Dichloroborane-dioxane: an exceptional reagent for the preparation of alkenyl- and alkylboronic acids

Terminal alkynes and alkenes were conveniently hydroborated to the corresponding alkenyl- and alkyldichloroboranes using dichloroborane-dioxane in dichloromethane. These dichloroboranes were hydrolyzed by water to the corresponding alkenyl- and alkylboronic acids in moderate to good yields. With terminal alkenes and alkynes boron was predominantly attached to terminal carbon. Alkynes gave exclusively trans-vinylboronic acids.     

A sensitive,specific method for the determination of tetraalkyllead compounds in air by gas chromatography/atomic absorption spectrometry

The development of a sensitive and specific method of determining individually the five tetraalkyllead compounds normally present in ambient air is described. The method is based on collection of the analytes on a porous polymer using a prefilter to destroy ozone and prevent decomposition of the sample during collection and storage. Two-stage thermal desorption, separation by gas chromatography and detection by modified flame atomic absorption spectrometry gives detection limits (3σ) of ca. 0.25 ng Pb m^?3 for tetramethyllead and 0.37 ng Pb m^?3 for tetraethyllead in an air sample of 80 dm³ collected over a 3–24 h period. Environmental sampling by this method in paralle with a wet chemical (iodine monochloride) method was used to validate the method. During the comparative study, higher organic lead levels were consistently found by the iodine monochloride method; it is postulated that this indicates the presence of vapour-phase tri-(or di)-alkyllead in excess of 1 ng Pb m^?3 in rural air. The versatility of the method is demonstrated by the results of atmospheric sampling at two locations, one rural and one at the kerbside in a city centre.     

Loading characteristics and chemical stability of headgroup‐functionalized poly(ethylene glycol)‐lipid ligand tethers on polypropylene capillary‐channeled polymer fibers

Polypropylene capillary‐channeled polymer fibers have been modified by adsorption of headgroup‐functionalized poly(ethylene glycol)‐lipids to generate a species‐specific stationary phase. In order to study ligand binding characteristics, a fluorescein‐labeled poly(ethylene glycol)‐lipid was used as a model system. Breakthrough curves and frontal analysis were employed to characterize the surface loading characteristics across a range of lipid concentrations and mobile phase flow rates. Efficient mass transfer and fluid transport yield a linear adsorption isotherm up to the maximum loading concentration of 3 mg/mL, at a linear velocity of 57.1 mm/s. Under these conditions, the dynamic binding capacity was found to be 1.52 mg/g of fiber support. Variation of the linear velocity from 8.6 to 57.1 mm/s showed only small changes in breakthrough volume. The maximum capacity of 1.8 mg/g is found under conditions of a load velocity of 34.2 mm/s and a concentration of 3 mg/mL lipid. Exposure of the lipid modified fibers to several challenge solvents reveals a chemically robust system, with only 50% acetonitrile and hexanes able to disrupt the lipid adsorption. The straightforward capillary‐channeled polymer fiber surface modification with headgroup‐functionalized lipids provides both a diverse yet practically robust ligand tethering system.     

A concise total synthesis of (+)-okaramine C

The first total synthesis of (+)-okaramine C is described. Our previously described selenocyclisation-oxidative deselenation sequence was used to establish a 3a-hydroxy-pyrrolo[2,3-b]indole core, which was modified by selective epimerisation to the common pyrrolo[2,3-b]indole of the okaramines.     

Forward scattering of pulses from a rough sea surface by Fourier synthesis of parabolic equation solutions

A variable depth step implementation of the range-dependent acoustic model (RAM) is applied to the modeling of forward scattering from a rough sea surface. The sea surface is treated within RAM simply as an internal interface between a water layer and an air upper halfspace. A comparison with a numerically exact integral equation is undertaken for the scattering of single frequencies from Pierson-Moskowitz sea surfaces. The method is extended to model the variability of linear frequency modulated pulses from a series of frozen sea surfaces in a shallow water waveguide. The subsequent effect of rough boundary scattering on the replica correlation process is investigated.     

A Symbolic Dance: The Interplay Between Movement,Notation, and Mathematics on a Journey Toward Solving Equations

This article analyzes the use of the software Grid Algebra with a mixed ability class of 21 nine-to-ten-year-old students who worked with complex formal notation involving all four arithmetic operations. Unlike many other models to support learning, Grid Algebra has formal notation ever present and allows students to “look through” that notation and interpret it either in terms of physical journeys on a grid or in terms of mathematical operations. A dynamic fluidity was found between the formal notation, imagery of movements on a grid, and the process of mathematical operations. This fluidity is interpreted as a “dance” between these three. The significant way in which this dynamic took place reflects the scaffolding and fading offered by the software, which was crucial to the students’ fluency with formal notation well beyond what has been reported from students of that age.     

Plasma Photocathodes

Plasma wakefield accelerators offer accelerating and focusing electric fields three to four orders of magnitude larger than state-of-the-art radiofrequency cavity-based accelerators. Plasma photocathodes can release ultracold electron populations within such plasma waves and thus open a path toward tunable production of well-defined, compact electron beams with normalized emittance and brightness many orders of magnitude better than state-of-the-art. Such beams will have far-reaching impact for applications such as light sources, but also open up new vistas on high energy and high field physics. This paper reviews the innovation of plasma photocathodes, and reports on the experimental progress, challenges, and future prospects of the approach. Details of the proof-of-concept demonstration of a plasma photocathode in 90° geometry at SLAC FACET within the E-210: Trojan Horse program are described. Using this experience, alongside theoretical and simulation-supported advances, an outlook is given on future realizations of plasma photocathodes such as the upcoming E-310: Trojan Horse-II program at FACET-II with prospects toward excellent witness beam parameter quality, tunability, and stability. Future installations of plasma photocathodes also at compact, hybrid plasma wakefield accelerators, will then boost capacities and open up novel capabilities for experiments at the forefront of interaction of high brightness electron and photon beams.     

Heterometallic 20-membered {Fe16Ln4} (Ln = Sm, Eu, Gd, Tb, Dy, Ho) metallo-ring aggregates

The reaction of triethanolamine (teaH(3)) with [Fe(III)(3)O(O(2)CCH(3))(6)(H(2)O)(3)]Cl·6H(2)O and Ln(NO(3))(3)·6H(2)O in acetonitrile yields [Fe(16)Ln(4)(tea)(8)(teaH)(12)(μ-O(2)CCH(3))(8)](NO(3))(4)·16H(2)O·xMeCN (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6); x = 10 or 11). These 20-membered metallo-ring complexes are the largest such single-stranded oxygen-bridged rings so far reported. The structure is stabilised by two of the acetate ligands, which form anti,anti-bridges across the centre of the ring, pinching the ring and giving it rigidity. The magnetic properties are dominated by the antiferromagnetic couplings between the Fe(III) centres. Although the Fe(2) and Fe(6) sub-chains within the ring are fully spin-compensated at low temperatures with S(subchain) = 0, coupling between the Gd(III) cations and the Fe(III) centres at the ends of the sub-chains (in 3) results in a pinning of the lanthanide spins. The (57)Fe M?ssbauer spectra of 3 and 5 obtained at low temperatures are consistent with the presence of Fe(III) intracluster strong antiferromagnetic coupling. The applied field spectrum for 3 reveals no magnetic hyperfine interaction apart from that of the nucleus with the applied field, while the one for 5 is a superposition of three subspectra which show contributions from each of the peripheral as well as from the central iron sites.