Structure of a scandium-(silicon-bridged Cp, Cp^*) complex

({η^5-3-[2-(Di-tert-butylphosphino)ethyl]-cyclopentadienyl} (dimethyl)(η^5-tetramethylcyclopentadienyl)silane)bis(trimethylsilyl)methylscandium, C_(33)H_(62)PScSi_3, M_r = 595.04, monoclinic, P2_1/n, ɑ = 14.449 (3), b = 12.807 (5), c = 20.848 (5) Å, β = 99.52 (2)º, V = 3804.8 (18) Å^3, Z = 4, D_x = 1.04 g cm^(-3), λ(Mo Kɑ)= 0.71073 Å,μ = 3.18 cm^(-1)F(000) = 1352, T = 296 K, final R = 0.108 for 3100 reflections with F_o^2 > 0, 0.054 for 1766 reflections with F_o^2 > 3σ(F_o^2). The Sc-C(l) bond [2.253 (8) Å] is insignificantly shorter than the 2.271 (7) Å found in a similar compound; the geometry about C(l) is nearly trigonal, with angles 118.5 (5), 116.0 (5) and 119.4(6)º

Directed Molecular Stacking for Engineered Fluorescent Three-Dimensional Reduced Graphene Oxide and Coronene Frameworks

[EN] Three‐dimensional fluorescent graphene frameworks with controlled porous morphologies are of significant importance for practical applications reliant on controlled structural and electronic properties, such as organic electronics and photochemistry. Here we report a synthetically accessible approach concerning directed aromatic stacking interactions to give rise to new fluorogenic 3D frameworks with tuneable porosities achieved through molecular variations. The binding interactions between the graphene‐like domains present in the in situ‐formed reduced graphene oxide (rGO) with functional porphyrin molecules lead to new hybrids via an unprecedented solvothermal reaction. Functional free‐base porphyrins featuring perfluorinated aryl groups or hexyl chains at their meso‐ and β‐positions were employed in turn to act as directing entities for the assembly of new graphene‐based and foam‐like frameworks and of their corresponding coronene‐based hybrids. Investigations in the dispersed phase and in thin‐film by XPS, SEM and FLIM shed light onto the nature of the aromatic stacking within functional rGO frameworks (denoted rGOFs) which was then modelled semi‐empirically and by DFT calculations. The pore sizes of the new emerging reduced graphene oxide hybrids are tuneable at the molecular level and mediated by the bonding forces with the functional porphyrins acting as the “molecular glue”. Single crystal X‐ray crystallography described the stacking of a perfluorinated porphyrin with coronene, which can be employed as a molecular model for understanding the local aromatic stacking order and charge transfer interactions within these rGOFs for the first time. This opens up a new route to controllable 3D framework morphologies and pore size from the Ångstrom to the micrometre scale. Theoretical modelling showed that the porosity of these materials is mainly due to the controlled inter‐planar distance between the rGO, coronene or graphene sheets. The host‐guest chemistry involves the porphyrins acting as guests held through π‐π stacking, as demonstrated by XPS. The objective of this study is also to shed light into the fundamental localised electronic and energy transfer properties in these new molecularly engineered porous and fluorogenic architectures, aiming in turn to understand how functional porphyrins may exert stacking control over the notoriously disordered local structure present in porous reduced graphene oxide fragments. By tuning the porosity and the distance between the graphene sheets using aromatic stacking with porphyrins, it is also possible to tune the electronic structure of the final nanohybrid material, as indicated by FLIM experiments on thin films. Such nanohybrids with highly controlled pores dimensions and morphologies open the way to new design and assembly of storage devices and applications incorporating π‐conjugated molecules and materials and their π‐stacks may be relevant towards selective separation membranes, water purification and biosensing applications.S.I.P. and S.W.B. thank The Royal Society and STFC for funding. B.Y.M. thanks the University of Bath for a studentship (ORS). D.G.C. thanks the Fundación General CSIC for funding (ComFuturo Program). Dr. Jose A. Ribeiro Martins, Professors Jeremy K. M. Sanders and Paul Raithby are acknowledged for training, helpful discussions and porphyrin supramolecular chemistry. The S.I.P. group thanks the EPSRC for funding to the Centre of Graphene Science (EP/K017160/1) and to the Centre for Doctoral Training in Sustainable Chemical Technologies (EP/L016354/1). The authors thank EPSRC National Service for Mass Spectrometry at Swansea and EPSRC National Service for Crystallography at Southampton for data collection. The authors also acknowledge the ERC for the Consolidator Grant O2SENSE (617107, 2014–2019)

Submesoscale CO2 variability across an upwelling front off Peru

As a major source for atmospheric CO2, the Peruvian upwelling region exhibits strong variability in surface fCO2 on short spatial and temporal scales. Understanding the physical processes driving the strong variability is of fundamental importance for constraining the effect of marine emissions from upwelling regions on the global CO2 budget. In this study, a frontal decay on length scales of (10 km) was observed off the Peruvian coast following a pronounced decrease in down-frontal (equatorward) wind speed with a time lag of 9 h. Simultaneously, the sea-to-air flux of CO2 on the inshore (cold) side of the front dropped from up to 80 to 10 mmol m−2 day−1, while the offshore (warm) side of the front was constantly outgassing at a rate of 10–20 mmol m−2 day−1. Based on repeated ship transects the decay of the front was observed to occur in two phases. The first phase was characterized by a development of coherent surface temperature anomalies which gained in amplitude over 6–9 h. The second phase was characterized by a disappearance of the surface temperature front within 6 h. Submesoscale mixed-layer instabilities were present but seem too slow to completely remove the temperature gradient in this short time period. Dynamics such as a pressure-driven gravity current appear to be a likely mechanism behind the evolution of the front

Software that goes with the flow in systems biology

A recent article in BMC Bioinformatics describes new advances in workflow systems for computational modeling in systems biology. Such systems can accelerate, and improve the consistency of, modeling through automation not only at the simulation and results-production stages, but also at the model-generation stage. Their work is a harbinger of the next generation of more powerful software for systems biologists

Magnesium-catalysed nitrile hydroboration

A β-diketiminato n-butylmagnesium complex is presented as a selective precatalyst for the reductive hydroboration of organic nitriles with pinacolborane (HBpin). Stoichiometric reactivity studies indicate that catalytic turnover ensues through the generation of magnesium aldimido, aldimidoborate and borylamido intermediates, which are formed in a sequence of intramolecular nitrile insertion and inter- and intramolecular B–H metathesis events. Kinetic studies highlight variations in mechanism for the catalytic dihydroboration of alkyl nitriles, aryl nitriles bearing electron withdrawing (Ar(EWG)CN) and aryl nitriles bearing electron donating (Ar(EDG)CN) substitution patterns. Kinetic isotope effects (KIEs) for catalysis performed with DBpin indicate that B–H bond breaking and C–H bond forming reactions are involved in the rate determining processes during the dihydroboration of alkyl nitriles and Ar(EDG)CN substrates, which display divergent first and second order rate dependences on [HBpin] respectively. In contrast, the hydroboration of Ar(EWG)CN substrates provides no KIE and HBpin is not implicated in the rate determining process during catalysis. Irrespective of these differences, a common mechanism is proposed in which the rate determining steps are deduced to vary through the establishment of several pre-equilibria, the relative positions of which are determined by the respective stabilities of the dimeric and monomeric magnesium aldimide and magnesium aldimidoborate intermediates as a result of adjustments to the basicity of the nitrile substrate. More generally, these observations indicate that homogeneous processes performed under heavier alkaline earth catalysis are likely to demonstrate previously unappreciated mechanistic diversity

Electron dynamics in planar radio frequency magnetron plasmas: II. Heating and energization mechanisms studied via a 2d3v particle-in-cell/Monte Carlo code

The present work investigates electron transport and heating mechanisms using an (r, z) particle-in-cell (PIC) simulation of a typical rf-driven axisymmetric magnetron discharge with a conducting target. It is shown that for the considered magnetic field topology the electron current flows through different channels in the (r, z) plane: a ``transverse'' one, which involves current flow through the electrons' magnetic confinement region (EMCR) above the racetrack, and two ''longitudinal'' ones. Electrons gain energy from the electric field along these channels following various mechanisms, which are rather distinct from those sustaining dc-powered magnetrons. The longitudinal power absorption involves mirror-effect heating (MEH), nonlinear electron resonance heating (NERH), magnetized bounce heating (MBH), and the heating by the ambipolar field at the sheath-presheath interface. The MEH and MBH represent two new mechanisms missing from the previous literature. The MEH is caused by a reversed electric field needed to overcome the mirror force generated in a nonuniform magnetic field to ensure sufficient flux of electrons to the powered electrode, and the MBH is related to a possibility for an electron to undergo multiple reflections from the expanding sheath in the longitudinal channels connected by the arc-like magnetic field. The electron heating in the transverse channel is caused mostly by the essentially collisionless Hall heating in the EMCR above the racetrack, generating a strong ExB azimuthal drift velocity. The latter mechanism results in an efficient electron energization, i.e., energy transfer from the electric field to electrons in the inelastic range. Since the main electron population energized by this mechanism remains confined within the discharge for a long time, its contribution to the ionization processes is dominant

Influence of plasma turbulence on microwave propagation

It is not fully understood how electromagnetic waves propagate through plasma density fluctuations when the size of the fluctuations is comparable with the wavelength of the incident radiation. In this paper, the perturbing effect of a turbulent plasma density layer on a traversing microwave beam is simulated with full-wave simulations. The deterioration of the microwave beam is calculated as a function of the characteristic turbulence structure size, the turbulence amplitude, the depth of the interaction zone and the size of the waist of the incident beam. The maximum scattering is observed for a structure size on the order of half the vacuum wavelength. The scattering and beam broadening was found to increase linearly with the depth of the turbulence layer and quadratically with the fluctuation strength. Consequences for experiments and 3D effects are considered.Comment: 16 pages, 13 figures. This is an author-created, un-copyedited version of an article submitted for publication in Plasma Physics and Controlled Fusion. IoP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from i