Paramagnetic species in catalysis research: A unified approach towards (the role of EPR in) heterogeneous, homogeneous and enzyme catalysis

Paramagnetic (open-shell) systems, including transition metal ions, radical intermediates and defect centres, are often involved in catalytic transformations. Despite the prevalence of such species in catalysis, there are relatively few studies devoted to their characterisation, compared to their diamagnetic counterparts. Electron Paramagnetic Resonance (EPR) is an ideal technique perfectly suited to characterise such reaction centres, providing valuable insights into the molecular and supramolecular structure, the electronic structure, the dynamics and even the concentration of the paramagnetic systems under investigation. Furthermore, as EPR is such a versatile technique, samples can be measured as liquids, solids (frozen solutions and powders) and single crystals, making it ideal for studies in heterogeneous, homogeneous and enzyme catalysis. Coupled with the higher resolving power of the pulsed, higher frequency and hyperfine techniques, unsurpassed detail on the structure of these catalytic centres can be obtained. In this Chapter, we provide an overview to demonstrate how advanced EPR methods can be successfully exploited in the study of open-shell paramagnetic reaction centres in heterogeneous, homogeneous and enzymatic catalysts, including heme-based enzymes for use in biocatalysts, polymerisation based catalysts, supported microporous heterogeneous catalytic centres to homogeneous metal complexes for small molecule actions

Dynamics near the critical point: the hot renormalization group in quantum field theory

The perturbative approach to the description of long wavelength excitations at high temperature breaks down near the critical point of a second order phase transition. We study the \emph{dynamics} of these excitations in a relativistic scalar field theory at and near the critical point via a renormalization group approach at high temperature and an $\epsilon$ expansion in $d=5-\epsilon$ space-time dimensions. The long wavelength physics is determined by a non-trivial fixed point of the renormalization group. At the critical point we find that the dispersion relation and width of quasiparticles of momentum $p$ is $\omega_p \sim p^{z}$ and $\Gamma_p \sim (z-1) \omega_p$ respectively, the group velocity of quasiparticles $v_g \sim p^{z-1}$ vanishes in the long wavelength limit at the critical point. Away from the critical point for $T\gtrsim T_c$ we find $\omega_p \sim \xi^{-z}[1+(p \xi)^{2z}]^{{1/2}}$ and $\Gamma_p \sim (z-1) \omega_p \frac{(p \xi)^{2z}}{1+(p \xi)^{2z}}$ with $\xi$ the finite temperature correlation length $\xi \propto |T-T_c|^{-\nu}$. The new \emph{dynamical} exponent $z$ results from anisotropic renormalization in the spatial and time directions. For a theory with O(N) symmetry we find $z=1+ \epsilon \frac{N+2}{(N+8)^2}+\mathcal{O}(\epsilon^2)$. Critical slowing down, i.e, a vanishing width in the long-wavelength limit, and the validity of the quasiparticle picture emerge naturally from this analysis.Comment: Discussion on new dynamical universality class. To appear in Phys. Rev.

Toward precision measurements in solar neutrinos

Solar neutrino physics enters a stage of precision measurements. In this connection we present a precise analytic description of the neutrino conversion in the context of LMA MSW solution of the solar neutrino problem. Using the adiabatic perturbation theory we derive an analytic formula for the $\nu_e$ survival probability which takes into account the non-adiabatic corrections and the regeneration effect inside the Earth. The probability is averaged over the neutrino production region. We find that the non-adiabatic corrections are of the order $10^{-9}-10^{-7}$. Using the formula for the Earth regeneration effect we discuss features of the zenith angle dependence of the $\nu_e$ flux. In particular, we show that effects of small structures at the surface of the Earth can be important.Comment: 26 pages, 6 figures. Version to appear in Nucl. Phys.

A Note on Domain Walls and the Parameter Space of N=1 Gauge Theories

We study the spectrum of BPS domain walls within the parameter space of N=1 U(N) gauge theories with adjoint matter and a cubic superpotential. Using a low energy description obtained by compactifying the theory on R^3 x S^1, we examine the wall spectrum by combining direct calculations at special points in the parameter space with insight drawn from the leading order potential between minimal walls, i.e those interpolating between adjacent vacua. We show that the multiplicity of composite BPS walls -- as characterised by the CFIV index -- exhibits discontinuities on marginal stability curves within the parameter space of the maximally confining branch. The structure of these marginal stability curves for large N appears tied to certain singularities within the matrix model description of the confining vacua.Comment: 33 pages, LaTeX, 6 eps figures; v2: references adde

Acute anal stretch inhibits NMDA-dependent pelvic-urethra reflex potentiation via spinal GABAergic inhibition in anesthetized rats

The impact of acute anal stretch on the pelvic-urethra reflex potentiation was examined in urethane-anesthetized rats by recording the external urethra sphincter electromyogram activity evoked by the pelvic afferent stimulation. Test stimulation (1 stimulation/30 s) evoked a baseline reflex activity with a single action potential that was abolished by gallamine (5 mg/kg iv). On the other hand, the repetitive stimulation (1 stimulation/1 s) induced spinal reflex potentiation (SRP) that was attenuated by intrathecal 6-cyano-7-nitroquinoxaline- 2,4-dione (a glutamatergic alpha-amino-3-hydroxy-5-methyl- 4-isoxazoleproprionat receptor antagonist, 100 mu M, 10 mu l) and D-2-amino-5-phosphonovalerate [a glutamatergic N-methyl-D-aspartate (NMDA) antagonist, 100 mu M, 10 mu l]. Acute anal stretch using a mosquito clamp with a distance of 4 mm exhibited no effect, whereas distances of 8 mm attenuated and 12 mm abolished the repetitive stimulation-induced SRP. Intrathecal NMDA (100 mu M, 10 mu l) reversed the abolition on SRP caused by anal stretch. On the other hand, pretreated bicuculline [gamma-aminobutyric acid (GABA) A receptor antagonist, 100 mu M, 10 mu l] but not hydroxysaclofen (GABA(B) receptor antagonist) counteracted the abolition on the repetitive stimulation-induced SRP caused by the anal stretch. All of the results suggested that anal stretch may be used as an adjunct to assist voiding dysfunction in patients with overactive urethra sphincter and that GABAergic neurotransmission is important in the neural mechanisms underlying external urethra sphincter activity inhibited by anal stretch

Intelligent Personal Assistants and the Intercultural Negotiations of Dataveillance in Platformed Households

The platformization of households is increasingly possible with the introduction of “intelligent personal assistants” (IPAs) embedded in smart, always-listening speakers and screens, such as Google Home and the Amazon Echo. These devices exemplify Zuboff’s “surveillance capitalism” by commodifying familial and social spaces and funneling data into corporate networks. However, the motivations driving the development of these platforms—and the dataveillance they afford—vary: Amazon appears focused on collecting user data to drive personalized sales across its shopping platform, while Google relies on its vast dataveillance infrastructure to build its AI-driven targeted advertising platform. This paper draws on cross-cultural focus groups regarding IPAs in the Netherlands and the United States. It reveals how respondents in these two countries articulate divergent ways of negotiating the dataveillance affordances and privacy concerns of these IPA platforms. These findings suggest the need for a nuanced approach to combating and limiting the potential harms of these home devices, which may otherwise be seen as equivalents

Metadevice of three dimensional split ring resonators

Split-ring resonator (SRR), a kind of building block for metamaterial unit cell, has attracted wide attentions due to the resonance excitation of electric and magnetic dipolar response. Here, different from prior published lectures, fundamental plasmon properties and potential applications in novel three dimensional vertical split-ring resonators (VSRRs ) are designed and investigated. The resonant properties arose from the electric and magnetic interactions between the VSRR s and light are firstly theoretically and experimentally studied (Fig. 1(a)). Tuning the configuration of VSRR unit cells is able to generate various novel coupling phenomena in VSRRs, such as plasmon hybridization and Fano resonance, as shown in Figs. 1(b) and 1(c) . Subsequently, the VSRR-based refractive-index sensor will be demonstrated. Due to the unique structural configuration, the enhanced plasmon fields localized in VSRR gaps can be lifted off from the dielectric substrate, allowing for the increase of sensing volume and enhancing the sensitivity (Fig. 1(d)) . We further perform a VSRR based metasurface for light manipulation in optical communication frequency, as shown in Fig. 1(e). Moreover, isotropic VSRRs are approached by optimizing the structural arrangement within a unit cell (Fig. 1(f)). Figure 1(g) shows the schematic for isotropic VSRR-based perfect absorber. By incorporating a metallic mirror with isotropic VSRRs, a stronger field confinement happens to enhance the absorption ability, benefitting the development of refractive index sensor. Finally, a transverse toroidal moment generated by normal incident optical wave at gold dumbbell-shaped aperture and a VSRR is designed and experimentally demonstrated , as shown in Fig. 1(h)

Search for direct production of charginos and neutralinos in events with three leptons and missing transverse momentum in √s = 7 TeV pp collisions with the ATLAS detector

A search for the direct production of charginos and neutralinos in final states with three electrons or muons and missing transverse momentum is presented. The analysis is based on 4.7 fb−1 of proton–proton collision data delivered by the Large Hadron Collider and recorded with the ATLAS detector. Observations are consistent with Standard Model expectations in three signal regions that are either depleted or enriched in Z-boson decays. Upper limits at 95% confidence level are set in R-parity conserving phenomenological minimal supersymmetric models and in simplified models, significantly extending previous results