Influence of Cyclodextrins on the Kinetics of Oxidation of Amino Acids and BSA by Hydrazyl Radicals

The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin.     

The microscopic investigation of structures of moving flux lines by neutron and muon techniques

We have used a variety of microscopic techniques to reveal the structure and motion of flux line arrangements, when the flux lines in low T _c type II superconductors are caused to move by a transport current. Using small-angle neutron scattering by the flux line lattice (FLL), we are able to demonstrate directly the alignment by motion of the nearest-neighbor FLL direction. This tends to be parallel to the direction of flux line motion, as had been suspected from two-dimensional simulations. We also see the destruction of the ordered FLL by plastic flow and the bending of flux lines. Another technique that our collaboration has employed is the direct measurement of flux line motion, using the ultra-high-resolution spectroscopy of the neutron spin-echo technique to observe the energy change of neutrons diffracted by moving flux lines. The muon spin rotation (μSR) technique gives the distribution of values of magnetic field within the FLL. We have recently succeeded in performing μSR measurements while the FLL is moving. Such measurements give complementary information about the local speed and orientation of the FLL motion. We conclude by discussing the possible application of this technique to thin film superconductors.     

Acute pancreatic graft fistula and peripancreatic fluid collection: demonstration by secretin-stimulated MRI

Peripancreatic fluid collections are among the common post pancreas transplant complications, which are mainly due to leakage from the anastomosis site to bowel and graft pancreatitis. Differentiation between these two entities is important because they are treated differently.In this case, secretin stimulated magnetic resonance cholangiopancreatography revealed gradual intraperitoneal fluid collection and accumulation of fluid in small bowel excluded leakage from the anastomosis of the pancreas to bowel and changed the management from surgery to medical treatment.     

Stereochemistry of nitrogen-containing heterocycles

The reduction of the - and -isomers of 2-methyl-4-oxooctahydro-1-pyrindine in the presence of Raney nickel and sodium in ethanol has been studied, and four isomers of 2-methyloctahydro-1-pyrindin-4-ol have been obtained. On the basis of an analysis of IR spectra, basicity constants, and the conditions for the reduction of the ketones, the most probable spatial structures have been assigned to all four piperidols.For part XIV, see [1].     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Substrate binding to cytochromes P450

P450s have attracted tremendous attention owing to not only their involvement in the metabolism of drug molecules and endogenous substrates but also the unusual nature of the reaction they catalyze, namely, the oxidation of unactivated C–H bonds. The binding of substrates to P450s, which is usually viewed as the first step in the catalytic cycle, has been studied extensively via a variety of biochemical and biophysical approaches. These studies were directed towards answering different questions related to P450s, including mechanism of oxidation, substrate properties, unusual substrate oxidation kinetics, function, and active-site features. Some of the substrate binding studies extending over a period of more than 40 years of dedicated work have been summarized in this review and categorized by the techniques employed in the binding studies.

Model electrochemical-mass spectrometric studies of the cytochrome P450-catalyzed oxidations of cyclic tertiary allylamines

Single-electron transfer and hydrogen atom transfer pathways have been proposed to account for the cytochrome P450-catalyzed alpha-carbon oxidations of amines. With the aid of electrochemistry-electrospray ionization mass spectrometry, the electrochemical potentials required for the one-electron oxidations of N-methyl- and selected N-cyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridinyl derivatives and the chemical fates of the resulting aminyl radical cations have been investigated. Comparison of the results of these studies with those observed in the corresponding enzyme catalyzed oxidations suggests that aminyl radical cations are not obligatory intermediates in the cytochrome P450-catalyzed alpha-carbon oxidations of this class of substrates.