verifying biogenic greenhouse gas emissions inventories with atmospheric CO₂ concentration data

Verifying national greenhouse gas (GHG) emissions inventories is a critical step to ensure that reported emissions data to the United Nations Framework Convention on Climate Change (UNFCCC) are accurate and representative of a country\u27s contribution to GHG concentrations in the atmosphere. Furthermore, verifying biogenic fluxes provides a check on estimated emissions associated with managing lands for carbon sequestration and other activities, which often have large uncertainties. We report here on the challenges and results associated with a case study using atmospheric measurements of CO₂ concentrations and inverse modeling to verify nationally-reported biogenic CO₂ emissions. The biogenic CO₂ emissions inventory was compiled for the Mid-Continent region of United States based on methods and data used by the US government for reporting to the UNFCCC, along with additional sources and sinks to produce a full carbon balance. The biogenic emissions inventory produced an estimated flux of −408 ± 136 Tg CO₂ for the entire study region, which was not statistically different from the biogenic flux of −478 ± 146 Tg CO₂ that was estimated using the atmospheric CO₂concentration data. At sub-regional scales, the spatial density of atmospheric observations did not appear sufficient to verify emissions in general. However, a difference between the inventory and inversion results was found in one isolated area of West-central Wisconsin. This part of the region is dominated by forestlands, suggesting that further investigation may be warranted into the forest C stock or harvested wood product data from this portion of the study area. The results suggest that observations of atmospheric CO₂ concentration data and inverse modeling could be used to verify biogenic emissions, and provide more confidence in biogenic GHG emissions reporting to the UNFCCC

AI reflections in 2020

We invited authors of selected Comments and Perspectives published in Nature Machine Intelligence in the latter half of 2019 and first half of 2020 to describe how their topic has developed, what their thoughts are about the challenges of 2020, and what they look forward to in 2021.Postprint (author's final draft

Physicians' use of the 5As in counseling obese patients: is the quality of counseling associated with patients' motivation and intention to lose weight?

<p>Abstract</p> <p>Background</p> <p>Physicians are encouraged to counsel obese patients to lose weight, but studies measuring the quality of physicians' counseling are rare. We sought to describe the quality of physicians' obesity counseling and to determine associations between the quality of counseling and obese patients' motivation and intentions to lose weight, key predictors of behavior change.</p> <p>Methods</p> <p>We conducted post-visit surveys with obese patients to assess physician's use of 5As counseling techniques and the overall patient-centeredness of the physician.. Patients also reported on their motivation to lose weight and their intentions to eat healthier and exercise. One-way ANOVAs were used to describe mean differences in number of counseling practices across levels of self-rated intention and motivation. Logistic regression analyses were conducted to assess associations between number of 5As counseling practices used and patient intention and motivation.</p> <p>Results</p> <p>137 patients of 23 physicians were included in the analysis. While 85% of the patients were counseled about obesity, physicians used only a mean of 5.3 (SD = 4.6) of 18 possible 5As counseling practices. Patients with higher levels of motivation and intentions reported receiving more 5As counseling techniques than those with lower levels. Each additional counseling practice was associated with higher odds of being motivated to lose weight (OR 1.31, CI 1.11-1.55), intending to eat better (OR 1.23, CI 1.06-1.44), and intending to exercise regularly (OR 1.14, CI 1.00-1.31). Patient centeredness of the physician was also positively associated with intentions to eat better (OR 2.96, CI 1.03-8.47) and exercise (OR 26.07, CI 3.70-83.93).</p> <p>Conclusions</p> <p>Quality of physician counseling (as measured using the 5As counseling framework and patient-centeredness scales) was associated with motivation to lose weight and intentions to change behavior. Future studies should determine whether higher quality obesity counseling leads to improved behavioral and weight outcomes.</p