Diastereoselective Radical-Type Cyclopropanation of Electron-Deficient Alkenes Mediated by the Highly Active Cobalt(II) Tetramethyltetraaza[14]annulene Catalyst

A new protocol for the catalytic synthesis of cyclopropanes using electron‐deficient alkenes is presented, which is catalysed by a series of affordable, easy to synthesise and highly active substituted cobalt(II) tetraaza[14]annulenes. These catalysts are compatible with the use of sodium tosylhydrazone salts as precursors to diazo compounds in one‐pot catalytic transformations to afford the desired cyclopropanes in almost quantitative yields. The reaction takes advantage of the metalloradical character of the Co complexes to activate the diazo compounds. The reaction is practical and fast, and proceeds from readily available starting materials. It does not require the slow addition of diazo reagents or tosylhydrazone salts or heating and tolerates many solvents, which include protic ones such as MeOH. The CoII complexes derived from the tetramethyltetraaza[14]annulene ligand are easier to prepare than cobalt(II) porphyrins and present a similar catalytic carbene radical reactivity but are more active. The reaction proceeds at 20 °C in a matter of minutes and even at −78 °C in a few hours. The catalytic system is robust and can operate with either the alkene or the diazo reagent as the limiting reagent, which inhibits the dimerisation of diazo compounds totally. The protocol has been applied to synthesise a variety of substituted cyclopropanes. High yields and selectivities were achieved for various substrates with an intrinsic preference for trans cyclopropanes

Thermoelectric Behaviour Near Magnetic Quantum Critical Point

We use the coupled 2d-spin-3d-fermion model proposed by Rosch {\sl et. al.} (Phys. Rev. Lett. {\bf 79}, 159 (1997)) to study the thermoelectric behaviour of a heavy fermion compound when it is close to an antiferromagnetic quantum critical point. When the low energy spin fluctuations are quasi two dimensional, as has been observed in ${\rm YbRh}_2{\rm Si}_2$ and ${\rm CeCu}_{6-x}{\rm Au}_x$, with a typical 2d ordering wavevector and 3d Fermi surface, the ``hot'' regions on the Fermi surface have a finite area. Due to enhanced scattering with the nearly critical spin fluctuations, the electrons in the hot region are strongly renormalized. We argue that there is an intermediate energy scale where the qualitative aspects of the renormalized hot electrons are captured by a weak-coupling perturbative calculation. Our examination of the electron self energy shows that the entropy carried by the hot electrons is larger than usual. This accounts for the anomalous logarithmic temperature dependence of specific heat observed in these materials. We show that the same mechanism produces logarithmic temperature dependence in thermopower. This has been observed in ${\rm CeCu}_{6-x}{\rm Au}_x$. We expect to see the same behaviour from future experiments on ${\rm YbRh}_2{\rm Si}_2$.Comment: RevTex, two-column, 7 pages, 2 figure

Anisotropic low field behavior and the observation of flux jumps in CeCoIn5

The magnetic behavior of the heavy fermion superconductor CeCoIn5 has been investigated. The low field magnetization data show flux jumps in the mixed state of the superconducting phase in a restricted range of temperature. These flux jumps begin to disappear below 1.7 K, and are completely absent at 1.5 K. The magnetization loops are asymmetric, suggesting that surface and geometrical factors dominate the pinning in this system. The lower critical field (Hc1), obtained from the magnetization data, shows a linear temperature dependence and is anisotropic. The calculated penetration depth is also anisotropic, which is consistent with the observation of an anisotropic superconducting gap in CeCoIn5. The critical currents, determined from the high field isothermal magnetization loops, are comparatively low (around 4000 A/cm2 at 1.6 K and 5 kOe).Comment: 4 pages 3 figure

Pressure Induced Change in the Magnetic Modulation of CeRhIn5

We report the results of a high pressure neutron diffraction study of the heavy fermion compound CeRhIn5 down to 1.8 K. CeRhIn5 is known to order magnetically below 3.8 K with an incommensurate structure. The application of hydrostatic pressure up to 8.6 kbar produces no change in the magnetic wave vector qm. At 10 kbar of pressure however, a sudden change in the magnetic structure occurs. Although the magnetic transition temperature remains the same, qm increases from (0.5, 0.5, 0.298) to (0.5, 0.5, 0.396). This change in the magnetic modulation may be the outcome of a change in the electronic character of this material at 10 kbar.Comment: 4 pages, 3 figures include

Interfacial structure and half-metallic ferromagnetism in Co2MnSi-based magnetic tunnel junctions

Copyright © 2006 The American Physical SocietyX-ray absorption (XAS) and x-ray magnetic circular dichroism (XMCD) techniques are utilized to explore the ferromagnetic/barrier interface in Co2MnSi full Heusler alloy magnetic tunnel junctions. Structural and magnetic properties of the interface region are studied as a function of the degree of site disorder in the alloy and for different degrees of barrier oxidation. Photoelectron scattering features that depend upon the degree of L2(1) ordering are observed in the XAS spectra. Additionally, the moments per 3d hole for Co and Mn atoms are found to be a sensitive function of both the degree of L2(1) ordering and the barrier oxidation state. Significantly, a multiplet structure is observed in the XMCD spectra that indicates a degree of localization of the moments and may result from the half-metallic ferromagnetism (HMF) in the alloy. The magnitude of this multiplet structure appears to vary with preparation conditions and could be utilized to ascertain the role of the constituent atoms in producing the HMF, and to examine methods for preserving the half-metallic state after barrier preparation. The changes in the magnetic structure caused by barrier oxidation could be reversed by inserting a thin Mg interface layer in order to suppress the oxidation of Mn in the Co2MnSi layer

Ultraviolet (UV) transparent plastic claddings warm crops and improve water use efficiency

Advances in the manufacturing of plastic cladding for protected crop cultivation have resulted in wavelength selective plastics capable of manipulating the transmission of solar radiation to include ultraviolet (UV: 280-400 nm). Commercial growers already utilising these plastics report early maturity associated with warmer crops. We hypothesised that UV-B radiation causes partial stomatal closure that reduces stomatal conductance and transpiration rate, thereby increasing leaf temperature (relative to air temperature). We tested this hypothesis by investigating leaf gas exchange and temperature responses of individual tomato leaves to UV-B and UV-A radiation provided by UV lamps in a controlled environment. Transient (90 min) exposure to UV-B radiation decreased stomatal conductance but had minimal impact on photosynthesis, thus increasing leaf temperature and instantaneous water use efficiency. Should this enhanced water use efficiency also occur at a whole plant/canopy scale, these responses may benefit growers of protected crops in arid climates where plastic clad polytunnels are often utilised. © 2020 International Society for Horticultural Science. All rights reserved

Analytic approximation and an improved method for computing the stress-energy of quantized scalar fields in Robertson-Walker spacetimes

An improved method is given for the computation of the stress-energy tensor of a quantized scalar field using adiabatic regularization. The method works for fields with arbitrary mass and curvature coupling in Robertson-Walker spacetimes and is particularly useful for spacetimes with compact spatial sections. For massless fields it yields an analytic approximation for the stress-energy tensor that is similar in nature to those obtained previously for massless fields in static spacetimes.Comment: RevTeX, 8 pages, no figure

Temperature dependence of the interface moments in Co2MnSi thin films

Copyright © 2008 American Institute of PhysicsX-ray magnetic circular dichroism (XMCD) is utilized to explore the temperature dependence of the interface moments in Co2MnSi (CMS) thin films capped with aluminum. By increasing the thickness of the capping layer, we demonstrate enhanced interface sensitivity of the measurements. L2(1)-ordered CMS films show no significant temperature dependence of either the Co or Mn interface moments. However, disordered CMS films show a decreased moment at low temperature possibly caused by increased Mn-Mn antiferromagnetic coupling. It is suggested that for ordered L2(1) CMS films the temperature dependence of the tunneling magnetoresistance is not related to changes in the interface moments