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.     

Intrinsic echolocation capability of Hector's dolphin, Cephalorhynchus hectori.

A sonar system's echolocation capabilities can be inferred from the ambiguity distribution (defined here in terms of the conventional signal response function) of each of its transmitted signals. Several records of sounds emitted by Hector's dolphin are analyzed. The computed ambiguity distributions indicate that the sonar clicks of Hector's dolphins should be capable of resolving the ranges of targets as close together as 2 cm apart, but that target velocities cannot be resolved to any useful degree from a single echo.     

Comparison of short range interactions in nematic liquid crystals A 2H-NMR study of 5CB-d19 as a solute

Previous studies using dideuterium as a solute have demonstrated the importance for orientation of the interaction between the solute molecular quadrupole moment and the average electric field gradient present in liquid crystals. With the aim of learning about additional orientational mechanisms, we have studied the temperature dependence of the ²H-NMR spectra of the liquid crystal 5CB-d₁₉ as the solute in three liquid crystal mixtures: 55 wt % 1132/EBBA, 56·5 wt % 1132/EBBA and 70 wt % 5CB/EBBA. In these mixtures, the contribution from the environment to the average electric field gradient at the ²H nucleus of dideuterium is zero. The spectra of 5CB-d₁₉ in the mixtures 55 wt % 1132/EBBA and 56·5 wt % 1132/EBBA are equivalent, but are different from those in 70 wt % 5CB/EBBA. The spectra of 5CB in 55 wt % 1132/EBBA and 70 wt % 5CB/EBBA are analysed using two different models for the short range potential, and param eters of the models are used to compare the potentials in the different mixtures. For a given spectral splitting of the chain C₁ deuteron, the reduced short range potential is the same in all three mixtures studied. The spectral differences observed are a consequence of different nematic-isotropic phase transition temperatures combined with the effect of trans/gauche-isomerization in the hydrocarbon chain.     

Speckle metrology employing LCTV spatial light modulators

Liquid crystal televisions have been employed as spatial light modulators in a variety of optical image processing applications. We have used such devices to develop techniques in speckle metrology for the electronic addition of speckle patterns and the display of speckle correlation, and also for the real-time display of object motion. Factors which affect the performance in terms of the useful working range and the accuracy of displacement measurement are discussed. Some modifications to the LCTV which should increase the potential of these devices as spatial light modulators, when used in both amplitude and phase modulation, are considered briefly.     

Castelnuovo-Mumford regularity by approximation

The Castelnuovo-Mumford regularity of a module gives a rough measure of its complexity. We bound the regularity of a module given a system of approximating modules whose regularities are known. Such approximations can arise naturally for modules constructed by inductive combinatorial means. We apply these methods to bound the regularity of ideals constructed as combinations of linear ideals and the module of derivations of a hyperplane arrangement as well as to give degree bounds for invariants of finite groups.     

An anisotropic fibre-network model for mechano-sorptive creep in paper

In this paper a simplified network model for mechano-sorptive creep is presented, which is a further development of an earlier paper [Strömbro, J., Gudmundson, P., 2008. Mechano-sorptive creep under compressive loading – a micromechanical model. International Journal of Solids and Structures 45 (9), 2420–2450.]. It is assumed that the anisotropic hygroexpansion of the fibres leads to large stresses at the fibre bonds when the moisture content changes. The resulting stress state will accelerate creep if the fibre material obeys a constitutive law that is non-linear. Fibre kinks are included in order to capture experimental observations of larger mechano-sorptive effects in compression than in tension. Moisture dependent material parameters and anisotropy in the fibre distribution have been introduced. Theoretical predictions based on the model are compared to experimental results for an anisotropic paper both under tensile and compressive loading at varying moisture content and it is found that the important features in the experiments are captured by the model. Different kinds of drying conditions have also been examined.     

Behaviour and design considerations for continuous flow closed-open-closed liquid microchannels

This paper introduces a method of combining open and closed microchannels in a single component in a novel way which couples the benefits of both open and closed microfluidic systems and introduces interesting on-chip microfluidic behaviour. Fluid behaviour in such a component, based on continuous pressure driven flow and surface tension, is discussed in terms of cross sectional flow behaviour, robustness, flow-pressure performance, and its application to microfluidic interfacing. The closed-open-closed microchannel possesses the versatility of upstream and downstream closed microfluidics along with open fluidic direct access. The device has the advantage of eliminating gas bubbles present upstream when these enter the open channel section. The unique behaviour of this device opens the door to applications including direct liquid sample interfacing without the need for additional and bulky sample tubing.