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761.
This research used electronic theory to model the biotransformation of 17α-ethinylestradiol (EE(2)) under aerobic conditions in mixed culture. The methodology involved determining the Frontier Electron Density (FED) for EE(2) and various metabolites, as well as invoking well-established degradation rules to predict transformation pathways. We show that measured EE(2) metabolites are in good agreement with what is expected based on FED-based modeling. Initiating reactions occur at Ring A, producing metabolites that have been experimentally detected. When OH-EE(2) and 6AH-EE(2) are transformed, Ring A is cleaved before Ring B. The metabolites involved in these pathways have different estrogenic potentials, as implied by our analysis of the log P values and the hydrogen bonding characteristics. The OH-EE(2) and 6AH-EE(2) transformation pathways also show redox-induced electron rearrangement (RIER), where oxidation reactions lead to the reduction of carbon units present along the bond axis. Sulfo-EE(2) appears to be difficult to biotransform. These findings clarify theoretical and practical aspects of EE(2) biotransformation. 相似文献
762.
A method for analyzing organoselenium and organic acid metabolites using laser desorption from graphite surfaces coupled to vacuum ultraviolet single photon ionization mass spectrometry (LD/SPI MS) is described. The 1-10-fmol sensitivity and linear dynamic range allows quantitative detection of selenomethionine, trimethylselenonium ion, methylselenogalactosamine, and 1beta-methylseleno-N-acetyl-D-galactosamine in complex biological samples such as human urine. In addition, common urinary metabolites such as tartronic, glutaric, orotic, uric, suberic, and hydroxyhippuric acids, are readily detected. Screening and quantitative detection of these organoselenium and organic acid metabolites is achieved within minutes. The results are also consistent with those obtained using high-performance liquid chromatography tandem mass spectrometry techniques. The study demonstrates the viability of matrix-free LD/SPI MS for molecular characterization and quantitative analysis of biological metabolites in the m/z 10-500 range that are present in complex biological fluids. 相似文献
763.
Deuterium for hydrogen exchange at amide sites in proteins is a well-established means of probing the stability of certain proteins and the effects of interactions with ligands and other proteins. When deuterium content is analyzed by mass spectrometry (MS) of digested peptides, corrections frequently need to be made for back-exchange that occurs during digestion, separation, and analysis. The back-exchange process is actually complex and deserving of analysis in a sequence-specific manner. Here an analysis of back-exchange in the decapeptide, angiotensin I, and a hexapeptide derived by digestion of a 15N-labeled carbohydrate-binding protein, galectin-3, is presented. Nuclear magnetic resonance (NMR) data are used to study back-exchange at specific sites in typical solvents used for separation and analysis, and the derived rates are found to be predictable using methods established for aqueous solvents. The predictability provides potentially new means of improving site specificity of MS analysis and new means of assigning NMR resonances for deuterium content analysis in peptides. 相似文献
764.
We tested the hypothesis that zebra mussels (Dreissena polymorpha) have positive effects on the toxin-producing cyanobacterium, Microcystis aeruginosa, at low phosphorus (P) concentrations, but negative effects on M. aeruginosa at high P, with a large-scale enclosure experiment in an oligotrophic lake. After three weeks, mussels had a significantly positive effect on M. aeruginosa at ambient P (total phosphorus, TP ∼10 μg L−1), and a significantly negative effect at high P (simulating a TP of ∼40 μg L−1 in lakes). Positive and negative effects were strong and very similar in magnitude. Thus, we were able to ameliorate a negative effect of Dreissena invasion on water quality (i.e., promotion of Microcystis) by adding P to water from an oligotrophic lake. Our results are congruent with many field observations of Microcystis response to Dreissena invasion across ecosystems of varying P availability. 相似文献
765.
J. F. Fernandez E. Nieto C. Moure P. Duran R. E. Newnham 《Journal of Materials Science》1995,30(21):5399-5404
The processing of porous PZT thick-film ceramics on Al2O3 has been studied. The films were screen-printed from a thixotropic ink of PZT with a 58% solids content. The thick films were sintered between 1000 and 1150°C for 2 h. The sintered films show a 10 m thickness and an average pore diameter ranging from 1–2 m. The PZT forms a continuous skeleton that can be filled with the desired polymer. Dense and continuous PZT films were fabricated by screen-printing PZT ink on previously electroded Al2O3 substrates with Ag/Pd 70/30 paste. Densification of the PZT was obtained by sintering near the liquidus temperature of the Ag-Pd system. 相似文献
766.
767.
This paper describes COLTHPF, a run-time support specifically designed for the co-ordination of concurrent and communicating HPF tasks. COLTHPF is implemented on top of MPI and requires only small changes to the run-time support of the HPF compiler used. Although the COLTHPF API can be used directly by programmers to write applications as a flat collection of interacting data-parallel tasks, we believe that it can be used more productively through a compiler of a simple high-level co-ordination language which facilitates programmers in structuring a set of data-parallel HPF tasks according to common forms of task-parallelism. The paper outlines design and implementation issues, and discusses the main differences from other approaches to exploiting task parallelism in the HPF framework. We show how COLTHPF can be used to implement common forms of parallelism, e.g. pipeline and processor farms, and we present experimental results regarding both synthetic micro-benchmarks and sample applications. The experiments were conducted on an SGI/Cray T3E using Adaptor, a public domain HPF compiler. Copyright © 1999 John Wiley & Sons, Ltd. 相似文献