Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

Comparison of fast field-cycling magnetic resonance imaging methods and future perspectives

ABSTRACT

Fast field-cycling (FFC) nuclear magnetic resonance relaxometry is a well-established method to determine the relaxation rates as a function of magnetic field strength. This so-called nuclear magnetic relaxation dispersion gives insight into the underlying molecular dynamics of a wide range of complex systems and has gained interest especially in the characterisation of biological tissues and diseases. The combination of FFC techniques with magnetic resonance imaging (MRI) offers a high potential for new types of image contrast more specific to pathological molecular dynamics. This article reviews the progress in FFC-MRI over the last decade and gives an overview of the hardware systems currently in operation. We discuss limitations and error correction strategies specific to FFC-MRI such as field stability and homogeneity, signal-to-noise ratio, eddy currents and acquisition time. We also report potential applications with impact in biology and medicine. Finally, we discuss the challenges and future applications in transferring the underlying molecular dynamics into novel types of image contrast by exploiting the dispersive properties of biological tissue or MRI contrast agents.     

T1Effects in Sequential Dynamic Susceptibility Contrast Experiments

Residual effects of an initial bolus of gadolinium contrast agent have been previously demonstrated in sequential dynamic susceptibility contrast MR experiments. While these residual effects quickly reach a saturation steady state, their etiology is uncertain, and they can lead to spurious estimates of hemodynamic parameters in activation experiments. The possible influence ofT₁effects is now investigated with experiments in whichT₁weighting is varied as well as with serial regionalT₁measurements. Little evidence for significant residualT₁effects is found, suggesting instead that susceptibility effects underlie these observations. An initial saturation dose of contrast agent minimizes this effect.     

Evolved gas analysis (EGA) of brick clays

Using a system based on non-dispersive infrared (NDIR) detectors, evolved gas analysis (EGA) was able to identify and quantify the principal volatiles produced by heating powdered samples of UK brick clays. From these results, atmospheric emissions likely to result from brick production can be predicted. In addition, EGA results for extruded brick clay test pieces are significantly different from those of powdered samples. Within an extruded brick clay body, evolved gases are contained within a pore system and evolved gas-solid phase reactions also occur. This EGA study provides further evidence on the nature of firing reactions within brick clay bodies. The qualitative and quantitative influence of heating rate — a key process condition in brick manufacture — on gas release is also outlined.Dedicated to Dr. Robert Mackenzie on the occasion of his 75th birthday     

A compact shock-assisted free-piston driver for impulse facilities

A free-piston driver that employs entropy-raising shock processes with diaphragm rupture has been constructed, which promises significant theoretical advantages over isentropic compression. Results from a range of conditions with helium and argon driver gases are reported. Significant performance gains were achieved in some test cases. Heat losses are shown to have a strong effect on driver processes. Measurements compare well with predictions from a quasi-one-dimensional numerical code. Received 7 September 1996 / Accepted 5 October 1996     

How to Build Robust Shared Control Systems

Previous researchers have designed shared control schemes with a view to minimising the likelihood that participants will conspire to perform an unauthorised act. But, human nature being what it is, systems inevitably fail; so shared control schemes should also be designed so that the police can identify conspirators after the fact. This requirement leads us to search for schemes with sparse access structures. We show how this can be done using ideas from coding theory. In particular, secret sharing schemes based on geometric codes whose dual [n,k,d] codes have d and n as their only nonzero weights are suitable. We determine their access structures and analyse their properties. We have found almost all of them, and established some relations among codes, designs and secret-sharing schemes.     

Thermomagnetic hysteresis and electrical transport in amorphous films

We report resistivity and magnetization measurements on an amorphous Ni₇₄Mn₂₄Pt₂ thin film in the temperature range of 3–300 K. Two significant features are apparent in both the magnetic susceptibility and electrical resistivity. A low-temperature (low-T) anomaly is observed at about 40 K, where a cusp appears in the resistivity, while a concomitant step-like increase in zero-field-cooled (ZFC) magnetization (M) appears with increasing temperature. The low-T anomaly is attributed to a crossover from a pure re-entrant spin-glass within individual domains to a mixed ferro-spin-glass regime at lower temperatures. By contrast, the high-temperature (high-T) anomaly, signaled by the appearance of hysteresis below 250 K, corresponds to the freezing of transverse spins in individual domains acting independently. Between the low-T and high-T anomalies a small but discernable magnetic hysteresis is observed for warming vs. cooling in the field-cooled (FC) case. This behavior clearly indicates the presence of domain structure in the sample, while the disappearance of this hysteresis at lower temperatures indicates the complete freezing of the spin orientation of these domains. According to these results, we have divided the magnetic state of this sample into three regions: at temperatures above 250 K, the sample behaves like a soft ferromagnet, exhibiting M vs. H loops with very small hysteresis (less than 5 Oe). As the temperature is lowered into the intermediate region (the range 40–250 K), spins become frozen randomly and progressively within the individual domains. These domains behave independently, rather than as a cooperative behavior of the sample. Weak irreversibility sets in, indicating the onset of transverse spin freezing within the domains. At temperatures below 40 K, the M vs. H loops exhibit larger hysteresis, for both the ZFC and FC cases, as in a pure spin-glass. We have also demonstrated giant noise in the resistivity at temperatures just below 250 K. Such noise can originate from fluctuations of the domains near the film surface because of competing effective bulk and surface anisotropy fields. The large observed amplitude may be explained by means of a large ferromagnetic anisotropy in the resistivity due to the large spin–orbit effect seen in NiMn systems. Finally, the low-T peak in the resistivity has been analyzed using Fisher and Langer's expression based on the Friedel Model proposed for critical transitions in transition metals (s–d systems). The fitted results are in satisfactory agreement with the predictions of this model.     

Isoperimetric estimates in products

In a product M ₁ × M ₂ of Riemannian manifolds, the least perimeter required to enclose given volume among general regions is at least 1/√ 2 times that among regions of product form, assuming that the isoperimetric profiles of M ₁ and M ₂ are concave. This result sharpens earlier work of Grigor'yan, generalizes results of Bollobás and Leader and of Barthe, and yields a lower bound on the Cheeger isoperimetric constant of a product.     

Zeros of functions with finite Dirichlet integral

In this paper, we refine a result of Nagel, Rudin, and Shapiro (1982) concerning the zeros of holomorphic functions on the unit disk with finite Dirichlet integral.