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.     

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     

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.     

A high performance liquid chromatographic assay for AMP-deaminase activity in the erythrocytes of healthy subjects and patients with inherited purine disorders

A novel method for measuring AMP-deaminase activity in human erythrocytes is presented, based on the determination of the reaction product, IMP, using high performance liquid chromatography. IMP formation was found to be proportional both to the incubation time and the amount of haemolysate over a wide range. The minimal detectable AMP-deaminase activity was more than 1000 times lower than the mean activity found in healthy controls (1083 nmol/h/mg Hb). No marked difference of activity was found in the patients with the following inherited purine disorders: familial juvenile gouty nephropathy and deficiencies of adenosine deaminase, hypoxanthine-guanine phosphoribosyltransferase or adenine phosphoribosyltransferase. The activity in the erythrocytes of patients with chronic renal failure was also similar to controls. The existence of subjects with low erythrocyte AMP-deaminase activity in the population has been confirmed.     

A simple solution of the van der Waerden permanent problem

The van der Waerden permanent problem was solved using mainly algebraic methods. A much simpler analytic proof is given using a new concept in optimization theory which may be of importance in the general theory of mathematical programming.     

Photosensitizers for tumor therapy: determination of bis(di-isobutyl octadecylsiloxy)silicon 2,3-naphthalocyanine (isoBOSINC) in rat tissue and serum by high-performance liquid chromatography.

Bis(di-isobutyl octadecylsiloxy)silicon 2,3-naphthalocyanine (isoBOSINC) is a synthetic potential photosensitizer for tumor therapy. A new method, which combines solvent extraction and several purification steps, has been developed to determine its presence in tissues. Separation and quantitation of isoBOSINC is done by high-performance liquid chromatography on a silica column with toluene as a mobile phase and using fluorescence detection (lambda ex = 365 nm, lambda em = 750 nm). For recovery studies, isoBOSINC was added to muscles at levels of 0.067 and 0.67 micrograms/g; the mean recoveries were 100%, with coefficients of variation of 6.1 and 6.4%, respectively. For liver samples, the amounts added were 0.67 and 6.7 micrograms/g and for serum 0.67 and 6.70 micrograms/ml. The mean recoveries for liver were 86 and 93%, with coefficients of variation of 7.7 and 4.4%, respectively. For serum, the mean recoveries were 99 and 96%, with coefficients of variation of 2.6 and 6.9%, respectively. Due to its low detection limit and selectivity, the method is appropriate for pharmacokinetic as well as tumor uptake studies following in vivo exposure to isoBOSINC. Preliminary data on tissue distribution of the photosensitizer in normal rats are also presented.