The Search for the Least-Coordinating Anion

Abstract

The brominated carborane, Br₆-CB₁₁ H₆- (structure 1) is the most recent candidate for the least coordinating anion. It has wide application to the chemistry of reactive cations. The closest approach to date to the long sought silylium ion, R₃Si⁺, utilized this anion in the structurally characterized compound (i-Pr₃Si^δ+)(Br₆-CB₁₁H₆ ^δ?)1 (structure 2).     

Efficient route to 2H-1,3-oxazines through ring expansion of isoxazoles by rhodium carbenoids

Studies related to the total synthesis of elisabethin C led to the discovery of a rhodium-catalyzed cascade sequence involving isoxazole ring expansion and a [4+3] cycloaddition. The scope of the isoxazole ring expansion was explored, resulting in the synthesis of a range of 2H-1,3-oxazines in 47-96% yield.     

Gravitational waves from a supercooled electroweak phase transition and their detection with pulsar timing arrays

We investigate the properties of a stochastic gravitational wave background produced by a first-order electroweak phase transition in the regime of extreme supercooling. We study a scenario whereby the percolation temperature that signifies the completion of the transition, \(T_\mathrm{p}\), is as low as a few MeV (nucleosynthesis temperature), while most of the true vacuum bubbles are formed much earlier at the nucleation temperature, \(T_\mathrm{n}\sim 50\) GeV. This implies that the gravitational wave spectrum is mainly produced by the collisions of large bubbles and characterised by a large amplitude and a peak frequency as low as \(f \sim 10^{-9}{-}10^{-7}\) Hz. We show that such a scenario can occur in (but not limited to) a model based on a non-linear realisation of the electroweak gauge group, so that the Higgs vacuum configuration is altered by a cubic coupling. In order to carefully quantify the evolution of the phase transition of this model over such a wide temperature range we go beyond the usual fast transition approximation, taking into account the expansion of the Universe as well as the behaviour of the nucleation probability at low temperatures. Our computation shows that there exists a range of parameters for which the gravitational wave spectrum lies at the edge between the exclusion limits of current pulsar timing array experiments and the detection band of the future Square Kilometre Array observatory.     

Identifying bryostatins and potential precursors from the bryozoan Bugula neritina

The bryozoan species Bugula neritina contains the anticancer agent bryostatin. Bryostatin has been extracted from these sessile marine invertebrates since the late 1960s from the Gulf of California, Gulf of Mexico, as well as various locations on the eastern and western rims of the Pacific Ocean. In this work we are focusing on animals harvested in the Gulf of Mexico near Alligator Point (Florida). Using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) we measure the concentration of 70 elements in B. neritina, a sea squirt, and the sediment from the point of harvesting. This data has helped us generate an extraction process for marine natural products. Combining UV/VIS absorbance measurements with Matrix Assisted Laser Desorption Ionization-Time of Flight-Mass Spectrometer (MALDI-TOF-MS), we demonstrated that the specific form of bryostatin extracted is a function of the solvent. A 9.4T Fourier Transform-Ion Cyclotron Resonance (FT-ICR) mass spectrometer, whose sensitivity, mass accuracy, and resolving power allowed the exact empirical formulas of potential precursors of bryostatin to be identified, was employed. Finally we examine extracts of 14 marine species of the Gulf of Mexico, from the sand trout (Cynoscion arenarius) to chicken liver sponge (Chrondrilla nucula), all recently collected, which had shown some medicinal activity thirty years ago in a National Cancer Institute study. By the MALDI-TOF-MS, we were able to identify mass spectral features that correspond to different variations of the basic bryostatin structure, which raises the question if the bryozoans are the original source of bryostatin.     

Facile, efficient conjugation of a trifunctional lanthanide chelate to a peripheral benzodiazepine receptor ligand

[reaction: see text] Receptor-mediated imaging and therapy of diseased tissue is rapidly gaining favor in the medical community. The synthesis and facile aqueous/organic coupling of a peripheral-type benzodiazepine receptor ligand to a cyclen-based fluorophore is described herein. The contrast agent QM-CTMC-PK11195, when chelated with lanthanides, produces bright luminescence and good MRI contrast and can potentially serve as an imaging and demarcation agent for certain types of cancers.     

The L'vov platform for furnace atomic absorption analysis

The L'vov Platform converts the Massmann-type graphite furnace into a furnace that provides a constant temperature environment for the more volatile metals. A very great reduction of matrix interferences for Pb, Cd and Tl is reported, so long as the matrix concentration provides a background signal during atomization that is small enough to be controlled by the deuterium arc background corrector. Interferences for Cu, Mn and Sn are also reduced to some extent. L'vov's recent theory relating to vapor phase thermodynamics makes it possible to predict both qualitatively and semi-quantitatively many of the remaining interference effects. This provides potential solutions to remaining problems which are herein explored. The continued test of interferences reported in the literature indicates that most are not present in the modern furnaces when they are used in an optimum manner.     

Reduction of temperature variation in the atomic absorption graphite furnace

The temperature variation that is experienced along the length of the graphite furnace tube of the Massmann design can be reduced by the use of a contoured tube. An analytical model of the steady-state temperature distribution along the graphite tube has been developed and has been shown to agree quite well with experimental data. Steady-state and time-dependent measurements along the length of the graphite tube are reported for different conditions. With conventional tubes at thermal equilibrium, there is a temperature difference exceeding 1000°C between the center and the ends when the center of the tube is at 2500°C. With a contoured tube this temperature gradient has been reduced to 100°C.     

Large angle production of stable particles heavier than the proton and a search for quarks at the CERN intersecting storage rings

Measurements have been performed on production of particles with mass 1.5 GeV/c² and charge $\text{?}\text{2}\text{3}$ for θ_lab = 62.5° and $\text{s}\text{= 53}\text{GeV}$. At p_T = 0.7 GeV/c the relative rate of production of antideuterons to π^? is (5 ± 1) × 10^?5. The deuteron to antideuteron ratio is 3.7 ± 1.2. No new stable particle has been amongst 0.7 × 10⁸ charged particles entering our detector.     

Reduction of strained polycycles: how much strain can a pyrene anion take?

The reduction of a series of [n](2,7)pyrenophanes (n = 7-10) with lithium or potassium metal shows that the strain in the system, controlled by the length of the tether, determines the nature of the reduction products. The reduction of [7](2,7)pyrenophane (2) and [2]metacyclo[2](2,7)pyrenophane (3) leads to reductive dimerization followed by novel intramolecular sigma-bond formation as a means of escaping strained anti-aromaticity. [8](2,7)Pyrenophane (4) affords only reductive dimerization, and no two-electron reduction is observed. The reduction of [9](2,7) pyrenophane (5) and [10](2,7)pyrenophane (6) leads to reductive dimerization, followed by the formation of a dianionic anti-aromatic species, which eventually cleaves the solvent, THF-d(8). The similarity between the reduction of the latter systems and the reduction of pyrene (1) is discussed.