Reactivity of electrochemically generated rhenium (II) Tricarbonyl alpha-diimine complexes: a reinvestigation of the oxidation of luminescent Re(CO)3(alpha-Diimine)Cl and related compounds

The oxidative electrochemistry of luminescent rhenium (I) complexes of the type Re(CO) 3(LL)Cl, 1, and Re(CO) 3(LL)Br, 2, where LL is an alpha-diimine, was re-examined in acetonitrile. These compounds undergo metal-based one-electron oxidations, the products of which undergo rapid chemical reaction. Cyclic voltammetry results imply that the electrogenerated rhenium (II) species 1 ( + ) and 2 ( + ) disproportionate, yielding [Re(CO) 3(LL)(CH 3CN)] (+), 7, and additional products. Double potential step chronocoulometry experiments confirm that 1 ( + ) and 2 ( + ) react via second-order processes and, furthermore, indicate that the rate of disproportionation is influenced by the basicity and steric requirements of the alpha-diimine ligands. The simultaneous generation of rhenium (I) and (III) carbonyl products was detected upon the bulk oxidation of 1 using infrared spectroelectrochemistry. The rhenium (III) products are assigned as [Re(CO) 3(LL)Cl 2] (+), 5; an inner-sphere electron-transfer mechanism of the disproportionation is proposed on the basis of the apparent chloride transfer. Chemically irreversible two-electron reduction of 5 yields 1 and Cl (-). No direct spectroscopic evidence was obtained for the generation of rhenium (III) tricarbonyl bromide disproportionation products, [Re(CO) 3(LL)Br 2] (+), 6; this is attributed to their relatively rapid decomposition to 7 and dibromine. In addition, the 17-electron radical cations, 7 ( + ), were successfully characterized using infrared spectroelectrochemistry.     

Nitrofurazone accumulates in avian eyes--a replacement for semicarbazide as a marker of abuse

Intact nitrofurazone is present in whole eyes of chickens fed varying levels of this banned antibiotic and may therefore be used as an alternative to the controversial marker residue, semicarbazide, to monitor for abuse of this drug in primary production.     

An asymmetric nitro-Mannich reaction applicable to alkyl, aryl, and heterocyclic imines

[reaction: see text] A protocol for the enantioselective nitro-Mannich coupling between alkyl, aryl, and heterocyclic p-methoxybenzylimines and trimethylsilylnitropropanate catalyzed by a chiral tBu-BOX Cu(II) catalyst is described. It uses the lowest reported loading of commercially available metal catalyst and chiral ligand, and gives the highest yields and selectivities for a broad substrate range including nonaromatic aldimines. The resultant beta-nitroamines are obtained in 70-94% enantiomeric excess in good yield and can be readily reduced to synthetically useful 1,2-diamines.     

Combinatorial approach to study enzyme/surface interactions

A fast combinatorial approach to access information about the immobilization behavior and kinetics of enzymes on a variation of surfaces is presented. As a test system, Candida Antarctica Lipase B was immobilized on a self-assembled monolayer bearing a gradient of surface energy. The respective immobilization behavior was monitored by Fourier transform infrared micro-spectroscopy. In addition, the activity of the immobilized enzyme was monitored over the entire film in real time with a specially developed fluorescence activity assay embedded into a siloxane gel. It was found that the highest amount of active protein was immobilized on the hydrophilic end of the gradient surface. This effect is associated with a higher surface roughness of this area resulting in hydrophobic micro-environments in which the enzyme gets immobilized.     

A Cyclopropabenzenylidenethenone (propadienone) via a new route to alkylidenecycloproparenes

Reaction of 1,1-dichloro-2,5-diphenylcyclopropabenzene 6 with Meldrum's acid 8 in the presence of pyridine leads to coupling of the cycloproparenyl cation 7 with the stabilized diketo anion 9. Subsequent, spontaneous, base-induced dehydrochlorination gives the alkylidenecyclopropabenzene 11 in a one-pot reaction. Flash vacuum thermolysis of 11 at 650 degrees C ejects acetone and carbon dioxide, giving cyclopropabenzenylidenethenone 12 that is isolated in an Ar matrix at 20 K and characterized by a strong ketene band at 2107 cm(-1) in the IR spectrum. [reaction: see text]     

Development of a 3-D, multi-nuclear continuous wave NMR imaging system

The development of a 3-D, multi-nuclear continuous wave NMR imaging (CW-NMRI) system is described and its imaging capability is demonstrated on a range of materials exhibiting extremely short T(2) relaxation values. A variety of radiofrequency resonators were constructed and incorporated into a new gradient and field offset coil assembly, while the overall system design was modified to minimise microphonic noise which was present in an earlier prototype system. The chemically combined (27)Al in a high temperature refractory cement was imaged, and the CW-NMRI system was found to be sensitive to small differences in (27)Al content in these samples. The penetration of (23)Na in salt water into samples of ordinary Portland cement (OPC) was investigated, with enhanced uptake observed for samples with larger pore size distributions. The solid (13)C component in a carbonated cement sample was also imaged, as were the (7)Li nuclei in a sample of powdered Li(2)CO(3). A spatial resolution of 1mm was measured in an image of a rigid polymeric material exhibiting a principal T( *)(2) value of 16.3 micros. Finally, a high-resolution 3-D image of this rigid polymer is presented.     

The synthesis and directed ortho-lithiation of 4-tert-butylsulfinyl[2.2]paracyclophane

The ortho-lithiation of one diastereoisomer of 4-tert-butylsulfinyl[2.2]paracyclophane is the key step to the synthesis of a range of 4,5-disubstituted [2.2]paracyclophane derivatives.     

Improving pulse sequences for 3D DOSY: COSY-IDOSY

An improved pulse sequence for measuring diffusion-ordered COSY spectra is achieved by incorporating the diffusion encoding directly into the evolution and detection periods of a gradient-enhanced COSY sequence, giving improved sensitivity and a 32-fold reduction in minimum experiment time.