CO2 reduction with protons and electrons at a boron-based reaction center.

Borohydrides are widely used reducing agents in chemical synthesis and have emerging energy applications as hydrogen storage materials and reagents for the reduction of CO2. Unfortunately, the high energy cost associated with the multistep preparation of borohydrides starting from alkali metals precludes large scale implementation of these latter uses. One potential solution to this issue is the direct synthesis of borohydrides from the protonation of reduced boron compounds. We herein report reactions of the redox series [Au(B2P2)] n (n = +1, 0, -1) (B2P2, 9,10-bis(2-(diisopropylphosphino)phenyl)-9,10-dihydroboranthrene) and their conversion into corresponding mono- and diborohydride complexes. Crucially, the monoborohydride can be accessed via protonation of [Au(B2P2)]-, a masked borane dianion equivalent accessible at relatively mild potentials (-2.05 V vs. Fc/Fc+). This species reduces CO2 to produce the corresponding formate complex. Cleavage of the formate complex can be achieved by reduction (ca. -1.7 V vs. Fc/Fc+) or by the addition of electrophiles including H+. Additionally, direct reaction of [Au(B2P2)]- with CO2 results in reductive disproportion to release CO and generate a carbonate complex. Together, these reactions constitute a synthetic cycle for CO2 reduction at a boron-based reaction center that proceeds through a B-H unit generated via protonation of a reduced borane with weak organic acids

The results of the in-flight attitude sensor calibration for the Arthur Holly Compton Gamma Ray Observatory

The Arthur Holly Compton Gamma Ray Observatory (GRO) was launched by the shuttle Atlantis in April 1991. This paper presents the results of the attitude sensor calibration that was performed during the early mission. The GSFC Flight Dynamics Facility (FDF) performed an alignment calibration of the two fixed-head star trackers (FHST's) and two fine Sun sensors (FSS's) on board Compton GRO. The results show a 27-arcsecond shift between the bore sights of the FHST's with respect to prelaunch measurements. The alignments of the two FSS's shifted by 0.20 and 0.05 degree. During the same time period, the Compton GRO science teams performed an alignment calibration of the science instruments with respect to the attitude reported by the on board computer (OBC). In order to preserve these science alignments, FDF adjusted the overall alignments of the FHST's and FSS's, obtained by the FDF calibration, such that when up linked to the OBC, the shift in the OBC-determined attitude is minimized. FDF also calibrated the inertial reference unit (IRU), which consists of three dual-axis gyroscopes. The observed gyro bias matched the bias that was solved for by the OBC. This bias drifted during the first 6 days after release. The results of the FDF calibration of scale factor and alignment shifts showed changes that were of the same order as their uncertainties

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

Theory of nuclear excitation by electron capture for heavy ions

We investigate the resonant process of nuclear excitation by electron capture, in which a continuum electron is captured into a bound state of an ion with the simultaneous excitation of the nucleus. In order to derive the cross section a Feshbach projection operator formalism is introduced. Nuclear states and transitions are described by a nuclear collective model and making use of experimental data. Transition rates and total cross sections for NEEC followed by the radiative decay of the excited nucleus are calculated for various heavy ion collision systems

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

Evaluating implicit feedback models using searcher simulations

In this article we describe an evaluation of relevance feedback (RF) algorithms using searcher simulations. Since these algorithms select additional terms for query modification based on inferences made from searcher interaction, not on relevance information searchers explicitly provide (as in traditional RF), we refer to them as implicit feedback models. We introduce six different models that base their decisions on the interactions of searchers and use different approaches to rank query modification terms. The aim of this article is to determine which of these models should be used to assist searchers in the systems we develop. To evaluate these models we used searcher simulations that afforded us more control over the experimental conditions than experiments with human subjects and allowed complex interaction to be modeled without the need for costly human experimentation. The simulation-based evaluation methodology measures how well the models learn the distribution of terms across relevant documents (i.e., learn what information is relevant) and how well they improve search effectiveness (i.e., create effective search queries). Our findings show that an implicit feedback model based on Jeffrey's rule of conditioning outperformed other models under investigation

The localization transition at finite temperatures: electric and thermal transport

The Anderson localization transition is considered at finite temperatures. This includes the electrical conductivity as well as the electronic thermal conductivity and the thermoelectric coefficients. An interesting critical behavior of the latter is found. A method for characterizing the conductivity critical exponent, an important signature of the transition, using the conductivity and thermopower measurements, is outlined.Comment: Article for the book: "50 Years of Anderson Localization", edited by E. Abrahams (World Scientific, Singapore, 2010

Mobile app and app store analysis, testing and optimisation

This talk presents results on analysis and testing of mobile apps and app stores, reviewing the work of the UCL App Analysis Group (UCLappA) on App Store Mining and Analysis. The talk also covers the work of the UCL CREST centre on Genetic Improvement, applicable to app improvement and optimisation

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