Facile Si–H bond activation and hydrosilylation catalysis mediated by a nickel–borane complex

Metal–borane complexes are emerging as promising systems for study in the context of bifunctional catalysis. Herein we describe diphosphineborane nickel complexes that activate Si–H bonds and catalyze the hydrosilylation of aldehydes. Treatment of [^(Mes)DPB^(Ph)]Ni (1) ([^(Mes)DPB^Ph] = ^(Mes)B(o-Ph_2PC_6H_4)_2) with organosilanes affords the complexes [^(Mes)DPB^(Ph)](μ-H)NiE (E = SiH_2Ph (3), SiHPh_2 (4)). Complex 4 is in solution equilibrium with 1 and the thermodynamic and kinetic parameters of their exchange have been characterized by NMR spectroscopy. Complex 1 is a catalyst for the hydrosilylation of a range of para-substituted benzaldehydes. Mechanistic studies on this reaction via multinuclear NMR spectroscopy are consistent with the intermediacy of a borohydrido-Ni-siloxyalkyl species

Sensitivity of Ag/Al Interface Specific Resistances to Interfacial Intermixing

We have measured an Ag/Al interface specific resistance, 2AR(Ag/Al)(111) = 1.4 fOhm-m^2, that is twice that predicted for a perfect interface, 50% larger than for a 2 ML 50%-50% alloy, and even larger than our newly predicted 1.3 fOhmm^2 for a 4 ML 50%-50% alloy. Such a large value of 2ARAg/Al(111) confirms a predicted sensitivity to interfacial disorder and suggests an interface greater than or equal to 4 ML thick. From our calculations, a predicted anisotropy ratio, 2AR(Ag/Al)(001)/2AR(Ag/Al)(111), of more then 4 for a perfect interface, should be reduced to less than 2 for a 4 ML interface, making it harder to detect any such anisotropy.Comment: 3 pages, 2 figures, 1 table. In Press: Journal of Applied Physic

Modeling canopy-induced turbulence in the Earth system: a unified parameterization of turbulent exchange within plant canopies and the roughness sublayer (CLM-ml v0)

Land surface models used in climate models neglect the roughness sublayer and parameterize within-canopy turbulence in an ad hoc manner. We implemented a roughness sublayer turbulence parameterization in a multilayer canopy model (CLM-ml v0) to test if this theory provides a tractable parameterization extending from the ground through the canopy and the roughness sublayer. We compared the canopy model with the Community Land Model (CLM4.5) at seven forest, two grassland, and three cropland AmeriFlux sites over a range of canopy heights, leaf area indexes, and climates. CLM4.5 has pronounced biases during summer months at forest sites in midday latent heat flux, sensible heat flux, gross primary production, nighttime friction velocity, and the radiative temperature diurnal range. The new canopy model reduces these biases by introducing new physics. Advances in modeling stomatal conductance and canopy physiology beyond what is in CLM4.5 substantially improve model performance at the forest sites. The signature of the roughness sublayer is most evident in nighttime friction velocity and the diurnal cycle of radiative temperature, but is also seen in sensible heat flux. Within-canopy temperature profiles are markedly different compared with profiles obtained using Monin–Obukhov similarity theory, and the roughness sublayer produces cooler daytime and warmer nighttime temperatures. The herbaceous sites also show model improvements, but the improvements are related less systematically to the roughness sublayer parameterization in these canopies. The multilayer canopy with the roughness sublayer turbulence improves simulations compared with CLM4.5 while also advancing the theoretical basis for surface flux parameterizations

Identifying Planetary Biosignature Impostors: Spectral Features of CO and O4 Resulting from Abiotic O2/O3 Production

O2 and O3 have been long considered the most robust individual biosignature gases in a planetary atmosphere, yet multiple mechanisms that may produce them in the absence of life have been described. However, these abiotic planetary mechanisms modify the environment in potentially identifiable ways. Here we briefly discuss two of the most detectable spectral discriminants for abiotic O2/O3: CO and O4. We produce the first explicit self-consistent simulations of these spectral discriminants as they may be seen by JWST. If JWST-NIRISS and/or NIRSpec observe CO (2.35, 4.6 um) in conjunction with CO2 (1.6, 2.0, 4.3 um) in the transmission spectrum of a terrestrial planet it could indicate robust CO2 photolysis and suggest that a future detection of O2 or O3 might not be biogenic. Strong O4 bands seen in transmission at 1.06 and 1.27 um could be diagnostic of a post-runaway O2-dominated atmosphere from massive H-escape. We find that for these false positive scenarios, CO at 2.35 um, CO2 at 2.0 and 4.3 um, and O4 at 1.27 um are all stronger features in transmission than O2/O3 and could be detected with SNRs $\gtrsim$ 3 for an Earth-size planet orbiting a nearby M dwarf star with as few as 10 transits, assuming photon-limited noise. O4 bands could also be sought in UV/VIS/NIR reflected light (at 0.345, 0.36, 0.38, 0.445, 0.475, 0.53, 0.57, 0.63, 1.06, and 1.27 um) by a next generation direct-imaging telescope such as LUVOIR/HDST or HabEx and would indicate an oxygen atmosphere too massive to be biologically produced.Comment: 7 pages, 4 figures, accepted to the Astrophysical Journal Letter

Khinchin theorem for integral points on quadratic varieties

We prove an analogue the Khinchin theorem for the Diophantine approximation by integer vectors lying on a quadratic variety. The proof is based on the study of a dynamical system on a homogeneous space of the orthogonal group. We show that in this system, generic trajectories visit a family of shrinking subsets infinitely often.Comment: 19 page

Detection of metastable electronic states by Penning trap mass spectrometry

State-of-the-art optical clocks achieve fractional precisions of $10^{-18}$ and below using ensembles of atoms in optical lattices or individual ions in radio-frequency traps. Promising candidates for novel clocks are highly charged ions (HCIs) and nuclear transitions, which are largely insensitive to external perturbations and reach wavelengths beyond the optical range, now becoming accessible to frequency combs. However, insufficiently accurate atomic structure calculations still hinder the identification of suitable transitions in HCIs. Here, we report on the discovery of a long-lived metastable electronic state in a HCI by measuring the mass difference of the ground and the excited state in Re, the first non-destructive, direct determination of an electronic excitation energy. This result agrees with our advanced calculations, and we confirmed them with an Os ion with the same electronic configuration. We used the high-precision Penning-trap mass spectrometer PENTATRAP, unique in its synchronous use of five individual traps for simultaneous mass measurements. The cyclotron frequency ratio $R$ of the ion in the ground state to the metastable state could be determined to a precision of $\delta R=1\cdot 10^{-11}$, unprecedented in the heavy atom regime. With a lifetime of about 130 days, the potential soft x-ray frequency reference at $\nu=4.86\cdot 10^{16}\,\text{Hz}$ has a linewidth of only $\Delta \nu\approx 5\cdot 10^{-8}\,\text{Hz}$, and one of the highest electronic quality factor ($Q=\frac{\nu}{\Delta \nu}\approx 10^{24}$) ever seen in an experiment. Our low uncertainty enables searching for more HCI soft x-ray clock transitions, needed for promising precision studies of fundamental physics in a thus far unexplored frontier

The interplay between extrinsic and intrinsic factors in determining migration decisions in brown trout (Salmo trutta): An experimental study

Many species are capable of facultative migration, but the relative roles of extrinsic versus intrinsic factors in generating diverse migratory tactics remain unclear. Here we explore the proximate drivers of facultative migration in brown trout in an experimental laboratory setting. The effects of reduced food, as a putative environmental cue, were examined in two populations: one that exhibits high rates of anadromy (sea-migration) in nature, and one that does not exhibit anadromy in nature. Juveniles derived from wild-caught parents were reared for two years under four environmental treatments: low food in years 1 and 2 (Low-Low); high food in years 1 and 2 (High-High), low food in year 1 and high in year 2 (Low-High), and vice versa (High-Low). Food restriction had a significant effect on migratory tactics, with the frequency of smolts (juveniles choosing migration) highest in the Low-Low treatment in both populations. No individuals became smolts in the High-High treatment, and intermediate smolting rates were observed in the Low-High and High-Low treatments. Higher overall smolting rates in the naturally anadromous population suggested an inherited component to anadromy/migration decisions, but both populations showed variability in migratory tactics. Importantly, some fish from the naturally non-anadromous population became smolts in the experiment, implying the capacity for migration was lying ‘dormant’, but they exhibited lower hypo-osmoregulatory function than smolts from the naturally anadromous population. Tactic frequencies in the naturally anadromous population were more affected by food in the 2nd year, while food in the 1st year appeared more important for the naturally non-anadromous population. Migratory tactics were also related to sex, but underpinned in both sexes by growth in key periods, size and energetic state. Collectively these results reveal how migration decisions are shaped by a complex interplay between extrinsic and intrinsic factors, informing our ability to predict how facultatively migratory populations will respond to environmental change

Isotope shift in the dielectronic recombination of three-electron ^{A}Nd^{57+}

Isotope shifts in dielectronic recombination spectra were studied for Li-like ^{A}Nd^{57+} ions with A=142 and A=150. From the displacement of resonance positions energy shifts \delta E^{142,150}(2s-2p_1/2)= 40.2(3)(6) meV (stat)(sys)) and \delta E^{142,150}(2s-2p_3/2) = 42.3(12)(20) meV of 2s-2p_j transitions were deduced. An evaluation of these values within a full QED treatment yields a change in the mean-square charge radius of ^{142,150}\delta = -1.36(1)(3) fm^2. The approach is conceptually new and combines the advantage of a simple atomic structure with high sensitivity to nuclear size.Comment: 10 pages, 3 figures, accepted for publication in Physical Review Letter

Identification of genes encoding antimicrobial proteins in Langerhans cells

Langerhans cells (LCs) reside in the epidermis where they are poised to mount an antimicrobial response against microbial pathogens invading from the outside environment. To elucidate potential pathways by which LCs contribute to host defense, we mined published LC transcriptomes deposited in GEO and the scientific literature for genes that participate in antimicrobial responses. Overall, we identified 31 genes in LCs that encode proteins that contribute to antimicrobial activity, ten of which were cross-validated in at least two separate experiments. Seven of these ten antimicrobial genes encode chemokines

Locating regional health policy: Institutions, politics, and practices

Poverty reduction and health became central in the agendas of Southern regional organisations in the last two decades. Yet, little is known about how these organisations address poverty, inclusion and social inequality, and how Southern regional formations are engaging in power constellations, institutions, processes, interests and ideological positions within different spheres of governance. This article reviews academic literatures spanning global social policy, regional studies and diplomacy studies, and the state of knowledge and understanding of the ‘place’ of regional actors in health governance as a global political practice therein. It identifies theoretical and thematic points of connection between disparate literatures and how these can be bridged through research focusing on the social policies of regional organisations and regional integration processes. This framework hence locates the contributions of each of the research articles of this Special Issue of Global Social Policy on the regional dimension of health policy and diplomacy in relation to Southern Africa and South America. It also highlights the ways in which the articles bring new evidence about how social relations of welfare are being (re)made over larger scales and how regional actors may initiate new norms to improve health rights in international arenas engaging in new forms of ‘regional’ diplomacy