Electrocatalytic reduction of carbon dioxide with a manganese(I)tricarbonyl complex containing a nonaromatic α‑diimine ligand

The 2e reduced anion [Mn(CO)3(iPr-DAB)]− (DAB = 1,4- diazabuta-1,3-diene, iPr = isopropyl) was shown to convert in the presence of CO2 and a small amount of water to the unstable complex [Mn(CO)3(iPr-DAB)(η1-OCO2H)] (OCO2H− = unidentate bicarbonate) that was further reductively transformed to give a stable catalytic intermediate denoted as X2, showing νs(OCO) 1672 and 1646 (sh) cm−1. The subsequent cathodic shift by ca. 650 mV in comparison to the single 2e cathodic wave of the parent [Mn(CO)3(iPr-DAB)Br] triggers the reduction of intermediate X2 and catalytic activity converting CO2 to CO. Infrared spectroelectrochemistry has revealed that the high excess of CO generated at the cathode leads to the conversion of [Mn(CO)3(iPr-DAB)]− to inactive [Mn(CO)5]−. In contrast, the five-coordinate anion [Mn(CO)3(pTol-DAB)]−(pTol = 4-tolyl) is completely inert toward both CO2 and H2O (solvolysis). This detailed spectroelectrochemical study is a further contribution to the development of sustainable electro- and photoelectrocatalysts of CO2 reduction based on abundant first-row transition metals, in particular manganese.

The long-run performance of IPOs: the case of the Stock Exchange of Mauritius

This study examines the long-run performance of initial public offerings on the Stock Exchange of Mauritius (SEM). The results show that the 3-year equally weighted cumulative adjusted returns average −16.5%. The magnitude of this underperformance is consistent with most reported studies in different developed and emerging markets. Based on multivariate regression models, firms with small issues and higher ex ante financial strength seem on average to experience greater long-run underperformance, supporting the divergence of opinion and overreaction hypotheses. On the other hand, Mauritian firms do not on average time their offerings to lower cost of capital and as such, there seems to be limited support for the windows of opportunity hypothesis.

Quantitative single-molecule localization microscopy combined with rule-based modeling reveals ligand-induced TNF-R1 reorganization toward higher-order oligomers

We report on the assembly of tumor necrosis factor receptor 1 (TNF-R1) prior to ligand activation and its ligand-induced reorganization at the cell membrane. We apply single-molecule localization microscopy to obtain quantitative information on receptor cluster sizes and copy numbers. Our data suggest a dimeric pre-assembly of TNF-R1, as well as receptor reorganization toward higher oligomeric states with stable populations comprising three to six TNF-R1. Our experimental results directly serve as input parameters for computational modeling of the ligand-receptor interaction. Simulations corroborate the experimental finding of higher-order oligomeric states. This work is a first demonstration how quantitative, super-resolution and advanced microscopy can be used for systems biology approaches at the single-molecule and single-cell level.

Joint data assimilation of satellite reflectance and net ecosystem exchange data constrains ecosystem carbon fluxes at a high-elevation subalpine forest

We utilized an ecosystem process model (SIPNET, simplified photosynthesis and evapotranspiration model) to estimate carbon fluxes of gross primary productivity and total ecosystem respiration of a high-elevation coniferous forest. The data assimilation routine incorporated aggregated twice-daily measurements of the net ecosystem exchange of CO2 (NEE) and satellite-based reflectance measurements of the fraction of absorbed photosynthetically active radiation (fAPAR) on an eight-day timescale. From these data we conducted a data assimilation experiment with fifteen different combinations of available data using twice-daily NEE, aggregated annual NEE, eight-day f AP AR, and average annual fAPAR. Model parameters were conditioned on three years of NEE and fAPAR data and results were evaluated to determine the information content from the different combinations of data streams. Across the data assimilation experiments conducted, model selection metrics such as the Bayesian Information Criterion and Deviance Information Criterion obtained minimum values when assimilating average annual fAPAR and twice-daily NEE data. Application of wavelet coherence analyses showed higher correlations between measured and modeled fAPAR on longer timescales ranging from 9 to 12 months. There were strong correlations between measured and modeled NEE (R2, coefficient of determination, 0.86), but correlations between measured and modeled eight-day fAPAR were quite poor (R2 = −0.94). We conclude that this inability to determine fAPAR on eight-day timescale would improve with the considerations of the radiative transfer through the plant canopy. Modeled fluxes when assimilating average annual fAPAR and annual NEE were comparable to corresponding results when assimilating twice-daily NEE, albeit at a greater uncertainty. Our results support the conclusion that for this coniferous forest twice-daily NEE data are a critical measurement stream for the data assimilation. The results from this modeling exercise indicate that for this coniferous forest, average annuals for satellite-based fAPAR measurements paired with annual NEE estimates may provide spatial detail to components of ecosystem carbon fluxes in proximity of eddy covariance towers. Inclusion of other independent data streams in the assimilation will also reduce uncertainty on modeled values.

Zero-Dimensional Units of Ligand-Bridged Gallium-Sulfide Supertetrahedra

The synthesis and characterization of the first anions containing two gallium-sulfide supertetrahedra linked via an organic moiety are described.

Understanding the link between single cell and population scale responses of Escherichia coli in differing ligand gradients

We formulate an agent-based population model of Escherichia coli cells which incorporates a description of the chemotaxis signalling cascade at the single cell scale. The model is used to gain insight into the link between the signalling cascade dynamics and the overall population response to differing chemoattractant gradients. Firstly, we consider how the observed variation in total (phosphorylated and unphosphorylated) signalling protein concentration affects the ability of cells to accumulate in differing chemoattractant gradients. Results reveal that a variation in total cell protein concentration between cells may be a mechanism for the survival of cell colonies across a wide range of differing environments. We then study the response of cells in the presence of two different chemoattractants.In doing so we demonstrate that the population scale response depends not on the absolute concentration of each chemoattractant but on the sensitivity of the chemoreceptors to their respective concentrations. Our results show the clear link between single cell features and the overall environment in which cells reside.

Synthesis and evaluation of a novel hydrophilic 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine ligand for separating actinide(III) from lanthanide(III)

We report the synthesis and evaluation of a novel hydrophilic 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) ligand containing carboxylate groups as a selective aqueous complexing agent for the minor actinides over lanthanides. The novel ligand is able to complex and separate Am(III) from Eu(III) in alkaline solutions selectively.

Impact of Interbasin Exchange on the Atlantic Overturning Circulation

The ther mohaline exchange between the Atlantic and the Souther n Ocean is analyzed, using a dataset based on WOCE hydrographic data. It is shown that the salt and heat transports brought about by the South Atlantic subtropical gyre play an essential role in the Atlantic heat and salt budgets. It is found that on average the exported North Atlantic Deep W ater (NADW) is fresher than the retur n flows (basically composed of ther mocline and inter mediate water), indicating that the overtur ning circulation (OC) exports freshwater from the Atlantic. The sensitivity of the OC to interbasin fluxes of heat and salt is studied in a 2 D model, representing the Atlantic between 60 8 N and 30 8 S. The model is forced by mixed boundar y conditions at the sur face, and by realistic fluxes of heat and salt at its 30 8 S boundar y. The model circulation tur ns out to be ver y sensitive to net buoyancy fluxes through the sur face. Both net sur face cooling and net sur face saltening are sources of potential energy and impact positively on the circulation strength. The vertical distributions of the lateral fluxes tend to stabilize the stratification, and, as they extract potential energy from the system, tend to weaken the flow . These results imply that a change in the composition of the NADW retur n transports, whether by a change in the ratio ther mocline/inter mediate water , o r by a change in their ther mohaline characteristics, might influence the Atlantic OC considerably . It is also shown that the circulation is much more sensitive to changes in the shape of the lateral buoyancy flux than to changes in the shape of the sur face buoyancy flux, as the latter does not explicitly impact on the potential energy of the system. It is concluded that interocean fluxes of heat and salt are important for the strength and operation of the Atlantic ther mohaline circulation, and should be correctly represented in models that are used for climate sensitivity studies.

Cambium non est mutuum: exchange and interest rates in medieval Europe

A major gap in our understanding of the medieval economy concerns interest rates, especially relating to commercial credit. Although direct evidence about interest rates is scattered and anecdotal, there is much more surviving information about exchange rates. Since both contemporaries and historians have suggested that exchange and rechange transactions could be used to disguise the charging of interest in order to circumvent the usury prohibition, it should be possible to back out the interest rates from exchange rates. The following analysis is based on a new dataset of medieval exchange rates collected from commercial correspondence in the archive of Francesco di Marco Datini of Prato, c.1383-1411. It demonstrates that the time value of money was consistently incorporated into market exchange rates. Moreover, these implicit interest rates are broadly comparable to those received from other types of commercial loan and investment. Although on average profitable, the return on any individual exchange and rechange transaction did involve a degree of uncertainty that may have justified their non-usurious nature. However, there were also practical reasons why medieval merchants may have used foreign exchange transactions as a means of extending credit.

Retinoid-Related Receptor (ROR) alpha mRNA Expression Is Altered in the Brain of Male Mice Lacking All Ligand-Binding Thyroid Hormone Receptor (TR) Isoforms

In the vertebrate brain, the thalamus serves as a relay and integration station for diverse neuronal information en route from the periphery to the cortex. Deficiency of TH during development results in severe cerebral abnormalities similar to those seen in the mouse when the retinoic acid receptor (ROR)α gene is disrupted. To investigate the effect of the thyroid hormone recep-tors (TRs) on RORalpha gene expression, we used intact male mice, in which the genes encoding the α and beta TRs have been deleted. In situ hybridization for RORalpha mRNA revealed that this gene is expressed in specific areas of the brain including the thalamus, pons, cerebellum, cortex, and hippocampus. Our quantitative data showed differences in RORalpha mRNA expression in different subthalamic nuclei between wild-type and knock-out mice. For example, the centromedial nucleus of the thalamus, which plays a role in mediating nociceptive and visceral information from the brainstem to the basal ganglia and cortical regions, has less expression of RORalpha mRNA in the knockout mice (-37%) compared to the wild-type controls. Also, in the dorsal geniculate (+72%) and lateral posterior nuclei (+58%) we found more RORalpha mRNA in dKO as compared to dWT animals. Such differences in RORalpha mRNA expression may play a role in the behavioral alterations resulting from congenital hypothyroidism.

In silico identification and characterization of protein-ligand binding sites

Protein–ligand binding site prediction methods aim to predict, from amino acid sequence, protein–ligand interactions, putative ligands, and ligand binding site residues using either sequence information, structural information, or a combination of both. In silico characterization of protein–ligand interactions has become extremely important to help determine a protein’s functionality, as in vivo-based functional elucidation is unable to keep pace with the current growth of sequence databases. Additionally, in vitro biochemical functional elucidation is time-consuming, costly, and may not be feasible for large-scale analysis, such as drug discovery. Thus, in silico prediction of protein–ligand interactions must be utilized to aid in functional elucidation. Here, we briefly discuss protein function prediction, prediction of protein–ligand interactions, the Critical Assessment of Techniques for Protein Structure Prediction (CASP) and the Continuous Automated EvaluatiOn (CAMEO) competitions, along with their role in shaping the field. We also discuss, in detail, our cutting-edge web-server method, FunFOLD for the structurally informed prediction of protein–ligand interactions. Furthermore, we provide a step-by-step guide on using the FunFOLD web server and FunFOLD3 downloadable application, along with some real world examples, where the FunFOLD methods have been used to aid functional elucidation.