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.     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Characterization of low molecular weight hydrocarbon oligomers by laser desorption/ionization time-of-flight mass spectrometry using a solvent-free sample preparation method.

A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards.     

On the design of broadband quasioptical systems for submillimeter-wave radio-astronomy receivers

In this paper, we summarize the issues that should be considered when designing broadband quasioptical systems for submillimetre-wave radioastronomy receivers. We cover topics such as bandwidth, cross-talk, truncation, and aberrations, and we argue that it should be possible to manufacture high-efficiency systems that have several octaves of bandwidth. A key feature of the paper is that we use the language of multimode Gaussian optics throughout, and in this way, we emphasize that a receiver is a diffraction-limited imaging system rather than just a collection of components for guiding Gaussian beams. The whole discussion is conducted in terms of a particular system we are constructing for the James Clerk Maxwell Telescope in Hawaii.     

Plant processing by simultaneous lactic acid fermentation and enzyme hydrolysis

Traditional ensiling of plant material by anaerobic lactic acid fermentation was combined with enzymatic hydrolysis (ENLAC for short) with cell wall degrading enzymes (hemicellulases, cellulases, and pectinases) to increase fiber digestibility or to increase the recovery of cell content from plants. Such findings were made using 0.015% (w/w, wet basis) Phylacell® enzyme preparation by ENLAC of corn and corn-sorghum mixtures, but not of forage grasses. Addition to alfalfa of a mixture of cell wall degrading enzymes, such as NOVO Viscozyme® together with NOVO Celluclast® each at 0.2–1.0% (w/w, wet basis), resulted in more rapid ensiling and improvement of rumen digestibility of silage by 20%. After 20 d of ensiling at 25 °C when the same enzymes were added to alfalfa at the 1.0% level, protein recovery by pressing increased by 35%, β-carotene recovery by 80%, and chlorophyll/xanthophyll recovery by 30%. ENLAC with the same enzymes also increased the recovery of sclareol from muscatel sage by 400%.

     

Global and local optimization using radial basis function response surface models

The focus of this paper is the optimization of complex multi-parameter systems. We consider systems in which the objective function is not known explicitly, and can only be evaluated through computationally intensive numerical simulation or through costly physical experiments. The objective function may also contain many local extrema which may be of interest. Given objective function values at a scattered set of parameter values, we develop a response surface model that can dramatically reduce the required computation time for parameter optimization runs. The response surface model is developed using radial basis functions, producing a model whose objective function values match those of the original system at all sampled data points. Interpolation to any other point is easily accomplished and generates a model which represents the system over the entire parameter space. This paper presents the details of the use of radial basis functions to transform scattered data points, obtained from a complex continuum mechanics simulation of explosive materials, into a response surface model of a function over the given parameter space. Response surface methodology and radial basis functions are discussed in general and are applied to a global optimization problem for an explosive oil well penetrator.     

Zero-temperature properties of randomly self-interacting polymers

We study the zero-temperature behavior of several simple models for randomly self-interacting polymers in one and 1+1 dimensions. Results are based on exact enumeration and closed-form expressions.     

The calculation of frequency-dependent hyperpolarizabilities including electron correlation effects

The theory for the calculation of the frequency-dependent hyperpolarizabilities β(?2ω; 0, ω), β(?ω; 0, ω), and β(0; ω, ?ω) is discussed. New relations between these tensors are derived for those wave functions that obey the time-dependent Hellmann–Feynman theorem (e.g., the self-consistent field [SCF] or the exact wave function). Using second-order Møller–Plesset perturbation theory (MP2), expressions are obtained for the hyperpolarizabilities in terms of derivatives of appropriately defined linear polarizability tensors with respect to a static electric field. Results are presented for ammonia and formaldehyde for the optical Kerr effect and for secondharmonic generation. These results indicate that it is desirable to determine the frequency-dependent contribution to the hyperopolarizability at the MP2 rather than the SCF level of theory, in cases where the static hyperpolarizability has a large contribution from electron correlation and/or where the frequency-dependent contribution may be more significant, such as for secondharmonic generation.