Substituted phenylarsonic acids; structures and spectroscopy

Full NMR and ESI-MS spectra, and differential scanning calorimeter data are presented for 15 substituted phenylarsonic acids, including two new fluoro-substituted examples. X-ray crystal structure determinations of five examples (phenylarsonic acid and the 4-fluoro-, 4-fluoro-3-nitro-, 3-amino-4-hydroxy- and 3-amino-4-methoxy-substituted derivatives) were determined and the H-bonding crystal-packing patterns analysed

Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS

Potassium isotopic (K-41/K-39) compositions are notoriously difficult to measure. TIMS measurements are hindered by variable fractionation patterns throughout individual runs and too few isotopes to apply an internal spike method for instrumental mass fractionation corrections. Internal fractionation corrections via the K-40/K-39 ratio can provide precise values but assume identical K-40/K-39 ratios (e.g. 0.05% (1sigma) in [1]); this is appropriate in some cases (e.g. identifying excess K-41) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25% precisions (1sigma) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as Ar-38H(+) and Ar-40H(+) and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2% (1sigma, e.g. [3]). Although these precisions may be acceptable for some concentration determinations, they do not resolve isotopic variation in terrestrial materials. Here we present data from a series of measurements made on the Thermo Scientific NEPTUNE Plus multi-collector ICP-MS that demonstrate the ability to make K-41/K-39 ratio measurements with 0.07% precisions (1sigma). These data, collected on NIST K standards, indicate the potential for MC-ICP-MS measurements to look for K isotopic variations at the sub-permil level. The NEPTUNE Plus can sufficiently resolve 39K and 41K from the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma and high-resolution mode. Measurements were made on small but flat, interference-free, plateaus (ca. 50 ppm by mass width for K-41). Although ICP-MS does not yield accurate K-41/K-39 values due to significant instrumental mass fractionation (ca. 6%), this bias can be sufficiently stable over the time required for several measurements so that relative K-41/K-39 values can be precisely determined via sample-standard bracketing. As cold plasma conditions can amplify matrix effects, experiments were conducted to test the matrix tolerance of measurements; the use of clean, matrix-matched samples and standards is critical. Limitations of the cold-plasma high-resolution MC-ICP-MS methodology with respect to matrix tolerance are discussed and compared with the limitations of TIMS methodologies

Age and sex-specific rates of leaf regeneration in the Mojave Desert moss Syntrichia caninervis

The extremely skewed female-biased sex ratio in the desert moss Syntrichia caninervis was investigated by assessing the regeneration capacity of detached leaves. Juvenile, green, yellow-green, and brown leaves equating to approximately 0, 2, 6, and 12 yr of age, respectively, were detached from individuals of S. caninervis collected from 10 field populations and grown in a growth chamber for 58 d at a light intensity of 33–128 µmol · m–2 · s–1. Younger leaves (0–2 yr old) tended to have a greater viability, regenerate more quickly, extend their protonemal filaments farther, produce shoots (gametophores) more quickly, produce more shoots, and accumulate a greater biomass than older leaves (6 and 12 yr old). Among younger leaf classes, regenerating female leaves were more likely to produce a shoot than male leaves and produced more shoots than male leaves. The sexes did not differ significantly in time until protonemal emergence, linear extension of protonemata, or rate of biomass accumulation. However, protonemata of male leaves tended to emerge more quickly and produce a greater total biomass, ultimately consisting mostly of protonemata, than did female leaves. The more rapid proliferation of shoots by female leaf regenerants may help to explain the rarity of males in this species

High-precision determination of lithium and magnesium isotopes utilising single column separation and multi-collector inductively coupled plasma mass spectrometry

Li and Mg isotopes are increasingly used as a combined tool within the geosciences. However, established methods require separate sample purification protocols utilising several column separation procedures. This study presents a single-step cation-exchange method for quantitative separation of trace levels of Li and Mg from multiple sample matrices

Molecular Responses to Thermal and Osmotic Stress in Arctic Intertidal Mussels (Mytilus edulis): The Limits of Resilience.

Increases in Arctic temperatures have accelerated melting of the Greenland icesheet, exposing intertidal organisms, such as the blue mussel Mytilus edulis, to high air temperatures and low salinities in summer. However, the interaction of these combined stressors is poorly described at the transcriptional level. Comparing expression profiles of M. edulis from experimentally warmed (30 °C and 33 °C) animals kept at control (23‱) and low salinities (15‱) revealed a significant lack of enrichment for Gene Ontology terms (GO), indicating that similar processes were active under all conditions. However, there was a progressive increase in the abundance of upregulated genes as each stressor was applied, with synergistic increases at 33 °C and 15‱, suggesting combined stressors push the animal towards their tolerance thresholds. Further analyses comparing the effects of salinity alone (23‱, 15‱ and 5‱) showed high expression of stress and osmoregulatory marker genes at the lowest salinity, implying that the cell is carrying out intracellular osmoregulation to maintain the cytosol as hyperosmotic. Identification of aquaporins and vacuolar-type ATPase transcripts suggested the cell may use fluid-filled cavities to excrete excess intracellular water, as previously identified in embryonic freshwater mussels. These results indicate that M. edulis has considerable resilience to heat stress and highly efficient mechanisms to acclimatise to lowered salinity in a changing world

Characterizing the Cool KOIs. VI. H- and K-band Spectra of Kepler M Dwarf Planet-Candidate Hosts

We present H- and K-band spectra for late-type Kepler Objects of Interest (the "Cool KOIs"): low-mass stars with transiting-planet candidates discovered by NASA's Kepler Mission that are listed on the NASA Exoplanet Archive. We acquired spectra of 103 Cool KOIs and used the indices and calibrations of Rojas-Ayala et al. to determine their spectral types, stellar effective temperatures and metallicities, significantly augmenting previously published values. We interpolate our measured effective temperatures and metallicities onto evolutionary isochrones to determine stellar masses, radii, luminosities and distances, assuming the stars have settled onto the main-sequence. As a choice of isochrones, we use a new suite of Dartmouth predictions that reliably include mid-to-late M dwarf stars. We identify five M4V stars: KOI-961 (confirmed as Kepler 42), KOI-2704, KOI-2842, KOI-4290, and the secondary component to visual binary KOI-1725, which we call KOI-1725 B. We also identify a peculiar star, KOI-3497, which has a Na and Ca lines consistent with a dwarf star but CO lines consistent with a giant. Visible-wavelength adaptive optics imaging reveals two objects within a 1 arc second diameter; however, the objects' colors are peculiar. The spectra and properties presented in this paper serve as a resource for prioritizing follow-up observations and planet validation efforts for the Cool KOIs, and are all available for download online using the "data behind the figure" feature.Comment: Accepted for publication in the Astrophysical Journal Supplement Series (ApJS). Data and table are available in the sourc

Dehydropolymerization of H3B·NMeH2 Using a [Rh(DPEphos)]+ Catalyst : The Promoting Effect of NMeH2

[Rh(κ2-PP-DPEphos){η2η2-H2B(NMe3)(CH2)2tBu}][BArF4] acts as an effective precatalyst for the dehydropolymerization of H3B·NMeH2 to form N-methylpolyaminoborane (H2BNMeH)n. Control of polymer molecular weight is achieved by variation of precatalyst loading (0.1-1 mol %, an inverse relationship) and use of the chain-modifying agent H2: with Mn ranging between 5 500 and 34 900 g/mol and between 1.5 and 1.8. H2 evolution studies (1,2-F2C6H4 solvent) reveal an induction period that gets longer with higher precatalyst loading and complex kinetics with a noninteger order in [Rh]TOTAL. Speciation studies at 10 mol % indicate the initial formation of the amino-borane bridged dimer, [Rh2(κ2-PP-DPEphos)2(μ-H)(μ-H2BN=HMe)][BArF4], followed by the crystallographically characterized amidodiboryl complex [Rh2(cis-κ2-PP-DPEphos)2(σ,μ-(H2B)2NHMe)][BArF4]. Adding ∼2 equiv of NMeH2 in tetrahydrofuran (THF) solution to the precatalyst removes this induction period, pseudo-first-order kinetics are observed, a half-order relationship to [Rh]TOTAL is revealed with regard to dehydrogenation, and polymer molecular weights are increased (e.g., Mn = 40 000 g/mol). Speciation studies suggest that NMeH2 acts to form the precatalysts [Rh(κ2-DPEphos)(NMeH2)2][BArF4] and [Rh(κ2-DPEphos)(H)2(NMeH2)2][BArF4], which were independently synthesized and shown to follow very similar dehydrogenation kinetics, and produce polymers of molecular weight comparable with [Rh(κ2-PP-DPEphos){ η2-H2B(NMe3)(CH2)2tBu}][BArF4], which has been doped with amine. This promoting effect of added amine in situ is shown to be general in other cationic Rh-based systems, and possible mechanistic scenarios are discussed

High-precision 41K/39K measurements by MC-ICP-MS indicate terrestrial variability of δ41K

Potassium is a major component in continental crust, the fourth-most abundant cation in seawater, and a key element in biological processes. Until recently, difficulties with existing analytical techniques hindered our ability to identify natural isotopic variability of potassium isotopes in terrestrial materials. However, measurement precision has greatly improved, and a range of K isotopic compositions has now been demonstrated in natural samples. In this study, we present a new technique for high-precision measurement of K isotopic ratios using high-resolution, cold plasma multi-collector mass spectrometry. We apply this technique to demonstrate natural variability in the ratio of 41K to 39K in a diverse group of geological and biological samples, including silicate and evaporite minerals, seawater, and plant and animal tissues. The total range in 41K/39K ratios is ca. 2.6‰, with a long-term external reproducibility of 0.17‰ (2σ, N=108). Seawater and seawater-derived evaporite minerals are systematically enriched in 41K compared to silicate minerals by ca. 0.6‰, a result consistent with recent findings (1, 2). Although our average bulk- silicate Earth value (-0.54‰) is indistinguishable from previously published values, we find systematic δ41K variability in some high-temperature sample suites, particularly those with evidence for the presence of fluids. The δ41K values of biological samples span a range of ca. 1.2‰ between terrestrial mammals, plants, and marine organisms. Implications of terrestrial K isotope variability for the atomic weight of K and K-based geochronology are discussed. Our results indicate that high-precision measurements of stable K isotopes, made using commercially available mass spectrometers, can provide unique insights into the chemistry of potassium in geological and biological systems