Synthesis and Hepatic Metabolism of Xanthobilirubinic Acid Regioisomers

Summary.  A set of four regioisomeric dipyrrinone propionic acids has been synthesized and their hepatic metabolism examined in rats: xanthobilirubinic acid and pseudo-xanthobilirubinic acid each with a propionic acid on a pyrrole ring; exo-ψ-xanthobilirubinic acid and endo-ψ-xanthobilirubinic acid, each with a propionic acid transposed to a lactam ring. After intravenous injection all four isomers were excreted to some degree in unchanged form in bile in normal rats. Xanthobilirubinic acid, the structurally closest dipyrrinone to bilirubin, and exo-ψ-xanthobilirubinic acid were excreted almost entirely in unchanged form. However, a small fraction of xanthobilirubinic acid acyl glucuronide was also detected. More extensive acyl glucuronidation was observed for pseudo-xanthobilirubinic acid, and endo-ψ-xanthobilirubinic acid underwent slow metabolism to unidentified more polar products that did not seem to be glucuronides.     

ELECTROSTATIC EFFECTS IN THE PHOTOREDUCTION OF FLAVINS BY EDTA

The anaerobic photoreduction of riboflavin, flavin mononucleotide, N(3)-carboxymethylriboflavin, N(3)-methyl-lumiflavin, and lumiflavin by EDTA was studied in aqueous solution over the pH range 2.5–10. The electrostatic effects of the electron donor-acceptor pair produce a secondary effect on the reactivity, and this effect can be predicted from the product of the charges (Z_D x Z_A). The trianonic and tetraanonic species of EDTA have nitrogens which are free from intramolecular hydrogen bonding, and these species are potentially the most reactive. However, in some pH regions the electrostatic effect can become the dominant factor when both the electron donor and acceptor become negatively charged. The excited states of flavins are susceptible to charge effects whether the charge is localized on the side chain or involves the isoalloxazine ring system.     

Applications of Fiber Optic Grating Technology to Multi-Parameter Measurement

Abstract

In this article, approaches reported in the literature for multi-parameter measurement relying on fiber grating technology are reviewed. Due to its importance, the particular case of temperature/strain simultaneous measurement is addressed in further detail, as well as the techniques and sensing heads for temperature-independent strain measurement. Specific criteria are also proposed for sensing head classification in the context of multi-parameter measurement.     

Structure of multiple-vacancy (oxygen) centers in irradiated silicon

Analysis of a new paramagnetic spin 1 spectrum, labeled Si-S1, indicates that it corresponds to the neutral charge state of the Si-B1 center in an excited spin-triplet state. An extension of this analysis to the Si-P1, -P2, -P3, -P4, and -P5 centers suggest that these centers comprise a family of defects which consist of a string of neighboring vacancies in a single (110) plane. In particular, it appears that the Si-P1 center is an odd ( 3)-vacancy defect; the Si-P2 center is a 2-vacancy, oxygen defect; the Si-P3 center is a 4-vacancy defect; the Si-P4 center is a 3-vacancy, oxygen defect of symmetry lower than C_2v ; and the Si-P5 center is a 3-vacancy, oxygen defect having C_2v symmetry.     

Interfacial alloy hydride destabilization in Mg/Pd thin films

Recently, a large increase in the equilibrium hydrogen pressure has been reported for MG thin films capped with a Pd layer. We show that this increase is due to intermixing of Mg and Pd, as opposed to a strain effect as previously claimed. Transmission electron microscopy and depth profiling x-ray photoemission spectroscopy are used to directly measure interfacial intermixing between Mg and Pd, and we find that intermixing and equilibrium hydrogen pressure both increase with annealing. We present a thermodynamic model of the effect of alloying on equilibrium pressure, and find that the observed equilibrium pressure increase is consistent with the observed thickness of the intermixed region, which is of the order of a few nm. We also show that stress measured during hydrogenation corresponds to a negligible increase in equilibrium pressure.     

The effect of pressure on the thermal decomposition of nitroalkanes catalyzed by amines

Abstract

Solutions of 1° and 2° nitroalkanes were thermolyzed in the presence of amines at hydrostatic pressures up to 1.5 GPa, and their rates of decomposition were measured. The probable mechanism of base catalyzed decomposition involves a bimolecular reaction of the aci-nitroalkane with the nitronate ion to yield a carbonyl compound, its corresponding oxime, and nitrite ion as the early rate determining steps. In the case of nitroethane, the products react further to give 3,4,5-trimethylisoxazole as a major product above 0.4 GPa. The effects of pressure on the rates of decomposition of nonacidic nitroalkanes, 2,2-dinitropropane and 2-methyl-2-nitropropane, were measured and used to infer the rate-controlling steps. 2,2-Dini-tropropane appears to undergo rearrangement to a nitrite, followed by homolysis to give acetone, NO and NO₂. 2-Methyl-2-nitropropane gives mostly isobutylene and HONO, probably via a 5-membered cyclic transition state.     

Adaptive multigrid algorithm for lattice QCD

We present a new multigrid solver that is suitable for the Dirac operator in the presence of disordered gauge fields. The key behind the success of the algorithm is an adaptive projection onto the coarse grids that preserves the near null space. The resulting algorithm has weak dependence on the gauge coupling and exhibits very little critical slowing down in the chiral limit. Results are presented for the Wilson-Dirac operator of the 2D U(1) Schwinger model.