Mechanistic analysis of an asymmetric palladium-catalyzed conjugate addition of arylboronic acids to β-substituted cyclic enones.

An asymmetric palladium-catalyzed conjugate addition reaction of arylboronic acids to enone substrates was investigated mechanistically. Desorption electrospray ionization coupled to mass spectrometry was used to identify intermediates of the catalytic cycle and delineate differences in substrate reactivity. Our findings provide evidence for the catalytic cycle proceeding through formation of an arylpalladium(II) cation, subsequent formation of an arylpalladium-enone complex, and, ultimately, formation of the new C-C bond. Reaction monitoring in both positive and negative ion modes revealed that 4-iodophenylboronic acid formed a relatively stable trimeric species under the reaction conditions

Students as neighbors: utilizing dialogue and deliberation to manage town-gown tensions

The integration of the university and its students into the broader Harrisonburg community has promoted increased interaction amongst JMU students, JMU faculty and staff, and community members. Navigating this complex relationship can be challenging and, in recent years, this relationship has become increasingly strained. The following research seeks to cultivate processes that aid in its improvement. The research finds that utilizing dialogue and deliberation as an approach to designing public process is a promising approach to mending and maintaining the relationship between JMU students and the broader Harrisonburg community, as well as to addressing town-gown tension at large. The research also employs a unique, flexible, methodology to allow for ongoing learning in developing a multi-phased, responsive process that helps participants move from understanding to finding sustainable solutions. The research offers insights into how information and perceptions that emerge in dialogic conversation can be used to design processes that transition into collaborative solutions for town-gown tensions

How chemical pressure affects the fundamental properties of rare-earth pnictides: an ARPES view

Angle-resolved photoelectron spectroscopy, supplemented by theoretical calculations has been applied to study the electronic structure of heavy-fermion material CeFePO, a homologue to the Fe-based high-temperature superconductors, and CeFeAs_0.7P_0.3O, where the applied chemical pressure results in a ferromagnetic order of the 4f moments. A comparative analysis reveals characteristic differences in the Fe-derived band structure for these materials, implying a rather different hybridization of valence electrons to the localized 4f orbitals. In particular, our results suggest that the ferromagnetism of Ce moments in CeFeAs_0.7P_0.3O is mediated mainly by Fe 3d_xz/yz orbitals, while the Kondo screening in CeFePO is instead due to a strong interaction of Fe 3d_3z^2-r^2 orbitals.Comment: 5 pages, 3 figures, accepted for publication in Phys. Rev. B (Rapid

A comparison of techniques to optimize measurement of voltage changes in electrical impedance tomography by minimizing phase shift errors

In electrical impedance tomography, errors due to stray capacitance may be reduced by optimization of the reference phase of the demodulator. Two possible methods, maximization of the demodulator output and minimization of reciprocity error have been assessed, applied to each electrode combination individually, or to all combinations as a whole. Using an EIT system with a single impedance measuring circuit and multiplexer to address the 16 electrodes, the methods were tested on resistor-capacitor networks, saline-filled tanks and humans during variation of the saline concentration of a constant fluid volume in the stomach. Optimization of each channel individually gave less error, particularly on humans, and maximization of the output of the demodulator was more robust. This method is, therefore, recommended to optimize systems and reduce systematic errors with similar EIT systems

CeFePO: f-d hybridization and quenching of superconductivity

Being homologue to the new, Fe-based type of high-temperature superconductors, CeFePO exhibits magnetism, Kondo and heavy-fermion phenomena. We experimentally studied the electronic structure of CeFePO by means of angle-resolved photoemission spectroscopy. In particular, contributions of the Ce 4f-derived states and their hybridization to the Fe 3d bands were explored using both symmetry selection rules for excitation and their photoionization cross-section variations as a function of photon energy. It was experimentally found - and later on confirmed by LDA as well as DMFT calculations - that the Ce 4f states hybridize to the Fe 3d states of d_{3z^2-r^2} symmetry near the Fermi level that discloses their participation in the occurring electron-correlation phenomena and provides insight into mechanism of superconductivity in oxopnictides.Comment: 5 pages, 3 figure

Asymptotic Sign-Solvability, Multiple Objective Linear Programming, and The Nonsubstitution Theorem

In this paper we investigate the asymptotic stability of dynamic, multiple-objective linear programs. In particular, we show that a generalization of the optimal partition stabilizes for a large class of data functions. This result is based on a new theorem about asymptotic sign-solvable systems. The stability properties of the generalized optimal partition are used to extend a dynamic version of the Nonsubstitution Theorem

The polarizability model for ferroelectricity in perovskite oxides

This article reviews the polarizability model and its applications to ferroelectric perovskite oxides. The motivation for the introduction of the model is discussed and nonlinear oxygen ion polarizability effects and their lattice dynamical implementation outlined. While a large part of this work is dedicated to results obtained within the self-consistent-phonon approximation (SPA), also nonlinear solutions of the model are handled which are of interest to the physics of relaxor ferroelectrics, domain wall motions, incommensurate phase transitions. The main emphasis is to compare the results of the model with experimental data and to predict novel phenomena.Comment: 55 pages, 35 figure

Determinants of anti-vascular action by combretastatin A-4 phosphate: role of nitric oxide

The anti-vascular action of the tubulin binding agent combretastatin A-4 phosphate (CA-4-P) has been quantified in two types of murine tumour, the breast adenocarcinoma CaNT and the round cell sarcoma SaS. The functional vascular volume, assessed using a fluorescent carbocyanine dye, was significantly reduced at 18 h after CA-4-P treatment in both tumour types, although the degree of reduction was very different in the two tumours. The SaS tumour, which has a higher nitric oxide synthase (NOS) activity than the CaNT tumour, showed ~10-fold greater resistance to vascular damage by CA-4-P. This is consistent with our previous findings, which showed that NO exerts a protective action against this drug. Simultaneous administration of CA-4-P with a NOS inhibitor, Nω-nitro-L-arginine (L-NNA), resulted in enhanced vascular damage and cytotoxicity in both tumour types. Administration of diethylamine NO, an NO donor, conferred protection against the vascular damaging effects. Following treatment with CA-4-P, neutrophil infiltration into the tumours, measured by myeloperoxidase (MPO) activity, was significantly increased. Levels of MPO activity also correlated with the levels of vascular injury and cytotoxicity measured in both tumour types. Neutrophilic MPO generates free radicals and may therefore contribute to the vascular damage associated with CA-4-P treatment. MPO activity was significantly increased in the presence of L-NNA, suggesting that the protective effect of NO against CA-4-P-induced vascular injury may be, at least partially, mediated by limiting neutrophil infiltration. The data are consistent with the hypothesis that neutrophil action contributes to vascular injury by CA-4-P and that NO generation acts to protect the tumour vasculature against CA4-P-induced injury. The protective effect of NO is probably associated with an anti-neutrophil action. © 2000 Cancer Research Campaig

Overcoming the risk of inaction from emissions uncertainty in smallholder agriculture

The potential for improving productivity and increasing the resilience of smallholder agriculture, while also contributing to climate change mitigation, has recently received considerable political attention (Beddington et al 2012). Financial support for improving smallholder agriculture could come from performance-based funding including sale of carbon credits or certified commodities, payments for ecosystem services, and nationally appropriate mitigation action (NAMA) budgets, as well as more traditional sources of development and environment finance. Monitoring the greenhouse gas fluxes associated with changes to agricultural practice is needed for performance-based mitigation funding, and efforts are underway to develop tools to quantify mitigation achieved and assess trade-offs and synergies between mitigation and other livelihood and environmental priorities (Olander 2012)