Mechanism, reactivity, and selectivity of nickel-catalyzed [4 + 4 + 2] cycloadditions of dienes and alkynes.

Density functional theory (DFT) calculations with B3LYP and M06 functionals elucidated the reactivities of alkynes and Z/E selectivity of cyclodecatriene products in the Ni-catalyzed [4 + 4 + 2] cycloadditions of dienes and alkynes. The Ni-mediated oxidative cyclization of butadienes determines the Z/E selectivity. Only the oxidative cyclization of one s-cis to one s-trans butadiene is facile and exergonic, leading to the observed 1Z,4Z,8E-cyclodecatriene product. The same step with two s-cis or s-trans butadienes is either kinetically or thermodynamically unfavorable, and the 1Z,4E,8E- and 1Z,4Z,8Z-cyclodecatriene isomers are not observed in experiments. In addition, the competition between the desired cooligomerization and [2 + 2 + 2] cycloadditions of alkynes depends on the coordination of alkynes. With either electron-deficient alkynes or alkynes with free hydroxyl groups, the coordination of alkynes is stronger than that of dienes, and alkyne trimerization prevails. With alkyl-substituted alkynes, the generation of alkyne-coordinated nickel complex is much less favorable, and the [4 + 4 + 2] cycloaddition occurs

High Resolution Spectroscopy and Spectropolarimetry of some late F-/early G-type sun-like stars as targets for Zeeman Doppler imaging

High resolution spectroscopy and spectropolarimetry have been undertaken at the Anglo-Australian Telescope in order to identify suitable targets for magnetic studies of young sun-like stars, for the proxy study of early solar evolution. This study involved the investigation of some variable late F-/early G-type sun-like stars originally identified by the Hipparcos mission. Of the 38 stars observed for this study, HIP 31021, HIP 64732, HIP 73780 were found to be spectroscopic binary stars while HIP 19072, HIP 67651 and HIP 75636 are also likely to be binaries while HIP 33111 could even be a triple system. Magnetic fields were detected on a number of the survey stars: HIP 21632, HIP 43720, HIP 48770, HIP 62517, HIP 71933, HIP 77144, HIP 89829, HIP 90899 and HIP 105388, making these stars good candidates for follow-up Zeeman Doppler imaging studies.Comment: 16 pages, 16 figures, 4 tables Accepted for publication in PAS

Alternating magnetic anisotropy of Li2_2(Li1−xTx_{1-x}T_x)N with TT = Mn, Fe, Co, and Ni

Substantial amounts of the transition metals Mn, Fe, Co, and Ni can be substituted for Li in single crystalline Li$_2$(Li$_{1-x}T_x$)N. Isothermal and temperature-dependent magnetization measurements reveal local magnetic moments with magnitudes significantly exceeding the spin-only value. The additional contributions stem from unquenched orbital moments that lead to rare-earth-like behavior of the magnetic properties. Accordingly, extremely large magnetic anisotropies have been found. Most notably, the magnetic anisotropy alternates as easy-plane $\rightarrow$ easy-axis $\rightarrow$ easy-plane $\rightarrow$ easy-axis when progressing from $T$ = Mn $\rightarrow$ Fe $\rightarrow$ Co $\rightarrow$ Ni. This behavior can be understood based on a perturbation approach in an analytical, single-ion model. The calculated magnetic anisotropies show a surprisingly good agreement with the experiment and capture the basic features observed for the different transition metals.Comment: 5 pages, 3 figures, published as PRB Rapid Communication, Fig. 3 update

ASAS Light Curves of Intermediate Mass Eclipsing Binaries and the Parameters of HI Mon

We present a catalog of 56 candidate intermediate mass eclipsing binary systems extracted from the 3rd data release of the All Sky Automated Survey. We gather pertinent observational data and derive orbital properties, including ephemerides, for these systems as a prelude to anticipated spectroscopic observations. We find that 37 of the 56, or ~66% of the systems are not identified in the Simbad Astronomical Database as known binaries. As a specific example, we show spectroscopic data obtained for the system HI Mon (B0 V + B0.5 V) observed at key orbital phases based on the computed ephemeris, and we present a combined spectroscopic and photometric solution for the system and give stellar parameters for each component.Comment: 83 pages, 63 figure

Target selection for the SUNS and DEBRIS surveys for debris discs in the solar neighbourhood

Debris discs - analogous to the Asteroid and Kuiper-Edgeworth belts in the Solar system - have so far mostly been identified and studied in thermal emission shortward of 100 um. The Herschel space observatory and the SCUBA-2 camera on the James Clerk Maxwell Telescope will allow efficient photometric surveying at 70 to 850 um, which allow for the detection of cooler discs not yet discovered, and the measurement of disc masses and temperatures when combined with shorter wavelength photometry. The SCUBA-2 Unbiased Nearby Stars (SUNS) survey and the DEBRIS Herschel Open Time Key Project are complimentary legacy surveys observing samples of ~500 nearby stellar systems. To maximise the legacy value of these surveys, great care has gone into the target selection process. This paper describes the target selection process and presents the target lists of these two surveys.Comment: 67 pages with full tables, 7 figures, accepted to MNRA

The search for habitable worlds: 1. The viability of a starshade mission

As part of NASA's mission to explore habitable planets orbiting nearby stars, this paper explores the detection and characterization capabilities of a 4-m space telescope plus 50-m starshade located at the Earth-Sun L2 point, a.k.a. the New Worlds Observer (NWO). Our calculations include the true spectral types and distribution of stars on the sky, an iterative target selection protocol designed to maximize efficiency based on prior detections, and realistic mission constraints. We carry out both analytical calculations and simulated observing runs for a wide range in exozodiacal background levels ({\epsilon} = 1 - 100 times the local zodi brightness) and overall prevalence of Earth-like terrestrial planets ({\eta}\oplus = 0.1 - 1). We find that even without any return visits, the NWO baseline architecture (IWA = 65 mas, limiting FPB = 4\times10-11) can achieve a 95% probability of detecting and spectrally characterizing at least one habitable Earth-like planet, and an expectation value of ~3 planets found, within the mission lifetime and {\Delta}V budgets, even in the worst-case scenario ({\eta}\oplus = 0.1 and {\epsilon} = 100 zodis for every target). This achievement requires about one year of integration time spread over the 5 year mission, leaving the remainder of the telescope time for UV-NIR General Astrophysics. Cost and technical feasibility considerations point to a "sweet spot" in starshade design near a 50-m starshade effective diameter, with 12 or 16 petals, at a distance of 70,000-100,000 km from the telescope.Comment: Refereed and accepted to PASP, scheduled for publication in the May 2012 issue (Vol. 124, No. 915

Isomeric triazines exhibit unique profiles of bioorthogonal reactivity.

Expanding the scope of bioorthogonal reactivity requires access to new and mutually compatible reagents. We report here that 1,2,4-triazines can be tuned to exhibit unique reaction profiles with biocompatible strained alkenes and alkynes. Computational analyses were used to identify candidate orthogonal reactions, and the predictions were experimentally verified. Notably, 5-substituted triazines, unlike their 6-substituted counterparts, undergo rapid [4 + 2] cycloadditions with a sterically encumbered strained alkyne. This unique, sterically controlled reactivity was exploited for dual bioorthogonal labeling. Mutually orthogonal triazines and cycloaddition chemistries will enable new multi-component imaging applications