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.     

Mineralogical analysis of auriferous ores from the El Diamante mine, Colombia

X-ray diffraction (XRD), Mössbauer spectrometry (MS), secondary ions mass spectroscopy (SIMS) and laser-ablation microprobe–inductively coupled plasma–mass spectrometry (LAM–ICP–MS) were used to study mineral samples of Colombian auriferous ores collected from the “El Diamante” mine, located in the municipality of Guachavez-Nariño, in Colombia. The samples were prepared as polished thin sections and polished sections. From XRD data, quartz, sphalerite and pyrite were detected and their respective cell parameters were estimated. From MS analyses, pyrite, arsenopyrite and chalcopyrite were identified; their respective hyperfine parameters and respective texture were deduced. Multiple regions of approximately 200 × 200 μm in each sample were analyzed with SIMS; the occurrence of “invisible gold” associated mainly with pyrite and secondarily with arsenopyrite could thus be assigned. It was also found that pyrite is of the arsenious type. Spots from 30 to 40 μm in diameter were analyzed with LAM–ICP–MS for pyrite, arsenopyrite and sphalerite; Au is “homogeneously” distributed inside the structure of the arsenious pyrite and the arsenopyrite (not as inclusions); the chemical composition indicates similarities of this “invisible gold”, forming a solid solution with arsenious pyrite and arsenopyrite. One hundred nineteen and 62 ppm of ‘invisible gold’ was quantified in 21 spots analyzed on pyrite and in 14 spots on arsenopyrite, respectively.     

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.     

Cover Picture

The cover picture shows in the background the whole cell of a methanotrophic bacterium on which are superimposed components of methane monooxygenase (the structure of the hydroxylase component (top), one of the two four-helix bundles that house the catalytic diiron centers (left)) and a schematic diagram of the catalytic cycle by which the enzyme converts dioxygen and methane into methanol and water. More about this unusual enzyme system is reported by Lippard et al. on p. 2782 ff.     

Time-resolved fluorescence spectra using time-correlated photon counting: Picosecond fluorescence in aqueous solutions of Cr(III) complexes at room temperature

A new procedure for measuring time-resolved emission spectra has been implemented. This technique has subnanosecond time resolution combined with the sensitivity and dynamic range needed to cope with extremely weak luminescence. Using this method the emissions of Cr(NH₃)₂ (NCS)₄^? and Cr(NCS)₆^3- in aqueous solution at room temperature have each been analyzed into two components. The fast component has a broad spectrum and is assigned to prompt fluorescence with lifetime below 100 ps. The slow component is dominated by phosphorescence but may include some delayed fluorescence. The phosphorescence lifetime is 5.5 ± 0.5 ns in Cr(NH₃)₂ (NCS)₄^? and 1.65 ± 0.1 ns in Cr(NCS)₆^3-. Order of magnitude estimates have been derived for other photophysical parameters.     

Pentacyclic triterpenes from <Emphasis Type="Italic">Sarcostemma clausum</Emphasis>

A homologous series of alkanoic acid (C₂–C₅) esters of germanicol was isolated from the methanolic extract of Sarcostemma clausum, of which germanicol-3-propionate and 3-pentanoate have not been previously described in the literature. In addition, taraxasterol, multiflorenol, and bauerenol were also isolated for the first time from the genus Sarcostemma. Structures were elucidated by chemical and spectroscopic methods (NMR, IR, SM) and by comparison with literature data.Published in Khimiya Prirodnykh Soedinenii, No. 6 pp. 464–466, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Does ionized diacetylene have a positive proton affinity?

Singly and doubly charged C₄H₃^+/2+ ions generated upon electron ionization (EI) of the neutral precursors 1,3-butadiene, benzene, and exo-methylene cyclopropane, respectively, are examined by sector-field mass-spectrometry. Charge stripping of the mass-selected monocations affords the corresponding dications and charge exchange of the C₄H₃²⁺ dications allows for the reverse redox process. Refined analysis and additional MS/MS studies suggest that the monocations are mixtures of isomeric ions formed upon ionization, whereas only a single type of dication seems to be formed. As an average of energy-resolved measurements, a vertical ionization energy of IE_v(C₄H₃⁺)=16.5±0.4 eV is derived. In addition to the experimental work, density functional theory is used for a computational exploration of the mono- and dicationic species. The best theoretical estimates are IE_a(C₄H₃⁺)=16.33 eV and IE_v(C₄H₃⁺)=16.49 eV for the most stable isomer H₂C=C---CCH⁺. Combination of the experimental and theoretical findings leads to the conclusion that the diacetylene cation C₄H₂⁺ has indeed a positive proton affinity of PA(C₄H₂⁺)=1.50±0.42 eV.