Gamma-ray spectroscopy with relativistic exotic heavy-ions

Feasibility of gamma-ray spectroscopy at relativistic energies with exotic heavy-ions and new generation of germanium detectors (segmented Clover) is discussed. An experiment with such detector array and radioactive is discussed.     

Pyridylphosphonium salts as alternatives to cyanopyridines in radical–radical coupling reactions

Radical couplings of cyanopyridine radical anions represent a valuable technology for functionalizing pyridines, which are prevalent throughout pharmaceuticals, agrochemicals, and materials. Installing the cyano group, which facilitates the necessary radical anion formation and stabilization, is challenging and limits the use of this chemistry to simple cyanopyridines. We discovered that pyridylphosphonium salts, installed directly and regioselectively from C–H precursors, are useful alternatives to cyanopyridines in radical–radical coupling reactions, expanding the scope of this reaction manifold to complex pyridines. Methods for both alkylation and amination of pyridines mediated by photoredox catalysis are described. Additionally, we demonstrate late-stage functionalization of pharmaceuticals, highlighting an advantage of pyridylphosphonium salts over cyanopyridines.

Cyanopyridines form dearomatized radical anions upon single-electron reduction and participate in photoredox coupling reactions. Pyridylphosphonium salts replicate that reactivity with a broader scope and increase the utility of these processes.

Modern photoredox catalysis and electrochemistry have enabled new synthetic methods that proceed via open-shell intermediates.¹ Under this regime, pyridine functionalization strategies have been developed where 4-cyanopyridines undergo single-electron reduction to form dearomatized radical species that couple with other stabilized radicals (Scheme 1A).² The cyano group is critical for efficient reactivity via pyridyl radical anions; alternatives such as 4-halopyridines more readily undergo elimination to pyridyl radicals after single-electron reduction resulting in a distinct set of coupling processes.³ We aimed to show that pyridylphosphonium salts could replicate the reactivity of cyanopyridines and allow a broader set of inputs into dearomatized pyridyl radical coupling reactions.⁴Open in a separate windowScheme 1Expansion of radical coupling reactions to complex pyridines.Cyanopyridines have facilitated pyridine alkylation, allylation, and alkenylation reactions providing access to valuable building blocks for medicinal and agrochemical programs.⁵ The cyano group is essential for these methods, but a problem arises when applying this chemistry to complex pyridines, such as those found in pharmaceutical and agrochemical candidates. These structures are often devoid of pre-installed functional groups, and it is often challenging to install a cyano group from C–H precursors regioselectively.⁶ We envisioned pyridylphosphonium salts, regioselectively constructed from the C–H bonds of a diverse set of pyridines, could serve as alternatives to cyanopyridines.⁷ Herein, we report couplings between alkyl BF₃K salts and preliminary studies of carboxylic acids and amines with pyridylphosphonium salts, including late-stage functionalization of complex pyridine-containing pharmaceuticals using this strategy.Recently, we reported a radical coupling reaction between a boryl-stabilized cyanopyridyl radical and a boryl-stabilized pyridylphosphonium radical.^7a The intermediate radicals arose via an unusual inner-sphere process that would be difficult to extend to other coupling reactions. A significant advance would be to show that pyridylphosphonium salts could function more generally as radical anion precursors and mimic the reactivity of cyano-pyridines. In particular, showing their viability in photoredox and electrochemical processes would translate to numerous synthetic transformations. To demonstrate this principle, we envisioned a redox-neutral alkylation reaction (Scheme 1B) via a radical coupling between radical zwitterion I, formed through single-electron reduction of a pyridylphosphonium salt (E^red_p/2 = −1.51 V vs. SCE) and benzyl radical II, resulting from single-electron oxidation of a BF₃K salt (E^red = +1.10 V vs. SCE for a primary benzylic salt).⁸ Loss of triphenylphosphine from dearomatized intermediate (III) would furnish the alkylated pyridine product. Notably, the redox events could invert, where the photocatalyst oxidizes the BF₃K salt first and reduces the pyridylphosphonium salt second, broadening the scope of amenable photocatalysts.We began our investigation by examining a series of photocatalysts for the coupling reaction of phosphonium salt 1a, formed with complete regioselectivity for the 4-position from 2-phenylpyridine, and benzylic BF₃K salt 2a under irradiation from a 455 nm Kessil light (Scheme 1B are potentially interchangeable.^1b The Adachi-type photocatalyst 3DPAFIPN improved the yield to 77% with a further increase to 82% after increasing the reaction concentration (entries 3 and 4). Adding 2,6-lutidine, previously shown as an effective additive for photoredox cross-coupling reactions of BF₃K salts by the Molander group,⁹ had no impact on the yield of 2-phenylpyridine salt 1a (entry 5) and the [Ir(ppy)₂(dtbbpy)]PF₆ catalyst was marginally less efficient under the same conditions (entry 6). We observed that 2,6-lutidine did substantially improve the yield when isomeric 3-Ph salt 1b was employed (entries 7 and 8); without 2,6-lutidine, the crude ¹H NMR indicates significant amounts of decomposition occurred, including 3-phenylpyridine, and the 4- vs. 2-position product ratio was 3 : 1. This outcome suggests that protiodephosphination and non-selective Minisci-type pathways can occur under these conditions. With 2,6-lutidine, the crude reaction pathway is cleaner, and the 4- vs. 2-position ratio improved to 8 : 1. At this point, we have not established the role of 2,6-lutidine, although it is conceivable that it reacts with BF₃ produced as the reaction progresses. In 2-substituted systems, steric hindrance around the pyridine N-atom of the salt would deter BF₃-coordination, whereas, in 3-substituted systems, such as salt 1b, coordination is more likely and may have a deleterious effect on the reaction (vide infra). Given the structural variation of pyridines that we anticipated applying to this process and how those structures could impact boron speciation during the reaction, we elected to use 2,6-lutidine as an additive in all subsequent reactions.¹⁰Optimization of pyridine alkylation, photocatalyst data and effect of BF₃·OEt₂ as an additive^a

On Criticality for Competing Influences of Boundary and External Field in the Ising Model

We continue a study of Schonmann (1994), Schonmann and Shlosman (1996), and Greenwood and Sun (1997) regarding the competing influences of boundary conditions and external field for the Ising model. We find a critical point B ₀ in the competing influences for low temperature in dimension d 2A7E; 2.     

Percolative transport in the vicinity of charge-order ferromagnetic transition in a hole-doped manganite

We report measurements of non-linear charge transport in epitaxial (La_1−x Pr _x )_0.7Ca_0.3MnO₃ thin films fabricated on (100) oriented SrTiO₃ single crystals by pulsed laser deposition. The end members of this series, namely Pr_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3MnO₃ are canonical charge-ordered (CO) and ferromagnetic manganites, respectively. The onset of the CO state in Pr_0.7Ca_0.3MnO₃ is manifested by a pronounced insulating behavior below ∼ 200 K. The CO state remains stable even when a large (∼ 2×10⁵ V/cm) electric field is applied across the thin film samples. However, on substitution of Pr with La, a crossover from the highly resistive CO state to a state of metallic character is observed at relatively low electric fields. The current-voltage characteristics of the samples at low temperatures show hysteretic and history dependent effects. The electric field driven charge transport in the system is modelled on the basis of an inhomogeneous medium consisting of ferromagnetic metallic clusters dispersed in a CO background.     

Pre-averaged kernel estimators for the drift function of a diffusion process in the presence of microstructure noise

We consider estimation of the drift function of a stationary diffusion process when we observe high-frequency data with microstructure noise over a long time interval. We propose to estimate the drift function at a point by a Nadaraya–Watson estimator that uses observations that have been pre-averaged to reduce the noise. We give conditions under which our estimator is consistent and asympotically normal. Its rate and asymptotic bias and variance are the same as those without microstructure noise. To use our method in data analysis, we propose a data-based cross-validation method to determine the bandwidth in the Nadaraya–Watson estimator. Via simulation, we study several methods of bandwidth choices, and compare our estimator to several existing estimators. In terms of mean squared error, our new estimator outperforms existing estimators.     

Twenty-five years of progress in vacuum arc research andutilization

Progress in understanding and applying vacuum arcs is reviewed. Laser diagnostics have demonstrated the existence of micron-sized regions in the cathode spot plasma having electron densities exceeding 10²⁶ m^-3. The expanding plasma produces a highly ionized jet whose ions typically have charge states of 1-3 and energies of 50-150 eV. Gas dynamic and explosive emission models have been formulated to explain cathode spot operation. In cases where the arc is constricted at the anode, forming an anode spot, or the anode is thermally isolated, forming a hot anode vacuum arc, material emitted from the anode may dominate the interelectrode plasma. Evaporation from liquid droplets may also provide a substantial component of the plasma, and the presence of these droplets can have deleterious consequences in applications. The vacuum arc has been extensively utilized as a plasma source, particularly for the deposition of protective coatings and thin films, and as a switching medium in electrical distribution circuit breakers     

An Inter-Temporal Multi-Goal Linear Programming Model for Optimizing University Tuition and Fee Structures

This paper reports on the use of a multi-goal linear programming model to establish the tuition and fee policy at a major state university over a three-year period. The process of establishing tuition and fee charges is characterized by multiple and conflicting goals. Further complicating the process is the fact that multiple parties are involved in or impact on the decision process, including the various academic and administrative units of the university, the state legislature, parents and students. The charges are established based on the institution's anticipated operating costs and fiscal needs, state-level policies and requirements, projected enrolment patterns, charges at peer institutions, and the university's philosophy concerning differential charges between various student categories. The modelling process employed provides university administration with the maximum possible flexibility in stating and prioritizing university goals and objectives regarding the tuition and fee structure.     

Homogeneous and inhomogeneous manifolds

All metaLindelöf, and most countably paracompact, homogeneous manifolds are Hausdorff. Metacompact manifolds are never rigid. Every countable group can be realized as the group of autohomeomorphisms of a Lindelöf manifold. There is a rigid foliation of the plane.

     

Electric power switches

A review is given of the physics and engineering behavior of arcs in vacuum and axial gas blast under the conditions found in high-voltage circuit breakers. The topics included are: the zero energy switch; current limiting switches; arc control; the gas-blast circuit breakers; the low-current gas-blast arc; arcing with ablation; interruption dynamics; arc modeling; vacuum as a switching element; the vacuum arc; the constricted arc; and the properties of SF₆