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Abstract Olefin carbofunctionalization reactions are indispensable tools for constructing diverse, functionalized scaffolds from simple starting materials. However, achieving precise control over regioselectivity in intermolecular reactions remains a formidable challenge. Here, we demonstrate that using PAd2 n Bu as a ligand enables regioselective heteroannulation of o-bromoanilines with branched 1,3-dienes through ligand control. This approach provides regiodivergent access to 3-substituted indolines, showcasing excellent regioselectivity and reactivity across a range of functionalized substrates. To gain further insights into the origin of selectivity control, we employ a data-driven strategy, developing a linear regression model using calculated parameters for phosphorus ligands. This model identifies four key parameters governing regioselectivity in this transformation, paving the way for future methodology development. Additionally, density functional theory calculations elucidate key selectivity-determining transition structures along the reaction pathway, corroborating our experimental observations and establishing a solid foundation for future advancements in regioselective olefin difunctionalization reactions.

Abstract Background ATP-regulated potassium channels (KATP) regulate pulmonary vascular tone and are involved in hypoxic pulmonary vasoconstriction (HPV). In patients with inflammation like sepsis or ARDS, HPV is impaired, resulting in a ventilation-perfusion mismatch and hypoxia. Since increase of vascular KATP channel Kir6.1 has been reported in animal models of endotoxemia, we studied the expression and physiological effects of Kir6.1 in murine endotoxemic lungs. We hypothesized that inhibition of overexpressed Kir6.1 increases HPV in endotoxemia. Methods Mice (C57BL/6; n = 55) with (n = 27) and without (n = 28) endotoxemia (35 mg/kg LPS i.p. for 18 h) were analyzed for Kir6.1 gene as well as protein expression and HPV was examined in isolated perfused mouse lungs with and without selective inhibition of Kir6.1 with PNU-37883A. Pulmonary artery pressure (PAP) and pressure-flow curves during normoxic (FiO2 0.21) and hypoxic (FiO2 0.01) ventilation were obtained. HPV was quantified as the increase in perfusion pressure in response to hypoxic ventilation in mmHg of baseline perfusion pressure (ΔPAP) in the presence and absence of PNU-37883A. Results Endotoxemia increases pulmonary Kir6.1 gene (+ 2.8 ± 0.3-fold) and protein expression (+ 2.1 ± 0.3-fold). Hypoxia increases HPV in lungs of control animals, while endotoxemia decreases HPV (∆PAP control: 9.2 ± 0.9 mmHg vs. LPS: 3.0 ± 0.7 mmHg, p

We compare the magnetic field data obtained from the flux-gate magnetometer (FGM) and the magnetic field data deduced from the gyration time of electrons measured by the electron drift instrument (EDI) onboard Cluster to determine the spin-axis offset of the FGM measurements. Data are used from orbits with their apogees in the magnetotail, when the magnetic field magnitude was between about 20 and 500 nT. Offset determination with the EDI–FGM comparison method is of particular interest for these orbits, because no data from solar wind are available in such orbits to apply the usual calibration methods using the Alfvén waves. In this paper, we examine the effects of the different measurement conditions, such as direction of the magnetic field relative to the spin plane and field magnitude in determining the FGM spin-axis offset, and also take into account the time-of-flight offset of the EDI measurements. It is shown that the method works best when the magnetic field magnitude is less than about 128 nT and when the magnetic field is aligned near the spin-axis direction. A remaining spin-axis offset of about 0.4 ∼ 0.6 nT was observed for Cluster 1 between July and October 2003. Using multipoint multi-instrument measurements by Cluster we further demonstrate the importance of the accurate determination of the spin-axis offset when estimating the magnetic field gradient.

The Earth's magnetosphere is populated by particles originating from the solar wind and the terrestrial ionosphere. A substantial fraction of the plasma from these sources are convected through the magnetotail lobes. In this paper, we present a statistical study of convective plasma transport through the Earth's magnetotail lobes for various geomagnetic conditions. The results are based on a combination of density measurements from the Electric Field and Waves Experiment (EFW) and convection velocities from the Electron Drift Instrument (EDI) on board the Cluster spacecraft. The results show that variations in the plasma flow is primarily attributed to changes in the convection velocity, whereas the plasma density remains fairly constant and shows little correlation with geomagnetic activity. During disturbed conditions there is also an increased abundance of heavier ions, which combined with enhanced convection, cause an accentuation of the mass flow. The convective transport is much slower than the field aligned transport. A substantial amount of plasma therefore escape downtail without ever reaching the central plasma sheet.

Low-energy ions escape from the ionosphere and constitute a large part of the magnetospheric content, especially in the geomagnetic tail lobes. However, they are normally invisible to spacecraft measurements, since the potential of a sunlit spacecraft in a tenuous plasma in many cases exceeds the energy-per-charge of the ions, and little is therefore known about their outflow properties far from the Earth. Here we present an extensive statistical study of cold ion outflows (0–60 eV) in the geomagnetic tail at geocentric distances from 5 to 19 RE using the Cluster spacecraft during the period from 2001 to 2005. Our results were obtained by a new method, relying on the detection of a wake behind the spacecraft. We show that the cold ions dominate in both flux and density in large regions of the magnetosphere. Most of the cold ions are found to escape from the Earth, which improves previous estimates of the global outflow. The local outflow in the magnetotail corresponds to a global outflow of the order of 1026 ions s−1. The size of the outflow depends on different solar and magnetic activity levels.

In this study, we investigate statistical, systematic variations of the high-latitude convection cell structure during northward IMF. Using 1-min-averages of Cluster/EDI electron drift observations above the Northern and Southern polar cap areas for six and a half years (February 2001 till July 2007), and mapping the spatially distributed measurements to a common reference plane at ionospheric level in a magnetic latitude/MLT grid, we obtained regular drift patterns according to the various IMF conditions. We focus on the particular conditions during northward IMF, where lobe cells at magnetic latitudes >80° with opposite (sunward) convection over the central polar cap are a permanent feature in addition to the main convection cells at lower latitudes. They are due to reconnection processes at the magnetopause boundary poleward of the cusp regions. Mapped EDI data have a particular good coverage within the central part of the polar cap, so that these patterns and their dependence on various solar wind conditions are well verified in a statistical sense. On average, 4-cell convection pattern are shown as regular structures during periods of nearly northward IMF with the tendency of a small shift toward negative clock angles. The positions of these high-latitude convection foci are within 79° to 85° magnetic latitude and 09:00–15:00 MLT. The MLT positions are approximately symmetric ±2 h about 11:30 MLT, i.e. slightly offset from midday toward prenoon hours, while the maximum (minimum) potential of the high-latitude cells is at higher magnetic latitudes near their maximum potential difference at ≈−10° to −15° clock angle for the North (South) Hemisphere. With increasing clock angle distances from ≈IMFBz+, a gradual transition occurs from the 4-cell pattern via a 3-cell to the common 2-cell convection pattern, in the course of which one of the medium-scale high-latitude dayside cells diminishes and disappears while the other intensifies and merges with the opposite main cell of the same polarity to form the large "round-shaped" convection cell when approaching a well-known IMFBy-dominated configuration. Opposite scenarios with interchanged roles of the respective cells occur for the opposite turning of the clock angle and at the Southern Hemisphere. The high-latitude dayside cells become more pronounced with increasing magnitude of the IMF vector.

A major part of the plasma in the Earth's magnetotail is populated through transport of plasma from the solar wind via the magnetotail lobes. In this paper, we present a statistical study of plasma convection in the lobes for different directions of the interplanetary magnetic field and for different geomagnetic disturbance levels. The data set used in this study consists of roughly 340 000 one-minute vector measurements of the plasma convection from the Cluster Electron Drift Instrument (EDI) obtained during the period February 2001 to June 2007. The results show that both convection magnitude and direction are largely controlled by the interplanetary magnetic field (IMF). For a southward IMF, there is a strong convection towards the central plasma sheet with convection velocities around 10 km s−1. During periods of northward IMF, the lobe convection is almost stagnant. A By dominated IMF causes a rotation of the convection patterns in the tail with an oppositely directed dawn-dusk component of the convection for the northern and southern lobe. Our results also show that there is an overall persistent duskward component, which is most likely a result of conductivity gradients in the footpoints of the magnetic field lines in the ionosphere.

Based on drift velocity measurements of the EDI instruments on Cluster during the years 2001–2006, we have constructed a database of high-latitude ionospheric convection velocities and associated solar wind and magnetospheric activity parameters. In an earlier paper (Haaland et al., 2007), we have described the method, consisting of an improved technique for calculating the propagation delay between the chosen solar wind monitor (ACE) and Earth's magnetosphere, filtering the data for periods of sufficiently stable IMF orientations, and mapping the EDI measurements from their high-altitude positions to ionospheric altitudes. The present paper extends this study, by looking at the spatial pattern of the variances of the convection velocities as a function of IMF orientation, and by performing sortings of the data according to the IMF magnitude in the GSM y-z plane, |ByzIMF|, the estimated reconnection electric field, Er,sw, the solar wind dynamic pressure, Pdyn, the season, and indices characterizing the ring current (Dst) and tail activity (ASYM-H). The variability of the high-latitude convection shows characteristic spatial patterns, which are mirror symmetric between the Northern and Southern Hemispheres with respect to the IMF By component. The latitude range of the highest variability zone varies with IMF Bz similar to the auroral oval extent. The magnitude of convection standard deviations is of the same order as, or even larger than, the convection magnitude itself. Positive correlations of polar cap activity are found with |ByzIMF| and with Er,sw, in particular. The strict linear increase for small magnitudes of Er,sw starts to deviate toward a flattened increase above about 2 mV/m. There is also a weak positive correlation with Pdyn. At very small values of Pdyn, a secondary maximum appears, which is even more pronounced for the correlation with solar wind proton density. Evidence for enhanced nightside convection during high nightside activity is presented.

We have used vector measurements of the electron drift velocity made by the Electron Drift Instrument (EDI) on Cluster between February 2001 and March 2006 to derive statistical maps of the high-latitude plasma convection. The EDI measurements, obtained at geocentric distances between ~4 and ~20 RE over both hemispheres, are mapped into the polar ionosphere, and sorted according to the clock-angle of the interplanetary magnetic field (IMF), measured at ACE and propagated to Earth, using best estimates of the orientation of the IMF variations. Only intervals of stable IMF are used, based on the magnitude of a "bias-vector" constructed from 30-min averages. The resulting data set consists of a total of 5862 h of EDI data. Contour maps of the electric potential in the polar ionosphere are subsequently derived from the mapped and averaged ionospheric drift vectors. Comparison with published statistical results based on Super Dual Auroral Radar Network (SuperDARN) radar and low-altitude satellite measurements shows excellent agreement between the average convection patterns, and in particular the lack of mirror-symmetry between the effects of positive and negative IMF By, the appearance of a duskward flow component for strongly southward IMF, and the general weakening of the average flows and potentials for northerly IMF directions. This agreement lends credence to the validity of the assumption underlying the mapping of the EDI data, namely that magnetic field lines are equipotentials. For strongly northward IMF the mapped EDI data show the clear emergence of two counter-rotating lobe cells with a channel of sunward flow between them. The total potential drops across the polar caps obtained from the mapped EDI data are intermediate between the radar and the low-altitude satellite results.

The four Cluster satellites each carry two instruments designed for measuring the electric field: a double-probe instrument (EFW) and an electron drift instrument (EDI). We compare data from the two instruments in a representative sample of plasma regions. The complementary merits and weaknesses of the two techniques are illustrated. EDI operations are confined to regions of magnetic fields above 30 nT and where wave activity and keV electron fluxes are not too high, while EFW can provide data everywhere, and can go far higher in sampling frequency than EDI. On the other hand, the EDI technique is immune to variations in the low energy plasma, while EFW sometimes detects significant nongeophysical electric fields, particularly in regions with drifting plasma, with ion energy (in eV) below the spacecraft potential (in volts). We show that the polar cap is a particularly intricate region for the double-probe technique, where large nongeophysical fields regularly contaminate EFW measurments of the DC electric field. We present a model explaining this in terms of enhanced cold plasma wake effects appearing when the ion flow energy is higher than the thermal energy but below the spacecraft potential multiplied by the ion charge. We suggest that these conditions, which are typical of the polar wind and occur sporadically in other regions containing a significant low energy ion population, cause a large cold plasma wake behind the spacecraft, resulting in spurious electric fields in EFW data. This interpretation is supported by an analysis of the direction of the spurious electric field, and by showing that use of active potential control alleviates the situation.

In this paper we report measurements of the convection obtained with the Electron Drift Instrument (EDI) on Cluster. We use 20 passes that cross the between its dayside and nightside boundaries (or vice versa) at geocentric distances ranging from about 5 to about 13RE, and at interspacecraft separations (transverse to the ambient magnetic field) between a few km and almost 10000km. We first illustrate the nature of the data by presenting four passes in detail. They demonstrate that the sense of convection (anti-sunward vs. sunward) essentially agrees with the expectations based on magnetic reconnection occurring on the dayside or poleward of the cusp. The most striking feature in the EDI data is the occurrence of large-amplitude fluctuations that are superimposed on the average velocities. One type of fluctuation appears to grow when approaching the dayside boundary. The examples also show that there is a variable degree of inter-spacecraft correlation, ranging from excellent to poor. We then present statistical results on all 20 passes. Plotting 10-min averages of the convection velocities vs. IMF Bz one recovers the expected dependence, albeit with large scatter. Looking at the variances computed over the same 10-min intervals, one confirms that there is indeed one type of contribution that grows towards the dayside boundary, but that variances can be high anywhere. Finally, computing the inter-spacecraft correlations as a function of their separation distance transverse to the magnetic field shows that the average correlation drops with increasing distance, but that even at distances as large as 5000km the correlation can be very good. To put those scales into context, the separation distances have also been scaled to ionospheric altitudes where they range between a few hundred meters and 600km.

In this paper, we use Cluster data from one magnetopause event on 5 July 2001 to compare predictions from various methods for determination of the velocity, orientation, and thickness of the magnetopause current layer. We employ established as well as new multi-spacecraft techniques, in which time differences between the crossings by the four spacecraft, along with the duration of each crossing, are used to calculate magnetopause speed, normal vector, and width. The timing is based on data from either the Cluster Magnetic Field Experiment (FGM) or the Electric Field Experiment (EFW) instruments. The multi-spacecraft results are compared with those derived from various single-spacecraft techniques, including minimum-variance analysis of the magnetic field and deHoffmann-Teller, as well as Minimum-Faraday-Residue analysis of plasma velocities and magnetic fields measured during the crossings. In order to improve the overall consistency between multi- and single-spacecraft results, we have also explored the use of hybrid techniques, in which timing information from the four spacecraft is combined with certain limited results from single-spacecraft methods, the remaining results being left for consistency checks. The results show good agreement between magnetopause orientations derived from appropriately chosen single-spacecraft techniques and those obtained from multi-spacecraft timing. The agreement between magnetopause speeds derived from single- and multi-spacecraft methods is quantitatively somewhat less good but it is evident that the speed can change substantially from one crossing to the next within an event. The magnetopause thickness varied substantially from one crossing to the next, within an event. It ranged from 5 to 10 ion gyroradii. The density profile was sharper than the magnetic profile: most of the density change occured in the earthward half of the magnetopause. Key words. Magnetospheric physics (magnetopause, cusp and boundary layers; instruments and techniques) – Space plasma physics (discontinuities)

EDI measures the drift velocity of artificially injected electron beams. From this drift velocity, the perpendicular electric field and the local magnetic field gradients can be deduced when employing different electron energies. The technique requires the injection of two electron beams at right angles to the magnetic field and the search for those directions within the plane that return the beams to their associated detectors after one or more gyrations. The drift velocity is then derived from the directions of the two beams and/or from the difference in their times-of-flight, measured via amplitude-modulation and coding of the emitted electron beams and correlation with the signal from the returning electrons. After careful adjustment of the control parameters, the beam recognition algorithms, and the onboard magnetometer calibrations during the commissioning phase, EDI is providing excellent data over a wide range of conditions. In this paper, we present first results in a variety of regions ranging from the polar cap, across the magnetopause, and well into the magnetosheath.Key words. Electron drift velocity (electric fields; plasma convection; instruments and techniques)

We examine two crossings of three Cluster satellites from the polar cap into the high-latitude plasma sheet at midnight local time, using data from the Electron Drift Instrument (EDI). EDI measures the full electron drift velocity in the plane perpendicular to the magnetic field for any field and drift directions. The context of the measured convection velocities is established by their relation to the intense enhancements in 1 keV electrons, also measured by EDI, as the satellites move from the polar cap into the plasma sheet boundary. In both cases presented here, the cross B convection in the polar cap is anti-sunward (toward the nightside plasma sheet) with a small duskward component. As the satellites enter the plasma sheet boundary region, the dawn-dusk convective flow component reverses its sign, and the flow in the meridianal plane (toward the center of the plasma sheet) drops substantially. The relatively stable convection in the polar cap becomes highly variable as the PSBL is encountered. The timing and sequence of the boundary crossings by the Cluster satellites are consistent with a relatively static structure on a time scale of the few minutes in satellite separations. In one of the two events, the plasma sheet boundary has a spatially separate structure that is crossed by the satellites before entering the plasma sheet.Key words. Magnetospheric physics (electric fields; magnetopause, cusp and boundary layers; instruments and techniques)

We present the first electron time-of-flight measurements obtained with the Electron Drift Instrument (EDI) on Equator-S. These measurements are made possible by amplitude-modulation and coding of the emitted electron beams and correlation with the signal from the returning electrons. The purpose of the time-of-flight measurements is twofold. First, they provide the drift velocity, and thus the electric field, when the distance the electrons drift in a gyro period becomes sufficiently large. Second, they provide the gyro time of the electrons emitted by the instrument, and thus the magnitude of the ambient magnetic field, allowing in-flight calibration of the flux-gate magnetometer with high precision. Results of both applications are discussed.Key words. Magnetospheric physics (electric fields; plasma convection; instruments and techniques)

We present the first triangulation measurements of electric fields with the electron drift instrument (EDI) on Equator-S. We show results from five high-data-rate passes of the satellite through the near-midnight equatorial region, at geocentric distances of approximately 5–6 RE, during geomagnetically quiet conditions. In a co-rotating frame of reference, the measured electric fields have magnitudes of a few tenths of mV/m, with the E × B drift generally directed sunward but with large variations. Temporal variations of the electric field on time scales of several seconds to minutes are large compared to the average magnitude. Comparisons of the "DC" baseline of the EDI-measured electric fields with the mapped Weimer ionospheric model and the Rowland and Wygant CRRES measurements yield reasonable agreement.Key words. Magnetospheric physics (electric fields; plasma convection; instruments and techniques)

The theoretical and computational studies of dye sensitized solar cells (DSSCs) can contribute to a deeper understanding of these types of solar cells. The DSSCs are the novel design of solar cells which could be used as power producing windows or skylights. They represent a particular promising approach to a direct conversion of sunlight into electrical energy at low cost and with high efficiency. The light adsorption occurs in dye molecules adsorbed on a highly porous structure of TiO2 film. Despite the progress in the efficiency and stability of these solar cells, there is still a room of research on some of their operational aspects that are still not understood. One process, for which there is limited information, is the time taken to upload the dye on the TiO2 nanoporous film. The processes followed experimentally for dye uptake is by dipping the TiO2 semiconductor electrode into the dye solution for periods of several hours to several days. However, such long dipping times are not economical for industrial production of DSSCs. The factors controlling this process are not yet fully investigated. We propose a simple model based on the Langmuir isotherms to study and understand the diffusion and adsorption of the dye molecules in TiO2 films. Our computational modelling results show that the adsorption of dye into the TiO2 nanotubes film is controlled by the diffusion coefficient, the adsorption-desorption ratio and the initial dye concentration. Our results show that the initial dye concentration plays an important role on the surface coverage. It is also noted that for a higher concentration shorter immersion time is needed for the sufficient surface coverage. Furthermore, it is observed that for the large values of the adsorption-desorption ratio there is a delay in the diffusion of dye molecules on the surface. [ABSTRACT FROM AUTHOR]

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BACKGROUND: The utility of cytomegalovirus (CMV) urine cultures was checked in patients with HIV (a) to identify those at risk for CMV retinitis and (b) to guide clinical decisions on treatment and prophylaxis of CMV retinitis. METHODS: HIV infected patients were tested for CMVuria by shell vial cell cultures. The prevalence of CMVuria was related to CD4 count, HIV risk group, and time before and after diagnosis of CMV retinitis. RESULTS: A total of 639 shell vial cell cultures were obtained from 266 HIV infected ophthalmic patients. Only 4% of all patients with a CD4 count > 400 x 10(6)/l shed CMV in their urine compared with 42% with a CD4 count < or = 50 x 10(6)/l. Twenty three of 25 patients with CMV retinitis had a CD4 count < or = 50 x 10(6)/l. Among 130 patients with a CD4 count < or = 50 x 10(6)/l (a) those who were CMVuric had a nearly sevenfold risk (p < 0.0001) of developing CMV retinitis (35%) compared with those who did not shed CMV in their urine (5%), and (b) CMVuria and CMV retinitis were more frequent in homosexuals (58%/25%) than in intravenous drug users (23%/15%). More than 1 year before diagnosis of CMV retinitis 18% of patients were CMVuric compared with 83% of patients who were CMV culture positive in the last 3 months. CMVuria under virustatic maintenance therapy is associated with worsening of retinitis in two thirds of cases. CONCLUSION: Ophthalmic screening of patients with HIV should include those with a CD4 count < or = 50 x 10(6)/l and focus on the subgroup with additional CMVuria. Screening of other patients can be dropped without undue risk in order to spare AIDS patients unnecessary hospital visits. CMVuria as a single finding, however, does not justify antiviral prophylaxis of CMV retinitis. [ABSTRACT FROM PUBLISHER]